Dichloridobis(3,5-dimethyl-1H-pyrazol-4-amine-κN2)cobalt(II)

Cai, X.-W.; Zhao, Y.-Y.; Han, G.-F.

doi:10.1107/S1600536808020461

metal-organic compounds

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Volume 64| Part 8| August 2008| Page m1012

doi:10.1107/S1600536808020461

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Dichloridobis(3,5-dimethyl-1H-pyrazol-4-amine-κN²)cobalt(II)

Xing-Wei Cai,^a ^* Yu-Yuan Zhao ^a and Guang-Fan Han ^a

^aSchool of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003, People's Republic of China
^*Correspondence e-mail: xin883@163.com

(Received 26 June 2008; accepted 3 July 2008; online 9 July 2008)

In the title compound, [CoCl₂(C₅H₉N₃)₂], the Co^II atom adopts a slightly distorted tetrahedral coordination geometry provided by two chloride anions and two N atoms from the organic ligands. The dihedral angle between the pyrazole rings is 85.91 (10)°. In the crystal structure, molecules are linked into a three-dimensional network by intermolecular N—H⋯N and N—H⋯Cl hydrogen-bonding interactions.

Related literature

For the crystal structures of related pyrazole compounds, see: Francisco et al. (1980 ); Murray et al. (1988 ); Zhao & Eichhorn (2005 ).

Experimental

Crystal data

[CoCl₂(C₅H₉N₃)₂]
M_r = 352.13
Triclinic, $[P \overline 1]$
a = 9.182 (3) Å
b = 9.191 (4) Å
c = 10.085 (3) Å
α = 94.807 (13)°
β = 106.105 (4)°
γ = 107.814 (12)°
V = 765.1 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 293 (2) K
0.25 × 0.15 × 0.04 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.836, T_max = 0.940
7916 measured reflections
3456 independent reflections
2579 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.102
S = 0.98
3456 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯Cl1	0.96	2.67	3.570 (5)	157
N2—H2A⋯N6ⁱ	0.86	1.98	2.835 (3)	175
N5—H5D⋯N3ⁱⁱ	0.86	2.08	2.919 (4)	164
N3—H3A⋯Cl2ⁱⁱⁱ	0.90	2.56	3.452 (3)	169
N6—H6B⋯Cl1^iv	0.90	2.72	3.457 (3)	140
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z+1; (iii) x, y+1, z; (iv) -x+1, -y, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020461/rz2230sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020461/rz2230Isup2.hkl

checkCIF report

Comment top

Pyrazolylmethane late-transition-metal complexes of the first row have shown great potential for the construction of magnetic devices. In the course of our studies of the coordination chemistry of these ligands with cobalt, the title compound was synthesized and we report its crystal structure here.

There have been a few crystal structures reported to date for four-coordinate metal complexes containing two coordinated pyrazoles and two coordinated halides, for examples, dichlorobis(1- phenyl-3,5-dimethylpyrazole)copper(II) (Francisco et al., 1980;), dibromobis(3,5-diphenylpyrazole)copper(II) (Murray et al., 1988) and dichlorobis(3,5-dimethylpyrazole) copper(II) (Zhao & Eichhorn, 2005). The Co—N (2.003 (2) and 2.006 (2) Å) and Co—Cl bond lengths (2.2373 (10) and 2.2829 (11) Å) are within the ranges expected. The dihedral angle formed by the pyrazole rings is 85.91 (10)°. An intramolecular C—H···Cl hydrogen bond (Table 1) helps to stabilzie the molecular conformation. In the crystal structure, molecules are linked by intermolecular N—H···N and N—H···Cl hydrogen bonding interactions to form a three-dimensional network (Table 1).

Related literature top

For the crystal structure of related pyrazole compounds, see: Francisco et al. (1980); Murray et al. (1988); Zhao & Eichhorn (2005).

Experimental top

3,5-Dimethyl-1H-pyrazol-4-amine (0.111 g, 1 mmol) was dissolved in ethanol (5 ml) and CoCl₂ (0.127 g, 1 mmol) in aqueous solution (5 ml) was added with stirring. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation at room temperature over several days

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Dichloridobis(3,5-dimethyl-1H-pyrazol-4-amine-κN²)cobalt(II) top

Crystal data top

[CoCl₂(C₅H₉N₃)₂]	Z = 2
M_r = 352.13	F(000) = 362
Triclinic, P1	D_x = 1.528 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.182 (3) Å	Cell parameters from 2030 reflections
b = 9.191 (4) Å	θ = 2.7–27.5°
c = 10.085 (3) Å	µ = 1.47 mm⁻¹
α = 94.807 (13)°	T = 293 K
β = 106.105 (4)°	Plate, colourless
γ = 107.814 (12)°	0.25 × 0.15 × 0.04 mm
V = 765.1 (5) Å³

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	3456 independent reflections
Radiation source: fine-focus sealed tube	2579 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.8°
CCD_Profile_fitting scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.836, T_max = 0.940	l = −13→13
7916 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0471P)²] where P = (F_o² + 2F_c²)/3
3456 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[CoCl₂(C₅H₉N₃)₂]	γ = 107.814 (12)°
M_r = 352.13	V = 765.1 (5) Å³
Triclinic, P1	Z = 2
a = 9.182 (3) Å	Mo Kα radiation
b = 9.191 (4) Å	µ = 1.47 mm⁻¹
c = 10.085 (3) Å	T = 293 K
α = 94.807 (13)°	0.25 × 0.15 × 0.04 mm
β = 106.105 (4)°

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	3456 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2579 reflections with I > 2σ(I)
T_min = 0.836, T_max = 0.940	R_int = 0.050
7916 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 0.98	Δρ_max = 0.35 e Å⁻³
3456 reflections	Δρ_min = −0.32 e Å⁻³
176 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	0.36013 (4)	0.23415 (4)	0.15884 (4)	0.03042 (13)
Cl1	0.21996 (10)	0.22767 (10)	−0.06317 (8)	0.0469 (2)
Cl2	0.24095 (9)	0.03437 (9)	0.25653 (8)	0.0412 (2)
C1	0.4561 (3)	0.5640 (3)	0.3357 (3)	0.0286 (6)
C2	0.3704 (3)	0.6573 (3)	0.3698 (3)	0.0287 (6)
C3	0.2086 (4)	0.5675 (3)	0.3138 (3)	0.0343 (7)
C4	0.6339 (4)	0.6063 (4)	0.3676 (3)	0.0423 (8)
H4A	0.6603	0.5134	0.3594	0.064*
H4B	0.6879	0.6646	0.4615	0.064*
H4C	0.6681	0.6683	0.3025	0.064*
C5	0.0604 (4)	0.6012 (4)	0.3138 (4)	0.0548 (10)
H5A	−0.0320	0.5235	0.2461	0.082*
H5B	0.0687	0.7017	0.2900	0.082*
H5C	0.0486	0.6001	0.4054	0.082*
C6	0.6694 (3)	0.2278 (3)	0.0980 (3)	0.0328 (6)
C7	0.7967 (3)	0.1765 (3)	0.1557 (3)	0.0289 (6)
C8	0.7838 (3)	0.1407 (3)	0.2824 (3)	0.0322 (6)
C9	0.6290 (5)	0.2806 (5)	−0.0382 (4)	0.0587 (10)
H9A	0.5146	0.2584	−0.0741	0.088*
H9B	0.6621	0.2270	−0.1039	0.088*
H9C	0.6841	0.3905	−0.0249	0.088*
C10	0.8851 (4)	0.0783 (4)	0.3884 (3)	0.0491 (9)
H10A	0.8390	0.0580	0.4624	0.074*
H10B	0.9923	0.1532	0.4267	0.074*
H10C	0.8894	−0.0164	0.3445	0.074*
N1	0.3517 (3)	0.4248 (3)	0.2644 (2)	0.0325 (5)
N2	0.2026 (3)	0.4300 (3)	0.2516 (3)	0.0382 (6)
H2A	0.1144	0.3540	0.2085	0.046*
N3	0.4325 (3)	0.8117 (3)	0.4457 (3)	0.0368 (6)
H3A	0.3934	0.8723	0.3907	0.044*
H3B	0.5407	0.8473	0.4675	0.044*
N4	0.5806 (3)	0.2228 (3)	0.1851 (2)	0.0335 (6)
N5	0.6537 (3)	0.1685 (3)	0.2974 (2)	0.0342 (6)
H5D	0.6207	0.1541	0.3687	0.041*
N6	0.9218 (3)	0.1729 (3)	0.1011 (3)	0.0362 (6)
H6A	0.8924	0.1782	0.0093	0.043*
H6B	0.9413	0.0835	0.1104	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0280 (2)	0.0327 (2)	0.0333 (2)	0.01479 (17)	0.00943 (16)	0.00507 (16)
Cl1	0.0451 (5)	0.0591 (5)	0.0349 (4)	0.0222 (4)	0.0057 (3)	0.0085 (4)
Cl2	0.0346 (4)	0.0415 (4)	0.0474 (5)	0.0122 (3)	0.0119 (3)	0.0154 (3)
C1	0.0293 (15)	0.0267 (15)	0.0297 (15)	0.0091 (11)	0.0094 (11)	0.0068 (11)
C2	0.0342 (16)	0.0288 (15)	0.0249 (14)	0.0114 (12)	0.0116 (11)	0.0057 (11)
C3	0.0357 (17)	0.0332 (17)	0.0374 (17)	0.0173 (13)	0.0117 (13)	0.0038 (13)
C4	0.0331 (17)	0.0422 (19)	0.049 (2)	0.0115 (14)	0.0106 (14)	0.0073 (15)
C5	0.039 (2)	0.048 (2)	0.078 (3)	0.0178 (16)	0.0199 (18)	−0.0025 (18)
C6	0.0285 (16)	0.0401 (17)	0.0332 (16)	0.0120 (12)	0.0133 (12)	0.0117 (13)
C7	0.0249 (14)	0.0283 (15)	0.0322 (15)	0.0085 (11)	0.0090 (11)	0.0005 (11)
C8	0.0262 (15)	0.0392 (17)	0.0314 (16)	0.0140 (12)	0.0075 (11)	0.0031 (12)
C9	0.056 (2)	0.096 (3)	0.053 (2)	0.045 (2)	0.0306 (18)	0.044 (2)
C10	0.049 (2)	0.070 (3)	0.0416 (19)	0.0387 (18)	0.0132 (15)	0.0163 (17)
N1	0.0281 (13)	0.0320 (14)	0.0392 (14)	0.0123 (10)	0.0121 (10)	0.0027 (11)
N2	0.0237 (13)	0.0328 (14)	0.0517 (17)	0.0064 (10)	0.0092 (11)	−0.0040 (12)
N3	0.0401 (15)	0.0314 (14)	0.0364 (14)	0.0109 (11)	0.0113 (11)	0.0016 (11)
N4	0.0322 (14)	0.0442 (15)	0.0313 (14)	0.0198 (11)	0.0122 (10)	0.0122 (11)
N5	0.0347 (14)	0.0486 (16)	0.0309 (13)	0.0232 (12)	0.0165 (10)	0.0146 (11)
N6	0.0297 (14)	0.0422 (15)	0.0398 (15)	0.0145 (11)	0.0148 (11)	0.0033 (11)

Geometric parameters (Å, º) top

Co1—N4	2.003 (2)	C6—C9	1.483 (4)
Co1—N1	2.006 (2)	C7—C8	1.373 (4)
Co1—Cl1	2.2373 (10)	C7—N6	1.412 (3)
Co1—Cl2	2.2829 (11)	C8—N5	1.340 (3)
C1—N1	1.337 (3)	C8—C10	1.488 (4)
C1—C2	1.409 (4)	C9—H9A	0.9600
C1—C4	1.490 (4)	C9—H9B	0.9600
C2—C3	1.384 (4)	C9—H9C	0.9600
C2—N3	1.416 (3)	C10—H10A	0.9600
C3—N2	1.341 (4)	C10—H10B	0.9600
C3—C5	1.486 (4)	C10—H10C	0.9600
C4—H4A	0.9600	N1—N2	1.355 (3)
C4—H4B	0.9600	N2—H2A	0.8600
C4—H4C	0.9600	N3—H3A	0.9000
C5—H5A	0.9600	N3—H3B	0.9000
C5—H5B	0.9600	N4—N5	1.364 (3)
C5—H5C	0.9600	N5—H5D	0.8600
C6—N4	1.349 (3)	N6—H6A	0.9001
C6—C7	1.391 (4)	N6—H6B	0.9000

N4—Co1—N1	116.07 (10)	N5—C8—C7	107.2 (2)
N4—Co1—Cl1	114.54 (7)	N5—C8—C10	122.7 (3)
N1—Co1—Cl1	103.32 (8)	C7—C8—C10	130.0 (3)
N4—Co1—Cl2	103.72 (7)	C6—C9—H9A	109.5
N1—Co1—Cl2	104.88 (8)	C6—C9—H9B	109.5
Cl1—Co1—Cl2	114.26 (4)	H9A—C9—H9B	109.5
N1—C1—C2	109.4 (2)	C6—C9—H9C	109.5
N1—C1—C4	122.5 (2)	H9A—C9—H9C	109.5
C2—C1—C4	128.1 (3)	H9B—C9—H9C	109.5
C3—C2—C1	106.1 (2)	C8—C10—H10A	109.5
C3—C2—N3	125.5 (2)	C8—C10—H10B	109.5
C1—C2—N3	128.4 (3)	H10A—C10—H10B	109.5
N2—C3—C2	106.3 (2)	C8—C10—H10C	109.5
N2—C3—C5	122.1 (3)	H10A—C10—H10C	109.5
C2—C3—C5	131.6 (3)	H10B—C10—H10C	109.5
C1—C4—H4A	109.5	C1—N1—N2	106.1 (2)
C1—C4—H4B	109.5	C1—N1—Co1	137.05 (19)
H4A—C4—H4B	109.5	N2—N1—Co1	116.27 (17)
C1—C4—H4C	109.5	C3—N2—N1	112.1 (2)
H4A—C4—H4C	109.5	C3—N2—H2A	124.0
H4B—C4—H4C	109.5	N1—N2—H2A	124.0
C3—C5—H5A	109.5	C2—N3—H3A	109.0
C3—C5—H5B	109.5	C2—N3—H3B	109.1
H5A—C5—H5B	109.5	H3A—N3—H3B	108.0
C3—C5—H5C	109.5	C6—N4—N5	105.4 (2)
H5A—C5—H5C	109.5	C6—N4—Co1	132.8 (2)
H5B—C5—H5C	109.5	N5—N4—Co1	120.26 (18)
N4—C6—C7	109.9 (3)	C8—N5—N4	111.3 (2)
N4—C6—C9	122.4 (3)	C8—N5—H5D	124.3
C7—C6—C9	127.7 (3)	N4—N5—H5D	124.3
C8—C7—C6	106.2 (2)	C7—N6—H6A	109.9
C8—C7—N6	126.4 (3)	C7—N6—H6B	109.9
C6—C7—N6	127.3 (3)	H6A—N6—H6B	108.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···Cl1	0.96	2.67	3.570 (5)	157
N2—H2A···N6ⁱ	0.86	1.98	2.835 (3)	175
N5—H5D···N3ⁱⁱ	0.86	2.08	2.919 (4)	164
N3—H3A···Cl2ⁱⁱⁱ	0.90	2.56	3.452 (3)	169
N6—H6B···Cl1^iv	0.90	2.72	3.457 (3)	140

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

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₅H₉N₃)₂]
M_r	352.13
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.182 (3), 9.191 (4), 10.085 (3)
α, β, γ (°)	94.807 (13), 106.105 (4), 107.814 (12)
V (Å³)	765.1 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.47
Crystal size (mm)	0.25 × 0.15 × 0.04

Data collection
Diffractometer	Rigaku Mercury2 (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.836, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	7916, 3456, 2579
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.102, 0.98
No. of reflections	3456
No. of parameters	176
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.32

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···Cl1	0.96	2.67	3.570 (5)	156.8
N2—H2A···N6ⁱ	0.86	1.98	2.835 (3)	175.3
N5—H5D···N3ⁱⁱ	0.86	2.08	2.919 (4)	163.6
N3—H3A···Cl2ⁱⁱⁱ	0.90	2.56	3.452 (3)	169.2
N6—H6B···Cl1^iv	0.90	2.72	3.457 (3)	140.1

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

References

Francisco, R. H. P., Lechat, J. R., Massabni, A. C., Melios, C. B. & Molina, M. (1980). J. Coord. Chem. 10, 149–153. CrossRef CAS Web of Science Google Scholar
Murray, J. J., Raptis, R. G. & Fackler, J. P. Jr (1988). Inorg. Chem. 27, 26–33. CSD CrossRef CAS Web of Science Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, N. & Eichhorn, D. M. (2005). Acta Cryst. E61, m822–m823. Web of Science CSD CrossRef IUCr Journals Google Scholar

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doi:10.1107/S1600536808020461

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