catena-Poly[[tetra­kis­(1H-pyrazole-κN2)copper(II)]-μ-hexa­fluoridosilicato-κ2F:F′]

Li, H.; Han, Q.; Chai, X.; Wang, J.; Yao, C.

doi:10.1107/S1600536812009531

metal-organic compounds

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Volume 68| Part 4| April 2012| Page m405

doi:10.1107/S1600536812009531

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catena-Poly[[tetrakis(1H-pyrazole-κN²)copper(II)]-μ-hexafluoridosilicato-κ²F:F′]

Hui Li,^a ^* Qiuping Han,^a Xiaochuan Chai,^a Jian Wang ^a and Chenzhong Yao ^a

^aDepartment of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000, People's Republic of China
^*Correspondence e-mail: lihuiwff@163.com

(Received 22 February 2012; accepted 4 March 2012; online 14 March 2012)

In the title one-dimensional coordination polymer, [Cu(SiF₆)(C₃H₄N₂)₄]_n, the Cu^II atom is coordinated by two hexafluoridosilicate F atoms and four pyrazole N atoms in a distorted trans-CuF₂N₄ octahedral environment. The dihedral angle between the planes of the pyrazlole rings in the asymmetric unit is 74.4 (3)°. The hexafluoridosilicate dianion acts as a bridging ligand, connecting the Cu^II atoms into a [1-10] chain. The Cu and Si atoms lie on special positions with 2/m site symmetry. In the crystal, intrachain N—H⋯F hydrogen bonds occur and weak C—H⋯F interactions link the chains.

Related literature

For background to coordination polymers with nitrogen-containing ligands, see: Li et al. (2011 ).

Experimental

Crystal data

[Cu(SiF₆)(C₃H₄N₂)₄]
M_r = 477.96
Monoclinic, C 2/c
a = 10.617 (2) Å
b = 12.108 (2) Å
c = 14.652 (3) Å
β = 95.07 (3)°
V = 1876.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.30 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.730, T_max = 0.771
7864 measured reflections
1665 independent reflections
1283 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.101
S = 1.16
1665 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	2.007 (4)
Cu1—N3	2.008 (3)
Cu1—F3	2.348 (2)
Si1—F1	1.679 (2)
Si1—F2	1.680 (3)
SI1—F3	1.695 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯F2ⁱ	0.86	1.99	2.849 (5)	174
N4—H4A⋯F1ⁱ	0.86	2.02	2.848 (4)	162
C1—H1⋯F2ⁱⁱ	0.93	2.46	3.317 (6)	153
Symmetry codes: (i) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812009531/hb6651sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009531/hb6651Isup2.hkl

checkCIF report

Comment top

In recent years, nitrogen-containing ligands have been extensively studied (Li et al., 2011). Pyrazole have been well used as a kind of N-containing ligands.

Single-crystal X-ray diffraction analysis reveals that the title compound (I) crystallizes in the monoclinic space group C2/c. For the title compound, the geometry of the Cu(II) ion is bound by four pyrazole ligands and two hexafluoridosilicate dianions, which illustrates a distorted octahedral coordination environment (Fig 1). The dihedral angle between the pyrazole rings is 105.6°.

Related literature top

For background to coordination polymers with nitrogen-containing ligands, see: Li et al. (2011).

Experimental top

A buffer layer of a solution (8 ml) of methanol and chloroform (1:1) was carefully layered over the chloroform solution of pyrazole (0.06 mmol, 6 ml). Then a methanol solution of CuSiF₆ (0.02 mmol, 6 ml) was layered over the buffer layer. The resultant reaction was left to stand at room temperature. After ca three weeks, colorless blocks appeared at the boundary. Yield: ~20% (based on pyrazole).

Structure description top

In recent years, nitrogen-containing ligands have been extensively studied (Li et al., 2011). Pyrazole have been well used as a kind of N-containing ligands.

For background to coordination polymers with nitrogen-containing ligands, see: Li et al. (2011).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. The crystal packing for (I).

catena-Poly[[tetrakis(1H-pyrazole-κN²)copper(II)]- µ-hexafluoridosilicato-κ²F:F'] top

Crystal data top

[Cu(SiF₆)(C₃H₄N₂)₄]	F(000) = 964
M_r = 477.96	D_x = 1.692 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7871 reflections
a = 10.617 (2) Å	θ = 3.0–27.5°
b = 12.108 (2) Å	µ = 1.30 mm⁻¹
c = 14.652 (3) Å	T = 293 K
β = 95.07 (3)°	Block, colorless
V = 1876.2 (6) Å³	0.25 × 0.22 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	1665 independent reflections
Radiation source: fine-focus sealed tube	1283 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
Detector resolution: 9 pixels mm^-1	θ_max = 25.0°, θ_min = 3.0°
ω scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −14→14
T_min = 0.730, T_max = 0.771	l = −17→17
7864 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.0309P)² + 3.0774P] where P = (F_o² + 2F_c²)/3
1665 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Cu(SiF₆)(C₃H₄N₂)₄]	V = 1876.2 (6) Å³
M_r = 477.96	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 10.617 (2) Å	µ = 1.30 mm⁻¹
b = 12.108 (2) Å	T = 293 K
c = 14.652 (3) Å	0.25 × 0.22 × 0.20 mm
β = 95.07 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	1665 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1283 reflections with I > 2σ(I)
T_min = 0.730, T_max = 0.771	R_int = 0.079
7864 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.16	Δρ_max = 0.44 e Å⁻³
1665 reflections	Δρ_min = −0.31 e Å⁻³
130 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
Cu1	0.2500	0.2500	0.5000	0.0262 (2)
F1	0.3887 (2)	−0.0988 (2)	0.4884 (2)	0.0540 (8)
F2	0.5087 (3)	0.0006 (2)	0.38606 (17)	0.0533 (8)
F3	0.3866 (2)	0.09883 (19)	0.48968 (18)	0.0429 (7)
Si1	0.5000	0.0000	0.5000	0.0313 (4)
N1	0.2744 (3)	0.2900 (3)	0.3698 (2)	0.0304 (9)
N2	0.2000 (3)	0.3633 (3)	0.3217 (3)	0.0362 (9)
H2A	0.1452	0.4044	0.3451	0.043*
N3	0.1011 (3)	0.1589 (3)	0.4510 (2)	0.0309 (9)
N4	−0.0206 (4)	0.1865 (3)	0.4494 (3)	0.0490 (11)
H4A	−0.0480	0.2459	0.4730	0.059*
C1	0.2212 (5)	0.3646 (4)	0.2340 (3)	0.0476 (13)
H1	0.1801	0.4084	0.1885	0.057*
C2	0.3147 (5)	0.2895 (4)	0.2227 (3)	0.0487 (14)
H2	0.3503	0.2723	0.1687	0.058*
C3	0.3449 (4)	0.2448 (4)	0.3085 (3)	0.0389 (11)
H3	0.4059	0.1907	0.3219	0.047*
C4	−0.0944 (5)	0.1099 (4)	0.4063 (4)	0.0611 (17)
H4	−0.1822	0.1118	0.3971	0.073*
C5	−0.0190 (5)	0.0291 (4)	0.3785 (3)	0.0522 (15)
H5	−0.0430	−0.0351	0.3467	0.063*
C6	0.1020 (4)	0.0633 (4)	0.4078 (3)	0.0446 (13)
H6	0.1749	0.0238	0.3984	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0254 (4)	0.0244 (4)	0.0285 (4)	0.0000 (4)	0.0012 (3)	−0.0008 (4)
F1	0.0361 (15)	0.0378 (16)	0.088 (2)	−0.0014 (13)	0.0064 (15)	−0.0160 (15)
F2	0.0553 (17)	0.0645 (19)	0.0392 (17)	0.0229 (16)	−0.0006 (14)	−0.0063 (15)
F3	0.0389 (15)	0.0348 (15)	0.0540 (18)	0.0193 (12)	−0.0006 (13)	−0.0025 (13)
Si1	0.0268 (9)	0.0263 (9)	0.0397 (11)	0.0087 (8)	−0.0032 (8)	−0.0072 (8)
N1	0.028 (2)	0.028 (2)	0.035 (2)	0.0005 (16)	−0.0005 (18)	0.0004 (17)
N2	0.035 (2)	0.038 (2)	0.036 (2)	0.0079 (18)	0.0058 (19)	0.0050 (19)
N3	0.026 (2)	0.028 (2)	0.039 (2)	−0.0013 (16)	0.0062 (17)	−0.0066 (17)
N4	0.034 (2)	0.031 (2)	0.080 (3)	0.0045 (19)	−0.005 (2)	−0.005 (2)
C1	0.042 (3)	0.064 (4)	0.036 (3)	−0.005 (3)	0.001 (2)	0.015 (3)
C2	0.047 (3)	0.069 (4)	0.032 (3)	−0.006 (3)	0.012 (2)	−0.007 (3)
C3	0.032 (2)	0.040 (3)	0.045 (3)	0.003 (2)	0.006 (2)	−0.004 (3)
C4	0.039 (3)	0.042 (3)	0.097 (5)	−0.009 (3)	−0.021 (3)	0.002 (3)
C5	0.062 (4)	0.041 (3)	0.052 (3)	−0.012 (3)	−0.009 (3)	−0.011 (3)
C6	0.038 (3)	0.041 (3)	0.057 (3)	−0.009 (2)	0.013 (3)	−0.018 (3)

Geometric parameters (Å, º) top

Cu1—N1ⁱ	2.007 (4)	N2—H2A	0.8600
Cu1—N1	2.007 (4)	N3—C6	1.320 (5)
Cu1—N3ⁱ	2.008 (3)	N3—N4	1.332 (5)
Cu1—N3	2.008 (3)	N4—C4	1.337 (6)
Cu1—F3ⁱ	2.348 (2)	N4—H4A	0.8600
Cu1—F3	2.348 (2)	C1—C2	1.366 (6)
Si1—F1	1.679 (2)	C1—H1	0.9300
Si1—F2	1.680 (3)	C2—C3	1.381 (6)
SI1—F3	1.695 (2)	C2—H2	0.9300
Si1—F1ⁱⁱ	1.679 (2)	C3—H3	0.9300
Si1—F2ⁱⁱ	1.680 (3)	C4—C5	1.350 (7)
Si1—F3ⁱⁱ	1.695 (2)	C4—H4	0.9300
N1—C3	1.336 (5)	C5—C6	1.381 (6)
N1—N2	1.345 (5)	C5—H5	0.9300
N2—C1	1.324 (6)	C6—H6	0.9300

N1ⁱ—Cu1—N1	180.0	C3—N1—N2	104.9 (4)
N1ⁱ—Cu1—N3ⁱ	87.50 (14)	C3—N1—Cu1	131.8 (3)
N1—Cu1—N3ⁱ	92.50 (14)	N2—N1—Cu1	122.6 (3)
N1ⁱ—Cu1—N3	92.50 (14)	C1—N2—N1	111.9 (4)
N1—Cu1—N3	87.50 (14)	C1—N2—H2A	124.0
N3ⁱ—Cu1—N3	180.00 (16)	N1—N2—H2A	124.0
N1ⁱ—Cu1—F3ⁱ	89.70 (12)	C6—N3—N4	105.1 (4)
N1—Cu1—F3ⁱ	90.30 (12)	C6—N3—Cu1	127.9 (3)
N3ⁱ—Cu1—F3ⁱ	91.15 (11)	N4—N3—Cu1	126.9 (3)
N3—Cu1—F3ⁱ	88.85 (11)	N3—N4—C4	111.2 (4)
N1ⁱ—Cu1—F3	90.30 (12)	N3—N4—H4A	124.4
N1—Cu1—F3	89.70 (12)	C4—N4—H4A	124.4
N3ⁱ—Cu1—F3	88.85 (11)	N2—C1—C2	107.3 (4)
N3—Cu1—F3	91.15 (11)	N2—C1—H1	126.3
F3ⁱ—Cu1—F3	180.0	C2—C1—H1	126.3
Si1—F3—Cu1	169.24 (15)	C1—C2—C3	105.2 (4)
F1ⁱⁱ—Si1—F1	180.00 (17)	C1—C2—H2	127.4
F1ⁱⁱ—Si1—F2ⁱⁱ	90.16 (15)	C3—C2—H2	127.4
F1—Si1—F2ⁱⁱ	89.84 (15)	N1—C3—C2	110.6 (4)
F1ⁱⁱ—Si1—F2	89.84 (15)	N1—C3—H3	124.7
F1—Si1—F2	90.16 (15)	C2—C3—H3	124.7
F2ⁱⁱ—Si1—F2	180.000 (1)	N4—C4—C5	107.8 (5)
F1ⁱⁱ—Si1—F3	89.69 (12)	N4—C4—H4	126.1
F1—Si1—F3	90.31 (12)	C5—C4—H4	126.1
F2ⁱⁱ—Si1—F3	89.49 (13)	C4—C5—C6	104.5 (4)
F2—Si1—F3	90.51 (13)	C4—C5—H5	127.8
F1ⁱⁱ—Si1—F3ⁱⁱ	90.31 (12)	C6—C5—H5	127.8
F1—Si1—F3ⁱⁱ	89.69 (12)	N3—C6—C5	111.4 (4)
F2ⁱⁱ—Si1—F3ⁱⁱ	90.51 (13)	N3—C6—H6	124.3
F2—Si1—F3ⁱⁱ	89.49 (13)	C5—C6—H6	124.3
F3—Si1—F3ⁱⁱ	180.0

N1ⁱ—Cu1—F3—Si1	−53.9 (8)	N1—Cu1—N3—C6	73.5 (4)
N1—Cu1—F3—Si1	126.1 (8)	F3ⁱ—Cu1—N3—C6	163.9 (4)
N3ⁱ—Cu1—F3—Si1	33.6 (8)	F3—Cu1—N3—C6	−16.1 (4)
N3—Cu1—F3—Si1	−146.4 (8)	N1ⁱ—Cu1—N3—N4	78.8 (4)
Cu1—F3—Si1—F1ⁱⁱ	−48.7 (8)	N1—Cu1—N3—N4	−101.2 (4)
Cu1—F3—Si1—F1	131.3 (8)	F3ⁱ—Cu1—N3—N4	−10.9 (4)
Cu1—F3—Si1—F2ⁱⁱ	41.4 (8)	F3—Cu1—N3—N4	169.1 (4)
Cu1—F3—Si1—F2	−138.6 (8)	C6—N3—N4—C4	0.0 (5)
N3ⁱ—Cu1—N1—C3	87.4 (4)	Cu1—N3—N4—C4	175.7 (3)
N3—Cu1—N1—C3	−92.6 (4)	N1—N2—C1—C2	−0.5 (5)
F3ⁱ—Cu1—N1—C3	178.5 (4)	N2—C1—C2—C3	0.5 (6)
F3—Cu1—N1—C3	−1.5 (4)	N2—N1—C3—C2	0.0 (5)
N3ⁱ—Cu1—N1—N2	−104.4 (3)	Cu1—N1—C3—C2	169.7 (3)
N3—Cu1—N1—N2	75.6 (3)	C1—C2—C3—N1	−0.3 (6)
F3ⁱ—Cu1—N1—N2	−13.2 (3)	N3—N4—C4—C5	0.0 (6)
F3—Cu1—N1—N2	166.8 (3)	N4—C4—C5—C6	0.0 (6)
C3—N1—N2—C1	0.3 (5)	N4—N3—C6—C5	0.0 (5)
Cu1—N1—N2—C1	−170.6 (3)	Cu1—N3—C6—C5	−175.7 (3)
N1ⁱ—Cu1—N3—C6	−106.5 (4)	C4—C5—C6—N3	0.0 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···F2ⁱⁱⁱ	0.86	1.99	2.849 (5)	174
N4—H4A···F1ⁱⁱⁱ	0.86	2.02	2.848 (4)	162
C1—H1···F2^iv	0.93	2.46	3.317 (6)	153

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

Experimental details

Crystal data
Chemical formula	[Cu(SiF₆)(C₃H₄N₂)₄]
M_r	477.96
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	10.617 (2), 12.108 (2), 14.652 (3)
β (°)	95.07 (3)
V (Å³)	1876.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.30
Crystal size (mm)	0.25 × 0.22 × 0.20

Data collection
Diffractometer	Rigaku Mercury CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.730, 0.771
No. of measured, independent and observed [I > 2σ(I)] reflections	7864, 1665, 1283
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.101, 1.16
No. of reflections	1665
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.31

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	2.007 (4)	Si1—F1	1.679 (2)
Cu1—N3	2.008 (3)	Si1—F2	1.680 (3)
Cu1—F3	2.348 (2)	SI1—F3	1.695 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···F2ⁱ	0.86	1.99	2.849 (5)	174
N4—H4A···F1ⁱ	0.86	2.02	2.848 (4)	162
C1—H1···F2ⁱⁱ	0.93	2.46	3.317 (6)	153

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

Acknowledgements

We thank the young scientist fund of the NSFC of China (51101138) and the College Research Program of Yuncheng University (2008114) for funding.

References

Li, Z. X., Chu, X., Cui, G. H., Liu, Y., Li, L. & Xue, G. L. (2011). CrystEngComm, 13, 1984–1989. Web of Science CSD CrossRef CAS Google Scholar
Rigaku/MSC (2005). 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

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