Di-μ-chloro-bis{chloro­[3,5-di­methyl-1-(thio­carbamoyl)­pyrazole-κ2N2,S]­cadmium(II)}

Radosavljević Evans, I.; Mészáros Szécsényi, K.; Leovac, V.M.

doi:10.1107/S1600536805006173

metal-organic compounds

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Volume 61| Part 4| April 2005| Pages m641-m643

https://doi.org/10.1107/S1600536805006173

Di-μ-chloro-bis{chloro[3,5-dimethyl-1-(thiocarbamoyl)pyrazole-κ²N²,S]cadmium(II)}¹ ¹

Ivana Radosavljević Evans,^a ^* Katalin Mészáros Szécsényi ^b and Vukadin M. Leovac ^b

^aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England, and ^bFaculty of Sciences, University of Novi Sad, Trg Dositeja Obradovica 3, 21000 Novi Sad, Serbia and Montenegro
^*Correspondence e-mail: ivana.radosavljevic@durham.ac.uk

(Received 17 February 2005; accepted 25 February 2005; online 4 March 2005)

The crystal structure of the title compound, [Cd₂Cl₄(C₆H₉N₃S)₂], has been determined. The compound is isomorphous with the previously reported Cu^II and Co^II complexes. It is centrosymmetric and contains binuclear molecular units with five-coordinate Cd atoms, doubly bridged by Cl atoms. The structure is stabilized by a two-dimensional network of hydrogen bonds involving the terminal Cl atoms as acceptors and thiocarbamoyl group N atoms as donors.

Comment

The complex of 3,5-dimethyl-1-(thiocarbamoyl)pyrazole with cadmium chloride was obtained as a part of our systematic studies on pyrazole-based complexes (Jaćimović et al., 1999 ; Tomić et al., 2000 ; Mészáros Szécsényi et al., 2001 ; Mészáros Szécsényi, Leovac, Češljević et al., 2003 ; Jaćimović et al., 2003 ). The ligand 3,5-dimethyl-1-(thiocarbamoyl)pyrazole, L, was synthesized by a reaction of thiosemicarbazide with acetylacetone in an acidic aqueous solution and its crystal structure was recently reported (Kovács et al., 2005 ).

The complexing ability of L was tested against a number of transition metal ions. The ligand has three potential donor atoms: the nitrogen of the pyrazole ring, the amino N atom and the S atom of the thiocarbamoyl group. In principle, it can take part in coordination as a bi- or monodentate neutral species (Radosavljevic Evans, Howard, Mészáros Szécsényi et al., 2004 ; Radosavljević Evans, Howard, Howard et al., 2004 ; Kovács et al., 2005). In addition, there is a possibility of the amino-group deprotonation, resulting in complexes of non-electrolytic character (Mészáros Szécsényi et al., 2003 ; Radosavljević Evans, Howard, Mészáros Szécsényi et al., 2004). The molecular structure of the coordination complex formed depends primarily on the characteristic bonding preferences of the central metal ion and the nature of the anion.

The crystal structure of the title compound, Cd₂L₂Cl₄, (I), consists of discrete neutral binuclear units (Fig. 1). The Cd centres are doubly bridged by Cl atoms, with a Cd⋯Cd distance of 3.763 (1) Å. The molecule is centrosymmetric, but the bridges within the Cd₂Cl₂ core are asymmetric, with Cd—Cl distances of 2.5393 (7) and 2.6174 (7) Å, and a bridging angle of 93.70 (2)°.

The Cd atoms are five-coordinate. Ligand L acts as a neutral bidentate ligand, coordinating through the N atom of the pyrazole ring and the thiocarbamoyl S atom. The Cd coordination is completed by two bridging and one terminal Cl atom. Pentacoordinate geometry can be described using the distortion parameter τ (Addison et al., 1984 ), where τ = 1 corresponds to an ideal trigonal bipyramid and τ = 0 to an ideal square pyramid. In the case of the title complex, τ = 0.69, suggesting that the coordination of the Cd atom is best described as distorted trigonal bipyramidal. The degree of distortion is slightly higher than in the isomorphous Cu^II and Co^II complexes (τ values of 0.75 and 0.77, respectively; Radosavljević Evans, Howard, Howard et al., 2004). The axial positions are occupied by a bridging Cl atom and the pyrazole nitrogen, with a Cl—Cd—N angle of 165.20 (6)°. The ligand bite angle is 75.10 (5)°, reflecting a larger degree of departure from the right angle expected for an ideal trigonal–bipyramidal environment than in the analogous Cu and Co complexes. Both the pyrazole ring and the thiocarbamoyl group are essentially planar, and they form a dihedral angle of 19.8 (5)°. The molecules are packed with the ligand pyrazole rings parallel (Fig. 2). Each terminal Cl atom acts as a hydrogen-bond acceptor for thiocarbamoyl NH groups in two adjacent molecules, with H⋯Cl distances of 2.34 and 2.47 Å (Table 2), giving rise to a two-dimensional hydrogen-bonding network in the structure.

Figure 1
The molecular structure of (I

), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The suffix A corresponds to the symmetry code (−x, −y, 1 − z).

Figure 2
The packing scheme for (I); red lines represent N—H⋯Cl hydrogen bonds.

Experimental

CdCl₂·H₂O (0.20 g, 1 mmol) was suspended in MeOH (10 ml). 3,5–Dimethyl-1-(thiocarbamoyl)pyrazole (0.31 g, 2 mmol) was added to the suspension. The reaction mixture was heated under reflux. After 30 min of heating, the resulting clear solution was left at room temperature. About 3 h later, the white precipitate was filtered off, washed with MeOH and air-dried (yield: 0.14 g, 41%). Needle-shaped single crystals were obtained by recrystallization from MeOH.

Crystal data

[Cd₂Cl₄(C₆H₉N₃S)₂]
M_r = 677.06
Triclinic, $[P\overline 1]$
a = 7.7442 (11) Å
b = 8.6866 (12) Å
c = 8.7559 (12) Å
α = 90.213 (3)°
β = 110.427 (3)°
γ = 103.074 (3)°
V = 535.46 (13) Å³
Z = 1
D_x = 2.100 Mg m⁻³
Mo Kα radiation
Cell parameters from 3323 reflections
θ = 4.8–60.1°
μ = 2.69 mm⁻¹
T = 150 K
Needle, white
0.10 × 0.04 × 0.04 mm

Data collection

Bruker SMART APEX diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.841, T_max = 0.900
6938 measured reflections
3102 independent reflections
2669 reflections with I > 2σ(I)
R_int = 0.018
θ_max = 30.1°
h = −10 → 10
k = −12 → 12
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.053
S = 0.91
2669 reflections
118 parameters
H-atom parameters not refined
w = [1 − (F_o − F_c)²/36σ²(F)]²/[2.82T₀(x) + 3.29T₁(x) + 1.36T₂(x)] where T_i are Chebychev polynomials and x = F_c/F_max (Watkin, 1994 ; Prince, 1982 )
(Δ/σ)_max = 0.001
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cd1—Cl2ⁱ	2.6174 (7)
Cd1—Cl2	2.5393 (7)
Cd1—S3	2.5768 (7)
Cd1—Cl4	2.4598 (7)
Cd1—N5	2.343 (2)
S3—C8	1.701 (3)
N5—N7	1.383 (3)
N5—C12	1.313 (3)
N6—C8	1.312 (3)
N7—C8	1.393 (3)
N7—C10	1.396 (3)
C9—C10	1.363 (4)
C9—C12	1.416 (4)
C10—C13	1.492 (4)
C11—C12	1.494 (4)

Cl2ⁱ—Cd1—Cl2	86.30 (2)
Cl2ⁱ—Cd1—S3	94.26 (3)
Cl2—Cd1—S3	120.31 (3)
Cl2ⁱ—Cd1—Cl4	98.40 (2)
Cl2—Cd1—Cl4	115.31 (2)
S3—Cd1—Cl4	123.50 (2)
Cl2ⁱ—Cd1—N5	165.20 (6)
Cl2—Cd1—N5	90.24 (6)
S3—Cd1—N5	75.10 (5)
Cl4—Cd1—N5	96.09 (6)
Cd1ⁱ—Cl2—Cd1	93.70 (2)
Cd1—S3—C8	101.41 (9)
Cd1—N5—N7	120.12 (16)
Cd1—N5—C12	131.48 (17)
N7—N5—C12	106.5 (2)
N5—N7—C8	118.6 (2)
N5—N7—C10	109.9 (2)
C8—N7—C10	131.4 (2)
N7—C8—S3	122.18 (19)
N7—C8—N6	117.9 (2)
S3—C8—N6	119.9 (2)
C10—C9—C12	106.8 (2)
N7—C10—C9	106.2 (2)
N7—C10—C13	125.8 (2)
C9—C10—C13	128.0 (2)
C11—C12—C9	128.2 (2)
C11—C12—N5	121.2 (2)
C9—C12—N5	110.7 (2)
Symmetry code: (i) -x,-y,1-z.

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H1⋯Cl4ⁱⁱ	1.00	2.34	3.252 (3)	151
N6—H2⋯Cl4ⁱⁱⁱ	1.00	2.47	3.232 (3)	133
Symmetry codes: (ii) 1-x,-y,2-z; (iii) x,y,1+z.

H atoms were placed geometrically after each cycle and treated as riding on their carrier atoms, with N/C—H = 1.00 Å and U_iso(H) = 1.2U_eq(N,C).

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ATOMS (Dowty, 2000 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805006173/wn6332sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805006173/wn6332Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: CRYSTALS.

(I) top

Crystal data top

[Cd₂Cl₄(C₆H₉N₃S)₂]	Z = 1
M_r = 677.06	F(000) = 328
Triclinic, P1	D_x = 2.100 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7442 (11) Å	Cell parameters from 3323 reflections
b = 8.6866 (12) Å	θ = 4.8–60.1°
c = 8.7559 (12) Å	µ = 2.69 mm⁻¹
α = 90.213 (3)°	T = 150 K
β = 110.427 (3)°	Needle, white
γ = 103.074 (3)°	0.10 × 0.04 × 0.04 mm
V = 535.46 (13) Å³

Data collection top

Bruker SMART APEX diffractometer	2669 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 30.1°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.841, T_max = 0.900	k = −12→12
6938 measured reflections	l = −12→12
3102 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H-atom parameters not refined
wR(F²) = 0.053	w = [1-(F_o-F_c)²/36σ²(F)]²/[2.82T₀(x) + 3.29T₁(x) + 1.36T₂(x)] where T_i are Chebychev polynomials and x = F_c/F_max (Watkin, 1994; Prince, 1982)
S = 0.91	(Δ/σ)_max = 0.001
2669 reflections	Δρ_max = 0.63 e Å⁻³
118 parameters	Δρ_min = −0.65 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
Cd1	0.21166 (3)	0.09432 (2)	0.68651 (2)	0.0173
Cl2	−0.09082 (9)	0.16729 (8)	0.50856 (8)	0.0205
S3	0.22169 (10)	−0.05068 (8)	0.94454 (8)	0.0211
Cl4	0.49608 (9)	0.21159 (8)	0.62265 (8)	0.0193
N5	0.2613 (3)	0.2944 (3)	0.8882 (3)	0.0175
N6	0.3136 (4)	0.0813 (3)	1.2401 (3)	0.0231
N7	0.2531 (3)	0.2553 (3)	1.0389 (3)	0.0162
C8	0.2656 (4)	0.1035 (3)	1.0841 (3)	0.0173
C9	0.2397 (4)	0.5060 (3)	1.0224 (3)	0.0196
C10	0.2381 (4)	0.3860 (3)	1.1223 (3)	0.0175
C11	0.2633 (4)	0.5273 (3)	0.7319 (3)	0.0233
C12	0.2552 (4)	0.4441 (3)	0.8791 (3)	0.0182
C13	0.2157 (4)	0.3880 (3)	1.2846 (3)	0.0231
H1	0.3246	−0.0261	1.2768	0.0209*
H2	0.3394	0.1718	1.3222	0.0209*
H3	0.1749	0.4869	1.2983	0.0301*
H4	0.3392	0.3889	1.3737	0.0294*
H5	0.1171	0.2926	1.2878	0.0294*
H6	0.2315	0.6163	1.0459	0.0241*
H7	0.2568	0.6397	0.7475	0.0285*
H8	0.1537	0.4721	0.6330	0.0285*
H9	0.3850	0.5258	0.7167	0.0285*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01818 (9)	0.01946 (9)	0.01484 (8)	0.00495 (6)	0.00638 (6)	0.00165 (6)
Cl2	0.0203 (3)	0.0195 (3)	0.0210 (3)	0.0074 (2)	0.0049 (2)	0.0008 (2)
S3	0.0304 (3)	0.0161 (3)	0.0166 (3)	0.0064 (2)	0.0077 (2)	0.0020 (2)
Cl4	0.0184 (3)	0.0215 (3)	0.0183 (3)	0.0044 (2)	0.0072 (2)	0.0016 (2)
N5	0.0220 (10)	0.0173 (10)	0.0140 (9)	0.0049 (8)	0.0075 (8)	0.0033 (7)
N6	0.0357 (13)	0.0198 (10)	0.0149 (10)	0.0106 (10)	0.0081 (9)	0.0035 (8)
N7	0.0175 (9)	0.0169 (10)	0.0139 (9)	0.0041 (8)	0.0053 (7)	0.0021 (7)
C8	0.0179 (11)	0.0166 (11)	0.0170 (11)	0.0042 (9)	0.0060 (9)	0.0025 (9)
C9	0.0203 (12)	0.0178 (11)	0.0222 (12)	0.0066 (9)	0.0082 (10)	0.0026 (9)
C10	0.0158 (10)	0.0178 (11)	0.0183 (11)	0.0038 (9)	0.0058 (9)	0.0001 (9)
C11	0.0273 (13)	0.0211 (12)	0.0226 (12)	0.0068 (10)	0.0098 (10)	0.0078 (10)
C12	0.0173 (11)	0.0186 (11)	0.0182 (11)	0.0046 (9)	0.0056 (9)	0.0037 (9)
C13	0.0305 (14)	0.0221 (12)	0.0210 (12)	0.0080 (11)	0.0135 (11)	0.0019 (10)

Geometric parameters (Å, º) top

Cd1—Cl2ⁱ	2.6174 (7)	N7—C10	1.396 (3)
Cd1—Cl2	2.5393 (7)	C9—C10	1.363 (4)
Cd1—S3	2.5768 (7)	C9—C12	1.416 (4)
Cd1—Cl4	2.4598 (7)	C9—H6	1.000
Cd1—N5	2.343 (2)	C10—C13	1.492 (4)
S3—C8	1.701 (3)	C11—C12	1.494 (4)
N5—N7	1.383 (3)	C11—H7	1.000
N5—C12	1.313 (3)	C11—H8	1.000
N6—C8	1.312 (3)	C11—H9	1.000
N6—H1	1.000	C13—H3	1.000
N6—H2	1.000	C13—H4	1.000
N7—C8	1.393 (3)	C13—H5	1.000

Cl2ⁱ—Cd1—Cl2	86.30 (2)	S3—C8—N6	119.9 (2)
Cl2ⁱ—Cd1—S3	94.26 (3)	C10—C9—C12	106.8 (2)
Cl2—Cd1—S3	120.31 (3)	C10—C9—H6	126.568
Cl2ⁱ—Cd1—Cl4	98.40 (2)	C12—C9—H6	126.659
Cl2—Cd1—Cl4	115.31 (2)	N7—C10—C9	106.2 (2)
S3—Cd1—Cl4	123.50 (2)	N7—C10—C13	125.8 (2)
Cl2ⁱ—Cd1—N5	165.20 (6)	C9—C10—C13	128.0 (2)
Cl2—Cd1—N5	90.24 (6)	C12—C11—H7	109.516
S3—Cd1—N5	75.10 (5)	C12—C11—H8	109.530
Cl4—Cd1—N5	96.09 (6)	H7—C11—H8	109.475
Cd1ⁱ—Cl2—Cd1	93.70 (2)	C12—C11—H9	109.354
Cd1—S3—C8	101.41 (9)	H7—C11—H9	109.476
Cd1—N5—N7	120.12 (16)	H8—C11—H9	109.477
Cd1—N5—C12	131.48 (17)	C11—C12—C9	128.2 (2)
N7—N5—C12	106.5 (2)	C11—C12—N5	121.2 (2)
C8—N6—H1	119.986	C9—C12—N5	110.7 (2)
C8—N6—H2	120.013	C10—C13—H3	106.901
H1—N6—H2	120.001	C10—C13—H4	110.079
N5—N7—C8	118.6 (2)	H3—C13—H4	110.121
N5—N7—C10	109.9 (2)	C10—C13—H5	110.123
C8—N7—C10	131.4 (2)	H3—C13—H5	110.121
N7—C8—S3	122.18 (19)	H4—C13—H5	109.467
N7—C8—N6	117.9 (2)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H1···Cl4ⁱⁱ	1.00	2.34	3.252 (3)	151
N6—H2···Cl4ⁱⁱⁱ	1.00	2.47	3.232 (3)	133

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

Footnotes

¹Transition metal complexes with pyrazole-based ligands, Part XX

Acknowledgements

This work was financed in part by the Ministry for Science and Environmental Protection of the Republic of Serbia (Project 1318 – Physicochemical, Structural and Biological Investigation of Complex Compounds). IRE thanks the EPSRC for an Academic Fellowship.

References

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