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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](N-C) = 0.005 Å
• R factor = 0.029
• wR factor = 0.080
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        Cu1

Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C3
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.49
PLAT420_ALERT_2_C D-H Without Acceptor       N6     -  *H6A    ...          ?

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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%.

S3. Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms with N—H 0.86 Å (thiosemicarbazide) [U_iso(H) = 1.2U_eq(N)].

The copper atom presents an abnormally elongated displacement ellipsoid perpendicular to the mirror plane, suggeesting some kind of disorder around its (average) symmetric position.

Computing details

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

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)

Crystal data

[Cu(CH5N3S)2(NCS)]	F(000) = 616
Mr = 303.90	Dx = 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) Å^3	Block, black
Z = 4	0.38 × 0.27 × 0.24 mm

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0469P)^2 + 0.712P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1077 reflections	Δρmax = 0.67 e Å^−3
86 parameters	Δρmin = −0.54 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0072 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S3^i	0.86	2.64	3.485 (3)	167
N1—H1B···N3^i	0.86	2.14	2.998 (4)	177
N2—H2···N7	0.86	2.24	3.093 (4)	175
N3—H3A···S2^ii	0.89	2.81	3.5481 (11)	141
N3—H3B···S2^iii	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.