Crystal structure of [3-(4,5-di­hydro-1,3-thia­zolin-2-yl-κN)-1,3-thia­zolidine-2-thione-κS2](1,3-thia­zol­idine-2-thione-κS2)copper(I) nitrate

Saithong, S.; Klongkleaw, P.; Pakawatchai, C.; Mokakul, J.

doi:10.1107/S160053681401544X

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ISSN: 2056-9890

Volume 70| Part 8| August 2014| Pages 91-93

doi:10.1107/S160053681401544X

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Crystal structure of [3-(4,5-dihydro-1,3-thiazolin-2-yl-κN)-1,3-thiazolidine-2-thione-κS²](1,3-thiazolidine-2-thione-κS²)copper(I) nitrate

Saowanit Saithong,^a ^* Pirawan Klongkleaw,^a Chaveng Pakawatchai ^a and Jedsada Mokakul ^a

^aDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: saowanit.sa@psu.ac.th

Edited by J. Simpson, University of Otago, New Zealand (Received 27 June 2014; accepted 2 July 2014; online 19 July 2014)

The mononuclear complex salt, [Cu(C₃H₅NS₂)(C₆H₈N₂S₃)]NO₃, contains a [C₉H₁₃CuN₃S₅]⁺ cation and an NO₃⁻ anion. All of the non-H atoms of the cation lie on a mirror plane, as do the N and one O atom of the nitrate anion, such that the planes of the cation and anion are mutually orthogonal. The cationic complex adopts a slightly distorted trigonal–planar geometry about the Cu^I cation. In the crystal, layers parallel to (010) are generated by N—H⋯O hydrogen bonds, supported by short S⋯O [3.196 (4) and 3.038 (3) Å] and S⋯S contacts [3.4392 (13) Å]. Adjacent layers are linked by C—H⋯O hydrogen bonds and weak π–π stacking interactions [centroid–centroid distance = 4.0045 (10) Å] between the thiazoline rings, forming a three-dimensional network. This stacking also imposes a close contact, of approximately 3.678 Å, between the Cu^I cations and the centroids of the six-membered chelate rings of molecules in adjacent layers.

Keywords: copper(II) complex; 1,3-thiazolidine-2-thione; 3-(2-thiazolin-2-yl)thiazolidine-2-thione; crystal structure.

CCDC reference: 1011568

1. Chemical context

1,3-Thiazolidine-2-thione (tzdSH: C₃H₅NS₂), is a well known heterocyclic thione/thiol ligand. Crystallographic studies and investigations of its modes of coordination have been reported (Raper et al., 1998 ; Ainscough et al., 1985 ; Kubiak & Głowiak, 1987 ; Cowie & Sielisch, 1988 ; Ballester et al., 1992 ; Fackler et al., 1992 ; Saithong et al., 2007 ). We are interested in the coordination behaviour and structure of tzdSH complexes with Cu^II cations. We have normally used Cu(NO₃)₂·3H₂O as the starting material with the possibility that the NO₃⁻ anions could function as simple counter-ions to balance the charge on the metal or alternatively act as a ligand to the metal ion (Ferrer et al., 2000 ; Pal et al., 2005 ; Khavasi et al., 2011 ). However, the tzdSH ligand could also act as a reducing agent during the reaction, converting Cu^II to Cu^I and forming 3-(2-thiazolin-2-yl)thiazolidine-2-thione [tztzdt or C₆H₈N₂S₃] in the process. A similar reduction reaction was described previously by Ainscough et al. (1985). Complexation of the resulting Cu^I cation to both the tztzdt ligand thus formed, and to tzdSH generates the title compound.

2. Structural commentary

The title compound is a mononuclear Cu^I complex and its structure is shown in Fig. 1. The Cu^I atom has a distorted trigonal–planar coordination geometry and is chelated by the exocyclic S3 atom and the N3 atom of the thiazolidine ring of the tztzdt ligand, forming a six-membered chelate ring. The trigonal coordination sphere is completed by the exocyclic S1 atom of the tzdSH ligand. The NO₃⁻ acts solely as counter-ion. The complex molecule is strictly planar as all non-hydrogen atoms of the complex lie on a mirror plane. Atoms N4 and O1 of the nitrate counter-ion also lie on a mirror plane, such that the mirror plane of the cationic complex is perpendicular to that of the NO₃⁻ anion. The Cu1—S1 [2.1774 (9) Å], and Cu1—N3 [1.956 (3) Å] bond lengths are not unusual in comparison with the mean values [Cu—S = 2.21 (3) and Cu—N = 1.99 (3) Å] found in the Cambridge Structural Database. In contrast, the Cu1—S1 distance of 2.1774 (9) Å is somewhat shorter than those previously reported for other Cu^I complexes of tzdSH [mean Cu—S = 2.33 (1) Å].

Figure 1
Molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) x, −y + ½, z.]

3. Supramolecular features

In the crystal, layers are generated parallel to (010) by classical N1—H1⋯O1 hydrogen bonds (Table 1) supported by short S2⋯O2 [3.038 (3) Å], S5⋯O2 [3.196 (4) Å] and S1⋯S4 [3.4392 (13) Å] contacts (Fig. 2). Adjacent layers are linked by C5—H5A⋯O1 hydrogen bonds and weak π–π stacking interactions [centroid–centroid distance 4.0045 (10) Å] between the thiazoline rings of a tzdSH ligand with those of tztzdt ligands in adjacent layers, forming a three-dimensional network. This stacking also imposes a close contact, of approximately 3.678 Å, between the copper cations and the centroids of the six-membered Cu1, S3, C4, N2, C7, N3 chelate rings of the molecules in the adjacent layers (Fig. 3). The three-dimensional network of stacked layers is shown in Fig. 4.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.84 (2)	2.25 (2)	2.981 (4)	146 (2)
N1—H1⋯O1ⁱⁱ	0.84 (2)	2.25 (2)	2.981 (4)	146 (2)
C5—H5A⋯O1ⁱⁱⁱ	0.97	2.62	3.388 (4)	136
Symmetry codes: (i) x+1, y, z; (ii) $[x+1, -y+{\script{1\over 2}}, z]$ ; (iii) -x, -y, -z+1.

Figure 2
Two-dimensional sheets of molecules parallel to (010). Hydrogen bonds are drawn as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 3
π–π stacking interactions between molecules. Centroid–centroid and unusual Cu1–centroid contacts are drawn as dotted lines with the centroids shown as coloured spheres. Hydrogen bonds are drawn as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 4
The overall packing of the title compound. Hydrogen bonds are drawn as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity.

4. Database survey

Only four discrete reports are given of transition-metal complexes with the metal atom chelated by the tztzdt ligand. All are copper complexes, three of Cu^I (Lobana et al., 2013 ) and the fourth a Cu^II coordination polymer (Ainscough et al., 1985). Complexes of tzdSH are more plentiful with 29 unique entries, ten of which involve Cu^I cations (see, for example: Lobana et al., 2013; Raper et al., 1998).

5. Synthesis and crystallization

1,3-Thiazolidine-2-thione (0.1 g, 0.084 mmol) was added to a solution of Cu(NO₃)₂·3H₂O (0.07 g, 0.039 mmol) in an MeOH: EtOH solvent mixture (1/1 v/v) at 340 K. The mixture was refluxed for 5 h. Rod-like yellow crystals appeared after the light-brown filtrate had been kept at room temperature for a day (yield 10%). The crystals melt and decompose at 434–436 K.

6. Refinement

The N1—H1 hydrogen atom was located in a difference map and its coordinates were refined with U_iso(H) = 1.2U_eq(N). The hydrogen atoms of the methylene groups were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.97 Å and U_iso = 1.2U_eq(C). Experimental details are given in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₃H₅NS₂)(C₆H₈N₂S₃)]NO₃
M_r	449.13
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	293
a, b, c (Å)	9.8937 (6), 6.9932 (5), 11.8054 (7)
β (°)	102.078 (1)
V (Å³)	798.72 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.04
Crystal size (mm)	0.35 × 0.12 × 0.06

Data collection
Diffractometer	Bruker APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.814, 1.000
No. of measured, independent and observed [I > 2s(I)] reflections	8700, 1534, 1402
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.07
No. of reflections	1534
No. of parameters	133
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.27
Computer programs: SMART (Bruker, 1998 ), SAINT (Bruker, 2003), ShelXle (Hübschle et al., 2011 ), SHELXTL (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1011568

Crystal structure: contains datablocks I, pk030-p21-m. DOI: 10.1107/S160053681401544X/sj5420sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681401544X/sj5420Isup2.hkl

checkCIF report

Chemical context top

1,3-Thiazolidine-2-thione (tzdSH: C₃H₅NS₂), is a well known, heterocyclic thione/thiol ligand. Crystallographic studies and investigations of its modes of coordination have been reported (Raper et al., 1998; Ainscough et al., 1985; Kubiak & Głowiak, 1987; Cowie & Sielisch, 1988; Ballester et al., 1992; Fackler et al., 1992; Saithong et al., 2007). We are interested in the coordination behaviour and structure of tzdSH complexes with Cu^II cations. We have normally used Cu(NO₃)₂^.3H₂O as the starting material with the possibility that the NO₃^- anions could function as simple counter-ions to balance the charge on the metal or alternatively act as a ligand to the metal ion (Ferrer et al., 2000; Pal et al., 2005; Khavasi et al., 2011). However, the tzdSH ligand could also act as a reducing agent during the reaction, converting Cu^II to Cu^I) and forming 3-(2-thiazolin-2-yl)thiazolidine-2-thione [tztzdt or C₆H₈N₂S₃] in the process. A similar reduction reaction was described previously by Ainscough et al. (1985). Complexation of the resulting Cu^I cation to both the tztzdt ligand thus formed, and to tzdSH generates the title compound.

Structural commentary top

The title compound is a mononuclear Cu^I complex and its structure is shown in Fig I. The Cu^I atom has a distorted trigonal–planar geometry and is chelated by the exocyclic S3 atom and the N3 atom of the thiazolidine ring of the tztzdt ligand, forming a six-membered chelate ring. The trigonal coordination sphere is completed by the exocyclic S1 atom of the tzdSH ligand. The NO₃^- acts solely as counter-ion. The complex molecule is strictly planar as all non-hydrogen atoms of the complex lie on a mirror plane. Atoms N4 and O1 of the nitrate counter-ion also lie on a mirror plane, such that the mirror plane of the cationic complex is perpendicular to that of the NO₃^- anion. The Cu1—S1 [2.1774 (9) Å], and Cu1—N3 [1.956 (3) Å] bond lengths are not unusual in comparison with the mean values [Cu—S = 2.21 (3) and Cu—N = 1.99 (3) Å] found in the Cambridge Structural Database. In contrast, the Cu1—S1 distance of 2.1774 (9) Å is somewhat shorter than those previously reported for other Cu^I complexes of tzdSH [mean Cu—S = 2.33 (1) Å].

Supramolecular features top

In the crystal, layers are generated parallel to the (010) plane by classical N1—H1···O1 hydrogen bonds (Table 1) supported by short S2···O2 [3.038 (3) Å], S5···O2 [3.196 (4) Å] and S1···S4 [3.4392 (13) Å] contacts (Fig 2). Adjacent layers are linked by C5—H5A···O1 hydrogen bonds and weak π–π stacking interactions [centroid–centroid distance 4.0045 (10) Å] between the thiazoline rings of a tzdSH ligand with those of tztzdt ligands in adjacent layers, forming a three-dimensional network. This stacking also imposes a close contact, of approximately 3.678 Å, between the copper cations and the centroids of the six-membered Cu1, S3, C4, N2, C7, N3 chelate rings of the molecules in the adjacent layers (Fig 3). The three dimensional network of stacked layers is shown in Fig. 4.

Database survey top

Only four discrete reports of transition-metal complexes with the metal atom chelated by the tztzdt ligand. All are copper complexes, three of Cu^I (Lobana et al., 2013) and the fourth a Cu^II coordination polymer (Ainscough et al., 1985). Complexes of tzdSH are more plentiful with 29 unique entries, ten of which involve Cu^I cations (see, for example, Lobana et al., 2013; Raper et al., 1998).

Synthesis and crystallization top

1,3-Thiazolidine-2-thione (0.1 g, 0.084 mmol) was added to a solution of Cu(NO₃)₂^.3H₂O (0.07 g, 0.039 mmol) in an MeOH: EtOH solvent mixture (1/1 v/v) at 340 K. The mixture was refluxed for 5 h. Rod-like yellow crystals appeared after the light-brown filtrate had been kept at room temperature for a day (yield 10%). The crystals melt and decompose at 434–436 K.

Refinement top

Related literature top

For related literature, see: Ainscough et al. (1985); Ballester et al. (1992); Cowie & Sielisch (1988); Fackler et al. (1992); Ferrer et al. (2000); Khavasi et al. (2011); Kubiak & Głowiak (1987); Lobana et al. (2013); Pal et al. (2005); Raper et al. (1998); Saithong et al. (2007).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: ShelXle (Hübschle et al., 2011) and SHELXTL (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) x, -y+1/2, z.]
	Fig. 2. Two-dimensional sheets of molecules parallel to (010). Hydrogen bonds are drawn as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 3. π–π stacking interactions between molecules. Centroid–centroid and unusual Cu1–centroid contacts are drawn as dotted lines with the centroids shown as coloured spheres. Hydrogen bonds are drawn as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 4. The overall packing of the title compound. Hydrogen bonds are drawn as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity.

[3-(4,5-Dihydro-1,3-thiazolin-2-yl-κN)-1,3-thiazolidine-2-thione-κS²](1,3-thiazolidine-2-thione-κS²)copper(I) nitrate top

Crystal data top

[Cu(C₃H₅NS₂)(C₆H₈N₂S₃)]NO₃	F(000) = 456
M_r = 449.13	D_x = 1.867 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 3943 reflections
a = 9.8937 (6) Å	θ = 2.5–28.0°
b = 6.9932 (5) Å	µ = 2.04 mm⁻¹
c = 11.8054 (7) Å	T = 293 K
β = 102.078 (1)°	Block, yellow
V = 798.72 (9) Å³	0.35 × 0.12 × 0.06 mm
Z = 2

Data collection top

Bruker APEX CCD area-detector diffractometer	1534 independent reflections
Radiation source: fine-focus sealed tube	1402 reflections with I > 2s(I)
Graphite monochromator	R_int = 0.026
Frames, each covering 0.3 ° in ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→11
T_min = 0.814, T_max = 1.000	k = −8→8
8700 measured reflections	l = −14→14

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 atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0471P)² + 0.3435P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1534 reflections	Δρ_max = 0.37 e Å⁻³
133 parameters	Δρ_min = −0.27 e Å⁻³
1 restraint	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0074 (13)

Crystal data top

[Cu(C₃H₅NS₂)(C₆H₈N₂S₃)]NO₃	V = 798.72 (9) Å³
M_r = 449.13	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 9.8937 (6) Å	µ = 2.04 mm⁻¹
b = 6.9932 (5) Å	T = 293 K
c = 11.8054 (7) Å	0.35 × 0.12 × 0.06 mm
β = 102.078 (1)°

Data collection top

Bruker APEX CCD area-detector diffractometer	1534 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1402 reflections with I > 2s(I)
T_min = 0.814, T_max = 1.000	R_int = 0.026
8700 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	1 restraint
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.37 e Å⁻³
1534 reflections	Δρ_min = −0.27 e Å⁻³
133 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 al 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	0.53707 (4)	0.2500	0.52014 (4)	0.05377 (19)
S1	0.75417 (8)	0.2500	0.60684 (7)	0.0471 (2)
S2	0.61224 (9)	0.2500	0.80799 (8)	0.0494 (2)
S3	0.34723 (10)	0.2500	0.58878 (8)	0.0641 (3)
S4	0.05567 (9)	0.2500	0.50537 (9)	0.0571 (3)
S5	0.28736 (10)	0.2500	0.15159 (7)	0.0527 (3)
N1	0.8731 (3)	0.2500	0.8311 (3)	0.0509 (7)
H1	0.951 (3)	0.2500	0.813 (3)	0.061*
N2	0.2147 (3)	0.2500	0.3586 (2)	0.0404 (6)
N3	0.4543 (3)	0.2500	0.3544 (2)	0.0446 (6)
C1	0.7591 (3)	0.2500	0.7514 (3)	0.0408 (7)
C2	0.7099 (4)	0.2500	0.9567 (3)	0.0565 (9)
H2A	0.6879	0.3626	0.9973	0.068*	0.50
H2B	0.6879	0.1374	0.9973	0.068*	0.50
C3	0.8615 (4)	0.2500	0.9509 (3)	0.0654 (11)
H3A	0.9066	0.3624	0.9897	0.079*	0.50
H3B	0.9066	0.1376	0.9897	0.079*	0.50
C4	0.2171 (3)	0.2500	0.4737 (3)	0.0434 (7)
C5	−0.0321 (4)	0.2500	0.3563 (4)	0.0737 (12)
H5A	−0.0901	0.1375	0.3396	0.088*	0.50
H5B	−0.0901	0.3625	0.3396	0.088*	0.50
C6	0.0736 (3)	0.2500	0.2847 (3)	0.0592 (10)
H6A	0.0618	0.3623	0.2354	0.071*	0.50
H6B	0.0618	0.1377	0.2354	0.071*	0.50
C7	0.3273 (3)	0.2500	0.3040 (3)	0.0392 (7)
C8	0.4694 (4)	0.2500	0.1485 (3)	0.0577 (9)
H8A	0.4926	0.1374	0.1085	0.069*	0.50
H8B	0.4926	0.3626	0.1085	0.069*	0.50
C9	0.5473 (4)	0.2500	0.2725 (3)	0.0542 (9)
H9A	0.6062	0.1379	0.2861	0.065*	0.50
H9B	0.6062	0.3621	0.2861	0.065*	0.50
N4	0.2237 (3)	0.2500	0.8549 (2)	0.0596 (9)
O1	0.1564 (3)	0.1019 (4)	0.8343 (2)	0.1071 (8)
O2	0.3440 (3)	0.2500	0.8948 (3)	0.1254 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0365 (3)	0.0762 (4)	0.0445 (3)	0.000	−0.00081 (18)	0.000
S1	0.0334 (4)	0.0643 (5)	0.0435 (5)	0.000	0.0076 (3)	0.000
S2	0.0366 (4)	0.0644 (5)	0.0474 (5)	0.000	0.0093 (4)	0.000
S3	0.0403 (5)	0.1106 (8)	0.0396 (5)	0.000	0.0045 (4)	0.000
S4	0.0369 (5)	0.0729 (6)	0.0632 (6)	0.000	0.0145 (4)	0.000
S5	0.0501 (5)	0.0668 (6)	0.0383 (4)	0.000	0.0025 (4)	0.000
N1	0.0345 (15)	0.0683 (19)	0.0471 (16)	0.000	0.0020 (12)	0.000
N2	0.0313 (13)	0.0443 (14)	0.0427 (15)	0.000	0.0010 (11)	0.000
N3	0.0350 (14)	0.0541 (16)	0.0438 (15)	0.000	0.0059 (11)	0.000
C1	0.0339 (16)	0.0407 (16)	0.0461 (18)	0.000	0.0046 (13)	0.000
C2	0.060 (2)	0.066 (2)	0.0425 (18)	0.000	0.0085 (16)	0.000
C3	0.053 (2)	0.091 (3)	0.047 (2)	0.000	−0.0020 (17)	0.000
C4	0.0358 (16)	0.0442 (17)	0.0495 (18)	0.000	0.0076 (14)	0.000
C5	0.039 (2)	0.110 (4)	0.068 (3)	0.000	0.0015 (18)	0.000
C6	0.0361 (18)	0.080 (3)	0.055 (2)	0.000	−0.0037 (16)	0.000
C7	0.0390 (17)	0.0391 (16)	0.0380 (16)	0.000	0.0044 (13)	0.000
C8	0.055 (2)	0.069 (2)	0.052 (2)	0.000	0.0168 (17)	0.000
C9	0.0401 (18)	0.072 (2)	0.052 (2)	0.000	0.0131 (15)	0.000
N4	0.0409 (17)	0.101 (3)	0.0340 (15)	0.000	0.0022 (12)	0.000
O1	0.110 (2)	0.0932 (18)	0.122 (2)	−0.0237 (16)	0.0328 (17)	−0.0061 (17)
O2	0.0409 (16)	0.273 (6)	0.0588 (18)	0.000	0.0021 (14)	0.000

Geometric parameters (Å, º) top

Cu1—N3	1.956 (3)	C2—C3	1.516 (5)
Cu1—S1	2.1774 (9)	C2—H2A	0.9700
Cu1—S3	2.1957 (10)	C2—H2B	0.9700
S1—C1	1.698 (3)	C3—H3A	0.9700
S2—C1	1.721 (3)	C3—H3B	0.9700
S2—C2	1.818 (4)	C5—C6	1.475 (6)
S3—C4	1.665 (3)	C5—H5A	0.9700
S4—C4	1.715 (3)	C5—H5B	0.9700
S4—C5	1.792 (4)	C6—H6A	0.9700
S5—C7	1.760 (3)	C6—H6B	0.9700
S5—C8	1.810 (4)	C8—C9	1.505 (5)
N1—C1	1.308 (4)	C8—H8A	0.9700
N1—C3	1.443 (5)	C8—H8B	0.9700
N1—H1	0.841 (19)	C9—H9A	0.9700
N2—C4	1.354 (4)	C9—H9B	0.9700
N2—C7	1.398 (4)	N4—O2	1.185 (4)
N2—C6	1.483 (4)	N4—O1	1.228 (3)
N3—C7	1.273 (4)	N4—O1ⁱ	1.228 (3)
N3—C9	1.468 (4)

N3—Cu1—S1	129.45 (8)	N2—C4—S4	113.4 (2)
N3—Cu1—S3	99.07 (8)	S3—C4—S4	114.7 (2)
S1—Cu1—S3	131.48 (4)	C6—C5—S4	107.9 (3)
C1—S1—Cu1	106.90 (11)	C6—C5—H5A	110.1
C1—S2—C2	93.06 (16)	S4—C5—H5A	110.1
C4—S3—Cu1	105.89 (12)	C6—C5—H5B	110.1
C4—S4—C5	93.88 (18)	S4—C5—H5B	110.1
C7—S5—C8	90.55 (16)	H5A—C5—H5B	108.4
C1—N1—C3	118.1 (3)	C5—C6—N2	110.9 (3)
C1—N1—H1	121 (3)	C5—C6—H6A	109.5
C3—N1—H1	121 (3)	N2—C6—H6A	109.5
C4—N2—C7	127.9 (3)	C5—C6—H6B	109.5
C4—N2—C6	114.0 (3)	N2—C6—H6B	109.5
C7—N2—C6	118.1 (3)	H6A—C6—H6B	108.1
C7—N3—C9	112.7 (3)	N3—C7—N2	126.0 (3)
C7—N3—Cu1	129.3 (2)	N3—C7—S5	117.8 (2)
C9—N3—Cu1	118.0 (2)	N2—C7—S5	116.2 (2)
N1—C1—S1	124.2 (3)	C9—C8—S5	106.8 (2)
N1—C1—S2	113.1 (2)	C9—C8—H8A	110.4
S1—C1—S2	122.75 (18)	S5—C8—H8A	110.4
C3—C2—S2	106.7 (3)	C9—C8—H8B	110.4
C3—C2—H2A	110.4	S5—C8—H8B	110.4
S2—C2—H2A	110.4	H8A—C8—H8B	108.6
C3—C2—H2B	110.4	N3—C9—C8	112.1 (3)
S2—C2—H2B	110.4	N3—C9—H9A	109.2
H2A—C2—H2B	108.6	C8—C9—H9A	109.2
N1—C3—C2	109.0 (3)	N3—C9—H9B	109.2
N1—C3—H3A	109.9	C8—C9—H9B	109.2
C2—C3—H3A	109.9	H9A—C9—H9B	107.9
N1—C3—H3B	109.9	O2—N4—O1	122.47 (18)
C2—C3—H3B	109.9	O2—N4—O1ⁱ	122.47 (18)
H3A—C3—H3B	108.3	O1—N4—O1ⁱ	115.0 (4)
N2—C4—S3	131.9 (3)

N3—Cu1—S1—C1	180.0	Cu1—S3—C4—S4	180.0
S3—Cu1—S1—C1	0.0	C5—S4—C4—N2	0.0
N3—Cu1—S3—C4	0.0	C5—S4—C4—S3	180.0
S1—Cu1—S3—C4	180.0	C4—S4—C5—C6	0.0
S1—Cu1—N3—C7	180.0	S4—C5—C6—N2	0.0
S3—Cu1—N3—C7	0.0	C4—N2—C6—C5	0.0
S1—Cu1—N3—C9	0.0	C7—N2—C6—C5	180.0
S3—Cu1—N3—C9	180.0	C9—N3—C7—N2	180.0
C3—N1—C1—S1	180.0	Cu1—N3—C7—N2	0.0
C3—N1—C1—S2	0.0	C9—N3—C7—S5	0.0
Cu1—S1—C1—N1	180.0	Cu1—N3—C7—S5	180.0
Cu1—S1—C1—S2	0.0	C4—N2—C7—N3	0.0
C2—S2—C1—N1	0.0	C6—N2—C7—N3	180.0
C2—S2—C1—S1	180.0	C4—N2—C7—S5	180.0
C1—S2—C2—C3	0.0	C6—N2—C7—S5	0.0
C1—N1—C3—C2	0.000 (1)	C8—S5—C7—N3	0.0
S2—C2—C3—N1	0.000 (1)	C8—S5—C7—N2	180.0
C7—N2—C4—S3	0.0	C7—S5—C8—C9	0.0
C6—N2—C4—S3	180.0	C7—N3—C9—C8	0.0
C7—N2—C4—S4	180.0	Cu1—N3—C9—C8	180.0
C6—N2—C4—S4	0.0	S5—C8—C9—N3	0.0
Cu1—S3—C4—N2	0.0

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.84 (2)	2.25 (2)	2.981 (4)	146 (2)
N1—H1···O1ⁱⁱⁱ	0.84 (2)	2.25 (2)	2.981 (4)	146 (2)
C5—H5A···O1^iv	0.97	2.62	3.388 (4)	136

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.841 (19)	2.25 (2)	2.981 (4)	146 (2)
N1—H1···O1ⁱⁱ	0.841 (19)	2.25 (2)	2.981 (4)	146 (2)
C5—H5A···O1ⁱⁱⁱ	0.97	2.62	3.388 (4)	135.8

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

Experimental details

Crystal data
Chemical formula	[Cu(C₃H₅NS₂)(C₆H₈N₂S₃)]NO₃
M_r	449.13
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	293
a, b, c (Å)	9.8937 (6), 6.9932 (5), 11.8054 (7)
β (°)	102.078 (1)
V (Å³)	798.72 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.04
Crystal size (mm)	0.35 × 0.12 × 0.06

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.814, 1.000
No. of measured, independent and observed [I > 2s(I)] reflections	8700, 1534, 1402
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.07
No. of reflections	1534
No. of parameters	133
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.27

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), ShelXle (Hübschle et al., 2011) and SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

We are grateful to the Center of Excellence for Innovation in Chemistry (PERCH–CIC), Office of the Higher Education Commission, Ministry of Education, and the Department of Chemistry, Faculty of Science, Prince of Songkla University, for financial support. We also thank Professor Dr Brian Hodgson, Faculty of Science, Prince of Songkla University, for reading the manuscript and providing valuable comments.

References

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Volume 70| Part 8| August 2014| Pages 91-93

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