Poly[di-μ-thiocyanato-κ2N:S;κ2S:N-bis­[2-(1H-1,2,3-triazol-1-yl-κN3)pyra­zine]cadmium(II)]

Liu, C.Q.; Xie, L.M.; Zhao, M.G.

doi:10.1107/S1600536809036332

metal-organic compounds

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Volume 65| Part 10| October 2009| Page m1211

doi:10.1107/S1600536809036332

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Poly[di-μ-thiocyanato-κ²N:S;κ²S:N-bis[2-(1H-1,2,3-triazol-1-yl-κN³)pyrazine]cadmium(II)]

Cheng Qi Liu,^a Long Miao Xie ^b and Ming Gen Zhao ^a ^*

^aDepartment of Chemistry, Xinzhou Teachers' University, Shanxi, Xinzhou 034000, People's Republic of China, and ^bDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: zhaominggen1957@yahoo.com.cn

(Received 14 July 2009; accepted 8 September 2009; online 12 September 2009)

In the title two-dimensional coordination polymer, [Cd(NCS)₂(C₆H₅N₅)₂]_n, the Cd^II ion (site symmetry $[\overline1]$ ) is coordinated by two N atoms from two 2-(1H-1,2,3-triazol-1-yl)pyrazine ligands and two N and two S atoms from four thiocyanate anions. The N—Cd bond lengths range from 2.323 (2) to 2.3655 (19) Å and the S—Cd bond length is 2.7117 (7) Å. The associated cisoid angles vary from 84.99 (7) to 95.01 (7)°, indicating that the Cd^II ion assumes a distorted octahedral geometry. In the complex, each thiocyanate anion functions as a bridging ligand, linking adjacent Cd^II ions with a separation of 6.4919 (6) Å, resulting in the formation of a two-dimensional sheet structure in the bc plane.

Related literature

For a related crystal structure, see: Yang & Shi (2008 ). For the synthesis of Cd^II complexes with thiocyanate anions and pyrazine derivatives as mixed bridging ligands, see: Li et al. (2008 ); Shi et al. (2007 ).

Experimental

Crystal data

[Cd(NCS)₂(C₆H₅N₅)₂]
M_r = 522.86
Monoclinic, P 2₁ /c
a = 12.5038 (15) Å
b = 10.7240 (13) Å
c = 7.3196 (9) Å
β = 106.476 (2)°
V = 941.2 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.41 mm⁻¹
T = 298 K
0.24 × 0.18 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.728, T_max = 0.806
5139 measured reflections
1923 independent reflections
1735 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.064
S = 1.03
1923 reflections
133 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected bond angless (°)

N6ⁱ—Cd1—N1	84.99 (7)
N6ⁱⁱ—Cd1—N1	95.01 (7)
N6ⁱⁱ—Cd1—S1ⁱⁱⁱ	91.07 (6)
N1—Cd1—S1ⁱⁱⁱ	94.56 (5)
N6ⁱⁱ—Cd1—S1	88.93 (6)
N1—Cd1—S1	85.44 (5)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x, -y+2, -z.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809036332/bv2122sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809036332/bv2122Isup2.hkl

checkCIF report

Comment top

2-(1H-1,2,3-triazol-1-yl)pyrazine is similar to 2-(pyrazol-1-yl)pyrazine (Yang & Shi 2008) in structure and therefore it should act as a bridging ligand. Our interest in synthesizing Cd^II complexes (Shi et al., 2007; Li et al., 2008) with thiocyanate anions and derivatives of pyrazine as mixed bridging ligands resulted in us selecting thiocyanato and 2-(1H-1,2,3-triazol-1-yl)pyrazine as ligands, but only the title complex was obtained, in which 2-(1H-1,2,3-triazol-1-yl)pyrazine only functions as a terminal ligand. Herein we report the crystal structure of the title complex.

The asymmetric unit and symmetry-related fragments of (I) are shown in Fig. 1, and Fig.1 and Table 1 reveal that Cd1 atom is in a distorted octahedral CdN₄S₂ coordination geometry. In the crystal each Cd^II ion is surrounded by four other symmetry-related Cd^II ions with separation with 6.4919 (6) Å and the adjacent Cd^II ions were bridged by one thiocyanato anions and it forms a two-dimensional sheet on bc plane as shown in Fig. 2. 2-(1H-1,2,3-triazol-1-yl)pyrazine only acts as a monodentate ligand.

Related literature top

For a related crystal structure, see: Yang & Shi (2008). For the synthesis of Cd^II complexes with thiocyanate anions and pyrazine derivatives as mixed bridging ligands, see: Li et al. (2008); Shi et al. (2007).

Experimental top

An 8 ml methanol solution of 2-(1H-1,2,3-triazol-1-yl)pyrazine (0.0401 g, 0.272 mmol), 5 ml water solution of Cd(ClO₄)₂.6H₂O (0.1120 g, 0.267 mmol) and 5 ml water solution of NaSCN (0.0435 g, 0.537 mmol) were mixed together and stirred for a few minutes. The colorless single crystals were obtained after the filtrate had been allowed to stand at room temperature for ten days.

Computing details top

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

Figures top

	Fig. 1. The coordination structure of (I) showing the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) -x, y - 1/2, -z + 1/2 (ii) -x, -y + 2, -z (iii) x, -y + 5/2, z - 1/2 (iv) -x, y + 1/2, -z - 1/2 (v) -x, y - 1/2, -z - 1/2 (iv) -x, y + 1/2, -z + 1/2]
	Fig. 2. Unit cell and the part of the two-dimensional sheet on bc plane.

Poly[di-µ-thiocyanato-κ²N:S;κ²S:N-bis[2-(1H-1,2,3-triazol-1-yl-κN³)pyrazine]cadmium(II)] top

Crystal data top

[Cd(NCS)₂(C₆H₅N₅)₂]	F(000) = 516
M_r = 522.86	D_x = 1.845 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3160 reflections
a = 12.5038 (15) Å	θ = 2.6–28.0°
b = 10.7240 (13) Å	µ = 1.41 mm⁻¹
c = 7.3196 (9) Å	T = 298 K
β = 106.476 (2)°	Block, colorless
V = 941.2 (2) Å³	0.24 × 0.18 × 0.16 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	1923 independent reflections
Radiation source: fine-focus sealed tube	1735 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 26.4°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.728, T_max = 0.806	k = −13→12
5139 measured reflections	l = −6→9

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0289P)² + 0.6077P] where P = (F_o² + 2F_c²)/3
1923 reflections	(Δ/σ)_max = 0.001
133 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Cd(NCS)₂(C₆H₅N₅)₂]	V = 941.2 (2) Å³
M_r = 522.86	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.5038 (15) Å	µ = 1.41 mm⁻¹
b = 10.7240 (13) Å	T = 298 K
c = 7.3196 (9) Å	0.24 × 0.18 × 0.16 mm
β = 106.476 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	1923 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1735 reflections with I > 2σ(I)
T_min = 0.728, T_max = 0.806	R_int = 0.023
5139 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.03	Δρ_max = 0.55 e Å⁻³
1923 reflections	Δρ_min = −0.34 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 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
C1	0.1593 (2)	0.7435 (2)	0.0075 (4)	0.0390 (6)
H1	0.0980	0.6904	−0.0225	0.047*
C2	0.2671 (2)	0.7082 (2)	0.0439 (4)	0.0405 (6)
H2	0.2951	0.6278	0.0441	0.049*
C3	0.44202 (19)	0.8353 (2)	0.1282 (3)	0.0348 (5)
C4	0.6101 (2)	0.7616 (3)	0.1322 (4)	0.0521 (7)
H4	0.6555	0.6987	0.1083	0.063*
C5	0.6582 (2)	0.8710 (3)	0.2116 (4)	0.0530 (7)
H5	0.7347	0.8817	0.2350	0.064*
C6	0.4896 (2)	0.9434 (3)	0.2156 (5)	0.0506 (7)
H6	0.4446	1.0041	0.2468	0.061*
C7	0.08801 (19)	1.2249 (2)	0.3671 (3)	0.0331 (5)
Cd1	0.0000	1.0000	0.0000	0.03129 (10)
N1	0.15559 (16)	0.86932 (18)	0.0222 (3)	0.0370 (5)
N2	0.25664 (17)	0.91457 (18)	0.0669 (3)	0.0393 (5)
N3	0.32500 (16)	0.81662 (17)	0.0798 (3)	0.0336 (4)
N4	0.50015 (18)	0.7423 (2)	0.0879 (4)	0.0464 (5)
N5	0.5982 (2)	0.9623 (3)	0.2560 (5)	0.0615 (7)
N6	0.07295 (19)	1.32994 (19)	0.3793 (3)	0.0452 (5)
S1	0.11190 (7)	1.07527 (6)	0.35667 (11)	0.0530 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0328 (13)	0.0276 (11)	0.0548 (16)	0.0003 (9)	0.0097 (11)	−0.0064 (11)
C2	0.0363 (13)	0.0268 (11)	0.0566 (16)	0.0025 (10)	0.0104 (12)	−0.0060 (11)
C3	0.0333 (12)	0.0363 (12)	0.0350 (12)	0.0027 (10)	0.0098 (10)	−0.0011 (10)
C4	0.0379 (15)	0.0618 (18)	0.0593 (19)	0.0058 (13)	0.0181 (13)	−0.0065 (15)
C5	0.0335 (14)	0.0681 (19)	0.0564 (18)	−0.0022 (13)	0.0113 (13)	0.0008 (15)
C6	0.0370 (14)	0.0413 (15)	0.070 (2)	0.0015 (12)	0.0094 (13)	−0.0099 (14)
C7	0.0310 (12)	0.0315 (12)	0.0370 (13)	−0.0020 (9)	0.0097 (10)	−0.0056 (10)
Cd1	0.02776 (14)	0.01935 (13)	0.04655 (17)	0.00164 (8)	0.01019 (11)	0.00206 (9)
N1	0.0321 (10)	0.0283 (10)	0.0496 (13)	0.0032 (8)	0.0098 (9)	−0.0009 (9)
N2	0.0340 (11)	0.0265 (10)	0.0578 (14)	0.0039 (8)	0.0134 (10)	−0.0011 (9)
N3	0.0311 (10)	0.0274 (9)	0.0415 (11)	0.0041 (8)	0.0087 (8)	−0.0024 (8)
N4	0.0379 (12)	0.0450 (12)	0.0575 (15)	0.0042 (10)	0.0157 (10)	−0.0089 (11)
N5	0.0397 (14)	0.0541 (14)	0.085 (2)	−0.0095 (12)	0.0082 (13)	−0.0145 (15)
N6	0.0462 (13)	0.0323 (11)	0.0571 (14)	0.0036 (9)	0.0145 (11)	−0.0081 (10)
S1	0.0712 (5)	0.0266 (3)	0.0485 (4)	0.0086 (3)	−0.0037 (3)	−0.0046 (3)

Geometric parameters (Å, º) top

C1—C2	1.352 (3)	C6—N5	1.322 (4)
C1—N1	1.355 (3)	C6—H6	0.9300
C1—H1	0.9300	C7—N6	1.150 (3)
C2—N3	1.356 (3)	C7—S1	1.638 (2)
C2—H2	0.9300	Cd1—N6ⁱ	2.323 (2)
C3—N4	1.316 (3)	Cd1—N6ⁱⁱ	2.323 (2)
C3—C6	1.375 (4)	Cd1—N1	2.3655 (19)
C3—N3	1.419 (3)	Cd1—N1ⁱⁱⁱ	2.3655 (19)
C4—N4	1.336 (4)	Cd1—S1ⁱⁱⁱ	2.7117 (7)
C4—C5	1.370 (4)	Cd1—S1	2.7117 (7)
C4—H4	0.9300	N1—N2	1.306 (3)
C5—N5	1.328 (4)	N2—N3	1.341 (3)
C5—H5	0.9300	N6—Cd1^iv	2.323 (2)

C2—C1—N1	108.6 (2)	N6ⁱⁱ—Cd1—N1ⁱⁱⁱ	84.99 (7)
C2—C1—H1	125.7	N1—Cd1—N1ⁱⁱⁱ	180.0
N1—C1—H1	125.7	N6ⁱ—Cd1—S1ⁱⁱⁱ	88.93 (6)
C1—C2—N3	104.2 (2)	N6ⁱⁱ—Cd1—S1ⁱⁱⁱ	91.07 (6)
C1—C2—H2	127.9	N1—Cd1—S1ⁱⁱⁱ	94.56 (5)
N3—C2—H2	127.9	N1ⁱⁱⁱ—Cd1—S1ⁱⁱⁱ	85.44 (5)
N4—C3—C6	123.3 (2)	N6ⁱ—Cd1—S1	91.07 (6)
N4—C3—N3	115.7 (2)	N6ⁱⁱ—Cd1—S1	88.93 (6)
C6—C3—N3	121.0 (2)	N1—Cd1—S1	85.44 (5)
N4—C4—C5	122.2 (3)	N1ⁱⁱⁱ—Cd1—S1	94.56 (5)
N4—C4—H4	118.9	S1ⁱⁱⁱ—Cd1—S1	180.0
C5—C4—H4	118.9	N2—N1—C1	109.69 (19)
N5—C5—C4	121.6 (3)	N2—N1—Cd1	121.04 (14)
N5—C5—H5	119.2	C1—N1—Cd1	129.10 (16)
C4—C5—H5	119.2	N1—N2—N3	106.19 (18)
N5—C6—C3	121.0 (3)	N2—N3—C2	111.33 (19)
N5—C6—H6	119.5	N2—N3—C3	119.93 (19)
C3—C6—H6	119.5	C2—N3—C3	128.7 (2)
N6—C7—S1	178.2 (3)	C3—N4—C4	115.1 (2)
N6ⁱ—Cd1—N6ⁱⁱ	180.0	C6—N5—C5	116.6 (3)
N6ⁱ—Cd1—N1	84.99 (7)	C7—N6—Cd1^iv	152.8 (2)
N6ⁱⁱ—Cd1—N1	95.01 (7)	C7—S1—Cd1	106.59 (9)
N6ⁱ—Cd1—N1ⁱⁱⁱ	95.01 (7)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+5/2, z−1/2; (iii) −x, −y+2, −z; (iv) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cd(NCS)₂(C₆H₅N₅)₂]
M_r	522.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.5038 (15), 10.7240 (13), 7.3196 (9)
β (°)	106.476 (2)
V (Å³)	941.2 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.41
Crystal size (mm)	0.24 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.728, 0.806
No. of measured, independent and observed [I > 2σ(I)] reflections	5139, 1923, 1735
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.064, 1.03
No. of reflections	1923
No. of parameters	133
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.34

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

Selected geometric parameters (Å, º) top

Cd1—N6ⁱ	2.323 (2)	Cd1—S1	2.7117 (7)
Cd1—N1	2.3655 (19)

N6ⁱ—Cd1—N1	84.99 (7)	N1—Cd1—S1ⁱⁱⁱ	94.56 (5)
N6ⁱⁱ—Cd1—N1	95.01 (7)	N6ⁱⁱ—Cd1—S1	88.93 (6)
N6ⁱⁱ—Cd1—S1ⁱⁱⁱ	91.07 (6)	N1—Cd1—S1	85.44 (5)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+5/2, z−1/2; (iii) −x, −y+2, −z.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, H., Xu, H. Y., Zhang, S. G. & Shi, J. M. (2008). J. Coord. Chem. 61, 2807–2813. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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Yang, L. Y. & Shi, J. M. (2008). Acta Cryst. E64, m1387. Web of Science CSD CrossRef IUCr Journals Google Scholar

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