The title compound, betaine 0.77-perhydrate 0.23-hydrate, (CH3)3N+CH2COO-·0.77H2O2·0.23H2O, crystallizes in the orthorhombic noncentrosymmetric space group Pca21. Chiral molecules of hydrogen peroxide are positionally disordered with water molecules in a ratio of 0.77:0.23. Betaine, 2-(trimethylazaniumyl)acetate, preserves its zwitterionic state, with a positively charged ammonium group and a negatively charged carboxylate group. The molecular conformation of betaine here differs from the conformations of both anhydrous betaine and its hydrate, mainly in the orientation of the carboxylate group with respect to the C-C-N skeleton. Hydrogen peroxide is linked via two hydrogen bonds to carboxylate groups, forming infinite chains along the crystallographic a axis, which are very similar to those in the crystal structure of betaine hydrate. The present work contributes to the understanding of the structure-forming factors for amino acid perhydrates, which are presently attracting much attention. A correlation is suggested between the ratio of amino acid zwitterions and hydrogen peroxide in the unit cell and the structural motifs present in the crystal structures of all currently known amino acids perhydrates. This can help to classify the crystal structures of amino acid perhydrates and to design new crystal structures.
Supporting information
CCDC references: 934616; 934617
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: Mercury (Macrae et al., 2008) and ORTEP-3 (Farrugia, 2012) for I_295K; Mercury (Macrae et al., 2008) for I_100K. For both compounds, software used to prepare material for publication: publCIF (Westrip, 2010).
(I_295K) 2-(Trimethylazaniumyl)acetate 0.77-perhydrate 0.23-hydrate
top
Crystal data top
C5H11NO2·0.77H2O2·0.23H2O | Dx = 1.286 Mg m−3 |
Mr = 147.44 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 4289 reflections |
a = 9.5819 (2) Å | θ = 2.1–31.9° |
b = 6.78424 (14) Å | µ = 0.11 mm−1 |
c = 11.7152 (3) Å | T = 295 K |
V = 761.56 (3) Å3 | Prism, colourless |
Z = 4 | 0.28 × 0.28 × 0.12 mm |
F(000) = 320.5 | |
Data collection top
Oxford Gemini Ultra R diffractometer | 2325 independent reflections |
Radiation source: fine-focus sealed tube | 2054 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 10.3457 pixels mm-1 | θmax = 30.5°, θmin = 3.0° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | k = −9→9 |
Tmin = 0.880, Tmax = 0.986 | l = −16→16 |
13549 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0363P)2 + 0.036P] where P = (Fo2 + 2Fc2)/3 |
2325 reflections | (Δ/σ)max < 0.001 |
117 parameters | Δρmax = 0.10 e Å−3 |
3 restraints | Δρmin = −0.09 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C2 | 0.30082 (11) | 0.08321 (17) | 0.36281 (10) | 0.0401 (2) | |
H2A | 0.3027 | −0.0307 | 0.3128 | 0.048* | |
H2B | 0.2223 | 0.0663 | 0.4142 | 0.048* | |
N1 | 0.27298 (9) | 0.26294 (12) | 0.29039 (9) | 0.03495 (19) | |
O3 | 0.45924 (9) | −0.08223 (15) | 0.47921 (10) | 0.0580 (3) | |
C1 | 0.43472 (12) | 0.08077 (17) | 0.43460 (10) | 0.0413 (2) | |
C5 | 0.14088 (15) | 0.2281 (2) | 0.22555 (13) | 0.0516 (3) | |
H5A | 0.1223 | 0.3391 | 0.1770 | 0.077* | |
H5B | 0.0650 | 0.2113 | 0.2782 | 0.077* | |
H5C | 0.1504 | 0.1115 | 0.1798 | 0.077* | |
C3 | 0.38854 (14) | 0.2933 (2) | 0.20713 (11) | 0.0489 (3) | |
H3A | 0.3984 | 0.1778 | 0.1605 | 0.073* | |
H3B | 0.4740 | 0.3168 | 0.2476 | 0.073* | |
H3C | 0.3677 | 0.4048 | 0.1596 | 0.073* | |
C4 | 0.25324 (19) | 0.44314 (19) | 0.36201 (12) | 0.0575 (3) | |
H4A | 0.3368 | 0.4684 | 0.4048 | 0.086* | |
H4B | 0.1768 | 0.4229 | 0.4137 | 0.086* | |
H4C | 0.2334 | 0.5538 | 0.3136 | 0.086* | |
O4 | 0.50714 (10) | 0.23128 (14) | 0.44387 (11) | 0.0605 (3) | |
O1 | 0.7958 (2) | 0.3214 (3) | 0.5961 (2) | 0.0504 (5) | 0.767 (8) |
H1O | 0.841 (3) | 0.236 (4) | 0.558 (2) | 0.060* | 0.767 (8) |
O2 | 0.6792 (3) | 0.1900 (5) | 0.6214 (3) | 0.0552 (6) | 0.767 (8) |
H2O | 0.629 (3) | 0.199 (3) | 0.563 (2) | 0.053 (7)* | 0.767 (8) |
O5 | 0.7313 (13) | 0.2456 (19) | 0.6121 (9) | 0.088 (5) | 0.233 (8) |
H3O | 0.753 (17) | 0.245 (15) | 0.545 (4) | 0.105* | 0.233 (8) |
H4O | 0.649 (6) | 0.26 (2) | 0.594 (16) | 0.105* | 0.233 (8) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.0373 (5) | 0.0406 (6) | 0.0423 (6) | −0.0025 (4) | −0.0012 (5) | 0.0078 (4) |
N1 | 0.0356 (4) | 0.0355 (4) | 0.0338 (4) | 0.0036 (4) | −0.0010 (4) | 0.0001 (4) |
O3 | 0.0480 (5) | 0.0624 (6) | 0.0635 (6) | 0.0054 (4) | −0.0029 (5) | 0.0251 (5) |
C1 | 0.0354 (5) | 0.0516 (6) | 0.0368 (5) | 0.0032 (4) | 0.0017 (4) | 0.0070 (5) |
C5 | 0.0444 (7) | 0.0560 (7) | 0.0545 (8) | −0.0001 (6) | −0.0154 (6) | 0.0043 (6) |
C3 | 0.0484 (7) | 0.0540 (7) | 0.0444 (6) | 0.0020 (6) | 0.0093 (5) | 0.0108 (5) |
C4 | 0.0686 (8) | 0.0499 (7) | 0.0541 (7) | 0.0179 (7) | −0.0069 (7) | −0.0157 (6) |
O4 | 0.0513 (5) | 0.0593 (6) | 0.0707 (6) | −0.0108 (5) | −0.0219 (5) | 0.0115 (5) |
O1 | 0.0465 (10) | 0.0416 (8) | 0.0629 (10) | −0.0006 (6) | −0.0011 (8) | −0.0128 (6) |
O2 | 0.0474 (11) | 0.0701 (11) | 0.0482 (9) | −0.0052 (9) | −0.0068 (9) | 0.0169 (8) |
O5 | 0.087 (11) | 0.111 (13) | 0.066 (6) | 0.034 (9) | −0.017 (8) | −0.032 (8) |
Geometric parameters (Å, º) top
C2—N1 | 1.5093 (14) | C3—H3A | 0.9600 |
C2—C1 | 1.5341 (15) | C3—H3B | 0.9600 |
C2—H2A | 0.9700 | C3—H3C | 0.9600 |
C2—H2B | 0.9700 | C4—H4A | 0.9600 |
N1—C3 | 1.4899 (15) | C4—H4B | 0.9600 |
N1—C4 | 1.4947 (15) | C4—H4C | 0.9600 |
N1—C5 | 1.4950 (16) | O1—O2 | 1.460 (3) |
O3—C1 | 1.2455 (14) | O1—H1O | 0.85 (3) |
C1—O4 | 1.2394 (14) | O2—H2O | 0.84 (3) |
C5—H5A | 0.9600 | O5—H3O | 0.81 (2) |
C5—H5B | 0.9600 | O5—H4O | 0.82 (2) |
C5—H5C | 0.9600 | | |
| | | |
N1—C2—C1 | 117.69 (9) | N1—C5—H5C | 109.5 |
N1—C2—H2A | 107.9 | H5A—C5—H5C | 109.5 |
C1—C2—H2A | 107.9 | H5B—C5—H5C | 109.5 |
N1—C2—H2B | 107.9 | N1—C3—H3A | 109.5 |
C1—C2—H2B | 107.9 | N1—C3—H3B | 109.5 |
H2A—C2—H2B | 107.2 | H3A—C3—H3B | 109.5 |
C3—N1—C4 | 110.40 (11) | N1—C3—H3C | 109.5 |
C3—N1—C5 | 108.57 (10) | H3A—C3—H3C | 109.5 |
C4—N1—C5 | 107.90 (10) | H3B—C3—H3C | 109.5 |
C3—N1—C2 | 110.38 (9) | N1—C4—H4A | 109.5 |
C4—N1—C2 | 111.57 (10) | N1—C4—H4B | 109.5 |
C5—N1—C2 | 107.91 (9) | H4A—C4—H4B | 109.5 |
O4—C1—O3 | 126.09 (11) | N1—C4—H4C | 109.5 |
O4—C1—C2 | 120.50 (10) | H4A—C4—H4C | 109.5 |
O3—C1—C2 | 113.42 (10) | H4B—C4—H4C | 109.5 |
N1—C5—H5A | 109.5 | O2—O1—H1O | 94.8 (17) |
N1—C5—H5B | 109.5 | O1—O2—H2O | 103.1 (18) |
H5A—C5—H5B | 109.5 | H3O—O5—H4O | 90 (10) |
| | | |
C1—C2—N1—C3 | 59.36 (13) | N1—C2—C1—O4 | 9.20 (17) |
C1—C2—N1—C4 | −63.78 (14) | N1—C2—C1—O3 | −170.72 (10) |
C1—C2—N1—C5 | 177.86 (11) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O4 | 0.84 (3) | 1.83 (3) | 2.668 (3) | 175 (2) |
O1—H1O···O3i | 0.85 (3) | 1.79 (3) | 2.638 (2) | 171 (3) |
Symmetry code: (i) x+1/2, −y, z. |
(I_100K) 2-(Trimethylazaniumyl)acetate 0.77-perhydrate 0.23-hydrate
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Crystal data top
C5H11NO2·0.76H2O2·0.24H2O | Dx = 1.326 Mg m−3 |
Mr = 147.36 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 8522 reflections |
a = 9.49160 (15) Å | θ = 2.1–32.6° |
b = 6.70620 (11) Å | µ = 0.11 mm−1 |
c = 11.5975 (2) Å | T = 100 K |
V = 738.21 (2) Å3 | Prism, colourless |
Z = 4 | 0.28 × 0.21 × 0.11 mm |
F(000) = 320.4 | |
Data collection top
Oxford Gemini Ultra R diffractometer | 2264 independent reflections |
Radiation source: fine-focus sealed tube | 2229 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 10.3457 pixels mm-1 | θmax = 30.5°, θmin = 3.0° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | k = −9→9 |
Tmin = 0.904, Tmax = 0.987 | l = −16→16 |
14434 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.065 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0368P)2 + 0.0572P] where P = (Fo2 + 2Fc2)/3 |
2264 reflections | (Δ/σ)max < 0.001 |
117 parameters | Δρmax = 0.24 e Å−3 |
3 restraints | Δρmin = −0.14 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C2 | 0.29813 (8) | 0.08280 (11) | 0.36339 (7) | 0.01352 (14) | |
H2A | 0.2993 | −0.0356 | 0.3124 | 0.016* | |
H2B | 0.2180 | 0.0663 | 0.4172 | 0.016* | |
N1 | 0.26953 (7) | 0.26385 (9) | 0.28966 (6) | 0.01165 (13) | |
O3 | 0.46219 (6) | −0.08424 (9) | 0.47878 (6) | 0.01963 (14) | |
C1 | 0.43466 (8) | 0.08217 (12) | 0.43454 (7) | 0.01431 (14) | |
C5 | 0.13541 (9) | 0.22658 (13) | 0.22434 (8) | 0.01790 (16) | |
H5A | 0.1173 | 0.3384 | 0.1720 | 0.027* | |
H5B | 0.0570 | 0.2138 | 0.2788 | 0.027* | |
H5C | 0.1444 | 0.1032 | 0.1796 | 0.027* | |
C3 | 0.38620 (9) | 0.29483 (13) | 0.20455 (8) | 0.01707 (15) | |
H3A | 0.3958 | 0.1759 | 0.1561 | 0.026* | |
H3B | 0.4747 | 0.3185 | 0.2459 | 0.026* | |
H3C | 0.3645 | 0.4104 | 0.1559 | 0.026* | |
C4 | 0.24943 (10) | 0.44776 (12) | 0.36163 (8) | 0.01905 (16) | |
H4A | 0.3362 | 0.4760 | 0.4044 | 0.029* | |
H4B | 0.1719 | 0.4264 | 0.4161 | 0.029* | |
H4C | 0.2270 | 0.5609 | 0.3114 | 0.029* | |
O4 | 0.50649 (7) | 0.23681 (9) | 0.44478 (7) | 0.02055 (14) | |
O1 | 0.79816 (11) | 0.32321 (15) | 0.59821 (8) | 0.0162 (3) | 0.762 (6) |
H1O | 0.8429 (19) | 0.244 (3) | 0.5573 (17) | 0.019* | 0.762 (6) |
O2 | 0.68070 (15) | 0.1860 (2) | 0.62277 (12) | 0.0186 (3) | 0.762 (6) |
H2O | 0.6256 (19) | 0.207 (2) | 0.5661 (16) | 0.015 (3)* | 0.762 (6) |
O5 | 0.7267 (7) | 0.2408 (8) | 0.6128 (4) | 0.030 (2) | 0.238 (6) |
H3O | 0.762 (9) | 0.332 (9) | 0.575 (7) | 0.036* | 0.238 (6) |
H4O | 0.714 (8) | 0.146 (7) | 0.570 (5) | 0.036* | 0.238 (6) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.0116 (3) | 0.0142 (3) | 0.0148 (3) | −0.0010 (2) | −0.0012 (3) | 0.0038 (3) |
N1 | 0.0109 (3) | 0.0127 (3) | 0.0114 (3) | 0.0015 (2) | −0.0003 (2) | 0.0001 (2) |
O3 | 0.0166 (3) | 0.0213 (3) | 0.0210 (3) | 0.0023 (2) | −0.0010 (2) | 0.0074 (2) |
C1 | 0.0112 (3) | 0.0199 (4) | 0.0118 (3) | 0.0014 (2) | 0.0012 (3) | 0.0018 (3) |
C5 | 0.0134 (3) | 0.0213 (4) | 0.0190 (4) | 0.0003 (3) | −0.0060 (3) | 0.0012 (3) |
C3 | 0.0161 (3) | 0.0195 (3) | 0.0156 (3) | 0.0015 (3) | 0.0046 (3) | 0.0037 (3) |
C4 | 0.0219 (4) | 0.0168 (3) | 0.0184 (4) | 0.0062 (3) | −0.0019 (3) | −0.0055 (3) |
O4 | 0.0162 (3) | 0.0214 (3) | 0.0240 (3) | −0.0037 (2) | −0.0066 (2) | 0.0045 (2) |
O1 | 0.0123 (5) | 0.0150 (5) | 0.0212 (5) | −0.0018 (4) | 0.0006 (3) | −0.0045 (3) |
O2 | 0.0139 (5) | 0.0243 (6) | 0.0176 (5) | −0.0032 (4) | −0.0014 (4) | 0.0056 (4) |
O5 | 0.033 (4) | 0.037 (4) | 0.0184 (18) | 0.017 (3) | −0.009 (2) | −0.008 (2) |
Geometric parameters (Å, º) top
C2—N1 | 1.5097 (10) | C3—H3A | 0.9800 |
C2—C1 | 1.5364 (10) | C3—H3B | 0.9800 |
C2—H2A | 0.9900 | C3—H3C | 0.9800 |
C2—H2B | 0.9900 | C4—H4A | 0.9800 |
N1—C3 | 1.4980 (10) | C4—H4B | 0.9800 |
N1—C4 | 1.5014 (10) | C4—H4C | 0.9800 |
N1—C5 | 1.5023 (10) | O1—O2 | 1.473 (2) |
O3—C1 | 1.2557 (9) | O1—H1O | 0.83 (2) |
C1—O4 | 1.2467 (10) | O2—H2O | 0.851 (19) |
C5—H5A | 0.9800 | O5—H3O | 0.83 (2) |
C5—H5B | 0.9800 | O5—H4O | 0.81 (2) |
C5—H5C | 0.9800 | | |
| | | |
N1—C2—C1 | 117.26 (6) | N1—C5—H5C | 109.5 |
N1—C2—H2A | 108.0 | H5A—C5—H5C | 109.5 |
C1—C2—H2A | 108.0 | H5B—C5—H5C | 109.5 |
N1—C2—H2B | 108.0 | N1—C3—H3A | 109.5 |
C1—C2—H2B | 108.0 | N1—C3—H3B | 109.5 |
H2A—C2—H2B | 107.2 | H3A—C3—H3B | 109.5 |
C3—N1—C4 | 110.27 (6) | N1—C3—H3C | 109.5 |
C3—N1—C5 | 108.49 (6) | H3A—C3—H3C | 109.5 |
C4—N1—C5 | 108.02 (6) | H3B—C3—H3C | 109.5 |
C3—N1—C2 | 110.60 (6) | N1—C4—H4A | 109.5 |
C4—N1—C2 | 111.63 (6) | N1—C4—H4B | 109.5 |
C5—N1—C2 | 107.71 (6) | H4A—C4—H4B | 109.5 |
O4—C1—O3 | 125.91 (8) | N1—C4—H4C | 109.5 |
O4—C1—C2 | 120.67 (7) | H4A—C4—H4C | 109.5 |
O3—C1—C2 | 113.41 (7) | H4B—C4—H4C | 109.5 |
N1—C5—H5A | 109.5 | O2—O1—H1O | 95.7 (12) |
N1—C5—H5B | 109.5 | O1—O2—H2O | 102.3 (11) |
H5A—C5—H5B | 109.5 | H3O—O5—H4O | 108 (9) |
| | | |
C1—C2—N1—C3 | 58.85 (8) | N1—C2—C1—O4 | 11.02 (11) |
C1—C2—N1—C4 | −64.32 (9) | N1—C2—C1—O3 | −169.31 (7) |
C1—C2—N1—C5 | 177.26 (7) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O4 | 0.851 (19) | 1.816 (19) | 2.6667 (16) | 177.0 (15) |
O1—H1O···O3i | 0.83 (2) | 1.81 (2) | 2.6288 (11) | 171.9 (18) |
Symmetry code: (i) x+1/2, −y, z. |
Selected geometric parameters (Å, °) for (I) at 295 and 100 K. top | (I) at 295 K | (I) at 100 K |
O3—C1 | 1.2455 (14) | 1.2557 (9) |
C1—O4 | 1.2394 (14) | 1.2467 (10) |
O1—O2 | 1.460 (3) | 1.473 (2) |
O1—H1O | 0.85 (3) | 0.83 (2) |
O2—H2O | 0.84 (3) | 0.851 (19) |
| | |
O4—C1—O3 | 126.09 (11) | 125.91 (8) |
O4—C1—C2 | 120.50 (10) | 120.67 (7) |
O3—C1—C2 | 113.42 (10) | 113.41 (7) |
O2—O1—H1O | 94.8 (17) | 95.7 (12) |
O1—O2—H2O | 103.1 (18) | 102.3 (11) |
| | |
H1O—O1—O2—H2O | -84 (2) | -88 (2) |
Hydrogen-bond geometry (Å, °) for (I) at 295 and 100 K. topD—H···A | D—H | H···A | D···A | D—H···A |
| | | | |
(I) at 295 K | | | | |
O2—H2O···O4 | 0.84 (3) | 1.83 (3) | 2.668 (3) | 175 (2) |
O1—H1O···O3 | 0.85 (3) | 1.79 (3) | 2.638 (2) | 171 (3) |
| | | | |
(I) at 100 K | | | | |
O2—H2O···O4i | 0.851 (19) | 1.816 (19) | 2.6667 (16) | 177.0 (15) |
O1—H1O···O3i | 0.83 (2) | 1.81 (2) | 2.6288 (11) | 171.9 (18) |
Symmetry code: (i) x+1/2, -y, z. |