Dibromidobis(3,5-dimethyl-1H-pyrazole-κN2)cobalt(II)

Tomyn, S.; Pavlenko, V.A.; Gumienna-Kontecka, E.; Penkova, L.; Kotova, N.V.

doi:10.1107/S1600536811039560

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1491

doi:10.1107/S1600536811039560

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Dibromidobis(3,5-dimethyl-1H-pyrazole-κN²)cobalt(II)

Stefania Tomyn,^a ^* Vadim A. Pavlenko,^a Elżbieta Gumienna-Kontecka,^b Larysa Penkova ^a and Natalia V. Kotova ^a

^aDepartment of Chemistry, National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, 01601 Kyiv, Ukraine, and ^bUniversity of Wrocław, Faculty of Chemistry, F. Joliot-Curie Street 14, 50-383 Wrocław, Poland
^*Correspondence e-mail: stefania.tomyn@gmail.com

(Received 23 September 2011; accepted 26 September 2011; online 5 October 2011)

In the mononuclear title complex, [CoBr₂(C₅H₈N₂)₂], the Co^II atom is coordinated by two N atoms from two monodentate 3,5-dimethylpyrazole ligands and two Br atoms in a highly distorted tetrahedral geometry. In the crystal, the complex molecules are linked by intermolecular N—H⋯Br hydrogen bonds into chains along [101]. An intramolecular N—H⋯Br hydrogen bond is also present.

Related literature

For related structures of pyrazole complexes, see: Krämer & Fritsky (2000 ); Sachse et al. (2008 ); Świątek-Kozłowska et al. (2000 ); Wörl et al. (2005a ,b ).

Experimental

Crystal data

[CoBr₂(C₅H₈N₂)₂]
M_r = 411.00
Monoclinic, P 2₁ /n
a = 8.4729 (4) Å
b = 14.1490 (8) Å
c = 12.5280 (6) Å
β = 100.152 (4)°
V = 1478.38 (13) Å³
Z = 4
Mo Kα radiation
μ = 6.55 mm⁻¹
T = 173 K
0.13 × 0.05 × 0.03 mm

Data collection

Oxford Diffraction KM-4 Xcalibur diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.420, T_max = 0.856
16432 measured reflections
4270 independent reflections
3182 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.072
S = 1.01
4270 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—Br1	2.3841 (4)
Co1—Br2	2.4025 (4)
Co1—N1	2.008 (2)
Co1—N3	2.001 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H8⋯Br1	0.80	2.90	3.406 (2)	123
N4—H16⋯Br1ⁱ	0.89	3.04	3.588 (2)	122
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811039560/hy2475sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811039560/hy2475Isup2.hkl

checkCIF report

Comment top

In the title mononuclear complex, the Co^II atom is coordinated by two N atoms from two monodentate 3,5-dimethylpyrazole ligands and two Br atoms in a highly distorted tetrahedral geometry (Table 1), with the bond angles of 100.49 (6)–119.259 (18)°. The C—C, C—N and N—N bond lengths in the pyrazole ring are normal for 3,5-disubstituted pyrazoles (Krämer & Fritsky, 2000; Sachse et al., 2008; Świątek-Kozłowska et al., 2000; Wörl et al., 2005a, b). The crystal packing shows a chain-specific arrangement of the molecules. Inside chain intermolecular contacts are ensured by hydrogen bonds between the N—H groups of the pyrazole rings and the bromine atoms (Table 2). Outside chain intermolecular contacts are provided by C—H···Br interactions [H1···Br2ⁱ = 2.99 Å, C4—H1···Br2ⁱ = 161°; symmetry code: (i) 5/2-x, -1/2+y, 1/2-z].

Related literature top

For related structures of pyrazole complexes, see: Krämer & Fritsky (2000); Sachse et al. (2008); Świątek-Kozłowska et al. (2000); Wörl et al. (2005a,b).

Experimental top

3,5-Dimethylpyrazole (0.192 g, 2 mmol) was added to a DMSO solution of CoBr₂.6H₂O (0.327 g, 1 mmol). The reaction mixture was stirred at 60°C until complete dissolution of the ligand occurred. The resulting blue solution was filtered off and left at room temperature. Block blue crystals suitable for X-ray analysis were isolated by slow evaporation of the resulting solution after several days (yield: 0.35 g, 85%). Analysis, calculated for C₁₀H₁₆Br₂CoN₄: C 29.22, H 3.92, N 13.63%; found: C 29.06, H 3.72, N 13.45%.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of the chain structure. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonds are omitted for clarity.

Dibromidobis(3,5-dimethyl-1H-pyrazole-κN²)cobalt(II) top

Crystal data top

[CoBr₂(C₅H₈N₂)₂]	F(000) = 804
M_r = 411.00	D_x = 1.847 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 20628 reflections
a = 8.4729 (4) Å	θ = 3.2–36.6°
b = 14.1490 (8) Å	µ = 6.55 mm⁻¹
c = 12.5280 (6) Å	T = 173 K
β = 100.152 (4)°	Block, blue
V = 1478.38 (13) Å³	0.13 × 0.05 × 0.03 mm
Z = 4

Data collection top

Oxford Diffraction KM-4 Xcalibur diffractometer	4270 independent reflections
Radiation source: fine-focus sealed tube	3182 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans	θ_max = 30.0°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	h = −11→10
T_min = 0.420, T_max = 0.856	k = −19→19
16432 measured reflections	l = −17→14

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)] = 0.035	Hydrogen site location: difference Fourier map
wR(F²) = 0.072	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0341P)²] where P = (F_o² + 2F_c²)/3
4270 reflections	(Δ/σ)_max = 0.002
158 parameters	Δρ_max = 0.95 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[CoBr₂(C₅H₈N₂)₂]	V = 1478.38 (13) Å³
M_r = 411.00	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.4729 (4) Å	µ = 6.55 mm⁻¹
b = 14.1490 (8) Å	T = 173 K
c = 12.5280 (6) Å	0.13 × 0.05 × 0.03 mm
β = 100.152 (4)°

Data collection top

Oxford Diffraction KM-4 Xcalibur diffractometer	4270 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	3182 reflections with I > 2σ(I)
T_min = 0.420, T_max = 0.856	R_int = 0.043
16432 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.01	Δρ_max = 0.95 e Å⁻³
4270 reflections	Δρ_min = −0.48 e Å⁻³
158 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.74035 (3)	0.35425 (2)	0.03635 (2)	0.02328 (8)
Br2	1.09369 (3)	0.362773 (19)	0.30921 (2)	0.01915 (8)
Co1	0.91684 (4)	0.27303 (2)	0.17569 (3)	0.01403 (9)
N1	1.0279 (3)	0.18556 (16)	0.08660 (17)	0.0158 (5)
N3	0.8064 (3)	0.19278 (16)	0.27161 (17)	0.0161 (5)
N2	0.9910 (3)	0.18170 (17)	−0.02369 (17)	0.0186 (5)
H8	0.9180	0.2106	−0.0580	0.022*
N4	0.8497 (3)	0.19199 (17)	0.38165 (17)	0.0172 (5)
H16	0.9309	0.2284	0.4122	0.021*
C3	1.1468 (3)	0.1234 (2)	0.1155 (2)	0.0182 (6)
C8	0.6852 (3)	0.13054 (19)	0.2490 (2)	0.0169 (5)
C2	1.1836 (3)	0.0794 (2)	0.0223 (2)	0.0224 (6)
H4	1.2613	0.0335	0.0197	0.027*
C7	0.6539 (3)	0.0909 (2)	0.3453 (2)	0.0209 (6)
H12	0.5757	0.0463	0.3522	0.025*
C1	1.0810 (3)	0.1181 (2)	−0.0648 (2)	0.0203 (6)
C6	0.7619 (3)	0.1308 (2)	0.4281 (2)	0.0190 (6)
C5	1.0621 (4)	0.1005 (3)	−0.1840 (2)	0.0284 (7)
H5	0.9504	0.0930	−0.2139	0.043*
H6	1.1189	0.0440	−0.1965	0.043*
H7	1.1047	0.1531	−0.2182	0.043*
C10	0.7905 (4)	0.1154 (2)	0.5480 (2)	0.0258 (7)
H13	0.8020	0.1753	0.5845	0.039*
H14	0.8865	0.0790	0.5690	0.039*
H15	0.7012	0.0819	0.5676	0.039*
C4	1.2209 (4)	0.1101 (2)	0.2318 (2)	0.0282 (7)
H1	1.2809	0.0522	0.2397	0.042*
H2	1.1381	0.1074	0.2751	0.042*
H3	1.2912	0.1621	0.2552	0.042*
C9	0.6051 (4)	0.1131 (2)	0.1345 (2)	0.0254 (7)
H9	0.5625	0.0500	0.1282	0.038*
H10	0.6818	0.1203	0.0871	0.038*
H11	0.5195	0.1576	0.1147	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02681 (16)	0.02181 (15)	0.01821 (14)	0.00448 (12)	−0.00429 (11)	0.00067 (11)
Br2	0.02102 (14)	0.01743 (14)	0.01725 (14)	−0.00396 (11)	−0.00142 (11)	−0.00094 (10)
Co1	0.01463 (17)	0.01501 (18)	0.01195 (16)	−0.00021 (15)	0.00096 (12)	−0.00028 (14)
N1	0.0175 (11)	0.0178 (12)	0.0112 (10)	0.0000 (9)	0.0002 (8)	0.0006 (9)
N3	0.0161 (11)	0.0198 (12)	0.0122 (10)	−0.0023 (10)	0.0019 (8)	−0.0010 (9)
N2	0.0195 (12)	0.0251 (13)	0.0107 (10)	0.0011 (10)	0.0014 (9)	0.0005 (9)
N4	0.0184 (11)	0.0202 (12)	0.0121 (10)	−0.0033 (10)	0.0003 (9)	−0.0009 (9)
C3	0.0183 (13)	0.0164 (14)	0.0188 (13)	0.0006 (11)	0.0003 (11)	−0.0028 (11)
C8	0.0172 (13)	0.0154 (13)	0.0175 (12)	−0.0011 (11)	0.0011 (10)	−0.0003 (10)
C2	0.0192 (14)	0.0275 (16)	0.0202 (13)	0.0059 (12)	0.0022 (11)	−0.0062 (12)
C7	0.0199 (14)	0.0224 (15)	0.0203 (14)	−0.0019 (12)	0.0037 (11)	0.0047 (12)
C1	0.0186 (13)	0.0250 (15)	0.0181 (13)	−0.0036 (12)	0.0057 (11)	−0.0046 (11)
C6	0.0185 (13)	0.0231 (15)	0.0163 (12)	0.0023 (12)	0.0055 (10)	0.0036 (11)
C5	0.0294 (17)	0.0402 (19)	0.0157 (14)	−0.0014 (15)	0.0044 (12)	−0.0065 (13)
C10	0.0316 (17)	0.0320 (17)	0.0149 (13)	0.0004 (14)	0.0074 (12)	0.0027 (12)
C4	0.0324 (17)	0.0285 (17)	0.0205 (15)	0.0126 (14)	−0.0041 (12)	−0.0029 (13)
C9	0.0278 (16)	0.0267 (16)	0.0191 (14)	−0.0130 (13)	−0.0030 (12)	0.0014 (12)

Geometric parameters (Å, º) top

Co1—Br1	2.3841 (4)	C2—H4	0.9300
Co1—Br2	2.4025 (4)	C7—C6	1.378 (4)
Co1—N1	2.008 (2)	C7—H12	0.9300
Co1—N3	2.001 (2)	C1—C5	1.495 (4)
N1—C3	1.338 (3)	C6—C10	1.495 (4)
N1—N2	1.363 (3)	C5—H5	0.9600
N3—C8	1.345 (3)	C5—H6	0.9600
N3—N4	1.363 (3)	C5—H7	0.9600
N2—C1	1.339 (4)	C10—H13	0.9600
N2—H8	0.8006	C10—H14	0.9600
N4—C6	1.340 (4)	C10—H15	0.9600
N4—H16	0.8899	C4—H1	0.9600
C3—C2	1.405 (4)	C4—H2	0.9600
C3—C4	1.493 (4)	C4—H3	0.9600
C8—C7	1.398 (4)	C9—H9	0.9600
C8—C9	1.495 (4)	C9—H10	0.9600
C2—C1	1.382 (4)	C9—H11	0.9600

N3—Co1—N1	107.38 (9)	N2—C1—C2	106.5 (2)
N3—Co1—Br1	114.45 (6)	N2—C1—C5	121.8 (3)
N1—Co1—Br1	100.66 (6)	C2—C1—C5	131.6 (3)
N3—Co1—Br2	100.49 (6)	N4—C6—C7	106.5 (2)
N1—Co1—Br2	114.62 (6)	N4—C6—C10	121.8 (2)
Br1—Co1—Br2	119.259 (18)	C7—C6—C10	131.7 (3)
C3—N1—N2	106.0 (2)	C1—C5—H5	109.5
C3—N1—Co1	131.23 (18)	C1—C5—H6	109.5
N2—N1—Co1	122.80 (17)	H5—C5—H6	109.5
C8—N3—N4	105.5 (2)	C1—C5—H7	109.5
C8—N3—Co1	131.74 (18)	H5—C5—H7	109.5
N4—N3—Co1	122.75 (17)	H6—C5—H7	109.5
C1—N2—N1	111.8 (2)	C6—C10—H13	109.5
C1—N2—H8	125.1	C6—C10—H14	109.5
N1—N2—H8	122.8	H13—C10—H14	109.5
C6—N4—N3	111.9 (2)	C6—C10—H15	109.5
C6—N4—H16	129.3	H13—C10—H15	109.5
N3—N4—H16	118.7	H14—C10—H15	109.5
N1—C3—C2	109.5 (2)	C3—C4—H1	109.5
N1—C3—C4	120.9 (2)	C3—C4—H2	109.5
C2—C3—C4	129.6 (3)	H1—C4—H2	109.5
N3—C8—C7	109.6 (2)	C3—C4—H3	109.5
N3—C8—C9	120.7 (2)	H1—C4—H3	109.5
C7—C8—C9	129.7 (3)	H2—C4—H3	109.5
C1—C2—C3	106.2 (3)	C8—C9—H9	109.5
C1—C2—H4	126.9	C8—C9—H10	109.5
C3—C2—H4	126.9	H9—C9—H10	109.5
C6—C7—C8	106.5 (3)	C8—C9—H11	109.5
C6—C7—H12	126.8	H9—C9—H11	109.5
C8—C7—H12	126.8	H10—C9—H11	109.5

N3—Co1—N1—C3	−63.3 (3)	N2—N1—C3—C4	178.7 (3)
Br1—Co1—N1—C3	176.7 (2)	Co1—N1—C3—C4	−0.2 (4)
Br2—Co1—N1—C3	47.4 (3)	N4—N3—C8—C7	−0.2 (3)
N3—Co1—N1—N2	118.0 (2)	Co1—N3—C8—C7	178.6 (2)
Br1—Co1—N1—N2	−2.1 (2)	N4—N3—C8—C9	179.5 (2)
Br2—Co1—N1—N2	−131.36 (18)	Co1—N3—C8—C9	−1.7 (4)
N1—Co1—N3—C8	−64.7 (3)	N1—C3—C2—C1	0.1 (3)
Br1—Co1—N3—C8	46.1 (3)	C4—C3—C2—C1	−179.2 (3)
Br2—Co1—N3—C8	175.1 (2)	N3—C8—C7—C6	−0.4 (3)
N1—Co1—N3—N4	114.0 (2)	C9—C8—C7—C6	179.9 (3)
Br1—Co1—N3—N4	−135.19 (18)	N1—N2—C1—C2	−1.0 (3)
Br2—Co1—N3—N4	−6.1 (2)	N1—N2—C1—C5	179.6 (3)
C3—N1—N2—C1	1.0 (3)	C3—C2—C1—N2	0.5 (3)
Co1—N1—N2—C1	−179.97 (19)	C3—C2—C1—C5	179.9 (3)
C8—N3—N4—C6	0.9 (3)	N3—N4—C6—C7	−1.1 (3)
Co1—N3—N4—C6	−178.14 (19)	N3—N4—C6—C10	178.2 (2)
N2—N1—C3—C2	−0.6 (3)	C8—C7—C6—N4	0.9 (3)
Co1—N1—C3—C2	−179.5 (2)	C8—C7—C6—C10	−178.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H8···Br1	0.80	2.90	3.406 (2)	123
N4—H16···Br1ⁱ	0.89	3.04	3.588 (2)	122

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[CoBr₂(C₅H₈N₂)₂]
M_r	411.00
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	8.4729 (4), 14.1490 (8), 12.5280 (6)
β (°)	100.152 (4)
V (Å³)	1478.38 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.55
Crystal size (mm)	0.13 × 0.05 × 0.03

Data collection
Diffractometer	Oxford Diffraction KM-4 Xcalibur diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.420, 0.856
No. of measured, independent and observed [I > 2σ(I)] reflections	16432, 4270, 3182
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.072, 1.01
No. of reflections	4270
No. of parameters	158
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −0.48

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—Br1	2.3841 (4)	Co1—N1	2.008 (2)
Co1—Br2	2.4025 (4)	Co1—N3	2.001 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H8···Br1	0.80	2.90	3.406 (2)	123
N4—H16···Br1ⁱ	0.89	3.04	3.588 (2)	122

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Acknowledgements

The financial support from the State Fund for Fundamental Research of Ukraine (grant No. F40.3/041) and the Swedish Institute (Visby Program) is gratefully acknowledged.

References

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