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

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ISSN: 2056-9890

catena-Poly[[bis­­(nitrato-κ2O,O′)cobalt(II)]-μ-4,4′-bis­­(pyrazol-1-ylmeth­yl)bi­phenyl-κ2N2:N2′]

aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, bEngineering Research Center of Pesticide of Heilongjiang Province, Heilongjiang University, Harbin 150080, People's Republic of China, and cDaqing New Century Industrial Co. Ltd, Daqing 163511, People's Republic of China
*Correspondence e-mail: hgf1000@163.com

(Received 1 May 2010; accepted 26 May 2010; online 29 May 2010)

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[Chen, J.-X., Goodgame, D. M. L., Menzer, S. & Williams, D. J. (1997). Polyhedron, 16, 1679-1687.]). For the isotypic Zn structure, see: Wang et al. (2010[Wang, X., Gao, J.-S., Ding, Z.-Y. & Hou, G.-F. (2010). Acta Cryst. E66, m700.]). For the synthesis and structure of a three-dimensional polymeric Zn(II) network compound, see: Zhu et al. (2002[Zhu, H.-F., Zhao, W., Okamura, T., Fei, B.-L., Sun, W.-Y. & Ueyama, N. (2002). New J. Chem. 26, 1277-1279.]).

[Scheme 1]

Experimental

Crystal data
  • [Co(NO3)2(C20H18N4)]

  • Mr = 497.33

  • Monoclinic, C 2/c

  • 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.814, Tmax = 0.834

  • 9940 measured reflections

  • 2346 independent reflections

  • 1931 reflections with I > 2σ(I)

  • Rint = 0.043

Refinement
  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 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

Table 1
Selected bond lengths (Å)

Co1—O1 2.0395 (18)
Co1—N1 2.0463 (18)
Co1—O2 2.3444 (19)

Data collection: RAPID-AUTO (Rigaku 1998[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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).

Structure description top

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).

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

Computing details top

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

Figures top
[Figure 1] 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.
[Figure 2] Fig. 2. A section of the chain structure of the title compound extending along the [1 0 1] direction.
catena-Poly[[bis(nitrato-κ2O,O')cobalt(II)]- µ-4,4'-bis(pyrazol-1-ylmethyl)biphenyl-κ2N2:N2'] top
Crystal data top
[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 top
Rigaku R-AXIS RAPID
diffractometer
2346 independent reflections
Radiation source: fine-focus sealed tube1931 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ω scanθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1818
Tmin = 0.814, Tmax = 0.834k = 1717
9940 measured reflectionsl = 1412
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.07 w = 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 = 0.31 e Å3
Crystal data top
[Co(NO3)2(C20H18N4)]V = 2069.5 (18) Å3
Mr = 497.33Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.133 (6) ŵ = 0.88 mm1
b = 13.631 (8) ÅT = 291 K
c = 10.806 (5) Å0.24 × 0.23 × 0.21 mm
β = 96.211 (18)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2346 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
1931 reflections with I > 2σ(I)
Tmin = 0.814, Tmax = 0.834Rint = 0.043
9940 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.07Δρmax = 0.39 e Å3
2346 reflectionsΔρmin = 0.31 e Å3
150 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
xyzUiso*/Ueq
C10.88489 (15)0.14358 (16)0.29942 (19)0.0386 (5)
H10.93330.16630.35750.046*
C20.79651 (15)0.18759 (17)0.2749 (2)0.0420 (5)
H20.77460.24360.31190.050*
C30.74852 (14)0.13104 (15)0.1848 (2)0.0367 (5)
H30.68670.14160.14840.044*
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)
H60.72420.12230.08870.046*
C70.60311 (14)0.07260 (16)0.18418 (19)0.0364 (5)
H70.59140.12840.23300.044*
C80.54120 (13)0.00614 (15)0.20021 (17)0.0301 (4)
C90.55799 (14)0.08674 (16)0.1228 (2)0.0391 (5)
H90.51690.14020.13120.047*
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) top
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)0.0000.01331 (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, º) top
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, z1/2; (ii) x+2, y, z+1/2.

Experimental details

Crystal data
Chemical formula[Co(NO3)2(C20H18N4)]
Mr497.33
Crystal system, space groupMonoclinic, C2/c
Temperature (K)291
a, b, c (Å)14.133 (6), 13.631 (8), 10.806 (5)
β (°) 96.211 (18)
V3)2069.5 (18)
Z4
Radiation typeMo Kα
µ (mm1)0.88
Crystal size (mm)0.24 × 0.23 × 0.21
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.814, 0.834
No. of measured, independent and
observed [I > 2σ(I)] reflections
9940, 2346, 1931
Rint0.043
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.091, 1.07
No. of reflections2346
No. of parameters150
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.31

Computer programs: RAPID-AUTO (Rigaku 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Co1—O12.0395 (18)Co1—O22.3444 (19)
Co1—N12.0463 (18)
 

Acknowledgements

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.

References

First citationChen, J.-X., Goodgame, D. M. L., Menzer, S. & Williams, D. J. (1997). Polyhedron, 16, 1679–1687.  CSD CrossRef CAS Web of Science Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWang, X., Gao, J.-S., Ding, Z.-Y. & Hou, G.-F. (2010). Acta Cryst. E66, m700.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationZhu, H.-F., Zhao, W., Okamura, T., Fei, B.-L., Sun, W.-Y. & Ueyama, N. (2002). New J. Chem. 26, 1277–1279.  Web of Science CSD CrossRef CAS Google Scholar

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