Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807060497/fj2074sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807060497/fj2074Isup2.hkl |
CCDC reference: 672765
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean (N-C) = 0.003 Å
- R factor = 0.020
- wR factor = 0.053
- Data-to-parameter ratio = 18.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro . ? PLAT163_ALERT_4_C Missing or Zero su (esd) on z-coordinate for ... ZN1 PLAT420_ALERT_2_C D-H Without Acceptor N5 - H2N5 ... ? PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 12
Alert level G ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.394 0.591 Tmin(prime) and Tmax expected: 0.604 0.613 RR(prime) = 0.676 Please check that your absorption correction is appropriate. REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.48 From the CIF: _reflns_number_total 3081 Count of symmetry unique reflns 1616 Completeness (_total/calc) 190.66% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1465 Fraction of Friedel pairs measured 0.907 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The preparation followed the procedure described by Venkataramanan, Dhanaraj, Wadhawan et al. (1995), i. e. according to the reaction scheme: ZnSO4·7H2O + 3 CS(NH2)2 → Zn[CS(NH2)2]3SO4
The used amounts were 40 g (0.139 M) of ZnSO4·7H2O, 31.67 g (0.416 M) of CS(NH2)2 and 440 g (24.42 M) of H2O. The mixture was stirred for ten minutes at 303 K. A clear solution was filtered yielding pH = 3.5. Then the mixture was left at 299–303 K for several days until crystals developed though the first crystals appeared at the surface after several hours.
The crystals were taken off, 20 g of them were dissolved at 323 K in 340 ml of distilled water. The solution was cooled down to room temperature and clear block-like crystals up to 5 mm as a maximal length developed in a course of several days.
All the H atoms were discernible in the difference Fourier map and even could be refined. Nevertheless, their coordinates were constrained in riding motion formalism: The pertinent distances equalled to 0.89 Å and Uiso(H) = 1.2Ueq(N).
The absolute configuration could be clearly determined. The Flack parameter included into the refinement equalled to -0.009 (7), however, in the submitted refinement the Flack parameter has not been used because of unambiguity of its value and the crystal was supposed to be in one domain state of the inversion twin only.
The calorimetric experiments were performed on PerkinElmer DSC 7 and Pyris Diamond differential scanning calorimeters using PYRIS Software (PerkinElmer, 2001), with m = 30 mg, a temperature interval of 93–533 K and scanning rate of 10 K/min. No reproducible DSC anomalies were detected until melting at 503 K. Before performing calorimetric measurement the sample was ground in an agate mortar and left in a desiccator for 5 days over P4O10.
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and HKL SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: JANA2000 (Petříček et al., 2000); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: JANA2000 (Petříček et al., 2000).
Fig. 1. View of the title molecule with anharmonic displacement parameters shown at the 50% probabality level. |
[Zn(SO4)(CH4N2S)3] | Dx = 1.910 Mg m−3 |
Mr = 389.8 | Melting point: 533 K |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 14983 reflections |
a = 11.1738 (2) Å | θ = 1–27.5° |
b = 7.8011 (1) Å | µ = 2.44 mm−1 |
c = 15.5424 (2) Å | T = 292 K |
V = 1354.80 (3) Å3 | Block, colourless |
Z = 4 | 0.2 × 0.2 × 0.2 mm |
F(000) = 792 |
Nonius KappaCCD diffractometer | 3081 independent reflections |
Radiation source: fine-focus sealed tube | 2961 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.035 |
ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: gaussian (Coppens & Hamilton, 1970) | h = −14→14 |
Tmin = 0.394, Tmax = 0.591 | k = −9→10 |
23153 measured reflections | l = −20→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.020 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 1.77 | Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0004I2] |
3081 reflections | (Δ/σ)max = 0.026 |
163 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
48 constraints | Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 1.25 (6) |
[Zn(SO4)(CH4N2S)3] | V = 1354.80 (3) Å3 |
Mr = 389.8 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 11.1738 (2) Å | µ = 2.44 mm−1 |
b = 7.8011 (1) Å | T = 292 K |
c = 15.5424 (2) Å | 0.2 × 0.2 × 0.2 mm |
Nonius KappaCCD diffractometer | 3081 independent reflections |
Absorption correction: gaussian (Coppens & Hamilton, 1970) | 2961 reflections with I > 3σ(I) |
Tmin = 0.394, Tmax = 0.591 | Rint = 0.035 |
23153 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 1.77 | Δρmax = 0.22 e Å−3 |
3081 reflections | Δρmin = −0.22 e Å−3 |
163 parameters |
Refinement. The Flack parameter converged to the value -0.009 (7), so it was excluded from the final refinement. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.563754 (19) | 0.65888 (3) | 0.58241 | 0.02306 (7) | |
S1 | 0.62660 (5) | 0.84508 (5) | 0.75220 (3) | 0.02168 (14) | |
O1 | 0.65466 (15) | 0.81436 (18) | 0.65829 (10) | 0.0325 (5) | |
O2 | 0.69547 (13) | 0.99703 (17) | 0.77799 (10) | 0.0299 (5) | |
O3 | 0.49795 (13) | 0.8767 (2) | 0.76043 (12) | 0.0337 (5) | |
O4 | 0.66348 (15) | 0.69514 (19) | 0.80145 (11) | 0.0353 (5) | |
S2 | 0.41946 (5) | 0.49762 (7) | 0.65242 (4) | 0.02863 (15) | |
C1 | 0.49270 (18) | 0.3368 (2) | 0.70768 (14) | 0.0271 (6) | |
N1 | 0.43115 (17) | 0.2539 (2) | 0.76720 (12) | 0.0359 (6) | |
H1N1 | 0.355183 | 0.281748 | 0.777261 | 0.0431* | |
H2N1 | 0.465667 | 0.170291 | 0.797218 | 0.0431* | |
N2 | 0.60402 (17) | 0.2915 (2) | 0.69193 (16) | 0.0436 (7) | |
H1N2 | 0.63528 | 0.200505 | 0.718132 | 0.0523* | |
H2N2 | 0.648045 | 0.351947 | 0.655082 | 0.0523* | |
S3 | 0.47868 (5) | 0.83168 (7) | 0.47628 (4) | 0.03033 (16) | |
C2 | 0.36195 (14) | 0.9411 (3) | 0.52285 (13) | 0.0294 (6) | |
N3 | 0.34955 (16) | 0.9625 (3) | 0.60612 (11) | 0.0423 (7) | |
N4 | 0.28047 (17) | 1.0067 (3) | 0.47049 (15) | 0.0475 (7) | |
S4 | 0.70388 (4) | 0.49833 (7) | 0.50572 (4) | 0.02851 (15) | |
C3 | 0.61496 (17) | 0.3997 (2) | 0.42887 (12) | 0.0281 (6) | |
N5 | 0.6647 (2) | 0.3571 (3) | 0.35501 (13) | 0.0485 (8) | |
H1N5 | 0.621843 | 0.303184 | 0.315059 | 0.0582* | |
H2N5 | 0.741154 | 0.382314 | 0.345092 | 0.0582* | |
N6 | 0.50170 (18) | 0.3643 (3) | 0.44185 (15) | 0.0465 (7) | |
H1N6 | 0.464178 | 0.406556 | 0.487697 | 0.0558* | |
H2N6 | 0.462341 | 0.298047 | 0.404815 | 0.0558* | |
H1N3 | 0.406905 | 0.927697 | 0.641814 | 0.0508* | |
H2N3 | 0.283796 | 1.011784 | 0.626906 | 0.0508* | |
H1N4 | 0.284995 | 0.98732 | 0.414156 | 0.057* | |
H2N4 | 0.221175 | 1.070178 | 0.491633 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02518 (13) | 0.02338 (12) | 0.02062 (13) | −0.00010 (8) | 0.00152 (9) | −0.00070 (9) |
S1 | 0.0236 (2) | 0.0245 (2) | 0.0169 (2) | 0.00020 (16) | 0.00171 (17) | 0.00148 (16) |
O1 | 0.0370 (9) | 0.0403 (8) | 0.0203 (8) | −0.0149 (7) | 0.0062 (6) | −0.0067 (6) |
O2 | 0.0364 (8) | 0.0289 (7) | 0.0245 (8) | −0.0035 (6) | −0.0026 (6) | −0.0036 (5) |
O3 | 0.0224 (8) | 0.0409 (8) | 0.0377 (9) | 0.0022 (7) | 0.0050 (6) | 0.0041 (7) |
O4 | 0.0373 (9) | 0.0328 (7) | 0.0359 (9) | 0.0047 (7) | 0.0032 (7) | 0.0130 (6) |
S2 | 0.0227 (2) | 0.0332 (3) | 0.0299 (3) | −0.00017 (19) | 0.00000 (19) | 0.0101 (2) |
C1 | 0.0269 (11) | 0.0266 (10) | 0.0279 (11) | −0.0041 (7) | −0.0056 (9) | 0.0024 (7) |
N1 | 0.0383 (11) | 0.0362 (11) | 0.0333 (10) | −0.0010 (8) | −0.0006 (8) | 0.0109 (9) |
N2 | 0.0334 (10) | 0.0385 (11) | 0.0589 (14) | 0.0058 (9) | 0.0048 (10) | 0.0201 (10) |
S3 | 0.0316 (3) | 0.0385 (3) | 0.0209 (3) | 0.0111 (2) | 0.0057 (2) | 0.00429 (19) |
C2 | 0.0305 (10) | 0.0316 (10) | 0.0260 (11) | 0.0045 (8) | 0.0018 (9) | 0.0029 (8) |
N3 | 0.0422 (11) | 0.0580 (12) | 0.0269 (11) | 0.0238 (10) | 0.0024 (8) | −0.0043 (8) |
N4 | 0.0446 (12) | 0.0665 (14) | 0.0313 (11) | 0.0299 (10) | −0.0023 (10) | 0.0023 (9) |
S4 | 0.0208 (2) | 0.0392 (3) | 0.0255 (3) | 0.00156 (19) | −0.00193 (19) | −0.01058 (18) |
C3 | 0.0304 (10) | 0.0297 (10) | 0.0243 (10) | 0.0040 (9) | −0.0034 (8) | −0.0049 (8) |
N5 | 0.0403 (12) | 0.0759 (16) | 0.0291 (11) | −0.0023 (11) | 0.0010 (9) | −0.0243 (10) |
N6 | 0.0329 (11) | 0.0620 (14) | 0.0446 (14) | −0.0099 (10) | −0.0018 (10) | −0.0263 (10) |
Zn1—O1 | 1.9732 (15) | N2—H1N2 | 0.89 |
Zn1—S2 | 2.3165 (6) | N2—H2N2 | 0.89 |
Zn1—S3 | 2.3326 (6) | C2—N3 | 1.312 (3) |
Zn1—S4 | 2.3326 (6) | C2—N4 | 1.324 (3) |
S1—O1 | 1.5120 (17) | N3—H1N3 | 0.89 |
S1—O2 | 1.4691 (14) | N3—H2N3 | 0.89 |
S1—O3 | 1.4641 (16) | N4—H1N4 | 0.89 |
S1—O4 | 1.4573 (16) | N4—H2N4 | 0.89 |
S2—C1 | 1.7266 (19) | C3—N5 | 1.318 (3) |
S3—C2 | 1.7188 (18) | C3—N6 | 1.311 (3) |
S4—C3 | 1.7336 (19) | N5—H1N5 | 0.89 |
C1—N1 | 1.322 (3) | N5—H2N5 | 0.89 |
C1—N2 | 1.316 (3) | N6—H1N6 | 0.89 |
N1—H1N1 | 0.89 | N6—H2N6 | 0.89 |
N1—H2N1 | 0.89 | ||
O1—Zn1—S2 | 114.29 (5) | H1N1—N1—H2N1 | 120.0 |
O1—Zn1—S3 | 106.09 (5) | C1—N2—H1N2 | 120.0 |
O1—Zn1—S4 | 106.85 (5) | C1—N2—H2N2 | 120.0 |
S2—Zn1—S3 | 111.24 (2) | H1N2—N2—H2N2 | 120.0 |
S2—Zn1—S4 | 114.56 (2) | N3—C2—N4 | 118.98 (18) |
S3—Zn1—S4 | 102.86 (2) | C2—N3—H1N3 | 120.0 |
O1—S1—O2 | 106.41 (9) | C2—N3—H2N3 | 120.0 |
O1—S1—O3 | 108.34 (10) | H1N3—N3—H2N3 | 120.0 |
O1—S1—O4 | 108.74 (9) | C2—N4—H1N4 | 120.0 |
O2—S1—O3 | 110.76 (9) | C2—N4—H2N4 | 120.0 |
O2—S1—O4 | 110.87 (9) | H1N4—N4—H2N4 | 120.0 |
O3—S1—O4 | 111.53 (10) | N5—C3—N6 | 119.2 (2) |
Zn1—S2—C1 | 107.35 (7) | C3—N5—H1N5 | 120.0 |
Zn1—S3—C2 | 107.37 (7) | C3—N5—H2N5 | 120.0 |
Zn1—S4—C3 | 101.86 (7) | H1N5—N5—H2N5 | 120.0 |
N1—C1—N2 | 119.39 (18) | C3—N6—H1N6 | 120.0 |
C1—N1—H1N1 | 120.0 | C3—N6—H2N6 | 120.0 |
C1—N1—H2N1 | 120.0 | H1N6—N6—H2N6 | 120.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O4i | 0.89 | 2.18 | 3.064 (3) | 171 |
N1—H2N1···O3ii | 0.89 | 2.39 | 3.038 (2) | 130 |
N1—H2N1···S3iii | 0.89 | 2.85 | 3.467 (2) | 128 |
N2—H1N2···O2ii | 0.89 | 1.96 | 2.848 (2) | 177 |
N2—H2N2···S4 | 0.89 | 2.66 | 3.496 (2) | 157 |
N3—H1N3···O3 | 0.89 | 2.14 | 2.992 (2) | 159 |
N3—H2N3···O1iv | 0.89 | 2.04 | 2.903 (3) | 163 |
N3—H2N3···O2iv | 0.89 | 2.55 | 3.194 (2) | 130 |
N4—H1N4···O2v | 0.89 | 2.13 | 3.004 (3) | 167 |
N4—H2N4···S3iv | 0.89 | 2.83 | 3.601 (2) | 146 |
N5—H1N5···O3vi | 0.89 | 2.12 | 2.965 (3) | 159 |
N6—H1N6···S2 | 0.89 | 2.70 | 3.555 (2) | 160 |
N6—H2N6···O4vi | 0.89 | 2.14 | 2.895 (3) | 143 |
Symmetry codes: (i) x−1/2, −y+1, z; (ii) x, y−1, z; (iii) −x+1, −y+1, z+1/2; (iv) x−1/2, −y+2, z; (v) −x+1, −y+2, z−1/2; (vi) −x+1, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(SO4)(CH4N2S)3] |
Mr | 389.8 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 292 |
a, b, c (Å) | 11.1738 (2), 7.8011 (1), 15.5424 (2) |
V (Å3) | 1354.80 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.44 |
Crystal size (mm) | 0.2 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Gaussian (Coppens & Hamilton, 1970) |
Tmin, Tmax | 0.394, 0.591 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 23153, 3081, 2961 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.053, 1.77 |
No. of reflections | 3081 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.22 |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and HKL SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), JANA2000 (Petříček et al., 2000), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O4i | 0.89 | 2.18 | 3.064 (3) | 171 |
N1—H2N1···O3ii | 0.89 | 2.39 | 3.038 (2) | 130 |
N1—H2N1···S3iii | 0.89 | 2.85 | 3.467 (2) | 128 |
N2—H1N2···O2ii | 0.89 | 1.96 | 2.848 (2) | 177 |
N2—H2N2···S4 | 0.89 | 2.66 | 3.496 (2) | 157 |
N3—H1N3···O3 | 0.89 | 2.14 | 2.992 (2) | 159 |
N3—H2N3···O1iv | 0.89 | 2.04 | 2.903 (3) | 163 |
N3—H2N3···O2iv | 0.89 | 2.55 | 3.194 (2) | 130 |
N4—H1N4···O2v | 0.89 | 2.13 | 3.004 (3) | 167 |
N4—H2N4···S3iv | 0.89 | 2.83 | 3.601 (2) | 146 |
N5—H1N5···O3vi | 0.89 | 2.12 | 2.965 (3) | 159 |
N6—H1N6···S2 | 0.89 | 2.70 | 3.555 (2) | 160 |
N6—H2N6···O4vi | 0.89 | 2.14 | 2.895 (3) | 143 |
Symmetry codes: (i) x−1/2, −y+1, z; (ii) x, y−1, z; (iii) −x+1, −y+1, z+1/2; (iv) x−1/2, −y+2, z; (v) −x+1, −y+2, z−1/2; (vi) −x+1, −y+1, z−1/2. |
The title structure is a perspective semiorganic non-linear optical material (Ushasree et al., 1998, 2000). It can substitute potassium dihydrogenphosphate in technical applications (Ramabadran et al., 1992; Alex & Philip, 2001). It has an exceptionally wide acceptance angle for second harmonic generation (Ramabadran et al., 1992). Its resistence against laser induced damage is good (Venkataramanan, Subramanian & Bhat, 1995). However, the published structure determination (Andreetti et al., 1968) does not meet today's demands: The intensities in the cited work were provided via film technique; the H atoms have not been observed directly and the R-factors are higher than 0.09.
The second structure determination (Ushasree et al., 1998) has not provided the coordinates or the R-factors; the authors have only published the unit-cell parameters that corresponded to the those from the former structure determination though the the structure analysis has been performed.
Our structure determinations (this work and the low temperature study at 110 K (Krupková et al., 2007) have confirmed the previous structural studies.
Ouassaid et al. (1998) have reported two phase transitions at 60±2 and 122±2 K. These phase transitions have been measured by polarized Raman scattering. Thermal gravimetric analysis (TGA) peformed by Ushasree et al. (1998) revealed that the compound starts to decompose at 473 K. However, our experiments by differential scanning calorimetry revealed no phase transitions in the temperature interval 93–533 K. The comparison of the oresent structure determination with that at 110 K confirmed the same space group, however, some of the atoms were quite displaced with regard to the average value of the pertinent standard uncertainties (the largest displacement refers to the y-coordinate of N6 (Δ = 0.00721 in fractional coordinates). The lattice parameters at 110 K are: a = 11.0661 (2), b = 7.7339 (3), c = 15.5524 (3) Å. The indicators of the refinement are: Robs = 0.0180, wRobs = 0.0517, Rall = 0.0188, wRall 0.0519, Sall = 1.57, Sobs = 1.59, ρmax = 0.17, ρmin = -0.24. The unconstrained refinement of the H atoms found in the difference Fourier map for the structure determination at 110 K yielded the positions of the H atoms that were displaced in the interval 0.71–0.98 Å from the carrier nitrogen.
The elastic properties were determined by Alex & Philip (2001).
Since our colleagues have been interested in the dielectric properties, we have grown the crystals that were also suitable for the structure determination. Here we report the redetermination of the structure at room temperature. A tendency to twinning should be stressed that is probably due to the ratio of the lattice parameters b and c.