Poly[μ-1,3-thia­zolidine-2-thione-κ2S2:S2-μ-thio­cyanato-κ2S:N-copper(I)]

Saithong, S.; Pakawatchai, C.; Charmant, J.P.H.

doi:10.1107/S1600536807007441

metal-organic compounds

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Volume 63| Part 3| March 2007| Pages m857-m858

https://doi.org/10.1107/S1600536807007441

Poly[μ-1,3-thiazolidine-2-thione-κ²S²:S²-μ-thiocyanato-κ²S:N-copper(I)]

Saowanit Saithong,^a Chaveng Pakawatchai ^a ^* and Jonathan P. H. Charmant ^b

^aDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai 90112, Thailand, and ^bthe School of Chemistry, University of Bristol, Cantock's Close, Bristol BS 1TS, England
^*Correspondence e-mail: chaveng.p@psu.ac.th

(Received 31 January 2007; accepted 13 February 2007; online 28 February 2007)

The title compound, [Cu(SCN)(C₃H₅NS₂)]_n, was prepared from the direct reaction between copper(I) thiocyanate and 1,3-thiazolidine-2-thione. The structure is an infinite two-dimensional polymer, parallel to the ac plane, with tetrahedrally distorted Cu atoms which are coordinated by the S and N atoms of the thiocyanate ions, and by the thione S atom of 1,3-thiazolidine-2-thione molecules.

Comment

Heterocyclic thione compounds have received much attention due to their wide range of applications (Rapper, 1985 , 1994 , 1996 , 1997 ; Akrivos, 2001 ; Bell et al., 2004 ). Neutral thione molecules can coordinate to metal atoms in a variety of ways (Aslanidis et al., 2004 ). Likewise, the metal atoms in group IB are also interesting for use in synthesis with these ligands; the complexes have been applied in optical, electrical, magnetic and luminescent materials (Huang et al., 2004 ).

For this work, we used copper(I) thiocyanate as a starting material to interact directly with 1,3-thiazolidine-2-thione under mild reaction conditions. The structure of the title complex, (I), is depicted in Fig. 1. The title complex is a two-dimensional polymeric structure, the Cu centre having a distorted tetrahedral geometry and being coordinated by two 1,3-thiazolidine-2-thione molecules and two thiocyanate groups. Each 1,3-thiazolidine-2-thione molecule is bonded to Cu atoms via the thione S atom. The thiocyanate groups bridge two Cu centres. As a result, 12-membered rings are formed. The crystal packing shows a weak N—H⋯N hydrogen bond (Table 1).

Figure 1
The polymeric sheet structure of title complex, showing the atom-labelling. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.

Experimental

1,3-Thiazolidine-2-thione (0.125 g, 0.985 mmol) was dissolved in CH₃CN (30 ml); CuSCN (0.120 g, 0.985 mmol) was then added as a powder to the solution. The mixture was heated to 343 K and refluxed until the grey solid had changed colour to yellow (around 7 h). The yellow solid was filtered off and the yellow solution was kept at room temperature and allowed to evaporate slowly. Colourless needle-like crystals of the title complex were obtained.

Crystal data

[Cu(SCN)(C₃H₅NS₂)]
M_r = 240.82
Monoclinic, P 2₁ /c
a = 5.8370 (7) Å
b = 19.992 (3) Å
c = 6.9779 (9) Å
β = 106.391 (2)°
V = 781.17 (18) Å³
Z = 4
Mo Kα radiation
μ = 3.52 mm⁻¹
T = 293 (2) K
0.23 × 0.05 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.671, T_max = 0.940
6767 measured reflections
1871 independent reflections
1573 reflections with I > 2/s(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.108
S = 1.15
1871 reflections
94 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.73 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—H1⋯N2ⁱ	0.877 (19)	2.69 (3)	3.486 (5)	151 (4)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

H atoms bonded to C atoms were placed in geometrically idealized positions and refined using a riding model, with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C). The H atom bonded to nitrogen was located in a difference Fourier map. Its position was refined with a distance restraint [N—H = 0.89 (2) Å] and with U_iso(H) = 1.2U_eq(N).

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807007441/bt2264sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807007441/bt2264Isup2.hkl

Computing details top

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

Poly[µ-1,3-thiazoline-2-thione-κ²S²:S²-µ-thiocyanato-κ²S:N- copper(I)] top

Crystal data top

[Cu(SCN)(C₃H₅NS₂)]	F(000) = 480
M_r = 240.82	D_x = 2.048 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71074 Å
Hall symbol: -P 2ybc	Cell parameters from 1484 reflections
a = 5.8370 (7) Å	θ = 3.2–24.0°
b = 19.992 (3) Å	µ = 3.52 mm⁻¹
c = 6.9779 (9) Å	T = 293 K
β = 106.391 (2)°	Needle, colorless
V = 781.17 (18) Å³	0.23 × 0.05 × 0.02 mm
Z = 4

Data collection top

Bruker AXS D8 diffractometer	1871 independent reflections
Radiation source: sealed X-ray tube	1573 reflections with I > 2/s(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 8.366 pixels mm^-1	θ_max = 28.2°, θ_min = 2.0°
ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −25→26
T_min = 0.671, T_max = 0.940	l = −9→9
6767 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.0427P)² + 0.9712P] where P = (F_o² + 2F_c²)/3
1871 reflections	(Δ/σ)_max = 0.001
94 parameters	Δρ_max = 0.73 e Å⁻³
1 restraint	Δρ_min = −0.54 e Å⁻³

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
Cu1	0.17403 (10)	0.30184 (3)	1.19916 (9)	0.0394 (2)
S1	0.04782 (19)	0.29292 (5)	0.81538 (16)	0.0296 (2)
S2	0.1806 (2)	0.43839 (5)	0.82671 (18)	0.0359 (3)
N1	0.4138 (6)	0.34760 (17)	0.7097 (5)	0.0312 (8)
H1	0.453 (8)	0.3078 (13)	0.676 (7)	0.037*
N2	0.5112 (7)	0.3246 (2)	1.2443 (6)	0.0430 (9)
C1	0.2285 (7)	0.35495 (19)	0.7778 (6)	0.0255 (8)
C2	0.5562 (8)	0.4071 (2)	0.7042 (8)	0.0399 (11)
H2A	0.6123	0.4068	0.5860	0.048*
H2B	0.6935	0.4088	0.8213	0.048*
C3	0.3971 (8)	0.4660 (2)	0.7007 (8)	0.0408 (11)
H3A	0.3177	0.4792	0.5643	0.049*
H3B	0.4883	0.5037	0.7701	0.049*
S3	−0.06175 (18)	0.38930 (5)	1.25329 (17)	0.0335 (3)
C4	−0.3110 (7)	0.3499 (2)	1.2486 (6)	0.0288 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0300 (3)	0.0270 (3)	0.0662 (4)	0.0021 (2)	0.0215 (3)	0.0067 (3)
S1	0.0331 (5)	0.0212 (5)	0.0393 (6)	−0.0044 (4)	0.0178 (4)	−0.0041 (4)
S2	0.0378 (6)	0.0227 (5)	0.0548 (7)	−0.0044 (4)	0.0252 (5)	−0.0055 (5)
N1	0.0290 (17)	0.0251 (17)	0.044 (2)	0.0006 (14)	0.0175 (16)	0.0001 (16)
N2	0.0254 (18)	0.055 (2)	0.050 (2)	−0.0006 (18)	0.0129 (17)	0.001 (2)
C1	0.0303 (19)	0.0214 (19)	0.026 (2)	−0.0002 (16)	0.0104 (16)	0.0003 (15)
C2	0.030 (2)	0.039 (3)	0.056 (3)	−0.0020 (19)	0.022 (2)	0.005 (2)
C3	0.040 (2)	0.029 (2)	0.059 (3)	−0.0071 (19)	0.023 (2)	0.006 (2)
S3	0.0271 (5)	0.0261 (5)	0.0489 (7)	0.0013 (4)	0.0132 (5)	−0.0051 (5)
C4	0.026 (2)	0.032 (2)	0.028 (2)	0.0071 (17)	0.0073 (16)	0.0001 (17)

Geometric parameters (Å, º) top

Cu1—N2	1.957 (4)	N1—H1	0.877 (19)
Cu1—S1ⁱ	2.2641 (11)	N2—C4ⁱⁱⁱ	1.148 (5)
Cu1—S3	2.3211 (12)	C2—C3	1.495 (6)
Cu1—S1	2.5754 (13)	C2—H2A	0.9700
S1—C1	1.696 (4)	C2—H2B	0.9700
S1—Cu1ⁱⁱ	2.2641 (11)	C3—H3A	0.9700
S2—C1	1.741 (4)	C3—H3B	0.9700
S2—C3	1.817 (4)	S3—C4	1.646 (4)
N1—C1	1.307 (5)	C4—N2^iv	1.148 (5)
N1—C2	1.458 (5)

N2—Cu1—S1ⁱ	123.44 (13)	S1—C1—S2	122.0 (2)
N2—Cu1—S3	114.47 (13)	N1—C2—C3	106.7 (3)
S1ⁱ—Cu1—S3	107.71 (4)	N1—C2—H2A	110.4
N2—Cu1—S1	99.38 (12)	C3—C2—H2A	110.4
S1ⁱ—Cu1—S1	106.74 (4)	N1—C2—H2B	110.4
S3—Cu1—S1	102.28 (4)	C3—C2—H2B	110.4
C1—S1—Cu1ⁱⁱ	106.09 (14)	H2A—C2—H2B	108.6
C1—S1—Cu1	95.86 (14)	C2—C3—S2	105.5 (3)
Cu1ⁱⁱ—S1—Cu1	113.82 (5)	C2—C3—H3A	110.6
C1—S2—C3	91.4 (2)	S2—C3—H3A	110.6
C1—N1—C2	117.0 (3)	C2—C3—H3B	110.6
C1—N1—H1	120 (3)	S2—C3—H3B	110.6
C2—N1—H1	123 (3)	H3A—C3—H3B	108.8
C4ⁱⁱⁱ—N2—Cu1	165.4 (4)	C4—S3—Cu1	101.40 (15)
N1—C1—S1	126.1 (3)	N2^iv—C4—S3	177.6 (4)
N1—C1—S2	112.0 (3)

N2—Cu1—S1—C1	−35.10 (19)	Cu1—S1—C1—N1	112.1 (4)
S1ⁱ—Cu1—S1—C1	−164.36 (14)	Cu1ⁱⁱ—S1—C1—S2	174.6 (2)
S3—Cu1—S1—C1	82.65 (14)	Cu1—S1—C1—S2	−68.5 (2)
N2—Cu1—S1—Cu1ⁱⁱ	75.38 (14)	C3—S2—C1—N1	10.7 (3)
S1ⁱ—Cu1—S1—Cu1ⁱⁱ	−53.88 (8)	C3—S2—C1—S1	−168.8 (3)
S3—Cu1—S1—Cu1ⁱⁱ	−166.87 (4)	C1—N1—C2—C3	−22.8 (5)
S1ⁱ—Cu1—N2—C4ⁱⁱⁱ	−178.7 (15)	N1—C2—C3—S2	27.9 (5)
S3—Cu1—N2—C4ⁱⁱⁱ	−44.2 (16)	C1—S2—C3—C2	−22.4 (4)
S1—Cu1—N2—C4ⁱⁱⁱ	64.0 (16)	N2—Cu1—S3—C4	−168.86 (19)
C2—N1—C1—S1	−175.1 (3)	S1ⁱ—Cu1—S3—C4	−27.52 (15)
C2—N1—C1—S2	5.4 (5)	S1—Cu1—S3—C4	84.74 (15)
Cu1ⁱⁱ—S1—C1—N1	−4.8 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱⁱ	0.88 (2)	2.69 (3)	3.486 (5)	151 (4)

Symmetry code: (ii) x, −y+1/2, z−1/2.

Acknowledgements

We gratefully acknowledge financial support from the Royal Golden Jubilee PhD program (RGJ) and the Center for Innovation in Chemistry, Postgraduate Education and Research Programme in Chemistry (PERCH–CIC) and thank the Graduate School for their support. Finally, we also thank the Department of Chemistry, Prince of Songkla University and the School of Chemistry, University of Bristol (UK), for instrumental support.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 63| Part 3| March 2007| Pages m857-m858

https://doi.org/10.1107/S1600536807007441

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