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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): m718.
Published online 2010 May 29. doi:  10.1107/S160053681001977X
PMCID: PMC2979397

catena-Poly[[bis­(nitrato-κ2 O,O′)cobalt(II)]-μ-4,4′-bis­(pyrazol-1-ylmeth­yl)biphenyl-κ2 N 2:N 2′]

Abstract

In the title compound, [Co(NO3)2(C20H18N4)]n, the CoII atom lies on a crystallographic twofold axis and the coordination geometry can be considered as a slightly distorted tetra­hedron defined by two O atoms from two nitrate groups and two N atoms from two ligand mol­ecules. A distorted octa­hedron may be assumed when two of the symmetry-related nitrate O atoms with Co—O distances of 2.3449 (19) Å are added to the coordination environment. Another twofold axis, passing through the middle of the biphenyl bonds, is observed in the crystal structure. A chain is built up by the ligands linking the CoII ions along [101].

Related literature

For a related polymeric bis­(pyrazole) dinitratocobalt(II) structure, see: Chen et al. (1997 [triangle]). For the isotypic Zn structure, see: Wang et al. (2010 [triangle]). For the synthesis and structure of a three-dimensional polymeric Zn(II) network compound, see: Zhu et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m718-scheme1.jpg

Experimental

Crystal data

  • [Co(NO3)2(C20H18N4)]
  • M r = 497.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m718-efi3.jpg
  • a = 14.133 (6) Å
  • b = 13.631 (8) Å
  • c = 10.806 (5) Å
  • β = 96.211 (18)°
  • V = 2069.5 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.88 mm−1
  • T = 291 K
  • 0.24 × 0.23 × 0.21 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.814, T max = 0.834
  • 9940 measured reflections
  • 2346 independent reflections
  • 1931 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.091
  • S = 1.07
  • 2346 reflections
  • 150 parameters
  • H-atom parameters constrained
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: RAPID-AUTO (Rigaku 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681001977X/si2260sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001977X/si2260Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Special Funds for the Research of Scientific and Technological Innovative Talents of Harbin Municipal Science and Technology Bureau (2009­RFXXG027), the Key Projects Promotion Conference for Rejuvenating Northeastern Old Industrial Base of the Department of Education of Heilongjiang Province (1152gzd02) and Heilongjiang University for supporting this study.

supplementary crystallographic information

Comment

The structures of the metal derivative 1,4-bis(pyrazole) benzene are known for zinc and cobalt (Chen et al., 1997). In order to enrich the research of this kinds of ligand, a new ligand 4,4'-bis(pyrazole) biphenyl with longer spacer was synthesized. In here, we report the strucuture of the title compound, which is a isomorphic compound of our previous report (Wang et al., 2010).

The central Co atom lies on a crystallographic twofold axis and the coordination geometry can be considered as a slightly distorted tetrahedron defined by two O atoms from two nitrate groups and two N atoms from two ligand molecules. A distorted octahedron may be assumed when two of the C2 related nitrate oxygen atoms with Co—O distances of 2.345 (2) Å are added to the coordination environment. Another twofold axis, passing through the middle of the biphenyl bonds, is observed in the crystal structure (Figure 1, Table 1).

A one dimensional chain is built up by the ligands linking the CoII ions along the [1 0 1] direction (Figure 2).

Experimental

The 4,4'-bis(pyrazole-1-ylmethyl) biphenyl was synthesized by the reaction of pyrazole and 4,4'-bis(chloro) bibenzene under alkaline condition (Zhu et al., 2002). Cobalt(II) dinitrate hexahydrate (0.582 g, 2 mmol) and 4,4'-bis(pyrazole-1-ylmethyl) biphenyl (0.628 g, 2 mmol) were dissolved in ethanol (20 ml), purple block-shaped crystals separated from the filtered solution after several days.

Refinement

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of title compound, showing the atom-labeling scheme and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: i = -x + 1, y, -z - 1/2; ii = -x + 2, y, -z + 1/2.
Fig. 2.
A section of the chain structure of the title compound extending along the [1 0 1] direction.

Crystal data

[Co(NO3)2(C20H18N4)]F(000) = 1020
Mr = 497.33Dx = 1.596 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 7566 reflections
a = 14.133 (6) Åθ = 3.0–27.5°
b = 13.631 (8) ŵ = 0.88 mm1
c = 10.806 (5) ÅT = 291 K
β = 96.211 (18)°Block, brown
V = 2069.5 (18) Å30.24 × 0.23 × 0.21 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer2346 independent reflections
Radiation source: fine-focus sealed tube1931 reflections with I > 2σ(I)
graphiteRint = 0.043
ω scanθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −18→18
Tmin = 0.814, Tmax = 0.834k = −17→17
9940 measured reflectionsl = −14→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.045P)2 + 0.959P] where P = (Fo2 + 2Fc2)/3
2346 reflections(Δ/σ)max < 0.001
150 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = −0.30 e Å3

Special details

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)

xyzUiso*/Ueq
C10.88489 (15)−0.14358 (16)0.29942 (19)0.0386 (5)
H10.9333−0.16630.35750.046*
C20.79651 (15)−0.18759 (17)0.2749 (2)0.0420 (5)
H20.7746−0.24360.31190.050*
C30.74852 (14)−0.13104 (15)0.1848 (2)0.0367 (5)
H30.6867−0.14160.14840.044*
C40.78951 (16)0.02164 (16)0.0679 (2)0.0449 (6)
H4A0.84340.02500.01950.054*
H4B0.78690.08300.11280.054*
C50.69915 (14)0.01146 (16)−0.02073 (19)0.0350 (5)
C60.68227 (14)−0.06955 (16)−0.0965 (2)0.0385 (5)
H60.7242−0.1223−0.08870.046*
C70.60311 (14)−0.07260 (16)−0.18418 (19)0.0364 (5)
H70.5914−0.1284−0.23300.044*
C80.54120 (13)0.00614 (15)−0.20021 (17)0.0301 (4)
C90.55799 (14)0.08674 (16)−0.1228 (2)0.0391 (5)
H90.51690.1402−0.13120.047*
C100.63546 (14)0.08820 (16)−0.0331 (2)0.0402 (5)
H100.64470.14190.01990.048*
Co11.00000.03534 (3)0.25000.03214 (14)
N10.89123 (11)−0.06439 (12)0.22882 (15)0.0327 (4)
N20.80555 (11)−0.05793 (12)0.15780 (15)0.0304 (4)
N31.06867 (12)0.16070 (13)0.10362 (17)0.0382 (4)
O11.00539 (10)0.09498 (12)0.07781 (14)0.0456 (4)
O21.10495 (11)0.16308 (13)0.21497 (15)0.0497 (4)
O31.09153 (13)0.21630 (14)0.02403 (17)0.0627 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0360 (11)0.0383 (12)0.0379 (11)−0.0004 (9)−0.0118 (9)0.0046 (9)
C20.0409 (12)0.0387 (12)0.0445 (12)−0.0066 (9)−0.0036 (10)0.0068 (9)
C30.0260 (9)0.0406 (12)0.0412 (11)−0.0070 (8)−0.0065 (8)−0.0005 (9)
C40.0351 (11)0.0422 (13)0.0508 (13)−0.0093 (9)−0.0255 (10)0.0112 (10)
C50.0261 (10)0.0404 (12)0.0349 (11)−0.0042 (8)−0.0127 (8)0.0051 (9)
C60.0305 (10)0.0395 (11)0.0420 (12)0.0085 (9)−0.0115 (9)0.0005 (9)
C70.0328 (10)0.0365 (11)0.0366 (11)0.0047 (8)−0.0120 (9)−0.0068 (9)
C80.0213 (9)0.0374 (11)0.0292 (10)−0.0002 (7)−0.0088 (8)0.0017 (8)
C90.0315 (10)0.0393 (12)0.0431 (12)0.0081 (9)−0.0116 (9)−0.0053 (9)
C100.0372 (11)0.0381 (12)0.0412 (12)0.0003 (9)−0.0145 (9)−0.0090 (9)
Co10.0226 (2)0.0312 (2)0.0390 (2)0.000−0.01331 (15)0.000
N10.0240 (8)0.0335 (9)0.0366 (9)−0.0004 (6)−0.0146 (7)0.0010 (7)
N20.0225 (7)0.0329 (9)0.0327 (8)−0.0018 (6)−0.0111 (6)0.0002 (7)
N30.0337 (9)0.0333 (9)0.0462 (10)−0.0007 (7)−0.0020 (8)−0.0011 (8)
O10.0419 (8)0.0440 (9)0.0471 (9)−0.0118 (7)−0.0125 (7)0.0013 (7)
O20.0416 (8)0.0530 (10)0.0504 (9)−0.0103 (7)−0.0142 (7)−0.0041 (8)
O30.0737 (12)0.0549 (12)0.0594 (11)−0.0208 (9)0.0064 (9)0.0111 (9)

Geometric parameters (Å, °)

C1—N11.330 (3)C7—H70.9300
C1—C21.385 (3)C8—C91.386 (3)
C1—H10.9300C8—C8i1.498 (3)
C2—C31.364 (3)C9—C101.382 (3)
C2—H20.9300C9—H90.9300
C3—N21.334 (3)C10—H100.9300
C3—H30.9300Co1—O12.0395 (18)
C4—N21.457 (3)Co1—O1ii2.0395 (18)
C4—C51.517 (3)Co1—N12.0463 (18)
C4—H4A0.9700Co1—N1ii2.0463 (18)
C4—H4B0.9700Co1—O22.3444 (19)
C5—C101.377 (3)Co1—O2ii2.3444 (19)
C5—C61.380 (3)N1—N21.364 (2)
C6—C71.386 (3)N3—O31.216 (2)
C6—H60.9300N3—O21.256 (2)
C7—C81.384 (3)N3—O11.275 (2)
N1—C1—C2110.92 (18)C5—C10—C9121.14 (19)
N1—C1—H1124.5C5—C10—H10119.4
C2—C1—H1124.5C9—C10—H10119.4
C3—C2—C1105.08 (19)O1—Co1—O1ii133.02 (10)
C3—C2—H2127.5O1—Co1—N1105.33 (6)
C1—C2—H2127.5O1ii—Co1—N1105.37 (7)
N2—C3—C2108.24 (17)O1—Co1—N1ii105.37 (7)
N2—C3—H3125.9O1ii—Co1—N1ii105.33 (6)
C2—C3—H3125.9N1—Co1—N1ii96.74 (10)
N2—C4—C5114.35 (17)O1—Co1—O257.99 (6)
N2—C4—H4A108.7O1ii—Co1—O286.45 (7)
C5—C4—H4A108.7N1—Co1—O2162.95 (6)
N2—C4—H4B108.7N1ii—Co1—O291.76 (8)
C5—C4—H4B108.7O1—Co1—O2ii86.45 (7)
H4A—C4—H4B107.6O1ii—Co1—O2ii57.99 (6)
C10—C5—C6118.75 (18)N1—Co1—O2ii91.76 (8)
C10—C5—C4119.24 (19)N1ii—Co1—O2ii162.95 (6)
C6—C5—C4121.82 (19)O2—Co1—O2ii84.08 (10)
C5—C6—C7120.29 (19)C1—N1—N2105.32 (15)
C5—C6—H6119.9C1—N1—Co1124.84 (13)
C7—C6—H6119.9N2—N1—Co1129.07 (13)
C8—C7—C6120.99 (19)C3—N2—N1110.44 (16)
C8—C7—H7119.5C3—N2—C4130.38 (16)
C6—C7—H7119.5N1—N2—C4119.18 (15)
C7—C8—C9118.34 (17)O3—N3—O2123.31 (18)
C7—C8—C8i121.46 (14)O3—N3—O1121.13 (18)
C9—C8—C8i120.19 (13)O2—N3—O1115.56 (18)
C10—C9—C8120.40 (19)N3—O1—Co1100.08 (12)
C10—C9—H9119.8N3—O2—Co186.31 (11)
C8—C9—H9119.8

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2260).

References

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  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
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  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, X., Gao, J.-S., Ding, Z.-Y. & Hou, G.-F. (2010). Acta Cryst. E66, m700. [PMC free article] [PubMed]
  • Zhu, H.-F., Zhao, W., Okamura, T., Fei, B.-L., Sun, W.-Y. & Ueyama, N. (2002). New J. Chem.26, 1277–1279.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography