Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802019785/dn6041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802019785/dn6041DGSsup2.hkl |
CCDC reference: 202322
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- Disorder in solvent or counterion
- R factor = 0.034
- wR factor = 0.097
- Data-to-parameter ratio = 12.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 12.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Colorless single crystals of DGS, were obtained by slow evaporation at room temperature of an equimolar solution of glycine and sulfuric acid.
In the initial refinement of the title compound, atom 2B showed high anisotropy of apparent thermal motion normal to the carboxyl plane. Final refinement was carried out with a model in which atoms O2B and C1B had a site-occupation factor of 0.5 (C1B/C11B and O2B/O21B), to simulate a dynamic disorder that occurs by a twist of the C1B—O2B arm. All H atoms were then fixed at localized positions. Riding isotropic displacement parameters were used for all H atoms.
Data collection: KappaCCD Reference Manual (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrujia, 1997) and PLUTON (Spek, 1990); software used to prepare material for publication: WinGX (Farrugia, 1999).
2C2H6NO2+·SO42− | F(000) = 1040 |
Mr = 248.23 | Dx = 1.65 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 12129 reflections |
a = 8.9350 (4) Å | θ = 3.6–26.4° |
b = 10.2770 (3) Å | µ = 0.35 mm−1 |
c = 21.7640 (3) Å | T = 293 K |
V = 1998.48 (11) Å3 | Prism, colorless |
Z = 8 | 0.5 × 0.4 × 0.3 mm |
Nonius KappaCCD diffractometer | 1844 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.092 |
Graphite monochromator | θmax = 26.4°, θmin = 3.2° |
ϕ scans | h = −11→11 |
12129 measured reflections | k = −12→12 |
1997 independent reflections | l = −27→25 |
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: difference Fourier map |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0331P)2 + 0.3591P] where P = (Fo2 + 2Fc2)/3 |
1997 reflections | (Δ/σ)max = 0.001 |
164 parameters | Δρmax = 0.25 e Å−3 |
24 restraints | Δρmin = −0.38 e Å−3 |
2C2H6NO2+·SO42− | V = 1998.48 (11) Å3 |
Mr = 248.23 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.9350 (4) Å | µ = 0.35 mm−1 |
b = 10.2770 (3) Å | T = 293 K |
c = 21.7640 (3) Å | 0.5 × 0.4 × 0.3 mm |
Nonius KappaCCD diffractometer | 1844 reflections with I > 2σ(I) |
12129 measured reflections | Rint = 0.092 |
1997 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 24 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.25 e Å−3 |
1997 reflections | Δρmin = −0.38 e Å−3 |
164 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S | −0.10690 (4) | 0.55788 (4) | 0.663471 (17) | 0.02355 (15) | |
O2A | 0.21628 (14) | −0.03292 (11) | 0.51481 (6) | 0.0326 (3) | |
O1 | −0.00956 (16) | 0.48644 (12) | 0.62094 (6) | 0.0415 (3) | |
O3 | −0.08780 (14) | 0.50816 (11) | 0.72625 (6) | 0.0333 (3) | |
O1A | 0.38658 (14) | 0.12148 (13) | 0.53549 (7) | 0.0409 (3) | |
H1A | 0.4201 | 0.0666 | 0.5591 | 0.061* | |
O2 | −0.07143 (15) | 0.69813 (12) | 0.66235 (6) | 0.0357 (3) | |
O4 | −0.26467 (14) | 0.53943 (13) | 0.64542 (7) | 0.0414 (3) | |
N1A | 0.07072 (16) | 0.12375 (13) | 0.43269 (7) | 0.0297 (3) | |
H6A | 0.0957 | 0.0487 | 0.4150 | 0.045* | |
H4A | 0.0430 | 0.1804 | 0.4039 | 0.045* | |
H5A | −0.0048 | 0.1107 | 0.4586 | 0.045* | |
N1B | 0.16743 (16) | 0.34925 (14) | 0.73588 (7) | 0.0321 (3) | |
H6B | 0.0914 | 0.4030 | 0.7285 | 0.048* | |
H5B | 0.2471 | 0.3951 | 0.7474 | 0.048* | |
H4B | 0.1423 | 0.2941 | 0.7657 | 0.048* | |
C2B | 0.2030 (2) | 0.2758 (2) | 0.67961 (10) | 0.0431 (5) | |
H3B | 0.2964 | 0.2293 | 0.6855 | 0.052* | |
H2B | 0.2165 | 0.3361 | 0.6458 | 0.052* | |
C1AB | 0.0806 (9) | 0.1794 (8) | 0.6633 (4) | 0.034 (2) | 0.50 |
O21B | 0.1050 (6) | 0.0918 (5) | 0.6278 (3) | 0.0689 (16) | 0.50 |
O1B | −0.05002 (14) | 0.21073 (12) | 0.68600 (6) | 0.0338 (3) | |
C1BB | 0.0690 (9) | 0.2089 (8) | 0.6509 (4) | 0.0335 (19) | 0.50 |
O22B | 0.0744 (6) | 0.1476 (6) | 0.6040 (2) | 0.0689 (15) | 0.50 |
C1A | 0.26723 (18) | 0.07554 (15) | 0.50827 (7) | 0.0274 (3) | |
C2A | 0.1997 (2) | 0.17554 (16) | 0.46640 (8) | 0.0352 (4) | |
H2A | 0.2748 | 0.2048 | 0.4373 | 0.042* | |
H3A | 0.1682 | 0.2501 | 0.4905 | 0.042* | |
H1B | −0.119 (3) | 0.158 (3) | 0.6712 (13) | 0.067 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S | 0.0196 (2) | 0.0202 (2) | 0.0309 (2) | 0.00172 (13) | 0.00215 (14) | 0.00150 (13) |
O2A | 0.0360 (7) | 0.0215 (5) | 0.0402 (6) | −0.0011 (5) | −0.0020 (5) | 0.0008 (5) |
O1 | 0.0424 (7) | 0.0317 (6) | 0.0505 (8) | 0.0098 (6) | 0.0231 (6) | 0.0052 (5) |
O3 | 0.0367 (7) | 0.0295 (6) | 0.0338 (6) | −0.0024 (5) | −0.0003 (5) | 0.0058 (5) |
O1A | 0.0378 (7) | 0.0370 (7) | 0.0479 (8) | −0.0103 (5) | −0.0159 (6) | 0.0112 (6) |
O2 | 0.0425 (7) | 0.0210 (6) | 0.0437 (7) | −0.0031 (5) | 0.0003 (5) | 0.0053 (5) |
O4 | 0.0243 (6) | 0.0425 (7) | 0.0575 (8) | 0.0043 (5) | −0.0109 (6) | −0.0169 (6) |
N1A | 0.0306 (7) | 0.0241 (6) | 0.0344 (7) | 0.0017 (5) | −0.0032 (6) | 0.0016 (5) |
N1B | 0.0244 (7) | 0.0291 (7) | 0.0427 (8) | −0.0014 (6) | −0.0085 (6) | −0.0009 (6) |
C2B | 0.0225 (8) | 0.0464 (11) | 0.0603 (12) | −0.0021 (7) | 0.0043 (8) | −0.0162 (9) |
C1AB | 0.033 (3) | 0.034 (4) | 0.035 (3) | −0.006 (2) | 0.006 (2) | −0.005 (3) |
O21B | 0.045 (3) | 0.081 (4) | 0.081 (4) | −0.013 (2) | 0.019 (2) | −0.052 (3) |
O1B | 0.0255 (6) | 0.0334 (6) | 0.0426 (7) | −0.0030 (5) | 0.0015 (5) | −0.0071 (5) |
C1BB | 0.030 (2) | 0.030 (3) | 0.040 (4) | 0.000 (2) | 0.006 (2) | −0.007 (3) |
O22B | 0.047 (3) | 0.088 (4) | 0.072 (3) | −0.017 (3) | 0.022 (2) | −0.048 (3) |
C1A | 0.0276 (8) | 0.0250 (7) | 0.0296 (7) | −0.0003 (6) | 0.0008 (6) | −0.0010 (6) |
C2A | 0.0399 (9) | 0.0246 (8) | 0.0411 (9) | −0.0057 (7) | −0.0111 (8) | 0.0053 (7) |
S—O1 | 1.4670 (12) | C2B—C1BB | 1.515 (8) |
S—O3 | 1.4686 (12) | C2B—C1AB | 1.517 (8) |
S—O4 | 1.4756 (13) | C1AB—O21B | 1.207 (8) |
S—O2 | 1.4761 (12) | C1AB—O1B | 1.307 (8) |
O2A—C1A | 1.212 (2) | O1B—C1BB | 1.310 (8) |
O1A—C1A | 1.308 (2) | C1BB—O22B | 1.201 (8) |
N1A—C2A | 1.466 (2) | C1A—C2A | 1.500 (2) |
N1B—C2B | 1.474 (2) | ||
O1—S—O3 | 110.12 (7) | O21B—C1AB—C2B | 120.4 (7) |
O1—S—O4 | 109.52 (8) | O1B—C1AB—C2B | 113.3 (6) |
O3—S—O4 | 108.30 (8) | C1AB—O1B—C1BB | 18.4 (6) |
O1—S—O2 | 110.55 (8) | O22B—C1BB—O1B | 122.4 (7) |
O3—S—O2 | 109.28 (7) | O22B—C1BB—C2B | 123.9 (7) |
O4—S—O2 | 109.04 (8) | O1B—C1BB—C2B | 113.3 (6) |
N1B—C2B—C1BB | 113.9 (3) | O2A—C1A—O1A | 125.78 (15) |
N1B—C2B—C1AB | 111.9 (3) | O2A—C1A—C2A | 123.36 (15) |
C1BB—C2B—C1AB | 15.9 (5) | O1A—C1A—C2A | 110.85 (14) |
O21B—C1AB—O1B | 125.9 (7) | N1A—C2A—C1A | 111.81 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···O1i | 0.82 | 1.77 | 2.567 (2) | 164 |
O1B—H1B···O4ii | 0.88 (3) | 1.70 (3) | 2.573 (2) | 172 (3) |
N1A—H4A···O2iii | 0.89 | 1.92 | 2.762 (2) | 156 |
N1B—H4B···O2iv | 0.89 | 1.96 | 2.838 (2) | 170 |
N1A—H5A···O2Av | 0.89 | 2.13 | 2.958 (2) | 154 |
N1B—H5B···O3vi | 0.89 | 1.96 | 2.851 (2) | 175 |
N1A—H6A···O21Bv | 0.89 | 2.48 | 3.018 (5) | 119 |
N1A—H6A···O22Bv | 0.89 | 2.56 | 3.177 (6) | 127 |
N1A—H6A···O4vii | 0.89 | 2.03 | 2.805 (2) | 145 |
N1B—H6B···O3 | 0.89 | 1.93 | 2.813 (2) | 170 |
C2A—H3A···O2Aviii | 0.97 | 2.51 | 3.264 (2) | 134 |
Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) −x−1/2, y−1/2, z; (iii) −x, −y+1, −z+1; (iv) −x, y−1/2, −z+3/2; (v) −x, −y, −z+1; (vi) x+1/2, y, −z+3/2; (vii) x+1/2, −y+1/2, −z+1; (viii) −x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | 2C2H6NO2+·SO42− |
Mr | 248.23 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 8.9350 (4), 10.2770 (3), 21.7640 (3) |
V (Å3) | 1998.48 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12129, 1997, 1844 |
Rint | 0.092 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.098, 1.10 |
No. of reflections | 1997 |
No. of parameters | 164 |
No. of restraints | 24 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.38 |
Computer programs: KappaCCD Reference Manual (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK, SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrujia, 1997) and PLUTON (Spek, 1990), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···O1i | 0.82 | 1.77 | 2.567 (2) | 164 |
O1B—H1B···O4ii | 0.88 (3) | 1.70 (3) | 2.573 (2) | 172 (3) |
N1A—H4A···O2iii | 0.89 | 1.92 | 2.762 (2) | 156 |
N1B—H4B···O2iv | 0.89 | 1.96 | 2.838 (2) | 170 |
N1A—H5A···O2Av | 0.89 | 2.13 | 2.958 (2) | 154 |
N1B—H5B···O3vi | 0.89 | 1.96 | 2.851 (2) | 175 |
N1A—H6A···O21Bv | 0.89 | 2.48 | 3.018 (5) | 119 |
N1A—H6A···O22Bv | 0.89 | 2.56 | 3.177 (6) | 127 |
N1A—H6A···O4vii | 0.89 | 2.03 | 2.805 (2) | 145 |
N1B—H6B···O3 | 0.89 | 1.93 | 2.813 (2) | 170 |
C2A—H3A···O2Aviii | 0.97 | 2.51 | 3.264 (2) | 134 |
Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) −x−1/2, y−1/2, z; (iii) −x, −y+1, −z+1; (iv) −x, y−1/2, −z+3/2; (v) −x, −y, −z+1; (vi) x+1/2, y, −z+3/2; (vii) x+1/2, −y+1/2, −z+1; (viii) −x+1/2, y+1/2, z. |
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Many glycine salts and adducts exhibit interesting dielectric properties, the most well known compound of this family being TGS (triglycine sulfate), which orders ferroelectrically below 322 K (Matthias et al., 1956). In addition of their main interest in the field of new materials chemistry (Siegel et al., 1998; Baker et al., 1992), hybrid compounds are of interest because of their electrical, magnetic and optical properties (Kagan et al., 1999; Hill, 1998). The present compound is a result from a search of new organic–inorganic hybrid materials (Benali-Cherif, Cherouana et al., 2002; Benali-Cherif, Abouimrane et al., 2002; Benali-Cherif, Bendheif et al., 2002; Benali-Cherif, Benguedouar et al., 2002.). The asymmetric unit of DGS contains two monoprotaned glycine molecules (C2H7NO2+) and one anionic sulfate molecule (SO42−). The mean bonds and angles in the SO42− group are 1.472 Å and 109.465°, respectively, showing a normal tetrahedral geometry for the S atom. Interatomic distances in the glycine cations compare well with distances observed in diglycine sulfate monohydrate (Cano et al., 1974). Although their carboxy skeletons are both planar, atom N1B is displaced from this plane by −0.170 (15) Å, whereas atom N1A is displaced by 0.075 (15) Å. The relevant torsion angles of the glycinium cations [O1A—C2A—C1A—N1A = 176.71 (15)° and N1B—C2B—C1B—O1B = 23.9 (7)°] indicate different conformations for the two glycinium cations in the asymmetric unit, viz. E for glycine A and Z for glycine B; this difference in conformation is not observed in diglycine selenate (Olejnik et al., 1975). The crystal structure is built of two layers of glycine B ions and sulfate groups inserted between layers of glycine A along b axis. The layers are linked together by an intricate network of hydrogen-bond interactions. The strongest of these bonds involves atoms O2A and O2B of the glycinium cations (A and B) as donors and O atoms of sulfate anions as acceptors [O1A—H1A···O1 = 2.567 (2) Å and O1B—H1B···O4 = 2.573 (2) Å]. Atom N1B forms three mean hydrogen bonds with sulfate anion [N1B—H4B···O2 = 2.838 (2) Å, N1B—H5B···O3 = 2.851 (2) Å and N1B—H6B···O3 = 2.813 (2) Å]. Weak hydrogen bonds are observed in the glycine A layers, between N and O atoms [N1A—H5A···O2A = 2.958 (2) Å] and between C and O atoms [C2A—H3A···O2A = 3.264 (2) Å].