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The crystal structure of diglycinium sulfate (DGS), 2C2H6NO2+·SO42-, consists of two layers of glycinium and sulfate groups inserted between a layer of glycinium cations linked by strong hydrogen bonds. The two glycinium cations have different conformations, viz. E for glycine A and Z for glycine B.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802019785/dn6041sup1.cif
Contains datablocks global, DGS

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802019785/dn6041DGSsup2.hkl
Contains datablock DGS

CCDC reference: 202322

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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


Yellow Alert 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

Comment top

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].

Experimental top

Colorless single crystals of DGS, were obtained by slow evaporation at room temperature of an equimolar solution of glycine and sulfuric acid.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1997) view of the title compound with the atomic labelling scheme. Displacement are drawn at the 50% probability level.
[Figure 2] Fig. 2. PLUTON (Spek, 1990) view of the title compound, showing the immediate hydrogen-bonded surrounding of the anion and cations.
(DGS) top
Crystal data top
2C2H6NO2+·SO42F(000) = 1040
Mr = 248.23Dx = 1.65 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 12129 reflections
a = 8.9350 (4) Åθ = 3.6–26.4°
b = 10.2770 (3) ŵ = 0.35 mm1
c = 21.7640 (3) ÅT = 293 K
V = 1998.48 (11) Å3Prism, colorless
Z = 80.5 × 0.4 × 0.3 mm
Data collection top
Nonius KappaCCD
diffractometer
1844 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.092
Graphite monochromatorθmax = 26.4°, θmin = 3.2°
ϕ scansh = 1111
12129 measured reflectionsk = 1212
1997 independent reflectionsl = 2725
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: difference Fourier map
wR(F2) = 0.098H 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 parametersΔρmax = 0.25 e Å3
24 restraintsΔρmin = 0.38 e Å3
Crystal data top
2C2H6NO2+·SO42V = 1998.48 (11) Å3
Mr = 248.23Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.9350 (4) ŵ = 0.35 mm1
b = 10.2770 (3) ÅT = 293 K
c = 21.7640 (3) Å0.5 × 0.4 × 0.3 mm
Data collection top
Nonius KappaCCD
diffractometer
1844 reflections with I > 2σ(I)
12129 measured reflectionsRint = 0.092
1997 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03424 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.25 e Å3
1997 reflectionsΔρmin = 0.38 e Å3
164 parameters
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
xyzUiso*/UeqOcc. (<1)
S0.10690 (4)0.55788 (4)0.663471 (17)0.02355 (15)
O2A0.21628 (14)0.03292 (11)0.51481 (6)0.0326 (3)
O10.00956 (16)0.48644 (12)0.62094 (6)0.0415 (3)
O30.08780 (14)0.50816 (11)0.72625 (6)0.0333 (3)
O1A0.38658 (14)0.12148 (13)0.53549 (7)0.0409 (3)
H1A0.42010.06660.55910.061*
O20.07143 (15)0.69813 (12)0.66235 (6)0.0357 (3)
O40.26467 (14)0.53943 (13)0.64542 (7)0.0414 (3)
N1A0.07072 (16)0.12375 (13)0.43269 (7)0.0297 (3)
H6A0.09570.04870.41500.045*
H4A0.04300.18040.40390.045*
H5A0.00480.11070.45860.045*
N1B0.16743 (16)0.34925 (14)0.73588 (7)0.0321 (3)
H6B0.09140.40300.72850.048*
H5B0.24710.39510.74740.048*
H4B0.14230.29410.76570.048*
C2B0.2030 (2)0.2758 (2)0.67961 (10)0.0431 (5)
H3B0.29640.22930.68550.052*
H2B0.21650.33610.64580.052*
C1AB0.0806 (9)0.1794 (8)0.6633 (4)0.034 (2)0.50
O21B0.1050 (6)0.0918 (5)0.6278 (3)0.0689 (16)0.50
O1B0.05002 (14)0.21073 (12)0.68600 (6)0.0338 (3)
C1BB0.0690 (9)0.2089 (8)0.6509 (4)0.0335 (19)0.50
O22B0.0744 (6)0.1476 (6)0.6040 (2)0.0689 (15)0.50
C1A0.26723 (18)0.07554 (15)0.50827 (7)0.0274 (3)
C2A0.1997 (2)0.17554 (16)0.46640 (8)0.0352 (4)
H2A0.27480.20480.43730.042*
H3A0.16820.25010.49050.042*
H1B0.119 (3)0.158 (3)0.6712 (13)0.067 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0196 (2)0.0202 (2)0.0309 (2)0.00172 (13)0.00215 (14)0.00150 (13)
O2A0.0360 (7)0.0215 (5)0.0402 (6)0.0011 (5)0.0020 (5)0.0008 (5)
O10.0424 (7)0.0317 (6)0.0505 (8)0.0098 (6)0.0231 (6)0.0052 (5)
O30.0367 (7)0.0295 (6)0.0338 (6)0.0024 (5)0.0003 (5)0.0058 (5)
O1A0.0378 (7)0.0370 (7)0.0479 (8)0.0103 (5)0.0159 (6)0.0112 (6)
O20.0425 (7)0.0210 (6)0.0437 (7)0.0031 (5)0.0003 (5)0.0053 (5)
O40.0243 (6)0.0425 (7)0.0575 (8)0.0043 (5)0.0109 (6)0.0169 (6)
N1A0.0306 (7)0.0241 (6)0.0344 (7)0.0017 (5)0.0032 (6)0.0016 (5)
N1B0.0244 (7)0.0291 (7)0.0427 (8)0.0014 (6)0.0085 (6)0.0009 (6)
C2B0.0225 (8)0.0464 (11)0.0603 (12)0.0021 (7)0.0043 (8)0.0162 (9)
C1AB0.033 (3)0.034 (4)0.035 (3)0.006 (2)0.006 (2)0.005 (3)
O21B0.045 (3)0.081 (4)0.081 (4)0.013 (2)0.019 (2)0.052 (3)
O1B0.0255 (6)0.0334 (6)0.0426 (7)0.0030 (5)0.0015 (5)0.0071 (5)
C1BB0.030 (2)0.030 (3)0.040 (4)0.000 (2)0.006 (2)0.007 (3)
O22B0.047 (3)0.088 (4)0.072 (3)0.017 (3)0.022 (2)0.048 (3)
C1A0.0276 (8)0.0250 (7)0.0296 (7)0.0003 (6)0.0008 (6)0.0010 (6)
C2A0.0399 (9)0.0246 (8)0.0411 (9)0.0057 (7)0.0111 (8)0.0053 (7)
Geometric parameters (Å, º) top
S—O11.4670 (12)C2B—C1BB1.515 (8)
S—O31.4686 (12)C2B—C1AB1.517 (8)
S—O41.4756 (13)C1AB—O21B1.207 (8)
S—O21.4761 (12)C1AB—O1B1.307 (8)
O2A—C1A1.212 (2)O1B—C1BB1.310 (8)
O1A—C1A1.308 (2)C1BB—O22B1.201 (8)
N1A—C2A1.466 (2)C1A—C2A1.500 (2)
N1B—C2B1.474 (2)
O1—S—O3110.12 (7)O21B—C1AB—C2B120.4 (7)
O1—S—O4109.52 (8)O1B—C1AB—C2B113.3 (6)
O3—S—O4108.30 (8)C1AB—O1B—C1BB18.4 (6)
O1—S—O2110.55 (8)O22B—C1BB—O1B122.4 (7)
O3—S—O2109.28 (7)O22B—C1BB—C2B123.9 (7)
O4—S—O2109.04 (8)O1B—C1BB—C2B113.3 (6)
N1B—C2B—C1BB113.9 (3)O2A—C1A—O1A125.78 (15)
N1B—C2B—C1AB111.9 (3)O2A—C1A—C2A123.36 (15)
C1BB—C2B—C1AB15.9 (5)O1A—C1A—C2A110.85 (14)
O21B—C1AB—O1B125.9 (7)N1A—C2A—C1A111.81 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O1i0.821.772.567 (2)164
O1B—H1B···O4ii0.88 (3)1.70 (3)2.573 (2)172 (3)
N1A—H4A···O2iii0.891.922.762 (2)156
N1B—H4B···O2iv0.891.962.838 (2)170
N1A—H5A···O2Av0.892.132.958 (2)154
N1B—H5B···O3vi0.891.962.851 (2)175
N1A—H6A···O21Bv0.892.483.018 (5)119
N1A—H6A···O22Bv0.892.563.177 (6)127
N1A—H6A···O4vii0.892.032.805 (2)145
N1B—H6B···O30.891.932.813 (2)170
C2A—H3A···O2Aviii0.972.513.264 (2)134
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x1/2, y1/2, z; (iii) x, y+1, z+1; (iv) x, y1/2, 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 formula2C2H6NO2+·SO42
Mr248.23
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)8.9350 (4), 10.2770 (3), 21.7640 (3)
V3)1998.48 (11)
Z8
Radiation typeMo Kα
µ (mm1)0.35
Crystal size (mm)0.5 × 0.4 × 0.3
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
12129, 1997, 1844
Rint0.092
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.098, 1.10
No. of reflections1997
No. of parameters164
No. of restraints24
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O1i0.821.772.567 (2)164
O1B—H1B···O4ii0.88 (3)1.70 (3)2.573 (2)172 (3)
N1A—H4A···O2iii0.891.922.762 (2)156
N1B—H4B···O2iv0.891.962.838 (2)170
N1A—H5A···O2Av0.892.132.958 (2)154
N1B—H5B···O3vi0.891.962.851 (2)175
N1A—H6A···O21Bv0.892.483.018 (5)119
N1A—H6A···O22Bv0.892.563.177 (6)127
N1A—H6A···O4vii0.892.032.805 (2)145
N1B—H6B···O30.891.932.813 (2)170
C2A—H3A···O2Aviii0.972.513.264 (2)134
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x1/2, y1/2, z; (iii) x, y+1, z+1; (iv) x, y1/2, 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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