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.
Supporting information
CCDC references: 166493; 166494
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).
(295k) 38% Brominated Betaine Calcium Chloride Dihydrate
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Crystal data top
(C5H11NO2)·(CaCl1.28Br0.72)·2(H2O) | Dx = 1.60 Mg m−3 |
Mr = 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 | Rint = 0.051 |
Radiation source: Orphée reactor Saclay France | θmax = 50.0°, θmin = 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 | Δρmax = 0.49 e Å−3 |
S = 1.03 | Δρmin = −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)·(CaCl1.28Br0.72)·2(H2O) | V = 1227 (5) Å3 |
Mr = 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 | Rint = 0.051 |
3119 measured reflections | θmax = 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 | Δρmax = 0.49 e Å−3 |
531 reflections | Δρmin = −0.38 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | 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—H8ix | 2.63 (1) |
N0—O1i | 2.851 (4) | H1—C2i | 2.643 (7) |
N0—O1 | 2.851 (4) | H1—H5x | 2.750 (12) |
Cl0—Br0 | 0.347 (7) | H1—O3ix | 2.778 (9) |
Cl0—H8iv | 2.305 (6) | H1—H5i | 2.894 (11) |
Cl0—H7v | 2.366 (6) | H1—H6i | 2.899 (9) |
Cl0—H6vi | 2.601 (6) | H2—C1i | 1.053 (13) |
Cl0—H5vii | 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—H7v | 2.199 (9) | H2—H5i | 2.292 (14) |
Br0—H8iv | 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—H6vi | 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—Ca0viii | 2.271 (5) | H3—N0i | 2.116 (7) |
O1—Ca0v | 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—Br0v | 2.87 (1) |
O2—C4 | 1.222 (5) | H3—Cl0v | 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—H7xi | 2.638 (11) |
O3—Ca0 | 2.371 (4) | H4—C1 | 2.658 (11) |
O3—Ca0i | 2.371 (4) | H4—C1i | 2.658 (11) |
O3—H4iv | 2.69 (1) | H4—O3xi | 2.69 (1) |
O3—H1vi | 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—H1xii | 2.750 (12) |
C1—H6i | 2.563 (6) | H5—Cl0vii | 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—Cl0ix | 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—Br0ix | 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—H4iv | 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—Br0xi | 2.23 (1) |
C3—O2 | 2.292 (5) | H8—Cl0xi | 2.305 (6) |
C3—O1i | 2.388 (5) | H8—H1vi | 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
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Crystal data top
(C5H11NO2)·(CaCl1.23Br0.77)·2(H2O) | Dx = 1.66 Mg m−3 |
Mr = 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 | Rint = 0.058 |
Radiation source: Orphée reactor Saclay France | θmax = 37.9°, θmin = 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 | Δρmax = 1.32 e Å−3 |
1569 reflections | Δρmin = −1.14 e Å−3 |
Crystal data top
(C5H11NO2)·(CaCl1.23Br0.77)·2(H2O) | V = 1190 (6) Å3 |
Mr = 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 | Rint = 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 | Δρmax = 1.32 e Å−3 |
1569 reflections | Δρmin = −1.14 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | 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—H81ix | 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—O31ix | 2.817 (6) |
N0—C1 | 1.493 (2) | H12—H61 | 2.870 (7) |
N0—C22 | 1.495 (2) | H12—H51vii | 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—H72viii | 2.875 (9) |
N0—H31 | 2.127 (5) | H2—H82viii | 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—H52iv | 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—H11x | 2.739 (7) |
Br1—H81ii | 2.149 (8) | H31—C3 | 2.765 (5) |
Br1—H72iii | 2.244 (8) | H31—C4 | 2.836 (5) |
Br1—H52iv | 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—H82v | 2.306 (6) | H32—H31 | 2.422 (9) |
Cl2—H61v | 2.700 (6) | H32—C21 | 2.652 (6) |
Cl2—Ca0 | 2.798 (4) | H32—C4 | 2.751 (6) |
Cl2—H42v | 2.869 (6) | H32—C3 | 2.766 (5) |
Cl2—H41vi | 2.995 (7) | H32—Br1iii | 2.846 (8) |
Br2—H82v | 2.232 (9) | H32—Cl1iii | 2.856 (6) |
Br2—H71iii | 2.295 (9) | H32—H51 | 2.987 (9) |
Br2—H61v | 2.769 (9) | H41—C21 | 1.079 (6) |
Br2—Ca0 | 2.824 (9) | H41—H51 | 1.78 (1) |
Br2—H42v | 2.919 (9) | H41—H31 | 1.785 (8) |
O1—C4 | 1.252 (2) | H41—N0 | 2.097 (5) |
O1—O2 | 2.223 (3) | H41—H71ix | 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—O31ix | 2.549 (6) |
O1—C3 | 2.410 (3) | H41—C1 | 2.636 (6) |
O1—H42iv | 2.669 (6) | H41—C3 | 2.673 (6) |
O1—N0 | 2.862 (2) | H41—H2 | 2.958 (9) |
O1—C21 | 2.968 (3) | H41—Cl2iv | 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—H52iv | 2.909 (6) | H42—C3 | 2.614 (6) |
O31—H71 | 0.963 (5) | H42—C1 | 2.661 (7) |
O31—H81 | 0.974 (6) | H42—O1vi | 2.669 (6) |
O31—Ca0 | 2.369 (4) | H42—Cl2viii | 2.869 (6) |
O31—H41ii | 2.549 (6) | H42—Br2viii | 2.919 (9) |
O31—H12ii | 2.817 (6) | H42—C4vi | 2.974 (6) |
O32—H72 | 0.966 (5) | H42—O32viii | 2.983 (8) |
O32—H82 | 0.971 (5) | H51—C21 | 1.096 (6) |
O32—Ca0 | 2.366 (4) | H51—H41 | 1.78 (1) |
O32—H11v | 2.793 (6) | H51—H31 | 1.801 (8) |
O32—H42v | 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—H61x | 2.479 (7) |
C1—N0 | 1.493 (2) | H51—H11x | 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—H12x | 2.876 (8) |
C1—H61 | 2.545 (5) | H51—H62x | 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—H72viii | 2.612 (8) |
C21—C22 | 2.447 (3) | H52—Cl1vi | 2.631 (6) |
C21—C3 | 2.481 (2) | H52—C21 | 2.687 (7) |
C21—H2 | 2.608 (6) | H52—Br1vi | 2.739 (8) |
C21—H32 | 2.652 (6) | H52—H11 | 2.899 (8) |
C21—H12 | 2.678 (5) | H52—O2vi | 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—H51vii | 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—Cl2viii | 2.700 (6) |
C22—H11 | 2.633 (5) | H61—Br2viii | 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—Cl1ix | 2.777 (6) |
C3—H42 | 2.614 (6) | H62—H51vii | 2.909 (8) |
C3—H11 | 2.631 (5) | H62—Br1ix | 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—H52v | 2.612 (8) |
C4—H42iv | 2.974 (6) | H72—H2v | 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—Br1ix | 2.149 (8) |
H11—N0 | 2.115 (5) | H81—Cl1ix | 2.211 (7) |
H11—H61 | 2.286 (7) | H81—H12ii | 2.540 (8) |
H11—H42 | 2.405 (8) | H81—Ca0 | 2.903 (6) |
H11—H51vii | 2.589 (7) | H82—O32 | 0.971 (5) |
H11—H82viii | 2.590 (8) | H82—H72 | 1.551 (7) |
H11—C3 | 2.631 (5) | H82—Br2viii | 2.232 (9) |
H11—C22 | 2.633 (5) | H82—Cl2viii | 2.306 (6) |
H11—H31vii | 2.739 (7) | H82—H11v | 2.590 (8) |
H11—O32viii | 2.793 (6) | H82—H61 | 2.813 (7) |
H11—H52 | 2.899 (8) | H82—H2v | 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)·(CaCl1.28Br0.72)·2(H2O) | (C5H11NO2)·(CaCl1.23Br0.77)·2(H2O) |
Mr | 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)] |
Rint | 0.051 | 0.058 |
θmax (°) | 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 |
Δρmax, Δρmin (e Å−3) | 0.49, −0.38 | 1.32, −1.14 |