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

Abstract

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,

• a = 14.088 (3) Å

• b = 13.780 (3) Å

• c = 10.744 (2) Å

• β = 95.76 (3)°

• V = 2075.2 (7) ų

• 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[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 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

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.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

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

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, 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).

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). 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

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 U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

[Zn(NO3)2(C20H18N4)]	F(000) = 1032
Mr = 503.77	Dx = 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

Rigaku R-AXIS RAPID diffractometer	2361 independent reflections
Radiation source: fine-focus sealed tube	2107 reflections with I > 2σ(I)
graphite	Rint = 0.027
ω scan	θmax = 27.5°, θmin = 3.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→18
Tmin = 0.595, Tmax = 0.728	k = −17→17
9881 measured reflections	l = −13→12

Refinement

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(Fo2) + (0.0366P)2 + 1.1611P] where P = (Fo2 + 2Fc2)/3
2361 reflections	(Δ/σ)max = 0.001
150 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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.