metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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 CoII 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[Krämer, R. & Fritsky, I. O. (2000). Eur. J. Org. Chem. pp. 3505-3510.]); Sachse et al. (2008[Sachse, A., Penkova, L., Noel, G., Dechert, S., Varzatskii, O. A., Fritsky, I. O. & Meyer, F. (2008). Synthesis, pp. 800-806.]); Świątek-Kozłowska et al. (2000[Świątek-Kozłowska, J., Fritsky, I. O., Dobosz, A., Karaczyn, A., Dudarenko, N. M., Sliva, T. Yu., Gumienna-Kontecka, E. & Jerzykiewicz, L. (2000). J. Chem. Soc. Dalton Trans. pp. 4064-4068.]); Wörl et al. (2005a[Wörl, S., Fritsky, I. O., Hellwinkel, D., Pritzkow, H. & Krämer, R. (2005a). Eur. J. Inorg. Chem. pp. 759-765.],b[Wörl, S., Pritzkow, H., Fritsky, I. O. & Krämer, R. (2005b). Dalton Trans. pp. 27-29.]).

[Scheme 1]

Experimental

Crystal data
  • [CoBr2(C5H8N2)2]

  • Mr = 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.]) Tmin = 0.420, Tmax = 0.856

  • 16432 measured reflections

  • 4270 independent reflections

  • 3182 reflections with I > 2σ(I)

  • Rint = 0.043

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.072

  • S = 1.01

  • 4270 reflections

  • 158 parameters

  • H-atom parameters constrained

  • Δρmax = 0.95 e Å−3

  • Δρmin = −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 DA 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[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

In the title mononuclear complex, the CoII 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%.

Refinement top

The highest positive peak on the residual map was found at 1.38 Å from H8 atom and the deepest hole at 1.05 Å from Br2 atom. H atoms on C atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 (CH) and 0.96 (CH3) Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C). H atoms on N atoms were located from a difference Fourier map and refined as riding atoms, with Uiso(H) = 1.2Ueq(N).

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
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] 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
Mr = 411.00Dx = 1.847 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 20628 reflections
a = 8.4729 (4) Åθ = 3.2–36.6°
b = 14.1490 (8) ŵ = 6.55 mm1
c = 12.5280 (6) ÅT = 173 K
β = 100.152 (4)°Block, blue
V = 1478.38 (13) Å30.13 × 0.05 × 0.03 mm
Z = 4
Data collection top
Oxford Diffraction KM-4 Xcalibur
diffractometer
4270 independent reflections
Radiation source: fine-focus sealed tube3182 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ω scansθmax = 30.0°, θmin = 3.2°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)
h = 1110
Tmin = 0.420, Tmax = 0.856k = 1919
16432 measured reflectionsl = 1714
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: difference Fourier map
wR(F2) = 0.072H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0341P)2]
where P = (Fo2 + 2Fc2)/3
4270 reflections(Δ/σ)max = 0.002
158 parametersΔρmax = 0.95 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
[CoBr2(C5H8N2)2]V = 1478.38 (13) Å3
Mr = 411.00Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.4729 (4) ŵ = 6.55 mm1
b = 14.1490 (8) ÅT = 173 K
c = 12.5280 (6) Å0.13 × 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)
Tmin = 0.420, Tmax = 0.856Rint = 0.043
16432 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.01Δρmax = 0.95 e Å3
4270 reflectionsΔρmin = 0.48 e Å3
158 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.74035 (3)0.35425 (2)0.03635 (2)0.02328 (8)
Br21.09369 (3)0.362773 (19)0.30921 (2)0.01915 (8)
Co10.91684 (4)0.27303 (2)0.17569 (3)0.01403 (9)
N11.0279 (3)0.18556 (16)0.08660 (17)0.0158 (5)
N30.8064 (3)0.19278 (16)0.27161 (17)0.0161 (5)
N20.9910 (3)0.18170 (17)0.02369 (17)0.0186 (5)
H80.91800.21060.05800.022*
N40.8497 (3)0.19199 (17)0.38165 (17)0.0172 (5)
H160.93090.22840.41220.021*
C31.1468 (3)0.1234 (2)0.1155 (2)0.0182 (6)
C80.6852 (3)0.13054 (19)0.2490 (2)0.0169 (5)
C21.1836 (3)0.0794 (2)0.0223 (2)0.0224 (6)
H41.26130.03350.01970.027*
C70.6539 (3)0.0909 (2)0.3453 (2)0.0209 (6)
H120.57570.04630.35220.025*
C11.0810 (3)0.1181 (2)0.0648 (2)0.0203 (6)
C60.7619 (3)0.1308 (2)0.4281 (2)0.0190 (6)
C51.0621 (4)0.1005 (3)0.1840 (2)0.0284 (7)
H50.95040.09300.21390.043*
H61.11890.04400.19650.043*
H71.10470.15310.21820.043*
C100.7905 (4)0.1154 (2)0.5480 (2)0.0258 (7)
H130.80200.17530.58450.039*
H140.88650.07900.56900.039*
H150.70120.08190.56760.039*
C41.2209 (4)0.1101 (2)0.2318 (2)0.0282 (7)
H11.28090.05220.23970.042*
H21.13810.10740.27510.042*
H31.29120.16210.25520.042*
C90.6051 (4)0.1131 (2)0.1345 (2)0.0254 (7)
H90.56250.05000.12820.038*
H100.68180.12030.08710.038*
H110.51950.15760.11470.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02681 (16)0.02181 (15)0.01821 (14)0.00448 (12)0.00429 (11)0.00067 (11)
Br20.02102 (14)0.01743 (14)0.01725 (14)0.00396 (11)0.00142 (11)0.00094 (10)
Co10.01463 (17)0.01501 (18)0.01195 (16)0.00021 (15)0.00096 (12)0.00028 (14)
N10.0175 (11)0.0178 (12)0.0112 (10)0.0000 (9)0.0002 (8)0.0006 (9)
N30.0161 (11)0.0198 (12)0.0122 (10)0.0023 (10)0.0019 (8)0.0010 (9)
N20.0195 (12)0.0251 (13)0.0107 (10)0.0011 (10)0.0014 (9)0.0005 (9)
N40.0184 (11)0.0202 (12)0.0121 (10)0.0033 (10)0.0003 (9)0.0009 (9)
C30.0183 (13)0.0164 (14)0.0188 (13)0.0006 (11)0.0003 (11)0.0028 (11)
C80.0172 (13)0.0154 (13)0.0175 (12)0.0011 (11)0.0011 (10)0.0003 (10)
C20.0192 (14)0.0275 (16)0.0202 (13)0.0059 (12)0.0022 (11)0.0062 (12)
C70.0199 (14)0.0224 (15)0.0203 (14)0.0019 (12)0.0037 (11)0.0047 (12)
C10.0186 (13)0.0250 (15)0.0181 (13)0.0036 (12)0.0057 (11)0.0046 (11)
C60.0185 (13)0.0231 (15)0.0163 (12)0.0023 (12)0.0055 (10)0.0036 (11)
C50.0294 (17)0.0402 (19)0.0157 (14)0.0014 (15)0.0044 (12)0.0065 (13)
C100.0316 (17)0.0320 (17)0.0149 (13)0.0004 (14)0.0074 (12)0.0027 (12)
C40.0324 (17)0.0285 (17)0.0205 (15)0.0126 (14)0.0041 (12)0.0029 (13)
C90.0278 (16)0.0267 (16)0.0191 (14)0.0130 (13)0.0030 (12)0.0014 (12)
Geometric parameters (Å, º) top
Co1—Br12.3841 (4)C2—H40.9300
Co1—Br22.4025 (4)C7—C61.378 (4)
Co1—N12.008 (2)C7—H120.9300
Co1—N32.001 (2)C1—C51.495 (4)
N1—C31.338 (3)C6—C101.495 (4)
N1—N21.363 (3)C5—H50.9600
N3—C81.345 (3)C5—H60.9600
N3—N41.363 (3)C5—H70.9600
N2—C11.339 (4)C10—H130.9600
N2—H80.8006C10—H140.9600
N4—C61.340 (4)C10—H150.9600
N4—H160.8899C4—H10.9600
C3—C21.405 (4)C4—H20.9600
C3—C41.493 (4)C4—H30.9600
C8—C71.398 (4)C9—H90.9600
C8—C91.495 (4)C9—H100.9600
C2—C11.382 (4)C9—H110.9600
N3—Co1—N1107.38 (9)N2—C1—C2106.5 (2)
N3—Co1—Br1114.45 (6)N2—C1—C5121.8 (3)
N1—Co1—Br1100.66 (6)C2—C1—C5131.6 (3)
N3—Co1—Br2100.49 (6)N4—C6—C7106.5 (2)
N1—Co1—Br2114.62 (6)N4—C6—C10121.8 (2)
Br1—Co1—Br2119.259 (18)C7—C6—C10131.7 (3)
C3—N1—N2106.0 (2)C1—C5—H5109.5
C3—N1—Co1131.23 (18)C1—C5—H6109.5
N2—N1—Co1122.80 (17)H5—C5—H6109.5
C8—N3—N4105.5 (2)C1—C5—H7109.5
C8—N3—Co1131.74 (18)H5—C5—H7109.5
N4—N3—Co1122.75 (17)H6—C5—H7109.5
C1—N2—N1111.8 (2)C6—C10—H13109.5
C1—N2—H8125.1C6—C10—H14109.5
N1—N2—H8122.8H13—C10—H14109.5
C6—N4—N3111.9 (2)C6—C10—H15109.5
C6—N4—H16129.3H13—C10—H15109.5
N3—N4—H16118.7H14—C10—H15109.5
N1—C3—C2109.5 (2)C3—C4—H1109.5
N1—C3—C4120.9 (2)C3—C4—H2109.5
C2—C3—C4129.6 (3)H1—C4—H2109.5
N3—C8—C7109.6 (2)C3—C4—H3109.5
N3—C8—C9120.7 (2)H1—C4—H3109.5
C7—C8—C9129.7 (3)H2—C4—H3109.5
C1—C2—C3106.2 (3)C8—C9—H9109.5
C1—C2—H4126.9C8—C9—H10109.5
C3—C2—H4126.9H9—C9—H10109.5
C6—C7—C8106.5 (3)C8—C9—H11109.5
C6—C7—H12126.8H9—C9—H11109.5
C8—C7—H12126.8H10—C9—H11109.5
N3—Co1—N1—C363.3 (3)N2—N1—C3—C4178.7 (3)
Br1—Co1—N1—C3176.7 (2)Co1—N1—C3—C40.2 (4)
Br2—Co1—N1—C347.4 (3)N4—N3—C8—C70.2 (3)
N3—Co1—N1—N2118.0 (2)Co1—N3—C8—C7178.6 (2)
Br1—Co1—N1—N22.1 (2)N4—N3—C8—C9179.5 (2)
Br2—Co1—N1—N2131.36 (18)Co1—N3—C8—C91.7 (4)
N1—Co1—N3—C864.7 (3)N1—C3—C2—C10.1 (3)
Br1—Co1—N3—C846.1 (3)C4—C3—C2—C1179.2 (3)
Br2—Co1—N3—C8175.1 (2)N3—C8—C7—C60.4 (3)
N1—Co1—N3—N4114.0 (2)C9—C8—C7—C6179.9 (3)
Br1—Co1—N3—N4135.19 (18)N1—N2—C1—C21.0 (3)
Br2—Co1—N3—N46.1 (2)N1—N2—C1—C5179.6 (3)
C3—N1—N2—C11.0 (3)C3—C2—C1—N20.5 (3)
Co1—N1—N2—C1179.97 (19)C3—C2—C1—C5179.9 (3)
C8—N3—N4—C60.9 (3)N3—N4—C6—C71.1 (3)
Co1—N3—N4—C6178.14 (19)N3—N4—C6—C10178.2 (2)
N2—N1—C3—C20.6 (3)C8—C7—C6—N40.9 (3)
Co1—N1—C3—C2179.5 (2)C8—C7—C6—C10178.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H8···Br10.802.903.406 (2)123
N4—H16···Br1i0.893.043.588 (2)122
Symmetry code: (i) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[CoBr2(C5H8N2)2]
Mr411.00
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)8.4729 (4), 14.1490 (8), 12.5280 (6)
β (°) 100.152 (4)
V3)1478.38 (13)
Z4
Radiation typeMo Kα
µ (mm1)6.55
Crystal size (mm)0.13 × 0.05 × 0.03
Data collection
DiffractometerOxford Diffraction KM-4 Xcalibur
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.420, 0.856
No. of measured, independent and
observed [I > 2σ(I)] reflections
16432, 4270, 3182
Rint0.043
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.072, 1.01
No. of reflections4270
No. of parameters158
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—Br12.3841 (4)Co1—N12.008 (2)
Co1—Br22.4025 (4)Co1—N32.001 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H8···Br10.802.903.406 (2)123
N4—H16···Br1i0.893.043.588 (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

First citationBrandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationKrämer, R. & Fritsky, I. O. (2000). Eur. J. Org. Chem. pp. 3505–3510.  Google Scholar
First citationOxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.  Google Scholar
First citationSachse, A., Penkova, L., Noel, G., Dechert, S., Varzatskii, O. A., Fritsky, I. O. & Meyer, F. (2008). Synthesis, pp. 800–806.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationŚwiątek-Kozłowska, J., Fritsky, I. O., Dobosz, A., Karaczyn, A., Dudarenko, N. M., Sliva, T. Yu., Gumienna-Kontecka, E. & Jerzykiewicz, L. (2000). J. Chem. Soc. Dalton Trans. pp. 4064–4068.  Google Scholar
First citationWörl, S., Fritsky, I. O., Hellwinkel, D., Pritzkow, H. & Krämer, R. (2005a). Eur. J. Inorg. Chem. pp. 759–765.  Google Scholar
First citationWörl, S., Pritzkow, H., Fritsky, I. O. & Krämer, R. (2005b). Dalton Trans. pp. 27–29.  Google Scholar

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