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

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

doi:10.1107/S1600536810018738

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page m700

https://doi.org/10.1107/S1600536810018738

Open

access

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

Xue Wang,^a Jin-Sheng Gao,^a,^b ^* 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 19 May 2010; online 22 May 2010)

In the title compound, [Zn(NO₃)₂(C₂₀H₁₈N₄)]_n, the Zn^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 Zn—O distances of 2.528 (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. A chain along [101] is built up by the ligands linking the Zn^II ions.

Related literature

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

Experimental

Crystal data

[Zn(NO₃)₂(C₂₀H₁₈N₄)]
M_r = 503.77
Monoclinic, C 2/c
a = 14.088 (3) Å
b = 13.780 (3) Å
c = 10.744 (2) Å
β = 95.76 (3)°
V = 2075.2 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.24 mm⁻¹
T = 291 K
0.47 × 0.31 × 0.27 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.595, T_max = 0.728
9881 measured reflections
2361 independent reflections
2107 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.072
S = 1.07
2361 reflections
150 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected bond lengths (Å)

N1—Zn1	2.0240 (14)
O1—Zn1	2.0169 (14)
O2—Zn1	2.5277 (16)

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/S1600536810018738/si2259sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018738/si2259Isup2.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, and which are used in the preparation of coordination compound with zinc dinitrate.

The central Zn 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 Zn—O distances of 2.528 (2) Å are added (Table 1) to the coordination environment. Another twofold axis, passing through the middle of the biphenyl bonds, is observed in the crystal structure (Figure 1).

A one dimensional chain is built up by the ligands linking the Zn^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 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). Zinc(II) dinitrate hexahydrate (0.595 g, 2 mmol) and 4,4'-bis(pyrazole-1-ylmethyl) biphenyl (0.618 g, 2 mmol) were dissolved in ethanol (20 ml), colorless block-shaped crystals of the title compound were obtained by slow evaporation of ethanol solution after several days.

Structure description top

A one dimensional chain is built up by the ligands linking the Zn^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 the title compound, showing the atom-labeling scheme and displacement ellipsoids drawn at the 50% probability level. symmetry codes: i = -x + 1, y, -z - 0.5; ii = -x + 2, y, -z + 0.5
	Fig. 2. A view of the one dimensional structure of the title compound extending along the [1 0 1] direction.

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

Crystal data top

[Zn(NO₃)₂(C₂₀H₁₈N₄)]	F(000) = 1032
M_r = 503.77	D_x = 1.612 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8577 reflections
a = 14.088 (3) Å	θ = 3.5–27.5°
b = 13.780 (3) Å	µ = 1.24 mm⁻¹
c = 10.744 (2) Å	T = 291 K
β = 95.76 (3)°	Block, colorless
V = 2075.2 (7) Å³	0.47 × 0.31 × 0.27 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2361 independent reflections
Radiation source: fine-focus sealed tube	2107 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scan	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→18
T_min = 0.595, T_max = 0.728	k = −17→17
9881 measured reflections	l = −13→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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0366P)² + 1.1611P] where P = (F_o² + 2F_c²)/3
2361 reflections	(Δ/σ)_max = 0.001
150 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Zn(NO₃)₂(C₂₀H₁₈N₄)]	V = 2075.2 (7) Å³
M_r = 503.77	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.088 (3) Å	µ = 1.24 mm⁻¹
b = 13.780 (3) Å	T = 291 K
c = 10.744 (2) Å	0.47 × 0.31 × 0.27 mm
β = 95.76 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2361 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2107 reflections with I > 2σ(I)
T_min = 0.595, T_max = 0.728	R_int = 0.027
9881 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.07	Δρ_max = 0.29 e Å⁻³
2361 reflections	Δρ_min = −0.30 e Å⁻³
150 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.88226 (13)	0.85458 (13)	0.30265 (17)	0.0400 (4)
H1	0.9299	0.8328	0.3623	0.048*
C2	0.79425 (13)	0.81078 (13)	0.27656 (17)	0.0422 (4)
H2	0.7719	0.7555	0.3138	0.051*
C3	0.74719 (12)	0.86596 (12)	0.18459 (17)	0.0378 (4)
H3	0.6857	0.8550	0.1472	0.045*
C4	0.79018 (13)	1.01784 (13)	0.06773 (19)	0.0448 (5)
H4A	0.8446	1.0209	0.0192	0.054*
H4B	0.7877	1.0785	0.1132	0.054*
C5	0.70008 (12)	1.00840 (13)	−0.02129 (16)	0.0344 (4)
C6	0.68292 (12)	0.92829 (13)	−0.09799 (17)	0.0394 (4)
H6	0.7250	0.8761	−0.0910	0.047*
C7	0.60321 (12)	0.92531 (13)	−0.18549 (16)	0.0371 (4)
H7	0.5913	0.8701	−0.2345	0.045*
C8	0.54112 (11)	1.00366 (12)	−0.20065 (15)	0.0304 (3)
C9	0.55789 (12)	1.08310 (12)	−0.12237 (16)	0.0379 (4)
H9	0.5164	1.1357	−0.1299	0.045*
C10	0.63608 (12)	1.08471 (13)	−0.03278 (16)	0.0392 (4)
H10	0.6456	1.1379	0.0203	0.047*
N1	0.88943 (9)	0.93271 (10)	0.23026 (13)	0.0336 (3)
N2	0.80483 (9)	0.93853 (10)	0.15759 (12)	0.0307 (3)
N3	1.06552 (11)	1.16224 (10)	0.10426 (14)	0.0389 (3)
O1	1.00867 (10)	1.09113 (9)	0.08271 (13)	0.0476 (3)
O2	1.10427 (11)	1.17141 (11)	0.21293 (14)	0.0588 (4)
O3	1.08004 (13)	1.21789 (11)	0.02032 (15)	0.0678 (5)
Zn1	1.0000	1.027091 (19)	0.2500	0.03491 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0374 (9)	0.0386 (9)	0.0404 (9)	0.0011 (7)	−0.0139 (7)	0.0046 (8)
C2	0.0406 (10)	0.0393 (9)	0.0449 (10)	−0.0062 (7)	−0.0043 (8)	0.0060 (8)
C3	0.0263 (8)	0.0419 (9)	0.0430 (9)	−0.0074 (7)	−0.0070 (7)	−0.0014 (8)
C4	0.0330 (9)	0.0453 (10)	0.0506 (11)	−0.0088 (7)	−0.0235 (8)	0.0106 (8)
C5	0.0252 (8)	0.0407 (8)	0.0342 (9)	−0.0030 (6)	−0.0121 (6)	0.0055 (7)
C6	0.0300 (8)	0.0422 (9)	0.0424 (9)	0.0094 (7)	−0.0135 (7)	−0.0017 (8)
C7	0.0343 (9)	0.0380 (9)	0.0359 (8)	0.0042 (7)	−0.0123 (7)	−0.0071 (7)
C8	0.0227 (8)	0.0379 (8)	0.0285 (8)	−0.0009 (6)	−0.0080 (6)	0.0003 (6)
C9	0.0301 (8)	0.0374 (9)	0.0428 (9)	0.0065 (7)	−0.0122 (7)	−0.0038 (7)
C10	0.0372 (9)	0.0378 (9)	0.0386 (9)	−0.0014 (7)	−0.0151 (7)	−0.0064 (7)
N1	0.0238 (6)	0.0356 (7)	0.0377 (7)	−0.0008 (5)	−0.0151 (5)	0.0003 (6)
N2	0.0214 (6)	0.0342 (6)	0.0337 (7)	−0.0018 (5)	−0.0113 (5)	−0.0008 (6)
N3	0.0339 (8)	0.0359 (7)	0.0456 (8)	−0.0004 (6)	−0.0022 (6)	0.0005 (7)
O1	0.0461 (8)	0.0409 (7)	0.0521 (8)	−0.0107 (6)	−0.0130 (6)	0.0012 (6)
O2	0.0503 (9)	0.0668 (9)	0.0550 (8)	−0.0159 (7)	−0.0154 (7)	−0.0043 (7)
O3	0.0858 (12)	0.0570 (9)	0.0600 (9)	−0.0229 (9)	0.0047 (8)	0.0089 (8)
Zn1	0.02434 (15)	0.03443 (16)	0.04240 (18)	0.000	−0.01422 (11)	0.000

Geometric parameters (Å, º) top

C1—N1	1.338 (2)	C7—H7	0.9300
C1—C2	1.382 (2)	C8—C9	1.386 (2)
C1—H1	0.9300	C8—C8ⁱ	1.490 (3)
C2—C3	1.365 (2)	C9—C10	1.388 (2)
C2—H2	0.9300	C9—H9	0.9300
C3—N2	1.338 (2)	C10—H10	0.9300
C3—H3	0.9300	N1—N2	1.3602 (17)
C4—N2	1.459 (2)	N1—Zn1	2.0240 (14)
C4—C5	1.516 (2)	N3—O3	1.217 (2)
C4—H4A	0.9700	N3—O2	1.245 (2)
C4—H4B	0.9700	N3—O1	1.2721 (19)
C5—C10	1.383 (2)	O1—Zn1	2.0169 (14)
C5—C6	1.384 (3)	O2—Zn1	2.5277 (16)
C6—C7	1.391 (2)	Zn1—O1ⁱⁱ	2.0169 (14)
C6—H6	0.9300	Zn1—N1ⁱⁱ	2.0240 (14)
C7—C8	1.389 (2)

N1—C1—C2	110.62 (15)	C8—C9—C10	120.55 (15)
N1—C1—H1	124.7	C8—C9—H9	119.7
C2—C1—H1	124.7	C10—C9—H9	119.7
C3—C2—C1	105.32 (16)	C5—C10—C9	120.98 (16)
C3—C2—H2	127.3	C5—C10—H10	119.5
C1—C2—H2	127.3	C9—C10—H10	119.5
N2—C3—C2	108.18 (15)	C1—N1—N2	105.55 (13)
N2—C3—H3	125.9	C1—N1—Zn1	123.95 (11)
C2—C3—H3	125.9	N2—N1—Zn1	130.02 (11)
N2—C4—C5	114.01 (14)	C3—N2—N1	110.32 (13)
N2—C4—H4A	108.8	C3—N2—C4	130.89 (13)
C5—C4—H4A	108.8	N1—N2—C4	118.79 (13)
N2—C4—H4B	108.8	O3—N3—O2	122.73 (16)
C5—C4—H4B	108.8	O3—N3—O1	120.02 (16)
H4A—C4—H4B	107.6	O2—N3—O1	117.25 (15)
C10—C5—C6	118.68 (14)	N3—O1—Zn1	105.56 (10)
C10—C5—C4	119.23 (16)	N3—O2—Zn1	81.99 (10)
C6—C5—C4	121.94 (16)	O1ⁱⁱ—Zn1—O1	128.11 (8)
C5—C6—C7	120.45 (15)	O1ⁱⁱ—Zn1—N1	105.05 (6)
C5—C6—H6	119.8	O1—Zn1—N1	107.61 (6)
C7—C6—H6	119.8	O1ⁱⁱ—Zn1—N1ⁱⁱ	107.61 (6)
C8—C7—C6	120.83 (15)	O1—Zn1—N1ⁱⁱ	105.05 (6)
C8—C7—H7	119.6	N1—Zn1—N1ⁱⁱ	100.03 (8)
C6—C7—H7	119.6	O1ⁱⁱ—Zn1—O2	83.36 (6)
C9—C8—C7	118.41 (14)	O1—Zn1—O2	55.06 (5)
C9—C8—C8ⁱ	120.32 (11)	N1—Zn1—O2	160.46 (5)
C7—C8—C8ⁱ	121.27 (11)	N1ⁱⁱ—Zn1—O2	93.94 (6)

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

Experimental details

Crystal data
Chemical formula	[Zn(NO₃)₂(C₂₀H₁₈N₄)]
M_r	503.77
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	291
a, b, c (Å)	14.088 (3), 13.780 (3), 10.744 (2)
β (°)	95.76 (3)
V (Å³)	2075.2 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.24
Crystal size (mm)	0.47 × 0.31 × 0.27

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.595, 0.728
No. of measured, independent and observed [I > 2σ(I)] reflections	9881, 2361, 2107
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.072, 1.07
No. of reflections	2361
No. of parameters	150
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.30

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

Selected bond lengths (Å) top

N1—Zn1	2.0240 (14)	O2—Zn1	2.5277 (16)
O1—Zn1	2.0169 (14)

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 Science and Technology Planning Project of Heilongjiang Province (GZ08A401) 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
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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.