(Tetra­oxidoselenato-κO)tris­(thio­urea-κS)zinc(II)

Krupková, R.; Fábry, J.; Císařová, I.; Vaněk, P.

doi:10.1107/S1600536808000743

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m342-m343

doi:10.1107/S1600536808000743

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(Tetraoxidoselenato-κO)tris(thiourea-κS)zinc(II)

Radmila Krupková,^a Jan Fábry,^a ^* Ivana Císařová ^b and Přemysl Vaněk ^a

^aInstitute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Praha 8, Czech Republic, and ^bDepartment of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 8, 128 43 Praha 2, Czech Republic
^*Correspondence e-mail: fabry@fzu.cz

(Received 7 January 2008; accepted 9 January 2008; online 11 January 2008)

The title structure, [Zn(SeO₄)(CH₄N₂S)₃], is isomorphous with sulfatotris(thiourea)zinc(II). In both structures, the Zn²⁺ cation is coordinated in a tetrahedral geometry. The corresponding intramolecular distances are quite similar except for the Se—O and S—O distances. Although the hydrogen-bonding patterns are similar, there are some differences; in the title structure all the H atoms are involved in the hydrogen-bond pattern, in contrast to the situation in sulfatotris(thiourea)zinc(II). No reproducible anomalies were detected by differential scanning calorimetry in the range 93–463 K until decomposition started at the higher temperature.

Related literature

For related literature, see: Krupková et al. (2007 ); Alex & Phillip (2001 ); Becker & Coppens (1974 ); PerkinElmer (2001 ); Ramabadran et al. (1992 ); Ushasree et al. (1998 , 2000 ); Venkataramanan et al. (1995 ).

Experimental

Crystal data

[Zn(SeO₄)(CH₄N₂S)₃]
M_r = 436.7
Orthorhombic, P c a 2₁
a = 11.2045 (2) Å
b = 7.8824 (1) Å
c = 15.7960 (2) Å
V = 1395.08 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.83 mm⁻¹
T = 292 K
0.35 × 0.25 × 0.1 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: Gaussian (Coppens & Hamilton, 1970 ) T_min = 0.223, T_max = 0.602
23449 measured reflections
3150 independent reflections
3004 reflections with I > 3σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.050
S = 1.52
3150 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 1492 Friedel pairs
Flack parameter: −0.020 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O4ⁱ*	0.89	2.20	3.066 (3)	164
N1—H2N1⋯O3ⁱⁱ*	0.89	2.38	3.072 (3)	135
N2—H1N2⋯O2ⁱⁱ*	0.89	1.98	2.852 (3)	167
N2—H2N2⋯S3	0.89	2.63	3.497 (3)	166
N3—H1N3⋯O3*	0.89	2.17	2.988 (3)	152
N3—H2N3⋯O1ⁱⁱⁱ*	0.89	2.04	2.895 (3)	160
N4—H1N4⋯O2^iv*	0.89	2.12	2.999 (3)	168
N4—H2N4⋯S2ⁱⁱⁱ	0.89	2.86	3.643 (2)	148
N5—H1N5⋯O3^v*	0.89	2.06	2.938 (3)	170
N5—H2N5⋯O4^vi	0.89	2.57	3.297 (3)	139
N6—H1N6⋯S1	0.89	2.73	3.577 (3)	159
N6—H2N6⋯O4^v*	0.89	2.19	2.905 (3)	137
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+1, z]$ ; (ii) x, y+1, z; (iii) $[x+{\script{1\over 2}}, -y, z]$ ; (iv) $[-x+1, -y, z+{\script{1\over 2}}]$ ; (v) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ . * indicates that the pertinent hydrogen bond is also present in Zn[(SC(NH₂)₂]₃(SO₄) (Krupková et al., 2007).

Data collection: COLLECT (Hooft, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1997 ); program(s) used to refine structure: (JANA2000; Petříček et al., 2000 ); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: JANA2000.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000743/bq2062sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000743/bq2062Isup2.hkl

checkCIF report

Comment top

Zinc [tris(thiourea)]sulfate, isomorphous to the title structure, is reported to be 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 & Phillip, 2001). It has also an exceptionally wide acceptance angle for second harmonic generation (Ramabadran et al., 1992). Its resistance against laser induced damage is good (Venkataramanan et al., 1995).

We have synthesized the title compound since it is expected that it might show similar interesting properties as its known isostructural counterpart (Krupková et al., 2007). As a part of our on-going study of the title compound we report here its structure determination. The investigation od dielectric and optical properties is in progress.

The common features and differences between the hydrogen-bond patterns in both isostructural compounds are shown in Tab. 1. This table shows that the stronger hydrogen bonds are common for both isostructural compounds.

Related literature top

For related literature, see: Krupková et al. (2007); Alex & Phillip (2001); Becker & Coppens (1974); PerkinElmer (2001); Ramabadran et al. (1992); Ushasree et al. (1998, 2000); Venkataramanan et al. (1995).

Experimental top

The title compound has been prepared in a similar way as zinc[tris(thiourea)] sulfate. The preparation was carried out in two steps according to following equations:

(1) [ZnCO₃][Zn(OH)₂] + 2H₂SeO₄ + 3H₂O → 2ZnSeO₄.6H₂O + CO₂

(2) 4ZnSeO₄.6H₂O + 3 CS(NH₂)₂ → Zn[CS(NH₂)₂]₃}[SeO₄]

5.0 g (0.222 M) of ZnCO₃[Zn(OH)₂] dissolved in 3.6 g (0.2 M) of distilled H₂O reacted with 6.45 g (96%) H₂SeO₄ (0.0427 M) at room temperature. After the neutralization white suspension was obtained. The suspension into which had been poured 50 ml of distilled H₂O was heated at 60°C for 30 minutes. The solution became clearer and its pH=4.

Then, at 50°C was added 10.14 g (0.1332 M) of thiourea. The solution became orange-coloured and under stirring it was kept at 50°C for another 10 minutes. An orange precipitate has developed to which another 100 ml of distilled water was added. The mixture was stirred for another 20 minutes and then cooled down to room temperature. After two days, transparent crystals of length of 0.5 mm appeared at the walls of the beaker while an orange precipitate covered its bottom. Next day the precipitate was filtered off, some orange-tinged crystals have been isolated as seeds that were introduced into the filtrate. After a week clear transparent crystals appeared of the size of 1 cm, of the similar HABITUS as zinc[tris(thiourea)] sulfate (Alex & Phillip, 2001).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1997); 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

Fig. 1. View of the title molecule with anisotropic displacement parameters shown at the 30% probability level.

(Tetraoxidoselenato-κO)tris(thiourea-κS)zinc(II) top

Crystal data top

[Zn(SeO₄)(CH₄N₂S)₃]	F(000) = 864
M_r = 436.7	D_x = 2.079 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2c -2ac	Cell parameters from 14388 reflections
a = 11.2045 (2) Å	θ = 1.0–27.5°
b = 7.8824 (1) Å	µ = 4.83 mm⁻¹
c = 15.7960 (2) Å	T = 292 K
V = 1395.08 (4) Å³	Prism, colourless
Z = 4	0.35 × 0.25 × 0.1 mm

Data collection top

Nonius KappaCCD diffractometer	3150 independent reflections
Radiation source: fine-focus sealed tube	3004 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: gaussian (Coppens & Hamilton, 1970)	h = −14→14
T_min = 0.223, T_max = 0.602	k = −10→10
23449 measured reflections	l = −19→20

Refinement top

Refinement on F²	Weighting scheme based on measured s.u.'s w = 1/[σ²(I) + 0.0004I²]
R[F² > 2σ(F²)] = 0.022	(Δ/σ)_max = 0.005
wR(F²) = 0.050	Δρ_max = 0.36 e Å⁻³
S = 1.52	Δρ_min = −0.25 e Å⁻³
3150 reflections	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
163 parameters	Extinction coefficient: 1.65 (5)
0 restraints	Absolute structure: Flack (1983), 1492 Friedel pairs
48 constraints	Absolute structure parameter: −0.020 (6)
H-atom parameters constrained

Crystal data top

[Zn(SeO₄)(CH₄N₂S)₃]	V = 1395.08 (4) Å³
M_r = 436.7	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 11.2045 (2) Å	µ = 4.83 mm⁻¹
b = 7.8824 (1) Å	T = 292 K
c = 15.7960 (2) Å	0.35 × 0.25 × 0.1 mm

Data collection top

Nonius KappaCCD diffractometer	3150 independent reflections
Absorption correction: gaussian (Coppens & Hamilton, 1970)	3004 reflections with I > 3σ(I)
T_min = 0.223, T_max = 0.602	R_int = 0.039
23449 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.050	Δρ_max = 0.36 e Å⁻³
S = 1.52	Δρ_min = −0.25 e Å⁻³
3150 reflections	Absolute structure: Flack (1983), 1492 Friedel pairs
163 parameters	Absolute structure parameter: −0.020 (6)
0 restraints

Special details top

Refinement. The Flack parameter converged to the value -0.020 (6), so it was excluded from the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.43588 (3)	0.34032 (3)	0.42203 (2)	0.02479 (9)
Se1	0.37373 (2)	0.15124 (3)	0.247798	0.02293 (7)
O1	0.34191 (19)	0.1846 (2)	0.34926 (13)	0.0363 (6)
O2	0.29853 (18)	−0.0173 (2)	0.22066 (12)	0.0317 (6)
O3	0.51627 (17)	0.1169 (2)	0.23987 (16)	0.0372 (6)
O4	0.33169 (19)	0.3147 (2)	0.19315 (15)	0.0392 (6)
S1	0.57849 (6)	0.49589 (8)	0.34906 (5)	0.03060 (19)
C1	0.5054 (2)	0.6544 (2)	0.29483 (16)	0.0290 (8)
N1	0.5667 (2)	0.7339 (3)	0.23498 (16)	0.0401 (8)
N2	0.3957 (2)	0.7021 (3)	0.31154 (18)	0.0447 (9)
S2	0.52313 (7)	0.17226 (9)	0.52667 (5)	0.0327 (2)
C2	0.64030 (18)	0.0636 (3)	0.48127 (17)	0.0314 (8)
N3	0.6501 (2)	0.0405 (4)	0.39895 (16)	0.0468 (9)
N4	0.7222 (2)	0.0025 (3)	0.53155 (17)	0.0460 (9)
S3	0.29592 (6)	0.50137 (8)	0.49583 (5)	0.03039 (18)
C3	0.3845 (2)	0.5992 (3)	0.57094 (15)	0.0295 (7)
N5	0.3360 (3)	0.6436 (3)	0.64329 (16)	0.0453 (9)
N6	0.4979 (2)	0.6351 (3)	0.55684 (18)	0.0455 (9)
H1n1	0.63954	0.698311	0.22123	0.0482*
H2n1	0.534956	0.822806	0.208546	0.0482*
H1n2	0.359482	0.77757	0.278428	0.0536*
H2n2	0.35742	0.658874	0.355973	0.0536*
H1n3	0.59099	0.071809	0.364689	0.0562*
H2n3	0.71576	−0.006424	0.377612	0.0562*
H1n4	0.718708	0.022995	0.58691	0.0552*
H2n4	0.781526	−0.059533	0.510475	0.0552*
H1n5	0.373839	0.715311	0.677503	0.0543*
H2n5	0.265147	0.601891	0.658106	0.0543*
H1n6	0.535457	0.589501	0.512718	0.0546*
H2n6	0.536798	0.705007	0.591462	0.0546*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02747 (16)	0.02426 (15)	0.02265 (16)	0.00004 (11)	0.00160 (12)	−0.00106 (11)
Se1	0.02532 (13)	0.02427 (12)	0.01920 (13)	−0.00028 (8)	0.00161 (10)	0.00140 (11)
O1	0.0414 (12)	0.0444 (10)	0.0231 (9)	−0.0183 (9)	0.0063 (9)	−0.0069 (8)
O2	0.0396 (10)	0.0290 (9)	0.0264 (10)	−0.0047 (7)	−0.0031 (8)	−0.0027 (6)
O3	0.0268 (9)	0.0441 (10)	0.0408 (12)	0.0020 (8)	0.0042 (10)	0.0047 (10)
O4	0.0401 (11)	0.0336 (9)	0.0441 (12)	0.0049 (8)	0.0048 (10)	0.0138 (9)
S1	0.0252 (3)	0.0343 (3)	0.0323 (3)	0.0001 (2)	0.0004 (3)	0.0102 (3)
C1	0.0314 (15)	0.0266 (12)	0.0291 (14)	−0.0051 (10)	−0.0037 (11)	0.0013 (10)
N1	0.0423 (14)	0.0369 (12)	0.0412 (15)	0.0019 (10)	0.0037 (11)	0.0138 (11)
N2	0.0364 (14)	0.0400 (13)	0.0575 (18)	0.0084 (12)	0.0078 (13)	0.0189 (12)
S2	0.0354 (4)	0.0400 (4)	0.0227 (3)	0.0119 (3)	0.0055 (3)	0.0041 (2)
C2	0.0356 (14)	0.0326 (13)	0.0260 (14)	0.0060 (11)	0.0011 (11)	0.0012 (10)
N3	0.0477 (16)	0.0652 (17)	0.0276 (13)	0.0260 (14)	0.0023 (11)	−0.0063 (12)
N4	0.0435 (15)	0.0629 (17)	0.0315 (13)	0.0267 (12)	−0.0011 (11)	0.0021 (12)
S3	0.0228 (3)	0.0406 (3)	0.0279 (3)	0.0011 (2)	−0.0020 (3)	−0.0110 (3)
C3	0.0324 (13)	0.0296 (12)	0.0266 (14)	0.0035 (10)	−0.0047 (11)	−0.0045 (11)
N5	0.0384 (15)	0.0655 (17)	0.0320 (14)	−0.0047 (12)	0.0003 (12)	−0.0218 (12)
N6	0.0328 (14)	0.0620 (17)	0.0418 (16)	−0.0102 (11)	0.0010 (12)	−0.0253 (12)

Geometric parameters (Å, º) top

Zn1—O1	1.984 (2)	C3—N5	1.313 (4)
Zn1—S1	2.3207 (8)	C3—N6	1.321 (3)
Zn1—S2	2.3330 (8)	N1—H1n1	0.89
Zn1—S3	2.3302 (7)	N1—H2n1	0.89
Se1—O1	1.663 (2)	N2—H1n2	0.89
Se1—O2	1.6307 (18)	N2—H2n2	0.89
Se1—O3	1.6246 (19)	N3—H1n3	0.89
Se1—O4	1.621 (2)	N3—H2n3	0.89
S1—C1	1.722 (2)	N4—H1n4	0.89
C1—N1	1.326 (3)	N4—H2n4	0.89
C1—N2	1.313 (4)	N5—H1n5	0.89
S2—C2	1.724 (2)	N5—H2n5	0.89
C2—N3	1.317 (4)	N6—H1n6	0.89
C2—N4	1.306 (3)	N6—H2n6	0.89
S3—C3	1.729 (2)

Se1—Zn1—S1	88.22 (2)	H1n1—N1—H2n1	120.0
Se1—Zn1—S2	115.80 (2)	C1—N2—H1n2	120.0
Se1—Zn1—S3	122.45 (2)	C1—N2—H2n2	120.0
S1—Zn1—S2	111.31 (3)	H1n2—N2—H2n2	120.0
S1—Zn1—S3	115.09 (3)	C2—N3—H1n3	120.0
S2—Zn1—S3	103.70 (3)	C2—N3—H2n3	120.0
O1—Se1—O2	105.75 (10)	H1n3—N3—H2n3	120.0
O1—Se1—O3	108.14 (11)	C2—N4—H1n4	120.0
O1—Se1—O4	108.98 (11)	C2—N4—H2n4	120.0
O2—Se1—O3	110.62 (10)	H1n4—N4—H2n4	120.0
O2—Se1—O4	110.95 (10)	C3—N5—H1n5	120.0
O3—Se1—O4	112.15 (11)	C3—N5—H2n5	120.0
S1—C1—N1	116.84 (19)	H1n5—N5—H2n5	120.0
S1—C1—N2	123.6 (2)	C3—N6—H1n6	120.0
N1—C1—N2	119.5 (2)	C3—N6—H2n6	120.0
S2—C2—N3	122.86 (19)	H1n6—N6—H2n6	120.0
S2—C2—N4	117.7 (2)	H1n1—N1—H2n1	120.0
N3—C2—N4	119.4 (2)	H1n2—N2—H2n2	120.0
S3—C3—N5	118.6 (2)	H1n3—N3—H2n3	120.0
S3—C3—N6	122.2 (2)	H1n4—N4—H2n4	120.0
N5—C3—N6	119.2 (2)	H1n5—N5—H2n5	120.0
C1—N1—H1n1	120.0	H1n6—N6—H2n6	120.0
C1—N1—H2n1	120.0

Experimental details

Crystal data
Chemical formula	[Zn(SeO₄)(CH₄N₂S)₃]
M_r	436.7
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	292
a, b, c (Å)	11.2045 (2), 7.8824 (1), 15.7960 (2)
V (Å³)	1395.08 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.83
Crystal size (mm)	0.35 × 0.25 × 0.1

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Gaussian (Coppens & Hamilton, 1970)
T_min, T_max	0.223, 0.602
No. of measured, independent and observed [I > 3σ(I)] reflections	23449, 3150, 3004
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.050, 1.52
No. of reflections	3150
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.25
Absolute structure	Flack (1983), 1492 Friedel pairs
Absolute structure parameter	−0.020 (6)

Computer programs: COLLECT (Hooft, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1997), (JANA2000; Petříček et al., 2000), PLATON (Spek, 2003).

Tab. 1. Hydrogen-bond geometry (Å, °). */y indicates that the pertinent hydrogen bond is also present in Zn[(SC(NH₂)₂]₃(SO₄), Krupková et al. (2007). top

D-H···A	D-H	H···A	D···A	D-H···A	*
N1-H1N1···O4ⁱ	0.89	2.20	3.066 (3)	164	y
N1-H2N1···O3ⁱⁱ	0.89	2.38	3.072 (3)	135	y
N2-H1N2···O2ⁱⁱ	0.89	1.98	2.852 (3)	167	y
N2-H2N2···S3	0.89	2.63	3.497 (3)	166
N3-H1N3···O3	0.89	2.17	2.988 (3)	152	y
N3-H2N3···O1ⁱⁱⁱ	0.89	2.04	2.895 (3)	160	y
N4-H1N4···O2^iV	0.89	2.12	2.999 (3)	168	y
N4-H2N4···S2ⁱⁱⁱ	0.89	2.86	3.643 (3)	148
N5-H1N5···O3^V	0.89	2.06	2.938 (3)	170	y
N5-H2N5···O4^Vi	0.89	2.57	3.297 (3)	139
N6-H1N6···S1	0.89	2.73	3.577 (3)	159
N6-H2N6···O4^v	0.89	2.19	2.905 (3)	137	y

Symmetry codes:(i) 1/2+x,-y+1, z; (ii) x, y+1, z; (iii) 1/2+x, -y, z; (iv) 1-x, -y, 1/2+z; (v) 1-x, 1-y, 1/2+z; (vi) 1/2-x, y, 1/2+z.

Acknowledgements

Support under a CZ–US grant as part of the KONTAKT program (Czech Ministry of Education, Youth and Sports), No. 1P05ME 785, is gratefully acknowledged.

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