The crystal structures of three compounds of glycine and inorganic materials are presented and discussed. The orthorhombic structure of glycinesulfatodilithium(I), [Li2(SO4)(C2H5NO2)]n, consists of corrugated sheets of [LiO4] and [SO4] tetrahedra. The glycine molecules are located between these sheets. The main features of the monoclinic structure of diaquadichloroglycinenickel(II), [NiCl2(C2H5NO2)(H2O)2]n, are helical chains of [NiO4Cl2] octahedra connected by glycine molecules. The orthorhombic structure of triaquaglycinesulfatozinc(II), [Zn(SO4)(C2H5NO2)(H2O)3]n, is made up of [O3SOZnO5] clusters. These clusters are linked by glycine molecules into zigzag chains. All three compounds are examples of non-centrosymmetric glycine compounds.
Supporting information
CCDC references: 243586; 243587; 243588
The crystals of the title compounds were grown from aqueous solutions of glycine and lithium sulfate, nickel dichloride or zinc sulfate, respectively, in a stochiometric ratio. The solutions were evaporated slowly at a temperature of approximately 295 K over a period of four months. The syntheses yielded crystals of up to several millimeters in diameter.
For all compounds, data collection: COLLECT (Nonius, 2003); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: DIAMOND (Bergerhoff et al., 1997) for (I); ATOMS (Dowty, 1999) for (II), (III). For all compounds, software used to prepare material for publication: SHELXL97.
Crystal data top
[Li2(SO4)(C2H5O2N)] | Dx = 1.953 Mg m−3 |
Mr = 185.01 | Melting point: not determined K |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 1054 reflections |
a = 16.423 (3) Å | θ = 4.1–30.0° |
b = 5.005 (1) Å | µ = 0.49 mm−1 |
c = 7.654 (2) Å | T = 293 K |
V = 629.1 (2) Å3 | Prism, colourless |
Z = 4 | 0.40 × 0.20 × 0.20 mm |
F(000) = 376 | |
Data collection top
Nonius Kappa CCD diffractometer | 1653 independent reflections |
Radiation source: fine-focus sealed tube | 1582 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 9 pixels mm-1 | θmax = 30.0°, θmin = 4.3° |
ϕ and ω scans | h = −22→23 |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | k = −7→7 |
Tmin = 0.827, Tmax = 0.908 | l = −10→10 |
1653 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.025 | w = 1/[σ2(Fo2) + (0.0387P)2 + 0.088P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.066 | (Δ/σ)max = 0.001 |
S = 1.09 | Δρmax = 0.28 e Å−3 |
1653 reflections | Δρmin = −0.36 e Å−3 |
130 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.013 (7) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.021 (4) |
Crystal data top
[Li2(SO4)(C2H5O2N)] | V = 629.1 (2) Å3 |
Mr = 185.01 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 16.423 (3) Å | µ = 0.49 mm−1 |
b = 5.005 (1) Å | T = 293 K |
c = 7.654 (2) Å | 0.40 × 0.20 × 0.20 mm |
Data collection top
Nonius Kappa CCD diffractometer | 1653 independent reflections |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | 1582 reflections with I > 2σ(I) |
Tmin = 0.827, Tmax = 0.908 | Rint = 0.000 |
1653 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | All H-atom parameters refined |
wR(F2) = 0.066 | Δρmax = 0.28 e Å−3 |
S = 1.09 | Δρmin = −0.36 e Å−3 |
1653 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
130 parameters | Absolute structure parameter: 0.021 (4) |
1 restraint | |
Special details top
Experimental. Single-crystal X-ray intensity data were collected at 293 K on a Nonius Kappa diffractometer with CCD-area detector, using 282 frames with phi- and omega-increments of 1 degrees and a counting time of 20 s per frame. The crystal- to-detector-distance was 30 mm. The whole ewald sphere was measured. The reflection data were processed with the Nonius program suite DENZO-SMN and corrected for Lorentz, polarization, background and absorption effects (Otwinowski and Minor, 1997). The crystal structure was determined by Direct methods (SHELXS97, Sheldrick, 1997) and subsequent Fourier and difference Fourier syntheses, followed by full-matrix least-squares refinements on F2 (SHELXL97, Sheldrick, 1997). All hydrogen atoms were refined freely. |
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 | |
Li1 | 0.6948 (3) | 0.7389 (6) | 0.4648 (5) | 0.0179 (8) | |
Li2 | 0.7977 (2) | 0.2373 (7) | 0.5271 (5) | 0.0201 (8) | |
S | 0.668617 (16) | 0.23198 (5) | 0.24330 (12) | 0.01183 (11) | |
O1S | 0.58049 (6) | 0.2620 (2) | 0.2328 (5) | 0.0247 (3) | |
O2S | 0.69785 (7) | 0.3563 (3) | 0.40610 (17) | 0.0203 (3) | |
O3S | 0.70821 (8) | 0.3604 (3) | 0.09065 (18) | 0.0196 (3) | |
O4S | 0.69165 (5) | −0.05380 (17) | 0.2446 (3) | 0.01856 (19) | |
O1 | 0.60013 (8) | 0.8445 (3) | 0.59255 (17) | 0.0234 (3) | |
O2 | 0.61244 (9) | 0.8091 (3) | 0.8828 (2) | 0.0266 (3) | |
C1 | 0.59173 (7) | 0.9283 (2) | 0.7464 (3) | 0.0167 (2) | |
C2 | 0.55194 (11) | 1.1987 (3) | 0.7733 (2) | 0.0227 (4) | |
H1C | 0.5123 (18) | 1.183 (6) | 0.863 (4) | 0.039 (7)* | |
H2C | 0.5921 (15) | 1.320 (5) | 0.810 (3) | 0.034 (6)* | |
N | 0.51813 (10) | 1.3043 (4) | 0.6094 (2) | 0.0266 (3) | |
H1N | 0.5538 (18) | 1.294 (5) | 0.530 (5) | 0.043 (7)* | |
H2N | 0.471 (2) | 1.205 (6) | 0.597 (5) | 0.064 (9)* | |
H3N | 0.4959 (18) | 1.452 (6) | 0.627 (4) | 0.052 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Li1 | 0.0202 (16) | 0.0154 (19) | 0.0182 (19) | 0.0008 (10) | −0.0008 (14) | 0.0011 (11) |
Li2 | 0.0257 (19) | 0.0181 (19) | 0.0166 (19) | 0.0004 (11) | −0.0002 (15) | 0.0021 (11) |
S | 0.01380 (15) | 0.01120 (15) | 0.01050 (15) | 0.00120 (9) | 0.0003 (2) | 0.0005 (2) |
O1S | 0.0128 (5) | 0.0316 (5) | 0.0296 (8) | 0.0031 (3) | 0.0002 (7) | 0.0056 (6) |
O2S | 0.0305 (6) | 0.0165 (7) | 0.0138 (6) | 0.0024 (5) | −0.0042 (5) | −0.0034 (6) |
O3S | 0.0250 (6) | 0.0154 (6) | 0.0183 (6) | 0.0023 (5) | 0.0076 (5) | 0.0051 (6) |
O4S | 0.0316 (5) | 0.0114 (4) | 0.0127 (4) | 0.0032 (3) | −0.0005 (6) | 0.0003 (6) |
O1 | 0.0256 (6) | 0.0248 (6) | 0.0199 (6) | 0.0035 (5) | 0.0041 (5) | −0.0024 (6) |
O2 | 0.0307 (7) | 0.0295 (7) | 0.0197 (7) | 0.0047 (6) | −0.0049 (6) | 0.0041 (6) |
C1 | 0.0148 (5) | 0.0172 (5) | 0.0181 (5) | −0.0018 (4) | 0.0000 (8) | 0.0012 (8) |
C2 | 0.0307 (8) | 0.0189 (6) | 0.0183 (10) | 0.0023 (6) | −0.0039 (6) | −0.0016 (6) |
N | 0.0350 (8) | 0.0245 (7) | 0.0203 (7) | 0.0119 (6) | −0.0020 (6) | −0.0023 (6) |
Geometric parameters (Å, º) top
Li1—O1 | 1.911 (4) | O3S—Li1iii | 1.958 (4) |
Li1—O3Si | 1.958 (4) | O4S—Li2iii | 1.973 (5) |
Li1—O2S | 1.968 (4) | O4S—Li1vi | 1.980 (4) |
Li1—O4Sii | 1.980 (4) | O1—C1 | 1.258 (3) |
Li2—O2iii | 1.878 (4) | O2—C1 | 1.249 (3) |
Li2—O3Siv | 1.950 (4) | C1—C2 | 1.517 (2) |
Li2—O4Si | 1.973 (5) | C2—N | 1.470 (2) |
Li2—O2S | 1.976 (4) | C2—H1C | 0.95 (3) |
S—O1S | 1.4573 (11) | C2—H2C | 0.94 (3) |
S—O2S | 1.4732 (17) | N—H1N | 0.84 (3) |
S—O4S | 1.4796 (9) | N—H2N | 0.92 (4) |
S—O3S | 1.4837 (17) | N—H3N | 0.83 (3) |
O3S—Li2v | 1.950 (4) | | |
| | | |
O1—Li1—O3Si | 108.9 (2) | O2iii—Li2—Li1 | 100.67 (16) |
O1—Li1—O2S | 114.0 (2) | O3Siv—Li2—Li1 | 143.47 (16) |
O3Si—Li1—O2S | 113.21 (19) | O4Si—Li2—Li1 | 75.27 (14) |
O1—Li1—O4Sii | 105.62 (18) | O2S—Li2—Li1 | 38.93 (8) |
O3Si—Li1—O4Sii | 106.10 (19) | Si—Li2—Li1 | 61.04 (11) |
O2S—Li1—O4Sii | 108.42 (19) | S—Li2—Li1 | 60.69 (7) |
O1—Li1—Sii | 86.87 (13) | Li1vi—Li2—Li1 | 109.87 (11) |
O3Si—Li1—Sii | 97.93 (13) | O2iii—Li2—Li1iv | 124.0 (2) |
O2S—Li1—Sii | 132.03 (18) | O3Siv—Li2—Li1iv | 75.82 (15) |
O4Sii—Li1—Sii | 24.72 (6) | O4Si—Li2—Li1iv | 32.07 (9) |
O1—Li1—Li2ii | 98.32 (15) | O2S—Li2—Li1iv | 119.9 (2) |
O3Si—Li1—Li2ii | 38.60 (9) | Si—Li2—Li1iv | 56.32 (10) |
O2S—Li1—Li2ii | 144.83 (17) | S—Li2—Li1iv | 137.78 (19) |
O4Sii—Li1—Li2ii | 73.69 (13) | Li1vi—Li2—Li1iv | 100.27 (14) |
Sii—Li1—Li2ii | 59.96 (10) | Li1—Li2—Li1iv | 100.00 (14) |
O1—Li1—Li2 | 126.58 (16) | O1S—S—O2S | 109.07 (13) |
O3Si—Li1—Li2 | 74.29 (10) | O1S—S—O4S | 110.73 (6) |
O2S—Li1—Li2 | 39.12 (14) | O2S—S—O4S | 108.62 (11) |
O4Sii—Li1—Li2 | 125.18 (15) | O1S—S—O3S | 110.32 (12) |
Sii—Li1—Li2 | 146.52 (12) | O2S—S—O3S | 109.89 (6) |
Li2ii—Li1—Li2 | 109.87 (11) | O4S—S—O3S | 108.18 (10) |
O1—Li1—Li2v | 122.8 (2) | O1S—S—Li1vi | 104.84 (11) |
O3Si—Li1—Li2v | 117.6 (2) | O2S—S—Li1vi | 79.86 (10) |
O2S—Li1—Li2v | 76.61 (14) | O3S—S—Li1vi | 137.11 (10) |
O4Sii—Li1—Li2v | 31.94 (9) | O1S—S—Li2iii | 103.61 (12) |
Sii—Li1—Li2v | 56.42 (10) | O2S—S—Li2iii | 138.41 (10) |
Li2ii—Li1—Li2v | 97.92 (14) | O3S—S—Li2iii | 81.03 (10) |
Li2—Li1—Li2v | 97.67 (13) | Li1vi—S—Li2iii | 67.26 (6) |
O2iii—Li2—O3Siv | 111.8 (2) | O1S—S—Li2 | 137.07 (15) |
O2iii—Li2—O4Si | 109.00 (19) | O4S—S—Li2 | 79.94 (10) |
O3Siv—Li2—O4Si | 107.9 (2) | O3S—S—Li2 | 104.69 (10) |
O2iii—Li2—O2S | 108.6 (2) | Li1vi—S—Li2 | 60.45 (11) |
O3Siv—Li2—O2S | 111.51 (19) | Li2iii—S—Li2 | 105.71 (8) |
O4Si—Li2—O2S | 108.00 (19) | Li2iii—O4S—Li1vi | 116.00 (10) |
O2iii—Li2—Si | 91.25 (14) | O2—C1—O1 | 126.41 (13) |
O3Siv—Li2—Si | 131.57 (19) | O2—C1—C2 | 115.5 (2) |
O4Si—Li2—Si | 24.49 (6) | O1—C1—C2 | 118.13 (18) |
O2S—Li2—Si | 99.28 (14) | N—C2—C1 | 111.59 (16) |
O2iii—Li2—S | 97.43 (16) | N—C2—H1C | 112.8 (18) |
O3Siv—Li2—S | 97.75 (15) | C1—C2—H1C | 108.7 (19) |
O4Si—Li2—S | 132.06 (17) | N—C2—H2C | 106.8 (16) |
O2S—Li2—S | 24.11 (8) | C1—C2—H2C | 108.3 (16) |
Si—Li2—S | 121.71 (12) | H1C—C2—H2C | 109 (2) |
O2iii—Li2—Li1vi | 119.99 (16) | C2—N—H1N | 109 (2) |
O3Siv—Li2—Li1vi | 38.77 (13) | C2—N—H2N | 102 (2) |
O4Si—Li2—Li1vi | 127.87 (14) | H1N—N—H2N | 118 (3) |
O2S—Li2—Li1vi | 73.32 (10) | C2—N—H3N | 110 (2) |
Si—Li2—Li1vi | 148.74 (12) | H1N—N—H3N | 118 (3) |
S—Li2—Li1vi | 59.60 (7) | H2N—N—H3N | 97 (3) |
Symmetry codes: (i) −x+3/2, y+1/2, z+1/2; (ii) x, y+1, z; (iii) −x+3/2, y−1/2, z−1/2; (iv) −x+3/2, y−1/2, z+1/2; (v) −x+3/2, y+1/2, z−1/2; (vi) x, y−1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O1Sii | 0.84 (3) | 2.32 (4) | 3.066 (4) | 147 (3) |
N—H2N···O2vii | 0.92 (4) | 2.14 (4) | 2.816 (2) | 130 (3) |
N—H3N···O1Sviii | 0.83 (3) | 2.07 (3) | 2.868 (2) | 160 (3) |
Symmetry codes: (ii) x, y+1, z; (vii) −x+1, −y+2, z−1/2; (viii) −x+1, −y+2, z+1/2. |
Crystal data top
[NiCl2(C2H5O2N)(H2O)2] | F(000) = 244 |
Mr = 240.71 | Dx = 2.142 Mg m−3 |
Monoclinic, P21 | Melting point: not determined K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 8.203 (2) Å | Cell parameters from 1197 reflections |
b = 5.475 (1) Å | θ = 4.1–30.0° |
c = 8.311 (2) Å | µ = 3.27 mm−1 |
β = 90.97 (3)° | T = 293 K |
V = 373.21 (14) Å3 | Prism, green |
Z = 2 | 0.20 × 0.10 × 0.10 mm |
Data collection top
Nonius Kappa CCD diffractometer | 2170 independent reflections |
Radiation source: fine-focus sealed tube | 2142 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 9 pixels mm-1 | θmax = 30.0°, θmin = 4.5° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | k = −7→7 |
Tmin = 0.561, Tmax = 0.736 | l = −11→11 |
2170 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.016 | w = 1/[σ2(Fo2) + (0.0166P)2 + 0.065P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.038 | (Δ/σ)max = 0.003 |
S = 1.13 | Δρmax = 0.29 e Å−3 |
2170 reflections | Δρmin = −0.34 e Å−3 |
128 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.127 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.002 (8) |
Crystal data top
[NiCl2(C2H5O2N)(H2O)2] | V = 373.21 (14) Å3 |
Mr = 240.71 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.203 (2) Å | µ = 3.27 mm−1 |
b = 5.475 (1) Å | T = 293 K |
c = 8.311 (2) Å | 0.20 × 0.10 × 0.10 mm |
β = 90.97 (3)° | |
Data collection top
Nonius Kappa CCD diffractometer | 2170 independent reflections |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | 2142 reflections with I > 2σ(I) |
Tmin = 0.561, Tmax = 0.736 | Rint = 0.000 |
2170 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.016 | All H-atom parameters refined |
wR(F2) = 0.038 | Δρmax = 0.29 e Å−3 |
S = 1.13 | Δρmin = −0.34 e Å−3 |
2170 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
128 parameters | Absolute structure parameter: 0.002 (8) |
1 restraint | |
Special details top
Experimental. Single-crystal X-ray intensity data were collected at 293 K on a Nonius Kappa diffractometer with CCD-area detector, using 318 frames with an omega-increment of 2 degrees and a counting time of 30 s per frame. The crystal to detector distance was 25 mm. The whole ewald sphere was measured. The reflection data were processed with the Nonius program suite DENZO-SMN and corrected for Lorentz, polarization, background and absorption effects (Otwinowski and Minor, 1997). The crystal structure was determined by automatic patterson methods (SHELXS97, Sheldrick, 1997) and subsequent Fourier and difference Fourier syntheses, followed by full-matrix least-squares refinements on F2 (SHELXL97, Sheldrick, 1997). All hydrogen atoms were refined freely. |
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 | |
Ni | 0.784803 (18) | 0.78457 (3) | 0.334887 (18) | 0.01347 (6) | |
Cl1 | 0.54116 (4) | 0.54991 (7) | 0.25002 (4) | 0.02017 (8) | |
Cl2 | 0.77352 (4) | 0.99840 (7) | 0.08732 (4) | 0.02162 (9) | |
O1 | 1.00165 (12) | 0.4518 (2) | 0.58500 (13) | 0.0183 (2) | |
O2 | 0.76111 (13) | 0.6377 (2) | 0.56224 (13) | 0.0179 (2) | |
C1 | 0.86615 (16) | 0.5169 (3) | 0.63931 (16) | 0.0149 (2) | |
C2 | 0.8260 (2) | 0.4484 (4) | 0.8103 (2) | 0.0277 (4) | |
H1C | 0.830 (3) | 0.259 (6) | 0.821 (3) | 0.041 (6)* | |
H2C | 0.895 (3) | 0.509 (5) | 0.879 (3) | 0.043 (7)* | |
N | 0.66229 (16) | 0.5314 (3) | 0.85727 (17) | 0.0212 (3) | |
H1N | 0.648 (4) | 0.541 (8) | 0.960 (4) | 0.074 (10)* | |
H2N | 0.580 (5) | 0.435 (8) | 0.804 (5) | 0.090 (13)* | |
H3N | 0.637 (5) | 0.679 (8) | 0.814 (5) | 0.086 (13)* | |
O1W | 0.92928 (14) | 0.4953 (2) | 0.26258 (14) | 0.0200 (2) | |
H1W1 | 0.889 (4) | 0.364 (6) | 0.225 (4) | 0.063 (9)* | |
H2W1 | 0.964 (3) | 0.449 (6) | 0.364 (4) | 0.046 (7)* | |
O2W | 0.65320 (18) | 1.0653 (3) | 0.43031 (17) | 0.0329 (3) | |
H1W2 | 0.598 (3) | 1.046 (7) | 0.520 (4) | 0.063 (9)* | |
H2W2 | 0.631 (3) | 1.180 (6) | 0.386 (4) | 0.047 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.01401 (8) | 0.01378 (9) | 0.01262 (9) | 0.00057 (6) | 0.00000 (5) | 0.00155 (7) |
Cl1 | 0.01818 (15) | 0.02103 (17) | 0.02124 (16) | −0.00242 (12) | −0.00178 (11) | 0.00289 (13) |
Cl2 | 0.02621 (17) | 0.02273 (18) | 0.01585 (15) | −0.00328 (13) | −0.00192 (12) | 0.00540 (13) |
O1 | 0.0166 (5) | 0.0224 (5) | 0.0160 (5) | 0.0052 (4) | 0.0011 (4) | 0.0028 (4) |
O2 | 0.0175 (5) | 0.0220 (5) | 0.0143 (5) | 0.0047 (4) | 0.0007 (4) | 0.0052 (4) |
C1 | 0.0165 (6) | 0.0140 (6) | 0.0142 (6) | −0.0013 (5) | 0.0000 (4) | 0.0013 (5) |
C2 | 0.0197 (7) | 0.0439 (11) | 0.0198 (7) | 0.0079 (7) | 0.0042 (6) | 0.0145 (7) |
N | 0.0212 (6) | 0.0249 (7) | 0.0177 (6) | −0.0015 (5) | 0.0042 (4) | −0.0010 (5) |
O1W | 0.0228 (5) | 0.0183 (5) | 0.0191 (5) | 0.0032 (4) | 0.0006 (4) | −0.0011 (4) |
O2W | 0.0459 (8) | 0.0223 (6) | 0.0312 (6) | 0.0161 (6) | 0.0197 (6) | 0.0100 (6) |
Geometric parameters (Å, º) top
Ni—O2W | 2.0457 (14) | C2—H1C | 1.04 (4) |
Ni—O2 | 2.0658 (11) | C2—H2C | 0.86 (3) |
Ni—O1W | 2.0732 (12) | N—H1N | 0.86 (3) |
Ni—O1i | 2.0762 (11) | N—H2N | 0.96 (4) |
Ni—Cl2 | 2.3677 (6) | N—H3N | 0.91 (4) |
Ni—Cl1 | 2.4688 (6) | O1W—H1W1 | 0.85 (4) |
O1—C1 | 1.2582 (17) | O1W—H2W1 | 0.92 (3) |
O2—C1 | 1.2534 (18) | O2W—H1W2 | 0.89 (3) |
C1—C2 | 1.512 (2) | O2W—H2W2 | 0.75 (3) |
C2—N | 1.477 (2) | | |
| | | |
O2W—Ni—O2 | 83.08 (5) | N—C2—C1 | 112.68 (13) |
O2W—Ni—O1W | 173.85 (5) | N—C2—H1C | 108.1 (14) |
O2—Ni—O1W | 91.76 (5) | C1—C2—H1C | 108.7 (14) |
O2W—Ni—O1i | 89.56 (6) | N—C2—H2C | 107.1 (17) |
O2—Ni—O1i | 88.30 (5) | C1—C2—H2C | 112.0 (17) |
O1W—Ni—O1i | 86.93 (5) | H1C—C2—H2C | 108 (2) |
O2W—Ni—Cl2 | 87.27 (4) | C2—N—H1N | 115 (2) |
O2—Ni—Cl2 | 169.89 (3) | C2—N—H2N | 110 (2) |
O1W—Ni—Cl2 | 98.05 (4) | H1N—N—H2N | 113 (3) |
O1i—Ni—Cl2 | 94.64 (4) | C2—N—H3N | 112 (3) |
O2W—Ni—Cl1 | 94.11 (5) | H1N—N—H3N | 108 (4) |
O2—Ni—Cl1 | 88.31 (4) | H2N—N—H3N | 99 (3) |
O1W—Ni—Cl1 | 89.06 (4) | Ni—O1W—H1W1 | 122 (2) |
O1i—Ni—Cl1 | 174.67 (3) | Ni—O1W—H2W1 | 96.6 (18) |
Cl2—Ni—Cl1 | 89.40 (3) | H1W1—O1W—H2W1 | 102 (3) |
O2—C1—O1 | 124.74 (13) | Ni—O2W—H1W2 | 121 (2) |
O2—C1—C2 | 116.91 (13) | Ni—O2W—H2W2 | 125 (2) |
O1—C1—C2 | 118.35 (13) | H1W2—O2W—H2W2 | 113 (3) |
Symmetry code: (i) −x+2, y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···Cl1ii | 0.86 (3) | 2.58 (3) | 3.4296 (17) | 167 (3) |
N—H2N···Cl1iii | 0.96 (4) | 2.37 (4) | 3.2372 (16) | 150 (4) |
N—H3N···Cl1iv | 0.91 (4) | 2.55 (4) | 3.4042 (17) | 156 (4) |
O1W—H1W1···Cl2v | 0.85 (4) | 2.49 (4) | 3.3304 (14) | 174 (3) |
O1W—H2W1···O1 | 0.92 (3) | 1.86 (3) | 2.7451 (17) | 161 (3) |
O2W—H1W2···Cl1iv | 0.89 (3) | 2.24 (3) | 3.1226 (16) | 172 (3) |
O2W—H2W2···Cl1vi | 0.75 (3) | 2.43 (3) | 3.1756 (15) | 176 (3) |
Symmetry codes: (ii) x, y, z+1; (iii) −x+1, y−1/2, −z+1; (iv) −x+1, y+1/2, −z+1; (v) x, y−1, z; (vi) x, y+1, z. |
Crystal data top
[Zn(SO4)(C2H5O2N)(H2O)3] | Dx = 2.206 Mg m−3 |
Mr = 290.55 | Melting point: not determined K |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 2456 reflections |
a = 8.440 (2) Å | θ = 3.5–37.8° |
b = 8.278 (2) Å | µ = 3.08 mm−1 |
c = 12.521 (3) Å | T = 293 K |
V = 874.8 (4) Å3 | Prism, colourless |
Z = 4 | 0.10 × 0.05 × 0.05 mm |
F(000) = 592 | |
Data collection top
Nonius Kappa CCD diffractometer | 4460 independent reflections |
Radiation source: fine-focus sealed tube | 3901 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 9 pixels mm-1 | θmax = 37.8°, θmin = 3.5° |
ω–scans | h = −14→14 |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | k = −14→14 |
Tmin = 0.748, Tmax = 0.861 | l = −21→21 |
4460 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.030 | w = 1/[σ2(Fo2) + (0.023P)2 + 0.336P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.067 | (Δ/σ)max = 0.001 |
S = 1.02 | Δρmax = 0.64 e Å−3 |
4460 reflections | Δρmin = −0.47 e Å−3 |
172 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0018 (8) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.006 (3) |
Crystal data top
[Zn(SO4)(C2H5O2N)(H2O)3] | V = 874.8 (4) Å3 |
Mr = 290.55 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 8.440 (2) Å | µ = 3.08 mm−1 |
b = 8.278 (2) Å | T = 293 K |
c = 12.521 (3) Å | 0.10 × 0.05 × 0.05 mm |
Data collection top
Nonius Kappa CCD diffractometer | 4460 independent reflections |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | 3901 reflections with I > 2σ(I) |
Tmin = 0.748, Tmax = 0.861 | Rint = 0.000 |
4460 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | All H-atom parameters refined |
wR(F2) = 0.067 | Δρmax = 0.64 e Å−3 |
S = 1.02 | Δρmin = −0.47 e Å−3 |
4460 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
172 parameters | Absolute structure parameter: 0.006 (3) |
1 restraint | |
Special details top
Experimental. Single-crystal X-ray intensity data were collected at 293 K on a Nonius Kappa diffractometer with CCD-area detector, using 476 frames with an omega-increment of 2 degrees and a counting time of 100 s per frame. The crystal to detector distance was 25 mm. The whole ewald sphere was measured. The reflection data were processed with the Nonius program suite DENZO-SMN and corrected for Lorentz, polarization, background and absorption effects (Otwinowski and Minor, 1997). The crystal structure was determined by automatic patterson methods (SHELXS97, Sheldrick, 1997) and subsequent Fourier and difference Fourier syntheses, followed by full-matrix least-squares refinements on F2 (SHELXL97, Sheldrick, 1997). All hydrogen atoms were refined freely. The crystals proved to racemic twins, therefore TWIN refinement was employed. |
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 | |
Zn | 0.04955 (2) | 0.19651 (2) | 0.497340 (18) | 0.01759 (5) | |
S | 0.02497 (5) | 0.27959 (5) | 0.75223 (4) | 0.01762 (7) | |
O1S | −0.1399 (2) | 0.2522 (2) | 0.78387 (15) | 0.0325 (3) | |
O2S | 0.1220 (2) | 0.1356 (2) | 0.77214 (14) | 0.0294 (3) | |
O3S | 0.0306 (2) | 0.32374 (19) | 0.63729 (12) | 0.0290 (3) | |
O4S | 0.0917 (2) | 0.4204 (2) | 0.81091 (14) | 0.0284 (3) | |
O1 | 0.27904 (15) | 0.11371 (17) | 0.50738 (15) | 0.0246 (3) | |
O2 | 0.51595 (18) | 0.03689 (17) | 0.56383 (14) | 0.0262 (3) | |
C1 | 0.4077 (2) | 0.1384 (2) | 0.55399 (14) | 0.0171 (3) | |
C2 | 0.4362 (2) | 0.3058 (2) | 0.60084 (19) | 0.0231 (3) | |
H1C | 0.370 (5) | 0.318 (5) | 0.660 (3) | 0.049 (10)* | |
H2C | 0.416 (4) | 0.386 (5) | 0.539 (3) | 0.038 (9)* | |
N | 0.5949 (3) | 0.3198 (3) | 0.6477 (2) | 0.0326 (4) | |
H1N | 0.668 (5) | 0.306 (4) | 0.590 (3) | 0.043 (10)* | |
H2N | 0.606 (5) | 0.406 (7) | 0.688 (4) | 0.067 (12)* | |
H3N | 0.592 (6) | 0.254 (7) | 0.688 (5) | 0.077 (17)* | |
O1W | 0.1282 (2) | 0.41992 (19) | 0.43295 (13) | 0.0243 (3) | |
H1W1 | 0.065 (4) | 0.460 (4) | 0.406 (3) | 0.027 (8)* | |
H2W1 | 0.195 (6) | 0.404 (5) | 0.399 (4) | 0.066 (14)* | |
O2W | 0.0595 (2) | 0.1182 (2) | 0.33418 (14) | 0.0268 (3) | |
H1W2 | 0.150 (5) | 0.120 (5) | 0.317 (3) | 0.045 (10)* | |
H2W2 | 0.015 (6) | 0.030 (6) | 0.318 (4) | 0.070 (13)* | |
O3W | −0.19955 (18) | 0.2132 (2) | 0.47292 (13) | 0.0249 (3) | |
H1W3 | −0.218 (5) | 0.223 (5) | 0.403 (4) | 0.059 (12)* | |
H2W3 | −0.223 (5) | 0.120 (6) | 0.477 (4) | 0.066 (13)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn | 0.01679 (7) | 0.01588 (8) | 0.02010 (8) | 0.00075 (6) | −0.00041 (9) | 0.00027 (8) |
S | 0.01806 (16) | 0.01866 (16) | 0.01614 (16) | −0.00037 (13) | 0.00055 (13) | 0.00120 (14) |
O1S | 0.0208 (7) | 0.0430 (10) | 0.0338 (8) | −0.0044 (6) | 0.0043 (6) | 0.0028 (7) |
O2S | 0.0280 (7) | 0.0230 (7) | 0.0371 (9) | 0.0044 (6) | −0.0079 (6) | 0.0046 (6) |
O3S | 0.0494 (10) | 0.0202 (6) | 0.0173 (6) | 0.0033 (6) | 0.0047 (6) | 0.0017 (5) |
O4S | 0.0273 (7) | 0.0261 (7) | 0.0319 (8) | 0.0000 (6) | −0.0051 (6) | −0.0085 (6) |
O1 | 0.0170 (5) | 0.0229 (5) | 0.0339 (8) | 0.0015 (4) | −0.0035 (6) | −0.0044 (6) |
O2 | 0.0231 (6) | 0.0169 (6) | 0.0387 (8) | 0.0039 (5) | −0.0089 (6) | −0.0068 (6) |
C1 | 0.0167 (6) | 0.0175 (7) | 0.0173 (6) | −0.0006 (5) | 0.0016 (5) | −0.0011 (5) |
C2 | 0.0213 (8) | 0.0170 (7) | 0.0311 (9) | −0.0001 (6) | −0.0020 (6) | −0.0047 (7) |
N | 0.0244 (8) | 0.0311 (10) | 0.0425 (11) | 0.0000 (7) | −0.0061 (8) | −0.0173 (9) |
O1W | 0.0271 (7) | 0.0212 (6) | 0.0244 (7) | 0.0012 (5) | 0.0038 (5) | 0.0051 (5) |
O2W | 0.0269 (7) | 0.0261 (7) | 0.0274 (7) | −0.0008 (6) | 0.0007 (5) | −0.0073 (6) |
O3W | 0.0192 (6) | 0.0250 (7) | 0.0305 (8) | 0.0005 (5) | −0.0016 (5) | 0.0038 (5) |
Geometric parameters (Å, º) top
Zn—O3S | 2.0507 (16) | C2—N | 1.467 (3) |
Zn—O1 | 2.0584 (13) | C2—H1C | 0.93 (4) |
Zn—O2i | 2.1229 (15) | C2—H2C | 1.03 (4) |
Zn—O1W | 2.1238 (16) | N—H1N | 0.95 (4) |
Zn—O3W | 2.1290 (16) | N—H2N | 0.88 (5) |
Zn—O2W | 2.1449 (18) | N—H3N | 0.75 (6) |
S—O1S | 1.4642 (18) | O1W—H1W1 | 0.71 (3) |
S—O2S | 1.4675 (16) | O1W—H2W1 | 0.72 (5) |
S—O3S | 1.4857 (17) | O2W—H1W2 | 0.79 (4) |
S—O4S | 1.4888 (16) | O2W—H2W2 | 0.85 (5) |
O1—C1 | 1.249 (2) | O3W—H1W3 | 0.89 (5) |
O2—C1 | 1.248 (2) | O3W—H2W3 | 0.80 (5) |
C1—C2 | 1.524 (3) | | |
| | | |
O3S—Zn—O1 | 101.09 (7) | O1—C1—C2 | 117.75 (16) |
O3S—Zn—O2i | 97.00 (7) | N—C2—C1 | 111.71 (16) |
O1—Zn—O2i | 78.38 (6) | N—C2—H1C | 103 (3) |
O3S—Zn—O1W | 84.35 (7) | C1—C2—H1C | 108 (2) |
O1—Zn—O1W | 91.10 (7) | N—C2—H2C | 113.6 (18) |
O2i—Zn—O1W | 169.47 (6) | C1—C2—H2C | 106 (2) |
O3S—Zn—O3W | 90.70 (7) | H1C—C2—H2C | 115 (3) |
O1—Zn—O3W | 163.65 (6) | C2—N—H1N | 106 (2) |
O2i—Zn—O3W | 89.05 (6) | C2—N—H2N | 113 (3) |
O1W—Zn—O3W | 101.40 (7) | H1N—N—H2N | 117 (3) |
O3S—Zn—O2W | 166.43 (7) | C2—N—H3N | 101 (4) |
O1—Zn—O2W | 85.45 (7) | H1N—N—H3N | 116 (5) |
O2i—Zn—O2W | 95.96 (7) | H2N—N—H3N | 102 (6) |
O1W—Zn—O2W | 83.64 (7) | Zn—O1W—H1W1 | 110 (3) |
O3W—Zn—O2W | 85.50 (6) | Zn—O1W—H2W1 | 108 (4) |
O1S—S—O2S | 111.00 (11) | H1W1—O1W—H2W1 | 113 (5) |
O1S—S—O3S | 109.29 (11) | Zn—O2W—H1W2 | 107 (3) |
O2S—S—O3S | 110.28 (10) | Zn—O2W—H2W2 | 118 (3) |
O1S—S—O4S | 110.34 (10) | H1W2—O2W—H2W2 | 112 (4) |
O2S—S—O4S | 109.94 (10) | Zn—O3W—H1W3 | 109 (3) |
O3S—S—O4S | 105.87 (10) | Zn—O3W—H2W3 | 100 (3) |
O2—C1—O1 | 124.95 (17) | H1W3—O3W—H2W3 | 96 (4) |
O2—C1—C2 | 117.30 (16) | | |
Symmetry code: (i) x−1/2, −y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O3Wii | 0.95 (4) | 2.00 (4) | 2.929 (3) | 164 (3) |
N—H2N···O4Siii | 0.88 (5) | 2.11 (5) | 2.967 (3) | 165 (4) |
N—H3N···O2Wiv | 0.75 (6) | 2.49 (6) | 3.151 (3) | 148 (5) |
O1W—H1W1···O4Sv | 0.71 (3) | 2.04 (4) | 2.744 (2) | 171 (4) |
O1W—H2W1···O4Svi | 0.72 (5) | 2.12 (5) | 2.815 (2) | 164 (5) |
O2W—H1W2···O2Svi | 0.79 (4) | 2.01 (4) | 2.802 (2) | 177 (4) |
O2W—H2W2···O2Svii | 0.85 (5) | 1.88 (5) | 2.714 (2) | 167 (5) |
O3W—H1W3···O1Sviii | 0.89 (5) | 1.93 (5) | 2.747 (2) | 152 (4) |
O3W—H2W3···O1i | 0.80 (5) | 1.97 (5) | 2.746 (2) | 164 (4) |
Symmetry codes: (i) x−1/2, −y, z; (ii) x+1, y, z; (iii) x+1/2, −y+1, z; (iv) −x+1/2, y, z+1/2; (v) −x, −y+1, z−1/2; (vi) −x+1/2, y, z−1/2; (vii) −x, −y, z−1/2; (viii) −x−1/2, y, z−1/2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | [Li2(SO4)(C2H5O2N)] | [NiCl2(C2H5O2N)(H2O)2] | [Zn(SO4)(C2H5O2N)(H2O)3] |
Mr | 185.01 | 240.71 | 290.55 |
Crystal system, space group | Orthorhombic, Pna21 | Monoclinic, P21 | Orthorhombic, Pca21 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 16.423 (3), 5.005 (1), 7.654 (2) | 8.203 (2), 5.475 (1), 8.311 (2) | 8.440 (2), 8.278 (2), 12.521 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 90.97 (3), 90 | 90, 90, 90 |
V (Å3) | 629.1 (2) | 373.21 (14) | 874.8 (4) |
Z | 4 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.49 | 3.27 | 3.08 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 | 0.20 × 0.10 × 0.10 | 0.10 × 0.05 × 0.05 |
|
Data collection |
Diffractometer | Nonius Kappa CCD diffractometer | Nonius Kappa CCD diffractometer | Nonius Kappa CCD diffractometer |
Absorption correction | Multi-scan (Otwinowski & Minor, 1997) | Multi-scan (Otwinowski & Minor, 1997) | Multi-scan (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.827, 0.908 | 0.561, 0.736 | 0.748, 0.861 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1653, 1653, 1582 | 2170, 2170, 2142 | 4460, 4460, 3901 |
Rint | 0.000 | 0.000 | 0.000 |
(sin θ/λ)max (Å−1) | 0.704 | 0.704 | 0.862 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.066, 1.09 | 0.016, 0.038, 1.13 | 0.030, 0.067, 1.02 |
No. of reflections | 1653 | 2170 | 4460 |
No. of parameters | 130 | 128 | 172 |
No. of restraints | 1 | 1 | 1 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.28, −0.36 | 0.29, −0.34 | 0.64, −0.47 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | 0.021 (4) | 0.002 (8) | 0.006 (3) |
Selected bond lengths (Å) for (I) topLi1—O1 | 1.911 (4) | O3S—Li2v | 1.950 (4) |
Li1—O3Si | 1.958 (4) | O3S—Li1iii | 1.958 (4) |
Li1—O2S | 1.968 (4) | O4S—Li2iii | 1.973 (5) |
Li1—O4Sii | 1.980 (4) | O1—C1 | 1.258 (3) |
Li2—O2iii | 1.878 (4) | O2—C1 | 1.249 (3) |
Li2—O3Siv | 1.950 (4) | C1—C2 | 1.517 (2) |
Li2—O4Si | 1.973 (5) | C2—N | 1.470 (2) |
Li2—O2S | 1.976 (4) | C2—H1C | 0.95 (3) |
S—O1S | 1.4573 (11) | C2—H2C | 0.94 (3) |
S—O2S | 1.4732 (17) | N—H1N | 0.84 (3) |
S—O4S | 1.4796 (9) | N—H2N | 0.92 (4) |
S—O3S | 1.4837 (17) | N—H3N | 0.83 (3) |
Symmetry codes: (i) −x+3/2, y+1/2, z+1/2; (ii) x, y+1, z; (iii) −x+3/2, y−1/2, z−1/2; (iv) −x+3/2, y−1/2, z+1/2; (v) −x+3/2, y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O1Sii | 0.84 (3) | 2.32 (4) | 3.066 (4) | 147 (3) |
N—H2N···O2vi | 0.92 (4) | 2.14 (4) | 2.816 (2) | 130 (3) |
N—H3N···O1Svii | 0.83 (3) | 2.07 (3) | 2.868 (2) | 160 (3) |
Symmetry codes: (ii) x, y+1, z; (vi) −x+1, −y+2, z−1/2; (vii) −x+1, −y+2, z+1/2. |
Selected bond lengths (Å) for (II) topNi—O2W | 2.0457 (14) | C2—H1C | 1.04 (4) |
Ni—O2 | 2.0658 (11) | C2—H2C | 0.86 (3) |
Ni—O1W | 2.0732 (12) | N—H1N | 0.86 (3) |
Ni—O1i | 2.0762 (11) | N—H2N | 0.96 (4) |
Ni—Cl2 | 2.3677 (6) | N—H3N | 0.91 (4) |
Ni—Cl1 | 2.4688 (6) | O1W—H1W1 | 0.85 (4) |
O1—C1 | 1.2582 (17) | O1W—H2W1 | 0.92 (3) |
O2—C1 | 1.2534 (18) | O2W—H1W2 | 0.89 (3) |
C1—C2 | 1.512 (2) | O2W—H2W2 | 0.75 (3) |
C2—N | 1.477 (2) | | |
Symmetry code: (i) −x+2, y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···Cl1ii | 0.86 (3) | 2.58 (3) | 3.4296 (17) | 167 (3) |
N—H2N···Cl1iii | 0.96 (4) | 2.37 (4) | 3.2372 (16) | 150 (4) |
N—H3N···Cl1iv | 0.91 (4) | 2.55 (4) | 3.4042 (17) | 156 (4) |
O1W—H1W1···Cl2v | 0.85 (4) | 2.49 (4) | 3.3304 (14) | 174 (3) |
O1W—H2W1···O1 | 0.92 (3) | 1.86 (3) | 2.7451 (17) | 161 (3) |
O2W—H1W2···Cl1iv | 0.89 (3) | 2.24 (3) | 3.1226 (16) | 172 (3) |
O2W—H2W2···Cl1vi | 0.75 (3) | 2.43 (3) | 3.1756 (15) | 176 (3) |
Symmetry codes: (ii) x, y, z+1; (iii) −x+1, y−1/2, −z+1; (iv) −x+1, y+1/2, −z+1; (v) x, y−1, z; (vi) x, y+1, z. |
Selected bond lengths (Å) for (III) topZn—O3S | 2.0507 (16) | C2—N | 1.467 (3) |
Zn—O1 | 2.0584 (13) | C2—H1C | 0.93 (4) |
Zn—O2i | 2.1229 (15) | C2—H2C | 1.03 (4) |
Zn—O1W | 2.1238 (16) | N—H1N | 0.95 (4) |
Zn—O3W | 2.1290 (16) | N—H2N | 0.88 (5) |
Zn—O2W | 2.1449 (18) | N—H3N | 0.75 (6) |
S—O1S | 1.4642 (18) | O1W—H1W1 | 0.71 (3) |
S—O2S | 1.4675 (16) | O1W—H2W1 | 0.72 (5) |
S—O3S | 1.4857 (17) | O2W—H1W2 | 0.79 (4) |
S—O4S | 1.4888 (16) | O2W—H2W2 | 0.85 (5) |
O1—C1 | 1.249 (2) | O3W—H1W3 | 0.89 (5) |
O2—C1 | 1.248 (2) | O3W—H2W3 | 0.80 (5) |
C1—C2 | 1.524 (3) | | |
Symmetry code: (i) x−1/2, −y, z. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O3Wii | 0.95 (4) | 2.00 (4) | 2.929 (3) | 164 (3) |
N—H2N···O4Siii | 0.88 (5) | 2.11 (5) | 2.967 (3) | 165 (4) |
N—H3N···O2Wiv | 0.75 (6) | 2.49 (6) | 3.151 (3) | 148 (5) |
O1W—H1W1···O4Sv | 0.71 (3) | 2.04 (4) | 2.744 (2) | 171 (4) |
O1W—H2W1···O4Svi | 0.72 (5) | 2.12 (5) | 2.815 (2) | 164 (5) |
O2W—H1W2···O2Svi | 0.79 (4) | 2.01 (4) | 2.802 (2) | 177 (4) |
O2W—H2W2···O2Svii | 0.85 (5) | 1.88 (5) | 2.714 (2) | 167 (5) |
O3W—H1W3···O1Sviii | 0.89 (5) | 1.93 (5) | 2.747 (2) | 152 (4) |
O3W—H2W3···O1i | 0.80 (5) | 1.97 (5) | 2.746 (2) | 164 (4) |
Symmetry codes: (i) x−1/2, −y, z; (ii) x+1, y, z; (iii) x+1/2, −y+1, z; (iv) −x+1/2, y, z+1/2; (v) −x, −y+1, z−1/2; (vi) −x+1/2, y, z−1/2; (vii) −x, −y, z−1/2; (viii) −x−1/2, y, z−1/2. |
In the course of our search for new non-centrosymmetric compounds, we have investigated compounds of glycine and inorganic materials. The Cambridge Structural Database (CSD; Allen, 2002) contains over 200 glycine compounds, nearly a third of which are non-centrosymmetric. However, in most of these substances, glyince is combined with other organic molecules. Only 20 compounds of glycine and inorganic materials were found. We focus here exclusively on such compounds, rather than structures containing other organic molecules. In contrast to the chiral amino acids, non-chiral glycine (as a structural unit) cannot enforce non-centrosymmetry of a crystal structure. However, many compounds of glycine are polar [e.g. glycine sodium nitrate, space group Cc (Krishnakumar et al., 2001), glycine calcium dichloride, space group Pb21a (Ravikumar et al., 1986), glycine calcium dibromide, space group Pbc21 (Mohana Rao & Natarajan, 1980) and glycine zinc chloride, space group Pbn21 (Hariharan et al., 1989)]. Even two of the three polymorphs of pure glycine are non-centrosymmetric, namely β-glycine (space group P21; Drebushchak et al., 2002) and γ-glycine (space group P32; Shimon et al., 1986). Since the glycine molecule as an amphoteric can assume cationic, anionic and zwitterionic forms, the molecule can combine with anionic, cationic and overall neutral chemical constituents, and thus a large number of possible glycine compounds exist. We have therefore started a study of such compounds of glycine and inorganic materials. We present here three new non-centrosymmetric structures of this type. All three represent new structure types, i.e. no isostructural compounds are known.
The structure of glycine lithium sulfate (Fig. 1) is composed of corrugated sheets of [LiO4] tetrahedra and [SO4] tetrahedra parallel to (001). These sheets consist of three crystallographically different tetrahedra (around Li1, Li2 and S) that are connected by common corners (represented by atoms O2S, O3S and O4S; Fig. 4). The tip of each tetrahedron (i.e. the corner not connected to other tetrahedra) faces away from the sheet. Since the O atoms forming the tips of the Li1- and Li2-tetrahedra belong to the carboxyl group of the glycine molecule, these neighboring tips are close to one another [O1—O2 = 2.238 (2) Å], twisting the polyhedra towards the glycine molecule and corrugating the sheets (Fig. 5). Consequently, the glycine molecules are located in the interstices between the sheets. The sheets are therefore connected only by weak hydrogen bonds. It is interesting to note that the carboxyl groups, which effect the corrugation of the sheet, are spread more than usual; the O1—C1—O2 angle is 126.4 (2) ° and the O1—O2 distance is 2.238 (2) Å. The average values of these parameters based on literature data are 125.2° and 2.214 Å, respectively. A test for possible higher symmetry, using the program PLATON (Spek, 2000), suggests the space group Pnma, with a probability of 92%. However, refinement in this space group shows that the position of the NH3 group does not suit this symmetry (imagine these alleged mirror planes horizontally in Fig. 5).
The crystal structure of glycine nickel dichloride dihydrate (Fig. 2) is altogether different. It is composed of distorted [NiO4Cl2] octhedra, with atoms Cl1 and Cl2 located at adjacent corners. The two opposite corners are occupied by O atoms from the carboxyl group of the glycine molecule (O1 and O2). The two remaining corners are occupied by O atoms of water molecules (O1W and O2W). Atoms O1 and O2 of one Ni coordination sphere belong to two different glycine molecules. Thus each molecule connects two Ni polyhedra, forming infinite chains along [010]. Each chain is actually a left-handed helix around a 21 screw axis (Fig. 6). These chains are connected to one another by hydrogen bonds. Similar chains are common in L-malates, e.g. copper dihydrogen dimalate (Fleck et al., 2004).
Glycine zinc sulfate trihydrate (Fig. 3) can also be described as having a chain structure. Slightly irregular [ZnO6] octahedra are connected to [SO4] tetrahedra by one common corner, namely atom O3S, thus forming [O3SOZnO5] clusters (Fig. 7). Three corners of the [ZnO6] octahedra are occupied by O atoms of water molecules. The remaining two corners are occupied by O atoms from the caboxyl group of the glycine molecules. Thus these [O3SOZnO5] zinc sulfate clusters are connected to one another by the glycine molecules, thus forming zigzag chains along [100]. The chain is not a spiral, as reported for the above nickel compound, but can be described by means of the a-glide plane in (010). More than 70 years ago, Dubský & Rabas (1931) described a pentahydrate, (C2H5NO2)ZnSO4·5H2O. However, in our experiments, we obtained only the trihydrate, which in turn was not reported by Dubský & Rabas (1931).
We have compared the geometry of the glycine molecules in the title compounds and in α-glycine (Legros & Kvick, 1980), β-glycine (Drebushchak et al., 2002), γ-glycine (Shimon et al., 1986), glycine nickel sulfate hydrate (Peterkova et al., 1991) and glycine zinc chloride (Hariharan et al., 1989). Obviously, the molecular conformation is the geometrical feature with the highest degree of freedom. Comparing the O—C1—C2—N torsion angles (assuming no chemical difference between the two O atoms of the carboxyl group) we found more or less antiperiplanar (i.e. trans) conformations. In some compounds, large deviations from the ideal trans conformation (i.e. a torsion angle of 180 °) were observed [e.g. −157.4 (2) ° in β-glycine and −163.4 (2) ° in glycine zinc chloride]. In the title compounds, the torsion angles are −170.98 (15) (glycine lithium sulfate), −178.78 (13) (glycine nickel dichloride dihydrate) and −176.85 (18) ° (glycine zinc sulfate trihydrate). The differences in the interatomic distances and angles are much smaller. None of the distances and angles deviate significantly from the average values calculated from the structural data of the above compounds [C1—O1 = 1.25 (2) Å, C1—O2 = 1.26 (2) Å, C1—C2 = 1.52 (2) Å, C2—N = 1.48 (1) Å and O1—C1—O2 = 125.7 (19) °; cf. Tables XXX). The only noteworthy deviation from these values occurs in glycine zinc chloride, where both carboxyl O atoms are virtually equidistant from the C atom. Obviously, the mesomeric effect is more pronounced in this salt than in the other compounds.