Poly[di-μ3-azido-μ2-4,4′-bipyridine-dicopper(I)]

Liu, F.-C.; Ouyang, J.

doi:10.1107/S1600536807061569

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m6

https://doi.org/10.1107/S1600536807061569

Open

access

Poly[di-μ₃-azido-μ₂-4,4′-bipyridine-dicopper(I)]

Fu-Chen Liu ^a ^* and Jie Ouyang ^a

^aSchool of Chemistry and Chemical, Engineering, Tianjin University of Technology, Tianjin 300191, People's Republic of China
^*Correspondence e-mail: fencer@mail.nankai.edu.cn

(Received 7 November 2007; accepted 21 November 2007; online 6 December 2007)

In the crystal structure of the title compound, [Cu₂(N₃)₂(C₁₀H₈N₂)]_n, each Cu^I 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.

Related literature

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

Experimental

Crystal data

[Cu₂(N₃)₂(C₁₀H₈N₂)]
M_r = 367.32
Monoclinic, P 2₁ /n
a = 8.8107 (18) Å
b = 8.0616 (16) Å
c = 9.2636 (19) Å
β = 112.53 (3)°
V = 607.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.50 mm⁻¹
T = 293 (2) K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.456, T_max = 0.501
6162 measured reflections
1391 independent reflections
1163 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.074
S = 1.14
1391 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—N2	1.920 (2)
Cu1—N1	1.986 (2)
Cu1—N4ⁱ	2.077 (2)
Cu1—N4ⁱⁱ	2.381 (2)
Cu1—Cu1ⁱⁱⁱ	3.0061 (9)

N2—Cu1—N1	133.23 (10)
N2—Cu1—N4ⁱ	114.75 (10)
N1—Cu1—N4ⁱ	106.83 (9)
N2—Cu1—N4ⁱⁱ	104.35 (10)
N1—Cu1—N4ⁱⁱ	91.66 (9)
N4ⁱ—Cu1—N4ⁱⁱ	95.50 (8)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (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; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807061569/nc2073sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807061569/nc2073Isup2.hkl

checkCIF report

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 µ_1,1 coordination into [(Cu^IN₃)₂ dimers, which are located on centres of inversion. These dimers are additionally connected by the azide anions via µ_1,3 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.

Structure description top

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

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

	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.
	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)]	F(000) = 364
M_r = 367.32	D_x = 2.007 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.8107 (18) Å	Cell parameters from 5570 reflections
b = 8.0616 (16) Å	θ = 3.5–27.5°
c = 9.2636 (19) Å	µ = 3.50 mm⁻¹
β = 112.53 (3)°	T = 293 K
V = 607.7 (2) Å³	Prism, red
Z = 2	0.24 × 0.22 × 0.20 mm

Data collection top

Bruker P4 diffractometer	1391 independent reflections
Radiation source: fine-focus sealed tube	1163 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.5°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −10→10
T_min = 0.456, T_max = 0.501	l = −12→12
6162 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0275P)² + 0.2141P] where P = (F_o² + 2F_c²)/3
1391 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Cu₂(N₃)₂(C₁₀H₈N₂)]	V = 607.7 (2) Å³
M_r = 367.32	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.8107 (18) Å	µ = 3.50 mm⁻¹
b = 8.0616 (16) Å	T = 293 K
c = 9.2636 (19) Å	0.24 × 0.22 × 0.20 mm
β = 112.53 (3)°

Data collection top

Bruker P4 diffractometer	1391 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1163 reflections with I > 2σ(I)
T_min = 0.456, T_max = 0.501	R_int = 0.034
6162 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.14	Δρ_max = 0.31 e Å⁻³
1391 reflections	Δρ_min = −0.28 e Å⁻³
91 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	0.43386 (4)	0.13310 (4)	0.37825 (4)	0.04726 (15)
N1	0.6334 (2)	0.2628 (3)	0.4012 (2)	0.0364 (5)
N2	0.2044 (3)	0.1876 (3)	0.3036 (3)	0.0514 (6)
N3	0.1145 (2)	0.2903 (3)	0.2295 (2)	0.0342 (5)
N4	0.0161 (3)	0.3872 (3)	0.1542 (3)	0.0412 (5)
C1	0.6300 (3)	0.4272 (4)	0.3839 (3)	0.0441 (7)
H1A	0.5282	0.4796	0.3449	0.053*
C2	0.7694 (3)	0.5243 (3)	0.4207 (3)	0.0406 (6)
H2A	0.7598	0.6386	0.4069	0.049*
C3	0.9233 (3)	0.4506 (3)	0.4784 (3)	0.0300 (5)
C4	0.9264 (3)	0.2788 (3)	0.4954 (3)	0.0411 (6)
H4A	1.0263	0.2229	0.5336	0.049*
C5	0.7814 (3)	0.1914 (4)	0.4556 (3)	0.0428 (6)
H5A	0.7871	0.0768	0.4674	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0334 (2)	0.0455 (2)	0.0562 (3)	−0.00674 (14)	0.00983 (16)	0.00118 (16)
N1	0.0340 (11)	0.0380 (13)	0.0349 (11)	−0.0035 (9)	0.0106 (9)	0.0023 (9)
N2	0.0373 (14)	0.0513 (15)	0.0563 (15)	0.0053 (11)	0.0076 (11)	0.0137 (12)
N3	0.0310 (11)	0.0382 (12)	0.0320 (11)	−0.0059 (10)	0.0105 (9)	−0.0034 (10)
N4	0.0400 (12)	0.0387 (13)	0.0411 (13)	0.0048 (10)	0.0113 (10)	0.0017 (10)
C1	0.0300 (14)	0.0388 (15)	0.0554 (17)	0.0020 (12)	0.0073 (12)	0.0065 (13)
C2	0.0376 (14)	0.0280 (14)	0.0511 (16)	−0.0010 (11)	0.0115 (12)	0.0034 (11)
C3	0.0332 (13)	0.0335 (14)	0.0256 (12)	−0.0019 (10)	0.0139 (10)	0.0015 (10)
C4	0.0334 (14)	0.0361 (15)	0.0547 (17)	0.0020 (11)	0.0179 (12)	0.0050 (12)
C5	0.0408 (15)	0.0316 (14)	0.0577 (18)	−0.0031 (12)	0.0209 (13)	0.0060 (12)

Geometric parameters (Å, º) top

Cu1—N2	1.920 (2)	N4—Cu1^v	2.381 (2)
Cu1—N1	1.986 (2)	C1—C2	1.384 (4)
Cu1—N4ⁱ	2.077 (2)	C1—H1A	0.9300
Cu1—N4ⁱⁱ	2.381 (2)	C2—C3	1.387 (4)
Cu1—Cu1ⁱⁱⁱ	3.0061 (9)	C2—H2A	0.9300
N1—C1	1.334 (4)	C3—C4	1.393 (4)
N1—C5	1.335 (3)	C3—C3^vi	1.485 (5)
N2—N3	1.170 (3)	C4—C5	1.379 (4)
N3—N4	1.177 (3)	C4—H4A	0.9300
N4—Cu1^iv	2.077 (2)	C5—H5A	0.9300

N2—Cu1—N1	133.23 (10)	Cu1^iv—N4—Cu1^v	84.50 (8)
N2—Cu1—N4ⁱ	114.75 (10)	N1—C1—C2	123.7 (2)
N1—Cu1—N4ⁱ	106.83 (9)	N1—C1—H1A	118.1
N2—Cu1—N4ⁱⁱ	104.35 (10)	C2—C1—H1A	118.1
N1—Cu1—N4ⁱⁱ	91.66 (9)	C1—C2—C3	119.8 (2)
N4ⁱ—Cu1—N4ⁱⁱ	95.50 (8)	C1—C2—H2A	120.1
N2—Cu1—Cu1ⁱⁱⁱ	119.05 (8)	C3—C2—H2A	120.1
N1—Cu1—Cu1ⁱⁱⁱ	102.88 (7)	C2—C3—C4	116.3 (2)
N4ⁱ—Cu1—Cu1ⁱⁱⁱ	52.04 (6)	C2—C3—C3^vi	121.9 (3)
N4ⁱⁱ—Cu1—Cu1ⁱⁱⁱ	43.46 (6)	C4—C3—C3^vi	121.8 (3)
C1—N1—C5	116.6 (2)	C5—C4—C3	120.1 (2)
C1—N1—Cu1	122.16 (17)	C5—C4—H4A	119.9
C5—N1—Cu1	120.66 (18)	C3—C4—H4A	119.9
N3—N2—Cu1	139.1 (2)	N1—C5—C4	123.5 (3)
N2—N3—N4	175.8 (3)	N1—C5—H5A	118.3
N3—N4—Cu1^iv	124.77 (19)	C4—C5—H5A	118.3
N3—N4—Cu1^v	116.26 (18)

N2—Cu1—N1—C1	10.3 (3)	N2—N3—N4—Cu1^iv	169 (4)
N4ⁱ—Cu1—N1—C1	162.5 (2)	N2—N3—N4—Cu1^v	−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—C2	170.3 (2)
N2—Cu1—N1—C5	−179.0 (2)	N1—C1—C2—C3	0.4 (4)
N4ⁱ—Cu1—N1—C5	−26.8 (2)	C1—C2—C3—C4	0.0 (4)
N4ⁱⁱ—Cu1—N1—C5	69.5 (2)	C1—C2—C3—C3^vi	−179.2 (3)
Cu1ⁱⁱⁱ—Cu1—N1—C5	27.1 (2)	C2—C3—C4—C5	0.0 (4)
N1—Cu1—N2—N3	17.2 (4)	C3^vi—C3—C4—C5	179.3 (3)
N4ⁱ—Cu1—N2—N3	−133.4 (3)	C1—N1—C5—C4	0.9 (4)
N4ⁱⁱ—Cu1—N2—N3	123.5 (3)	Cu1—N1—C5—C4	−170.4 (2)
Cu1ⁱⁱⁱ—Cu1—N2—N3	167.9 (3)	C3—C4—C5—N1	−0.5 (4)
Cu1—N2—N3—N4	165 (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.

Experimental details

Crystal data
Chemical formula	[Cu₂(N₃)₂(C₁₀H₈N₂)]
M_r	367.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.8107 (18), 8.0616 (16), 9.2636 (19)
β (°)	112.53 (3)
V (Å³)	607.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.50
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker P4
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.456, 0.501
No. of measured, independent and observed [I > 2σ(I)] reflections	6162, 1391, 1163
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.074, 1.14
No. of reflections	1391
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.28

Computer programs: SMART (Bruker, 1998), SHELXTL (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97(Sheldrick, 1997).

Selected geometric parameters (Å, º) top

Cu1—N2	1.920 (2)	Cu1—N4ⁱⁱ	2.381 (2)
Cu1—N1	1.986 (2)	Cu1—Cu1ⁱⁱⁱ	3.0061 (9)
Cu1—N4ⁱ	2.077 (2)

N2—Cu1—N1	133.23 (10)	N2—Cu1—N4ⁱⁱ	104.35 (10)
N2—Cu1—N4ⁱ	114.75 (10)	N1—Cu1—N4ⁱⁱ	91.66 (9)
N1—Cu1—N4ⁱ	106.83 (9)	N4ⁱ—Cu1—N4ⁱⁱ	95.50 (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.

Acknowledgements

The authors acknowledge financial support from Tianjin Municipal Education Commission (No. 20060503).

References

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. Google Scholar
Han, S.-J., Manson, J.-L., Kim, J. & Miller, J.-S. (2000). Inorg. Chem. 39, 4182–4185. Web of Science CSD CrossRef PubMed CAS Google Scholar
Liu, C.-M., Yu, Z., Xiong, R.-G., Liu, K. & You, X.-Z. (1999). Inorg. Chem. Commun. 2, 31–34. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar