catena Poly[[bis­­(iso­thio­cyanato κN)copper(II)]bis­­(μ 1,1′ methyl­enedi 1H imidazole κN3:κN3′)]

metal-organic papers

Acta Cryst.(2006). E62, m523–m525 doi:10.1107/S1600536806004843 Cuiet al. _[Cu(NCS)

2(C7H8N4)2]

m523

Structure Reports Online

ISSN 1600-5368

catena

-Poly[[bis(isothiocyanato-

j

N

)copper(II)]-bis(

l

-1,1

_{-methylenedi-1}

_H

-imidazole-j

N

:

j

N

)]

Guang-Hua Cui,a* Gui-Ying

Dongaand Joan Ribasb

a

College of Chemical Engineering and Biotechnology, Hebei Polytechnic University, Tangshan 063009, People’s Republic of China, andb_{Departament de Quı´mica Inorga`nica,}

Universitat de Barcelona, Diagonal 6487, 08028-Barcelona, Spain

Correspondence e-mail: tscghua@126.com

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.003 A˚

Rfactor = 0.030

wRfactor = 0.071

Data-to-parameter ratio = 14.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 1 February 2006 Accepted 9 February 2006

#2006 International Union of Crystallography

All rights reserved

The title crystal structure, [Cu(NCS)2(C7H8N4)2]n, comprises

one-dimensional chains propagating in the a-axis direction. The CuII atoms, which have crystallographic 2/m site symmetry, are coordinated by six N atoms from four 1,10 -methylenedi-1H-imidazole ligands and two NCS anions, giving a slightly disorted octahedral coordination geometry. The 1,10-methylenedi-1H-imidazole ligand adopts a bis-monodentate bridging mode, linking the CuII_atoms.

Comment

Copper complexes with imidazole ligands are of considerable interest as models for the active site of copper proteins such as haemocyanin, azurin and plastocyanin (Chen et al., 1994; Kirchner & Krebs, 1987). Some metal complexes with alkyl-linked bisimidazole ligands have been used successfully to construct three-dimensional networks (Wuet al., 1997; Maet al., 2004; Cui et al., 2005). In order to further examine the structural features of copper complexes with this class of ligand, the crystal structure determination of the title compound, (I), was carried out.

The structure of (I) comprises a one-dimensional neutral double [Cu(NCS)2(L)2] chain [L is 1,10-methylenedi-1H

-imidazole]. Within a chain, the coordination geometry of each CuIIatom is slightly distorted octahedral (Fig. 1 and Table 1). The CuIIatom, lying on a position of site symmetry 2/m, is six-coordinated by four N atoms from four symmetry-related L

ligands, with a unique Cu—N distance of 2.0440 (17) A˚ . The coordination is completed by two N atoms from two NCS anions. The NCS anions are trans-coordinated to the CuII atoms, occupying the axial positions with a unique Cu—N distance of 2.425 (3) A˚ ; this is elongated, most likely due to Jahn–Teller effects. The cis-N—Cu—N bond angles deviate only slightly from ideal octahedral values (90_{) ranging from} 87.55 (9) to 92.45 (9)_{. EachLligand coordinates to two Cu}II

closest CuII atoms within a chain is 8.877 (2) A˚ and the dihedral angle between the two imidazole planes in one L

ligand is 71.5 (2)_.

Experimental

The ligand L was prepared according to the reported procedure (Schu¨tze & Schubert, 1959). A mixture of Cu(NO3)2 (0.126 g,

1 mmol) and KSCN (0.196 g, 2 mmol) in water (30 ml) was stirred at room temperature for 30 min.L(0.296 g, 2 mmol) was added and the resulting solution was refluxed for 3 h. The blue precipitate that was obtained was filtered off, washed with water and dissolved in a minimum amount of aqueous ammonia (14M). Blue single crystals were obtained by slow evaporation of the ammoniacal solution of the solid at room temperature over three days (68% yield based on Cu).

Analysis calculated for C16H16CuN10S2: C 40.37, H 3.39, N 29.42%;

found: C 40.31, H 3.34, N 29.21%.

Crystal data

[Cu(NCS)2(C7H8N4)2] Mr= 476.05

Orthorhombic,Cmca a= 8.877 (3) A˚

b= 15.602 (6) A˚

c= 14.170 (4) A˚

V= 1962.5 (12) A˚3 Z= 4

Dx= 1.611 Mg m 3

MoKradiation Cell parameters from 932

reflections

= 2.6–26.2 = 1.35 mm1 T= 293 (2) K Block, blue

0.200.180.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.774,Tmax= 0.813

5534 measured reflections

1082 independent reflections 872 reflections withI> 2(I)

Rint= 0.044

max= 26.5

h=11!10

k=19!19

l=17!14

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.030} wR(F2_{) = 0.071} S= 1.05 1082 reflections 74 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0384P)2

+ 0.5699P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.24 e A˚

3

min=0.30 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

Cu1—N1i

2.0440 (17) Cu1—N3 2.425 (3) S1—C5 1.638 (4)

N1—C3 1.313 (2) N2—C1 1.375 (3) N2—C4 1.455 (2)

N1i—Cu1—N1ii 92.45 (9) N1i —Cu1—N1iii 87.55 (9) N1ii —Cu1—N1iii 180.00 (8) N1i—Cu1—N3 89.23 (7)

N1iii—Cu1—N3 90.77 (7) C3—N1—C2 105.88 (16) C3—N1—Cu1 126.34 (13) C5—N3—Cu1 154.8 (2)

Symmetry codes: (i)xþ1;yþ1;z; (ii)x;yþ1;z; (iii)xþ1;y;z.

H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 A˚ , and included in the final cycles of refinement using a riding model, withUiso(H) = 1.2Ueq(C).

Data collection:SMART(Bruker, 1998); cell refinement:SAINT

(Bruker, 1999); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL (Bruker, 1999); software used to prepare material for publication:SHELXTL.

The authors thank Hebei Polytechnic University for supporting this work. JR acknowledges financial support from the Spanish Government (grant No. BQU2003/00539).

References

Bruker (1998).SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (1999). SAINT and SHELXTL. Bruker AXS Inc., Madison,

Wisconsin, USA.

Chen, S., Richardson, J. F. & Buchanan, R. M. (1994).Inorg. Chem.33, 2376– 2382.

metal-organic papers

m524

2(C7H8N4)2] Acta Cryst.(2006). E62, m523–m525

Figure 1

Part of the structure of (I), showing the coordination environment of atom Cu1. Displacement ellipsoids are drawn at the 30% probability level. [symmetry codes: (A)x+ 1,y+ 1,z; (B)x,y+ 1,z; (C)

x+ 1,y,z; (D)x,y,z].

Figure 2

Cui, G.-H., Li, J.-R., Tian, J.-L., Bu, X.-H. & Batten, S. R. (2005).Cryst. Growth Des.5, 1775–1780.

Kirchner, C. & Krebs, B. (1987).Inorg. Chem.26, 3569–3576.

Ma, J.-F., Yang, J., Zheng, G.-L., Zhang, Y.-M., Li, F.-F. & Liu, J.-F. (2004).

Polyhedron,23, 553–559.

Schu¨tze, W. & Schubert, H. (1959).J. Prakt. Chem.8, 306–313.

Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

Wu, L.-P., Yamagiwa, Y., Kuroda-Sowa, K., Kamikawa, T. & Munakata, M. (1997).Inorg. Chim. Acta,256, 155–159.

metal-organic papers

Acta Cryst.(2006). E62, m523–m525 Cuiet al. _[Cu(NCS)

supporting information

sup-1 Acta Cryst. (2006). E62, m523–m525

supporting information

Acta Cryst. (2006). E62, m523–m525 [https://doi.org/10.1107/S1600536806004843]

catena

-Poly[[bis(isothiocyanato-

κ

N

)copper(II)]bis(

µ

-1,1

′

-methylenedi-1

H

-imidazole-

κ

N

:

κ

N

)]

Guang-Hua Cui, Gui-Ying Dong and Joan Ribas

catena-Poly[[bis(isothiocyanato-κN)copper(II)]bis(µ-1,1′-methylenedi-1H- imidazole-κN3_:κN3′_)]

Crystal data

[Cu(NCS)2(C7H8N4)2]

Mr = 476.05

Orthorhombic, Cmca

Hall symbol: -C 2bc 2

a = 8.877 (3) Å

b = 15.602 (6) Å

c = 14.170 (4) Å

V = 1962.5 (12) Å3

Z = 4

F(000) = 972

Dx = 1.611 Mg m−3

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 932 reflections

θ = 2.6–26.2°

µ = 1.35 mm−1

T = 293 K

Block, blue

0.20 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.774, Tmax = 0.813

5534 measured reflections 1082 independent reflections

872 reflections with I > 2σ(I)

Rint = 0.044

θmax = 26.5°, θmin = 2.6°

h = −11→10

k = −19→19

l = −17→14

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.030}

wR(F2_{) = 0.071}

S = 1.05

1082 reflections 74 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0384P)2 + 0.5699P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.24 e Å−3

Δρmin = −0.30 e Å−3

Special details

supporting information

sup-2 Acta Cryst. (2006). E62, m523–m525

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Cu1 0.5000 0.5000 0.0000 0.02288 (16)

S1 0.5000 0.66345 (6) 0.31088 (7) 0.0567 (3)

N1 0.33373 (18) 0.43299 (10) 0.06719 (11) 0.0242 (4)

N2 0.13513 (18) 0.40312 (10) 0.15403 (11) 0.0240 (4)

N3 0.5000 0.60686 (18) 0.1242 (2) 0.0419 (7)

C1 0.1915 (2) 0.32644 (14) 0.12179 (17) 0.0386 (6)

H1A 0.1537 0.2720 0.1344 0.046*

C2 0.3122 (2) 0.34561 (13) 0.06839 (17) 0.0369 (5)

H2A 0.3720 0.3058 0.0370 0.044*

C3 0.2247 (2) 0.46553 (13) 0.11852 (14) 0.0247 (4)

H3A 0.2108 0.5238 0.1291 0.030*

C4 0.0000 0.4136 (2) 0.2110 (2) 0.0273 (7)

H4A 0.0000 0.3715 0.2614 0.033*

H4B 0.0000 0.4701 0.2395 0.033*

C5 0.5000 0.62989 (18) 0.2014 (2) 0.0310 (7)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Cu1 0.0153 (2) 0.0240 (3) 0.0293 (3) 0.000 0.000 0.0071 (2)

S1 0.0852 (8) 0.0423 (5) 0.0424 (5) 0.000 0.000 −0.0108 (4)

N1 0.0201 (8) 0.0227 (9) 0.0300 (9) −0.0017 (7) −0.0002 (7) 0.0026 (7)

N2 0.0173 (8) 0.0275 (9) 0.0273 (9) 0.0000 (6) 0.0008 (7) 0.0028 (7)

N3 0.0444 (18) 0.0398 (17) 0.0414 (17) 0.000 0.000 −0.0049 (14)

C1 0.0295 (12) 0.0217 (11) 0.0647 (16) −0.0015 (9) 0.0104 (11) 0.0047 (11)

C2 0.0276 (12) 0.0232 (11) 0.0598 (15) 0.0009 (9) 0.0114 (11) −0.0016 (10)

C3 0.0207 (10) 0.0239 (10) 0.0295 (11) 0.0006 (8) −0.0010 (8) 0.0020 (8)

C4 0.0180 (14) 0.0394 (17) 0.0244 (15) 0.000 0.000 0.0007 (12)

C5 0.0278 (16) 0.0186 (14) 0.047 (2) 0.000 0.000 0.0037 (14)

Geometric parameters (Å, º)

Cu1—N1i _{2.0440 (17) N2—C1 1.375 (3)}

Cu1—N1ii _{2.0440 (17) N2—C4 1.455 (2)}

Cu1—N1iii _{2.0440 (17) N3—C5 1.150 (4)}

Cu1—N1 2.0440 (17) C1—C2 1.345 (3)

Cu1—N3 2.425 (3) C1—H1A 0.9300

Cu1—N3i _{2.425 (3) C2—H2A 0.9300}

S1—C5 1.638 (4) C3—H3A 0.9300

supporting information

sup-3 Acta Cryst. (2006). E62, m523–m525

N1—C2 1.377 (3) C4—H4A 0.9700

N2—C3 1.354 (2) C4—H4B 0.9700

N1i_—Cu1—N1ii _{92.45 (9) C3—N2—C4 127.6 (2)}

N1i_—Cu1—N1iii _{87.55 (9) C1—N2—C4 125.59 (19)}

N1ii_—Cu1—N1iii _{180.00 (8) C5—N3—Cu1 154.8 (2)}

N1i_{—Cu1—N1 180.0 C2—C1—N2 106.46 (19)}

N1ii_{—Cu1—N1 87.55 (9) C2—C1—H1A 126.8}

N1iii_{—Cu1—N1 92.45 (9) N2—C1—H1A 126.8}

N1i_{—Cu1—N3 89.23 (7) C1—C2—N1 109.75 (19)}

N1ii_{—Cu1—N3 89.23 (7) C1—C2—H2A 125.1}

N1iii_{—Cu1—N3 90.77 (7) N1—C2—H2A 125.1}

N1—Cu1—N3 90.77 (7) N1—C3—N2 111.14 (17)

N1i_—Cu1—N3i _{90.77 (7) N1—C3—H3A 124.4}

N1ii_—Cu1—N3i _{90.77 (7) N2—C3—H3A 124.4}

N1iii_—Cu1—N3i _{89.23 (7) N2}iv_{—C4—N2 111.1 (2)}

N1—Cu1—N3i _{89.23 (7) N2}iv_{—C4—H4A 109.4}

N3—Cu1—N3i _{180.00 (13) N2—C4—H4A 109.4}

C3—N1—C2 105.88 (16) N2iv_{—C4—H4B 109.4}

C3—N1—Cu1 126.34 (13) N2—C4—H4B 109.4

C2—N1—Cu1 127.78 (14) H4A—C4—H4B 108.0

C3—N2—C1 106.77 (17) N3—C5—S1 179.6 (3)

N1ii_{—Cu1—N1—C3 −56.28 (15) C3—N2—C1—C2 0.0 (2)}

N1iii_{—Cu1—N1—C3 123.72 (15) C4—N2—C1—C2 176.93 (19)}

N3—Cu1—N1—C3 32.91 (17) N2—C1—C2—N1 0.6 (3)

N3i_{—Cu1—N1—C3 −147.09 (17) C3—N1—C2—C1 −1.0 (2)}

N1ii_{—Cu1—N1—C2 123.7 (2) Cu1—N1—C2—C1 179.05 (15)}

N1iii_{—Cu1—N1—C2 −56.3 (2) C2—N1—C3—N2 1.0 (2)}

N3—Cu1—N1—C2 −147.11 (18) Cu1—N1—C3—N2 −179.05 (12)

N3i_{—Cu1—N1—C2 32.89 (18) C1—N2—C3—N1 −0.6 (2)}

N1i_{—Cu1—N3—C5 −133.77 (5) C4—N2—C3—N1 −177.48 (18)}

N1ii_{—Cu1—N3—C5 133.77 (5) C3—N2—C4—N2}iv _{100.9 (3)}

N1iii_{—Cu1—N3—C5 −46.23 (5) C1—N2—C4—N2}iv _{−75.4 (3)}

N1—Cu1—N3—C5 46.23 (5)