(Thio­cyanato-κN)bis­(thio­semicarbazide-κS)copper(I)

Jia, L.; Ma, S.; Li, D.

doi:10.1107/S1600536808013068

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m796

doi:10.1107/S1600536808013068

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(Thiocyanato-κN)bis(thiosemicarbazide-κS)copper(I)

Li Jia,^a Shouxin Ma ^b and Dacheng Li ^c ^*

^aLiaoCheng Vocational and Technical College, Liaocheng, Shandong 252000, People's Republic of China, ^bShandong Vocational Animal Science and Veterinary College, Weifang, Shandong 261000, People's Republic of China, and ^cSchool of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: lidacheng62@lcu.edu.cn

(Received 11 April 2008; accepted 3 May 2008; online 10 May 2008)

In the title complex, [Cu(CH₅N₃S)₂(NCS)], the non-H part of the molecule is strictly planar, lying on the mirror plane at y = 0.25. The Cu atom lies at the centre of a triangle formed by the coordination of three monodentate groups, viz. two thiosemicarbazide ligands and one NCS⁻ anion. Weak intermolecular N—H⋯S interactions generate a two-dimensional network.

Related literature

For related thiosemicarbazide metal complexes, see: Capacchi et al. (1968 ). For related literature, see: Chattopadhyay et al. (1991 ).

Experimental

Crystal data

[Cu(CH₅N₃S)₂(NCS)]
M_r = 303.90
Orthorhombic, P n m a
a = 11.488 (2) Å
b = 6.6085 (12) Å
c = 14.650 (3) Å
V = 1112.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.50 mm⁻¹
T = 298 (2) K
0.38 × 0.27 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.44, T_max = 0.55
5593 measured reflections
1077 independent reflections
947 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.080
S = 1.05
1077 reflections
86 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S3ⁱ	0.86	2.64	3.485 (3)	167
N1—H1B⋯N3ⁱ	0.86	2.14	2.998 (4)	177
N2—H2⋯N7	0.86	2.24	3.093 (4)	175
N3—H3A⋯S2ⁱⁱ	0.89	2.81	3.5481 (11)	141
N3—H3B⋯S2ⁱⁱⁱ	0.89	2.72	3.5481 (11)	155
N4—H4A⋯S2^iv	0.86	2.65	3.501 (3)	170
N4—H4B⋯N7	0.86	2.32	3.161 (4)	167
N5—H5⋯S3^v	0.86	2.64	3.342 (3)	140
N6—H6A⋯S1^vi	0.89	2.88	3.5144 (12)	130
N6—H6B⋯S1^vii	0.89	2.75	3.5144 (11)	144
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013068/bg2183sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013068/bg2183Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazide can behave as a chelating agent(Chattopadhyay et al.,1991) or as a monodentate ligand(Capacchi et al., 1968). Among the different N,S donors studies,thiosemicarbazides and thiosemicarbazines are of special interest as both of these free ligands and their copper complexes exhibit a variety of biological activities including antitumour activity(Chattopadhyay et al.,1991). In this paper, Cu(CH₅N₃S)₂(NCS) was synthesized by the reaction of CuCl₂.6H₂O, thiosemicarbazide and NaSCN at room temperature and the structure of the resulting complex is presented herein. The non-H part of the molecule is strictly planar, lying on the mirror plane at y=0.25. The Cu atom lies at the centre of a planar triangle formed by coordination of three monodentate groups, two thiosemicarbazide ligands and one NCS anion (Fig. 1). The Cu—S bond length (2.2415 (13) Å) is comparable to those in [Cu(SC(NH₂)NHNH₂)Cl₂] (2.266 (1) Å,Chattopadhyay et al., 1991), while the Cu—N bond is shorter than the corresponding value therein (2.002 (4)Å).

In the crystal structure, weak intermolecular C—H···S interactions determine a two-dimensional network.

Related literature top

For related thiosemicarbazide metal complexes, see: Capacchi et al. (1968). For related literature, see: Chattopadhyay et al. (1991).

Experimental top

Copper chloride dihydrate (0.3 mmol 51.2 mg) was dissolved in absolute methanol (10 ml), and was added dropwise to a solution of an equate ligand thiosemicarbazide in MeOH (10 ml). The solution was stirred for 10 minutes, then NaSCN was added. The solution became bottle-green. The mother liquid was placed at room temperature, and single crystals were obtained on standing. Elemental analysis for C₃H₁₀Cu N₇S₃ calculated: C 36.03, H 10.08, N %; found: C 36.12, H 10.26, N 98.05%.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The crystal structure of the title compound showing the atomic numbering and 30% probability displacement ellipsoids. N-bound H atoms have been omitted for clarity.

(Thiocyanato-κN)bis(thiosemicarbazide-κS)copper(I) top

Crystal data top

[Cu(CH₅N₃S)₂(NCS)]	F(000) = 616
M_r = 303.90	D_x = 1.815 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3130 reflections
a = 11.488 (2) Å	θ = 2.3–28.2°
b = 6.6085 (12) Å	µ = 2.50 mm⁻¹
c = 14.650 (3) Å	T = 298 K
V = 1112.2 (4) Å³	Block, black
Z = 4	0.38 × 0.27 × 0.24 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1077 independent reflections
Radiation source: fine-focus sealed tube	947 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.44, T_max = 0.55	k = −7→7
5593 measured reflections	l = −17→10

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)] = 0.029	H-atom parameters constrained
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0469P)² + 0.712P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1077 reflections	Δρ_max = 0.67 e Å⁻³
86 parameters	Δρ_min = −0.54 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0072 (9)

Crystal data top

[Cu(CH₅N₃S)₂(NCS)]	V = 1112.2 (4) Å³
M_r = 303.90	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 11.488 (2) Å	µ = 2.50 mm⁻¹
b = 6.6085 (12) Å	T = 298 K
c = 14.650 (3) Å	0.38 × 0.27 × 0.24 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1077 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	947 reflections with I > 2σ(I)
T_min = 0.44, T_max = 0.55	R_int = 0.021
5593 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.05	Δρ_max = 0.67 e Å⁻³
1077 reflections	Δρ_min = −0.54 e Å⁻³
86 parameters

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	Occ. (<1)
Cu1	0.28439 (4)	0.2500	0.53244 (3)	0.0689 (3)
N1	0.1200 (2)	0.2500	0.25507 (19)	0.0338 (6)
H1A	0.1489	0.2500	0.2009	0.041*
H1B	0.0458	0.2500	0.2625	0.041*
N2	0.3047 (2)	0.2500	0.31376 (19)	0.0361 (7)
H2	0.3483	0.2500	0.3615	0.043*
N3	0.3600 (2)	0.2500	0.22780 (18)	0.0348 (6)
H3A	0.3244	0.1616	0.1914	0.052*	0.50
H3B	0.3555	0.3732	0.2035	0.052*	0.50
N4	0.4655 (2)	0.2500	0.7081 (2)	0.0457 (8)
H4A	0.5262	0.2500	0.7423	0.055*
H4B	0.4729	0.2500	0.6496	0.055*
N5	0.3516 (2)	0.2500	0.83438 (18)	0.0349 (7)
H5	0.2839	0.2500	0.8594	0.042*
N6	0.4526 (2)	0.2500	0.88959 (19)	0.0414 (7)
H6A	0.4426	0.1645	0.9359	0.062*	0.50
H6B	0.4647	0.3741	0.9112	0.062*	0.50
N7	0.4475 (3)	0.2500	0.4928 (2)	0.0415 (7)
S1	0.13368 (7)	0.2500	0.43541 (6)	0.0335 (2)
S2	0.23512 (7)	0.2500	0.68064 (5)	0.0318 (2)
S3	0.68866 (8)	0.2500	0.47665 (7)	0.0528 (3)
C1	0.1893 (3)	0.2500	0.3264 (2)	0.0283 (7)
C2	0.3611 (3)	0.2500	0.7450 (2)	0.0286 (7)
C3	0.5450 (3)	0.2500	0.4851 (2)	0.0278 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0292 (3)	0.1520 (7)	0.0256 (3)	0.000	−0.00124 (17)	0.000
N1	0.0205 (13)	0.0557 (17)	0.0252 (13)	0.000	−0.0003 (10)	0.000
N2	0.0214 (13)	0.0632 (18)	0.0237 (14)	0.000	−0.0002 (11)	0.000
N3	0.0254 (13)	0.0517 (17)	0.0274 (15)	0.000	0.0048 (11)	0.000
N4	0.0261 (15)	0.088 (2)	0.0236 (14)	0.000	−0.0024 (11)	0.000
N5	0.0260 (13)	0.0529 (17)	0.0259 (15)	0.000	−0.0030 (11)	0.000
N6	0.0339 (15)	0.0617 (19)	0.0285 (15)	0.000	−0.0088 (12)	0.000
N7	0.0338 (18)	0.0549 (19)	0.0357 (16)	0.000	0.0011 (13)	0.000
S1	0.0242 (4)	0.0521 (5)	0.0242 (4)	0.000	0.0021 (3)	0.000
S2	0.0232 (4)	0.0477 (5)	0.0243 (4)	0.000	−0.0017 (3)	0.000
S3	0.0279 (5)	0.0971 (8)	0.0333 (5)	0.000	−0.0009 (4)	0.000
C1	0.0242 (15)	0.0345 (16)	0.0263 (16)	0.000	−0.0003 (12)	0.000
C2	0.0256 (15)	0.0335 (16)	0.0265 (16)	0.000	−0.0038 (12)	0.000
C3	0.0286 (18)	0.0395 (18)	0.0152 (14)	0.000	0.0017 (12)	0.000

Geometric parameters (Å, º) top

Cu1—N7	1.962 (3)	N4—H4A	0.8600
Cu1—S1	2.2401 (10)	N4—H4B	0.8600
Cu1—S2	2.2437 (10)	N5—C2	1.314 (4)
N1—C1	1.313 (4)	N5—N6	1.414 (4)
N1—H1A	0.8600	N5—H5	0.8600
N1—H1B	0.8600	N6—H6A	0.8900
N2—C1	1.339 (4)	N6—H6B	0.8900
N2—N3	1.410 (4)	N7—C3	1.126 (4)
N2—H2	0.8600	S1—C1	1.721 (3)
N3—H3A	0.8900	S2—C2	1.727 (3)
N3—H3B	0.8900	S3—C3	1.655 (3)
N4—C2	1.315 (4)

N7—Cu1—S1	123.38 (10)	C2—N5—H5	119.9
N7—Cu1—S2	121.85 (10)	N6—N5—H5	119.9
S1—Cu1—S2	114.77 (4)	N5—N6—H6A	109.3
C1—N1—H1A	120.0	N5—N6—H6B	109.4
C1—N1—H1B	120.0	H6A—N6—H6B	109.5
H1A—N1—H1B	120.0	C3—N7—Cu1	168.5 (3)
C1—N2—N3	124.7 (3)	C1—S1—Cu1	107.58 (11)
C1—N2—H2	117.7	C2—S2—Cu1	108.46 (11)
N3—N2—H2	117.7	N1—C1—N2	119.4 (3)
N2—N3—H3A	109.2	N1—C1—S1	120.9 (2)
N2—N3—H3B	109.4	N2—C1—S1	119.7 (2)
H3A—N3—H3B	109.5	N5—C2—N4	119.0 (3)
C2—N4—H4A	120.0	N5—C2—S2	118.3 (2)
C2—N4—H4B	120.0	N4—C2—S2	122.7 (3)
H4A—N4—H4B	120.0	N7—C3—S3	178.6 (3)
C2—N5—N6	120.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S3ⁱ	0.86	2.64	3.485 (3)	167
N1—H1B···N3ⁱ	0.86	2.14	2.998 (4)	177
N2—H2···N7	0.86	2.24	3.093 (4)	175
N3—H3A···S2ⁱⁱ	0.89	2.81	3.5481 (11)	141
N3—H3B···S2ⁱⁱⁱ	0.89	2.72	3.5481 (11)	155
N4—H4A···S2^iv	0.86	2.65	3.501 (3)	170
N4—H4B···N7	0.86	2.32	3.161 (4)	167
N5—H5···S3^v	0.86	2.64	3.342 (3)	140
N6—H6A···S1^vi	0.89	2.88	3.5144 (12)	130
N6—H6B···S1^vii	0.89	2.75	3.5144 (11)	144

Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x+1/2, −y, z−1/2; (iii) −x+1/2, −y+1, z−1/2; (iv) x+1/2, y, −z+3/2; (v) x−1/2, y, −z+3/2; (vi) −x+1/2, −y, z+1/2; (vii) −x+1/2, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(CH₅N₃S)₂(NCS)]
M_r	303.90
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	11.488 (2), 6.6085 (12), 14.650 (3)
V (Å³)	1112.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.50
Crystal size (mm)	0.38 × 0.27 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.44, 0.55
No. of measured, independent and observed [I > 2σ(I)] reflections	5593, 1077, 947
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.05
No. of reflections	1077
No. of parameters	86
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.54

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S3ⁱ	0.86	2.64	3.485 (3)	167.3
N1—H1B···N3ⁱ	0.86	2.14	2.998 (4)	176.5
N2—H2···N7	0.86	2.24	3.093 (4)	175.0
N3—H3A···S2ⁱⁱ	0.89	2.81	3.5481 (11)	141.3
N3—H3B···S2ⁱⁱⁱ	0.89	2.72	3.5481 (11)	155.3
N4—H4A···S2^iv	0.86	2.65	3.501 (3)	169.5
N4—H4B···N7	0.86	2.32	3.161 (4)	167.0
N5—H5···S3^v	0.86	2.64	3.342 (3)	139.7
N6—H6A···S1^vi	0.89	2.88	3.5144 (12)	129.9
N6—H6B···S1^vii	0.89	2.75	3.5144 (11)	144.4

Acknowledgements

We acknowledge the Natural Science Foundation of Liaocheng University (X051002) for support.

References

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