Poly[di­pyridine­copper(II) μ cyano copper(II) tri μ cyano]

metal-organic papers

Acta Cryst.(2005). E61, m1393–m1395 doi:10.1107/S1600536805019148 Puet al. _[Cu

2(CN)4(C5H5N)2]

m1393

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

Poly[dipyridinecopper(II)-

l

-cyano-copper(II)-tri-

l

-cyano]

Xiaohua Pu, Xiaoming Jiang, Yibin Wei, Yanping Li and Pin Yang*

Institute of Molecular Science, Chemical Biology and Molecular Engineering Laboratory of Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, People’s Republic of China

Correspondence e-mail: yangpin@sxu.edu.cn

Key indicators

Single-crystal X-ray study

T= 273 K

Mean(C–C) = 0.006 A˚

Rfactor = 0.030

wRfactor = 0.077

Data-to-parameter ratio = 14.4

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

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The crystal structure of the title compound, [Cu(C5H5N)2

-{Cu(CN)4}]n, comprises [Cu(py)2] 2+

(py is pyridine) and [Cu(CN)4]

2

subunits which are connected through bridging cyano groups to form a three-dimensional network, with Cu

atoms located on sites of symmetry 2/mand 222 for the cation

and anion, respectively.

Comment

The magnetic properties of low-dimensional solids are

presently the subject of intense study.

Tetracyano-nickelates(II) are suitable model compounds for magnetic studies at low temperatures because the tetracyanonickelate anion may bridge paramagnetic ions partially coordinated with amine ligands and thus form molecular, one-, two- and three-dimensional structures. In contrast, the use of tetra-cyanocuprate(II) as a bridging unit in a multidimensional structure has rarely been reported. We have designed and

synthesized a novel coordination polymer, poly[

-cyano-tetracyanodipyridinedicopper(II)], [Cu(py)2{Cu(CN)4}]n (py

is pyridine), (I), the structure of which is reported here.

Part of the title complex is shown in Fig. 1 and some features of the molecular geometry are listed in Table 1. The complex consists of a neutral three-dimensional network with

stoichiometry Cu(py)2Cu(CN)4. The structure contains two

types of copper(II) coordination environments. Atom Cu1 in the [Cu(CN)4]

2

unit lies on a position of crystallographic symmetry 222 and is in a slightly distorted tetrahedral coor-dination geometry. The briging cyano groups are all related by

symmetry, with N C—Cu and C N—Cu angles of 174.6 (3)

and 168.8 (3)_{, respectively. Atom Cu2 of the {Cu(py)}

2} 2+

unit, lying on a position of symmetry 2/m, is in a slightly distorted

octahedral coordination environment. Four N atoms of the

C N ligand lie in the equatorial plane [Cu—N = 2.144 (3) A˚ ]

and two N atoms of the pyridine ligands are in axial positions

[Cu—N = 2.139 (4) A˚ ]. An extended three-dimensional

structure is formed through the cyano groups acting as

bridging groups. The distance between Cu1 and Cu2 is

5.259 (4) A˚ . In the related cyano-bridged complex

[Cu2(medpt)2Ni(CN)4

-(ClO4)2]2.5H2O [medpt = bis(3-aminopropyl)methylamine],

[Ni(CN)4] 2

subunits coordinate through all four cyano ligands to form a criss-crossed one-dimensional chain of connected square–pyramidal CuIIcations (Majiet al., 2001). In the title complex, the tetrahedral [Cu(CN)4]2 unit

contrib-utes to the formation of this three-dimensional network structure (Fig. 2).

Experimental

All chemicals were of reagent grade, commercially available from the Beijing Chemical Reagents Company of China, and were used without further purification. A pyridine–methanol (5 ml, 5:95 (v/v) solution of CuCl22H2O (0.0511 g, 0.3 mmol) was prepared. This solution was added to a methanol solution (5 ml) of KCN (0.0384 g, 0.59 mmol). The resulting solution was stirred for 24 h, filtered and the filtrate allowed to stand at room temperature. Yellow crystals of the title compound appeared after two weeks of slow evaporation of the solution.

Crystal data

[Cu2(CN)4(C5H5N)2] Mr= 389.36 Orthorhombic,Cccm a= 9.231 (3) A˚

b= 13.375 (4) A˚

c= 13.354 (4) A˚

V= 1648.8 (9) A˚3 Z= 4

Dx= 1.569 Mg m

3

MoKradiation Cell parameters from 4561

reflections

= 2.7–26.7

= 2.58 mm1 T= 273 (2) K Block, yellow 0.400.200.20 mm

Data collection

Bruker SMART CCD diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 2000)

Tmin= 0.404,Tmax= 0.595

3933 measured reflections

806 independent reflections 726 reflections withI> 2(I)

Rint= 0.031

max= 25.5

h=11!10

k=9!16

l=13!16

Refinement

Refinement onF2 R[F2> 2(F2)] = 0.030

wR(F2_{) = 0.077} S= 1.00 806 reflections 56 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0459P)2

+ 1.7229P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.43 e A˚

3 min=0.26 e A˚ 3

Table 1

Selected geometric parameters (A˚ ,_).

Cu1—C1 2.011 (3) Cu2—N2 2.139 (4)

Cu2—N1 2.144 (3) N1—C1 1.144 (4)

C1i

—Cu1—C1 105.29 (17) C1ii

—Cu1—C1 113.68 (17) C1iii

—Cu1—C1 109.55 (17) N2iv

—Cu2—N2 180 N2—Cu2—N1v

90.67 (10) N2—Cu2—N1 89.33 (10)

N1—Cu2—N1 89.23 (14) N1v

—Cu2—N1 90.77 (14) N1—Cu2—N1iv

180 C1—N1—Cu2 168.8 (3) N1—C1—Cu1 174.6 (3)

Symmetry codes: (i)xþ2;y;zþ1

2; (ii)x;yþ1;zþ 1

2; (iii)xþ2;yþ1;z; (iv)

xþ5 2;yþ

1

2;zþ1; (v)xþ 5 2;yþ

1 2;z.

metal-organic papers

m1394

2(CN)4(C5H5N)2] Acta Cryst.(2005). E61, m1393–m1395

Figure 1

A view of part of the title compound. H atoms have been omitted for clarity. Ellipsoids are drawn at the 30% probability level. [Symmetry codes: (A)x+ 2,y+ 1,z; (B)x+ 2,y,z+1

2; (C)x,y+ 1,z+ 1 2;

(D)x+5 2,y+

1

2,z+ 1; (E)x+ 5 2,y+

1

2,z; (F)x,y,z+ 1.]

Figure 2

H atoms were placed in geometrically idealized positions, with Csp2_{= 0.93 A˚ , and constrained to ride on their parent atoms, with}

Uiso(H) = 1.2Ueq(C).

Data collection:SMART(Bruker, 2000); cell refinement:SAINT

(Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97(Sheldrick, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 2000); molecular graphics:

SHELXTL(Sheldrick, 1999) andPLATON(Spek, 2003); software used to prepare material for publication:SHELXTL.

This work was supported financially by the National Natural Science Foundation of China (grant No. 20171031). The

authors are also indebted to Professor Miao-Li Zhu for helpful discussions.

References

Bruker (2000).SMART(Version 5.0) andSAINT(Version 6.02). Bruker AXS Inc., Madison, Wisconsin, USA.

Maji, T. K., Mukherjee, P. S., Mostafa, G., Zangrando, E. & Chaudhuri, N. R. (2001).Chem. Commun.pp. 1368–1369.

Sheldrick, G. M. (1999).SHELXTL/PC. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2000).SHELXS97,SHELXL97andSADABS. University of Go¨ttingen, Germany.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

metal-organic papers

Acta Cryst.(2005). E61, m1393–m1395 Puet al. _[Cu

supporting information

sup-1

Acta Cryst. (2005). E61, m1393–m1395

supporting information

Acta Cryst. (2005). E61, m1393–m1395 [https://doi.org/10.1107/S1600536805019148]

Poly[dipyridinecopper(II)-

µ

-cyano-copper(II)-tri-

µ

-cyano]

Xiaohua Pu, Xiaoming Jiang, Yibin Wei, Yanping Li and Pin Yang

Poly[µ-cyano-tetracyanodipyridinedicopper(II)]

Crystal data

[Cu2(CN)4(C5H5N)2]

Mr = 389.36

Orthorhombic, Cccm

Hall symbol: -C 2 2 c

a = 9.231 (3) Å

b = 13.375 (4) Å

c = 13.354 (4) Å

V = 1648.8 (9) Å3

Z = 4

F(000) = 776

Dx = 1.569 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4561 reflections

θ = 2.7–26.7°

µ = 2.58 mm−1

T = 273 K Block, yellow

0.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 2000)

Tmin = 0.404, Tmax = 0.595

3933 measured reflections 806 independent reflections 726 reflections with I > 2σ(I)

Rint = 0.031

θmax = 25.5°, θmin = 2.7°

h = −11→10

k = −9→16

l = −13→16

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.030}

wR(F2_{) = 0.077}

S = 1.00 806 reflections 56 parameters 1 restraint

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) + (0.0459P)2 + 1.7229P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.43 e Å−3 Δρmin = −0.26 e Å−3

Special details

supporting information

sup-2

Acta Cryst. (2005). E61, m1393–m1395

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 1.0000 0.5000 0.2500 0.0292 (2)

Cu2 1.2500 0.2500 0.5000 0.0316 (2)

N1 1.1774 (3) 0.3525 (2) 0.3873 (2) 0.0451 (7)

N2 1.0402 (4) 0.1821 (3) 0.5000 0.0439 (9)

C1 1.1191 (3) 0.4088 (2) 0.3368 (2) 0.0380 (7)

C2 0.9716 (4) 0.1615 (3) 0.4162 (3) 0.0664 (11)

H2 1.0179 0.1751 0.3559 0.080*

C3 0.8357 (5) 0.1211 (4) 0.4134 (4) 0.0894 (16)

H3 0.7909 0.1083 0.3524 0.107*

C4 0.7675 (7) 0.1001 (6) 0.5000 0.089 (2)

H4 0.6755 0.0717 0.5000 0.107*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Cu1 0.0358 (4) 0.0257 (4) 0.0261 (4) 0.000 0.000 0.000 Cu2 0.0353 (4) 0.0312 (4) 0.0281 (4) 0.0042 (3) 0.000 0.000 N1 0.0521 (16) 0.0404 (15) 0.0426 (15) 0.0023 (13) −0.0030 (12) 0.0074 (13) N2 0.047 (2) 0.042 (2) 0.043 (2) −0.0018 (18) 0.000 0.000 C1 0.0428 (16) 0.0374 (16) 0.0339 (15) −0.0021 (14) −0.0011 (13) 0.0023 (14) C2 0.066 (2) 0.081 (3) 0.052 (2) −0.016 (2) −0.0049 (18) −0.005 (2) C3 0.081 (3) 0.106 (4) 0.081 (3) −0.046 (3) −0.022 (2) −0.006 (3) C4 0.067 (4) 0.092 (5) 0.108 (5) −0.038 (4) 0.000 0.000

Geometric parameters (Å, º)

Cu1—C1i _{2.011 (3) N1—C1 1.144 (4)}

Cu1—C1ii _{2.011 (3) N2—C2 1.315 (4)}

Cu1—C1iii _{2.011 (3) N2—C2}v _{1.315 (4)}

Cu1—C1 2.011 (3) C2—C3 1.366 (6)

Cu2—N2iv _{2.139 (4) C2—H2 0.9300}

Cu2—N2 2.139 (4) C3—C4 1.347 (6)

Cu2—N1v _{2.144 (3) C3—H3 0.9300}

Cu2—N1vi _{2.144 (3) C4—C3}v _{1.347 (6)}

Cu2—N1 2.144 (3) C4—H4 0.9300

Cu2—N1iv _{2.144 (3)}

supporting information

sup-3

Acta Cryst. (2005). E61, m1393–m1395

C1i_{—Cu1—C1 105.29 (17) C1—N1—Cu2 168.8 (3)}

C1ii_{—Cu1—C1 113.68 (17) C2—N2—C2}v _{116.7 (4)}

C1iii_{—Cu1—C1 109.55 (17) C2—N2—Cu2 121.6 (2)}

N2iv_{—Cu2—N2 180.0 C2}v_{—N2—Cu2 121.6 (2)}

N2iv_—Cu2—N1v _{90.67 (10) N1—C1—Cu1 174.6 (3)}

N2—Cu2—N1v _{89.33 (10) N2—C2—C3 123.2 (4)}

N2iv_—Cu2—N1vi _{89.33 (10) N2—C2—H2 118.4}

N2—Cu2—N1vi _{90.67 (10) C3—C2—H2 118.4}

N1v_—Cu2—N1vi _{180.0 C4—C3—C2 119.2 (5)}

N2iv_{—Cu2—N1 90.67 (10) C4—C3—H3 120.4}

N2—Cu2—N1 89.33 (10) C2—C3—H3 120.4

N1v_{—Cu2—N1 89.23 (14) C3}v_{—C4—C3 118.4 (6)}

N1vi_{—Cu2—N1 90.77 (14) C3}v_{—C4—H4 120.8}

N2iv_—Cu2—N1iv _{89.33 (10) C3—C4—H4 120.8}

N2—Cu2—N1iv _{90.67 (10)}

N2iv_{—Cu2—N1—C1 −133.9 (14) N1}v_{—Cu2—N2—C2}v _{−44.4 (4)}

N2—Cu2—N1—C1 46.1 (14) N1vi_{—Cu2—N2—C2}v _{135.6 (4)}

N1v_{—Cu2—N1—C1 −43.2 (14) N1—Cu2—N2—C2}v _{−133.7 (4)}

N1vi_{—Cu2—N1—C1 136.8 (14) N1}iv_{—Cu2—N2—C2}v _{46.3 (4)}

N1v_{—Cu2—N2—C2 133.7 (4) C2}v_{—N2—C2—C3 0.3 (8)}

N1vi_{—Cu2—N2—C2 −46.3 (4) Cu2—N2—C2—C3 −177.9 (4)}

N1—Cu2—N2—C2 44.4 (4) N2—C2—C3—C4 −0.6 (9)

N1iv_{—Cu2—N2—C2 −135.6 (4) C2—C3—C4—C3}v _{0.9 (12)}