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′)zinc(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 19 May 2010; online 22 May 2010)

In the title compound, [Zn(NO3)2(C20H18N4)]n, the ZnII 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 ZnII ions.

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 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
  • [Zn(NO3)2(C20H18N4)]

  • Mr = 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.595, Tmax = 0.728

  • 9881 measured reflections

  • 2361 independent reflections

  • 2107 reflections with I > 2σ(I)

  • Rint = 0.027

Refinement
  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.072

  • S = 1.07

  • 2361 reflections

  • 150 parameters

  • H-atom parameters constrained

  • Δρmax = 0.29 e Å−3

  • Δρmin = −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[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, 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 ZnII 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.

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, 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 ZnII ions along the [1 0 1] direction (Figure 2).

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).

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 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
[Figure 2] 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:N2'] top
Crystal data top
[Zn(NO3)2(C20H18N4)]F(000) = 1032
Mr = 503.77Dx = 1.612 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8577 reflections
a = 14.088 (3) Åθ = 3.5–27.5°
b = 13.780 (3) ŵ = 1.24 mm1
c = 10.744 (2) ÅT = 291 K
β = 95.76 (3)°Block, colorless
V = 2075.2 (7) Å30.47 × 0.31 × 0.27 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2361 independent reflections
Radiation source: fine-focus sealed tube2107 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scanθmax = 27.5°, θmin = 3.5°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1818
Tmin = 0.595, Tmax = 0.728k = 1717
9881 measured reflectionsl = 1312
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0366P)2 + 1.1611P]
where P = (Fo2 + 2Fc2)/3
2361 reflections(Δ/σ)max = 0.001
150 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
[Zn(NO3)2(C20H18N4)]V = 2075.2 (7) Å3
Mr = 503.77Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.088 (3) ŵ = 1.24 mm1
b = 13.780 (3) ÅT = 291 K
c = 10.744 (2) Å0.47 × 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)
Tmin = 0.595, Tmax = 0.728Rint = 0.027
9881 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.07Δρmax = 0.29 e Å3
2361 reflectionsΔρmin = 0.30 e Å3
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
xyzUiso*/Ueq
C10.88226 (13)0.85458 (13)0.30265 (17)0.0400 (4)
H10.92990.83280.36230.048*
C20.79425 (13)0.81078 (13)0.27656 (17)0.0422 (4)
H20.77190.75550.31380.051*
C30.74719 (12)0.86596 (12)0.18459 (17)0.0378 (4)
H30.68570.85500.14720.045*
C40.79018 (13)1.01784 (13)0.06773 (19)0.0448 (5)
H4A0.84461.02090.01920.054*
H4B0.78771.07850.11320.054*
C50.70008 (12)1.00840 (13)0.02129 (16)0.0344 (4)
C60.68292 (12)0.92829 (13)0.09799 (17)0.0394 (4)
H60.72500.87610.09100.047*
C70.60321 (12)0.92531 (13)0.18549 (16)0.0371 (4)
H70.59130.87010.23450.045*
C80.54112 (11)1.00366 (12)0.20065 (15)0.0304 (3)
C90.55789 (12)1.08310 (12)0.12237 (16)0.0379 (4)
H90.51641.13570.12990.045*
C100.63608 (12)1.08471 (13)0.03278 (16)0.0392 (4)
H100.64561.13790.02030.047*
N10.88943 (9)0.93271 (10)0.23026 (13)0.0336 (3)
N20.80483 (9)0.93853 (10)0.15759 (12)0.0307 (3)
N31.06552 (11)1.16224 (10)0.10426 (14)0.0389 (3)
O11.00867 (10)1.09113 (9)0.08271 (13)0.0476 (3)
O21.10427 (11)1.17141 (11)0.21293 (14)0.0588 (4)
O31.08004 (13)1.21789 (11)0.02032 (15)0.0678 (5)
Zn11.00001.027091 (19)0.25000.03491 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0374 (9)0.0386 (9)0.0404 (9)0.0011 (7)0.0139 (7)0.0046 (8)
C20.0406 (10)0.0393 (9)0.0449 (10)0.0062 (7)0.0043 (8)0.0060 (8)
C30.0263 (8)0.0419 (9)0.0430 (9)0.0074 (7)0.0070 (7)0.0014 (8)
C40.0330 (9)0.0453 (10)0.0506 (11)0.0088 (7)0.0235 (8)0.0106 (8)
C50.0252 (8)0.0407 (8)0.0342 (9)0.0030 (6)0.0121 (6)0.0055 (7)
C60.0300 (8)0.0422 (9)0.0424 (9)0.0094 (7)0.0135 (7)0.0017 (8)
C70.0343 (9)0.0380 (9)0.0359 (8)0.0042 (7)0.0123 (7)0.0071 (7)
C80.0227 (8)0.0379 (8)0.0285 (8)0.0009 (6)0.0080 (6)0.0003 (6)
C90.0301 (8)0.0374 (9)0.0428 (9)0.0065 (7)0.0122 (7)0.0038 (7)
C100.0372 (9)0.0378 (9)0.0386 (9)0.0014 (7)0.0151 (7)0.0064 (7)
N10.0238 (6)0.0356 (7)0.0377 (7)0.0008 (5)0.0151 (5)0.0003 (6)
N20.0214 (6)0.0342 (6)0.0337 (7)0.0018 (5)0.0113 (5)0.0008 (6)
N30.0339 (8)0.0359 (7)0.0456 (8)0.0004 (6)0.0022 (6)0.0005 (7)
O10.0461 (8)0.0409 (7)0.0521 (8)0.0107 (6)0.0130 (6)0.0012 (6)
O20.0503 (9)0.0668 (9)0.0550 (8)0.0159 (7)0.0154 (7)0.0043 (7)
O30.0858 (12)0.0570 (9)0.0600 (9)0.0229 (9)0.0047 (8)0.0089 (8)
Zn10.02434 (15)0.03443 (16)0.04240 (18)0.0000.01422 (11)0.000
Geometric parameters (Å, º) top
C1—N11.338 (2)C7—H70.9300
C1—C21.382 (2)C8—C91.386 (2)
C1—H10.9300C8—C8i1.490 (3)
C2—C31.365 (2)C9—C101.388 (2)
C2—H20.9300C9—H90.9300
C3—N21.338 (2)C10—H100.9300
C3—H30.9300N1—N21.3602 (17)
C4—N21.459 (2)N1—Zn12.0240 (14)
C4—C51.516 (2)N3—O31.217 (2)
C4—H4A0.9700N3—O21.245 (2)
C4—H4B0.9700N3—O11.2721 (19)
C5—C101.383 (2)O1—Zn12.0169 (14)
C5—C61.384 (3)O2—Zn12.5277 (16)
C6—C71.391 (2)Zn1—O1ii2.0169 (14)
C6—H60.9300Zn1—N1ii2.0240 (14)
C7—C81.389 (2)
N1—C1—C2110.62 (15)C8—C9—C10120.55 (15)
N1—C1—H1124.7C8—C9—H9119.7
C2—C1—H1124.7C10—C9—H9119.7
C3—C2—C1105.32 (16)C5—C10—C9120.98 (16)
C3—C2—H2127.3C5—C10—H10119.5
C1—C2—H2127.3C9—C10—H10119.5
N2—C3—C2108.18 (15)C1—N1—N2105.55 (13)
N2—C3—H3125.9C1—N1—Zn1123.95 (11)
C2—C3—H3125.9N2—N1—Zn1130.02 (11)
N2—C4—C5114.01 (14)C3—N2—N1110.32 (13)
N2—C4—H4A108.8C3—N2—C4130.89 (13)
C5—C4—H4A108.8N1—N2—C4118.79 (13)
N2—C4—H4B108.8O3—N3—O2122.73 (16)
C5—C4—H4B108.8O3—N3—O1120.02 (16)
H4A—C4—H4B107.6O2—N3—O1117.25 (15)
C10—C5—C6118.68 (14)N3—O1—Zn1105.56 (10)
C10—C5—C4119.23 (16)N3—O2—Zn181.99 (10)
C6—C5—C4121.94 (16)O1ii—Zn1—O1128.11 (8)
C5—C6—C7120.45 (15)O1ii—Zn1—N1105.05 (6)
C5—C6—H6119.8O1—Zn1—N1107.61 (6)
C7—C6—H6119.8O1ii—Zn1—N1ii107.61 (6)
C8—C7—C6120.83 (15)O1—Zn1—N1ii105.05 (6)
C8—C7—H7119.6N1—Zn1—N1ii100.03 (8)
C6—C7—H7119.6O1ii—Zn1—O283.36 (6)
C9—C8—C7118.41 (14)O1—Zn1—O255.06 (5)
C9—C8—C8i120.32 (11)N1—Zn1—O2160.46 (5)
C7—C8—C8i121.27 (11)N1ii—Zn1—O293.94 (6)
Symmetry codes: (i) x+1, y, z1/2; (ii) x+2, y, z+1/2.

Experimental details

Crystal data
Chemical formula[Zn(NO3)2(C20H18N4)]
Mr503.77
Crystal system, space groupMonoclinic, C2/c
Temperature (K)291
a, b, c (Å)14.088 (3), 13.780 (3), 10.744 (2)
β (°) 95.76 (3)
V3)2075.2 (7)
Z4
Radiation typeMo Kα
µ (mm1)1.24
Crystal size (mm)0.47 × 0.31 × 0.27
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.595, 0.728
No. of measured, independent and
observed [I > 2σ(I)] reflections
9881, 2361, 2107
Rint0.027
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.072, 1.07
No. of reflections2361
No. of parameters150
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—Zn12.0240 (14)O2—Zn12.5277 (16)
O1—Zn12.0169 (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

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 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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