metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Tris(allyl­thio­urea-κS)bromidozinc(II) bromide

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 ZnII atom is coordinated by one Br atom and the S atoms of three N-allyl­thio­urea ligands in a distorted tetra­hedral geometry. The ZnII 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[Gambino, D., Kremer, E. & Baran, E. J. (2002). Spectrochim. Acta, A58, 3085-3092.]); Olijnyk et al. (2003[Olijnyk, V. V., Filinchuk, Ya. E. & Pandiak, N. L. (2003). Z. Anorg. Allg. Chem. 629, 1904-1905.]). For similar structures of N-allyl­thio­urea coordination compounds, see: Zhang et al. (1990[Zhang, N., Jiang, M. H., Yuan, D. R., Xu, D., Yu, W. T. & Tao, X. T. (1990). Chin. Sci. Bull. 35, 646-649.]); Yuan et al. (1990[Yuan, D. R., Zhang, N., Tao, X. T., Xu, D. & Jiang, M. H. (1990). Chin. Phys. Lett. 7, 334-336.]); Hou et al. (1993[Hou, W. B., Yuan, D. R., Xu, D., Zhang, N., Yu, W. T., Liu, M. G., Tao, X. T., Sun, S. Y. & Jiang, M. H. (1993). J. Cryst. Growth, 133, 71-74.]); Sun et al. (2004[Sun, H.-Q., Yu, W.-T., Yuan, D.-R., Wang, X.-Q. & Gang, X. (2004). Acta Cryst. E60, m1431-m1433.]). For compounds that have similar Zn—Br bond lengths, see: Bermejo et al. (2000[Bermejo, E., Castineiras, A., Dominguez, R., Carballo, R., Maichle-Mossmer, C., Strähle, J., Liberta, A. E. & West, D. X. (2000). Z. Anorg. Allg. Chem. 626, 878-884.], 2001[Bermejo, E., Castineiras, A., Fostiak, L. M., Garcia, I., Llamas-Saiz, A. L., Swearingen, J. K. & West, D. X. (2001). Z. Naturforsch. Teil B, 56, 1297-1305.]); Castineiras et al. (2000[Castineiras, A., Garcia, I., Bermejo, E. & West, D. X. (2000). Z. Naturforsch. Teil B, 55, 511-518.]).

[Scheme 1]

Experimental

Crystal data
  • [ZnBr(C4H8N2S)3]Br

  • Mr = 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[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.265, Tmax = 0.294

  • 2605 measured reflections

  • 1359 independent reflections

  • 1305 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.33 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 522 Friedel pairs

  • Flack parameter: 0.047 (8)

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999[Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL; software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


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 ZnII 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.

Refinement top

H atoms were placed geometrically (C—H = 0.93 - 0.97 Å, N—H = 0.86 Å) and refined using the riding model approximation, with Uiso = 1.2Ueq.

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
[Figure 1] 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]BrDx = 1.762 Mg m3
Mr = 573.74Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 2071 reflections
a = 11.3591 (2) Åθ = 2.5–27.5°
c = 14.5172 (4) ŵ = 5.13 mm1
V = 1622.19 (6) Å3T = 296 K
Z = 3Block, colourless
F(000) = 8580.35 × 0.32 × 0.32 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1359 independent reflections
Radiation source: fine-focus sealed tube1305 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
ϕ and ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 1314
Tmin = 0.265, Tmax = 0.294k = 1410
2605 measured reflectionsl = 1518
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.019H-atom parameters constrained
wR(F2) = 0.045 w = 1/[σ2(Fo2) + (0.P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max = 0.001
1359 reflectionsΔρmax = 0.25 e Å3
73 parametersΔρmin = 0.33 e Å3
1 restraintAbsolute structure: Flack (1983), 522 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.047 (8)
Crystal data top
[ZnBr(C4H8N2S)3]BrZ = 3
Mr = 573.74Mo Kα radiation
Trigonal, R3µ = 5.13 mm1
a = 11.3591 (2) ÅT = 296 K
c = 14.5172 (4) Å0.35 × 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)
Tmin = 0.265, Tmax = 0.294Rint = 0.018
2605 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.019H-atom parameters constrained
wR(F2) = 0.045Δρmax = 0.25 e Å3
S = 0.95Δρmin = 0.33 e Å3
1359 reflectionsAbsolute structure: Flack (1983), 522 Friedel pairs
73 parametersAbsolute 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
xyzUiso*/Ueq
Zn10.33330.66670.59387 (3)0.02676 (12)
Br20.33330.66670.33457 (3)0.03334 (12)
Br10.33330.66670.76360 (3)0.04428 (15)
S10.19315 (8)0.43514 (7)0.56132 (5)0.03569 (18)
N20.2489 (3)0.2409 (2)0.53827 (17)0.0356 (5)
H20.17810.19930.57270.043*
N10.3941 (3)0.4382 (2)0.46202 (16)0.0380 (6)
H1A0.43790.40090.44020.046*
H1B0.41900.52110.44830.046*
C20.3134 (3)0.1641 (3)0.5097 (2)0.0397 (7)
H2A0.28220.08610.55010.048*
H2B0.41070.22070.51880.048*
C10.2880 (3)0.3680 (3)0.51681 (16)0.0280 (5)
C30.2890 (4)0.1143 (4)0.4121 (2)0.0526 (9)
H30.33230.06730.39310.063*
C40.2152 (5)0.1295 (4)0.3523 (3)0.0690 (11)
H4A0.16970.17570.36770.083*
H4B0.20690.09430.29320.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02154 (17)0.02154 (17)0.0372 (3)0.01077 (8)0.0000.000
Br20.03343 (18)0.03343 (18)0.0332 (2)0.01672 (9)0.0000.000
Br10.0489 (2)0.0489 (2)0.0351 (2)0.02443 (11)0.0000.000
S10.0256 (4)0.0211 (3)0.0567 (4)0.0089 (3)0.0086 (3)0.0029 (3)
N20.0387 (14)0.0236 (12)0.0457 (11)0.0164 (11)0.0132 (11)0.0082 (10)
N10.0420 (15)0.0247 (12)0.0473 (12)0.0166 (12)0.0169 (11)0.0073 (10)
C20.0461 (19)0.0288 (15)0.0507 (15)0.0236 (14)0.0055 (14)0.0045 (13)
C10.0317 (15)0.0225 (14)0.0312 (11)0.0146 (12)0.0006 (11)0.0038 (10)
C30.061 (2)0.0367 (18)0.063 (2)0.0268 (18)0.0123 (18)0.0036 (16)
C40.079 (3)0.058 (2)0.059 (2)0.026 (2)0.005 (2)0.0069 (18)
Geometric parameters (Å, º) top
Zn1—S1i2.3426 (7)N1—H1A0.8600
Zn1—S12.3426 (7)N1—H1B0.8600
Zn1—S1ii2.3426 (7)C2—C31.499 (5)
Zn1—Br12.4640 (6)C2—H2A0.9700
S1—C11.727 (3)C2—H2B0.9700
N2—C11.318 (4)C3—C41.278 (6)
N2—C21.452 (4)C3—H30.9300
N2—H20.8600C4—H4A0.9300
N1—C11.327 (3)C4—H4B0.9300
S1i—Zn1—S1116.038 (14)N2—C2—H2A108.2
S1i—Zn1—S1ii116.038 (14)C3—C2—H2A108.2
S1—Zn1—S1ii116.038 (13)N2—C2—H2B108.2
S1i—Zn1—Br1101.64 (2)C3—C2—H2B108.2
S1—Zn1—Br1101.64 (2)H2A—C2—H2B107.4
S1ii—Zn1—Br1101.64 (2)N2—C1—N1120.5 (3)
C1—S1—Zn1110.33 (10)N2—C1—S1116.9 (2)
C1—N2—C2126.6 (3)N1—C1—S1122.6 (2)
C1—N2—H2116.7C4—C3—C2127.0 (4)
C2—N2—H2116.7C4—C3—H3116.5
C1—N1—H1A120.0C2—C3—H3116.5
C1—N1—H1B120.0C3—C4—H4A120.0
H1A—N1—H1B120.0C3—C4—H4B120.0
N2—C2—C3116.3 (3)H4A—C4—H4B120.0
S1i—Zn1—S1—C1141.40 (9)C2—N2—C1—S1179.4 (2)
S1ii—Zn1—S1—C10.08 (10)Zn1—S1—C1—N2145.88 (19)
Br1—Zn1—S1—C1109.34 (9)Zn1—S1—C1—N135.4 (2)
C1—N2—C2—C375.8 (4)N2—C2—C3—C41.8 (6)
C2—N2—C1—N11.8 (4)
Symmetry codes: (i) x+y, x+1, z; (ii) y+1, xy+1, z.

Experimental details

Crystal data
Chemical formula[ZnBr(C4H8N2S)3]Br
Mr573.74
Crystal system, space groupTrigonal, R3
Temperature (K)296
a, c (Å)11.3591 (2), 14.5172 (4)
V3)1622.19 (6)
Z3
Radiation typeMo Kα
µ (mm1)5.13
Crystal size (mm)0.35 × 0.32 × 0.32
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.265, 0.294
No. of measured, independent and
observed [I > 2σ(I)] reflections
2605, 1359, 1305
Rint0.018
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.045, 0.95
No. of reflections1359
No. of parameters73
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.33
Absolute structureFlack (1983), 522 Friedel pairs
Absolute structure parameter0.047 (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

First citationAltomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.  Web of Science CrossRef CAS IUCr Journals
First citationBermejo, E., Castineiras, A., Dominguez, R., Carballo, R., Maichle-Mossmer, C., Strähle, J., Liberta, A. E. & West, D. X. (2000). Z. Anorg. Allg. Chem. 626, 878–884.  CrossRef CAS
First citationBermejo, E., Castineiras, A., Fostiak, L. M., Garcia, I., Llamas-Saiz, A. L., Swearingen, J. K. & West, D. X. (2001). Z. Naturforsch. Teil B, 56, 1297–1305.  CAS
First citationBruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationCastineiras, A., Garcia, I., Bermejo, E. & West, D. X. (2000). Z. Naturforsch. Teil B, 55, 511–518.  CAS
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals
First citationGambino, D., Kremer, E. & Baran, E. J. (2002). Spectrochim. Acta, A58, 3085–3092.  CrossRef
First citationHou, W. B., Yuan, D. R., Xu, D., Zhang, N., Yu, W. T., Liu, M. G., Tao, X. T., Sun, S. Y. & Jiang, M. H. (1993). J. Cryst. Growth, 133, 71–74.  CAS
First citationOlijnyk, V. V., Filinchuk, Ya. E. & Pandiak, N. L. (2003). Z. Anorg. Allg. Chem. 629, 1904–1905.  Web of Science CSD CrossRef
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSun, H.-Q., Yu, W.-T., Yuan, D.-R., Wang, X.-Q. & Gang, X. (2004). Acta Cryst. E60, m1431–m1433.  Web of Science CSD CrossRef IUCr Journals
First citationYuan, D. R., Zhang, N., Tao, X. T., Xu, D. & Jiang, M. H. (1990). Chin. Phys. Lett. 7, 334–336.  CAS
First citationZhang, N., Jiang, M. H., Yuan, D. R., Xu, D., Yu, W. T. & Tao, X. T. (1990). Chin. Sci. Bull. 35, 646–649.  CAS

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds