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Three novel complexes, namely, penta-μ-acetato-bis(μ2-2-{[2-(6-chloropyridin-2-yl)hydrazinylidene]methyl}-6-methoxyphenolato)-μ-formato-tetramanganese(II), [Mn4(C13H11ClN3O2)2(C2H3O2)5.168(CHO2)0.832], 1, hexa-μ2-acetato-bis(μ2-2-{[2-(6-bromopyridin-2-yl)hydrazinylidene]methyl}-6-methoxyphenolato)tetramanganese(II), [Mn4(C13H11BrN3O2)2(C2H3O2)6], 2, and catena-poly[[μ2-acetato-acetatoaqua(μ2-2-{[2-(6-chloropyridin-2-yl)hydrazinylidene]methyl}-6-methoxyphenolato)dimanganese(II)]-μ2-acetato], [Mn2(C13H11ClN3O2)(C2H3O2)3(H2O)]n, 3, have been synthesized using solvothermal methods. Complexes 1–3 were characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. Complexes 1 and 2 are tetranuclear manganese clusters, while complex 3 has a one-dimensional network based on tetranuclear Mn4(L1)2(CH3COO)6(H2O)2 building units (L1 is 2-{[2-(6-chloropyridin-2-yl)hydrazinylidene]methyl}-6-methoxyphenolate). Magnetic studies reveal that complexes 1–3 display dominant antiferromagnetic interactions between MnII ions through μ2-O bridges. In addition, 1–3 also display favourable electrochemiluminescence (ECL) properties.
Keywords: magnetic property; electrochemicaluminescence; ECL; crystal structure; manganese; one-dimensional coordination polymer.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620001850/jx3055sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S2053229620001850/jx3055complex1sup2.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229620001850/jx3055complex2sup3.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229620001850/jx3055complex3sup4.hkl |
 | Portable Document Format (PDF) file https://doi.org/10.1107/S2053229620001850/jx3055sup5.pdf |
 | Chemdraw file https://doi.org/10.1107/S2053229620001850/jx3055complex1sup6.cdx |
| Chemdraw file https://doi.org/10.1107/S2053229620001850/jx3055complex2sup7.cdx |
| Chemdraw file https://doi.org/10.1107/S2053229620001850/jx3055complex3sup8.cdx |
CCDC references: 1982925; 1982926; 1982927
Computing details top
For all structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
Penta-µ-acetato-bis(µ2-2-{[2-(6-chloropyridin-2-yl)hydrazinylidene]\
methyl}-6-methoxyphenolato)-µ-formato-tetramanganese(II) (complex1) top
Crystal data top
| [Mn4(C13H11ClN3O2)2(C2H3O2)5.168(CHO2)0.832] | Z = 1 |
| Mr = 1115.75 | F(000) = 565.3 |
| Triclinic, P1 | Dx = 1.681 Mg m−3 |
| a = 8.5495 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 11.0550 (7) Å | Cell parameters from 1377 reflections |
| c = 12.5947 (7) Å | θ = 3.7–22.7° |
| α = 76.143 (5)° | µ = 1.32 mm−1 |
| β = 73.110 (6)° | T = 293 K |
| γ = 81.533 (6)° | Block, yellow |
| V = 1102.02 (14) Å3 | 0.25 × 0.22 × 0.18 mm |
Data collection top
| Agilent SuperNova Single Source diffractometer with an Eos detector | 3895 independent reflections |
| Radiation source: SuperNova (Mo) X-ray Source | 2393 reflections with I > 2σ(I) |
| Mirror monochromator | Rint = 0.036 |
| Detector resolution: 16.0233 pixels mm-1 | θmax = 25.0°, θmin = 3.5° |
| ω scans | h = −10→10 |
| Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −13→13 |
| Tmin = 0.726, Tmax = 0.789 | l = −14→14 |
| 6708 measured reflections |
Refinement top
| Refinement on F2 | 9 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
| wR(F2) = 0.136 | w = 1/[σ2(Fo2) + (0.0487P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.005 |
| 3877 reflections | Δρmax = 0.56 e Å−3 |
| 306 parameters | Δρmin = −0.42 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. The diffraction data of 1–3 were collected on a SuperNova, Single source at offset, Eos with graphite monochromated Mo-Ka radiation (λ = 0.71073Å), using the ω–θ scan mode in the ranges 3.46° ≤ θ ≤ 25.1° (1), 3.42° ≤ θ ≤ 25.01° (2), 3.41° ≤ θ ≤ 25.00° (3). The raw frame data were integrated with the CrysAlisPro program. The structures 1-3 were solved by direct methods using SHELXT (Sheldrick, 2015, 2015a) and refined by full-matrix least-squares on F2 using SHELXL-2018 within the OLEX-2 GUI (Dolomanov, et al. 2009). An empirical absorption correction was applied with spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. All non-hydrogen atoms were refined anisotropically. Computer programs: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35, SHELXL (Sheldrick, 2015), Olex2 (Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Mn1 | 0.50279 (10) | 0.26363 (7) | 0.16494 (6) | 0.0453 (3) | |
| Mn2 | 0.42431 (10) | 0.41042 (8) | 0.38041 (6) | 0.0462 (3) | |
| Cl1 | 0.7656 (3) | −0.00084 (19) | 0.17452 (14) | 0.1058 (8) | |
| O1 | 0.3776 (4) | 0.4258 (3) | 0.2165 (3) | 0.0468 (9) | |
| O4 | 0.4569 (4) | 0.4130 (3) | 0.6966 (3) | 0.0550 (10) | |
| O2 | 0.1935 (4) | 0.5489 (3) | 0.3682 (3) | 0.0546 (10) | |
| O3 | 0.3578 (5) | 0.4294 (4) | 0.5494 (3) | 0.0580 (11) | |
| O6 | 0.3727 (5) | 0.1349 (4) | 0.2934 (3) | 0.0652 (11) | |
| O8 | 0.6521 (5) | 0.3038 (4) | 0.3741 (3) | 0.0641 (11) | |
| N3 | 0.4102 (5) | 0.3493 (4) | 0.0135 (3) | 0.0435 (11) | |
| O7 | 0.7190 (5) | 0.2922 (4) | 0.1933 (3) | 0.0654 (12) | |
| N2 | 0.4772 (5) | 0.2915 (4) | −0.0779 (3) | 0.0468 (11) | |
| H2 | 0.450468 | 0.319692 | −0.140651 | 0.056* | |
| N1 | 0.6193 (5) | 0.1491 (4) | 0.0338 (3) | 0.0484 (11) | |
| O5 | 0.2978 (6) | 0.2401 (4) | 0.4336 (3) | 0.0763 (13) | |
| C12 | 0.2542 (6) | 0.4992 (4) | 0.1895 (4) | 0.0401 (12) | |
| C6 | 0.3059 (6) | 0.4432 (5) | −0.0008 (4) | 0.0445 (13) | |
| H6 | 0.284731 | 0.467962 | −0.071582 | 0.053* | |
| C7 | 0.2185 (6) | 0.5139 (5) | 0.0848 (4) | 0.0406 (12) | |
| C18 | 0.7550 (7) | 0.2887 (5) | 0.2844 (5) | 0.0479 (13) | |
| C5 | 0.5856 (6) | 0.1898 (5) | −0.0666 (4) | 0.0428 (13) | |
| C11 | 0.1518 (6) | 0.5711 (5) | 0.2661 (4) | 0.0444 (13) | |
| C10 | 0.0255 (7) | 0.6518 (5) | 0.2419 (4) | 0.0549 (15) | |
| H10 | −0.038850 | 0.697230 | 0.294766 | 0.066* | |
| C8 | 0.0877 (7) | 0.5989 (5) | 0.0603 (4) | 0.0530 (15) | |
| H8 | 0.065741 | 0.609511 | −0.009599 | 0.064* | |
| C16 | 0.3095 (7) | 0.1461 (6) | 0.3938 (5) | 0.0604 (16) | |
| C9 | −0.0076 (7) | 0.6663 (5) | 0.1375 (5) | 0.0616 (16) | |
| H9 | −0.094127 | 0.721650 | 0.120273 | 0.074* | |
| C4 | 0.6567 (7) | 0.1297 (5) | −0.1574 (5) | 0.0581 (16) | |
| H4 | 0.633678 | 0.160907 | −0.227093 | 0.070* | |
| C1 | 0.7252 (7) | 0.0473 (5) | 0.0431 (5) | 0.0581 (16) | |
| C2 | 0.7970 (8) | −0.0167 (6) | −0.0395 (5) | 0.0703 (19) | |
| H2A | 0.869419 | −0.086961 | −0.027798 | 0.084* | |
| C19 | 0.9315 (7) | 0.2641 (6) | 0.2826 (5) | 0.0732 (19) | |
| H19A | 0.941214 | 0.228481 | 0.358002 | 0.110* | |
| H19B | 0.983181 | 0.341122 | 0.254647 | 0.110* | |
| H19C | 0.983951 | 0.206746 | 0.233870 | 0.110* | |
| C3 | 0.7590 (8) | 0.0259 (6) | −0.1422 (5) | 0.0705 (18) | |
| H3 | 0.803982 | −0.017004 | −0.200764 | 0.085* | |
| C13 | 0.1218 (8) | 0.6348 (6) | 0.4414 (5) | 0.0716 (19) | |
| H13A | 0.005181 | 0.629915 | 0.466926 | 0.107* | |
| H13B | 0.145315 | 0.718248 | 0.400829 | 0.107* | |
| H13C | 0.166780 | 0.613924 | 0.505714 | 0.107* | |
| C17 | 0.2359 (9) | 0.0308 (6) | 0.4754 (6) | 0.096 (2) | |
| H17A | 0.227492 | −0.028545 | 0.433177 | 0.144* | |
| H17B | 0.128664 | 0.054299 | 0.519784 | 0.144* | |
| H17C | 0.304898 | −0.006056 | 0.524704 | 0.144* | |
| C14 | 0.400 (13) | 0.365 (7) | 0.627 (7) | 0.050 (9) | 0.584 (17) |
| C15 | 0.3987 (18) | 0.2325 (10) | 0.6550 (11) | 0.078 (5) | 0.584 (17) |
| H15A | 0.379483 | 0.203783 | 0.735598 | 0.117* | 0.584 (17) |
| H15B | 0.502782 | 0.195748 | 0.617451 | 0.117* | 0.584 (17) |
| H15C | 0.313333 | 0.208546 | 0.630769 | 0.117* | 0.584 (17) |
| C14' | 0.405 (18) | 0.371 (11) | 0.644 (10) | 0.050 (9) | 0.416 (17) |
| H14' | 0.391620 | 0.285726 | 0.668056 | 0.060* | 0.416 (17) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.0510 (5) | 0.0518 (5) | 0.0366 (4) | 0.0036 (4) | −0.0148 (4) | −0.0169 (4) |
| Mn2 | 0.0524 (5) | 0.0550 (6) | 0.0343 (4) | 0.0012 (4) | −0.0122 (4) | −0.0176 (4) |
| Cl1 | 0.1356 (18) | 0.1106 (16) | 0.0745 (12) | 0.0645 (14) | −0.0556 (13) | −0.0363 (11) |
| O1 | 0.049 (2) | 0.054 (2) | 0.045 (2) | 0.0107 (19) | −0.0211 (18) | −0.0238 (17) |
| O4 | 0.067 (3) | 0.065 (3) | 0.040 (2) | −0.018 (2) | −0.019 (2) | −0.0129 (19) |
| O2 | 0.051 (2) | 0.068 (3) | 0.050 (2) | 0.014 (2) | −0.0151 (19) | −0.032 (2) |
| O3 | 0.066 (3) | 0.077 (3) | 0.035 (2) | 0.004 (2) | −0.014 (2) | −0.025 (2) |
| O6 | 0.077 (3) | 0.063 (3) | 0.052 (2) | −0.010 (2) | −0.006 (2) | −0.018 (2) |
| O8 | 0.063 (3) | 0.076 (3) | 0.051 (2) | 0.019 (2) | −0.018 (2) | −0.022 (2) |
| N3 | 0.051 (3) | 0.048 (3) | 0.033 (2) | −0.005 (2) | −0.009 (2) | −0.014 (2) |
| O7 | 0.062 (3) | 0.084 (3) | 0.053 (2) | −0.003 (2) | −0.026 (2) | −0.008 (2) |
| N2 | 0.056 (3) | 0.058 (3) | 0.031 (2) | 0.000 (2) | −0.016 (2) | −0.016 (2) |
| N1 | 0.052 (3) | 0.054 (3) | 0.041 (3) | 0.000 (2) | −0.011 (2) | −0.016 (2) |
| O5 | 0.104 (4) | 0.069 (3) | 0.058 (3) | −0.025 (3) | −0.006 (2) | −0.026 (2) |
| C12 | 0.036 (3) | 0.041 (3) | 0.044 (3) | −0.002 (2) | −0.011 (3) | −0.011 (2) |
| C6 | 0.056 (4) | 0.051 (3) | 0.030 (3) | −0.004 (3) | −0.015 (3) | −0.012 (2) |
| C7 | 0.039 (3) | 0.045 (3) | 0.035 (3) | −0.002 (2) | −0.011 (2) | −0.004 (2) |
| C18 | 0.048 (3) | 0.044 (3) | 0.052 (3) | −0.005 (3) | −0.016 (3) | −0.007 (3) |
| C5 | 0.044 (3) | 0.052 (3) | 0.036 (3) | −0.007 (3) | −0.010 (3) | −0.014 (3) |
| C11 | 0.042 (3) | 0.048 (3) | 0.046 (3) | −0.001 (3) | −0.015 (3) | −0.013 (3) |
| C10 | 0.052 (4) | 0.061 (4) | 0.052 (4) | 0.010 (3) | −0.012 (3) | −0.024 (3) |
| C8 | 0.056 (4) | 0.057 (4) | 0.047 (3) | 0.004 (3) | −0.020 (3) | −0.009 (3) |
| C16 | 0.060 (4) | 0.059 (4) | 0.062 (4) | −0.013 (3) | −0.010 (3) | −0.017 (3) |
| C9 | 0.060 (4) | 0.060 (4) | 0.063 (4) | 0.016 (3) | −0.024 (3) | −0.013 (3) |
| C4 | 0.067 (4) | 0.064 (4) | 0.045 (3) | −0.001 (3) | −0.012 (3) | −0.021 (3) |
| C1 | 0.059 (4) | 0.061 (4) | 0.054 (4) | 0.015 (3) | −0.017 (3) | −0.020 (3) |
| C2 | 0.075 (5) | 0.062 (4) | 0.069 (4) | 0.019 (4) | −0.013 (4) | −0.026 (4) |
| C19 | 0.051 (4) | 0.102 (5) | 0.071 (4) | 0.002 (4) | −0.023 (3) | −0.024 (4) |
| C3 | 0.077 (5) | 0.065 (4) | 0.074 (5) | 0.011 (4) | −0.014 (4) | −0.039 (4) |
| C13 | 0.078 (5) | 0.084 (5) | 0.060 (4) | 0.014 (4) | −0.012 (3) | −0.047 (3) |
| C17 | 0.115 (6) | 0.084 (5) | 0.083 (5) | −0.047 (5) | 0.002 (5) | −0.017 (4) |
| C14 | 0.055 (4) | 0.064 (10) | 0.04 (3) | −0.001 (8) | −0.016 (16) | −0.018 (14) |
| C15 | 0.088 (8) | 0.076 (7) | 0.081 (7) | −0.010 (6) | −0.036 (6) | −0.019 (6) |
| C14' | 0.055 (4) | 0.064 (10) | 0.04 (3) | −0.001 (8) | −0.016 (16) | −0.018 (14) |
Geometric parameters (Å, º) top
| Mn1—O1 | 2.090 (3) | C6—C7 | 1.447 (6) |
| Mn1—O6 | 2.049 (4) | C7—C8 | 1.407 (6) |
| Mn1—N3 | 2.225 (4) | C18—C19 | 1.487 (7) |
| Mn1—O7 | 2.063 (4) | C5—C4 | 1.400 (7) |
| Mn1—N1 | 2.236 (4) | C11—C10 | 1.354 (6) |
| Mn2—O1 | 2.178 (3) | C10—H10 | 0.9300 |
| Mn2—O4i | 2.211 (4) | C10—C9 | 1.391 (7) |
| Mn2—O2 | 2.331 (3) | C8—H8 | 0.9300 |
| Mn2—O3 | 2.092 (3) | C8—C9 | 1.368 (7) |
| Mn2—O8 | 2.113 (3) | C16—C17 | 1.520 (8) |
| Mn2—O5 | 2.176 (4) | C9—H9 | 0.9300 |
| Cl1—C1 | 1.732 (6) | C4—H4 | 0.9300 |
| O1—C12 | 1.308 (5) | C4—C3 | 1.347 (7) |
| O4—C14 | 1.36 (9) | C1—C2 | 1.346 (7) |
| O4—C14' | 1.11 (12) | C2—H2A | 0.9300 |
| O2—C11 | 1.389 (5) | C2—C3 | 1.381 (8) |
| O2—C13 | 1.432 (6) | C19—H19A | 0.9600 |
| O3—C14 | 1.18 (9) | C19—H19B | 0.9600 |
| O3—C14' | 1.36 (12) | C19—H19C | 0.9600 |
| O6—C16 | 1.251 (7) | C3—H3 | 0.9300 |
| O8—C18 | 1.244 (6) | C13—H13A | 0.9600 |
| N3—N2 | 1.388 (5) | C13—H13B | 0.9600 |
| N3—C6 | 1.279 (6) | C13—H13C | 0.9600 |
| O7—C18 | 1.262 (6) | C17—H17A | 0.9600 |
| N2—H2 | 0.8600 | C17—H17B | 0.9600 |
| N2—C5 | 1.355 (6) | C17—H17C | 0.9600 |
| N1—C5 | 1.336 (6) | C14—C15 | 1.42 (8) |
| N1—C1 | 1.341 (6) | C15—H15A | 0.9600 |
| O5—C16 | 1.238 (7) | C15—H15B | 0.9600 |
| C12—C7 | 1.406 (6) | C15—H15C | 0.9600 |
| C12—C11 | 1.414 (7) | C14'—H14' | 0.9300 |
| C6—H6 | 0.9300 | ||
| O1—Mn1—N3 | 81.07 (14) | N1—C5—N2 | 117.7 (4) |
| O1—Mn1—N1 | 152.64 (14) | N1—C5—C4 | 121.9 (5) |
| O6—Mn1—O1 | 98.32 (15) | O2—C11—C12 | 113.0 (4) |
| O6—Mn1—N3 | 120.01 (16) | C10—C11—O2 | 124.1 (5) |
| O6—Mn1—O7 | 112.43 (15) | C10—C11—C12 | 123.0 (5) |
| O6—Mn1—N1 | 101.38 (16) | C11—C10—H10 | 120.2 |
| N3—Mn1—N1 | 72.70 (15) | C11—C10—C9 | 119.7 (5) |
| O7—Mn1—O1 | 94.02 (15) | C9—C10—H10 | 120.2 |
| O7—Mn1—N3 | 127.51 (15) | C7—C8—H8 | 119.4 |
| O7—Mn1—N1 | 95.79 (16) | C9—C8—C7 | 121.2 (5) |
| O1—Mn2—O4i | 85.99 (13) | C9—C8—H8 | 119.4 |
| O1—Mn2—O2 | 70.85 (12) | O6—C16—C17 | 115.7 (6) |
| O4i—Mn2—O2 | 80.18 (14) | O5—C16—O6 | 127.7 (6) |
| O3—Mn2—O1 | 153.66 (14) | O5—C16—C17 | 116.6 (6) |
| O3—Mn2—O4i | 97.81 (14) | C10—C9—H9 | 120.1 |
| O3—Mn2—O2 | 84.06 (14) | C8—C9—C10 | 119.7 (5) |
| O3—Mn2—O8 | 99.81 (15) | C8—C9—H9 | 120.1 |
| O3—Mn2—O5 | 89.18 (15) | C5—C4—H4 | 120.5 |
| O8—Mn2—O1 | 106.08 (13) | C3—C4—C5 | 119.1 (5) |
| O8—Mn2—O4i | 92.44 (15) | C3—C4—H4 | 120.5 |
| O8—Mn2—O2 | 172.11 (15) | N1—C1—Cl1 | 114.5 (4) |
| O8—Mn2—O5 | 90.51 (17) | N1—C1—C2 | 125.3 (5) |
| O5—Mn2—O1 | 85.88 (15) | C2—C1—Cl1 | 120.3 (5) |
| O5—Mn2—O4i | 171.83 (14) | C1—C2—H2A | 121.2 |
| O5—Mn2—O2 | 96.44 (15) | C1—C2—C3 | 117.5 (5) |
| Mn1—O1—Mn2 | 103.11 (13) | C3—C2—H2A | 121.2 |
| C12—O1—Mn1 | 132.4 (3) | C18—C19—H19A | 109.5 |
| C12—O1—Mn2 | 120.5 (3) | C18—C19—H19B | 109.5 |
| C14'—O4—Mn2i | 119 (6) | C18—C19—H19C | 109.5 |
| C11—O2—Mn2 | 115.6 (3) | H19A—C19—H19B | 109.5 |
| C11—O2—C13 | 117.3 (4) | H19A—C19—H19C | 109.5 |
| C13—O2—Mn2 | 124.9 (3) | H19B—C19—H19C | 109.5 |
| C14—O3—Mn2 | 129 (4) | C4—C3—C2 | 119.8 (6) |
| C14'—O3—Mn2 | 136 (5) | C4—C3—H3 | 120.1 |
| C16—O6—Mn1 | 126.3 (4) | C2—C3—H3 | 120.1 |
| C18—O8—Mn2 | 123.8 (3) | O2—C13—H13A | 109.5 |
| N2—N3—Mn1 | 114.3 (3) | O2—C13—H13B | 109.5 |
| C6—N3—Mn1 | 129.5 (3) | O2—C13—H13C | 109.5 |
| C6—N3—N2 | 116.3 (4) | H13A—C13—H13B | 109.5 |
| C18—O7—Mn1 | 130.8 (4) | H13A—C13—H13C | 109.5 |
| N3—N2—H2 | 120.6 | H13B—C13—H13C | 109.5 |
| C5—N2—N3 | 118.8 (4) | C16—C17—H17A | 109.5 |
| C5—N2—H2 | 120.6 | C16—C17—H17B | 109.5 |
| C5—N1—Mn1 | 116.4 (3) | C16—C17—H17C | 109.5 |
| C5—N1—C1 | 116.4 (4) | H17A—C17—H17B | 109.5 |
| C1—N1—Mn1 | 127.1 (3) | H17A—C17—H17C | 109.5 |
| C16—O5—Mn2 | 134.5 (4) | H17B—C17—H17C | 109.5 |
| O1—C12—C7 | 123.1 (4) | O4—C14—C15 | 115 (6) |
| O1—C12—C11 | 120.0 (4) | O3—C14—O4 | 121 (6) |
| C7—C12—C11 | 116.8 (4) | O3—C14—C15 | 124 (6) |
| N3—C6—H6 | 117.5 | C14—C15—H15A | 109.7 |
| N3—C6—C7 | 124.9 (4) | C14—C15—H15B | 109.8 |
| C7—C6—H6 | 117.5 | C14—C15—H15C | 108.9 |
| C12—C7—C6 | 123.9 (4) | H15A—C15—H15B | 109.5 |
| C12—C7—C8 | 119.6 (5) | H15A—C15—H15C | 109.5 |
| C8—C7—C6 | 116.4 (4) | H15B—C15—H15C | 109.5 |
| O8—C18—O7 | 123.8 (5) | O4—C14'—O3 | 127 (10) |
| O8—C18—C19 | 119.1 (5) | O4—C14'—H14' | 116.3 |
| O7—C18—C19 | 117.1 (5) | O3—C14'—H14' | 116.3 |
| N2—C5—C4 | 120.4 (4) |
| Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O4ii | 0.86 | 2.05 | 2.879 (5) | 161 |
| C15—H15A···Cl1iii | 0.96 | 2.58 | 3.133 (1) | 117 |
| Symmetry codes: (ii) x, y, z−1; (iii) −x+1, −y, −z+1. |
Hexa-µ2-acetato-bis(µ2-2-{[2-(6-bromopyridin-2-yl)hydrazinylidene]\
methyl}-6-methoxyphenolato)tetramanganese(II) (complex2) top
Crystal data top
| [Mn4(C13H11BrN3O2)2(C2H3O2)6] | F(000) = 1216 |
| Mr = 1216.32 | Dx = 1.761 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 14.6015 (4) Å | Cell parameters from 4376 reflections |
| b = 19.1875 (7) Å | θ = 4.0–27.6° |
| c = 8.2747 (3) Å | µ = 2.89 mm−1 |
| β = 98.376 (3)° | T = 289 K |
| V = 2293.58 (14) Å3 | Block, yellow |
| Z = 2 | 0.23 × 0.19 × 0.15 mm |
Data collection top
| Agilent SuperNova Single Source diffractometer with an Eos detector | 4024 independent reflections |
| Radiation source: SuperNova (Mo) X-ray Source | 3225 reflections with I > 2σ(I) |
| Mirror monochromator | Rint = 0.038 |
| Detector resolution: 16.0233 pixels mm-1 | θmax = 25.0°, θmin = 3.4° |
| ω scans | h = −17→17 |
| Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −22→22 |
| Tmin = 0.522, Tmax = 0.649 | l = −9→9 |
| 16303 measured reflections |
Refinement top
| Refinement on F2 | 7 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
| wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0591P)2 + 4.9728P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = 0.001 |
| 4024 reflections | Δρmax = 0.48 e Å−3 |
| 302 parameters | Δρmin = −0.96 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. The diffraction data of 1–3 were collected on a SuperNova, Single source at offset, Eos with graphite monochromated Mo-Ka radiation (λ = 0.71073Å), using the ω–θ scan mode in the ranges 3.46° ≤ θ ≤ 25.1° (1), 3.42° ≤ θ ≤ 25.01° (2), 3.41° ≤ θ ≤ 25.00° (3). The raw frame data were integrated with the CrysAlisPro program. The structures 1-3 were solved by direct methods using SHELXT (Sheldrick, 2015, 2015a) and refined by full-matrix least-squares on F2 using SHELXL-2018 within the OLEX-2 GUI (Dolomanov, et al. 2009). An empirical absorption correction was applied with spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. All non-hydrogen atoms were refined anisotropically. Computer programs: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35, SHELXL (Sheldrick, 2015), Olex2 (Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| Mn1 | 0.34478 (4) | 0.41016 (3) | 0.88522 (8) | 0.02911 (18) | |
| Br1 | 0.41548 (4) | 0.26102 (3) | 1.12503 (8) | 0.0580 (2) | |
| Mn2 | 0.12475 (4) | 0.46323 (4) | 0.87969 (8) | 0.03374 (19) | |
| O1 | 0.25280 (19) | 0.48775 (15) | 0.7859 (4) | 0.0352 (7) | |
| N1 | 0.4884 (2) | 0.36644 (18) | 0.9583 (4) | 0.0310 (8) | |
| O2 | 0.0930 (2) | 0.53959 (18) | 0.6574 (4) | 0.0452 (8) | |
| O6 | 0.3353 (2) | 0.43307 (17) | 1.1312 (4) | 0.0416 (8) | |
| N3 | 0.4430 (2) | 0.47777 (18) | 0.7716 (4) | 0.0320 (8) | |
| C11 | 0.1697 (3) | 0.5682 (3) | 0.6052 (6) | 0.0406 (11) | |
| C1 | 0.5126 (3) | 0.3121 (2) | 1.0575 (5) | 0.0357 (10) | |
| N2 | 0.5341 (2) | 0.4586 (2) | 0.8074 (5) | 0.0425 (10) | |
| H2 | 0.576118 | 0.481247 | 0.766672 | 0.051* | |
| C6 | 0.4268 (3) | 0.5318 (2) | 0.6820 (6) | 0.0394 (11) | |
| H6 | 0.477667 | 0.554978 | 0.652188 | 0.047* | |
| C12 | 0.2550 (3) | 0.5367 (2) | 0.6762 (5) | 0.0333 (10) | |
| O5 | 0.1853 (3) | 0.4113 (2) | 1.0986 (5) | 0.0608 (10) | |
| C15 | 0.2610 (3) | 0.4193 (2) | 1.1853 (5) | 0.0349 (10) | |
| C5 | 0.5574 (3) | 0.4028 (2) | 0.9092 (6) | 0.0349 (10) | |
| C7 | 0.3359 (3) | 0.5603 (3) | 0.6222 (6) | 0.0395 (11) | |
| C4 | 0.6507 (3) | 0.3867 (3) | 0.9572 (6) | 0.0440 (12) | |
| H4 | 0.696956 | 0.412719 | 0.919527 | 0.053* | |
| C2 | 0.6017 (3) | 0.2929 (3) | 1.1131 (6) | 0.0484 (12) | |
| H2A | 0.615158 | 0.255316 | 1.183419 | 0.058* | |
| C3 | 0.6718 (3) | 0.3329 (3) | 1.0590 (7) | 0.0509 (13) | |
| H3 | 0.733545 | 0.321833 | 1.093975 | 0.061* | |
| C10 | 0.1679 (4) | 0.6210 (3) | 0.4936 (7) | 0.0583 (15) | |
| H10 | 0.111929 | 0.641586 | 0.451105 | 0.070* | |
| C8 | 0.3321 (4) | 0.6149 (3) | 0.5074 (7) | 0.0563 (14) | |
| H8 | 0.386526 | 0.631292 | 0.474999 | 0.068* | |
| C16 | 0.2663 (5) | 0.4094 (4) | 1.3643 (7) | 0.076 (2) | |
| H16A | 0.311283 | 0.374042 | 1.400207 | 0.113* | |
| H16B | 0.206867 | 0.395229 | 1.389202 | 0.113* | |
| H16C | 0.284222 | 0.452363 | 1.419289 | 0.113* | |
| C9 | 0.2501 (4) | 0.6439 (3) | 0.4436 (8) | 0.0700 (18) | |
| H9 | 0.248607 | 0.679131 | 0.366135 | 0.084* | |
| O8 | 0.1296 (2) | 0.36745 (17) | 0.7398 (4) | 0.0467 (8) | |
| C13 | 0.1891 (3) | 0.3256 (2) | 0.7100 (5) | 0.0355 (10) | |
| C14 | 0.1573 (4) | 0.2652 (3) | 0.6029 (8) | 0.0642 (17) | |
| H14A | 0.203569 | 0.254107 | 0.535524 | 0.096* | |
| H14B | 0.100418 | 0.276888 | 0.534978 | 0.096* | |
| H14C | 0.147635 | 0.225624 | 0.669456 | 0.096* | |
| O3 | 0.1355 (2) | 0.5629 (2) | 1.0040 (4) | 0.0517 (9) | |
| C18 | 0.0720 (3) | 0.5866 (3) | 1.0728 (6) | 0.0414 (11) | |
| C17 | 0.0078 (4) | 0.5773 (3) | 0.6236 (8) | 0.0635 (16) | |
| H17A | −0.038709 | 0.554452 | 0.675402 | 0.095* | |
| H17B | −0.011700 | 0.578833 | 0.507779 | 0.095* | |
| H17C | 0.016647 | 0.623925 | 0.665101 | 0.095* | |
| C19 | 0.0629 (4) | 0.6646 (3) | 1.0761 (8) | 0.0662 (16) | |
| H19A | 0.033616 | 0.680684 | 0.971362 | 0.099* | |
| H19B | 0.123238 | 0.685200 | 1.100717 | 0.099* | |
| H19C | 0.026075 | 0.677650 | 1.158288 | 0.099* | |
| O4 | 0.0169 (2) | 0.54980 (19) | 1.1397 (4) | 0.0484 (9) | |
| O7 | 0.2754 (2) | 0.32986 (16) | 0.7610 (4) | 0.0404 (8) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.0204 (3) | 0.0318 (4) | 0.0361 (4) | −0.0024 (3) | 0.0074 (2) | −0.0001 (3) |
| Br1 | 0.0457 (3) | 0.0553 (4) | 0.0733 (4) | −0.0032 (2) | 0.0103 (3) | 0.0166 (3) |
| Mn2 | 0.0211 (3) | 0.0381 (4) | 0.0433 (4) | 0.0013 (3) | 0.0088 (3) | 0.0021 (3) |
| O1 | 0.0307 (15) | 0.0363 (17) | 0.0409 (17) | 0.0038 (13) | 0.0135 (13) | 0.0127 (14) |
| N1 | 0.0225 (17) | 0.0328 (19) | 0.038 (2) | −0.0032 (15) | 0.0065 (15) | −0.0037 (16) |
| O2 | 0.0352 (17) | 0.0481 (19) | 0.052 (2) | 0.0060 (15) | 0.0040 (15) | 0.0122 (16) |
| O6 | 0.0432 (18) | 0.0416 (18) | 0.0439 (18) | −0.0046 (15) | 0.0189 (15) | −0.0015 (15) |
| N3 | 0.0261 (18) | 0.033 (2) | 0.037 (2) | −0.0041 (15) | 0.0086 (15) | 0.0003 (17) |
| C11 | 0.041 (3) | 0.042 (3) | 0.038 (3) | 0.000 (2) | 0.005 (2) | −0.001 (2) |
| C1 | 0.032 (2) | 0.036 (2) | 0.039 (2) | −0.0019 (19) | 0.0069 (19) | −0.004 (2) |
| N2 | 0.0228 (18) | 0.048 (2) | 0.060 (3) | −0.0067 (17) | 0.0169 (17) | 0.009 (2) |
| C6 | 0.035 (2) | 0.042 (3) | 0.044 (3) | −0.013 (2) | 0.014 (2) | −0.001 (2) |
| C12 | 0.038 (2) | 0.030 (2) | 0.032 (2) | −0.0012 (19) | 0.0047 (18) | −0.0004 (19) |
| O5 | 0.052 (2) | 0.062 (2) | 0.063 (2) | −0.0180 (18) | −0.0086 (18) | 0.024 (2) |
| C15 | 0.035 (2) | 0.030 (2) | 0.041 (2) | −0.0030 (19) | 0.008 (2) | −0.0018 (19) |
| C5 | 0.027 (2) | 0.035 (2) | 0.045 (3) | −0.0041 (19) | 0.0113 (18) | −0.012 (2) |
| C7 | 0.038 (2) | 0.041 (3) | 0.040 (3) | −0.003 (2) | 0.009 (2) | 0.004 (2) |
| C4 | 0.024 (2) | 0.047 (3) | 0.062 (3) | −0.005 (2) | 0.012 (2) | −0.005 (3) |
| C2 | 0.035 (3) | 0.050 (3) | 0.059 (3) | 0.008 (2) | 0.001 (2) | −0.001 (3) |
| C3 | 0.024 (2) | 0.056 (3) | 0.072 (4) | 0.005 (2) | 0.002 (2) | −0.012 (3) |
| C10 | 0.051 (3) | 0.058 (3) | 0.062 (3) | 0.001 (3) | −0.004 (3) | 0.020 (3) |
| C8 | 0.058 (3) | 0.053 (3) | 0.060 (3) | −0.011 (3) | 0.016 (3) | 0.024 (3) |
| C16 | 0.072 (4) | 0.115 (6) | 0.044 (3) | −0.031 (4) | 0.023 (3) | −0.008 (3) |
| C9 | 0.074 (4) | 0.064 (4) | 0.071 (4) | −0.006 (3) | 0.007 (3) | 0.041 (3) |
| O8 | 0.0327 (17) | 0.0407 (18) | 0.068 (2) | 0.0005 (15) | 0.0132 (16) | −0.0127 (17) |
| C13 | 0.035 (2) | 0.034 (2) | 0.038 (2) | −0.001 (2) | 0.0070 (19) | −0.003 (2) |
| C14 | 0.041 (3) | 0.053 (3) | 0.094 (5) | −0.004 (3) | −0.004 (3) | −0.027 (3) |
| O3 | 0.0273 (16) | 0.061 (2) | 0.070 (2) | −0.0042 (16) | 0.0184 (16) | −0.0199 (19) |
| C18 | 0.027 (2) | 0.050 (3) | 0.046 (3) | 0.001 (2) | 0.000 (2) | −0.010 (2) |
| C17 | 0.035 (3) | 0.070 (4) | 0.082 (4) | 0.020 (3) | −0.004 (3) | 0.015 (3) |
| C19 | 0.055 (3) | 0.059 (4) | 0.087 (4) | 0.009 (3) | 0.021 (3) | 0.002 (3) |
| O4 | 0.0233 (16) | 0.058 (2) | 0.066 (2) | −0.0022 (15) | 0.0121 (15) | −0.0047 (18) |
| O7 | 0.0296 (16) | 0.0371 (17) | 0.0536 (19) | 0.0005 (13) | 0.0025 (14) | −0.0074 (15) |
Geometric parameters (Å, º) top
| Mn1—O1 | 2.092 (3) | C5—C4 | 1.397 (6) |
| Mn1—N1 | 2.257 (3) | C7—C8 | 1.410 (7) |
| Mn1—O6 | 2.107 (3) | C4—H4 | 0.9300 |
| Mn1—N3 | 2.240 (3) | C4—C3 | 1.340 (7) |
| Mn1—O7 | 2.038 (3) | C2—H2A | 0.9300 |
| Br1—C1 | 1.875 (4) | C2—C3 | 1.404 (7) |
| Mn2—O1 | 2.178 (3) | C3—H3 | 0.9300 |
| Mn2—O2 | 2.344 (3) | C10—H10 | 0.9300 |
| Mn2—O5 | 2.143 (4) | C10—C9 | 1.397 (8) |
| Mn2—O8 | 2.178 (3) | C8—H8 | 0.9300 |
| Mn2—O3 | 2.166 (4) | C8—C9 | 1.354 (8) |
| Mn2—O4i | 2.066 (3) | C16—H16A | 0.9600 |
| O1—C12 | 1.310 (5) | C16—H16B | 0.9600 |
| N1—C1 | 1.341 (6) | C16—H16C | 0.9600 |
| N1—C5 | 1.337 (5) | C9—H9 | 0.9300 |
| O2—C11 | 1.372 (6) | O8—C13 | 1.234 (5) |
| O2—C17 | 1.431 (6) | C13—C14 | 1.492 (7) |
| O6—C15 | 1.260 (5) | C13—O7 | 1.273 (5) |
| N3—N2 | 1.369 (5) | C14—H14A | 0.9600 |
| N3—C6 | 1.276 (6) | C14—H14B | 0.9600 |
| C11—C12 | 1.430 (6) | C14—H14C | 0.9600 |
| C11—C10 | 1.368 (7) | O3—C18 | 1.242 (5) |
| C1—C2 | 1.365 (6) | C18—C19 | 1.503 (7) |
| N2—H2 | 0.8600 | C18—O4 | 1.258 (6) |
| N2—C5 | 1.375 (6) | C17—H17A | 0.9600 |
| C6—H6 | 0.9300 | C17—H17B | 0.9600 |
| C6—C7 | 1.454 (7) | C17—H17C | 0.9600 |
| C12—C7 | 1.398 (6) | C19—H19A | 0.9600 |
| O5—C15 | 1.237 (5) | C19—H19B | 0.9600 |
| C15—C16 | 1.484 (7) | C19—H19C | 0.9600 |
| O1—Mn1—N1 | 152.63 (12) | N1—C5—C4 | 123.1 (4) |
| O1—Mn1—O6 | 95.88 (12) | N2—C5—C4 | 119.4 (4) |
| O1—Mn1—N3 | 80.59 (12) | C12—C7—C6 | 122.7 (4) |
| O6—Mn1—N1 | 90.45 (13) | C12—C7—C8 | 120.3 (4) |
| O6—Mn1—N3 | 114.90 (13) | C8—C7—C6 | 117.0 (4) |
| N3—Mn1—N1 | 72.61 (13) | C5—C4—H4 | 120.8 |
| O7—Mn1—O1 | 95.53 (12) | C3—C4—C5 | 118.4 (4) |
| O7—Mn1—N1 | 103.19 (12) | C3—C4—H4 | 120.8 |
| O7—Mn1—O6 | 123.18 (13) | C1—C2—H2A | 121.7 |
| O7—Mn1—N3 | 121.86 (13) | C1—C2—C3 | 116.6 (5) |
| O1—Mn2—O2 | 70.55 (11) | C3—C2—H2A | 121.7 |
| O1—Mn2—O8 | 84.09 (12) | C4—C3—C2 | 120.6 (4) |
| O5—Mn2—O1 | 97.59 (13) | C4—C3—H3 | 119.7 |
| O5—Mn2—O2 | 164.62 (13) | C2—C3—H3 | 119.7 |
| O5—Mn2—O8 | 90.88 (15) | C11—C10—H10 | 120.0 |
| O5—Mn2—O3 | 90.97 (15) | C11—C10—C9 | 120.0 (5) |
| O8—Mn2—O2 | 97.38 (13) | C9—C10—H10 | 120.0 |
| O3—Mn2—O1 | 88.40 (12) | C7—C8—H8 | 119.6 |
| O3—Mn2—O2 | 79.23 (14) | C9—C8—C7 | 120.9 (5) |
| O3—Mn2—O8 | 172.43 (12) | C9—C8—H8 | 119.6 |
| O4i—Mn2—O1 | 154.17 (13) | C15—C16—H16A | 109.5 |
| O4i—Mn2—O2 | 86.19 (13) | C15—C16—H16B | 109.5 |
| O4i—Mn2—O5 | 107.12 (15) | C15—C16—H16C | 109.5 |
| O4i—Mn2—O8 | 88.06 (13) | H16A—C16—H16B | 109.5 |
| O4i—Mn2—O3 | 98.40 (13) | H16A—C16—H16C | 109.5 |
| Mn1—O1—Mn2 | 103.98 (12) | H16B—C16—H16C | 109.5 |
| C12—O1—Mn1 | 134.7 (3) | C10—C9—H9 | 119.9 |
| C12—O1—Mn2 | 120.7 (3) | C8—C9—C10 | 120.3 (5) |
| C1—N1—Mn1 | 127.2 (3) | C8—C9—H9 | 119.9 |
| C5—N1—Mn1 | 115.9 (3) | C13—O8—Mn2 | 137.2 (3) |
| C5—N1—C1 | 116.6 (4) | O8—C13—C14 | 117.2 (4) |
| C11—O2—Mn2 | 114.8 (3) | O8—C13—O7 | 125.8 (4) |
| C11—O2—C17 | 117.6 (4) | O7—C13—C14 | 117.0 (4) |
| C17—O2—Mn2 | 122.4 (3) | C13—C14—H14A | 109.5 |
| C15—O6—Mn1 | 118.7 (3) | C13—C14—H14B | 109.5 |
| N2—N3—Mn1 | 114.5 (3) | C13—C14—H14C | 109.5 |
| C6—N3—Mn1 | 129.6 (3) | H14A—C14—H14B | 109.5 |
| C6—N3—N2 | 115.8 (4) | H14A—C14—H14C | 109.5 |
| O2—C11—C12 | 113.8 (4) | H14B—C14—H14C | 109.5 |
| C10—C11—O2 | 124.9 (4) | C18—O3—Mn2 | 122.3 (3) |
| C10—C11—C12 | 121.3 (5) | O3—C18—C19 | 116.5 (5) |
| N1—C1—Br1 | 116.4 (3) | O3—C18—O4 | 124.3 (5) |
| N1—C1—C2 | 124.7 (4) | O4—C18—C19 | 119.1 (4) |
| C2—C1—Br1 | 118.9 (4) | O2—C17—H17A | 109.5 |
| N3—N2—H2 | 120.4 | O2—C17—H17B | 109.5 |
| N3—N2—C5 | 119.2 (3) | O2—C17—H17C | 109.5 |
| C5—N2—H2 | 120.4 | H17A—C17—H17B | 109.5 |
| N3—C6—H6 | 117.0 | H17A—C17—H17C | 109.5 |
| N3—C6—C7 | 125.9 (4) | H17B—C17—H17C | 109.5 |
| C7—C6—H6 | 117.0 | C18—C19—H19A | 109.5 |
| O1—C12—C11 | 118.7 (4) | C18—C19—H19B | 109.5 |
| O1—C12—C7 | 124.1 (4) | C18—C19—H19C | 109.5 |
| C7—C12—C11 | 117.2 (4) | H19A—C19—H19B | 109.5 |
| C15—O5—Mn2 | 131.0 (3) | H19A—C19—H19C | 109.5 |
| O6—C15—C16 | 117.3 (4) | H19B—C19—H19C | 109.5 |
| O5—C15—O6 | 124.3 (4) | C18—O4—Mn2i | 137.0 (3) |
| O5—C15—C16 | 118.3 (4) | C13—O7—Mn1 | 127.7 (3) |
| N1—C5—N2 | 117.5 (4) |
| Symmetry code: (i) −x, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O6ii | 0.86 | 2.18 | 2.817 (5) | 130 |
| C4—H4···O3ii | 0.93 | 2.48 | 3.240 (1) | 139 |
| Symmetry code: (ii) −x+1, −y+1, −z+2. |
catena-Poly[[µ2-acetato-acetatoaqua(µ2-2-{[2-(6-chloropyridin-\
2-yl)hydrazinylidene]methyl}-6-methoxyphenolato)dimanganese(II)]-µ2-acetato] (complex3) top
Crystal data top
| [Mn2(C13H11ClN3O2)(C2H3O2)3(H2O)] | F(000) = 1184 |
| Mr = 581.72 | Dx = 1.668 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.5288 (14) Å | Cell parameters from 1369 reflections |
| b = 31.321 (3) Å | θ = 3.5–20.9° |
| c = 9.2665 (13) Å | µ = 1.26 mm−1 |
| β = 110.631 (17)° | T = 293 K |
| V = 2316.6 (6) Å3 | Block, yellow |
| Z = 4 | 0.20 × 0.18 × 0.15 mm |
Data collection top
| Agilent SuperNova Single Source diffractometer with an Eos detector | 4058 independent reflections |
| Radiation source: SuperNova (Mo) X-ray Source | 1923 reflections with I > 2σ(I) |
| Mirror monochromator | Rint = 0.162 |
| Detector resolution: 16.0233 pixels mm-1 | θmax = 25.0°, θmin = 3.4° |
| ω scans | h = −10→10 |
| Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −37→36 |
| Tmin = 0.777, Tmax = 0.829 | l = −10→11 |
| 16044 measured reflections |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.092 | H-atom parameters constrained |
| wR(F2) = 0.286 | w = 1/[σ2(Fo2) + (0.1255P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 4058 reflections | Δρmax = 1.17 e Å−3 |
| 307 parameters | Δρmin = −0.65 e Å−3 |
| 6 restraints |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. The diffraction data of 1–3 were collected on a SuperNova, Single source at offset, Eos with graphite monochromated Mo-Ka radiation (λ = 0.71073Å), using the ω–θ scan mode in the ranges 3.46° ≤ θ ≤ 25.1° (1), 3.42° ≤ θ ≤ 25.01° (2), 3.41° ≤ θ ≤ 25.00° (3). The raw frame data were integrated with the CrysAlisPro program. The structures 1-3 were solved by direct methods using SHELXT (Sheldrick, 2015, 2015a) and refined by full-matrix least-squares on F2 using SHELXL-2018 within the OLEX-2 GUI (Dolomanov, et al. 2009). An empirical absorption correction was applied with spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. All non-hydrogen atoms were refined anisotropically. Computer programs: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35, SHELXL (Sheldrick, 2015), Olex2 (Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| Mn1 | 0.7144 (2) | 0.20392 (4) | 0.13745 (16) | 0.0558 (5) | |
| Mn2 | 0.73263 (18) | 0.08931 (4) | 0.15077 (15) | 0.0491 (5) | |
| Cl1 | 1.0815 (4) | 0.03551 (10) | 0.4028 (3) | 0.0873 (10) | |
| O4 | 0.5827 (8) | 0.14296 (17) | 0.0491 (7) | 0.0523 (16) | |
| O2 | 0.7194 (8) | 0.1019 (2) | 0.3842 (7) | 0.0591 (17) | |
| N3 | 0.5800 (9) | 0.0598 (2) | −0.0771 (8) | 0.0466 (18) | |
| O5 | 0.4242 (9) | 0.2145 (2) | 0.0308 (8) | 0.0673 (19) | |
| N2 | 0.6301 (9) | 0.0195 (2) | −0.0966 (8) | 0.057 (2) | |
| H2 | 0.575657 | 0.005739 | −0.179523 | 0.068* | |
| C4 | 0.8116 (12) | −0.0405 (3) | −0.0098 (11) | 0.053 (2) | |
| H4 | 0.754478 | −0.055015 | −0.100697 | 0.063* | |
| O7 | 0.9594 (8) | 0.1171 (2) | 0.1682 (8) | 0.071 (2) | |
| C12 | 0.4379 (13) | 0.1470 (3) | −0.0705 (11) | 0.053 (2) | |
| N1 | 0.8460 (10) | 0.0239 (2) | 0.1389 (9) | 0.054 (2) | |
| C7 | 0.3726 (11) | 0.1149 (3) | −0.1844 (9) | 0.046 (2) | |
| C5 | 0.7643 (11) | 0.0004 (3) | 0.0117 (10) | 0.050 (2) | |
| O1 | 0.5732 (9) | 0.0477 (2) | 0.2636 (8) | 0.072 (2) | |
| O6 | 0.9704 (9) | 0.1865 (2) | 0.2152 (10) | 0.088 (2) | |
| C6 | 0.4482 (12) | 0.0739 (3) | −0.1772 (11) | 0.048 (2) | |
| H6 | 0.392899 | 0.055258 | −0.256867 | 0.058* | |
| C19 | 1.0350 (13) | 0.1519 (3) | 0.2082 (11) | 0.058 (3) | |
| C11 | 0.3459 (13) | 0.1855 (3) | −0.0880 (12) | 0.056 (3) | |
| C2 | 1.0266 (13) | −0.0364 (4) | 0.2347 (12) | 0.069 (3) | |
| H2A | 1.114317 | −0.048508 | 0.314878 | 0.083* | |
| C9 | 0.1425 (14) | 0.1617 (4) | −0.3224 (13) | 0.071 (3) | |
| H9 | 0.045726 | 0.166427 | −0.407367 | 0.085* | |
| C1 | 0.9769 (12) | 0.0045 (4) | 0.2430 (11) | 0.060 (3) | |
| C3 | 0.9406 (13) | −0.0594 (3) | 0.1009 (12) | 0.063 (3) | |
| H3 | 0.971745 | −0.087247 | 0.088443 | 0.076* | |
| C10 | 0.2018 (14) | 0.1933 (4) | −0.2106 (13) | 0.070 (3) | |
| H10 | 0.144857 | 0.218992 | −0.218933 | 0.084* | |
| C13 | 0.6156 (12) | 0.0730 (3) | 0.3756 (11) | 0.055 (2) | |
| C8 | 0.2243 (13) | 0.1244 (4) | −0.3081 (11) | 0.065 (3) | |
| H8 | 0.180634 | 0.103775 | −0.383916 | 0.077* | |
| C14 | 0.5458 (15) | 0.0672 (4) | 0.4992 (12) | 0.083 (4) | |
| H14A | 0.468463 | 0.043733 | 0.473640 | 0.125* | |
| H14B | 0.635075 | 0.061326 | 0.594669 | 0.125* | |
| H14C | 0.488546 | 0.092753 | 0.509639 | 0.125* | |
| C18 | 1.2233 (14) | 0.1498 (4) | 0.2459 (16) | 0.090 (4) | |
| H18A | 1.255511 | 0.120885 | 0.235623 | 0.135* | |
| H18B | 1.253617 | 0.167805 | 0.176124 | 0.135* | |
| H18C | 1.279848 | 0.159324 | 0.349822 | 0.135* | |
| C15 | 0.3335 (17) | 0.2522 (3) | 0.0364 (15) | 0.105 (5) | |
| H15A | 0.399043 | 0.269536 | 0.121895 | 0.158* | |
| H15B | 0.310357 | 0.267966 | −0.057719 | 0.158* | |
| H15C | 0.230010 | 0.244621 | 0.048908 | 0.158* | |
| O8 | 0.7141 (9) | 0.2222 (2) | −0.0891 (7) | 0.0664 (19) | |
| C16 | 0.7389 (11) | 0.2076 (3) | −0.2053 (10) | 0.048 (2) | |
| C17 | 0.7694 (14) | 0.1615 (3) | −0.2128 (12) | 0.073 (3) | |
| H17A | 0.762992 | 0.147765 | −0.122430 | 0.109* | |
| H17B | 0.686290 | 0.149595 | −0.302923 | 0.109* | |
| H17C | 0.878691 | 0.157104 | −0.217923 | 0.109* | |
| O9 | 0.7428 (9) | 0.23038 (19) | −0.3151 (7) | 0.0668 (19) | |
| O3 | 0.6797 (10) | 0.1900 (2) | 0.3564 (8) | 0.087 (2) | |
| H3A | 0.713893 | 0.211384 | 0.421014 | 0.130* | |
| H3B | 0.737143 | 0.167364 | 0.399834 | 0.130* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.0875 (12) | 0.0305 (9) | 0.0519 (9) | 0.0000 (7) | 0.0275 (9) | −0.0006 (6) |
| Mn2 | 0.0705 (10) | 0.0326 (8) | 0.0459 (8) | −0.0056 (7) | 0.0225 (8) | −0.0033 (6) |
| Cl1 | 0.099 (2) | 0.074 (2) | 0.0658 (17) | −0.0076 (17) | 0.0008 (16) | −0.0027 (15) |
| O4 | 0.076 (4) | 0.026 (3) | 0.054 (4) | −0.003 (3) | 0.021 (4) | 0.002 (3) |
| O2 | 0.081 (5) | 0.045 (4) | 0.055 (4) | −0.012 (4) | 0.028 (4) | −0.008 (3) |
| N3 | 0.059 (5) | 0.031 (4) | 0.049 (4) | −0.002 (4) | 0.019 (4) | −0.004 (3) |
| O5 | 0.092 (5) | 0.047 (4) | 0.070 (4) | 0.007 (4) | 0.037 (4) | −0.013 (3) |
| N2 | 0.068 (5) | 0.041 (5) | 0.053 (5) | 0.016 (4) | 0.012 (4) | −0.008 (4) |
| C4 | 0.071 (7) | 0.036 (6) | 0.050 (5) | 0.002 (5) | 0.020 (5) | −0.012 (4) |
| O7 | 0.079 (5) | 0.048 (5) | 0.084 (5) | −0.016 (4) | 0.026 (4) | −0.005 (4) |
| C12 | 0.066 (6) | 0.035 (6) | 0.061 (6) | −0.001 (5) | 0.026 (6) | 0.011 (4) |
| N1 | 0.070 (5) | 0.041 (5) | 0.052 (5) | −0.014 (4) | 0.022 (4) | −0.007 (4) |
| C7 | 0.055 (5) | 0.044 (6) | 0.038 (5) | −0.002 (5) | 0.014 (5) | 0.010 (4) |
| C5 | 0.065 (6) | 0.037 (5) | 0.052 (5) | −0.007 (5) | 0.026 (5) | −0.005 (4) |
| O1 | 0.090 (5) | 0.069 (5) | 0.056 (4) | −0.018 (4) | 0.024 (4) | −0.016 (4) |
| O6 | 0.082 (5) | 0.059 (6) | 0.108 (6) | 0.010 (4) | 0.016 (5) | −0.017 (4) |
| C6 | 0.057 (6) | 0.041 (6) | 0.049 (5) | −0.009 (5) | 0.023 (5) | −0.001 (4) |
| C19 | 0.073 (7) | 0.044 (7) | 0.051 (6) | −0.010 (6) | 0.015 (5) | −0.003 (5) |
| C11 | 0.078 (7) | 0.044 (6) | 0.060 (6) | 0.010 (5) | 0.040 (6) | 0.003 (5) |
| C2 | 0.076 (7) | 0.066 (8) | 0.061 (7) | 0.025 (6) | 0.017 (6) | 0.011 (6) |
| C9 | 0.073 (7) | 0.077 (9) | 0.061 (7) | 0.001 (7) | 0.024 (6) | 0.011 (6) |
| C1 | 0.055 (6) | 0.068 (8) | 0.053 (6) | −0.001 (6) | 0.013 (5) | 0.004 (5) |
| C3 | 0.081 (7) | 0.048 (6) | 0.077 (7) | 0.010 (6) | 0.048 (7) | 0.002 (5) |
| C10 | 0.082 (8) | 0.057 (8) | 0.074 (7) | 0.024 (6) | 0.030 (7) | 0.018 (6) |
| C13 | 0.065 (6) | 0.045 (6) | 0.048 (6) | 0.002 (5) | 0.011 (5) | 0.005 (5) |
| C8 | 0.081 (7) | 0.062 (8) | 0.046 (6) | −0.002 (6) | 0.017 (6) | 0.004 (5) |
| C14 | 0.099 (9) | 0.092 (10) | 0.060 (7) | −0.002 (7) | 0.029 (7) | 0.006 (6) |
| C18 | 0.088 (9) | 0.062 (9) | 0.137 (12) | −0.013 (7) | 0.061 (9) | −0.012 (7) |
| C15 | 0.157 (13) | 0.047 (8) | 0.114 (10) | 0.031 (8) | 0.051 (10) | −0.021 (7) |
| O8 | 0.105 (5) | 0.047 (4) | 0.057 (4) | 0.003 (4) | 0.040 (4) | 0.003 (3) |
| C16 | 0.066 (6) | 0.038 (6) | 0.038 (5) | 0.005 (5) | 0.014 (5) | 0.002 (4) |
| C17 | 0.117 (9) | 0.041 (6) | 0.079 (7) | −0.001 (6) | 0.057 (7) | −0.003 (5) |
| O9 | 0.117 (6) | 0.041 (4) | 0.051 (4) | 0.011 (4) | 0.040 (4) | 0.008 (3) |
| O3 | 0.158 (7) | 0.049 (5) | 0.058 (4) | 0.001 (5) | 0.043 (5) | 0.002 (3) |
Geometric parameters (Å, º) top
| Mn1—O4 | 2.220 (6) | O6—C19 | 1.229 (11) |
| Mn1—O5 | 2.343 (7) | C6—H6 | 0.9300 |
| Mn1—O6 | 2.116 (8) | C19—C18 | 1.521 (14) |
| Mn1—O8 | 2.175 (6) | C11—C10 | 1.370 (14) |
| Mn1—O9i | 2.100 (6) | C2—H2A | 0.9300 |
| Mn1—O3 | 2.195 (6) | C2—C1 | 1.358 (14) |
| Mn2—O4 | 2.121 (6) | C2—C3 | 1.399 (14) |
| Mn2—O2 | 2.240 (6) | C9—H9 | 0.9300 |
| Mn2—N3 | 2.252 (7) | C9—C10 | 1.392 (15) |
| Mn2—O7 | 2.075 (7) | C9—C8 | 1.343 (14) |
| Mn2—N1 | 2.286 (8) | C3—H3 | 0.9300 |
| Mn2—O1 | 2.375 (7) | C10—H10 | 0.9300 |
| Cl1—C1 | 1.733 (10) | C13—C14 | 1.476 (13) |
| O4—C12 | 1.343 (10) | C8—H8 | 0.9300 |
| O2—C13 | 1.247 (10) | C14—H14A | 0.9600 |
| N3—N2 | 1.364 (9) | C14—H14B | 0.9600 |
| N3—C6 | 1.260 (11) | C14—H14C | 0.9600 |
| O5—C11 | 1.401 (11) | C18—H18A | 0.9600 |
| O5—C15 | 1.423 (11) | C18—H18B | 0.9600 |
| N2—H2 | 0.8600 | C18—H18C | 0.9600 |
| N2—C5 | 1.366 (11) | C15—H15A | 0.9600 |
| C4—H4 | 0.9300 | C15—H15B | 0.9600 |
| C4—C5 | 1.378 (12) | C15—H15C | 0.9600 |
| C4—C3 | 1.349 (13) | O8—C16 | 1.254 (10) |
| O7—C19 | 1.252 (10) | C16—C17 | 1.474 (12) |
| C12—C7 | 1.421 (12) | C16—O9 | 1.252 (10) |
| C12—C11 | 1.418 (12) | C17—H17A | 0.9600 |
| N1—C5 | 1.355 (10) | C17—H17B | 0.9600 |
| N1—C1 | 1.337 (11) | C17—H17C | 0.9600 |
| C7—C6 | 1.426 (12) | O3—H3A | 0.8769 |
| C7—C8 | 1.408 (12) | O3—H3B | 0.8753 |
| O1—C13 | 1.254 (11) | ||
| O4—Mn1—O5 | 69.1 (2) | N3—C6—H6 | 115.7 |
| O6—Mn1—O4 | 103.4 (3) | C7—C6—H6 | 115.7 |
| O6—Mn1—O5 | 172.0 (3) | O7—C19—C18 | 115.0 (9) |
| O6—Mn1—O8 | 92.7 (3) | O6—C19—O7 | 126.1 (10) |
| O6—Mn1—O3 | 95.3 (3) | O6—C19—C18 | 118.8 (9) |
| O8—Mn1—O4 | 92.4 (2) | O5—C11—C12 | 111.7 (9) |
| O8—Mn1—O5 | 85.0 (2) | C10—C11—O5 | 125.2 (9) |
| O8—Mn1—O3 | 171.8 (3) | C10—C11—C12 | 123.0 (10) |
| O9i—Mn1—O4 | 157.8 (3) | C1—C2—H2A | 121.3 |
| O9i—Mn1—O5 | 88.6 (3) | C1—C2—C3 | 117.4 (10) |
| O9i—Mn1—O6 | 98.8 (3) | C3—C2—H2A | 121.3 |
| O9i—Mn1—O8 | 84.6 (2) | C10—C9—H9 | 119.9 |
| O9i—Mn1—O3 | 92.5 (2) | C8—C9—H9 | 119.9 |
| O3—Mn1—O4 | 87.4 (2) | C8—C9—C10 | 120.3 (11) |
| O3—Mn1—O5 | 87.2 (3) | N1—C1—Cl1 | 114.2 (8) |
| O4—Mn2—O2 | 93.6 (2) | N1—C1—C2 | 125.8 (10) |
| O4—Mn2—N3 | 81.4 (3) | C2—C1—Cl1 | 120.0 (8) |
| O4—Mn2—N1 | 152.7 (3) | C4—C3—C2 | 118.6 (9) |
| O4—Mn2—O1 | 106.3 (2) | C4—C3—H3 | 120.7 |
| O2—Mn2—N3 | 140.2 (2) | C2—C3—H3 | 120.7 |
| O2—Mn2—N1 | 111.7 (3) | C11—C10—C9 | 118.4 (10) |
| O2—Mn2—O1 | 55.9 (2) | C11—C10—H10 | 120.8 |
| N3—Mn2—N1 | 72.6 (3) | C9—C10—H10 | 120.8 |
| N3—Mn2—O1 | 87.5 (2) | O2—C13—O1 | 120.1 (9) |
| O7—Mn2—O4 | 95.8 (3) | O2—C13—C14 | 120.7 (9) |
| O7—Mn2—O2 | 102.3 (3) | O1—C13—C14 | 119.1 (10) |
| O7—Mn2—N3 | 117.4 (3) | C7—C8—H8 | 118.3 |
| O7—Mn2—N1 | 88.9 (3) | C9—C8—C7 | 123.5 (10) |
| O7—Mn2—O1 | 149.2 (3) | C9—C8—H8 | 118.3 |
| N1—Mn2—O1 | 81.2 (2) | C13—C14—H14A | 109.5 |
| Mn2—O4—Mn1 | 111.7 (3) | C13—C14—H14B | 109.5 |
| C12—O4—Mn1 | 115.0 (5) | C13—C14—H14C | 109.5 |
| C12—O4—Mn2 | 132.5 (5) | H14A—C14—H14B | 109.5 |
| C13—O2—Mn2 | 95.0 (6) | H14A—C14—H14C | 109.5 |
| N2—N3—Mn2 | 113.6 (6) | H14B—C14—H14C | 109.5 |
| C6—N3—Mn2 | 128.1 (6) | C19—C18—H18A | 109.5 |
| C6—N3—N2 | 117.9 (8) | C19—C18—H18B | 109.5 |
| C11—O5—Mn1 | 112.3 (5) | C19—C18—H18C | 109.5 |
| C11—O5—C15 | 116.9 (9) | H18A—C18—H18B | 109.5 |
| C15—O5—Mn1 | 127.5 (7) | H18A—C18—H18C | 109.5 |
| N3—N2—H2 | 119.1 | H18B—C18—H18C | 109.5 |
| C5—N2—N3 | 121.8 (8) | O5—C15—H15A | 109.5 |
| C5—N2—H2 | 119.1 | O5—C15—H15B | 109.5 |
| C5—C4—H4 | 120.0 | O5—C15—H15C | 109.5 |
| C3—C4—H4 | 120.0 | H15A—C15—H15B | 109.5 |
| C3—C4—C5 | 120.1 (9) | H15A—C15—H15C | 109.5 |
| C19—O7—Mn2 | 139.1 (7) | H15B—C15—H15C | 109.5 |
| O4—C12—C7 | 123.5 (8) | C16—O8—Mn1 | 142.2 (6) |
| O4—C12—C11 | 119.0 (9) | O8—C16—C17 | 118.8 (8) |
| C11—C12—C7 | 117.4 (9) | O9—C16—O8 | 123.5 (8) |
| C5—N1—Mn2 | 115.6 (6) | O9—C16—C17 | 117.7 (8) |
| C1—N1—Mn2 | 129.2 (7) | C16—C17—H17A | 109.5 |
| C1—N1—C5 | 115.1 (9) | C16—C17—H17B | 109.5 |
| C12—C7—C6 | 123.2 (8) | C16—C17—H17C | 109.5 |
| C8—C7—C12 | 117.4 (9) | H17A—C17—H17B | 109.5 |
| C8—C7—C6 | 119.4 (9) | H17A—C17—H17C | 109.5 |
| N2—C5—C4 | 120.8 (9) | H17B—C17—H17C | 109.5 |
| N1—C5—N2 | 116.3 (8) | C16—O9—Mn1ii | 133.9 (6) |
| N1—C5—C4 | 122.9 (9) | Mn1—O3—H3A | 111.0 |
| C13—O1—Mn2 | 88.6 (6) | Mn1—O3—H3B | 110.5 |
| C19—O6—Mn1 | 129.6 (7) | H3A—O3—H3B | 107.9 |
| N3—C6—C7 | 128.6 (9) |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1iii | 0.86 | 2.08 | 2.818 (10) | 144 |
| O3—H3A···O8i | 0.88 | 2.08 | 2.794 (10) | 138 |
| O3—H3A···O9iv | 0.88 | 2.44 | 3.162 (9) | 140 |
| O3—H3B···O2 | 0.88 | 2.06 | 2.782 (10) | 139 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (iii) −x+1, −y, −z; (iv) x, y, z+1. |
