catena-Poly[[chloridocopper(II)]bis­(μ-3,3′,5,5′-tetra­methyl-4,4′-methylene­dipyrazole)[chloridocopper(II)]-di-μ-chlorido]

Wang, Z.-M.

doi:10.1107/S1600536808006909

metal-organic compounds

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doi:10.1107/S1600536808006909

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catena-Poly[[chloridocopper(II)]bis(μ-3,3′,5,5′-tetramethyl-4,4′-methylenedipyrazole)[chloridocopper(II)]-di-μ-chlorido]

Zhi-Min Wang ^a ^*

^aCollege of Biology and Environmental Engineering, Zhejiang shuren University, Hangzhou 310015, People's Republic of China
^*Correspondence e-mail: hslj2004@126.com

(Received 10 March 2008; accepted 12 March 2008; online 14 March 2008)

In the title compound, [Cu₂Cl₄(C₁₁H₁₆N₄)]_n, the Cu atom is coordinated by two N atoms of two 3,3′,5,5′-tetramethyl-4,4′-methylenedipyrazole (H₂mbdpz) ligands, two bridging Cl atoms and one terminal Cl atom, forming a square-pyramidal geometry. The bridging Cl atoms and the bridging H₂mbdpz ligands connect the Cu atoms to build up an extended one-dimensional chain. The chains are further connected through N—H⋯Cl hydrogen bonds to build up a two-dimensional layer in the (011) plane. An inversion centre lies between every pair of adjacent Cu atoms.

Related literature

For related literature, see: Kaes et al. (1998 ); Yaghi et al. (1998 ); Yagi et al. (2002 ); Nassimbeni (2003 ).

Experimental

Crystal data

[Cu₂Cl₄(C₁₁H₁₆N₄)]
M_r = 677.44
Triclinic, $[P \overline 1]$
a = 8.759 (3) Å
b = 8.879 (3) Å
c = 9.735 (3) Å
α = 79.269 (6)°
β = 63.584 (5)°
γ = 86.922 (5)°
V = 665.8 (4) Å³
Z = 1
Mo Kα radiation
μ = 2.03 mm⁻¹
T = 298 (2) K
0.26 × 0.23 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.621, T_max = 0.699
3354 measured reflections
2331 independent reflections
1541 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.178
S = 0.99
2331 reflections
167 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −1.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl1ⁱ	0.86	2.43	3.242 (6)	157
N4—H4⋯Cl1ⁱⁱ	0.86	2.34	3.172 (6)	164
Symmetry codes: (i) x+1, y+1, z-1; (ii) -x+1, -y, -z+2.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808006909/dn2323sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808006909/dn2323Isup2.hkl

checkCIF report

Comment top

Considerable research efforts have been devoted to searching for new and better inclusion compounds. One of the main reasons is their potential for eventual applications in a variety of technologically useful processes (Nassimbeni, 2003). In the past performance, the majority of cases in one-dimensional coordination networks was focused on bis-monodentate ligand (Yaghi et al., 1998), while a few examples of bis-bidentate, bis-tridentate ones were documented(Kaes et al., 1998). Here, we reported a 1-D complexes using the bis-bidentate ligand 4,4'-methylene-bis(3,5-dimethylpyrazole) (H₂mbdpz).

In the title compound (I), the copper atom is coordinated by two nitrogen atoms of the H₂mbdpz ligand, two bridging chlorine atom and one terminal chlorine, forming a square-pyramidal geometry (Fig. 1). The average Cu—N bond lengths, 1.999 (3) Å, is longer than those observed in other copper complexes (Yagi et al., 2002). The average Cu—Cl bond lengths is 2.439 (3) Å. the bridging chlorine atoms and the bridging H₂mbdpz ligands connect the copper atoms to build up an extended one dimensionnal chain (Fig. 1). The chains are further connected through N—H···Cl hydrogen bonds to build up a two-dimensionnal layer along the (0 1 1) plane (Table 1).

Related literature top

For related literature, see: Kaes et al. (1998); Yaghi et al. (1998); Yagi et al. (2002); Nassimbeni (2003).

Experimental top

CuCl₂(0.028 g, 0.015 mmol), H₂mbdpz(0.023 g, 0.012 mmol) were added to methanol. The mixture was heated for ten hours under reflux. The resultant was then filtered to give a pure solution. Two weeks later suitable single crystals for X-Ray diffraction analysis were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of compound (I) with the atom-labelling scheme. Ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 1 - x, 1 - y, 1 - z; (ii) 1 - x, -y, 2 - z].

catena-Poly[[chloridocopper(II)]bis(µ-3,3',5,5'-tetramethyl-4,4'- methylenedipyrazole)[chloridocopper(II)]-di-µ-chlorido] top

Crystal data top

[Cu₂Cl₄(C₁₁H₁₆N₄)]	Z = 1
M_r = 677.44	F(000) = 346
Triclinic, P1	D_x = 1.689 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.759 (3) Å	Cell parameters from 2334 reflections
b = 8.879 (3) Å	θ = 2.3–25.2°
c = 9.735 (3) Å	µ = 2.03 mm⁻¹
α = 79.269 (6)°	T = 298 K
β = 63.584 (5)°	Block, blue
γ = 86.922 (5)°	0.26 × 0.23 × 0.19 mm
V = 665.8 (4) Å³

Data collection top

Bruker APEXII area-detector diffractometer	2331 independent reflections
Radiation source: fine-focus sealed tube	1541 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 25.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→9
T_min = 0.621, T_max = 0.699	k = −7→10
3354 measured reflections	l = −11→11

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.1072P)²] where P = (F_o² + 2F_c²)/3
2331 reflections	(Δ/σ)_max = 0.001
167 parameters	Δρ_max = 0.79 e Å⁻³
0 restraints	Δρ_min = −1.14 e Å⁻³

Crystal data top

[Cu₂Cl₄(C₁₁H₁₆N₄)]	γ = 86.922 (5)°
M_r = 677.44	V = 665.8 (4) Å³
Triclinic, P1	Z = 1
a = 8.759 (3) Å	Mo Kα radiation
b = 8.879 (3) Å	µ = 2.03 mm⁻¹
c = 9.735 (3) Å	T = 298 K
α = 79.269 (6)°	0.26 × 0.23 × 0.19 mm
β = 63.584 (5)°

Data collection top

Bruker APEXII area-detector diffractometer	2331 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1541 reflections with I > 2σ(I)
T_min = 0.621, T_max = 0.699	R_int = 0.033
3354 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 0.99	Δρ_max = 0.79 e Å⁻³
2331 reflections	Δρ_min = −1.14 e Å⁻³
167 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	0.36691 (10)	0.08450 (10)	0.90150 (9)	0.0298 (3)
Cl1	0.1132 (2)	0.0034 (2)	1.1136 (2)	0.0345 (5)
Cl2	0.4814 (2)	−0.1536 (2)	0.9274 (2)	0.0355 (5)
N1	0.7388 (7)	0.7150 (7)	0.1354 (6)	0.0310 (14)
N2	0.8962 (6)	0.7124 (6)	0.1260 (6)	0.0301 (14)
H2	0.9629	0.7922	0.0931	0.036*
N3	0.5561 (7)	0.1394 (7)	0.6871 (6)	0.0332 (14)
N4	0.7207 (7)	0.1464 (7)	0.6647 (6)	0.0364 (15)
H4	0.7525	0.1184	0.7371	0.044*
C1	0.4005 (9)	0.1972 (9)	0.5280 (8)	0.0386 (18)
H1A	0.3168	0.1271	0.6123	0.058*
H1B	0.4246	0.1673	0.4308	0.058*
H1C	0.3574	0.2989	0.5284	0.058*
C2	0.5597 (8)	0.1946 (7)	0.5478 (8)	0.0282 (15)
C3	0.7295 (8)	0.2400 (7)	0.4356 (7)	0.0284 (15)
C4	0.8263 (9)	0.2018 (8)	0.5166 (8)	0.0343 (17)
C5	1.0159 (9)	0.2144 (10)	0.4652 (9)	0.045 (2)
H5A	1.0463	0.3166	0.4655	0.068*
H5B	1.0764	0.1921	0.3618	0.068*
H5C	1.0455	0.1425	0.5356	0.068*
C6	0.7909 (9)	0.3024 (8)	0.2656 (8)	0.0320 (17)
H6A	0.7166	0.2605	0.2311	0.038*
H6B	0.9039	0.2644	0.2102	0.038*
C7	0.8000 (8)	0.4739 (7)	0.2171 (7)	0.0265 (15)
C8	0.6772 (8)	0.5694 (7)	0.1915 (7)	0.0252 (15)
C9	0.5023 (9)	0.5253 (8)	0.2174 (9)	0.0382 (18)
H9A	0.4223	0.5283	0.3234	0.057*
H9B	0.5027	0.4234	0.1972	0.057*
H9C	0.4699	0.5959	0.1482	0.057*
C10	0.9385 (8)	0.5715 (8)	0.1735 (7)	0.0267 (15)
C11	1.1096 (9)	0.5461 (9)	0.1710 (9)	0.042 (2)
H11A	1.1906	0.6210	0.0904	0.064*
H11B	1.1453	0.4451	0.1508	0.064*
H11C	1.1028	0.5560	0.2701	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0340 (5)	0.0250 (5)	0.0293 (5)	0.0015 (4)	−0.0153 (4)	0.0012 (4)
Cl1	0.0322 (9)	0.0351 (11)	0.0354 (10)	−0.0042 (8)	−0.0186 (8)	0.0064 (8)
Cl2	0.0457 (11)	0.0258 (10)	0.0402 (10)	0.0037 (8)	−0.0242 (9)	−0.0050 (8)
N1	0.028 (3)	0.028 (3)	0.033 (3)	−0.001 (3)	−0.013 (3)	0.003 (3)
N2	0.024 (3)	0.024 (3)	0.038 (3)	−0.003 (2)	−0.014 (3)	0.006 (3)
N3	0.033 (3)	0.035 (4)	0.029 (3)	0.008 (3)	−0.015 (3)	0.000 (3)
N4	0.037 (4)	0.043 (4)	0.034 (3)	0.001 (3)	−0.024 (3)	0.002 (3)
C1	0.039 (4)	0.043 (5)	0.036 (4)	0.002 (4)	−0.019 (4)	−0.004 (4)
C2	0.033 (4)	0.019 (3)	0.037 (4)	0.002 (3)	−0.020 (3)	−0.003 (3)
C3	0.035 (4)	0.018 (4)	0.029 (4)	0.004 (3)	−0.014 (3)	−0.001 (3)
C4	0.040 (4)	0.034 (4)	0.028 (4)	0.002 (3)	−0.018 (3)	0.003 (3)
C5	0.035 (4)	0.061 (6)	0.041 (5)	−0.001 (4)	−0.023 (4)	0.002 (4)
C6	0.037 (4)	0.028 (4)	0.029 (4)	0.010 (3)	−0.016 (3)	−0.001 (3)
C7	0.031 (4)	0.023 (4)	0.026 (4)	0.001 (3)	−0.014 (3)	−0.004 (3)
C8	0.029 (4)	0.021 (3)	0.021 (3)	0.004 (3)	−0.009 (3)	0.000 (3)
C9	0.032 (4)	0.031 (4)	0.060 (5)	−0.007 (3)	−0.028 (4)	−0.007 (4)
C10	0.021 (3)	0.033 (4)	0.022 (3)	−0.003 (3)	−0.007 (3)	−0.001 (3)
C11	0.035 (4)	0.047 (5)	0.041 (4)	0.011 (4)	−0.016 (4)	−0.004 (4)

Geometric parameters (Å, º) top

Cu1—N3	1.993 (5)	C3—C4	1.386 (9)
Cu1—N1ⁱ	2.009 (6)	C3—C6	1.495 (9)
Cu1—Cl1	2.2926 (19)	C4—C5	1.510 (9)
Cu1—Cl2	2.310 (2)	C5—H5A	0.9600
Cu1—Cl2ⁱⁱ	2.712 (2)	C5—H5B	0.9600
Cl2—Cu1ⁱⁱ	2.712 (2)	C5—H5C	0.9600
N1—N2	1.340 (7)	C6—C7	1.504 (9)
N1—C8	1.346 (8)	C6—H6A	0.9700
N1—Cu1ⁱ	2.009 (6)	C6—H6B	0.9700
N2—C10	1.343 (8)	C7—C10	1.386 (9)
N2—H2	0.8600	C7—C8	1.414 (9)
N3—C2	1.340 (8)	C8—C9	1.499 (9)
N3—N4	1.362 (7)	C9—H9A	0.9600
N4—C4	1.332 (8)	C9—H9B	0.9600
N4—H4	0.8600	C9—H9C	0.9600
C1—C2	1.489 (9)	C10—C11	1.493 (9)
C1—H1A	0.9600	C11—H11A	0.9600
C1—H1B	0.9600	C11—H11B	0.9600
C1—H1C	0.9600	C11—H11C	0.9600
C2—C3	1.422 (9)

N3—Cu1—N1ⁱ	88.7 (2)	N4—C4—C5	120.3 (6)
N3—Cu1—Cl1	165.01 (18)	C3—C4—C5	131.7 (6)
N1ⁱ—Cu1—Cl1	88.83 (16)	C4—C5—H5A	109.5
N3—Cu1—Cl2	89.48 (17)	C4—C5—H5B	109.5
N1ⁱ—Cu1—Cl2	174.58 (17)	H5A—C5—H5B	109.5
Cl1—Cu1—Cl2	91.58 (7)	C4—C5—H5C	109.5
N3—Cu1—Cl2ⁱⁱ	100.44 (18)	H5A—C5—H5C	109.5
N1ⁱ—Cu1—Cl2ⁱⁱ	100.88 (18)	H5B—C5—H5C	109.5
Cl1—Cu1—Cl2ⁱⁱ	94.55 (7)	C3—C6—C7	117.1 (6)
Cl2—Cu1—Cl2ⁱⁱ	84.47 (7)	C3—C6—H6A	108.0
Cu1—Cl2—Cu1ⁱⁱ	95.53 (7)	C7—C6—H6A	108.0
N2—N1—C8	105.5 (5)	C3—C6—H6B	108.0
N2—N1—Cu1ⁱ	120.4 (4)	C7—C6—H6B	108.0
C8—N1—Cu1ⁱ	133.3 (5)	H6A—C6—H6B	107.3
N1—N2—C10	112.6 (5)	C10—C7—C8	104.7 (6)
N1—N2—H2	123.7	C10—C7—C6	126.9 (6)
C10—N2—H2	123.7	C8—C7—C6	128.1 (6)
C2—N3—N4	105.8 (5)	N1—C8—C7	110.2 (6)
C2—N3—Cu1	133.1 (5)	N1—C8—C9	121.6 (6)
N4—N3—Cu1	120.4 (4)	C7—C8—C9	128.3 (6)
C4—N4—N3	111.6 (5)	C8—C9—H9A	109.5
C4—N4—H4	124.2	C8—C9—H9B	109.5
N3—N4—H4	124.2	H9A—C9—H9B	109.5
C2—C1—H1A	109.5	C8—C9—H9C	109.5
C2—C1—H1B	109.5	H9A—C9—H9C	109.5
H1A—C1—H1B	109.5	H9B—C9—H9C	109.5
C2—C1—H1C	109.5	N2—C10—C7	106.9 (5)
H1A—C1—H1C	109.5	N2—C10—C11	120.3 (6)
H1B—C1—H1C	109.5	C7—C10—C11	132.8 (7)
N3—C2—C3	110.0 (6)	C10—C11—H11A	109.5
N3—C2—C1	120.3 (6)	C10—C11—H11B	109.5
C3—C2—C1	129.7 (6)	H11A—C11—H11B	109.5
C4—C3—C2	104.5 (6)	C10—C11—H11C	109.5
C4—C3—C6	127.9 (6)	H11A—C11—H11C	109.5
C2—C3—C6	127.5 (6)	H11B—C11—H11C	109.5
N4—C4—C3	108.0 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱⁱⁱ	0.86	2.43	3.242 (6)	157
N4—H4···Cl1ⁱⁱ	0.86	2.34	3.172 (6)	164

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

Experimental details

Crystal data
Chemical formula	[Cu₂Cl₄(C₁₁H₁₆N₄)]
M_r	677.44
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.759 (3), 8.879 (3), 9.735 (3)
α, β, γ (°)	79.269 (6), 63.584 (5), 86.922 (5)
V (Å³)	665.8 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.03
Crystal size (mm)	0.26 × 0.23 × 0.19

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.621, 0.699
No. of measured, independent and observed [I > 2σ(I)] reflections	3354, 2331, 1541
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.178, 0.99
No. of reflections	2331
No. of parameters	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −1.14

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱ	0.86	2.43	3.242 (6)	156.6
N4—H4···Cl1ⁱⁱ	0.86	2.34	3.172 (6)	163.8

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

Acknowledgements

The author is grateful to Shuren University for financial support.

References

Bruker (2004). APEX2. Bruker AXS Inc, Madison, Wisconsin, USA. Google Scholar
Kaes, C., Hosseini, M. W., Richard, C. E. F., Skelton, B. B. & White, A. (1998). Angew. Chem. Int. Ed. 37, 920–922. CrossRef CAS Google Scholar
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Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

catena-Poly[[chloridocopper(II)]bis­­(μ-3,3′,5,5′-tetra­methyl-4,4′-methylene­di­pyrazole)[chloridocopper(II)]-di-μ-chlorido]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

catena-Poly[[chloridocopper(II)]bis(μ-3,3′,5,5′-tetramethyl-4,4′-methylenedipyrazole)[chloridocopper(II)]-di-μ-chlorido]