Structure of the X-phase of 38% brominated betaine calcium chloride dihydrate

Vieira, L.G.; Hernandez, O.; Ribeiro, J.L.; Cousson, A.; Kiat, J.-M.; Chaves, M.R.; Almeida, A.; Klöpperpieper, A.

doi:10.1107/S0108768101001525

Structure of the X-phase of 38% brominated betaine calcium chloride dihydrate

L. G. Vieira, O. Hernandez, J. L. Ribeiro, A. Cousson, J.-M. Kiat, M. R. Chaves, A. Almeida and A. Klöpperpieper

The structures of the high- and low-temperature phases of 38% brominated BCCD [betaine (trimethylammonioacetate) calcium chloride dihydrate], the latter being known as the X-phase, have been determined by single-crystal neutron diffraction at 295 and 20 K, respectively. The symmetry of the X-phase is described by the P2₁2₁2₁ space group. The distortion with respect to the high-temperature Pnma phase is characterized by anti-symmetric displacements of the betaine molecules as well as of the Ca octahedra. On the basis of a symmetry-mode analysis, we propose an interpretation of the direct phase transition that occurs around 80 K between these two phases.

Keywords: betaine; symmetry.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768101001525/lc0032sup1.cif Contains datablocks global, 295k, 20k
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768101001525/lc0032295Ksup2.hkl Contains datablock 295K
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768101001525/lc003220Ksup3.hkl Contains datablock 20K

CCDC references: 166493; 166494

Computing details top

Data reduction: COLL5 (Lehmann & Larsen, 1974) for 295k; PRON (Scherf, 1998) for (20k). For both compounds, program(s) used to refine structure: CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996); molecular graphics: CAMERON (Watkin, Prout & Pearce, 1996); software used to prepare material for publication: CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996).

Figures top

(295k) 38% Brominated Betaine Calcium Chloride Dihydrate top

Crystal data top

(C₅H₁₁NO₂)·(CaCl_1.28Br_0.72)·2(H₂O)	D_x = 1.60 Mg m⁻³
M_r = 296.2	Neutron radiation, λ = 1.531 Å
Orthorhombic, Pnma	Cell parameters from 45 reflections
a = 11.02 (3) Å	θ = 11.7–30.1°
b = 10.27 (2) Å	µ = 0.44 mm⁻¹
c = 10.85 (2) Å	T = 295 K
V = 1227 (5) Å³	Cube, colourless
Z = 4	2.0 × 2.0 × 2.0 mm
F(000) = 603.8

Data collection top

Orphée reactor (Saclay, France): 6T2 four-circle diffractometer	R_int = 0.051
Radiation source: Orphée reactor Saclay France	θ_max = 50.0°, θ_min = 5.7°
Pyrolytic graphite (0 0 2) monochromator	h = −10→10
Between 2θ = 0 and 45° : ω, between 2θ = 45 and 80° : ω–θ scans and between 2θ = 80 and 120° : ω–2θ scans	k = −8→9
3119 measured reflections	l = −10→10
666 independent reflections	2 standard reflections every 240 min
531 reflections with F ² > 1σ(F ²)	intensity decay: <1%

Refinement top

Refinement on F	All H-atom parameters refined
Least-squares matrix: user-defined blocks	Chebychev polynomial with 5 parameters, Carruthers & Watkin , 1979, 0.711 0.634 0.751 0.261 0.226
R[F² > 2σ(F²)] = 0.052	(Δ/σ)_max = 0.080
wR(F²) = 0.042	Δρ_max = 0.49 e Å⁻³
S = 1.03	Δρ_min = −0.38 e Å⁻³
531 reflections	Extinction correction: Larson 1970 Crystallographic Computing eq 22
151 parameters	Extinction coefficient: 13.7 (21)

Crystal data top

(C₅H₁₁NO₂)·(CaCl_1.28Br_0.72)·2(H₂O)	V = 1227 (5) Å³
M_r = 296.2	Z = 4
Orthorhombic, Pnma	Neutron radiation, λ = 1.531 Å
a = 11.02 (3) Å	µ = 0.44 mm⁻¹
b = 10.27 (2) Å	T = 295 K
c = 10.85 (2) Å	2.0 × 2.0 × 2.0 mm

Data collection top

Orphée reactor (Saclay, France): 6T2 four-circle diffractometer	R_int = 0.051
3119 measured reflections	θ_max = 50.0°
666 independent reflections	2 standard reflections every 240 min
531 reflections with F ² > 1σ(F ²)	intensity decay: <1%

Refinement top

R[F² > 2σ(F²)] = 0.052	151 parameters
wR(F²) = 0.042	All H-atom parameters refined
S = 1.03	Δρ_max = 0.49 e Å⁻³
531 reflections	Δρ_min = −0.38 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ca0	0.1940 (4)	0.2500	0.2246 (4)	0.0412
N0	0.4810 (2)	0.2500	0.6675 (2)	0.0552
Cl0	0.2993 (3)	0.4541 (3)	0.0919 (3)	0.0471	0.640 (5)
Br0	0.3155 (6)	0.4307 (7)	0.0756 (7)	0.0363	0.360 (5)
O1	0.5368 (3)	0.2500	0.4109 (3)	0.0582
O2	0.3440 (4)	0.2500	0.3635 (4)	0.0743
O3	0.0906 (3)	0.4042 (4)	0.3489 (3)	0.0690
C1	0.4191 (5)	0.2500	0.7886 (3)	0.0816
C2	0.5564 (4)	0.3698 (5)	0.6585 (3)	0.1094
C3	0.3872 (3)	0.2500	0.5701 (3)	0.0396
C4	0.4271 (3)	0.2500	0.4380 (3)	0.0396
H1	0.3613 (7)	0.1640 (8)	0.7966 (6)	0.1128
H2	0.4854 (11)	0.2500	0.8585 (8)	0.1711
H3	0.6107 (7)	0.367 (1)	0.5758 (7)	0.1297
H4	0.4987 (12)	0.4541 (11)	0.6614 (11)	0.1663
H5	0.6155 (8)	0.3674 (15)	0.7366 (8)	0.1944
H6	0.3297 (5)	0.1662 (7)	0.5854 (5)	0.0839
H7	0.0047 (5)	0.4051 (6)	0.3648 (5)	0.0784
H8	0.1266 (5)	0.4429 (6)	0.4186 (5)	0.0745

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca0	0.035 (2)	0.050 (3)	0.039 (2)	0.0000	−0.0033 (19)	0.0000
N0	0.0427 (15)	0.089 (2)	0.0343 (14)	0.0000	−0.0017 (11)	0.0000
Cl0	0.046 (2)	0.038 (2)	0.0578 (19)	0.0076 (18)	0.0004 (17)	0.0066 (16)
Br0	0.028 (4)	0.033 (5)	0.048 (4)	−0.011 (4)	0.011 (4)	−0.010 (4)
O1	0.034 (2)	0.096 (4)	0.045 (3)	0.0000	0.0032 (17)	0.0000
O2	0.046 (3)	0.124 (5)	0.053 (3)	0.0000	−0.018 (2)	0.0000
O3	0.0492 (19)	0.085 (3)	0.073 (2)	0.015 (2)	0.0003 (19)	−0.0261 (19)
C1	0.092 (4)	0.111 (5)	0.042 (3)	0.0000	0.016 (3)	0.0000
C2	0.096 (3)	0.158 (5)	0.075 (2)	−0.082 (3)	0.030 (2)	−0.051 (3)
C3	0.0313 (19)	0.047 (3)	0.041 (2)	0.0000	0.0039 (14)	0.0000
C4	0.031 (2)	0.049 (2)	0.0384 (18)	0.0000	−0.0061 (17)	0.0000
H1	0.116 (6)	0.137 (7)	0.086 (4)	−0.009 (5)	0.046 (4)	0.023 (5)
H2	0.112 (9)	0.36 (3)	0.041 (6)	0.0000	−0.004 (5)	0.0000
H3	0.114 (6)	0.177 (8)	0.098 (5)	−0.083 (6)	0.046 (4)	−0.056 (6)
H4	0.214 (12)	0.106 (8)	0.18 (1)	−0.080 (8)	0.086 (9)	−0.063 (7)
H5	0.117 (7)	0.363 (16)	0.103 (6)	−0.115 (9)	0.000 (5)	−0.061 (9)
H6	0.067 (3)	0.111 (5)	0.074 (3)	−0.056 (4)	0.008 (3)	0.004 (3)
H7	0.057 (3)	0.085 (4)	0.093 (4)	0.004 (4)	0.007 (3)	−0.010 (3)
H8	0.072 (4)	0.084 (4)	0.067 (4)	0.013 (3)	−0.005 (3)	−0.018 (3)

Bond lengths (Å) top

Ca0—O2	2.237 (6)	C3—C2	2.431 (4)
Ca0—O2ⁱ	2.237 (6)	C3—C2ⁱ	2.431 (4)
Ca0—O1ⁱⁱ	2.271 (5)	C3—H4ⁱ	2.623 (9)
Ca0—O1ⁱⁱⁱ	2.271 (5)	C3—H4	2.623 (9)
Ca0—O3ⁱ	2.371 (4)	C3—H1	2.626 (7)
Ca0—O3	2.371 (4)	C3—H1ⁱ	2.626 (7)
Ca0—Cl0	2.795 (4)	C3—H3	2.741 (7)
Ca0—Cl0ⁱ	2.795 (4)	C3—H3ⁱ	2.741 (7)
Ca0—Br0	2.801 (8)	C4—O2	1.222 (5)
Ca0—Br0ⁱ	2.801 (8)	C4—O2ⁱ	1.222 (5)
Ca0—H8	2.984 (6)	C4—O1ⁱ	1.244 (5)
Ca0—H8ⁱ	2.984 (6)	C4—O1	1.244 (5)
N0—C3	1.478 (4)	C4—C3	1.499 (4)
N0—C3ⁱ	1.478 (4)	C4—C3ⁱ	1.499 (4)
N0—C1	1.480 (5)	C4—H6	2.109 (6)
N0—C1ⁱ	1.480 (5)	C4—H6ⁱ	2.109 (6)
N0—C2	1.488 (4)	C4—N0	2.560 (4)
N0—C2ⁱ	1.488 (4)	C4—N0ⁱ	2.560 (4)
N0—H5	2.052 (9)	C4—H3	2.788 (7)
N0—H5ⁱ	2.052 (9)	C4—H3ⁱ	2.788 (7)
N0—H2	2.071 (9)	H1—C1	1.09 (1)
N0—H2ⁱ	2.071 (9)	H1—C1ⁱ	1.09 (1)
N0—H6	2.077 (5)	H1—H2	1.761 (13)
N0—H6ⁱ	2.077 (5)	H1—H2ⁱ	1.761 (13)
N0—H4ⁱ	2.106 (11)	H1—H1ⁱ	1.766 (17)
N0—H4	2.106 (11)	H1—N0	2.117 (7)
N0—H3	2.116 (7)	H1—N0ⁱ	2.117 (7)
N0—H3ⁱ	2.116 (7)	H1—H6	2.317 (8)
N0—H1	2.117 (7)	H1—H4ⁱ	2.431 (11)
N0—H1ⁱ	2.117 (7)	H1—C3	2.626 (7)
N0—C4ⁱ	2.560 (4)	H1—C3ⁱ	2.626 (7)
N0—C4	2.560 (4)	H1—H8^ix	2.63 (1)
N0—O1ⁱ	2.851 (4)	H1—C2ⁱ	2.643 (7)
N0—O1	2.851 (4)	H1—H5^x	2.750 (12)
Cl0—Br0	0.347 (7)	H1—O3^ix	2.778 (9)
Cl0—H8^iv	2.305 (6)	H1—H5ⁱ	2.894 (11)
Cl0—H7^v	2.366 (6)	H1—H6ⁱ	2.899 (9)
Cl0—H6^vi	2.601 (6)	H2—C1ⁱ	1.053 (13)
Cl0—H5^vii	2.77 (1)	H2—C1	1.053 (13)
Cl0—Ca0	2.795 (4)	H2—H1	1.761 (13)
Cl0—Ca0ⁱ	2.795 (4)	H2—H1ⁱ	1.761 (13)
Cl0—H3ⁱⁱ	2.903 (7)	H2—N0ⁱ	2.071 (9)
Br0—Cl0	0.347 (7)	H2—N0	2.071 (9)
Br0—H7^v	2.199 (9)	H2—H5ⁱ	2.292 (14)
Br0—H8^iv	2.23 (1)	H2—H5	2.292 (14)
Br0—Ca0ⁱ	2.801 (8)	H2—C2ⁱ	2.614 (9)
Br0—Ca0	2.801 (8)	H2—C2	2.614 (9)
Br0—H3ⁱⁱ	2.87 (1)	H2—H4ⁱ	2.997 (15)
Br0—H6^vi	2.901 (9)	H2—H4	2.997 (15)
O1—C4	1.244 (5)	H3—C2	1.079 (7)
O1—C4ⁱ	1.244 (5)	H3—H5	1.745 (12)
O1—O2	2.186 (6)	H3—H4	1.785 (14)
O1—O2ⁱ	2.186 (6)	H3—N0	2.116 (7)
O1—Ca0^viii	2.271 (5)	H3—N0ⁱ	2.116 (7)
O1—Ca0^v	2.271 (5)	H3—O1ⁱ	2.303 (7)
O1—H3	2.303 (7)	H3—O1	2.303 (7)
O1—H3ⁱ	2.303 (7)	H3—H3ⁱ	2.40 (2)
O1—C3ⁱ	2.388 (5)	H3—C2ⁱ	2.661 (11)
O1—C3	2.388 (5)	H3—C3	2.741 (7)
O1—N0ⁱ	2.851 (4)	H3—C3ⁱ	2.741 (7)
O1—N0	2.851 (4)	H3—C4ⁱ	2.788 (7)
O1—C2	2.962 (4)	H3—C4	2.788 (7)
O1—C2ⁱ	2.962 (4)	H3—Br0^v	2.87 (1)
O2—C4	1.222 (5)	H3—Cl0^v	2.903 (7)
O2—C4ⁱ	1.222 (5)	H3—H5ⁱ	2.974 (16)
O2—O1	2.186 (6)	H4—C2	1.074 (18)
O2—O1ⁱ	2.186 (6)	H4—H5	1.76 (2)
O2—Ca0ⁱ	2.237 (6)	H4—H3	1.785 (14)
O2—Ca0	2.237 (6)	H4—N0ⁱ	2.106 (11)
O2—C3ⁱ	2.292 (5)	H4—N0	2.106 (11)
O2—C3	2.292 (5)	H4—H6ⁱ	2.382 (12)
O2—H6	2.561 (6)	H4—H1ⁱ	2.431 (11)
O2—H6ⁱ	2.561 (6)	H4—C3	2.623 (9)
O3—H8	0.943 (8)	H4—C3ⁱ	2.623 (9)
O3—H7	0.961 (7)	H4—H7^xi	2.638 (11)
O3—Ca0	2.371 (4)	H4—C1	2.658 (11)
O3—Ca0ⁱ	2.371 (4)	H4—C1ⁱ	2.658 (11)
O3—H4^iv	2.69 (1)	H4—O3^xi	2.69 (1)
O3—H1^vi	2.778 (9)	H4—H2	2.997 (15)
C1—H2ⁱ	1.053 (13)	H4—H2ⁱ	2.997 (15)
C1—H2	1.053 (13)	H5—C2	1.069 (11)
C1—H1ⁱ	1.09 (1)	H5—H3	1.745 (12)
C1—H1	1.09 (1)	H5—H4	1.76 (2)
C1—N0ⁱ	1.480 (5)	H5—N0	2.052 (9)
C1—N0	1.480 (5)	H5—N0ⁱ	2.052 (9)
C1—C3ⁱ	2.396 (5)	H5—H2	2.292 (14)
C1—C3	2.396 (5)	H5—H2ⁱ	2.292 (14)
C1—C2	2.407 (5)	H5—H5ⁱ	2.41 (3)
C1—C2ⁱ	2.407 (5)	H5—C1	2.54 (1)
C1—H5ⁱ	2.54 (1)	H5—C1ⁱ	2.54 (1)
C1—H5	2.54 (1)	H5—C2ⁱ	2.660 (14)
C1—H6	2.563 (6)	H5—H1^xii	2.750 (12)
C1—H6ⁱ	2.563 (6)	H5—Cl0^vii	2.77 (1)
C1—H4ⁱ	2.658 (11)	H5—H1ⁱ	2.894 (11)
C1—H4	2.658 (11)	H5—H3ⁱ	2.974 (16)
C2—H5	1.069 (11)	H6—C3	1.081 (6)
C2—H4	1.074 (18)	H6—C3ⁱ	1.081 (6)
C2—H3	1.079 (7)	H6—H6ⁱ	1.720 (14)
C2—N0ⁱ	1.488 (4)	H6—N0	2.077 (5)
C2—N0	1.488 (4)	H6—N0ⁱ	2.077 (5)
C2—C1	2.407 (5)	H6—C4	2.109 (6)
C2—C1ⁱ	2.407 (5)	H6—C4ⁱ	2.109 (6)
C2—C3	2.431 (4)	H6—H1	2.317 (8)
C2—C3ⁱ	2.431 (4)	H6—H4ⁱ	2.382 (12)
C2—C2ⁱ	2.460 (11)	H6—O2ⁱ	2.561 (6)
C2—H2	2.614 (9)	H6—O2	2.561 (6)
C2—H2ⁱ	2.614 (9)	H6—C1	2.563 (6)
C2—H1ⁱ	2.643 (7)	H6—C1ⁱ	2.563 (6)
C2—H6ⁱ	2.647 (7)	H6—Cl0^ix	2.601 (6)
C2—H5ⁱ	2.660 (14)	H6—C2ⁱ	2.647 (7)
C2—H3ⁱ	2.661 (11)	H6—H1ⁱ	2.899 (9)
C2—O1ⁱ	2.962 (4)	H6—Br0^ix	2.901 (9)
C2—O1	2.962 (4)	H7—O3	0.961 (7)
C3—H6	1.081 (6)	H7—H8	1.515 (8)
C3—H6ⁱ	1.081 (6)	H7—Br0ⁱⁱ	2.199 (9)
C3—N0	1.478 (4)	H7—Cl0ⁱⁱ	2.366 (6)
C3—N0ⁱ	1.478 (4)	H7—H4^iv	2.638 (11)
C3—C4ⁱ	1.499 (4)	H8—O3	0.943 (8)
C3—C4	1.499 (4)	H8—H7	1.515 (8)
C3—O2ⁱ	2.292 (5)	H8—Br0^xi	2.23 (1)
C3—O2	2.292 (5)	H8—Cl0^xi	2.305 (6)
C3—O1ⁱ	2.388 (5)	H8—H1^vi	2.63 (1)
C3—O1	2.388 (5)	H8—Ca0ⁱ	2.984 (6)
C3—C1	2.396 (5)	H8—Ca0	2.984 (6)
C3—C1ⁱ	2.396 (5)

Symmetry codes: (i) x, −y+1/2, z; (ii) x−1/2, y, −z+1/2; (iii) x−1/2, −y+1/2, −z+1/2; (iv) −x+1/2, −y+1, z−1/2; (v) x+1/2, y, −z+1/2; (vi) −x+1/2, y+1/2, z−1/2; (vii) −x+1, −y+1, −z+1; (viii) x+1/2, −y+1/2, −z+1/2; (ix) −x+1/2, y−1/2, z+1/2; (x) x−1/2, −y+1/2, −z+3/2; (xi) −x+1/2, −y+1, z+1/2; (xii) x+1/2, −y+1/2, −z+3/2.

(20k) 38% Brominated Betaine Calcium Chloride Dihydrate top

Crystal data top

(C₅H₁₁NO₂)·(CaCl_1.23Br_0.77)·2(H₂O)	D_x = 1.66 Mg m⁻³
M_r = 298.4	Neutron radiation, λ = 0.8308 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 37 reflections
a = 11.04 (3) Å	θ = 14.1–26.0°
b = 10.22 (3) Å	µ = 0.45 mm⁻¹
c = 10.55 (2) Å	T = 20 K
V = 1190 (6) Å³	Cube, colourless
Z = 4	2.0 × 2.0 × 2.0 mm
F(000) = 603.8

Data collection top

Orphée reactor (Saclay, France): 5C2 four-circle diffractometer	R_int = 0.058
Radiation source: Orphée reactor Saclay France	θ_max = 37.9°, θ_min = 3.1°
Copper (2 2 0) monochromator	h = 0→16
ω scans	k = 0→15
2687 measured reflections	l = −15→3
2687 independent reflections	1 standard reflections every 450 min
2275 reflections with F ² > 3σ(F ²)	intensity decay: <1.5%

Refinement top

Refinement on F	253 parameters
Least-squares matrix: user-defined blocks	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.051	Chebychev polynomial with 3 parameters, Carruthers & Watkin , 1979, 1.30 -1.12 0.889
wR(F²) = 0.041	(Δ/σ)_max = 0.073
S = 1.07	Δρ_max = 1.32 e Å⁻³
1569 reflections	Δρ_min = −1.14 e Å⁻³

Crystal data top

(C₅H₁₁NO₂)·(CaCl_1.23Br_0.77)·2(H₂O)	V = 1190 (6) Å³
M_r = 298.4	Z = 4
Orthorhombic, P2₁2₁2₁	Neutron radiation, λ = 0.8308 Å
a = 11.04 (3) Å	µ = 0.45 mm⁻¹
b = 10.22 (3) Å	T = 20 K
c = 10.55 (2) Å	2.0 × 2.0 × 2.0 mm

Data collection top

Orphée reactor (Saclay, France): 5C2 four-circle diffractometer	R_int = 0.058
2687 measured reflections	1 standard reflections every 450 min
2687 independent reflections	intensity decay: <1.5%
2275 reflections with F ² > 3σ(F ²)

Refinement top

R[F² > 2σ(F²)] = 0.051	253 parameters
wR(F²) = 0.041	All H-atom parameters refined
S = 1.07	Δρ_max = 1.32 e Å⁻³
1569 reflections	Δρ_min = −1.14 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ca0	0.1923 (2)	0.2631 (3)	0.2258 (2)	0.0088
N0	0.4846 (1)	0.20595 (13)	0.67561 (12)	0.0060
Cl1	0.3074 (3)	0.4513 (3)	0.0776 (3)	0.0072	0.578 (8)
Br1	0.3124 (6)	0.4395 (6)	0.0676 (5)	0.0027	0.422 (8)
Cl2	0.2999 (3)	0.0496 (3)	0.1040 (2)	0.0072	0.649 (7)
Br2	0.3015 (7)	0.0566 (8)	0.0894 (6)	0.0027	0.351 (7)
O1	0.53600 (17)	0.2525 (3)	0.4136 (2)	0.0095
O2	0.34021 (18)	0.2791 (2)	0.3715 (2)	0.0107
O31	0.0825 (2)	0.4365 (3)	0.3208 (3)	0.0167
O32	0.0896 (2)	0.1286 (3)	0.3735 (2)	0.0140
C1	0.42523 (16)	0.1960 (2)	0.80237 (17)	0.0103
C21	0.58739 (17)	0.2998 (2)	0.68580 (19)	0.0130
C22	0.53025 (18)	0.0736 (2)	0.63900 (19)	0.0119
C3	0.38999 (14)	0.2518 (2)	0.58341 (17)	0.0067
C4	0.42674 (14)	0.26050 (18)	0.44441 (16)	0.0055
H11	0.3515 (4)	0.1250 (6)	0.7966 (4)	0.0247
H12	0.3884 (5)	0.2898 (5)	0.8306 (5)	0.0273
H2	0.4927 (5)	0.1629 (6)	0.8693 (5)	0.0299
H31	0.6351 (4)	0.3061 (7)	0.5953 (5)	0.0310
H32	0.5817 (5)	0.0808 (5)	0.5511 (5)	0.0296
H41	0.5515 (6)	0.3941 (5)	0.7124 (7)	0.0370
H42	0.4530 (5)	0.0097 (5)	0.6286 (7)	0.0322
H51	0.6479 (5)	0.2640 (8)	0.7605 (6)	0.0386
H52	0.5890 (6)	0.0386 (6)	0.7143 (5)	0.0351
H61	0.3149 (4)	0.1833 (5)	0.5910 (4)	0.0221
H62	0.3586 (5)	0.3481 (5)	0.6145 (5)	0.0256
H71	−0.0020 (4)	0.4269 (6)	0.3415 (6)	0.0314
H72	0.0033 (4)	0.1179 (5)	0.3845 (5)	0.02790
H81	0.1204 (5)	0.4715 (6)	0.3970 (6)	0.0329
H82	0.1279 (5)	0.0788 (6)	0.4409 (5)	0.0283

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca0	0.0048 (8)	0.0125 (11)	0.009 (1)	−0.0003 (8)	−0.0016 (8)	0.0012 (8)
N0	0.0028 (4)	0.0095 (5)	0.0057 (4)	0.0001 (4)	0.0006 (4)	−0.0004 (4)
Cl1	0.0072 (3)	0.0072 (3)	0.0072 (3)	0.0008 (3)	0.0008 (3)	0.0008 (3)
Br1	0.0027 (5)	0.0027 (5)	0.0027 (5)	−0.0010 (5)	−0.0010 (5)	−0.0010 (5)
Cl2	0.0072 (3)	0.0072 (3)	0.0072 (3)	0.0008 (3)	0.0008 (3)	0.0008 (3)
Br2	0.0027 (5)	0.0027 (5)	0.0027 (5)	−0.0010 (5)	−0.0010 (5)	−0.0010 (5)
O1	0.0040 (7)	0.0151 (8)	0.0095 (8)	0.0023 (7)	0.0021 (7)	0.0032 (8)
O2	0.0033 (7)	0.0199 (11)	0.0090 (8)	−0.0002 (6)	−0.0035 (7)	0.0006 (8)
O31	0.012 (1)	0.0186 (11)	0.019 (1)	0.0049 (9)	0.0031 (9)	−0.002 (1)
O32	0.0101 (9)	0.017 (1)	0.0151 (9)	−0.0014 (8)	0.0019 (8)	0.0029 (9)
C1	0.0085 (7)	0.0159 (8)	0.0064 (7)	0.0004 (7)	0.0007 (6)	0.0012 (6)
C21	0.0086 (7)	0.0179 (8)	0.0124 (7)	−0.0058 (7)	−0.0008 (7)	−0.0008 (8)
C22	0.0110 (8)	0.0126 (8)	0.0122 (8)	0.0042 (7)	0.0040 (6)	0.0028 (7)
C3	0.0036 (6)	0.0095 (6)	0.0068 (6)	0.0006 (6)	0.0003 (5)	−0.0007 (6)
C4	0.0011 (6)	0.0089 (7)	0.0065 (6)	0.0003 (5)	−0.0001 (5)	−0.0011 (6)
H11	0.0192 (19)	0.034 (2)	0.0205 (19)	−0.0039 (17)	0.0060 (15)	0.0045 (18)
H12	0.036 (2)	0.0224 (19)	0.024 (2)	0.0046 (19)	0.0093 (19)	−0.0057 (18)
H2	0.028 (2)	0.044 (3)	0.0179 (18)	0.008 (2)	−0.0041 (17)	0.005 (2)
H31	0.0218 (19)	0.048 (3)	0.024 (2)	−0.015 (2)	0.0086 (17)	−0.005 (2)
H32	0.024 (2)	0.032 (2)	0.033 (2)	0.0076 (19)	0.016 (2)	0.0045 (19)
H41	0.035 (3)	0.022 (2)	0.054 (4)	−0.008 (2)	0.005 (3)	−0.016 (2)
H42	0.0215 (19)	0.0201 (19)	0.055 (3)	−0.0023 (16)	0.006 (2)	−0.003 (2)
H51	0.019 (2)	0.061 (4)	0.035 (3)	−0.015 (3)	−0.012 (2)	0.011 (3)
H52	0.042 (3)	0.038 (3)	0.025 (2)	0.024 (3)	−0.004 (2)	0.007 (2)
H61	0.0112 (14)	0.033 (2)	0.0223 (18)	−0.0096 (15)	−0.0011 (14)	0.0040 (17)
H62	0.026 (2)	0.029 (2)	0.022 (2)	0.0121 (18)	0.0006 (17)	−0.0006 (17)
H71	0.016 (2)	0.033 (2)	0.045 (3)	−0.0007 (17)	0.010 (2)	−0.004 (2)
H72	0.0159 (19)	0.033 (2)	0.035 (2)	0.0002 (17)	0.0047 (18)	0.002 (2)
H81	0.032 (2)	0.034 (3)	0.032 (3)	−0.000 (2)	−0.001 (2)	−0.013 (2)
H82	0.026 (2)	0.032 (3)	0.027 (2)	0.0029 (19)	−0.0037 (18)	0.007 (2)

Bond lengths (Å) top

Ca0—O2	2.248 (3)	H11—H62	2.983 (7)
Ca0—O1ⁱ	2.273 (3)	H12—C1	1.084 (5)
Ca0—O32	2.366 (4)	H12—H11	1.770 (8)
Ca0—O31	2.369 (4)	H12—H2	1.782 (8)
Ca0—Cl1	2.786 (4)	H12—N0	2.130 (5)
Ca0—Br1	2.792 (7)	H12—H62	2.380 (7)
Ca0—Cl2	2.798 (4)	H12—H41	2.436 (9)
Ca0—Br2	2.824 (9)	H12—H81^ix	2.540 (8)
Ca0—H81	2.903 (6)	H12—C3	2.638 (5)
Ca0—H71	2.982 (6)	H12—C21	2.678 (5)
N0—C21	1.490 (2)	H12—O31^ix	2.817 (6)
N0—C1	1.493 (2)	H12—H61	2.870 (7)
N0—C22	1.495 (2)	H12—H51^vii	2.876 (8)
N0—C3	1.502 (2)	H12—H51	2.970 (7)
N0—H61	2.088 (4)	H2—C1	1.080 (5)
N0—H2	2.093 (5)	H2—H11	1.780 (7)
N0—H42	2.095 (5)	H2—H12	1.782 (8)
N0—H41	2.097 (5)	H2—N0	2.093 (5)
N0—H51	2.098 (5)	H2—H51	2.307 (8)
N0—H52	2.103 (5)	H2—H52	2.328 (8)
N0—H62	2.112 (5)	H2—C21	2.608 (6)
N0—H11	2.115 (5)	H2—C22	2.629 (6)
N0—H32	2.124 (5)	H2—H72^viii	2.875 (9)
N0—H31	2.127 (5)	H2—H82^viii	2.906 (8)
N0—H12	2.130 (5)	H2—H41	2.958 (9)
N0—C4	2.583 (2)	H31—C21	1.092 (5)
N0—O1	2.862 (2)	H31—H41	1.785 (8)
Cl1—H81ⁱⁱ	2.211 (7)	H31—H51	1.801 (8)
Cl1—H72ⁱⁱⁱ	2.310 (6)	H31—N0	2.127 (5)
Cl1—H52^iv	2.631 (6)	H31—O1	2.275 (6)
Cl1—H62ⁱⁱ	2.777 (6)	H31—H32	2.422 (9)
Cl1—Ca0	2.786 (4)	H31—C22	2.683 (6)
Cl1—H32ⁱ	2.856 (6)	H31—H11^x	2.739 (7)
Br1—H81ⁱⁱ	2.149 (8)	H31—C3	2.765 (5)
Br1—H72ⁱⁱⁱ	2.244 (8)	H31—C4	2.836 (5)
Br1—H52^iv	2.739 (8)	H32—C22	1.090 (5)
Br1—Ca0	2.792 (7)	H32—H52	1.777 (8)
Br1—H32ⁱ	2.846 (8)	H32—H42	1.793 (8)
Br1—H62ⁱⁱ	2.919 (7)	H32—N0	2.124 (5)
Cl2—H71ⁱⁱⁱ	2.274 (6)	H32—O1	2.332 (6)
Cl2—H82^v	2.306 (6)	H32—H31	2.422 (9)
Cl2—H61^v	2.700 (6)	H32—C21	2.652 (6)
Cl2—Ca0	2.798 (4)	H32—C4	2.751 (6)
Cl2—H42^v	2.869 (6)	H32—C3	2.766 (5)
Cl2—H41^vi	2.995 (7)	H32—Br1ⁱⁱⁱ	2.846 (8)
Br2—H82^v	2.232 (9)	H32—Cl1ⁱⁱⁱ	2.856 (6)
Br2—H71ⁱⁱⁱ	2.295 (9)	H32—H51	2.987 (9)
Br2—H61^v	2.769 (9)	H41—C21	1.079 (6)
Br2—Ca0	2.824 (9)	H41—H51	1.78 (1)
Br2—H42^v	2.919 (9)	H41—H31	1.785 (8)
O1—C4	1.252 (2)	H41—N0	2.097 (5)
O1—O2	2.223 (3)	H41—H71^ix	2.345 (8)
O1—Ca0ⁱⁱⁱ	2.273 (3)	H41—H62	2.413 (9)
O1—H31	2.275 (6)	H41—H12	2.436 (9)
O1—H32	2.332 (6)	H41—O31^ix	2.549 (6)
O1—C3	2.410 (3)	H41—C1	2.636 (6)
O1—H42^iv	2.669 (6)	H41—C3	2.673 (6)
O1—N0	2.862 (2)	H41—H2	2.958 (9)
O1—C21	2.968 (3)	H41—Cl2^iv	2.995 (7)
O2—C4	1.241 (2)	H42—C22	1.080 (6)
O2—O1	2.223 (3)	H42—H52	1.778 (9)
O2—Ca0	2.248 (3)	H42—H32	1.793 (8)
O2—C3	2.320 (3)	H42—N0	2.095 (5)
O2—H61	2.530 (5)	H42—H61	2.372 (8)
O2—H62	2.667 (5)	H42—H11	2.405 (8)
O2—H52^iv	2.909 (6)	H42—C3	2.614 (6)
O31—H71	0.963 (5)	H42—C1	2.661 (7)
O31—H81	0.974 (6)	H42—O1^vi	2.669 (6)
O31—Ca0	2.369 (4)	H42—Cl2^viii	2.869 (6)
O31—H41ⁱⁱ	2.549 (6)	H42—Br2^viii	2.919 (9)
O31—H12ⁱⁱ	2.817 (6)	H42—C4^vi	2.974 (6)
O32—H72	0.966 (5)	H42—O32^viii	2.983 (8)
O32—H82	0.971 (5)	H51—C21	1.096 (6)
O32—Ca0	2.366 (4)	H51—H41	1.78 (1)
O32—H11^v	2.793 (6)	H51—H31	1.801 (8)
O32—H42^v	2.983 (8)	H51—N0	2.098 (5)
C1—H2	1.080 (5)	H51—H2	2.307 (8)
C1—H12	1.084 (5)	H51—H52	2.44 (1)
C1—H11	1.092 (5)	H51—H61^x	2.479 (7)
C1—N0	1.493 (2)	H51—H11^x	2.589 (7)
C1—C3	2.412 (3)	H51—C1	2.592 (5)
C1—C21	2.417 (3)	H51—C22	2.668 (7)
C1—C22	2.425 (3)	H51—H12^x	2.876 (8)
C1—H61	2.545 (5)	H51—H62^x	2.909 (8)
C1—H52	2.592 (6)	H51—H12	2.970 (7)
C1—H51	2.592 (5)	H51—H32	2.987 (9)
C1—H62	2.625 (5)	H52—C22	1.087 (5)
C1—H41	2.636 (6)	H52—H32	1.777 (8)
C1—H42	2.661 (7)	H52—H42	1.778 (9)
C21—H41	1.079 (6)	H52—N0	2.103 (5)
C21—H31	1.092 (5)	H52—H2	2.328 (8)
C21—H51	1.096 (6)	H52—H51	2.44 (1)
C21—N0	1.490 (2)	H52—C1	2.592 (6)
C21—C1	2.417 (3)	H52—H72^viii	2.612 (8)
C21—C22	2.447 (3)	H52—Cl1^vi	2.631 (6)
C21—C3	2.481 (2)	H52—C21	2.687 (7)
C21—H2	2.608 (6)	H52—Br1^vi	2.739 (8)
C21—H32	2.652 (6)	H52—H11	2.899 (8)
C21—H12	2.678 (5)	H52—O2^vi	2.909 (6)
C21—H62	2.681 (5)	H61—C3	1.088 (4)
C21—H52	2.687 (7)	H61—H62	1.770 (8)
C21—O1	2.968 (3)	H61—N0	2.088 (4)
C22—H42	1.080 (6)	H61—C4	2.130 (5)
C22—H52	1.087 (5)	H61—H11	2.286 (7)
C22—H32	1.090 (5)	H61—H42	2.372 (8)
C22—N0	1.495 (2)	H61—H51^vii	2.479 (7)
C22—C1	2.425 (3)	H61—O2	2.530 (5)
C22—C21	2.447 (3)	H61—C1	2.545 (5)
C22—C3	2.462 (3)	H61—C22	2.676 (5)
C22—H2	2.629 (6)	H61—Cl2^viii	2.700 (6)
C22—H11	2.633 (5)	H61—Br2^viii	2.769 (9)
C22—H51	2.668 (7)	H61—H82	2.813 (7)
C22—H61	2.676 (5)	H61—H12	2.870 (7)
C22—H31	2.683 (6)	H62—C3	1.094 (5)
C3—H61	1.088 (4)	H62—H61	1.770 (8)
C3—H62	1.094 (5)	H62—N0	2.112 (5)
C3—N0	1.502 (2)	H62—C4	2.142 (5)
C3—C4	1.524 (2)	H62—H12	2.380 (7)
C3—O2	2.320 (3)	H62—H41	2.413 (9)
C3—O1	2.410 (3)	H62—C1	2.625 (5)
C3—C1	2.412 (3)	H62—O2	2.667 (5)
C3—C22	2.462 (3)	H62—C21	2.681 (5)
C3—C21	2.481 (2)	H62—Cl1^ix	2.777 (6)
C3—H42	2.614 (6)	H62—H51^vii	2.909 (8)
C3—H11	2.631 (5)	H62—Br1^ix	2.919 (7)
C3—H12	2.638 (5)	H62—H11	2.983 (7)
C3—H41	2.673 (6)	H71—O31	0.963 (5)
C3—H31	2.765 (5)	H71—H81	1.541 (8)
C3—H32	2.766 (5)	H71—Cl2ⁱ	2.274 (6)
C4—O2	1.241 (2)	H71—Br2ⁱ	2.295 (9)
C4—O1	1.252 (2)	H71—H41ⁱⁱ	2.345 (8)
C4—C3	1.524 (2)	H71—Ca0	2.982 (6)
C4—H61	2.130 (5)	H72—O32	0.966 (5)
C4—H62	2.142 (5)	H72—H82	1.551 (7)
C4—N0	2.583 (2)	H72—Br1ⁱ	2.244 (8)
C4—H32	2.751 (6)	H72—Cl1ⁱ	2.310 (6)
C4—H31	2.836 (5)	H72—H52^v	2.612 (8)
C4—H42^iv	2.974 (6)	H72—H2^v	2.875 (9)
H11—C1	1.092 (5)	H81—O31	0.974 (6)
H11—H12	1.770 (8)	H81—H71	1.541 (8)
H11—H2	1.780 (7)	H81—Br1^ix	2.149 (8)
H11—N0	2.115 (5)	H81—Cl1^ix	2.211 (7)
H11—H61	2.286 (7)	H81—H12ⁱⁱ	2.540 (8)
H11—H42	2.405 (8)	H81—Ca0	2.903 (6)
H11—H51^vii	2.589 (7)	H82—O32	0.971 (5)
H11—H82^viii	2.590 (8)	H82—H72	1.551 (7)
H11—C3	2.631 (5)	H82—Br2^viii	2.232 (9)
H11—C22	2.633 (5)	H82—Cl2^viii	2.306 (6)
H11—H31^vii	2.739 (7)	H82—H11^v	2.590 (8)
H11—O32^viii	2.793 (6)	H82—H61	2.813 (7)
H11—H52	2.899 (8)	H82—H2^v	2.906 (8)

Symmetry codes: (i) x−1/2, −y+1/2, −z+1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) x+1/2, −y+1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1; (v) −x+1/2, −y, z−1/2; (vi) −x+1, y−1/2, −z+1; (vii) x−1/2, −y+1/2, −z+3/2; (viii) −x+1/2, −y, z+1/2; (ix) −x+1/2, −y+1, z+1/2; (x) x+1/2, −y+1/2, −z+3/2.

Experimental details

	(295k)	(20k)
Crystal data
Chemical formula	(C₅H₁₁NO₂)·(CaCl_1.28Br_0.72)·2(H₂O)	(C₅H₁₁NO₂)·(CaCl_1.23Br_0.77)·2(H₂O)
M_r	296.2	298.4
Crystal system, space group	Orthorhombic, Pnma	Orthorhombic, P2₁2₁2₁
Temperature (K)	295	20
a, b, c (Å)	11.02 (3), 10.27 (2), 10.85 (2)	11.04 (3), 10.22 (3), 10.55 (2)
V (Å³)	1227 (5)	1190 (6)
Z	4	4
Radiation type	Neutron, λ = 1.531 Å	Neutron, λ = 0.8308 Å
µ (mm⁻¹)	0.44	0.45
Crystal size (mm)	2.0 × 2.0 × 2.0	2.0 × 2.0 × 2.0

Data collection
Diffractometer	Orphée reactor (Saclay, France): 6T2 four-circle diffractometer	Orphée reactor (Saclay, France): 5C2 four-circle diffractometer
Absorption correction	–	–
No. of measured, independent and observed reflections	3119, 666, 531 [F ² > 1σ(F ²)]	2687, 2687, 2275 [F ² > 3σ(F ²)]
R_int	0.051	0.058
θ_max (°)	50.0	37.9
(sin θ/λ)_max (Å⁻¹)	0.500	0.740

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.042, 1.03	0.051, 0.041, 1.07
No. of reflections	531	1569
No. of parameters	151	253
No. of restraints	?	?
H-atom treatment	All H-atom parameters refined	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.38	1.32, −1.14

Computer programs: COLL5 (Lehmann & Larsen, 1974), PRON (Scherf, 1998), CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996), CAMERON (Watkin, Prout & Pearce, 1996).

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