The title compound, C44H52N4·C2H5OH, is a calix[4]pyrrole-type macrocycle acting as a receptor, by means of hydrogen-bond interactions to an ethanol solvent. The pyrrole groups are arranged in a 1,3-alternate conformation which gives rise to disorder in the ethanol guest, due to its ability to coordinate both above and below the plane of the macrocycle.
Supporting information
CCDC reference: 159864
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.027 Å
- H-atom completeness 97%
- Disorder in main residue
- R factor = 0.088
- wR factor = 0.267
- Data-to-parameter ratio = 12.9
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
SHFSU_01 Alert B The absolute value of parameter shift to su ratio > 0.10
Absolute value of the parameter shift to su ratio given 0.189
Additional refinement cycles may be required.
Alert Level C:
RFACR_01 Alert C The value of the weighted R factor is > 0.25
Weighted R factor given 0.267
PLAT_301 Alert C Main Residue Disorder ........................ 4.00 Perc.
PLAT_302 Alert C Anion/Solvent Disorder ....................... 38.00 Perc.
PLAT_360 Alert C Short C(sp3)-C(sp3) Bond C5 - C7 = 1.40 Ang.
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C46 H58 N4 O1
Atom count from the _atom_site data: C46 H56 N4 O1
CELLZ_01
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C46 H58 N4 O
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 184.00 184.00 0.00
H 232.00 224.00 8.00
N 16.00 16.00 0.00
O 4.00 4.00 0.00
Difference between formula and atom_site contents detected.
WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
4 Alert Level C = Please check
Dicyclopropyl ketone and pyrrole (1:1) were stirred in ethanol in the presence
of methanesulfonic acid (catalytic quantity) for 24 h. The products were
column chromatographed on silica-gel 60 with a chloroform eluent and (I) was
then crystallized from ethanol.
The ethanol guest molecule exhibits disorder (see above), which produces unusual
geometric parameters. The anisotropic displacement parameters were constrained
to their isotropic equivalent through the use of the ISOR command. Attempts to
restrain bond lengths resulted in an unstable refinement. Therefore, the
geometry of the ethanol molecule was freely refined, which caused difficulty
in convergence resulting in a high parameter shift to standard uncertainty
ratio. The methyl H atoms of the ethanol molecule were not included as they
refined very poorly, due to the nature of the disorder. An attempt was made to
solve and refine the structure in the non-centrosymmetric equivalent space
group Cc in order to resolve the disordered solvent problem. However,
the ethanol molecule occupied two discrete positions and the refinement was
problematic to correlation effects. Checks with the ADDSYM and NEWSYM modules
of the PLATON package (Spek, 1990), in addition to intensity
statistics, confirmed the centrosymmetric nature of the structure.
Cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO, COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1993) and PLATON (Spek, 1990).
Crystal data top
C44H52N4·C2H6O | F(000) = 1472 |
Mr = 682.96 | Dx = 1.180 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 23.908 (5) Å | Cell parameters from 26741 reflections |
b = 7.6861 (15) Å | θ = 3.1–26.4° |
c = 22.947 (5) Å | µ = 0.07 mm−1 |
β = 114.31 (3)° | T = 150 K |
V = 3843.0 (13) Å3 | Plate, colourless |
Z = 4 | 0.22 × 0.15 × 0.05 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1983 reflections with I > 2σ(I) |
ϕ and ω scans to fill Ewald sphere | Rint = 0.084 |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | θmax = 25.3°, θmin = 3.1° |
Tmin = 0.984, Tmax = 0.997 | h = −28→28 |
25105 measured reflections | k = −9→9 |
3463 independent reflections | l = −27→26 |
Refinement top
Refinement on F2 | 36 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.088 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.267 | (Δ/σ)max = 0.189 |
S = 1.58 | Δρmax = 0.57 e Å−3 |
3463 reflections | Δρmin = −0.37 e Å−3 |
269 parameters | |
Crystal data top
C44H52N4·C2H6O | V = 3843.0 (13) Å3 |
Mr = 682.96 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 23.908 (5) Å | µ = 0.07 mm−1 |
b = 7.6861 (15) Å | T = 150 K |
c = 22.947 (5) Å | 0.22 × 0.15 × 0.05 mm |
β = 114.31 (3)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3463 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 1983 reflections with I > 2σ(I) |
Tmin = 0.984, Tmax = 0.997 | Rint = 0.084 |
25105 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.088 | 36 restraints |
wR(F2) = 0.267 | H-atom parameters constrained |
S = 1.58 | (Δ/σ)max = 0.189 |
3463 reflections | Δρmax = 0.57 e Å−3 |
269 parameters | Δρmin = −0.37 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | −0.1041 (5) | 0.0915 (15) | 0.2239 (5) | 0.056 (3) | |
H1 | −0.0821 | −0.0046 | 0.2328 | 0.067* | |
N2 | 0.0200 (5) | 0.1262 (16) | 0.3564 (5) | 0.058 (4) | |
H2 | 0.0196 | 0.2207 | 0.3346 | 0.07* | |
C1 | −0.1348 (6) | 0.082 (2) | 0.1034 (7) | 0.071 (5) | |
C2 | −0.1628 (8) | 0.217 (3) | 0.0479 (7) | 0.094 (7) | |
H2A | −0.2059 | 0.2497 | 0.0392 | 0.113* | |
C3 | −0.1274 (9) | 0.363 (4) | 0.0347 (9) | 0.119 (9) | |
H3A | −0.1482 | 0.4771 | 0.0215 | 0.142* | |
H3B | −0.0826 | 0.3695 | 0.0609 | 0.142* | |
C4 | −0.1511 (10) | 0.215 (4) | −0.0096 (9) | 0.140 (11) | |
H4A | −0.1863 | 0.2374 | −0.051 | 0.168* | |
H4B | −0.121 | 0.13 | −0.0117 | 0.168* | |
C5 | −0.1773 (9) | −0.069 (3) | 0.0794 (11) | 0.106 (7) | |
H5 | −0.1837 | −0.1074 | 0.0355 | 0.127* | |
C6 | −0.2334 (9) | −0.095 (3) | 0.0945 (11) | 0.116 (8) | |
H6A | −0.24 | −0.0127 | 0.1241 | 0.139* | |
H6B | −0.2712 | −0.1435 | 0.0605 | 0.139* | |
C7 | −0.1791 (10) | −0.204 (3) | 0.1193 (11) | 0.114 (8) | |
H7A | −0.1521 | −0.1941 | 0.1654 | 0.137* | |
H7B | −0.183 | −0.3241 | 0.1022 | 0.137* | |
C8 | −0.1336 (6) | 0.162 (2) | 0.1630 (6) | 0.057 (4) | |
C9 | −0.1622 (7) | 0.308 (2) | 0.1705 (7) | 0.074 (5) | |
H9 | −0.1862 | 0.3847 | 0.1373 | 0.089* | |
C10 | −0.1505 (7) | 0.325 (2) | 0.2346 (7) | 0.071 (5) | |
H10 | −0.1657 | 0.416 | 0.2522 | 0.085* | |
C11 | −0.1139 (6) | 0.1923 (19) | 0.2682 (6) | 0.054 (4) | |
C12 | −0.0917 (7) | 0.148 (2) | 0.3378 (6) | 0.060 (4) | |
C13 | −0.1372 (7) | 0.032 (2) | 0.3503 (7) | 0.073 (5) | |
H13 | −0.1246 | 0.0041 | 0.3966 | 0.088* | |
C14 | −0.2048 (8) | 0.050 (3) | 0.3138 (10) | 0.107 (7) | |
H14A | −0.2309 | 0.0401 | 0.3378 | 0.129* | |
H14B | −0.2198 | 0.1331 | 0.2777 | 0.129* | |
C15 | −0.1729 (8) | −0.108 (3) | 0.3070 (10) | 0.099 (7) | |
H15A | −0.1793 | −0.2171 | 0.3266 | 0.119* | |
H15B | −0.1682 | −0.1243 | 0.2665 | 0.119* | |
C16 | −0.0855 (13) | 0.321 (3) | 0.3753 (8) | 0.113 (9) | |
H16 | −0.1287 | 0.3613 | 0.3628 | 0.135* | |
C17 | −0.0571 (11) | 0.339 (3) | 0.4431 (8) | 0.123 (9) | |
H17A | −0.0216 | 0.264 | 0.4678 | 0.148* | |
H17B | −0.0827 | 0.3761 | 0.4656 | 0.148* | |
C18 | −0.0528 (16) | 0.463 (5) | 0.3901 (15) | 0.077 (11) | 0.5 |
H18A | −0.0747 | 0.5755 | 0.3822 | 0.093* | 0.5 |
H18B | −0.0139 | 0.4639 | 0.3844 | 0.093* | 0.5 |
C18' | −0.116 (2) | 0.407 (8) | 0.400 (2) | 0.148 (18) | 0.5 |
C19 | −0.0307 (6) | 0.059 (2) | 0.3623 (7) | 0.064 (5) | |
C20 | −0.0104 (8) | −0.086 (3) | 0.3990 (10) | 0.113 (7) | |
H20 | −0.0349 | −0.1612 | 0.4116 | 0.136* | |
C21 | 0.0520 (9) | −0.105 (3) | 0.4151 (10) | 0.120 (7) | |
H21 | 0.0772 | −0.1964 | 0.4404 | 0.144* | |
C22 | 0.0710 (7) | 0.028 (2) | 0.3887 (7) | 0.076 (5) | |
O01 | 0 | 0.386 (3) | 0.25 | 0.066 (4) | 0.5 |
H01 | 0.0363 | 0.3492 | 0.2647 | 0.099* | 0.25 |
C01 | 0 | 0.539 (14) | 0.25 | 0.225 (5) | 0.5 |
H01A | −0.0252 | 0.5543 | 0.2037 | 0.271* | 0.25 |
H01B | 0.0426 | 0.5544 | 0.2541 | 0.271* | 0.25 |
C02 | −0.007 (7) | −0.318 (14) | 0.266 (7) | 0.177 (5) | 0.25 |
H02A | −0.0331 | −0.3229 | 0.2894 | 0.265* | 0.25 |
H02B | −0.0258 | −0.244 | 0.2284 | 0.265* | 0.25 |
H02C | 0.0334 | −0.2698 | 0.2942 | 0.265* | 0.25 |
O02 | 0 | −0.174 (6) | 0.25 | 0.129 (5) | 0.5 |
H02 | −0.0027 | −0.1732 | 0.2123 | 0.194* | 0.25 |
C01' | 0 | 0.535 (17) | 0.25 | 0.220 (5) | 0.5 |
H01C | 0.0088 | 0.4536 | 0.2221 | 0.329* | 0.25 |
H01D | −0.0417 | 0.5155 | 0.2466 | 0.329* | 0.25 |
H01E | 0.0294 | 0.5173 | 0.2944 | 0.329* | 0.25 |
C02' | −0.004 (11) | −0.320 (18) | 0.266 (9) | 0.192 (5) | 0.25 |
H02D | 0.0246 | −0.3201 | 0.3114 | 0.23* | 0.25 |
H02E | −0.0456 | −0.3201 | 0.266 | 0.23* | 0.25 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.041 (6) | 0.062 (7) | 0.058 (6) | 0.003 (5) | 0.014 (5) | −0.001 (5) |
N2 | 0.041 (6) | 0.080 (8) | 0.048 (6) | −0.006 (6) | 0.014 (5) | 0.018 (5) |
C1 | 0.035 (8) | 0.109 (11) | 0.063 (8) | −0.006 (8) | 0.015 (6) | −0.028 (8) |
C2 | 0.046 (9) | 0.184 (18) | 0.040 (8) | 0.018 (11) | 0.005 (7) | −0.010 (10) |
C3 | 0.071 (12) | 0.22 (2) | 0.065 (10) | 0.010 (14) | 0.026 (9) | 0.042 (13) |
C4 | 0.084 (13) | 0.28 (3) | 0.050 (10) | 0.038 (18) | 0.019 (9) | −0.016 (15) |
C5 | 0.076 (12) | 0.128 (16) | 0.112 (14) | −0.017 (12) | 0.036 (10) | −0.024 (12) |
C6 | 0.047 (11) | 0.159 (19) | 0.133 (17) | −0.017 (12) | 0.028 (11) | −0.028 (14) |
C7 | 0.105 (15) | 0.117 (15) | 0.114 (15) | −0.003 (13) | 0.039 (12) | −0.017 (13) |
C8 | 0.034 (7) | 0.091 (10) | 0.043 (7) | 0.006 (7) | 0.011 (5) | −0.001 (7) |
C9 | 0.066 (9) | 0.104 (11) | 0.051 (8) | 0.034 (9) | 0.024 (7) | 0.018 (8) |
C10 | 0.072 (9) | 0.094 (10) | 0.052 (7) | 0.037 (8) | 0.031 (6) | 0.008 (7) |
C11 | 0.042 (7) | 0.073 (9) | 0.049 (7) | 0.000 (7) | 0.021 (6) | 0.000 (7) |
C12 | 0.048 (8) | 0.083 (10) | 0.048 (7) | −0.007 (7) | 0.020 (6) | 0.006 (7) |
C13 | 0.044 (8) | 0.119 (13) | 0.059 (8) | −0.011 (8) | 0.024 (6) | 0.011 (9) |
C14 | 0.049 (9) | 0.18 (2) | 0.100 (12) | −0.002 (12) | 0.039 (8) | 0.027 (13) |
C15 | 0.083 (11) | 0.127 (15) | 0.097 (11) | −0.041 (11) | 0.048 (9) | −0.001 (11) |
C16 | 0.16 (2) | 0.111 (15) | 0.053 (10) | 0.001 (14) | 0.025 (11) | −0.007 (10) |
C17 | 0.116 (15) | 0.20 (2) | 0.057 (10) | −0.001 (16) | 0.043 (10) | −0.029 (12) |
C18 | 0.07 (2) | 0.08 (2) | 0.08 (2) | −0.004 (17) | 0.022 (16) | −0.019 (17) |
C18' | 0.12 (3) | 0.24 (5) | 0.13 (2) | −0.02 (3) | 0.09 (2) | −0.09 (3) |
C19 | 0.040 (8) | 0.090 (10) | 0.059 (8) | −0.008 (7) | 0.017 (6) | 0.027 (7) |
C20 | 0.056 (10) | 0.145 (14) | 0.136 (13) | 0.005 (11) | 0.038 (9) | 0.089 (11) |
C21 | 0.056 (10) | 0.158 (14) | 0.140 (13) | 0.015 (11) | 0.035 (9) | 0.107 (11) |
C22 | 0.042 (8) | 0.113 (12) | 0.065 (8) | 0.006 (9) | 0.015 (7) | 0.037 (9) |
O01 | 0.081 (6) | 0.053 (6) | 0.065 (6) | 0 | 0.031 (4) | 0 |
C01 | 0.327 (6) | 0.123 (7) | 0.300 (7) | 0 | 0.204 (4) | 0 |
C02 | 0.294 (6) | 0.093 (7) | 0.193 (7) | −0.003 (5) | 0.149 (4) | 0.000 (5) |
O02 | 0.122 (6) | 0.104 (6) | 0.147 (7) | 0 | 0.041 (4) | 0 |
C01' | 0.319 (6) | 0.136 (7) | 0.296 (7) | 0 | 0.219 (4) | 0 |
C02' | 0.319 (6) | 0.106 (7) | 0.190 (7) | −0.002 (5) | 0.146 (4) | 0.000 (5) |
Geometric parameters (Å, º) top
N1—C11 | 1.374 (19) | C12—C16 | 1.56 (3) |
N1—C8 | 1.391 (17) | C13—C15 | 1.47 (2) |
N2—C22 | 1.365 (19) | C13—C14 | 1.49 (2) |
N2—C19 | 1.374 (19) | C14—C15 | 1.48 (3) |
C1—C5 | 1.49 (3) | C16—C18' | 1.28 (5) |
C1—C8 | 1.49 (2) | C16—C18 | 1.30 (4) |
C1—C22i | 1.52 (2) | C16—C17 | 1.42 (3) |
C1—C2 | 1.56 (2) | C17—C18' | 1.44 (5) |
C2—C4 | 1.46 (3) | C17—C18 | 1.58 (4) |
C2—C3 | 1.51 (3) | C19—C20 | 1.36 (2) |
C3—C4 | 1.48 (3) | C20—C21 | 1.39 (3) |
C5—C7 | 1.40 (3) | C21—C22 | 1.36 (3) |
C5—C6 | 1.53 (3) | C22—C1i | 1.52 (2) |
C6—C7 | 1.45 (3) | O01—C01 | 1.18 (11) |
C8—C9 | 1.36 (2) | C01—C02ii | 1.19 (15) |
C9—C10 | 1.39 (2) | C02—C01iii | 1.19 (15) |
C10—C11 | 1.36 (2) | O02—C02' | 1.20 (15) |
C11—C12 | 1.501 (19) | C01'—C02'iv | 1.19 (18) |
C12—C19 | 1.49 (2) | C02'—C01'iii | 1.19 (18) |
C12—C13 | 1.52 (2) | | |
| | | |
C11—N1—C8 | 110.7 (11) | C19—C12—C16 | 109.1 (14) |
C22—N2—C19 | 111.4 (13) | C11—C12—C16 | 107.8 (13) |
C5—C1—C8 | 114.4 (16) | C13—C12—C16 | 108.1 (16) |
C5—C1—C22i | 109.4 (15) | C15—C13—C14 | 59.8 (13) |
C8—C1—C22i | 111.4 (11) | C15—C13—C12 | 124.2 (15) |
C5—C1—C2 | 102.5 (14) | C14—C13—C12 | 122.1 (15) |
C8—C1—C2 | 108.3 (14) | C15—C14—C13 | 59.6 (12) |
C22i—C1—C2 | 110.5 (15) | C13—C15—C14 | 60.6 (13) |
C4—C2—C3 | 59.6 (16) | C18'—C16—C18 | 81 (3) |
C4—C2—C1 | 123.8 (19) | C18'—C16—C17 | 64 (2) |
C3—C2—C1 | 124.8 (14) | C18—C16—C17 | 71 (2) |
C4—C3—C2 | 58.4 (15) | C18'—C16—C12 | 138 (3) |
C2—C4—C3 | 62.0 (15) | C18—C16—C12 | 140 (3) |
C7—C5—C1 | 122.5 (18) | C17—C16—C12 | 125.5 (19) |
C7—C5—C6 | 59.2 (16) | C16—C17—C18' | 53 (2) |
C1—C5—C6 | 123.3 (19) | C16—C17—C18 | 51.0 (16) |
C7—C6—C5 | 55.9 (15) | C18'—C17—C18 | 67 (3) |
C5—C7—C6 | 64.9 (16) | C16—C18—C17 | 58.3 (19) |
C9—C8—N1 | 105.5 (12) | C16—C18'—C17 | 63 (3) |
C9—C8—C1 | 129.6 (13) | C20—C19—N2 | 105.3 (14) |
N1—C8—C1 | 124.8 (13) | C20—C19—C12 | 130.7 (15) |
C8—C9—C10 | 108.9 (13) | N2—C19—C12 | 123.7 (13) |
C11—C10—C9 | 109.3 (14) | C19—C20—C21 | 108.9 (16) |
C10—C11—N1 | 105.6 (12) | C22—C21—C20 | 108.6 (16) |
C10—C11—C12 | 129.6 (14) | C21—C22—N2 | 105.7 (15) |
N1—C11—C12 | 124.5 (13) | C21—C22—C1i | 131.0 (15) |
C19—C12—C11 | 111.5 (13) | N2—C22—C1i | 122.8 (14) |
C19—C12—C13 | 108.8 (13) | O01—C01—C02ii | 157 (9) |
C11—C12—C13 | 111.4 (11) | C01'iii—C02'—O02 | 139 (10) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y+1, z; (iii) x, y−1, z; (iv) −x, y+1, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O02 | 0.88 | 2.25 | 3.08 (3) | 157 |
N2—H2···O01 | 0.88 | 2.2 | 3.03 (2) | 158 |
O01—H01···N1i | 0.84 | 2.5 | 3.23 (2) | 145 |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | C44H52N4·C2H6O |
Mr | 682.96 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 23.908 (5), 7.6861 (15), 22.947 (5) |
β (°) | 114.31 (3) |
V (Å3) | 3843.0 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.22 × 0.15 × 0.05 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.984, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25105, 3463, 1983 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.600 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.088, 0.267, 1.58 |
No. of reflections | 3463 |
No. of parameters | 269 |
No. of restraints | 36 |
H-atom treatment | H-atom parameters constrained |
(Δ/σ)max | 0.189 |
Δρmax, Δρmin (e Å−3) | 0.57, −0.37 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O02 | 0.88 | 2.25 | 3.08 (3) | 157 |
N2—H2···O01 | 0.88 | 2.2 | 3.03 (2) | 158 |
O01—H01···N1i | 0.84 | 2.5 | 3.23 (2) | 145 |
Symmetry code: (i) −x, y, −z+1/2. |
There has been considerable interest over the past decade in the application of calix[4]pyrroles as anion and neutral substrate receptors (Sessler & Gale, 2000). A large number of pyrrolic macrocycles with a wide range of substituents have been shown to coordinate a variety of anions and neutral molecules via a combination of hydrogen-bonding and electrostatic interactions.
The structure of the title compound, (I) (Fig. 1), is the meso-octacyclopropyl derivative of calix[4]pyrrole, coordinated through hydrogen-bonding interactions (see Table 1) to an ethanol guest molecule. The symmetry of the macrocycle is approximately fourfold; however, due to the orientational flexibility of the cyclopropyl groups, it possesses crystallographic twofold symmetry. The geometry of the macrocyclic ring is in reasonable accordance with expected values and related structures (Sessler & Gale, 2000) in the Cambridge Structural Database (Allen et al., 1983). The macrocycle adopts a 1,3-alternate conformation such that adjacent pyrrole rings are orientated in opposite directions. This orientation is observed in the methyl analogue (Gale et al., 1996) and is presumably due to steric interactions within the macrocycle.
In these systems, the geometry of the macrocyclic backbone is of particular importance in determining receptor properties. The nitrogen–nitrogen cross-ring distances are 4.61 (3) and 4.57 (3) Å for N1···N1i and N2···N2i, respectively [symmetry code: (i) -x, y, 0.5 - z]. The meso-C atoms deviate from coplanarity, with an average r.m.s. deviation of 0.2541 (5) Å from their plane, with the dihedral angles between this plane and the pyrrole rings being 57.26 (5) and 56.63 (6)° for the N1 and N2 rings, respectively. The average angles about these meso-C atoms are 109.41 (2) and 109.45 (2)° for C1 and C12, respectively, indicating a strain-free macrocycle. The cavity formed by the meso-C atoms is 5.07 (5) Å in length and has a diagonal distance of 7.15 (4) Å. A comparison with the same geometric parameters of the methyl analogue (Gale et al., 1996), which has no guest molecule present, shows (I) to have a similar macrocyclic geometry, thus demonstrating that the interaction with the ethanol solvent has little effect on the backbone geometry. However, the pyrrole rings are significantly more angled into the cavity than in the methyl substituted case [average N···N = 4.83 (4) Å and average dihedral between pyrrole and meso-C atom plane = 71.5 (2)°], which is presumably due to the interactions with the ethanol guest molecule.
The ethanol guest molecule exhibits disorder, whereby a 50% occupied molecule hydrogen bonds through the alcohol group to a macrocycle above it with the remaining 50% associating via the same mechanism to a macrocycle below it (see Fig. 2). This disorder is assumed to be induced by the alternating orientation of the pyrrole rings in the macrocycle, whereby hydrogen bonding is possible both above and below the calix[4]pyrrole plane. This mode of interaction between guest and host produces a supramolecular assembly of one dimensional `columns'.