[1-(4-Hydr­oxy-2-oxidobenzyl­idene)-4-phenyl­thio­semicarbazonato-κ3N,O,S](1,10-phenanthroline-κ2N,N′)zinc(II)–4,4′-bipyridine (2/1)

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

doi:10.1107/S1600536809026245

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m920

doi:10.1107/S1600536809026245

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[1-(4-Hydroxy-2-oxidobenzylidene)-4-phenylthiosemicarbazonato-κ³N,O,S](1,10-phenanthroline-κ²N,N′)zinc(II)–4,4′-bipyridine (2/1)

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

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

(Received 23 June 2009; accepted 6 July 2009; online 15 July 2009)

The Zn^II atom in the title compound, [Zn(C₁₄H₁₁N₃O₂S)(C₁₂H₈N₂)]·0.5C₁₀H₈N₂, is N,N′-chelated by the N-heterocycle and N,O,S-chelated by the deprotonated Schiff base in a square-pyramidal environment. The hydroxy group of the Schiff base is a hydrogen-bond donor to 4,4′-bipyridine, which is located about a center of inversion, resulting in the formation of a supramolecular trimeric unit.

Related literature

For [1-(4-hydroxy-2-oxidobenzylidene)-4-phenylthiosemicarbazonato](1,10-phenanthroline)zinc dimethyl sulfoxide disolvate hydrate, see: Tan et al. (2009 ). For other N-heterocyclic adducts of zinc 1-(2-oxidobenzylidene)-4-phenylthiosemicarbonates, see: Deng et al. (2007 ); Seena & Kurup (2008 ).

Experimental

Crystal data

[Zn(C₁₄H₁₁N₃O₂S)(C₁₂H₈N₂)]·0.5C₁₀H₈N₂
M_r = 608.98
Monoclinic, P 2₁ /c
a = 11.6372 (6) Å
b = 9.8376 (5) Å
c = 23.288 (1) Å
β = 92.417 (3)°
V = 2663.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 140 K
0.10 × 0.04 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.903, T_max = 0.979
14867 measured reflections
4681 independent reflections
2918 reflections with I > 2σ(I)
R_int = 0.089

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.117
S = 0.98
4681 reflections
378 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N6	0.84 (5)	2.01 (5)	2.839 (6)	168 (6)

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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/S1600536809026245/tk2484sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026245/tk2484Isup2.hkl

checkCIF report

Related literature top

For the [1-(4-hydroxy-2-oxidobenzylidene)-4-phenylthiosemicarbonato](1,10-phenanthroline)zinc DMSO hydrate, see: Tan et al. (2009). For other N-heterocyclic adducts of zinc 1-(2-oxidobenzylidene)-4-phenylthiosemicarbonates, see: Deng et al. (2007); Seena & Kurup (2008).

Experimental top

Zinc acetate monohydrate (0.22 g, 1 mmol), 2,4-dihydroxybenzaldehyde 4-phenylthiosemicarbazone (0.29 g, 1 mmol) and 1,10-phenanthroline (0.18 g, 1 mmol) were heated in ethanol (50 ml). The product was isolated and reacted with 4,4'-bipyridine (0.15 g, 1 mmol) in DMF to give a yellow solution. A small amount of tiny crystals were isolated when the mixture was set aside for a week.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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)(C₁₄H₁₁N₃O₂S)^.0.5C₁₀H₈N₂ at the 70% probability level. Only atoms comprising the asymmetric unit are labelled; the 4,4'-bipyridine molecule is located about a center of inversion. Hydrogen atoms are drawn as spheres of arbitrary radii.

[1-(4-Hydroxy-2-oxidobenzylidene)-4-phenylthiosemicarbazonato- κ³N,O,S](1,10-phenanthroline- κ²N,N')zinc(II)–4,4'-bipyridine (2/1) top

Crystal data top

[Zn(C₁₄H₁₁N₃O₂S)(C₁₂H₈N₂)]·0.5C₁₀H₈N₂	F(000) = 1252
M_r = 608.98	D_x = 1.519 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1335 reflections
a = 11.6372 (6) Å	θ = 2.4–20.2°
b = 9.8376 (5) Å	µ = 1.04 mm⁻¹
c = 23.288 (1) Å	T = 140 K
β = 92.417 (3)°	Prism, yellow
V = 2663.7 (2) Å³	0.10 × 0.04 × 0.02 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	4681 independent reflections
Radiation source: fine-focus sealed tube	2918 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.089
ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.903, T_max = 0.979	k = −11→11
14867 measured reflections	l = −27→27

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0515P)²] where P = (F_o² + 2F_c²)/3
4681 reflections	(Δ/σ)_max = 0.001
378 parameters	Δρ_max = 0.38 e Å⁻³
2 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Zn(C₁₄H₁₁N₃O₂S)(C₁₂H₈N₂)]·0.5C₁₀H₈N₂	V = 2663.7 (2) Å³
M_r = 608.98	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.6372 (6) Å	µ = 1.04 mm⁻¹
b = 9.8376 (5) Å	T = 140 K
c = 23.288 (1) Å	0.10 × 0.04 × 0.02 mm
β = 92.417 (3)°

Data collection top

Bruker SMART APEX diffractometer	4681 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2918 reflections with I > 2σ(I)
T_min = 0.903, T_max = 0.979	R_int = 0.089
14867 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	2 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.38 e Å⁻³
4681 reflections	Δρ_min = −0.40 e Å⁻³
378 parameters

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

	x	y	z	U_iso*/U_eq
Zn1	0.67107 (4)	0.62440 (5)	0.56348 (2)	0.02152 (16)
S1	0.82614 (10)	0.50702 (12)	0.52318 (5)	0.0236 (3)
O1	0.5106 (2)	0.6211 (3)	0.58865 (12)	0.0257 (7)
O2	0.2250 (3)	0.7085 (4)	0.72356 (16)	0.0416 (9)
H2	0.188 (5)	0.738 (6)	0.6945 (16)	0.07 (2)*
N1	0.7189 (3)	0.5107 (4)	0.63475 (15)	0.0216 (9)
N2	0.8294 (3)	0.4544 (4)	0.63924 (15)	0.0256 (9)
N3	0.9923 (3)	0.4067 (4)	0.59142 (16)	0.0263 (10)
H3	1.029 (3)	0.427 (5)	0.5604 (12)	0.036 (15)*
N4	0.6154 (3)	0.7367 (4)	0.48877 (15)	0.0218 (9)
N5	0.7320 (3)	0.8198 (4)	0.58516 (15)	0.0222 (9)
N6	0.1202 (3)	0.8459 (4)	0.62781 (18)	0.0371 (11)
C1	0.4781 (4)	0.6105 (5)	0.64195 (18)	0.0242 (10)
C2	0.3686 (4)	0.6607 (5)	0.6553 (2)	0.0272 (12)
H2A	0.3205	0.6984	0.6254	0.033*
C3	0.3294 (4)	0.6565 (5)	0.7103 (2)	0.0327 (13)
C4	0.3969 (4)	0.5966 (5)	0.7542 (2)	0.0380 (14)
H4	0.3703	0.5929	0.7922	0.046*
C5	0.5007 (4)	0.5436 (6)	0.7423 (2)	0.0364 (13)
H5A	0.5445	0.5004	0.7724	0.044*
C6	0.5469 (4)	0.5492 (5)	0.68749 (19)	0.0261 (11)
C7	0.6604 (4)	0.4965 (5)	0.68069 (19)	0.0259 (11)
H7	0.6954	0.4477	0.7120	0.031*
C8	0.8810 (4)	0.4554 (4)	0.59072 (19)	0.0217 (11)
C9	1.0617 (4)	0.3594 (5)	0.63889 (19)	0.0237 (11)
C10	1.0185 (4)	0.2924 (5)	0.68556 (19)	0.0281 (12)
H10	0.9378	0.2823	0.6887	0.034*
C11	1.0937 (4)	0.2399 (5)	0.7278 (2)	0.0353 (13)
H11	1.0642	0.1921	0.7594	0.042*
C12	1.2121 (4)	0.2566 (5)	0.7242 (2)	0.0365 (13)
H12	1.2633	0.2211	0.7533	0.044*
C13	1.2540 (4)	0.3249 (5)	0.6781 (2)	0.0376 (14)
H13	1.3346	0.3377	0.6757	0.045*
C14	1.1812 (4)	0.3749 (5)	0.63541 (19)	0.0276 (11)
H14	1.2116	0.4202	0.6034	0.033*
C15	0.5563 (4)	0.6950 (5)	0.44181 (19)	0.0253 (11)
H15	0.5412	0.6006	0.4374	0.030*
C16	0.5157 (4)	0.7832 (6)	0.3990 (2)	0.0365 (14)
H16	0.4727	0.7499	0.3664	0.044*
C17	0.5390 (4)	0.9194 (6)	0.4048 (2)	0.0331 (13)
H17	0.5125	0.9813	0.3759	0.040*
C18	0.6018 (4)	0.9676 (5)	0.45336 (19)	0.0281 (12)
C19	0.6260 (4)	1.1078 (5)	0.4628 (2)	0.0367 (13)
H19	0.5970	1.1731	0.4359	0.044*
C20	0.6895 (4)	1.1493 (5)	0.5093 (2)	0.0380 (14)
H20	0.7080	1.2429	0.5136	0.046*
C21	0.7297 (4)	1.0533 (5)	0.5525 (2)	0.0307 (12)
C22	0.7924 (4)	1.0906 (5)	0.6035 (2)	0.0345 (13)
H22	0.8121	1.1830	0.6104	0.041*
C23	0.8244 (4)	0.9928 (5)	0.6427 (2)	0.0339 (13)
H23	0.8681	1.0161	0.6767	0.041*
C24	0.7919 (4)	0.8584 (5)	0.63216 (19)	0.0294 (12)
H24	0.8137	0.7912	0.6599	0.035*
C25	0.7022 (4)	0.9150 (4)	0.54532 (19)	0.0202 (10)
C26	0.6384 (4)	0.8709 (5)	0.49423 (18)	0.0212 (10)
C27	0.1329 (4)	0.9783 (5)	0.6168 (2)	0.0398 (14)
H27	0.1749	1.0319	0.6443	0.048*
C28	0.0887 (4)	1.0418 (5)	0.5679 (2)	0.0343 (13)
H28	0.1017	1.1361	0.5624	0.041*
C29	0.0256 (4)	0.9682 (5)	0.52677 (19)	0.0281 (12)
C30	0.0133 (5)	0.8298 (5)	0.5379 (2)	0.0347 (13)
H30	−0.0280	0.7736	0.5110	0.042*
C31	0.0606 (4)	0.7748 (5)	0.5876 (2)	0.0378 (13)
H31	0.0504	0.6802	0.5938	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0209 (3)	0.0191 (3)	0.0250 (3)	0.0013 (3)	0.0065 (2)	0.0033 (3)
S1	0.0228 (7)	0.0254 (7)	0.0230 (6)	0.0049 (5)	0.0050 (5)	0.0021 (5)
O1	0.0252 (18)	0.0252 (17)	0.0272 (17)	0.0055 (16)	0.0083 (14)	0.0099 (16)
O2	0.028 (2)	0.058 (3)	0.041 (2)	0.0082 (19)	0.0113 (19)	−0.001 (2)
N1	0.019 (2)	0.020 (2)	0.026 (2)	0.0015 (17)	0.0051 (17)	−0.0013 (17)
N2	0.022 (2)	0.029 (2)	0.026 (2)	0.0051 (18)	0.0033 (18)	0.0001 (18)
N3	0.025 (2)	0.033 (3)	0.022 (2)	0.0056 (19)	0.0056 (19)	0.0049 (19)
N4	0.024 (2)	0.020 (2)	0.022 (2)	0.0007 (17)	0.0064 (17)	−0.0015 (17)
N5	0.022 (2)	0.025 (2)	0.020 (2)	0.0028 (17)	0.0074 (18)	0.0015 (17)
N6	0.024 (2)	0.044 (3)	0.044 (3)	0.005 (2)	0.010 (2)	−0.012 (2)
C1	0.022 (3)	0.023 (3)	0.028 (3)	−0.006 (2)	0.011 (2)	−0.005 (2)
C2	0.021 (3)	0.033 (3)	0.028 (3)	−0.001 (2)	0.006 (2)	0.004 (2)
C3	0.018 (3)	0.044 (3)	0.037 (3)	−0.002 (2)	0.009 (2)	−0.005 (2)
C4	0.032 (3)	0.062 (4)	0.020 (3)	0.000 (3)	0.009 (2)	−0.003 (3)
C5	0.025 (3)	0.058 (4)	0.027 (3)	0.000 (3)	0.001 (2)	−0.001 (3)
C6	0.022 (3)	0.035 (3)	0.022 (2)	−0.003 (2)	0.002 (2)	−0.004 (2)
C7	0.029 (3)	0.029 (3)	0.020 (2)	0.001 (2)	0.004 (2)	0.004 (2)
C8	0.020 (3)	0.017 (3)	0.028 (3)	0.000 (2)	0.003 (2)	0.000 (2)
C9	0.024 (3)	0.023 (3)	0.025 (2)	0.008 (2)	0.001 (2)	−0.002 (2)
C10	0.027 (3)	0.026 (3)	0.031 (3)	0.007 (2)	−0.003 (2)	0.002 (2)
C11	0.036 (3)	0.043 (3)	0.027 (3)	0.010 (3)	0.001 (2)	0.002 (3)
C12	0.032 (3)	0.051 (4)	0.026 (3)	0.013 (3)	−0.002 (2)	−0.002 (3)
C13	0.026 (3)	0.050 (4)	0.036 (3)	0.007 (3)	−0.001 (3)	−0.009 (3)
C14	0.027 (3)	0.028 (3)	0.028 (2)	0.001 (2)	0.005 (2)	−0.003 (2)
C15	0.024 (3)	0.026 (3)	0.026 (3)	0.002 (2)	0.007 (2)	−0.007 (2)
C16	0.027 (3)	0.064 (4)	0.019 (3)	0.008 (3)	0.001 (2)	−0.006 (3)
C17	0.028 (3)	0.050 (4)	0.022 (3)	0.013 (3)	0.010 (2)	0.012 (2)
C18	0.027 (3)	0.032 (3)	0.027 (3)	0.009 (2)	0.012 (2)	0.008 (2)
C19	0.025 (3)	0.033 (3)	0.052 (3)	0.010 (3)	0.015 (3)	0.021 (3)
C20	0.028 (3)	0.021 (3)	0.067 (4)	0.005 (2)	0.022 (3)	0.009 (3)
C21	0.024 (3)	0.029 (3)	0.040 (3)	0.002 (2)	0.016 (2)	−0.005 (3)
C22	0.024 (3)	0.029 (3)	0.052 (3)	−0.007 (2)	0.015 (3)	−0.016 (3)
C23	0.028 (3)	0.037 (3)	0.037 (3)	−0.009 (3)	0.005 (2)	−0.015 (3)
C24	0.027 (3)	0.037 (3)	0.025 (3)	0.000 (2)	0.006 (2)	−0.001 (2)
C25	0.017 (2)	0.014 (2)	0.030 (3)	−0.0016 (19)	0.012 (2)	−0.001 (2)
C26	0.018 (2)	0.020 (2)	0.026 (2)	0.007 (2)	0.0075 (19)	−0.001 (2)
C27	0.028 (3)	0.038 (3)	0.053 (4)	0.002 (3)	−0.002 (3)	−0.022 (3)
C28	0.032 (3)	0.024 (3)	0.047 (3)	0.002 (2)	0.002 (3)	−0.012 (3)
C29	0.018 (3)	0.029 (3)	0.038 (3)	−0.003 (2)	0.011 (2)	−0.012 (2)
C30	0.039 (3)	0.026 (3)	0.041 (3)	−0.006 (2)	0.009 (3)	−0.007 (2)
C31	0.035 (3)	0.028 (3)	0.051 (3)	−0.007 (3)	0.011 (3)	−0.003 (3)

Geometric parameters (Å, º) top

Zn1—O1	1.981 (3)	C11—C12	1.394 (7)
Zn1—N1	2.058 (4)	C11—H11	0.9500
Zn1—N5	2.103 (4)	C12—C13	1.373 (7)
Zn1—N4	2.138 (3)	C12—H12	0.9500
Zn1—S1	2.3692 (12)	C13—C14	1.370 (6)
S1—C8	1.748 (4)	C13—H13	0.9500
O1—C1	1.317 (5)	C14—H14	0.9500
O2—C3	1.365 (6)	C15—C16	1.389 (6)
O2—H2	0.84 (5)	C15—H15	0.9500
N1—C7	1.299 (5)	C16—C17	1.373 (7)
N1—N2	1.401 (5)	C16—H16	0.9500
N2—C8	1.302 (5)	C17—C18	1.402 (7)
N3—C8	1.380 (6)	C17—H17	0.9500
N3—C9	1.419 (6)	C18—C26	1.399 (6)
N3—H3	0.88 (3)	C18—C19	1.423 (7)
N4—C15	1.332 (5)	C19—C20	1.347 (7)
N4—C26	1.352 (6)	C19—H19	0.9500
N5—C24	1.328 (5)	C20—C21	1.445 (7)
N5—C25	1.353 (5)	C20—H20	0.9500
N6—C27	1.336 (7)	C21—C25	1.406 (6)
N6—C31	1.340 (6)	C21—C22	1.414 (7)
C1—C2	1.413 (6)	C22—C23	1.368 (7)
C1—C6	1.434 (6)	C22—H22	0.9500
C2—C3	1.379 (6)	C23—C24	1.394 (7)
C2—H2A	0.9500	C23—H23	0.9500
C3—C4	1.392 (7)	C24—H24	0.9500
C4—C5	1.356 (7)	C25—C26	1.442 (6)
C4—H4	0.9500	C27—C28	1.379 (7)
C5—C6	1.406 (6)	C27—H27	0.9500
C5—H5A	0.9500	C28—C29	1.386 (6)
C6—C7	1.435 (6)	C28—H28	0.9500
C7—H7	0.9500	C29—C30	1.394 (7)
C9—C10	1.384 (6)	C29—C29ⁱ	1.495 (9)
C9—C14	1.405 (6)	C30—C31	1.371 (7)
C10—C11	1.388 (6)	C30—H30	0.9500
C10—H10	0.9500	C31—H31	0.9500

O1—Zn1—N1	88.77 (13)	C13—C12—C11	119.3 (5)
O1—Zn1—N5	104.84 (13)	C13—C12—H12	120.3
N1—Zn1—N5	103.07 (14)	C11—C12—H12	120.3
O1—Zn1—N4	89.56 (13)	C14—C13—C12	120.9 (5)
N1—Zn1—N4	177.58 (14)	C14—C13—H13	119.6
N5—Zn1—N4	79.07 (14)	C12—C13—H13	119.6
O1—Zn1—S1	148.49 (10)	C13—C14—C9	120.2 (5)
N1—Zn1—S1	82.54 (10)	C13—C14—H14	119.9
N5—Zn1—S1	106.62 (10)	C9—C14—H14	119.9
N4—Zn1—S1	98.00 (10)	N4—C15—C16	123.0 (5)
C8—S1—Zn1	92.34 (15)	N4—C15—H15	118.5
C1—O1—Zn1	126.3 (3)	C16—C15—H15	118.5
C3—O2—H2	113 (4)	C17—C16—C15	118.6 (5)
C7—N1—N2	114.0 (4)	C17—C16—H16	120.7
C7—N1—Zn1	126.1 (3)	C15—C16—H16	120.7
N2—N1—Zn1	119.4 (3)	C16—C17—C18	120.2 (5)
C8—N2—N1	112.8 (4)	C16—C17—H17	119.9
C8—N3—C9	128.7 (4)	C18—C17—H17	119.9
C8—N3—H3	114 (3)	C26—C18—C17	116.9 (4)
C9—N3—H3	116 (3)	C26—C18—C19	120.0 (5)
C15—N4—C26	118.1 (4)	C17—C18—C19	123.0 (5)
C15—N4—Zn1	129.6 (3)	C20—C19—C18	121.1 (5)
C26—N4—Zn1	112.1 (3)	C20—C19—H19	119.4
C24—N5—C25	118.6 (4)	C18—C19—H19	119.4
C24—N5—Zn1	128.2 (3)	C19—C20—C21	120.8 (5)
C25—N5—Zn1	113.2 (3)	C19—C20—H20	119.6
C27—N6—C31	115.6 (5)	C21—C20—H20	119.6
O1—C1—C2	118.5 (4)	C25—C21—C22	117.3 (5)
O1—C1—C6	123.8 (4)	C25—C21—C20	118.9 (5)
C2—C1—C6	117.7 (4)	C22—C21—C20	123.8 (5)
C3—C2—C1	122.0 (4)	C23—C22—C21	119.6 (5)
C3—C2—H2A	119.0	C23—C22—H22	120.2
C1—C2—H2A	119.0	C21—C22—H22	120.2
O2—C3—C2	122.1 (4)	C22—C23—C24	119.0 (5)
O2—C3—C4	118.2 (4)	C22—C23—H23	120.5
C2—C3—C4	119.7 (4)	C24—C23—H23	120.5
C5—C4—C3	119.5 (4)	N5—C24—C23	123.0 (5)
C5—C4—H4	120.2	N5—C24—H24	118.5
C3—C4—H4	120.2	C23—C24—H24	118.5
C4—C5—C6	123.3 (5)	N5—C25—C21	122.5 (4)
C4—C5—H5A	118.4	N5—C25—C26	117.8 (4)
C6—C5—H5A	118.4	C21—C25—C26	119.8 (4)
C5—C6—C1	117.7 (4)	N4—C26—C18	123.1 (4)
C5—C6—C7	118.3 (4)	N4—C26—C25	117.6 (4)
C1—C6—C7	123.9 (4)	C18—C26—C25	119.2 (4)
N1—C7—C6	124.6 (4)	N6—C27—C28	124.0 (5)
N1—C7—H7	117.7	N6—C27—H27	118.0
C6—C7—H7	117.7	C28—C27—H27	118.0
N2—C8—N3	117.0 (4)	C27—C28—C29	120.2 (5)
N2—C8—S1	128.2 (4)	C27—C28—H28	119.9
N3—C8—S1	114.7 (3)	C29—C28—H28	119.9
C10—C9—C14	119.4 (4)	C28—C29—C30	115.9 (5)
C10—C9—N3	123.7 (4)	C28—C29—C29ⁱ	122.6 (5)
C14—C9—N3	116.8 (4)	C30—C29—C29ⁱ	121.5 (5)
C9—C10—C11	119.6 (5)	C31—C30—C29	120.1 (5)
C9—C10—H10	120.2	C31—C30—H30	119.9
C11—C10—H10	120.2	C29—C30—H30	119.9
C10—C11—C12	120.6 (5)	N6—C31—C30	124.1 (5)
C10—C11—H11	119.7	N6—C31—H31	117.9
C12—C11—H11	119.7	C30—C31—H31	117.9

O1—Zn1—S1—C8	−90.8 (2)	C8—N3—C9—C10	33.2 (7)
N1—Zn1—S1—C8	−15.58 (18)	C8—N3—C9—C14	−151.2 (5)
N5—Zn1—S1—C8	85.89 (18)	C14—C9—C10—C11	−0.9 (7)
N4—Zn1—S1—C8	166.81 (18)	N3—C9—C10—C11	174.7 (4)
N1—Zn1—O1—C1	27.9 (4)	C9—C10—C11—C12	1.4 (7)
N5—Zn1—O1—C1	−75.3 (4)	C10—C11—C12—C13	−0.5 (8)
N4—Zn1—O1—C1	−153.8 (4)	C11—C12—C13—C14	−0.9 (8)
S1—Zn1—O1—C1	101.5 (4)	C12—C13—C14—C9	1.4 (7)
O1—Zn1—N1—C7	−18.6 (4)	C10—C9—C14—C13	−0.5 (7)
N5—Zn1—N1—C7	86.4 (4)	N3—C9—C14—C13	−176.3 (4)
S1—Zn1—N1—C7	−168.2 (4)	C26—N4—C15—C16	−1.2 (7)
O1—Zn1—N1—N2	169.6 (3)	Zn1—N4—C15—C16	173.0 (3)
N5—Zn1—N1—N2	−85.5 (3)	N4—C15—C16—C17	1.1 (7)
S1—Zn1—N1—N2	19.9 (3)	C15—C16—C17—C18	−0.5 (7)
C7—N1—N2—C8	172.2 (4)	C16—C17—C18—C26	0.2 (7)
Zn1—N1—N2—C8	−14.9 (5)	C16—C17—C18—C19	−178.2 (5)
O1—Zn1—N4—C15	−73.6 (4)	C26—C18—C19—C20	3.6 (7)
N5—Zn1—N4—C15	−178.8 (4)	C17—C18—C19—C20	−178.1 (5)
S1—Zn1—N4—C15	75.7 (4)	C18—C19—C20—C21	−3.3 (7)
O1—Zn1—N4—C26	101.0 (3)	C19—C20—C21—C25	0.3 (7)
N5—Zn1—N4—C26	−4.3 (3)	C19—C20—C21—C22	−177.2 (5)
S1—Zn1—N4—C26	−109.7 (3)	C25—C21—C22—C23	0.8 (7)
O1—Zn1—N5—C24	95.4 (4)	C20—C21—C22—C23	178.3 (4)
N1—Zn1—N5—C24	3.2 (4)	C21—C22—C23—C24	−1.5 (7)
N4—Zn1—N5—C24	−178.0 (4)	C25—N5—C24—C23	0.9 (7)
S1—Zn1—N5—C24	−82.8 (4)	Zn1—N5—C24—C23	−177.7 (3)
O1—Zn1—N5—C25	−83.3 (3)	C22—C23—C24—N5	0.7 (7)
N1—Zn1—N5—C25	−175.5 (3)	C24—N5—C25—C21	−1.7 (6)
N4—Zn1—N5—C25	3.3 (3)	Zn1—N5—C25—C21	177.1 (3)
S1—Zn1—N5—C25	98.5 (3)	C24—N5—C25—C26	179.2 (4)
Zn1—O1—C1—C2	156.0 (3)	Zn1—N5—C25—C26	−2.0 (5)
Zn1—O1—C1—C6	−24.9 (6)	C22—C21—C25—N5	0.9 (7)
O1—C1—C2—C3	−178.3 (4)	C20—C21—C25—N5	−176.8 (4)
C6—C1—C2—C3	2.5 (7)	C22—C21—C25—C26	180.0 (4)
C1—C2—C3—O2	178.1 (4)	C20—C21—C25—C26	2.3 (7)
C1—C2—C3—C4	−2.6 (8)	C15—N4—C26—C18	0.9 (6)
O2—C3—C4—C5	179.7 (5)	Zn1—N4—C26—C18	−174.4 (3)
C2—C3—C4—C5	0.3 (8)	C15—N4—C26—C25	179.8 (4)
C3—C4—C5—C6	2.0 (8)	Zn1—N4—C26—C25	4.6 (5)
C4—C5—C6—C1	−2.1 (8)	C17—C18—C26—N4	−0.3 (6)
C4—C5—C6—C7	176.5 (5)	C19—C18—C26—N4	178.0 (4)
O1—C1—C6—C5	−179.3 (4)	C17—C18—C26—C25	−179.3 (4)
C2—C1—C6—C5	−0.2 (7)	C19—C18—C26—C25	−0.9 (6)
O1—C1—C6—C7	2.2 (7)	N5—C25—C26—N4	−1.8 (6)
C2—C1—C6—C7	−178.7 (4)	C21—C25—C26—N4	179.0 (4)
N2—N1—C7—C6	177.8 (4)	N5—C25—C26—C18	177.2 (4)
Zn1—N1—C7—C6	5.5 (7)	C21—C25—C26—C18	−2.0 (6)
C5—C6—C7—N1	−170.8 (5)	C31—N6—C27—C28	0.2 (7)
C1—C6—C7—N1	7.7 (8)	N6—C27—C28—C29	0.8 (8)
N1—N2—C8—N3	177.6 (4)	C27—C28—C29—C30	−1.4 (7)
N1—N2—C8—S1	−4.2 (6)	C27—C28—C29—C29ⁱ	179.3 (5)
C9—N3—C8—N2	−2.7 (7)	C28—C29—C30—C31	1.1 (7)
C9—N3—C8—S1	178.8 (4)	C29ⁱ—C29—C30—C31	−179.6 (5)
Zn1—S1—C8—N2	16.5 (4)	C27—N6—C31—C30	−0.5 (7)
Zn1—S1—C8—N3	−165.2 (3)	C29—C30—C31—N6	−0.1 (8)

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N6	0.84 (5)	2.01 (5)	2.839 (6)	168 (6)

Experimental details

Crystal data
Chemical formula	[Zn(C₁₄H₁₁N₃O₂S)(C₁₂H₈N₂)]·0.5C₁₀H₈N₂
M_r	608.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	140
a, b, c (Å)	11.6372 (6), 9.8376 (5), 23.288 (1)
β (°)	92.417 (3)
V (Å³)	2663.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.10 × 0.04 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.903, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	14867, 4681, 2918
R_int	0.089
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.117, 0.98
No. of reflections	4681
No. of parameters	378
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.40

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), 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···N6	0.84 (5)	2.01 (5)	2.839 (6)	168 (6)

Acknowledgements

We thank the University of Malaya (PJP FS316/2008 C) and MOSTI (ESc 02-02-11-SF0033) for supporting this study. KWT thanks the Ministry of Higher Education for a SLAI scholarship.

References

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