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In the title compound, [Zn(SO4)(CH4N2S)3], the Zn2+ cation is coordinated in a tetra­hedral geometry by one O atom from a sulfate anion and the S atoms from three thio­urea ligands. There are weak N—H...O and N—H...S hydrogen bonds in the structure, some of which are bifurcated. The same crystal has also been investigated at 110 K, below a reported phase transition at 120 K. No change in the space group below 120 K was observed. On the other hand, the differences between the fractional coordinates of the corresponding atoms in the determinations at 292 and 110 K are as large as about 0.007 for the non-H atoms. Differential scanning calorimetry did not detect reproducible anomalies in the inter­val 93–503 K up to the melting point.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807060497/fj2074sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807060497/fj2074Isup2.hkl
Contains datablock I

CCDC reference: 672765

Key indicators

  • Single-crystal X-ray study
  • T = 292 K
  • Mean [sigma](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

Comment top

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.

Related literature top

For previous structure determinations, see: Krupková et al. (2007); Andreetti et al. (1968). Ramabadran et al. (1992). For related literature, see: Alex & Philip (2001); Becker & Coppens (1974); Ouassaid et al. (1998); PerkinElmer (2001); Ushasree et al. (1998, 2000); Venkataramanan, Dhanaraj, Wadhawan et al. (1995); Venkataramanan, Subramanian & Bhat (1995).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of the title molecule with anharmonic displacement parameters shown at the 50% probabality level.
sulfatotris(thiourea)zinc(II) top
Crystal data top
[Zn(SO4)(CH4N2S)3]Dx = 1.910 Mg m3
Mr = 389.8Melting point: 533 K
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 14983 reflections
a = 11.1738 (2) Åθ = 1–27.5°
b = 7.8011 (1) ŵ = 2.44 mm1
c = 15.5424 (2) ÅT = 292 K
V = 1354.80 (3) Å3Block, colourless
Z = 40.2 × 0.2 × 0.2 mm
F(000) = 792
Data collection top
Nonius KappaCCD
diffractometer
3081 independent reflections
Radiation source: fine-focus sealed tube2961 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.035
ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: gaussian
(Coppens & Hamilton, 1970)
h = 1414
Tmin = 0.394, Tmax = 0.591k = 910
23153 measured reflectionsl = 2018
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: difference Fourier map
wR(F2) = 0.053H-atom parameters constrained
S = 1.77Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0004I2]
3081 reflections(Δ/σ)max = 0.026
163 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.22 e Å3
48 constraintsExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 1.25 (6)
Crystal data top
[Zn(SO4)(CH4N2S)3]V = 1354.80 (3) Å3
Mr = 389.8Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 11.1738 (2) ŵ = 2.44 mm1
b = 7.8011 (1) ÅT = 292 K
c = 15.5424 (2) Å0.2 × 0.2 × 0.2 mm
Data collection top
Nonius KappaCCD
diffractometer
3081 independent reflections
Absorption correction: gaussian
(Coppens & Hamilton, 1970)
2961 reflections with I > 3σ(I)
Tmin = 0.394, Tmax = 0.591Rint = 0.035
23153 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0200 restraints
wR(F2) = 0.053H-atom parameters constrained
S = 1.77Δρmax = 0.22 e Å3
3081 reflectionsΔρmin = 0.22 e Å3
163 parameters
Special details top

Refinement. The Flack parameter converged to the value -0.009 (7), so it was excluded from the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.563754 (19)0.65888 (3)0.582410.02306 (7)
S10.62660 (5)0.84508 (5)0.75220 (3)0.02168 (14)
O10.65466 (15)0.81436 (18)0.65829 (10)0.0325 (5)
O20.69547 (13)0.99703 (17)0.77799 (10)0.0299 (5)
O30.49795 (13)0.8767 (2)0.76043 (12)0.0337 (5)
O40.66348 (15)0.69514 (19)0.80145 (11)0.0353 (5)
S20.41946 (5)0.49762 (7)0.65242 (4)0.02863 (15)
C10.49270 (18)0.3368 (2)0.70768 (14)0.0271 (6)
N10.43115 (17)0.2539 (2)0.76720 (12)0.0359 (6)
H1N10.3551830.2817480.7772610.0431*
H2N10.4656670.1702910.7972180.0431*
N20.60402 (17)0.2915 (2)0.69193 (16)0.0436 (7)
H1N20.635280.2005050.7181320.0523*
H2N20.6480450.3519470.6550820.0523*
S30.47868 (5)0.83168 (7)0.47628 (4)0.03033 (16)
C20.36195 (14)0.9411 (3)0.52285 (13)0.0294 (6)
N30.34955 (16)0.9625 (3)0.60612 (11)0.0423 (7)
N40.28047 (17)1.0067 (3)0.47049 (15)0.0475 (7)
S40.70388 (4)0.49833 (7)0.50572 (4)0.02851 (15)
C30.61496 (17)0.3997 (2)0.42887 (12)0.0281 (6)
N50.6647 (2)0.3571 (3)0.35501 (13)0.0485 (8)
H1N50.6218430.3031840.3150590.0582*
H2N50.7411540.3823140.3450920.0582*
N60.50170 (18)0.3643 (3)0.44185 (15)0.0465 (7)
H1N60.4641780.4065560.4876970.0558*
H2N60.4623410.2980470.4048150.0558*
H1N30.4069050.9276970.6418140.0508*
H2N30.2837961.0117840.6269060.0508*
H1N40.2849950.987320.4141560.057*
H2N40.2211751.0701780.4916330.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02518 (13)0.02338 (12)0.02062 (13)0.00010 (8)0.00152 (9)0.00070 (9)
S10.0236 (2)0.0245 (2)0.0169 (2)0.00020 (16)0.00171 (17)0.00148 (16)
O10.0370 (9)0.0403 (8)0.0203 (8)0.0149 (7)0.0062 (6)0.0067 (6)
O20.0364 (8)0.0289 (7)0.0245 (8)0.0035 (6)0.0026 (6)0.0036 (5)
O30.0224 (8)0.0409 (8)0.0377 (9)0.0022 (7)0.0050 (6)0.0041 (7)
O40.0373 (9)0.0328 (7)0.0359 (9)0.0047 (7)0.0032 (7)0.0130 (6)
S20.0227 (2)0.0332 (3)0.0299 (3)0.00017 (19)0.00000 (19)0.0101 (2)
C10.0269 (11)0.0266 (10)0.0279 (11)0.0041 (7)0.0056 (9)0.0024 (7)
N10.0383 (11)0.0362 (11)0.0333 (10)0.0010 (8)0.0006 (8)0.0109 (9)
N20.0334 (10)0.0385 (11)0.0589 (14)0.0058 (9)0.0048 (10)0.0201 (10)
S30.0316 (3)0.0385 (3)0.0209 (3)0.0111 (2)0.0057 (2)0.00429 (19)
C20.0305 (10)0.0316 (10)0.0260 (11)0.0045 (8)0.0018 (9)0.0029 (8)
N30.0422 (11)0.0580 (12)0.0269 (11)0.0238 (10)0.0024 (8)0.0043 (8)
N40.0446 (12)0.0665 (14)0.0313 (11)0.0299 (10)0.0023 (10)0.0023 (9)
S40.0208 (2)0.0392 (3)0.0255 (3)0.00156 (19)0.00193 (19)0.01058 (18)
C30.0304 (10)0.0297 (10)0.0243 (10)0.0040 (9)0.0034 (8)0.0049 (8)
N50.0403 (12)0.0759 (16)0.0291 (11)0.0023 (11)0.0010 (9)0.0243 (10)
N60.0329 (11)0.0620 (14)0.0446 (14)0.0099 (10)0.0018 (10)0.0263 (10)
Geometric parameters (Å, º) top
Zn1—O11.9732 (15)N2—H1N20.89
Zn1—S22.3165 (6)N2—H2N20.89
Zn1—S32.3326 (6)C2—N31.312 (3)
Zn1—S42.3326 (6)C2—N41.324 (3)
S1—O11.5120 (17)N3—H1N30.89
S1—O21.4691 (14)N3—H2N30.89
S1—O31.4641 (16)N4—H1N40.89
S1—O41.4573 (16)N4—H2N40.89
S2—C11.7266 (19)C3—N51.318 (3)
S3—C21.7188 (18)C3—N61.311 (3)
S4—C31.7336 (19)N5—H1N50.89
C1—N11.322 (3)N5—H2N50.89
C1—N21.316 (3)N6—H1N60.89
N1—H1N10.89N6—H2N60.89
N1—H2N10.89
O1—Zn1—S2114.29 (5)H1N1—N1—H2N1120.0
O1—Zn1—S3106.09 (5)C1—N2—H1N2120.0
O1—Zn1—S4106.85 (5)C1—N2—H2N2120.0
S2—Zn1—S3111.24 (2)H1N2—N2—H2N2120.0
S2—Zn1—S4114.56 (2)N3—C2—N4118.98 (18)
S3—Zn1—S4102.86 (2)C2—N3—H1N3120.0
O1—S1—O2106.41 (9)C2—N3—H2N3120.0
O1—S1—O3108.34 (10)H1N3—N3—H2N3120.0
O1—S1—O4108.74 (9)C2—N4—H1N4120.0
O2—S1—O3110.76 (9)C2—N4—H2N4120.0
O2—S1—O4110.87 (9)H1N4—N4—H2N4120.0
O3—S1—O4111.53 (10)N5—C3—N6119.2 (2)
Zn1—S2—C1107.35 (7)C3—N5—H1N5120.0
Zn1—S3—C2107.37 (7)C3—N5—H2N5120.0
Zn1—S4—C3101.86 (7)H1N5—N5—H2N5120.0
N1—C1—N2119.39 (18)C3—N6—H1N6120.0
C1—N1—H1N1120.0C3—N6—H2N6120.0
C1—N1—H2N1120.0H1N6—N6—H2N6120.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O4i0.892.183.064 (3)171
N1—H2N1···O3ii0.892.393.038 (2)130
N1—H2N1···S3iii0.892.853.467 (2)128
N2—H1N2···O2ii0.891.962.848 (2)177
N2—H2N2···S40.892.663.496 (2)157
N3—H1N3···O30.892.142.992 (2)159
N3—H2N3···O1iv0.892.042.903 (3)163
N3—H2N3···O2iv0.892.553.194 (2)130
N4—H1N4···O2v0.892.133.004 (3)167
N4—H2N4···S3iv0.892.833.601 (2)146
N5—H1N5···O3vi0.892.122.965 (3)159
N6—H1N6···S20.892.703.555 (2)160
N6—H2N6···O4vi0.892.142.895 (3)143
Symmetry codes: (i) x1/2, y+1, z; (ii) x, y1, z; (iii) x+1, y+1, z+1/2; (iv) x1/2, y+2, z; (v) x+1, y+2, z1/2; (vi) x+1, y+1, z1/2.

Experimental details

Crystal data
Chemical formula[Zn(SO4)(CH4N2S)3]
Mr389.8
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)292
a, b, c (Å)11.1738 (2), 7.8011 (1), 15.5424 (2)
V3)1354.80 (3)
Z4
Radiation typeMo Kα
µ (mm1)2.44
Crystal size (mm)0.2 × 0.2 × 0.2
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionGaussian
(Coppens & Hamilton, 1970)
Tmin, Tmax0.394, 0.591
No. of measured, independent and
observed [I > 3σ(I)] reflections
23153, 3081, 2961
Rint0.035
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.053, 1.77
No. of reflections3081
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O4i0.892.183.064 (3)171
N1—H2N1···O3ii0.892.393.038 (2)130
N1—H2N1···S3iii0.892.853.467 (2)128
N2—H1N2···O2ii0.891.962.848 (2)177
N2—H2N2···S40.892.663.496 (2)157
N3—H1N3···O30.892.142.992 (2)159
N3—H2N3···O1iv0.892.042.903 (3)163
N3—H2N3···O2iv0.892.553.194 (2)130
N4—H1N4···O2v0.892.133.004 (3)167
N4—H2N4···S3iv0.892.833.601 (2)146
N5—H1N5···O3vi0.892.122.965 (3)159
N6—H1N6···S20.892.703.555 (2)160
N6—H2N6···O4vi0.892.142.895 (3)143
Symmetry codes: (i) x1/2, y+1, z; (ii) x, y1, z; (iii) x+1, y+1, z+1/2; (iv) x1/2, y+2, z; (v) x+1, y+2, z1/2; (vi) x+1, y+1, z1/2.
 

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