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

Gao, J.-S.; Wang, X.; Ding, Z.-Y.; Hou, G.-F.

doi:10.1107/S160053681001977X

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page m718

https://doi.org/10.1107/S160053681001977X

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catena-Poly[[bis(nitrato-κ²O,O′)cobalt(II)]-μ-4,4′-bis(pyrazol-1-ylmethyl)biphenyl-κ²N²:N^2′]

Jin-Sheng Gao,^a,^b ^* Xue Wang,^a Zhi-Yong Ding ^c and Guang-Feng Hou ^b

^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 Co^II 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 Co^II ions along [101].

Related literature

For a related polymeric bis(pyrazole) dinitratocobalt(II) structure, see: Chen et al. (1997 ). For the isotypic Zn 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

Crystal data

[Co(NO₃)₂(C₂₀H₁₈N₄)]
M_r = 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 ) 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[F² > 2σ(F²)] = 0.036
wR(F²) = 0.091
S = 1.07
2346 reflections
150 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −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 ); cell refinement: RAPID-AUTO; 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.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681001977X/si2260Isup2.hkl

checkCIF report

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 Co^II 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.

Structure description top

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

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

	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.

catena-Poly[[bis(nitrato-κ²O,O')cobalt(II)]- µ-4,4'-bis(pyrazol-1-ylmethyl)biphenyl-κ²N²:N^2'] top

Crystal data top

[Co(NO₃)₂(C₂₀H₁₈N₄)]	F(000) = 1020
M_r = 497.33	D_x = 1.596 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7566 reflections
a = 14.133 (6) Å	θ = 3.0–27.5°
b = 13.631 (8) Å	µ = 0.88 mm⁻¹
c = 10.806 (5) Å	T = 291 K
β = 96.211 (18)°	Block, brown
V = 2069.5 (18) Å³	0.24 × 0.23 × 0.21 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2346 independent reflections
Radiation source: fine-focus sealed tube	1931 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scan	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→18
T_min = 0.814, T_max = 0.834	k = −17→17
9940 measured reflections	l = −14→12

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.045P)² + 0.959P] where P = (F_o² + 2F_c²)/3
2346 reflections	(Δ/σ)_max < 0.001
150 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Co(NO₃)₂(C₂₀H₁₈N₄)]	V = 2069.5 (18) Å³
M_r = 497.33	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.133 (6) Å	µ = 0.88 mm⁻¹
b = 13.631 (8) Å	T = 291 K
c = 10.806 (5) Å	0.24 × 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)
T_min = 0.814, T_max = 0.834	R_int = 0.043
9940 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.07	Δρ_max = 0.39 e Å⁻³
2346 reflections	Δρ_min = −0.31 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C1	0.88489 (15)	−0.14358 (16)	0.29942 (19)	0.0386 (5)
H1	0.9333	−0.1663	0.3575	0.046*
C2	0.79651 (15)	−0.18759 (17)	0.2749 (2)	0.0420 (5)
H2	0.7746	−0.2436	0.3119	0.050*
C3	0.74852 (14)	−0.13104 (15)	0.1848 (2)	0.0367 (5)
H3	0.6867	−0.1416	0.1484	0.044*
C4	0.78951 (16)	0.02164 (16)	0.0679 (2)	0.0449 (6)
H4A	0.8434	0.0250	0.0195	0.054*
H4B	0.7869	0.0830	0.1128	0.054*
C5	0.69915 (14)	0.01146 (16)	−0.02073 (19)	0.0350 (5)
C6	0.68227 (14)	−0.06955 (16)	−0.0965 (2)	0.0385 (5)
H6	0.7242	−0.1223	−0.0887	0.046*
C7	0.60311 (14)	−0.07260 (16)	−0.18418 (19)	0.0364 (5)
H7	0.5914	−0.1284	−0.2330	0.044*
C8	0.54120 (13)	0.00614 (15)	−0.20021 (17)	0.0301 (4)
C9	0.55799 (14)	0.08674 (16)	−0.1228 (2)	0.0391 (5)
H9	0.5169	0.1402	−0.1312	0.047*
C10	0.63546 (14)	0.08820 (16)	−0.0331 (2)	0.0402 (5)
H10	0.6447	0.1419	0.0199	0.048*
Co1	1.0000	0.03534 (3)	0.2500	0.03214 (14)
N1	0.89123 (11)	−0.06439 (12)	0.22882 (15)	0.0327 (4)
N2	0.80555 (11)	−0.05793 (12)	0.15780 (15)	0.0304 (4)
N3	1.06867 (12)	0.16070 (13)	0.10362 (17)	0.0382 (4)
O1	1.00539 (10)	0.09498 (12)	0.07781 (14)	0.0456 (4)
O2	1.10495 (11)	0.16308 (13)	0.21497 (15)	0.0497 (4)
O3	1.09153 (13)	0.21630 (14)	0.02403 (17)	0.0627 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0360 (11)	0.0383 (12)	0.0379 (11)	−0.0004 (9)	−0.0118 (9)	0.0046 (9)
C2	0.0409 (12)	0.0387 (12)	0.0445 (12)	−0.0066 (9)	−0.0036 (10)	0.0068 (9)
C3	0.0260 (9)	0.0406 (12)	0.0412 (11)	−0.0070 (8)	−0.0065 (8)	−0.0005 (9)
C4	0.0351 (11)	0.0422 (13)	0.0508 (13)	−0.0093 (9)	−0.0255 (10)	0.0112 (10)
C5	0.0261 (10)	0.0404 (12)	0.0349 (11)	−0.0042 (8)	−0.0127 (8)	0.0051 (9)
C6	0.0305 (10)	0.0395 (11)	0.0420 (12)	0.0085 (9)	−0.0115 (9)	0.0005 (9)
C7	0.0328 (10)	0.0365 (11)	0.0366 (11)	0.0047 (8)	−0.0120 (9)	−0.0068 (9)
C8	0.0213 (9)	0.0374 (11)	0.0292 (10)	−0.0002 (7)	−0.0088 (8)	0.0017 (8)
C9	0.0315 (10)	0.0393 (12)	0.0431 (12)	0.0081 (9)	−0.0116 (9)	−0.0053 (9)
C10	0.0372 (11)	0.0381 (12)	0.0412 (12)	0.0003 (9)	−0.0145 (9)	−0.0090 (9)
Co1	0.0226 (2)	0.0312 (2)	0.0390 (2)	0.000	−0.01331 (15)	0.000
N1	0.0240 (8)	0.0335 (9)	0.0366 (9)	−0.0004 (6)	−0.0146 (7)	0.0010 (7)
N2	0.0225 (7)	0.0329 (9)	0.0327 (8)	−0.0018 (6)	−0.0111 (6)	0.0002 (7)
N3	0.0337 (9)	0.0333 (9)	0.0462 (10)	−0.0007 (7)	−0.0020 (8)	−0.0011 (8)
O1	0.0419 (8)	0.0440 (9)	0.0471 (9)	−0.0118 (7)	−0.0125 (7)	0.0013 (7)
O2	0.0416 (8)	0.0530 (10)	0.0504 (9)	−0.0103 (7)	−0.0142 (7)	−0.0041 (8)
O3	0.0737 (12)	0.0549 (12)	0.0594 (11)	−0.0208 (9)	0.0064 (9)	0.0111 (9)

Geometric parameters (Å, º) top

C1—N1	1.330 (3)	C7—H7	0.9300
C1—C2	1.385 (3)	C8—C9	1.386 (3)
C1—H1	0.9300	C8—C8ⁱ	1.498 (3)
C2—C3	1.364 (3)	C9—C10	1.382 (3)
C2—H2	0.9300	C9—H9	0.9300
C3—N2	1.334 (3)	C10—H10	0.9300
C3—H3	0.9300	Co1—O1	2.0395 (18)
C4—N2	1.457 (3)	Co1—O1ⁱⁱ	2.0395 (18)
C4—C5	1.517 (3)	Co1—N1	2.0463 (18)
C4—H4A	0.9700	Co1—N1ⁱⁱ	2.0463 (18)
C4—H4B	0.9700	Co1—O2	2.3444 (19)
C5—C10	1.377 (3)	Co1—O2ⁱⁱ	2.3444 (19)
C5—C6	1.380 (3)	N1—N2	1.364 (2)
C6—C7	1.386 (3)	N3—O3	1.216 (2)
C6—H6	0.9300	N3—O2	1.256 (2)
C7—C8	1.384 (3)	N3—O1	1.275 (2)

N1—C1—C2	110.92 (18)	C5—C10—C9	121.14 (19)
N1—C1—H1	124.5	C5—C10—H10	119.4
C2—C1—H1	124.5	C9—C10—H10	119.4
C3—C2—C1	105.08 (19)	O1—Co1—O1ⁱⁱ	133.02 (10)
C3—C2—H2	127.5	O1—Co1—N1	105.33 (6)
C1—C2—H2	127.5	O1ⁱⁱ—Co1—N1	105.37 (7)
N2—C3—C2	108.24 (17)	O1—Co1—N1ⁱⁱ	105.37 (7)
N2—C3—H3	125.9	O1ⁱⁱ—Co1—N1ⁱⁱ	105.33 (6)
C2—C3—H3	125.9	N1—Co1—N1ⁱⁱ	96.74 (10)
N2—C4—C5	114.35 (17)	O1—Co1—O2	57.99 (6)
N2—C4—H4A	108.7	O1ⁱⁱ—Co1—O2	86.45 (7)
C5—C4—H4A	108.7	N1—Co1—O2	162.95 (6)
N2—C4—H4B	108.7	N1ⁱⁱ—Co1—O2	91.76 (8)
C5—C4—H4B	108.7	O1—Co1—O2ⁱⁱ	86.45 (7)
H4A—C4—H4B	107.6	O1ⁱⁱ—Co1—O2ⁱⁱ	57.99 (6)
C10—C5—C6	118.75 (18)	N1—Co1—O2ⁱⁱ	91.76 (8)
C10—C5—C4	119.24 (19)	N1ⁱⁱ—Co1—O2ⁱⁱ	162.95 (6)
C6—C5—C4	121.82 (19)	O2—Co1—O2ⁱⁱ	84.08 (10)
C5—C6—C7	120.29 (19)	C1—N1—N2	105.32 (15)
C5—C6—H6	119.9	C1—N1—Co1	124.84 (13)
C7—C6—H6	119.9	N2—N1—Co1	129.07 (13)
C8—C7—C6	120.99 (19)	C3—N2—N1	110.44 (16)
C8—C7—H7	119.5	C3—N2—C4	130.38 (16)
C6—C7—H7	119.5	N1—N2—C4	119.18 (15)
C7—C8—C9	118.34 (17)	O3—N3—O2	123.31 (18)
C7—C8—C8ⁱ	121.46 (14)	O3—N3—O1	121.13 (18)
C9—C8—C8ⁱ	120.19 (13)	O2—N3—O1	115.56 (18)
C10—C9—C8	120.40 (19)	N3—O1—Co1	100.08 (12)
C10—C9—H9	119.8	N3—O2—Co1	86.31 (11)
C8—C9—H9	119.8

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

Experimental details

Crystal data
Chemical formula	[Co(NO₃)₂(C₂₀H₁₈N₄)]
M_r	497.33
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	291
a, b, c (Å)	14.133 (6), 13.631 (8), 10.806 (5)
β (°)	96.211 (18)
V (Å³)	2069.5 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.24 × 0.23 × 0.21

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.814, 0.834
No. of measured, independent and observed [I > 2σ(I)] reflections	9940, 2346, 1931
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.091, 1.07
No. of reflections	2346
No. of parameters	150
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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—O1	2.0395 (18)	Co1—O2	2.3444 (19)
Co1—N1	2.0463 (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

Chen, J.-X., Goodgame, D. M. L., Menzer, S. & Williams, D. J. (1997). Polyhedron, 16, 1679–1687. CSD CrossRef CAS Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, X., Gao, J.-S., Ding, Z.-Y. & Hou, G.-F. (2010). Acta Cryst. E66, m700. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhu, 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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