(4-Hydr­oxy-2-oxidobenzaldehyde thio­semicarbazonato-κ3O2,N1,S)(1,10-phenanthroline-κ2N,N′)zinc(II) dimethyl sulfoxide disolvate monohydrate

Tan, K.W.; Ng, C.H.; Maah, M.J.; Ng, S.W.

doi:10.1107/S160053680804169X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages m61-m62

doi:10.1107/S160053680804169X

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(4-Hydroxy-2-oxidobenzaldehyde thiosemicarbazonato-κ³O²,N¹,S)(1,10-phenanthroline-κ²N,N′)zinc(II) dimethyl sulfoxide disolvate monohydrate

Kong Wai Tan,^a Chew Hee Ng,^b Mohd Jamil Maah ^c ^* and Seik Weng Ng ^c

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, ^bFaculty of Engineering and Science, Universiti Tunku Abdul Rahman, 53300 Kuala Lumpur, Malaysia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: mjamil@um.edu.my

(Received 3 December 2008; accepted 9 December 2008; online 13 December 2008)

The Zn^II atom in the title compound, [Zn(C₈H₇N₃O₂S)(C₁₂H₈N₂)]·2C₂H₆OS·H₂O, is N,N′-chelated by the N-heterocycle and N,O,S-chelated by the deprotonated Schiff base in a distorted square-pyramidal enviroment. Hydrogen bonds link the mononuclear molecule, the water and the dimethyl sulfoxide (DMSO) molecules into a linear chain motif. One DMSO molecule is disordered over two positions in respect of the S atom in an approximate 1:1 ratio.

Related literature

For reports of the metal derivatives of 2,4-dihydroxybenzaldehyde thiosemicarbazone, see: Broomhead & Dwyer (1961 ); Gingras et al. (1960 ); Liu et al. (1974 ); Luo et al. (1988 ); Mayadeo et al. (1986 ); Onuska et al. (1996 ); Shen & Li (2006 ); Zhu et al. (1991a ,b ).

Experimental

Crystal data

[Zn(C₈H₇N₃O₂S)(C₁₂H₈N₂)]·2C₂H₆OS·H₂O
M_r = 629.07
Triclinic, $[P \overline 1]$
a = 9.3582 (5) Å
b = 9.8181 (5) Å
c = 15.2913 (8) Å
α = 73.641 (3)°
β = 82.482 (4)°
γ = 88.059 (4)°
V = 1336.5 (1) Å³
Z = 2
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 100 (2) K
0.05 × 0.01 × 0.01 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.943, T_max = 0.988
12760 measured reflections
6125 independent reflections
3397 reflections with I > 2σ(I)
R_int = 0.097

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.211
S = 0.98
6125 reflections
344 parameters
27 restraints
H-atom parameters constrained
Δρ_max = 1.51 e Å⁻³
Δρ_min = −1.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.84	1.84	2.679 (6)	172
N3—H31⋯N2ⁱ	0.88	2.11	2.984 (8)	174
N3—H32⋯O4	0.88	2.33	3.074 (8)	143
O1w—H1w1⋯O1ⁱⁱ	0.84	2.11	2.911 (7)	160
O1w—H1w2⋯O2	0.84	2.25	3.055 (7)	161
Symmetry codes: (i) -x+2, -y+2, -z+2; (ii) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680804169X/sj2562sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680804169X/sj2562Isup2.hkl

checkCIF report

Related literature top

For reports of the metal derivatives of 2,4-dihydroxybenzaldehyde thiosemicarbazone, see: Broomhead & Dwyer (1961); Gingras et al. (1960); Liu et al. (1974); Luo et al. (1988); Mayadeo et al. (1986); Onuska et al. (1996); Shen & Li (2006); Zhu et al. (1991a,b).

Experimental top

Zinc acetate monohydrate (0.22 g, 1 mmol), 2,4-dihydroxybenzaldehyde thiosemicarbazone (0.21 g, 1 mmol) and 1,10-phenanthroline (0.20 g, 1 mmol) were heated in ethanol (50 ml) to give a yellow solution. The compound that separated on cooling the solution was recrystallized from DMSO.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid (Barbour, 2001) plot of Zn(C₁₂H₈N₂)(C₈H₇N₃O₂S)^.2DMSO^.H₂O at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii. The disorder in the DMSO is not shown.

(4-Hydroxy-2-oxidobenzaldehyde thiosemicarbazonato-κ³O²,N¹,S)(1,10- phenanthroline-κ²N,N')zinc(II) dimethyl sulfoxide disolvate monohydrate top

Crystal data top

[Zn(C₈H₇N₃O₂S)(C₁₂H₈N₂)]·2C₂H₆OS·H₂O	Z = 2
M_r = 629.07	F(000) = 652
Triclinic, P1	D_x = 1.563 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3582 (5) Å	Cell parameters from 932 reflections
b = 9.8181 (5) Å	θ = 2.2–21.9°
c = 15.2913 (8) Å	µ = 1.20 mm⁻¹
α = 73.641 (3)°	T = 100 K
β = 82.482 (4)°	Prism, yellow
γ = 88.059 (4)°	0.05 × 0.01 × 0.01 mm
V = 1336.5 (1) Å³

Data collection top

Bruker SMART APEX diffractometer	6125 independent reflections
Radiation source: fine-focus sealed tube	3397 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.097
ω scans	θ_max = 27.5°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.943, T_max = 0.988	k = −12→12
12760 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.211	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0989P)²] where P = (F_o² + 2F_c²)/3
6125 reflections	(Δ/σ)_max = 0.001
344 parameters	Δρ_max = 1.51 e Å⁻³
27 restraints	Δρ_min = −1.29 e Å⁻³

Crystal data top

[Zn(C₈H₇N₃O₂S)(C₁₂H₈N₂)]·2C₂H₆OS·H₂O	γ = 88.059 (4)°
M_r = 629.07	V = 1336.5 (1) Å³
Triclinic, P1	Z = 2
a = 9.3582 (5) Å	Mo Kα radiation
b = 9.8181 (5) Å	µ = 1.20 mm⁻¹
c = 15.2913 (8) Å	T = 100 K
α = 73.641 (3)°	0.05 × 0.01 × 0.01 mm
β = 82.482 (4)°

Data collection top

Bruker SMART APEX diffractometer	6125 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3397 reflections with I > 2σ(I)
T_min = 0.943, T_max = 0.988	R_int = 0.097
12760 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	27 restraints
wR(F²) = 0.211	H-atom parameters constrained
S = 0.98	Δρ_max = 1.51 e Å⁻³
6125 reflections	Δρ_min = −1.29 e Å⁻³
344 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.78197 (8)	1.15841 (8)	0.72088 (5)	0.0148 (2)
S1	0.86430 (18)	1.30637 (17)	0.80123 (11)	0.0196 (4)
S2	0.30700 (19)	0.28436 (18)	0.79460 (12)	0.0228 (4)
S3	1.2635 (3)	1.5316 (3)	0.9107 (2)	0.0249 (10)	0.564 (6)
S3'	1.1708 (4)	1.5622 (4)	0.9722 (3)	0.0235 (13)	0.436 (6)
O1	0.6115 (5)	1.0571 (4)	0.7064 (3)	0.0183 (10)
O2	0.4103 (5)	0.6534 (5)	0.6604 (3)	0.0206 (10)
H2	0.4048	0.5648	0.6818	0.031*
O3	0.4176 (5)	0.3697 (5)	0.7213 (3)	0.0254 (11)
O4	1.1918 (7)	1.4255 (6)	0.9740 (4)	0.067 (2)
O1W	0.5152 (5)	0.8171 (5)	0.4620 (4)	0.0352 (13)
H1W1	0.4596	0.8455	0.4217	0.053*
H1W2	0.4664	0.7745	0.5118	0.053*
N1	0.8024 (6)	1.0029 (6)	0.8431 (4)	0.0180 (12)
N2	0.8839 (6)	1.0295 (6)	0.9059 (4)	0.0173 (12)
N3	0.9991 (6)	1.1973 (6)	0.9465 (4)	0.0198 (12)
H31	1.0275	1.1297	0.9922	0.024*
H32	1.0243	1.2860	0.9385	0.024*
N4	0.7906 (6)	1.3147 (6)	0.5889 (4)	0.0169 (12)
N5	0.9576 (5)	1.0814 (5)	0.6433 (4)	0.0141 (11)
C1	0.6018 (7)	0.9163 (7)	0.7315 (4)	0.0166 (14)
C2	0.5111 (6)	0.8529 (6)	0.6879 (4)	0.0147 (13)
H2A	0.4559	0.9117	0.6439	0.018*
C3	0.4999 (7)	0.7065 (7)	0.7073 (4)	0.0177 (14)
C4	0.5791 (7)	0.6167 (7)	0.7718 (4)	0.0182 (14)
H4	0.5747	0.5165	0.7834	0.022*
C5	0.6633 (7)	0.6775 (7)	0.8177 (4)	0.0174 (14)
H5	0.7162	0.6171	0.8624	0.021*
C6	0.6750 (7)	0.8259 (6)	0.8015 (4)	0.0144 (13)
C7	0.7622 (6)	0.8737 (7)	0.8587 (4)	0.0152 (13)
H7	0.7915	0.8055	0.9108	0.018*
C8	0.9168 (7)	1.1651 (7)	0.8889 (4)	0.0163 (14)
C9	0.7054 (7)	1.4278 (6)	0.5623 (5)	0.0173 (14)
H9	0.6259	1.4427	0.6040	0.021*
C10	0.7303 (7)	1.5230 (7)	0.4761 (4)	0.0180 (14)
H10	0.6672	1.6012	0.4589	0.022*
C11	0.8459 (7)	1.5049 (7)	0.4152 (5)	0.0194 (14)
H11	0.8637	1.5712	0.3563	0.023*
C12	0.9394 (4)	1.3858 (3)	0.4409 (3)	0.0162 (13)
C14	1.0583 (4)	1.3616 (4)	0.3825 (2)	0.0191 (14)
H14	1.0802	1.4255	0.3230	0.023*
C15	1.1451 (4)	1.2440 (4)	0.4113 (2)	0.0189 (14)
H15	1.2264	1.2274	0.3714	0.023*
C16	1.1131 (4)	1.1505 (3)	0.4984 (3)	0.0180 (14)
C17	0.9942 (4)	1.1746 (4)	0.5568 (2)	0.0143 (13)
C13	0.9074 (4)	1.2923 (4)	0.5280 (2)	0.0147 (13)
C18	1.1962 (7)	1.0255 (7)	0.5292 (5)	0.0184 (14)
H18	1.2784	1.0062	0.4911	0.022*
C19	1.1562 (6)	0.9336 (7)	0.6142 (4)	0.0164 (14)
H19	1.2095	0.8493	0.6353	0.020*
C20	1.0360 (7)	0.9656 (6)	0.6694 (5)	0.0167 (14)
H20	1.0093	0.9013	0.7283	0.020*
C21	0.2630 (8)	0.1380 (7)	0.7548 (5)	0.0269 (16)
H21A	0.2223	0.1737	0.6967	0.040*
H21B	0.1922	0.0768	0.8007	0.040*
H21C	0.3503	0.0834	0.7452	0.040*
C22	0.4045 (8)	0.1879 (8)	0.8850 (5)	0.0302 (17)
H22A	0.4803	0.1322	0.8607	0.045*
H22B	0.3387	0.1240	0.9330	0.045*
H22C	0.4483	0.2545	0.9110	0.045*
C23	1.3333 (8)	1.6563 (9)	0.9636 (6)	0.040 (2)
H23A	1.2790	1.6460	1.0245	0.060*	0.564 (6)
H23B	1.3231	1.7535	0.9249	0.060*	0.564 (6)
H23C	1.4354	1.6364	0.9699	0.060*	0.564 (6)
H23D	1.4092	1.6188	0.9286	0.060*	0.436 (6)
H23E	1.3584	1.6458	1.0241	0.060*	0.436 (6)
H23F	1.3202	1.7551	0.9337	0.060*	0.436 (6)
C24	1.1292 (9)	1.6561 (9)	0.8566 (6)	0.053 (3)
H24A	1.0568	1.6040	0.8379	0.080*	0.564 (6)
H24B	1.1768	1.7262	0.8025	0.080*	0.564 (6)
H24C	1.0823	1.7047	0.9005	0.080*	0.564 (6)
H24D	1.0779	1.5941	0.8330	0.080*	0.436 (6)
H24E	1.2174	1.6865	0.8169	0.080*	0.436 (6)
H24F	1.0709	1.7375	0.8595	0.080*	0.436 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0175 (4)	0.0132 (4)	0.0153 (4)	−0.0021 (3)	−0.0029 (3)	−0.0061 (3)
S1	0.0279 (9)	0.0143 (8)	0.0187 (9)	−0.0024 (7)	−0.0078 (7)	−0.0056 (7)
S2	0.0245 (9)	0.0196 (9)	0.0275 (10)	−0.0028 (7)	−0.0038 (8)	−0.0111 (7)
S3	0.0274 (18)	0.0231 (18)	0.0235 (18)	−0.0044 (13)	0.0022 (14)	−0.0072 (14)
S3'	0.027 (2)	0.022 (2)	0.024 (2)	−0.0031 (16)	−0.0019 (17)	−0.0097 (17)
O1	0.019 (2)	0.009 (2)	0.028 (3)	−0.0014 (18)	−0.007 (2)	−0.0063 (19)
O2	0.023 (2)	0.015 (2)	0.027 (3)	−0.005 (2)	−0.006 (2)	−0.009 (2)
O3	0.030 (3)	0.025 (3)	0.027 (3)	−0.008 (2)	−0.004 (2)	−0.016 (2)
O4	0.110 (6)	0.026 (3)	0.072 (5)	−0.001 (4)	−0.061 (5)	−0.003 (3)
O1W	0.036 (3)	0.038 (3)	0.033 (3)	−0.009 (3)	−0.012 (2)	−0.008 (3)
N1	0.019 (3)	0.019 (3)	0.019 (3)	−0.003 (2)	−0.005 (2)	−0.008 (2)
N2	0.021 (3)	0.018 (3)	0.018 (3)	−0.002 (2)	−0.007 (2)	−0.012 (2)
N3	0.031 (3)	0.012 (3)	0.021 (3)	−0.002 (2)	−0.015 (3)	−0.007 (2)
N4	0.019 (2)	0.018 (2)	0.020 (3)	−0.004 (2)	−0.005 (2)	−0.013 (2)
N5	0.016 (3)	0.012 (3)	0.017 (3)	0.000 (2)	−0.009 (2)	−0.005 (2)
C1	0.015 (3)	0.018 (3)	0.020 (3)	−0.002 (3)	−0.006 (3)	−0.008 (3)
C2	0.011 (3)	0.016 (3)	0.019 (3)	−0.002 (2)	−0.002 (3)	−0.008 (3)
C3	0.018 (3)	0.017 (3)	0.019 (3)	−0.002 (3)	0.002 (3)	−0.009 (3)
C4	0.021 (3)	0.011 (3)	0.022 (4)	−0.007 (3)	0.005 (3)	−0.006 (3)
C5	0.017 (3)	0.015 (3)	0.019 (3)	−0.007 (3)	0.002 (3)	−0.004 (3)
C6	0.017 (3)	0.011 (3)	0.016 (3)	−0.002 (2)	0.003 (3)	−0.008 (3)
C7	0.016 (3)	0.015 (3)	0.012 (3)	−0.006 (3)	0.000 (3)	−0.001 (3)
C8	0.016 (3)	0.020 (3)	0.015 (3)	−0.005 (3)	0.001 (3)	−0.009 (3)
C9	0.018 (3)	0.015 (3)	0.023 (4)	0.004 (3)	−0.007 (3)	−0.009 (3)
C10	0.021 (3)	0.014 (3)	0.024 (4)	0.001 (3)	−0.007 (3)	−0.010 (3)
C11	0.022 (3)	0.013 (3)	0.021 (4)	−0.001 (3)	−0.004 (3)	−0.002 (3)
C12	0.019 (3)	0.015 (3)	0.019 (3)	−0.005 (2)	−0.007 (2)	−0.010 (2)
C14	0.024 (3)	0.015 (3)	0.020 (3)	−0.005 (3)	−0.002 (3)	−0.007 (3)
C15	0.016 (3)	0.020 (3)	0.025 (4)	−0.005 (3)	0.000 (3)	−0.014 (3)
C16	0.015 (3)	0.019 (3)	0.024 (4)	−0.006 (3)	−0.002 (3)	−0.012 (3)
C17	0.014 (3)	0.013 (3)	0.018 (3)	−0.007 (2)	−0.001 (3)	−0.009 (3)
C13	0.018 (3)	0.013 (3)	0.018 (3)	−0.003 (3)	−0.005 (3)	−0.011 (3)
C18	0.014 (3)	0.021 (3)	0.026 (4)	0.002 (3)	−0.008 (3)	−0.015 (3)
C19	0.013 (3)	0.016 (3)	0.023 (4)	0.003 (3)	−0.008 (3)	−0.009 (3)
C20	0.018 (3)	0.011 (3)	0.023 (3)	0.004 (3)	−0.005 (3)	−0.008 (3)
C21	0.029 (4)	0.020 (4)	0.035 (4)	−0.002 (3)	−0.004 (3)	−0.012 (3)
C22	0.038 (4)	0.026 (4)	0.026 (4)	−0.001 (3)	−0.009 (3)	−0.004 (3)
C23	0.043 (5)	0.037 (5)	0.042 (5)	−0.014 (4)	0.001 (4)	−0.014 (4)
C24	0.058 (6)	0.042 (5)	0.049 (6)	0.004 (5)	−0.026 (5)	0.012 (5)

Geometric parameters (Å, º) top

Zn1—O1	1.976 (4)	C6—C7	1.448 (9)
Zn1—N1	2.081 (5)	C7—H7	0.9500
Zn1—N5	2.143 (5)	C9—C10	1.381 (9)
Zn1—N4	2.157 (5)	C9—H9	0.9500
Zn1—S1	2.3542 (18)	C10—C11	1.373 (9)
S1—C8	1.744 (7)	C10—H10	0.9500
S2—O3	1.502 (5)	C11—C12	1.432 (7)
S2—C22	1.782 (7)	C11—H11	0.9500
S2—C21	1.790 (7)	C12—C14	1.3900
S3—O4	1.335 (7)	C12—C13	1.3900
S3—C23	1.825 (8)	C14—C15	1.3900
S3—C24	1.832 (8)	C14—H14	0.9500
S3—H23D	1.7249	C15—C16	1.3900
S3'—O4	1.342 (7)	C15—H15	0.9500
S3'—C23	1.777 (8)	C16—C17	1.3900
S3'—C24	1.834 (9)	C16—C18	1.427 (7)
O1—C1	1.329 (7)	C17—C13	1.3900
O2—C3	1.373 (8)	C18—C19	1.371 (9)
O2—H2	0.8400	C18—H18	0.9500
O1W—H1W1	0.8400	C19—C20	1.397 (9)
O1W—H1W2	0.8400	C19—H19	0.9500
N1—C7	1.282 (8)	C20—H20	0.9500
N1—N2	1.385 (7)	C21—H21A	0.9800
N2—C8	1.321 (8)	C21—H21B	0.9800
N3—C8	1.349 (8)	C21—H21C	0.9800
N3—H31	0.8800	C22—H22A	0.9800
N3—H32	0.8800	C22—H22B	0.9800
N4—C9	1.344 (8)	C22—H22C	0.9800
N4—C13	1.394 (6)	C23—H23A	0.9800
N5—C20	1.325 (8)	C23—H23B	0.9800
N5—C17	1.388 (6)	C23—H23C	0.9800
C1—C2	1.405 (8)	C23—H23D	0.9601
C1—C6	1.421 (9)	C23—H23E	0.9600
C2—C3	1.389 (9)	C23—H23F	0.9600
C2—H2A	0.9500	C24—H24A	0.9800
C3—C4	1.398 (9)	C24—H24B	0.9800
C4—C5	1.373 (9)	C24—H24C	0.9800
C4—H4	0.9500	C24—H24D	0.9599
C5—C6	1.413 (8)	C24—H24E	0.9600
C5—H5	0.9500	C24—H24F	0.9601

O1—Zn1—N1	89.26 (19)	C14—C12—C13	120.0
O1—Zn1—N5	104.25 (19)	C14—C12—C11	122.6 (4)
N1—Zn1—N5	94.6 (2)	C13—C12—C11	117.4 (4)
O1—Zn1—N4	95.47 (18)	C12—C14—C15	120.0
N1—Zn1—N4	172.4 (2)	C12—C14—H14	120.0
N5—Zn1—N4	78.52 (19)	C15—C14—H14	120.0
O1—Zn1—S1	143.98 (15)	C14—C15—C16	120.0
N1—Zn1—S1	82.37 (15)	C14—C15—H15	120.0
N5—Zn1—S1	111.28 (14)	C16—C15—H15	120.0
N4—Zn1—S1	97.11 (14)	C17—C16—C15	120.0
C8—S1—Zn1	93.9 (2)	C17—C16—C18	118.2 (4)
O3—S2—C22	105.7 (3)	C15—C16—C18	121.7 (4)
O3—S2—C21	105.6 (3)	N5—C17—C13	118.7 (3)
C22—S2—C21	97.8 (4)	N5—C17—C16	121.3 (3)
O4—S3—C23	111.0 (4)	C13—C17—C16	120.0
O4—S3—C24	107.3 (4)	C17—C13—C12	120.0
C23—S3—C24	93.9 (4)	C17—C13—N4	118.5 (3)
O4—S3—H23D	124.6	C12—C13—N4	121.5 (3)
C24—S3—H23D	111.8	C19—C18—C16	119.4 (6)
O4—S3'—C23	113.4 (5)	C19—C18—H18	120.3
O4—S3'—C24	106.8 (4)	C16—C18—H18	120.3
C23—S3'—C24	95.5 (4)	C18—C19—C20	119.2 (6)
C1—O1—Zn1	122.6 (4)	C18—C19—H19	120.4
C3—O2—H2	109.5	C20—C19—H19	120.4
S3—O4—S3'	57.4 (3)	N5—C20—C19	122.9 (6)
H1W1—O1W—H1W2	108.8	N5—C20—H20	118.5
C7—N1—N2	115.8 (5)	C19—C20—H20	118.5
C7—N1—Zn1	123.3 (4)	S2—C21—H21A	109.5
N2—N1—Zn1	119.9 (4)	S2—C21—H21B	109.5
C8—N2—N1	113.3 (5)	H21A—C21—H21B	109.5
C8—N3—H31	120.0	S2—C21—H21C	109.5
C8—N3—H32	120.0	H21A—C21—H21C	109.5
H31—N3—H32	120.0	H21B—C21—H21C	109.5
C9—N4—C13	119.3 (5)	S2—C22—H22A	109.5
C9—N4—Zn1	128.9 (4)	S2—C22—H22B	109.5
C13—N4—Zn1	111.7 (3)	H22A—C22—H22B	109.5
C20—N5—C17	119.0 (5)	S2—C22—H22C	109.5
C20—N5—Zn1	128.8 (4)	H22A—C22—H22C	109.5
C17—N5—Zn1	112.1 (3)	H22B—C22—H22C	109.5
O1—C1—C2	118.1 (6)	S3—C23—H23A	109.5
O1—C1—C6	124.0 (6)	S3'—C23—H23B	108.6
C2—C1—C6	117.8 (6)	S3—C23—H23B	109.5
C3—C2—C1	121.6 (6)	H23A—C23—H23B	109.5
C3—C2—H2A	119.2	S3'—C23—H23C	139.0
C1—C2—H2A	119.2	S3—C23—H23C	109.5
O2—C3—C2	117.8 (6)	H23A—C23—H23C	109.5
O2—C3—C4	121.4 (6)	H23B—C23—H23C	109.5
C2—C3—C4	120.8 (6)	S3'—C23—H23D	109.5
C5—C4—C3	118.0 (6)	S3'—C23—H23E	109.4
C5—C4—H4	121.0	S3—C23—H23E	132.4
C3—C4—H4	121.0	H23D—C23—H23E	109.5
C4—C5—C6	123.0 (6)	S3'—C23—H23F	109.6
C4—C5—H5	118.5	S3—C23—H23F	115.8
C6—C5—H5	118.5	H23D—C23—H23F	109.5
C5—C6—C1	118.5 (6)	H23E—C23—H23F	109.5
C5—C6—C7	116.5 (6)	S3—C24—H24A	109.5
C1—C6—C7	125.0 (6)	S3'—C24—H24A	110.7
N1—C7—C6	123.8 (6)	S3—C24—H24B	109.5
N1—C7—H7	118.1	S3'—C24—H24B	136.8
C6—C7—H7	118.1	H24A—C24—H24B	109.5
N2—C8—N3	116.1 (6)	S3—C24—H24C	109.5
N2—C8—S1	127.2 (5)	H24A—C24—H24C	109.5
N3—C8—S1	116.7 (5)	H24B—C24—H24C	109.5
N4—C9—C10	121.8 (6)	S3—C24—H24D	99.6
N4—C9—H9	119.1	S3'—C24—H24D	109.8
C10—C9—H9	119.1	S3—C24—H24E	76.3
C11—C10—C9	120.1 (6)	S3'—C24—H24E	109.4
C11—C10—H10	119.9	H24D—C24—H24E	109.5
C9—C10—H10	119.9	S3—C24—H24F	145.6
C10—C11—C12	119.8 (6)	S3'—C24—H24F	109.3
C10—C11—H11	120.1	H24D—C24—H24F	109.5
C12—C11—H11	120.1	H24E—C24—H24F	109.5

O1—Zn1—S1—C8	91.0 (3)	C1—C6—C7—N1	−11.7 (10)
N1—Zn1—S1—C8	12.9 (3)	N1—N2—C8—N3	−178.5 (5)
N5—Zn1—S1—C8	−79.0 (3)	N1—N2—C8—S1	2.1 (8)
N4—Zn1—S1—C8	−159.5 (3)	Zn1—S1—C8—N2	−13.0 (6)
N1—Zn1—O1—C1	−36.1 (5)	Zn1—S1—C8—N3	167.7 (5)
N5—Zn1—O1—C1	58.4 (5)	C13—N4—C9—C10	−0.1 (9)
N4—Zn1—O1—C1	137.9 (5)	Zn1—N4—C9—C10	176.3 (4)
S1—Zn1—O1—C1	−112.0 (5)	N4—C9—C10—C11	−1.0 (10)
C23—S3—O4—S3'	47.1 (4)	C9—C10—C11—C12	0.9 (9)
C24—S3—O4—S3'	−54.3 (4)	C10—C11—C12—C14	−179.9 (5)
C23—S3'—O4—S3	−49.9 (4)	C10—C11—C12—C13	0.2 (7)
C24—S3'—O4—S3	54.0 (4)	C13—C12—C14—C15	0.0
O1—Zn1—N1—C7	29.5 (5)	C11—C12—C14—C15	−179.9 (5)
N5—Zn1—N1—C7	−74.8 (5)	C12—C14—C15—C16	0.0
S1—Zn1—N1—C7	174.3 (5)	C14—C15—C16—C17	0.0
O1—Zn1—N1—N2	−161.9 (5)	C14—C15—C16—C18	177.5 (5)
N5—Zn1—N1—N2	93.9 (5)	C20—N5—C17—C13	176.9 (4)
S1—Zn1—N1—N2	−17.0 (4)	Zn1—N5—C17—C13	−7.0 (4)
C7—N1—N2—C8	−177.1 (6)	C20—N5—C17—C16	−1.7 (6)
Zn1—N1—N2—C8	13.4 (7)	Zn1—N5—C17—C16	174.5 (2)
O1—Zn1—N4—C9	74.9 (5)	C15—C16—C17—N5	178.5 (4)
N5—Zn1—N4—C9	178.4 (5)	C18—C16—C17—N5	0.9 (5)
S1—Zn1—N4—C9	−71.3 (5)	C15—C16—C17—C13	0.0
O1—Zn1—N4—C13	−108.5 (4)	C18—C16—C17—C13	−177.6 (4)
N5—Zn1—N4—C13	−5.0 (3)	N5—C17—C13—C12	−178.5 (4)
S1—Zn1—N4—C13	105.3 (3)	C16—C17—C13—C12	0.0
O1—Zn1—N5—C20	−85.1 (5)	N5—C17—C13—N4	2.6 (5)
N1—Zn1—N5—C20	5.2 (5)	C16—C17—C13—N4	−178.8 (4)
N4—Zn1—N5—C20	−177.9 (6)	C14—C12—C13—C17	0.0
S1—Zn1—N5—C20	88.8 (5)	C11—C12—C13—C17	179.9 (4)
N1—Zn1—N5—C17	−170.5 (3)	C14—C12—C13—N4	178.8 (4)
N4—Zn1—N5—C17	6.3 (3)	C11—C12—C13—N4	−1.3 (5)
S1—Zn1—N5—C17	−86.9 (3)	C9—N4—C13—C17	−180.0 (4)
Zn1—O1—C1—C2	−154.9 (4)	Zn1—N4—C13—C17	3.1 (4)
Zn1—O1—C1—C6	26.7 (8)	C9—N4—C13—C12	1.2 (7)
O1—C1—C2—C3	177.1 (6)	Zn1—N4—C13—C12	−175.7 (2)
C6—C1—C2—C3	−4.4 (9)	C17—C16—C18—C19	0.4 (7)
C1—C2—C3—O2	−179.0 (6)	C15—C16—C18—C19	−177.2 (4)
C1—C2—C3—C4	0.2 (10)	C16—C18—C19—C20	−0.9 (9)
O2—C3—C4—C5	−178.2 (6)	C17—N5—C20—C19	1.1 (9)
C2—C3—C4—C5	2.6 (9)	Zn1—N5—C20—C19	−174.3 (5)
C3—C4—C5—C6	−1.1 (10)	C18—C19—C20—N5	0.2 (10)
C4—C5—C6—C1	−3.1 (9)	O4—S3'—C23—S3	45.0 (4)
C4—C5—C6—C7	176.9 (6)	C24—S3'—C23—S3	−66.0 (3)
O1—C1—C6—C5	−175.9 (6)	O4—S3—C23—S3'	−44.3 (4)
C2—C1—C6—C5	5.7 (9)	C24—S3—C23—S3'	65.9 (3)
O1—C1—C6—C7	4.1 (10)	O4—S3—C24—S3'	49.6 (4)
C2—C1—C6—C7	−174.4 (6)	C23—S3—C24—S3'	−63.8 (3)
N2—N1—C7—C6	179.2 (5)	O4—S3'—C24—S3	−49.1 (4)
Zn1—N1—C7—C6	−11.8 (9)	C23—S3'—C24—S3	67.4 (3)
C5—C6—C7—N1	168.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.84	2.679 (6)	172
N3—H31···N2ⁱ	0.88	2.11	2.984 (8)	174
N3—H32···O4	0.88	2.33	3.074 (8)	143
O1w—H1w1···O1ⁱⁱ	0.84	2.11	2.911 (7)	160
O1w—H1w2···O2	0.84	2.25	3.055 (7)	161

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Zn(C₈H₇N₃O₂S)(C₁₂H₈N₂)]·2C₂H₆OS·H₂O
M_r	629.07
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.3582 (5), 9.8181 (5), 15.2913 (8)
α, β, γ (°)	73.641 (3), 82.482 (4), 88.059 (4)
V (Å³)	1336.5 (1)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.20
Crystal size (mm)	0.05 × 0.01 × 0.01

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.943, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	12760, 6125, 3397
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.211, 0.98
No. of reflections	6125
No. of parameters	344
No. of restraints	27
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.51, −1.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.84	2.679 (6)	172
N3—H31···N2ⁱ	0.88	2.11	2.984 (8)	174
N3—H32···O4	0.88	2.33	3.074 (8)	143
O1w—H1w1···O1ⁱⁱ	0.84	2.11	2.911 (7)	160
O1w—H1w2···O2	0.84	2.25	3.055 (7)	161

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+2, −z+1.

Acknowledgements

We thank the University of Malaya (PJP FS316/2008 C) for supporting this study; KWT thanks the Ministry of Higher Education for an SLAI scholarship.

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