catena-Poly[(μ-2-amino-1,3,4-thia­diazole-κ2N3:N4)di-μ-chlorido-cadmium]

Suen, M.-C.; Yeh, C.-W.; Jou, C.-H.

doi:10.1107/S1600536811027048

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1082

doi:10.1107/S1600536811027048

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catena-Poly[(μ-2-amino-1,3,4-thiadiazole-κ²N³:N⁴)di-μ-chlorido-cadmium]

Maw-Cherng Suen,^a ^* Chun-Wei Yeh ^b and Chi-Hsiung Jou ^c

^aDepartment of Material and Fiber, Nanya Institute of Technology, Chung-Li 320, Taiwan, ^bDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li, Taiwan, and ^cDepartment of Materials and Textiles, Oriental Institute of Technology, New Taipei City, Taiwan
^*Correspondence e-mail: sun@nanya.edu.tw

(Received 4 July 2011; accepted 6 July 2011; online 13 July 2011)

In the title coordination polymer, [CdCl₂(C₂H₃N₃S)]_n, the Cd^II cation is coordinated by four Cl⁻ anions and two N atoms from two trans 2-amino-1,3,4-thiadiazole (L) ligands in a distorted octahedral geometry. The L ligand and Cl⁻ anions bridge adjacent Cd cations, forming a polymeric chain along the b axis; the separation between adjacent Cd cations is 3.619 (1) Å. In the crystal, the polymeric chains are interlinking through N—H⋯Cl hydrogen bonds between the L ligands and Cl⁻ anions.

Related literature

For background to coordination polymers, see: Kitagawa et al. (2004 ); Chiang et al. (2008 ); Yeh et al. (2008 , 2009 ); Hsu et al. (2009 ). For related Cd coordination polymers, see: Suen & Wang (2007a ,b ).

Experimental

Crystal data

[CdCl₂(C₂H₃N₃S)]
M_r = 284.43
Monoclinic, P 2₁ /n
a = 7.7264 (6) Å
b = 7.2227 (6) Å
c = 12.7608 (11) Å
β = 95.489 (2)°
V = 708.86 (10) Å³
Z = 4
Mo Kα radiation
μ = 4.04 mm⁻¹
T = 297 K
0.48 × 0.46 × 0.34 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.170, T_max = 0.341
3718 measured reflections
1381 independent reflections
1354 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.056
S = 1.16
1381 reflections
83 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd—N1	2.361 (2)
Cd—N2ⁱ	2.341 (2)
Cd—Cl1	2.6262 (7)
Cd—Cl1ⁱⁱ	2.6697 (7)
Cd—Cl2	2.6583 (7)
Cd—Cl2ⁱⁱ	2.6222 (7)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Cl2ⁱⁱⁱ	0.86	2.60	3.390 (3)	154
N3—H3B⋯Cl2^iv	0.86	2.77	3.216 (3)	114
Symmetry codes: (iii) x, y+1, z; (iv) -x+2, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DAIMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811027048/xu5265sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027048/xu5265Isup2.hkl

checkCIF report

Comment top

The synthesis of metal coordination polymers has been a subject of intense research due to their interesting structural chemistry and potential applications in gas storage, separation, catalysis, magnetism, luminescence, and drug delivery (Kitagawa et al., 2004). Roles of anion, solvent and ligand comformations in self-assembly of coordination complexes containing polydentate nitrogen ligands are very intersting (Chiang et al., 2008; Yeh et al., 2008; Hsu et al., 2009; Yeh et al., 2009). Tha Cd(II) complexes containing polydentate ligands showing various type frameworks are also reported (Suen & Wang, 2007a,b). The Cd²⁺ cations are six-coordinate, which are coordinated with four Cl atoms and two N atoms from two L ligands (Fig. 1). The Cd···Cd distance separated by the bridging L ligands and Cl atoms is 10.257 (1) and 3.619 (1) Å. The one-dimensional polymeric chains are interlinking through N—H···Cl hydrogen bonds between the L ligands and Cl anions in the crystal structure (Fig. 2, Tab.1).

Related literature top

For background to coordination polymers, see: Kitagawa et al. (2004); Chiang et al. (2008); Yeh et al. (2008, 2009); Hsu et al. (2009). For related Cd(II) coordination polymers, see: Suen & Wang (2007a,b).

Experimental top

An aqueous solution (5.0 ml) of cadmium chloride (1.0 mmol) was layered carefully over a methanolic solution (5.0 ml) of 2-amino-1,3,4-thiadiazole (1.0 mmol) in a tube. Colourless crystals were obtained after several weeks. These were washed with methanol and collected in 68.7% yield.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DAIMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A portion of the one-dimensional chain. Ellipsoids are drawn at 30% probability level, and H atoms of spheres of arbitrary radius. Symmetry codes: (i) -x + 3/2, y - 1/2, -z + 3/2; (ii) -x + 3/2, y + 1/2, -z + 3/2.
	Fig. 2. The packing diagram shows the N—H···Cl hydrogen bonds among the one-dimensional Chains.

catena-Poly[(µ-2-amino-1,3,4-thiadiazole- κ²N³:N⁴)di-µ-chlorido-cadmium] top

Crystal data top

[CdCl₂(C₂H₃N₃S)]	F(000) = 536
M_r = 284.43	D_x = 2.665 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3467 reflections
a = 7.7264 (6) Å	θ = 2.7–26.0°
b = 7.2227 (6) Å	µ = 4.04 mm⁻¹
c = 12.7608 (11) Å	T = 297 K
β = 95.489 (2)°	Parallelepiped, colourless
V = 708.86 (10) Å³	0.48 × 0.46 × 0.34 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1381 independent reflections
Radiation source: fine-focus sealed tube	1354 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
T_min = 0.170, T_max = 0.341	k = −8→7
3718 measured reflections	l = −15→10

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)] = 0.021	H-atom parameters constrained
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0313P)² + 0.7123P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max = 0.001
1381 reflections	Δρ_max = 0.61 e Å⁻³
83 parameters	Δρ_min = −0.76 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0097 (6)

Crystal data top

[CdCl₂(C₂H₃N₃S)]	V = 708.86 (10) Å³
M_r = 284.43	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.7264 (6) Å	µ = 4.04 mm⁻¹
b = 7.2227 (6) Å	T = 297 K
c = 12.7608 (11) Å	0.48 × 0.46 × 0.34 mm
β = 95.489 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1381 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1354 reflections with I > 2σ(I)
T_min = 0.170, T_max = 0.341	R_int = 0.019
3718 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	1 restraint
wR(F²) = 0.056	H-atom parameters constrained
S = 1.16	Δρ_max = 0.61 e Å⁻³
1381 reflections	Δρ_min = −0.76 e Å⁻³
83 parameters

Special details top

Experimental. 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.

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
Cd	0.73571 (3)	0.17322 (3)	0.745512 (14)	0.02441 (12)
Cl1	0.51717 (10)	−0.08486 (9)	0.79344 (6)	0.02966 (18)
Cl2	0.97270 (10)	−0.06290 (9)	0.83088 (6)	0.03076 (18)
S	0.70167 (11)	0.40964 (10)	1.09911 (6)	0.03228 (19)
N1	0.7182 (3)	0.3292 (3)	0.90672 (19)	0.0253 (5)
N2	0.7623 (3)	0.5146 (3)	0.91436 (18)	0.0245 (5)
N3	0.7988 (4)	0.7503 (4)	1.0408 (2)	0.0412 (7)
H3A	0.8242	0.8302	0.9947	0.049*
H3B	0.7969	0.7827	1.1056	0.049*
C1	0.6831 (4)	0.2586 (4)	0.9949 (2)	0.0281 (6)
H1A	0.6504	0.1356	1.0016	0.034*
C2	0.7623 (4)	0.5757 (4)	1.0118 (2)	0.0260 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd	0.03477 (16)	0.01300 (14)	0.02532 (16)	0.00063 (7)	0.00221 (9)	−0.00127 (6)
Cl1	0.0319 (4)	0.0198 (3)	0.0383 (4)	−0.0011 (3)	0.0083 (3)	0.0025 (3)
Cl2	0.0327 (4)	0.0180 (3)	0.0395 (4)	−0.0019 (3)	−0.0070 (3)	0.0008 (3)
S	0.0457 (5)	0.0284 (4)	0.0229 (4)	−0.0039 (3)	0.0040 (3)	0.0012 (3)
N1	0.0344 (13)	0.0146 (11)	0.0270 (12)	0.0000 (9)	0.0037 (10)	−0.0012 (9)
N2	0.0324 (12)	0.0156 (11)	0.0255 (11)	−0.0012 (9)	0.0025 (9)	−0.0007 (9)
N3	0.0633 (19)	0.0271 (14)	0.0331 (14)	−0.0125 (13)	0.0037 (13)	−0.0069 (11)
C1	0.0370 (16)	0.0189 (14)	0.0282 (14)	−0.0014 (12)	0.0027 (11)	0.0014 (11)
C2	0.0298 (15)	0.0218 (14)	0.0258 (14)	0.0001 (11)	−0.0006 (11)	−0.0006 (10)

Geometric parameters (Å, º) top

Cd—N1	2.361 (2)	N1—C1	1.287 (4)
Cd—N2ⁱ	2.341 (2)	N1—N2	1.383 (3)
Cd—Cl1	2.6262 (7)	N2—C2	1.320 (4)
Cd—Cl1ⁱⁱ	2.6697 (7)	N2—Cdⁱⁱ	2.341 (2)
Cd—Cl2	2.6583 (7)	N3—C2	1.337 (4)
Cd—Cl2ⁱⁱ	2.6222 (7)	N3—H3A	0.8600
S—C1	1.715 (3)	N3—H3B	0.8600
S—C2	1.731 (3)	C1—H1A	0.9300

N2ⁱ—Cd—N1	177.00 (9)	C1—S—C2	87.11 (14)
N2ⁱ—Cd—Cl2ⁱⁱ	94.97 (6)	C1—N1—N2	113.1 (2)
N1—Cd—Cl2ⁱⁱ	83.84 (6)	C1—N1—Cd	127.38 (19)
N2ⁱ—Cd—Cl1	85.04 (6)	N2—N1—Cd	119.28 (16)
N1—Cd—Cl1	92.52 (6)	C2—N2—N1	111.6 (2)
Cl2ⁱⁱ—Cd—Cl1	102.52 (2)	C2—N2—Cdⁱⁱ	131.18 (19)
N2ⁱ—Cd—Cl2	88.94 (6)	N1—N2—Cdⁱⁱ	115.76 (16)
N1—Cd—Cl2	92.51 (6)	C2—N3—H3A	120.0
Cl2ⁱⁱ—Cd—Cl2	173.27 (2)	C2—N3—H3B	120.0
Cl1—Cd—Cl2	83.24 (2)	H3A—N3—H3B	120.0
N2ⁱ—Cd—Cl1ⁱⁱ	95.37 (6)	N1—C1—S	114.6 (2)
N1—Cd—Cl1ⁱⁱ	87.23 (6)	N1—C1—H1A	122.7
Cl2ⁱⁱ—Cd—Cl1ⁱⁱ	83.09 (2)	S—C1—H1A	122.7
Cl1—Cd—Cl1ⁱⁱ	174.324 (18)	N2—C2—N3	123.8 (3)
Cl2—Cd—Cl1ⁱⁱ	91.11 (2)	N2—C2—S	113.5 (2)
Cd—Cl1—Cdⁱ	86.22 (2)	N3—C2—S	122.6 (2)
Cdⁱ—Cl2—Cd	86.53 (2)

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl2ⁱⁱⁱ	0.86	2.60	3.390 (3)	154
N3—H3B···Cl2^iv	0.86	2.77	3.216 (3)	114

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

Experimental details

Crystal data
Chemical formula	[CdCl₂(C₂H₃N₃S)]
M_r	284.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	297
a, b, c (Å)	7.7264 (6), 7.2227 (6), 12.7608 (11)
β (°)	95.489 (2)
V (Å³)	708.86 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.04
Crystal size (mm)	0.48 × 0.46 × 0.34

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.170, 0.341
No. of measured, independent and observed [I > 2σ(I)] reflections	3718, 1381, 1354
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.056, 1.16
No. of reflections	1381
No. of parameters	83
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.76

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SAINT (Bruker, 2010, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DAIMOND (Brandenburg, 2010).

Selected bond lengths (Å) top

Cd—N1	2.361 (2)	Cd—Cl1ⁱⁱ	2.6697 (7)
Cd—N2ⁱ	2.341 (2)	Cd—Cl2	2.6583 (7)
Cd—Cl1	2.6262 (7)	Cd—Cl2ⁱⁱ	2.6222 (7)

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl2ⁱⁱⁱ	0.86	2.60	3.390 (3)	154
N3—H3B···Cl2^iv	0.86	2.77	3.216 (3)	114

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

Acknowledgements

We are grateful to the National Science Council of the Republic of China and the Nanya Institute of Technology for support.

References

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