Bis(μ-3,5-dimethyl-1,2,4-triazol-4-amine-κ2N1:N2)bis­[dichlorido­cobalt(II)]

Gong, Y.; Li, J.; Zhou, Y.; Qin, J.; Wu, X.

doi:10.1107/S1600536809021916

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page m791

doi:10.1107/S1600536809021916

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Bis(μ-3,5-dimethyl-1,2,4-triazol-4-amine-κ²N¹:N²)bis[dichloridocobalt(II)]

Yun Gong,^a ^* Jinghua Li,^b Yuchao Zhou,^a Jianbo Qin ^a and Xiaoxia Wu ^b

^aDepartment of Chemistry, College of Chemistry and Chemical Engineering, Chongqing University, 400044 Chongqing, People's Republic of China, and ^bDepartment of Pharmaceutical Chemistry, College of Chemistry and Chemical Engineering, Chongqing University, 400044 Chongqing, People's Republic of China
^*Correspondence e-mail: gongyun7211@yahoo.com.cn

(Received 14 May 2009; accepted 9 June 2009; online 17 June 2009)

In the centrosymmetric dinuclear compound, [Co₂Cl₄(C₄H₈N₄)₂], the Co^II atom is coordinated by N atoms from two 3,5-dimethyl-1,2,4-triazol-4-amine ligands and two Cl atoms in a distorted tetrahedral geometry. A six-membered ring is formed by four N atoms from two ligands and the two Co^II centers; the Co⋯Co distance is 3.756 (9) Å.

Related literature

For related compounds, see: Cheng et al. (2007 ); Lavrenova et al. (1992 ); Liu et al. (2003 ); Nockemann & Meyer (2007 ).

Experimental

Crystal data

[Co₂Cl₄(C₄H₈N₄)₂]
M_r = 483.95
Monoclinic, P 2₁ /c
a = 6.7412 (10) Å
b = 12.2094 (16) Å
c = 11.4423 (14) Å
β = 97.8270 (10)°
V = 933.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.36 mm⁻¹
T = 298 K
0.34 × 0.33 × 0.17 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.46, T_max = 0.67
4733 measured reflections
1638 independent reflections
1304 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.085
S = 1.07
1638 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—N2ⁱ	2.023 (3)
Co1—N1	2.030 (3)
Co1—Cl2	2.2154 (11)
Co1—Cl1	2.2382 (11)

N2ⁱ—Co1—N1	107.55 (11)
N2ⁱ—Co1—Cl2	108.46 (9)
N1—Co1—Cl2	108.50 (9)
N2ⁱ—Co1—Cl1	109.60 (9)
N1—Co1—Cl1	109.49 (9)
Cl2—Co1—Cl1	113.10 (5)
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 20008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021916/ng2584sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021916/ng2584Isup2.hkl

checkCIF report

Comment top

The rational design and synthesis of novel coordination polymers is of current interest in the field of supramolecular chemistry and crystal engineering, not only because of their intriguing structural motifs but also because of their potential applications in catalysis, molecular adsorption, magnetism, nonlinear optics, and molecular sensing. 1,2,4-Triazole and its derivatives possess good coordination ability due to the hetercyclic nitrogen atoms in the structure. Many polymers of 3,5-dimethyl-1,2,4-triazol-4-amine (Dmatrz) have been synthesized. In 1992, Lavrenova reported a series of metal-Dmatrz complexes, such as CuCl₂(Dmatrz)(0.5H₂O), CdCl₂(Dmatrz), Co(NO₃)₂(Dmatrz)₂(H₂O), Cu(NO₃)₂(Dmatrz)(0.5H₂O), Ni(NO₃)₂(Dmatrz)₂(H₂O), Zn(NO₃)₂(Dmatrz)₂, Cd(NO₃)₂(Dmatrz)₃ (Lavrenova et al., 1992). Other metal- Dmatrz complexes such as Cu(Dmatrz)SCN, Zn₂(Dmatrz)₂Cl₄, Ag₃(Dmatrz)₂(NO₃)₃ have also reported (Liu, et al., 2003; Cheng, et al., 2007; Nockemann, et al., 2007). However, so far coordination polymer constructed from CoCl₂ and Dmatrz has never been reported. In the present word, we solvothermally synthesized a CoCl₂-Dmatrz complex and it is reported here.

The molecular structure of the complex (I) (Fig. 1) has one one Co(II), one Dmatrz and two chlorine anions in its asymmetric unit. The Co(II) center is four-coordinated by four nitrogen atoms from two Dmatrz ligands and two chlorine atoms in a tetrahedral geometry. Each Dmatrz ligand links two Co(II) centers via its two neighboring nitrogen atoms with a Co···Co separation of 3.756 (9) Å (Fig.1). A six membered ring is formed via four nitrogen atoms from two Dmatrz ligands and two cobalt centers. The chlorine atoms can form hydrogen bonds with nitrogen atom from the uncoordinated amino group of Dmatrz. For example, The H4B···Cl2(ii) and N4···Cl2(ii) distances are 2.514 and 3.277 Å, respectively [Symmetry codes: (ii) -x + 1,-y,-z + 1]. The N4—H4B··· Cl2(ii) angle is 148.39 °.

Related literature top

For related compounds, see: Cheng et al. (2007); Lavrenova et al. (1992); Liu et al. (2003); Nockemann & Meyer (2007).

Experimental top

A mixture of Dmatrz(0.05 mmol, 0.006 g), CoCl₂(0.1 mmol, 0.024 g) and ethanol(5 mm l) was put into a Teflon-lined autoclave. The reaction mixture was heated at 120 centigrade for one and a half day, followed by slow cooling to room temperatrue and blue single crystals were collected. Elemental analyse found: C, 19.80; H, 3.39; N, 23.04; Cl, 29.28; Co, 24.45%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 20008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of (I), with the atomic numbering scheme and displacement ellipsoids at the 30% probability level. [Symmetry codes: (i) -x + 1,-y,-z + 1.]
	Fig. 2. Three dimensional supramolecular architecture constructed by intermolecular hydrogen bonds. The dotted lines indicate the hydrogen bonds.

Bis(µ-3,5-dimethyl-1,2,4-triazol-4-amine- κ²N¹:N²)bis[dichloridocobalt(II)] top

Crystal data top

[Co₂Cl₄(C₄H₈N₄)₂]	F(000) = 484
M_r = 483.95	D_x = 1.723 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4733 reflections
a = 6.7412 (10) Å	θ = 2.5–25.0°
b = 12.2094 (16) Å	µ = 2.36 mm⁻¹
c = 11.4423 (14) Å	T = 298 K
β = 97.827 (1)°	Block, blue
V = 933.0 (2) Å³	0.34 × 0.33 × 0.17 mm
Z = 2

Data collection top

Siemens CCD area-detector diffractometer	1638 independent reflections
Radiation source: fine-focus sealed tube	1304 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.46, T_max = 0.67	k = −14→14
4733 measured reflections	l = −13→8

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0358P)² + 1.1376P] where P = (F_o² + 2F_c²)/3
1638 reflections	(Δ/σ)_max = 0.001
102 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Co₂Cl₄(C₄H₈N₄)₂]	V = 933.0 (2) Å³
M_r = 483.95	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.7412 (10) Å	µ = 2.36 mm⁻¹
b = 12.2094 (16) Å	T = 298 K
c = 11.4423 (14) Å	0.34 × 0.33 × 0.17 mm
β = 97.827 (1)°

Data collection top

Siemens CCD area-detector diffractometer	1638 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1304 reflections with I > 2σ(I)
T_min = 0.46, T_max = 0.67	R_int = 0.023
4733 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.07	Δρ_max = 0.43 e Å⁻³
1638 reflections	Δρ_min = −0.58 e Å⁻³
102 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
Co1	0.59569 (7)	0.10736 (4)	0.40423 (4)	0.03186 (17)
Cl1	0.84618 (15)	0.10010 (9)	0.29461 (10)	0.0545 (3)
Cl2	0.44352 (17)	0.26855 (9)	0.39618 (12)	0.0652 (3)
N1	0.7034 (4)	0.0747 (2)	0.5750 (2)	0.0360 (7)
N2	0.6098 (4)	0.0089 (2)	0.6507 (2)	0.0345 (7)
N3	0.8558 (4)	0.0937 (2)	0.7526 (2)	0.0341 (7)
N4	0.9948 (5)	0.1233 (3)	0.8494 (3)	0.0505 (9)
H4A	0.9879	0.0948	0.9174	0.061*
H4B	1.0872	0.1700	0.8409	0.061*
C1	0.7059 (5)	0.0212 (3)	0.7575 (3)	0.0328 (8)
C2	0.8540 (5)	0.1240 (3)	0.6382 (3)	0.0365 (8)
C3	0.6643 (6)	−0.0339 (3)	0.8663 (3)	0.0476 (10)
H3A	0.6222	0.0194	0.9195	0.071*
H3B	0.7834	−0.0698	0.9030	0.071*
H3C	0.5602	−0.0871	0.8471	0.071*
C4	1.0012 (7)	0.1982 (4)	0.5962 (4)	0.0576 (12)
H4C	1.0375	0.1709	0.5233	0.086*
H4D	1.1183	0.2022	0.6541	0.086*
H4E	0.9437	0.2699	0.5837	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0308 (3)	0.0312 (3)	0.0334 (3)	−0.00153 (19)	0.00350 (19)	0.0033 (2)
Cl1	0.0476 (6)	0.0600 (6)	0.0604 (6)	−0.0015 (5)	0.0239 (5)	−0.0066 (5)
Cl2	0.0540 (7)	0.0417 (6)	0.0976 (9)	0.0137 (5)	0.0018 (6)	0.0003 (6)
N1	0.0369 (17)	0.0385 (16)	0.0317 (16)	−0.0077 (13)	0.0015 (13)	0.0046 (13)
N2	0.0335 (16)	0.0330 (15)	0.0364 (16)	−0.0055 (12)	0.0026 (13)	0.0025 (13)
N3	0.0354 (16)	0.0355 (16)	0.0301 (15)	−0.0018 (13)	−0.0004 (12)	−0.0044 (12)
N4	0.051 (2)	0.067 (2)	0.0298 (16)	−0.0194 (17)	−0.0085 (14)	−0.0041 (15)
C1	0.0337 (19)	0.0314 (18)	0.0329 (19)	0.0008 (15)	0.0026 (14)	−0.0022 (14)
C2	0.0371 (19)	0.0365 (19)	0.0353 (19)	−0.0045 (15)	0.0030 (15)	0.0000 (15)
C3	0.058 (3)	0.049 (2)	0.036 (2)	−0.0039 (19)	0.0052 (18)	0.0071 (17)
C4	0.061 (3)	0.067 (3)	0.045 (2)	−0.029 (2)	0.007 (2)	0.000 (2)

Geometric parameters (Å, º) top

Co1—N2ⁱ	2.023 (3)	N4—H4A	0.8600
Co1—N1	2.030 (3)	N4—H4B	0.8600
Co1—Cl2	2.2154 (11)	C1—C3	1.475 (5)
Co1—Cl1	2.2382 (11)	C2—C4	1.472 (5)
N1—C2	1.310 (4)	C3—H3A	0.9600
N1—N2	1.394 (4)	C3—H3B	0.9600
N2—C1	1.312 (4)	C3—H3C	0.9600
N2—Co1ⁱ	2.023 (3)	C4—H4C	0.9600
N3—C1	1.350 (4)	C4—H4D	0.9600
N3—C2	1.358 (4)	C4—H4E	0.9600
N3—N4	1.397 (4)

N2ⁱ—Co1—N1	107.55 (11)	N2—C1—N3	108.3 (3)
N2ⁱ—Co1—Cl2	108.46 (9)	N2—C1—C3	127.4 (3)
N1—Co1—Cl2	108.50 (9)	N3—C1—C3	124.3 (3)
N2ⁱ—Co1—Cl1	109.60 (9)	N1—C2—N3	108.1 (3)
N1—Co1—Cl1	109.49 (9)	N1—C2—C4	127.5 (3)
Cl2—Co1—Cl1	113.10 (5)	N3—C2—C4	124.4 (3)
C2—N1—N2	107.7 (3)	C1—C3—H3A	109.5
C2—N1—Co1	126.2 (2)	C1—C3—H3B	109.5
N2—N1—Co1	125.3 (2)	H3A—C3—H3B	109.5
C1—N2—N1	107.7 (3)	C1—C3—H3C	109.5
C1—N2—Co1ⁱ	126.9 (2)	H3A—C3—H3C	109.5
N1—N2—Co1ⁱ	124.1 (2)	H3B—C3—H3C	109.5
C1—N3—C2	108.1 (3)	C2—C4—H4C	109.5
C1—N3—N4	124.1 (3)	C2—C4—H4D	109.5
C2—N3—N4	127.6 (3)	H4C—C4—H4D	109.5
N3—N4—H4A	120.0	C2—C4—H4E	109.5
N3—N4—H4B	120.0	H4C—C4—H4E	109.5
H4A—N4—H4B	120.0	H4D—C4—H4E	109.5

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Co₂Cl₄(C₄H₈N₄)₂]
M_r	483.95
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.7412 (10), 12.2094 (16), 11.4423 (14)
β (°)	97.827 (1)
V (Å³)	933.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.36
Crystal size (mm)	0.34 × 0.33 × 0.17

Data collection
Diffractometer	Siemens CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.46, 0.67
No. of measured, independent and observed [I > 2σ(I)] reflections	4733, 1638, 1304
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.07
No. of reflections	1638
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.58

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 20008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Co1—N2ⁱ	2.023 (3)	Co1—Cl2	2.2154 (11)
Co1—N1	2.030 (3)	Co1—Cl1	2.2382 (11)

N2ⁱ—Co1—N1	107.55 (11)	N2ⁱ—Co1—Cl1	109.60 (9)
N2ⁱ—Co1—Cl2	108.46 (9)	N1—Co1—Cl1	109.49 (9)
N1—Co1—Cl2	108.50 (9)	Cl2—Co1—Cl1	113.10 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

This work was supported by the Natural Science Young Scholars Foundation of Chongqing University, the Large-scale Instrument and Equipment Open Foundation of Chongqing University, the Scientific Research Start-up Foundation of Chongqing University and Chongqing University Postgraduate Science and Innovation Fund.

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