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Acta Cryst. (2008). E64, m6    [ doi:10.1107/S1600536807061569 ]

Poly[di-[mu]3-azido-[mu]2-4,4'-bipyridine-dicopper(I)]

F.-C. Liu and J. Ouyang

Abstract top

In the crystal structure of the title compound, [Cu2(N3)2(C10H8N2)]n, each CuI atom is coordinated by two symmetry-related azide anions and 4,4'-bipyridine (bipy) ligands in a strongly distorted tetrahedral geometry. The Cu atom and the azide anion occupy general positions while the bipy molecule is located on a centre of inversion. Each two symmetry-related copper(I) cations and two symmetry-related azide anions form dimers, which are additionally connected by the anions into layers. These layers are linked by the 4,4'-bipyridine ligands into a three-dimensional coordination network.

Comment top

Because of its versatile coordination modes the azide ligand is a good candidate for the design of coordination polymers with novel structures. To extend the structural diversity, in most cases additional ligands like for example 4,4'-bipyridine were used for the preparation of metal-azido complexes (Han et al., 2000 and Liu et al., 1999). As a part of our ongoing investigations in this field we have investigated the title compound (I) which is a new copper(I)azido complex.

The asymmetric unit of the title compound consists of one copper(I) cation, one azide anion which occupy general positions and and half a 4,4'-bipyridine ligands which is located on a centre of inversion. Each two symmetry related copper(I) cations are connected by two symmetry related azide anions via µ1,1 coordination into [(CuIN3)2 dimers, which are located on centres of inversion. These dimers are additionally connected by the azide anions via µ1,3 coordination into layers, which are perpendicular to the b-/c-plane. These layers are linked by the 4,4'-bipyridine ligands into a three dimensional coordination network.

Related literature top

For related literature, see: Han et al. (2000); Liu et al. (1999).

Experimental top

A mixture of CuI(0.19 g, ca 1 mmol), NaN3 (0.065 g, ca 1 mmol), 4,4'-bpy (0.08 g, ca 1 mmol) and H2O (18 g, ca 1 mol) was sealed in a Teflon-lined autoclave and heated to 403 K for 2 days. On cooling to room temperature red crystals of the title compound are obtained in about 30% yield based on copper.

Refinement top

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C···H = 0.93 Å and Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97(Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top
[Figure 1] Fig. 1. Crystal structure of compound (I) with labeling and displacement ellipsoids drawn at the 40% probability level. Symmetry codes: A = -x + 1,-y,-z + 1, B = -x + 1/2,y - 1/2,-z + 1/2, C = x + 1/2,-y + 1/2,z + 1/2 and D = -x + 2,-y + 1,-z + 1.
[Figure 2] Fig. 2. Crystal structure of the title compound with view along the b axis. H atoms are omitted for clarity.
Poly[di-µ3-azido-µ2-4,4'-bipyridine-dicopper(I)] top
Crystal data top
[Cu2(N3)2(C10H8N2)]F000 = 364
Mr = 367.32Dx = 2.007 Mg m−3
Monoclinic, P2(1)/nMo Kα radiation
λ = 0.71073 Å
a = 8.8107 (18) ÅCell parameters from 5570 reflections
b = 8.0616 (16) Åθ = 3.5–27.5º
c = 9.2636 (19) ŵ = 3.50 mm−1
β = 112.53 (3)ºT = 293 (2) K
V = 607.7 (2) Å3Prism, red
Z = 20.24 × 0.22 × 0.20 mm
Data collection top
Bruker P4
diffractometer		1391 independent reflections
Radiation source: fine-focus sealed tube1163 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
Detector resolution: 0 pixels mm-1θmax = 27.5º
T = 293(2) Kθmin = 3.5º
ω scansh = −11→11
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		k = −10→10
Tmin = 0.456, Tmax = 0.501l = −12→12
6162 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.074  w = 1/[σ2(Fo2) + (0.0275P)2 + 0.2141P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max < 0.001
1391 reflectionsΔρmax = 0.31 e Å−3
91 parametersΔρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2(N3)2(C10H8N2)]V = 607.7 (2) Å3
Mr = 367.32Z = 2
Monoclinic, P2(1)/nMo Kα
a = 8.8107 (18) ŵ = 3.50 mm−1
b = 8.0616 (16) ÅT = 293 (2) K
c = 9.2636 (19) Å0.24 × 0.22 × 0.20 mm
β = 112.53 (3)º
Data collection top
Bruker P4
diffractometer		1391 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		1163 reflections with I > 2σ(I)
Tmin = 0.456, Tmax = 0.501Rint = 0.034
6162 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035Δρmax = 0.31 e Å−3
wR(F2) = 0.074Δρmin = −0.27 e Å−3
S = 1.14Absolute structure: ?
1391 reflectionsFlack parameter: ?
91 parametersRogers parameter: ?
H-atom parameters constrained
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
xyzUiso*/Ueq
Cu10.43386 (4)0.13310 (4)0.37825 (4)0.04726 (15)
N10.6334 (2)0.2628 (3)0.4012 (2)0.0364 (5)
N20.2044 (3)0.1876 (3)0.3036 (3)0.0514 (6)
N30.1145 (2)0.2903 (3)0.2295 (2)0.0342 (5)
N40.0161 (3)0.3872 (3)0.1542 (3)0.0412 (5)
C10.6300 (3)0.4272 (4)0.3839 (3)0.0441 (7)
H1A0.52820.47960.34490.053*
C20.7694 (3)0.5243 (3)0.4207 (3)0.0406 (6)
H2A0.75980.63860.40690.049*
C30.9233 (3)0.4506 (3)0.4784 (3)0.0300 (5)
C40.9264 (3)0.2788 (3)0.4954 (3)0.0411 (6)
H4A1.02630.22290.53360.049*
C50.7814 (3)0.1914 (4)0.4556 (3)0.0428 (6)
H5A0.78710.07680.46740.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0334 (2)0.0455 (2)0.0562 (3)−0.00674 (14)0.00983 (16)0.00118 (16)
N10.0340 (11)0.0380 (13)0.0349 (11)−0.0035 (9)0.0106 (9)0.0023 (9)
N20.0373 (14)0.0513 (15)0.0563 (15)0.0053 (11)0.0076 (11)0.0137 (12)
N30.0310 (11)0.0382 (12)0.0320 (11)−0.0059 (10)0.0105 (9)−0.0034 (10)
N40.0400 (12)0.0387 (13)0.0411 (13)0.0048 (10)0.0113 (10)0.0017 (10)
C10.0300 (14)0.0388 (15)0.0554 (17)0.0020 (12)0.0073 (12)0.0065 (13)
C20.0376 (14)0.0280 (14)0.0511 (16)−0.0010 (11)0.0115 (12)0.0034 (11)
C30.0332 (13)0.0335 (14)0.0256 (12)−0.0019 (10)0.0139 (10)0.0015 (10)
C40.0334 (14)0.0361 (15)0.0547 (17)0.0020 (11)0.0179 (12)0.0050 (12)
C50.0408 (15)0.0316 (14)0.0577 (18)−0.0031 (12)0.0209 (13)0.0060 (12)
Geometric parameters (Å, °) top
Cu1—N21.920 (2)N4—Cu1v2.381 (2)
Cu1—N11.986 (2)C1—C21.384 (4)
Cu1—N4i2.077 (2)C1—H1A0.9300
Cu1—N4ii2.381 (2)C2—C31.387 (4)
Cu1—Cu1iii3.0061 (9)C2—H2A0.9300
N1—C11.334 (4)C3—C41.393 (4)
N1—C51.335 (3)C3—C3vi1.485 (5)
N2—N31.170 (3)C4—C51.379 (4)
N3—N41.177 (3)C4—H4A0.9300
N4—Cu1iv2.077 (2)C5—H5A0.9300
N2—Cu1—N1133.23 (10)Cu1iv—N4—Cu1v84.50 (8)
N2—Cu1—N4i114.75 (10)N1—C1—C2123.7 (2)
N1—Cu1—N4i106.83 (9)N1—C1—H1A118.1
N2—Cu1—N4ii104.35 (10)C2—C1—H1A118.1
N1—Cu1—N4ii91.66 (9)C1—C2—C3119.8 (2)
N4i—Cu1—N4ii95.50 (8)C1—C2—H2A120.1
N2—Cu1—Cu1iii119.05 (8)C3—C2—H2A120.1
N1—Cu1—Cu1iii102.88 (7)C2—C3—C4116.3 (2)
N4i—Cu1—Cu1iii52.04 (6)C2—C3—C3vi121.9 (3)
N4ii—Cu1—Cu1iii43.46 (6)C4—C3—C3vi121.8 (3)
C1—N1—C5116.6 (2)C5—C4—C3120.1 (2)
C1—N1—Cu1122.16 (17)C5—C4—H4A119.9
C5—N1—Cu1120.66 (18)C3—C4—H4A119.9
N3—N2—Cu1139.1 (2)N1—C5—C4123.5 (3)
N2—N3—N4175.8 (3)N1—C5—H5A118.3
N3—N4—Cu1iv124.77 (19)C4—C5—H5A118.3
N3—N4—Cu1v116.26 (18)
N2—Cu1—N1—C110.3 (3)N2—N3—N4—Cu1iv169 (4)
N4i—Cu1—N1—C1162.5 (2)N2—N3—N4—Cu1v−89 (4)
N4ii—Cu1—N1—C1−101.3 (2)C5—N1—C1—C2−0.8 (4)
Cu1iii—Cu1—N1—C1−143.69 (19)Cu1—N1—C1—C2170.3 (2)
N2—Cu1—N1—C5−179.0 (2)N1—C1—C2—C30.4 (4)
N4i—Cu1—N1—C5−26.8 (2)C1—C2—C3—C40.0 (4)
N4ii—Cu1—N1—C569.5 (2)C1—C2—C3—C3vi−179.2 (3)
Cu1iii—Cu1—N1—C527.1 (2)C2—C3—C4—C50.0 (4)
N1—Cu1—N2—N317.2 (4)C3vi—C3—C4—C5179.3 (3)
N4i—Cu1—N2—N3−133.4 (3)C1—N1—C5—C40.9 (4)
N4ii—Cu1—N2—N3123.5 (3)Cu1—N1—C5—C4−170.4 (2)
Cu1iii—Cu1—N2—N3167.9 (3)C3—C4—C5—N1−0.5 (4)
Cu1—N2—N3—N4165 (4)
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+1/2, y+1/2, −z+1/2; (v) x−1/2, −y+1/2, z−1/2; (vi) −x+2, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N21.920 (2)Cu1—N4ii2.381 (2)
Cu1—N11.986 (2)Cu1—Cu1iii3.0061 (9)
Cu1—N4i2.077 (2)
N2—Cu1—N1133.23 (10)N2—Cu1—N4ii104.35 (10)
N2—Cu1—N4i114.75 (10)N1—Cu1—N4ii91.66 (9)
N1—Cu1—N4i106.83 (9)N4i—Cu1—N4ii95.50 (8)
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+1, −y, −z+1.
references
References top

Bruker (1998). SMART (Version 5.051), SAINT (Version 5.01), SADABS (Version 2.03) and SHELXTL (Version 6.1). Bruker AXS Inc., Madison, Wisconsin, USA.

Han, S.-J., Manson, J.-L., Kim, J. & Miller, J.-S. (2000). Inorg. Chem. 39, 4182–4185.

Liu, C.-M., Yu, Z., Xiong, R.-G., Liu, K. & You, X.-Z. (1999). Inorganic Chemistry Communications, 2, 31–34.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.