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Acta Cryst. (2007). E63, m2538    [ doi:10.1107/S1600536807018041 ]

Di-[mu]-iodo-bis[(4,4'-dimethyl-2,2'-bipyridine)copper(I)]

H. Feng, D.-C. Hu, H.-X. Guo, F. Zha and C.-Q. Hu

Abstract top

The title binuclear compound, [Cu2I2(C12H12N2)2], has crystallographic mirror symmetry. The Cu atoms are monovalent and have a tetrahedral environment. The molecules pack in a layer structure.

Comment top

4,4'-Dimethyl-2,2'-bipyridine, a commercially available bidentate chelating heterocyclic ligand, furnishes complexes from a large range of metal salts. The structure of the binuclear title compound, (I), obtained from copper(I) iodide is shown in Fig. 1. Each Cu atom is chelated by the heterocycle and two µ2-I atoms in a four-coordinate environment and shows tetrahedron geometry (Fig. 1). The two Cu—I bond lengths [2.5948 (9) and 2.6307 (9) Å] are comparable with those reported earlier (Kutoglu et al., 1991). The molecule has crystallographic mirror

symmetry and the structure is a binuclear layer compound. The two copper(I) atoms are separated by a distance of 2.5274 (14) Å indicating a strong CuI···CuI interaction, which is comparable with the CuI···CuI distance found previously (Che et al., 2000; Hou et al., 2004).

Related literature top

For related literature, see Che et al. (2000); Hou et al. (2004); Kutoglu et al. (1991).

Experimental top

4,4'-dimethyl-2,2'-bipyridine was commercially available and was used as received without further purification. This compound (0.0184 g, 0.1 mmol), together with a saturated potassium iodide solution containing copper(I) iodide (0.0190 g, 0.1 mmol), were dissolved in water (10 ml). Then the solution was placed and sealed in a 15 ml Teflon-lined stainless steel reactor and heated to 453 K for 72 h, then cooled down to room temperature at a rate of 5 K/h. Red block crystals were formed in about 50% yield.

Refinement top

H atoms were placed in calculated positions (C—H 0.93 Å; Uiso(H) = 1.2Ueq(C) for the ring H atoms and C—H 0.96 Å; Uiso(H) = 1.5Ueq(C) for the methyl groups) and were included in the refinement in the riding model approximation. The largest peak in the final difference map was 0.95 Å from atom I2.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) showing the atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are drawn as spheres of arbitrary radii. Atoms labeled with "a" are generated by the symmetry operation x, 1/2 − y, z.
Di-µ-iodo-bis[(4,4'-dimethyl-2,2'-bipyridine)copper(I)] top
Crystal data top
[Cu2I2(C12H12N2)2]F000 = 1440
Mr = 749.35Dx = 1.854 Mg m−3
Orthorhombic, PnmaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 2945 reflections
a = 11.162 (2) Åθ = 2.2–24.9º
b = 17.432 (4) ŵ = 3.90 mm−1
c = 13.794 (3) ÅT = 295 (2) K
V = 2684.0 (10) Å3Block, red
Z = 40.18 × 0.16 × 0.15 mm
Data collection top
Bruker APEX area-detector
diffractometer		3178 independent reflections
Radiation source: fine-focus sealed tube2373 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.031
T = 295(2) Kθmax = 27.5º
φ and ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −14→14
Tmin = 0.403, Tmax = 0.557k = −21→22
15856 measured reflectionsl = −8→17
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)] = 0.050H-atom parameters constrained
wR(F2) = 0.129  w = 1/[σ2(Fo2) + (0.0571P)2 + 3.2733P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
3178 reflectionsΔρmax = 1.53 e Å−3
150 parametersΔρmin = −0.78 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2I2(C12H12N2)2]V = 2684.0 (10) Å3
Mr = 749.35Z = 4
Orthorhombic, PnmaMo Kα
a = 11.162 (2) ŵ = 3.90 mm−1
b = 17.432 (4) ÅT = 295 (2) K
c = 13.794 (3) Å0.18 × 0.16 × 0.15 mm
Data collection top
Bruker APEX area-detector
diffractometer		3178 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		2373 reflections with I > 2σ(I)
Tmin = 0.403, Tmax = 0.557Rint = 0.031
15856 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.050150 parameters
wR(F2) = 0.129H-atom parameters constrained
S = 1.10Δρmax = 1.53 e Å−3
3178 reflectionsΔρmin = −0.78 e Å−3
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
Cu10.00472 (7)0.32249 (4)0.35891 (5)0.0652 (2)
I10.02234 (5)0.25000.19524 (4)0.05818 (19)
I2−0.04114 (7)0.25000.52201 (4)0.0760 (2)
N10.1340 (4)0.4068 (2)0.3767 (3)0.0523 (10)
N2−0.1010 (4)0.4200 (2)0.3583 (3)0.0484 (10)
C10.2528 (5)0.3975 (4)0.3846 (4)0.0640 (15)
H1A0.28400.34810.38090.077*
C20.3299 (5)0.4571 (4)0.3978 (4)0.0695 (16)
H2A0.41160.44740.40250.083*
C30.2893 (5)0.5313 (3)0.4042 (4)0.0603 (14)
C40.1643 (5)0.5412 (3)0.3960 (3)0.0519 (12)
H4A0.13120.59000.40060.062*
C50.0911 (4)0.4788 (3)0.3812 (3)0.0436 (10)
C6−0.0402 (4)0.4862 (3)0.3683 (3)0.0428 (10)
C7−0.0989 (5)0.5568 (3)0.3662 (3)0.0493 (12)
H7A−0.05520.60190.37300.059*
C8−0.2214 (5)0.5600 (3)0.3542 (4)0.0554 (13)
C9−0.2824 (5)0.4923 (3)0.3449 (4)0.0591 (14)
H9A−0.36510.49230.33700.071*
C10−0.2196 (5)0.4238 (3)0.3473 (4)0.0554 (13)
H10A−0.26220.37820.34100.066*
C110.3689 (6)0.5995 (4)0.4184 (5)0.090 (2)
H11A0.44240.58360.44840.136*
H11B0.32930.63620.45930.136*
H11C0.38590.62250.35670.136*
C12−0.2839 (6)0.6367 (3)0.3491 (5)0.0819 (19)
H12A−0.23070.67410.32160.123*
H12B−0.30670.65250.41320.123*
H12C−0.35410.63230.30930.123*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0990 (6)0.0276 (3)0.0688 (5)0.0008 (3)0.0047 (4)−0.0003 (3)
I10.0780 (4)0.0420 (3)0.0545 (3)0.0000.0019 (2)0.000
I20.1387 (6)0.0316 (3)0.0577 (4)0.0000.0104 (3)0.000
N10.069 (3)0.038 (2)0.051 (2)0.0070 (19)0.003 (2)0.0018 (18)
N20.067 (3)0.0310 (19)0.048 (2)−0.0040 (18)0.0057 (19)−0.0018 (16)
C10.076 (4)0.060 (3)0.056 (3)0.017 (3)−0.002 (3)0.002 (3)
C20.051 (3)0.099 (5)0.058 (4)0.011 (3)−0.004 (3)0.005 (3)
C30.064 (4)0.066 (4)0.051 (3)−0.006 (3)0.000 (2)0.000 (3)
C40.066 (3)0.042 (3)0.048 (3)−0.003 (2)0.004 (2)−0.003 (2)
C50.060 (3)0.037 (2)0.034 (2)0.003 (2)0.002 (2)0.0001 (18)
C60.060 (3)0.034 (2)0.035 (2)−0.001 (2)0.004 (2)0.0002 (18)
C70.062 (3)0.032 (2)0.054 (3)−0.001 (2)0.003 (2)−0.005 (2)
C80.064 (3)0.049 (3)0.052 (3)0.008 (2)0.005 (2)0.000 (2)
C90.052 (3)0.068 (4)0.057 (3)−0.005 (3)0.007 (2)0.003 (3)
C100.068 (4)0.048 (3)0.050 (3)−0.013 (3)0.003 (3)0.000 (2)
C110.064 (4)0.106 (5)0.101 (5)−0.024 (4)−0.003 (4)−0.006 (4)
C120.079 (4)0.062 (4)0.105 (5)0.020 (3)0.002 (4)−0.002 (4)
Geometric parameters (Å, °) top
Cu1—N22.069 (4)C4—H4A0.9300
Cu1—N12.074 (4)C5—C61.482 (7)
Cu1—Cu1i2.5274 (14)C6—C71.394 (6)
Cu1—I12.5948 (9)C7—C81.379 (7)
Cu1—I22.6307 (9)C7—H7A0.9300
N1—C11.341 (7)C8—C91.369 (7)
N1—C51.345 (6)C8—C121.509 (7)
N2—C101.334 (7)C9—C101.385 (7)
N2—C61.347 (6)C9—H9A0.9300
C1—C21.361 (8)C10—H10A0.9300
C1—H1A0.9300C11—H11A0.9600
C2—C31.374 (8)C11—H11B0.9600
C2—H2A0.9300C11—H11C0.9600
C3—C41.411 (8)C12—H12A0.9600
C3—C111.497 (8)C12—H12B0.9600
C4—C51.375 (6)C12—H12C0.9600
N2—Cu1—N179.37 (16)N1—C5—C4122.2 (5)
N2—Cu1—Cu1i145.23 (12)N1—C5—C6115.4 (4)
N1—Cu1—Cu1i135.10 (11)C4—C5—C6122.4 (4)
N2—Cu1—I1116.08 (11)N2—C6—C7121.2 (4)
N1—Cu1—I1113.27 (12)N2—C6—C5115.8 (4)
Cu1i—Cu1—I160.855 (17)C7—C6—C5123.0 (4)
N2—Cu1—I2106.69 (11)C8—C7—C6120.3 (5)
N1—Cu1—I2112.00 (12)C8—C7—H7A119.8
Cu1i—Cu1—I261.290 (17)C6—C7—H7A119.8
I1—Cu1—I2121.66 (3)C9—C8—C7118.0 (5)
Cu1—I1—Cu1i58.29 (3)C9—C8—C12122.0 (5)
Cu1i—I2—Cu157.42 (3)C7—C8—C12120.0 (5)
C1—N1—C5117.5 (5)C8—C9—C10119.4 (5)
C1—N1—Cu1127.8 (4)C8—C9—H9A120.3
C5—N1—Cu1114.8 (3)C10—C9—H9A120.3
C10—N2—C6118.0 (4)N2—C10—C9123.2 (5)
C10—N2—Cu1127.4 (3)N2—C10—H10A118.4
C6—N2—Cu1114.6 (3)C9—C10—H10A118.4
N1—C1—C2122.9 (5)C3—C11—H11A109.5
N1—C1—H1A118.5C3—C11—H11B109.5
C2—C1—H1A118.5H11A—C11—H11B109.5
C1—C2—C3121.3 (5)C3—C11—H11C109.5
C1—C2—H2A119.3H11A—C11—H11C109.5
C3—C2—H2A119.3H11B—C11—H11C109.5
C2—C3—C4115.8 (5)C8—C12—H12A109.5
C2—C3—C11124.1 (6)C8—C12—H12B109.5
C4—C3—C11120.0 (5)H12A—C12—H12B109.5
C5—C4—C3120.2 (5)C8—C12—H12C109.5
C5—C4—H4A119.9H12A—C12—H12C109.5
C3—C4—H4A119.9H12B—C12—H12C109.5
N2—Cu1—I1—Cu1i−140.73 (13)C1—C2—C3—C11−179.8 (6)
N1—Cu1—I1—Cu1i130.02 (12)C2—C3—C4—C5−0.8 (8)
I2—Cu1—I1—Cu1i−8.08 (5)C11—C3—C4—C5178.8 (5)
N2—Cu1—I2—Cu1i144.44 (12)C1—N1—C5—C4−1.7 (7)
N1—Cu1—I2—Cu1i−130.53 (12)Cu1—N1—C5—C4177.8 (4)
I1—Cu1—I2—Cu1i8.04 (4)C1—N1—C5—C6177.7 (4)
N2—Cu1—N1—C1−179.2 (5)Cu1—N1—C5—C6−2.7 (5)
Cu1i—Cu1—N1—C16.2 (5)C3—C4—C5—N11.8 (7)
I1—Cu1—N1—C1−65.2 (5)C3—C4—C5—C6−177.6 (4)
I2—Cu1—N1—C177.0 (5)C10—N2—C6—C7−0.7 (7)
N2—Cu1—N1—C51.4 (3)Cu1—N2—C6—C7178.0 (3)
Cu1i—Cu1—N1—C5−173.3 (2)C10—N2—C6—C5179.4 (4)
I1—Cu1—N1—C5115.3 (3)Cu1—N2—C6—C5−1.9 (5)
I2—Cu1—N1—C5−102.5 (3)N1—C5—C6—N23.1 (6)
N1—Cu1—N2—C10178.9 (4)C4—C5—C6—N2−177.5 (4)
Cu1i—Cu1—N2—C10−7.7 (5)N1—C5—C6—C7−176.8 (4)
I1—Cu1—N2—C1068.1 (4)C4—C5—C6—C72.7 (7)
I2—Cu1—N2—C10−71.1 (4)N2—C6—C7—C80.3 (7)
N1—Cu1—N2—C60.3 (3)C5—C6—C7—C8−179.8 (4)
Cu1i—Cu1—N2—C6173.7 (2)C6—C7—C8—C90.2 (8)
I1—Cu1—N2—C6−110.5 (3)C6—C7—C8—C12−178.2 (5)
I2—Cu1—N2—C6110.3 (3)C7—C8—C9—C10−0.3 (8)
C5—N1—C1—C20.6 (8)C12—C8—C9—C10178.1 (5)
Cu1—N1—C1—C2−178.8 (4)C6—N2—C10—C90.6 (7)
N1—C1—C2—C30.3 (9)Cu1—N2—C10—C9−177.9 (4)
C1—C2—C3—C4−0.2 (8)C8—C9—C10—N2−0.1 (8)
Symmetry codes: (i) x, −y+1/2, z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N22.069 (4)Cu1—I12.5948 (9)
Cu1—N12.074 (4)Cu1—I22.6307 (9)
Cu1—Cu1i2.5274 (14)
N2—Cu1—N179.37 (16)N2—Cu1—I2106.69 (11)
N2—Cu1—I1116.08 (11)N1—Cu1—I2112.00 (12)
N1—Cu1—I1113.27 (12)I1—Cu1—I2121.66 (3)
Symmetry codes: (i) x, −y+1/2, z.
Acknowledgements top

The authors thank the NorthWest Normal University for support.

references
References top

Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Che, C.-M., Mao, Z., Miskowski, V. M., Tse, M.-C., Chan, C.-K., Cheung, K.-K., Phillips, D. L. & Leung, K.-H. (2000). Angew. Chem. Int. Ed. 39. 4084-4088.

Hou, L., Li, D., Wu, T., Yin, Y.-G. & Ng, S. W. (2004). Acta Cryst. E60, m1181–m1182.

Kutoglu, A., Allmann, R., Folgado, J.-V., Atanasov, M. & Reinen, D. (1991). Z. Naturforsch. Teil B, 46, 1193–1199.

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

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