Bis(acetone 4-phenyl­thio­semi­carbazonato-κ2N1,S)zinc(II)

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

doi:10.1107/S1600536809028244

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m969

doi:10.1107/S1600536809028244

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Bis(acetone 4-phenylthiosemicarbazonato-κ²N¹,S)zinc(II)

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 16 July 2009; accepted 17 July 2009; online 22 July 2009)

The Zn^II atom in the title compound, [Zn(C₁₀H₁₂N₃S)₂], is N,S-chelated by the deprotonated Schiff base in a tetrahedral environment. The metal atom lies on a twofold rotation axis that relates one anion to the other. The amino H atom forms an intermolecular N—H⋯π interaction to an aromatic ring.

Related literature

For the two modifications of acetone 4-phenylthiosemicarbazone, see: Jian et al. (2005 ); Venkatraman et al. (2005 ).

Experimental

Crystal data

[Zn(C₁₀H₁₂N₃S)₂]
M_r = 477.94
Monoclinic, C 2/c
a = 23.5203 (5) Å
b = 7.2938 (2) Å
c = 15.1134 (5) Å
β = 122.761 (2)°
V = 2180.3 (1) Å³
Z = 4
Mo Kα radiation
μ = 1.34 mm⁻¹
T = 153 K
0.30 × 0.20 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.690, T_max = 0.936
6983 measured reflections
2488 independent reflections
1896 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.103
S = 1.10
2488 reflections
135 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Cgⁱ	0.86	2.86	3.671 (3)	157
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg is the centroid of the aromatic ring.

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/S1600536809028244/bt5011sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809028244/bt5011Isup2.hkl

checkCIF report

Related literature top

For the two modifications of acetone 4-phenylthiosemicarbazone, see: Jian et al. (2005); Venkatraman et al. (2005). Cg is the centroid of the aromatic ring

Experimental top

Zinc acetate monohydrate (0.22 g, 1 mmol) and 2,4-dihydroxybenzaldehyde 4-phenylthiosemicarbazone (0.29 g, 1 mmol) were heated in ethanol (50 ml) to form [1-(4-hydroxy-2-oxidobenzylidene)-4-phenylthiosemicarbazonato]zinc. The product was recrystallized from acetone, cleaved part of the anion.

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. Anisotropic displacement ellipsoid (Barbour, 2001) plot of Zn(C₁₀H₁₂N₃S)₂ at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.

Bis(acetone 4-phenylthiosemicarbazonato-κ²N¹,S)zinc(II) top

Crystal data top

[Zn(C₁₀H₁₂N₃S)₂]	F(000) = 992
M_r = 477.94	D_x = 1.456 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2390 reflections
a = 23.5203 (5) Å	θ = 3.8–28.0°
b = 7.2938 (2) Å	µ = 1.34 mm⁻¹
c = 15.1134 (5) Å	T = 153 K
β = 122.761 (2)°	Wedge, brown
V = 2180.3 (1) Å³	0.30 × 0.20 × 0.05 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2488 independent reflections
Radiation source: fine-focus sealed tube	1896 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −30→30
T_min = 0.690, T_max = 0.936	k = −9→9
6983 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0387P)² + 4.48P] where P = (F_o² + 2F_c²)/3
2488 reflections	(Δ/σ)_max = 0.001
135 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Zn(C₁₀H₁₂N₃S)₂]	V = 2180.3 (1) Å³
M_r = 477.94	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 23.5203 (5) Å	µ = 1.34 mm⁻¹
b = 7.2938 (2) Å	T = 153 K
c = 15.1134 (5) Å	0.30 × 0.20 × 0.05 mm
β = 122.761 (2)°

Data collection top

Bruker SMART APEX diffractometer	2488 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1896 reflections with I > 2σ(I)
T_min = 0.690, T_max = 0.936	R_int = 0.031
6983 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.10	Δρ_max = 0.40 e Å⁻³
2488 reflections	Δρ_min = −0.45 e Å⁻³
135 parameters

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

	x	y	z	U_iso*/U_eq
Zn1	0.5000	0.30141 (7)	0.2500	0.03064 (17)
S1	0.55393 (4)	0.14771 (13)	0.18550 (8)	0.0501 (3)
N1	0.58756 (10)	0.4440 (3)	0.34189 (19)	0.0245 (5)
N2	0.64335 (10)	0.3888 (3)	0.33788 (19)	0.0253 (5)
N3	0.68276 (11)	0.1943 (4)	0.2634 (2)	0.0336 (6)
H3	0.6712	0.1130	0.2154	0.040*
C1	0.75216 (12)	0.2404 (4)	0.3216 (2)	0.0255 (6)
C2	0.78857 (13)	0.1872 (4)	0.2775 (2)	0.0296 (6)
H2	0.7662	0.1268	0.2113	0.035*
C3	0.85719 (14)	0.2225 (4)	0.3300 (3)	0.0348 (7)
H3A	0.8816	0.1866	0.2993	0.042*
C4	0.89046 (13)	0.3090 (4)	0.4263 (3)	0.0332 (7)
H4	0.9376	0.3330	0.4620	0.040*
C5	0.85427 (13)	0.3606 (4)	0.4703 (2)	0.0289 (6)
H5	0.8770	0.4194	0.5370	0.035*
C6	0.78518 (13)	0.3275 (4)	0.4181 (2)	0.0283 (6)
H6	0.7608	0.3646	0.4486	0.034*
C7	0.63093 (13)	0.2588 (4)	0.2715 (2)	0.0275 (6)
C8	0.59964 (13)	0.5716 (4)	0.4081 (2)	0.0302 (7)
C9	0.66790 (15)	0.6551 (5)	0.4773 (3)	0.0456 (9)
H9A	0.7007	0.5590	0.5196	0.068*
H9B	0.6663	0.7453	0.5241	0.068*
H9C	0.6815	0.7159	0.4338	0.068*
C10	0.54313 (16)	0.6384 (5)	0.4182 (3)	0.0451 (9)
H10A	0.5039	0.5575	0.3784	0.068*
H10B	0.5307	0.7633	0.3903	0.068*
H10C	0.5578	0.6380	0.4925	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0144 (2)	0.0296 (3)	0.0436 (3)	0.000	0.0129 (2)	0.000
S1	0.0171 (3)	0.0539 (6)	0.0665 (7)	−0.0064 (3)	0.0143 (4)	−0.0345 (5)
N1	0.0156 (9)	0.0257 (12)	0.0320 (14)	0.0020 (9)	0.0128 (10)	0.0034 (11)
N2	0.0148 (10)	0.0287 (12)	0.0321 (14)	0.0015 (9)	0.0124 (10)	−0.0009 (11)
N3	0.0196 (11)	0.0373 (14)	0.0408 (16)	−0.0017 (10)	0.0143 (11)	−0.0158 (13)
C1	0.0168 (11)	0.0235 (14)	0.0328 (16)	0.0030 (10)	0.0113 (12)	0.0006 (12)
C2	0.0245 (13)	0.0303 (15)	0.0332 (17)	0.0041 (12)	0.0152 (13)	−0.0016 (14)
C3	0.0241 (14)	0.0429 (18)	0.0432 (19)	0.0065 (13)	0.0221 (14)	0.0041 (16)
C4	0.0189 (12)	0.0373 (17)	0.0398 (18)	0.0023 (12)	0.0136 (13)	0.0086 (15)
C5	0.0216 (13)	0.0264 (14)	0.0310 (17)	0.0007 (11)	0.0092 (12)	0.0040 (13)
C6	0.0219 (13)	0.0307 (16)	0.0328 (17)	0.0034 (11)	0.0152 (13)	0.0004 (13)
C7	0.0171 (12)	0.0299 (15)	0.0328 (17)	−0.0001 (11)	0.0116 (12)	−0.0030 (13)
C8	0.0228 (13)	0.0258 (15)	0.0408 (18)	0.0015 (11)	0.0165 (13)	−0.0037 (14)
C9	0.0297 (15)	0.0361 (19)	0.063 (2)	−0.0023 (13)	0.0197 (17)	−0.0213 (17)
C10	0.0321 (16)	0.046 (2)	0.062 (2)	0.0046 (14)	0.0284 (17)	−0.0102 (18)

Geometric parameters (Å, º) top

Zn1—N1	2.039 (2)	C3—C4	1.376 (5)
Zn1—N1ⁱ	2.039 (2)	C3—H3A	0.9500
Zn1—S1	2.2702 (8)	C4—C5	1.386 (4)
Zn1—S1ⁱ	2.2702 (8)	C4—H4	0.9500
S1—C7	1.754 (3)	C5—C6	1.390 (4)
N1—C8	1.281 (4)	C5—H5	0.9500
N1—N2	1.405 (3)	C6—H6	0.9500
N2—C7	1.294 (4)	C8—C9	1.492 (4)
N3—C7	1.372 (3)	C8—C10	1.499 (4)
N3—C1	1.413 (3)	C9—H9A	0.9800
N3—H3	0.8600	C9—H9B	0.9800
C1—C6	1.381 (4)	C9—H9C	0.9800
C1—C2	1.395 (4)	C10—H10A	0.9800
C2—C3	1.384 (4)	C10—H10B	0.9800
C2—H2	0.9500	C10—H10C	0.9800

N1—Zn1—N1ⁱ	118.66 (13)	C5—C4—H4	120.5
N1—Zn1—S1	87.20 (6)	C4—C5—C6	120.9 (3)
N1ⁱ—Zn1—S1	123.54 (7)	C4—C5—H5	119.6
N1—Zn1—S1ⁱ	123.54 (7)	C6—C5—H5	119.6
N1ⁱ—Zn1—S1ⁱ	87.20 (6)	C1—C6—C5	119.7 (3)
S1—Zn1—S1ⁱ	120.82 (6)	C1—C6—H6	120.1
C7—S1—Zn1	92.67 (9)	C5—C6—H6	120.1
C8—N1—N2	115.1 (2)	N2—C7—N3	118.8 (2)
C8—N1—Zn1	128.17 (17)	N2—C7—S1	128.47 (19)
N2—N1—Zn1	116.57 (17)	N3—C7—S1	112.8 (2)
C7—N2—N1	114.8 (2)	N1—C8—C9	123.0 (2)
C7—N3—C1	130.2 (3)	N1—C8—C10	118.8 (3)
C7—N3—H3	114.9	C9—C8—C10	118.2 (3)
C1—N3—H3	114.9	C8—C9—H9A	109.5
C6—C1—C2	119.5 (2)	C8—C9—H9B	109.5
C6—C1—N3	124.5 (2)	H9A—C9—H9B	109.5
C2—C1—N3	116.0 (3)	C8—C9—H9C	109.5
C3—C2—C1	120.1 (3)	H9A—C9—H9C	109.5
C3—C2—H2	120.0	H9B—C9—H9C	109.5
C1—C2—H2	120.0	C8—C10—H10A	109.5
C4—C3—C2	120.8 (3)	C8—C10—H10B	109.5
C4—C3—H3A	119.6	H10A—C10—H10B	109.5
C2—C3—H3A	119.6	C8—C10—H10C	109.5
C3—C4—C5	119.1 (2)	H10A—C10—H10C	109.5
C3—C4—H4	120.5	H10B—C10—H10C	109.5

N1—Zn1—S1—C7	4.02 (12)	C2—C3—C4—C5	0.0 (5)
N1ⁱ—Zn1—S1—C7	126.96 (13)	C3—C4—C5—C6	−0.6 (4)
S1ⁱ—Zn1—S1—C7	−123.93 (11)	C2—C1—C6—C5	−0.3 (4)
N1ⁱ—Zn1—N1—C8	52.6 (2)	N3—C1—C6—C5	177.8 (3)
S1—Zn1—N1—C8	179.7 (3)	C4—C5—C6—C1	0.7 (4)
S1ⁱ—Zn1—N1—C8	−54.6 (3)	N1—N2—C7—N3	−179.0 (2)
N1ⁱ—Zn1—N1—N2	−132.0 (2)	N1—N2—C7—S1	1.3 (4)
S1—Zn1—N1—N2	−4.85 (18)	C1—N3—C7—N2	3.8 (5)
S1ⁱ—Zn1—N1—N2	120.81 (17)	C1—N3—C7—S1	−176.5 (3)
C8—N1—N2—C7	179.4 (3)	Zn1—S1—C7—N2	−4.3 (3)
Zn1—N1—N2—C7	3.4 (3)	Zn1—S1—C7—N3	176.0 (2)
C7—N3—C1—C6	18.0 (5)	N2—N1—C8—C9	−0.7 (4)
C7—N3—C1—C2	−163.9 (3)	Zn1—N1—C8—C9	174.8 (2)
C6—C1—C2—C3	−0.3 (4)	N2—N1—C8—C10	−179.7 (3)
N3—C1—C2—C3	−178.5 (3)	Zn1—N1—C8—C10	−4.1 (4)
C1—C2—C3—C4	0.4 (5)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cgⁱⁱ	0.86	2.86	3.671 (3)	157

Symmetry code: (ii) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₁₀H₁₂N₃S)₂]
M_r	477.94
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	153
a, b, c (Å)	23.5203 (5), 7.2938 (2), 15.1134 (5)
β (°)	122.761 (2)
V (Å³)	2180.3 (1)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.34
Crystal size (mm)	0.30 × 0.20 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.690, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	6983, 2488, 1896
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.103, 1.10
No. of reflections	2488
No. of parameters	135
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.45

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
N3—H3···Cgⁱ	0.86	2.86	3.671 (3)	157

Symmetry code: (i) −x+3/2, y−1/2, −z+1/2.

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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