Tris(allyl­thio­urea-κS)bromidozinc(II) bromide

Sun, H.-Q.; Wang, X.-Q.; Jin, T.

doi:10.1107/S1600536811011809

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m543

doi:10.1107/S1600536811011809

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Tris(allylthiourea-κS)bromidozinc(II) bromide

Hai-Qing Sun,^a,^b ^* Xin-Qiang Wang ^b and Tao Jin ^a

^aSchool of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266510, People's Republic of China, and ^bState Key Laboratory of Crystal Materials, (Shandong University), Jinan 250100, People's Republic of China
^*Correspondence e-mail: sunhaiqing@sina.com

(Received 24 December 2010; accepted 30 March 2011; online 7 April 2011)

In the title compound, [ZnBr(C₄H₈N₂S)₃]Br, the Zn^II atom is coordinated by one Br atom and the S atoms of three N-allylthiourea ligands in a distorted tetrahedral geometry. The Zn^II atom and the two Br atoms are located on a threefold axis.

Related literature

For transition metal complexes containing allylthiourea ligands, see: Gambino et al. (2002 ); Olijnyk et al. (2003 ). For similar structures of N-allylthiourea coordination compounds, see: Zhang et al. (1990 ); Yuan et al. (1990 ); Hou et al. (1993 ); Sun et al. (2004 ). For compounds that have similar Zn—Br bond lengths, see: Bermejo et al. (2000 , 2001 ); Castineiras et al. (2000 ).

Experimental

Crystal data

[ZnBr(C₄H₈N₂S)₃]Br
M_r = 573.74
Trigonal, R 3
a = 11.3591 (2) Å
c = 14.5172 (4) Å
V = 1622.19 (6) Å³
Z = 3
Mo Kα radiation
μ = 5.13 mm⁻¹
T = 296 K
0.35 × 0.32 × 0.32 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.265, T_max = 0.294
2605 measured reflections
1359 independent reflections
1305 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.045
S = 0.95
1359 reflections
73 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 522 Friedel pairs
Flack parameter: 0.047 (8)

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL; software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011809/rn2081sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011809/rn2081Isup2.hkl

checkCIF report

Comment top

Coordination compounds with N-allylthiourea (abbreviated as ATU) ligands have many kinds of applications, such as electroplating (Gambino et al., 2002), radiotherapeutic (Olijnyk et al., 2003) and nonlinear optical materials(Zhang et al., 1990; Yuan et al., 1990; Hou et al., 1993; Sun et al., 2004).

The title compound consists of [ZnBr(ATU)₃]⁺ and Br^- ions. The Zn^II atom is coordinated to a Br atom and three ATU ligands through their S atoms in a distorted tetrahedral arrangement. The bond angles around the Zn atom range from 101.64 (2)° to 116.038 (14)°, which show an obvious deviation from the ideal tetrahedral value of 109.5°. Zn and Br1 atoms lie on the threefold axis which is perpendicular to the plane of the three S atoms. The Br2 atom also lies on the axis(Fig.1). The Zn—Br1 distance [2.4640 (6) Å] is comparable with the average values reported in other complexes containing Zn—Br bonds, e.g. 2.4367 (9) and 2.445 (1)Å (Bermejo et al., 2001), 2.4394 (8) and 2.4457 (7)Å (Castineiras et al., 2000), 2.4207 (7) and 2.4654 (8)Å (Bermejo et al., 2000).

Related literature top

For transition metal complexes containing allylthiourea ligands, see: Gambino et al. (2002); Olijnyk et al. (2003). For similar structures of N-allylthiourea coordination compounds, see: Zhang et al. (1990); Yuan et al. (1990); Hou et al. (1993); Sun et al. (2004). For compounds that have similar Zn—Br bond lengths, see: Bermejo et al. (2000, 2001); Castineiras et al. (2000).

Experimental top

To 2.252 g ZnBr₂ (0.01 mol) in 5 ml water, 3.486 g ATU (0.03 mol) in 10 ml water was slowly added with stirring. After standing for 1 h, the lower layer of oily solid was separated and dissolved in small volume of ethanol. Small single crystals of Zn[Br(ATU)₃]Br were obtained by slow evaporation of this solution.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecule structure of ATZB with 30% displacement ellipsoids. H atoms are omitted for clarity. [Symmetry codes: (A)-y + 1, x-y, z; (B)-x + y+1, -x + 1, z]

Tris(allylthiourea-κS)bromidozinc(II) bromide top

Crystal data top

[ZnBr(C₄H₈N₂S)₃]Br	D_x = 1.762 Mg m⁻³
M_r = 573.74	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 2071 reflections
a = 11.3591 (2) Å	θ = 2.5–27.5°
c = 14.5172 (4) Å	µ = 5.13 mm⁻¹
V = 1622.19 (6) Å³	T = 296 K
Z = 3	Block, colourless
F(000) = 858	0.35 × 0.32 × 0.32 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1359 independent reflections
Radiation source: fine-focus sealed tube	1305 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→14
T_min = 0.265, T_max = 0.294	k = −14→10
2605 measured reflections	l = −15→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.019	H-atom parameters constrained
wR(F²) = 0.045	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max = 0.001
1359 reflections	Δρ_max = 0.25 e Å⁻³
73 parameters	Δρ_min = −0.33 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 522 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.047 (8)

Crystal data top

[ZnBr(C₄H₈N₂S)₃]Br	Z = 3
M_r = 573.74	Mo Kα radiation
Trigonal, R3	µ = 5.13 mm⁻¹
a = 11.3591 (2) Å	T = 296 K
c = 14.5172 (4) Å	0.35 × 0.32 × 0.32 mm
V = 1622.19 (6) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	1359 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1305 reflections with I > 2σ(I)
T_min = 0.265, T_max = 0.294	R_int = 0.018
2605 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	H-atom parameters constrained
wR(F²) = 0.045	Δρ_max = 0.25 e Å⁻³
S = 0.95	Δρ_min = −0.33 e Å⁻³
1359 reflections	Absolute structure: Flack (1983), 522 Friedel pairs
73 parameters	Absolute structure parameter: 0.047 (8)
1 restraint

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

	x	y	z	U_iso*/U_eq
Zn1	0.3333	0.6667	0.59387 (3)	0.02676 (12)
Br2	0.3333	0.6667	0.33457 (3)	0.03334 (12)
Br1	0.3333	0.6667	0.76360 (3)	0.04428 (15)
S1	0.19315 (8)	0.43514 (7)	0.56132 (5)	0.03569 (18)
N2	0.2489 (3)	0.2409 (2)	0.53827 (17)	0.0356 (5)
H2	0.1781	0.1993	0.5727	0.043*
N1	0.3941 (3)	0.4382 (2)	0.46202 (16)	0.0380 (6)
H1A	0.4379	0.4009	0.4402	0.046*
H1B	0.4190	0.5211	0.4483	0.046*
C2	0.3134 (3)	0.1641 (3)	0.5097 (2)	0.0397 (7)
H2A	0.2822	0.0861	0.5501	0.048*
H2B	0.4107	0.2207	0.5188	0.048*
C1	0.2880 (3)	0.3680 (3)	0.51681 (16)	0.0280 (5)
C3	0.2890 (4)	0.1143 (4)	0.4121 (2)	0.0526 (9)
H3	0.3323	0.0673	0.3931	0.063*
C4	0.2152 (5)	0.1295 (4)	0.3523 (3)	0.0690 (11)
H4A	0.1697	0.1757	0.3677	0.083*
H4B	0.2069	0.0943	0.2932	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02154 (17)	0.02154 (17)	0.0372 (3)	0.01077 (8)	0.000	0.000
Br2	0.03343 (18)	0.03343 (18)	0.0332 (2)	0.01672 (9)	0.000	0.000
Br1	0.0489 (2)	0.0489 (2)	0.0351 (2)	0.02443 (11)	0.000	0.000
S1	0.0256 (4)	0.0211 (3)	0.0567 (4)	0.0089 (3)	0.0086 (3)	−0.0029 (3)
N2	0.0387 (14)	0.0236 (12)	0.0457 (11)	0.0164 (11)	0.0132 (11)	0.0082 (10)
N1	0.0420 (15)	0.0247 (12)	0.0473 (12)	0.0166 (12)	0.0169 (11)	0.0073 (10)
C2	0.0461 (19)	0.0288 (15)	0.0507 (15)	0.0236 (14)	0.0055 (14)	0.0045 (13)
C1	0.0317 (15)	0.0225 (14)	0.0312 (11)	0.0146 (12)	−0.0006 (11)	−0.0038 (10)
C3	0.061 (2)	0.0367 (18)	0.063 (2)	0.0268 (18)	0.0123 (18)	−0.0036 (16)
C4	0.079 (3)	0.058 (2)	0.059 (2)	0.026 (2)	−0.005 (2)	−0.0069 (18)

Geometric parameters (Å, º) top

Zn1—S1ⁱ	2.3426 (7)	N1—H1A	0.8600
Zn1—S1	2.3426 (7)	N1—H1B	0.8600
Zn1—S1ⁱⁱ	2.3426 (7)	C2—C3	1.499 (5)
Zn1—Br1	2.4640 (6)	C2—H2A	0.9700
S1—C1	1.727 (3)	C2—H2B	0.9700
N2—C1	1.318 (4)	C3—C4	1.278 (6)
N2—C2	1.452 (4)	C3—H3	0.9300
N2—H2	0.8600	C4—H4A	0.9300
N1—C1	1.327 (3)	C4—H4B	0.9300

S1ⁱ—Zn1—S1	116.038 (14)	N2—C2—H2A	108.2
S1ⁱ—Zn1—S1ⁱⁱ	116.038 (14)	C3—C2—H2A	108.2
S1—Zn1—S1ⁱⁱ	116.038 (13)	N2—C2—H2B	108.2
S1ⁱ—Zn1—Br1	101.64 (2)	C3—C2—H2B	108.2
S1—Zn1—Br1	101.64 (2)	H2A—C2—H2B	107.4
S1ⁱⁱ—Zn1—Br1	101.64 (2)	N2—C1—N1	120.5 (3)
C1—S1—Zn1	110.33 (10)	N2—C1—S1	116.9 (2)
C1—N2—C2	126.6 (3)	N1—C1—S1	122.6 (2)
C1—N2—H2	116.7	C4—C3—C2	127.0 (4)
C2—N2—H2	116.7	C4—C3—H3	116.5
C1—N1—H1A	120.0	C2—C3—H3	116.5
C1—N1—H1B	120.0	C3—C4—H4A	120.0
H1A—N1—H1B	120.0	C3—C4—H4B	120.0
N2—C2—C3	116.3 (3)	H4A—C4—H4B	120.0

S1ⁱ—Zn1—S1—C1	141.40 (9)	C2—N2—C1—S1	−179.4 (2)
S1ⁱⁱ—Zn1—S1—C1	−0.08 (10)	Zn1—S1—C1—N2	145.88 (19)
Br1—Zn1—S1—C1	−109.34 (9)	Zn1—S1—C1—N1	−35.4 (2)
C1—N2—C2—C3	−75.8 (4)	N2—C2—C3—C4	−1.8 (6)
C2—N2—C1—N1	1.8 (4)

Symmetry codes: (i) −x+y, −x+1, z; (ii) −y+1, x−y+1, z.

Experimental details

Crystal data
Chemical formula	[ZnBr(C₄H₈N₂S)₃]Br
M_r	573.74
Crystal system, space group	Trigonal, R3
Temperature (K)	296
a, c (Å)	11.3591 (2), 14.5172 (4)
V (Å³)	1622.19 (6)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	5.13
Crystal size (mm)	0.35 × 0.32 × 0.32

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.265, 0.294
No. of measured, independent and observed [I > 2σ(I)] reflections	2605, 1359, 1305
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.045, 0.95
No. of reflections	1359
No. of parameters	73
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.33
Absolute structure	Flack (1983), 522 Friedel pairs
Absolute structure parameter	0.047 (8)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Acknowledgements

The authors thank the State Key Laboratory of Crystal Materials Open Project (KF0804) for financial support.

References

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