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Acta Cryst. (2007). E63, m2880    [ doi:10.1107/S1600536807052841 ]

Tetrakis(2,2'-bipyridine)-1[kappa]4N,N';4[kappa]4N,N'-hexa-[mu]-iodido-1:2[kappa]4I:I;2:3[kappa]4I:I;3:4[kappa]4I:I-1,4-dicadmium(II)-2,3-disilver(I)

Y.-S. Jiang, H.-G. Yao, L.-J. Zou and Y.-L. An

Abstract top

The centrosymmetric title compound, [Ag2Cd2I6(C10H8N2)4], was synthesized by the reaction of CdI2, KAgI2 and 2,2'-bipyridine in dimethylformamide. The crystal structure contains an Ag2I6 chain and Cd(2,2'-bipyridine)2 units; the four 2,2'-bipyridine ligands are positioned at the ends of the molecule and [mu]2-iodo bridges link two Cd(2,2'-bipyridine)I2Ag units. The Cd atom exhibits a distorted octahedral geometry.

Comment top

Divers and useful physcial properties as well as large structural varitey have prompted the recent surge in design and synthesis of new hybrid organic-inorganic materials·These materials have attracted much attention of chemists and physicists, not due to variety of intriguing structure topologies, but also for their potential application in catalysis, materials science, medicine, magntochemistry, and optical materials (Cheetham, 1994; Yaghi et al., 1998; Wu et al., 2003; Niu et al., 2004). Among the various families of hybrid functional materials, silver(I) halides occupy an important role (Li et al., 2006; Rutherford, 1998). Up to now the structure of silver(I) halides containing Ag2I4, Ag3I6, Ag4I6, and Ag4I8 anions exhibit isolated anions, one-dimensional infinite chains, two- and three-dimensional frameworks (Meyer, 1963; Estienne, 1986; Helgsson & Jagner, 1991; Jones, 1992). In this paper we report the synthesis and structure of a new one-dimensional organic-inorganic hybrid compound Ag2I6[Cd(2,2'-bipyridine)2]2.

The structure of the compound contains an one-dimensional Ag2I6 chain: the six iodide atoms acting as bridges between the silver atoms (Fig. 1). Ag atoms are in a tetraherdal arrangement where AgI4 tetrahedra share all corners with the neighbouring metal atoms (Figs.1 and 2). The Ag—I distances range from 2.8036 (7)Å to 2.9058 (8) Å, while the Ag—I—Ag angle is 70.08 (2)°,and the I—Ag—I angles range from 95.96 (2)° to 118.40 (2)° (Table 1). In Ag2I6 the Ag···Ag separation is 3.2260 (11) Å. Cd(II) reveals a distorted octahedral geometry with two 2,2'-bipyridine ligands and two iodide atoms (Fig. 1). The Cd—I distances range from 2.8352 (6)Å to 2.9368 (6) Å, whereas Cd—N are in the range from 2.331 (5)Å to 2.407 (6) Å. The N—Cd—N angles range from 69.61 (17)° to 155.03 (18)°, I—Cd—I is 96.217 (17)°, and the N—Cd—I angles are from 86.86 (12)° to 171.04 (13)° (Table 1). Ag2I6 links adjacent Cd centres into the chains.

Related literature top

For related literature, see: Li et al. (2006); Cheetham (1994); Estienne (1986); Helgsson & Jagner (1991); Jones (1992); Meyer (1963); Niu et al. (2004); Rutherford (1998); Wu et al. (2003); Yaghi et al. (1998).

Experimental top

KAgI2 was prepared by dropping excessive KI/DMF solution into AgNO3/DMF solution·The title compound was synthesized by CdI2(0.074 g) and 2,2'-bipyridine (0.015 g) dissolved in DMF (2.5 ml) followed by dropping the KAgI2(4 ml) solution·The mixture was stirred for 2 m and then filtered off. The filtrate was kept at room temperature for five days and the deep-brown block crystals were obtained. Crystals were washed with ethanol and then with water.

Refinement top

H atoms were positioned geometrically with C—H = 0.93Å and allowed to ride during subsequent refinement with Uiso(H)=1.2Ueq(C).

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with the atom-labelling scheme and displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (i) −x + 2, −y, −z + 1. H atoms have been omitted.
Tetrakis(2,2-bipyridine)-1κ4N,N';4κ4N,N'- hexa-µ-iodido-1:2κ4I:I;2:3κ4I:I;3:4κ4I:I– 1,4-dicadmium(II)-2,3-disilver(I)(Ag—Ag) top
Crystal data top
[Ag2Cd2I6(C10H8N2)4]F000 = 1672
Mr = 1826.68Dx = 2.468 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
a = 8.9170 (6) ÅCell parameters from 6188 reflections
b = 21.5098 (15) Åθ = 2.5–26.3º
c = 12.8527 (9) ŵ = 5.44 mm−1
β = 94.374 (4)ºT = 293 (2) K
V = 2458.0 (3) Å3Block, brown
Z = 20.20 × 0.15 × 0.15 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer		4890 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
Monochromator: graphiteθmax = 28.5º
T = 293(2) Kθmin = 2.5º
φ and ω scansh = −11→11
Absorption correction: nonek = −25→28
14678 measured reflectionsl = −17→17
6188 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044  w = 1/[σ2(Fo2) + (0.0653P)2 + 1.6703P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.121(Δ/σ)max = 0.001
S = 1.00Δρmax = 1.19 e Å−3
6188 reflectionsΔρmin = −1.02 e Å−3
263 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0073 (3)
Secondary atom site location: difference Fourier map
Crystal data top
[Ag2Cd2I6(C10H8N2)4]V = 2458.0 (3) Å3
Mr = 1826.68Z = 2
Monoclinic, P21/nMo Kα
a = 8.9170 (6) ŵ = 5.44 mm−1
b = 21.5098 (15) ÅT = 293 (2) K
c = 12.8527 (9) Å0.20 × 0.15 × 0.15 mm
β = 94.374 (4)º
Data collection top
Bruker SMART APEXII CCD
diffractometer		6188 independent reflections
Absorption correction: none4890 reflections with I > 2σ(I)
14678 measured reflectionsRint = 0.045
Refinement top
R[F2 > 2σ(F2)] = 0.044263 parameters
wR(F2) = 0.121H-atom parameters constrained
S = 1.00Δρmax = 1.19 e Å−3
6188 reflectionsΔρmin = −1.02 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
Cd10.82840 (5)0.162316 (19)0.20025 (3)0.04285 (13)
I10.68673 (5)0.04486 (2)0.25574 (3)0.06171 (15)
I20.98594 (5)0.18259 (2)0.39736 (3)0.05907 (15)
I30.80925 (5)0.01176 (2)0.60922 (3)0.05752 (15)
Ag10.92118 (7)0.05126 (3)0.42222 (4)0.06661 (17)
N10.8859 (7)0.2636 (3)0.1342 (4)0.0571 (13)
N20.6309 (6)0.2308 (3)0.2223 (4)0.0583 (14)
N31.0127 (5)0.1145 (2)0.1076 (4)0.0456 (11)
N40.7331 (6)0.1421 (2)0.0239 (4)0.0494 (11)
C10.7836 (9)0.3074 (3)0.1394 (5)0.0608 (18)
C20.8089 (12)0.3669 (4)0.1002 (7)0.087 (3)
H2A0.73500.39730.10270.104*
C30.9371 (15)0.3803 (5)0.0595 (9)0.111 (4)
H3A0.95420.42030.03540.134*
C41.0433 (14)0.3358 (5)0.0530 (8)0.099 (3)
H4A1.13370.34420.02430.118*
C51.0125 (10)0.2774 (4)0.0907 (6)0.078 (2)
H5A1.08380.24620.08540.094*
C60.6409 (8)0.2892 (3)0.1866 (5)0.0616 (18)
C70.5247 (13)0.3303 (5)0.1890 (7)0.095 (3)
H7A0.53250.37050.16340.113*
C80.3968 (15)0.3105 (6)0.2302 (9)0.108 (4)
H8A0.31530.33740.23100.129*
C90.3850 (10)0.2524 (7)0.2702 (8)0.106 (4)
H9A0.29800.23960.29960.128*
C100.5080 (9)0.2125 (5)0.2658 (7)0.080 (2)
H10A0.50370.17270.29370.096*
C110.5951 (8)0.1549 (4)−0.0136 (5)0.0624 (17)
H11A0.53840.18230.02340.075*
C120.5298 (9)0.1296 (4)−0.1058 (6)0.072 (2)
H12A0.43150.1392−0.12970.086*
C130.6148 (10)0.0904 (4)−0.1598 (5)0.073 (2)
H13A0.57510.0727−0.22190.087*
C140.7597 (9)0.0772 (4)−0.1222 (5)0.0649 (18)
H14A0.81820.0499−0.15790.078*
C150.8172 (7)0.1048 (3)−0.0312 (4)0.0465 (13)
C161.1535 (7)0.1061 (3)0.1497 (6)0.0584 (15)
H16A1.17840.11890.21790.070*
C171.2614 (9)0.0791 (4)0.0943 (7)0.071 (2)
H17A1.35870.07410.12470.086*
C181.2264 (9)0.0599 (4)−0.0041 (7)0.074 (2)
H18A1.29980.0416−0.04170.089*
C191.0838 (9)0.0669 (3)−0.0490 (6)0.068 (2)
H19A1.05820.0532−0.11670.081*
C200.9763 (7)0.0957 (3)0.0103 (4)0.0483 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0466 (2)0.0396 (2)0.0428 (2)0.00666 (17)0.00627 (16)−0.00090 (15)
I20.0791 (3)0.0469 (3)0.0492 (2)−0.0079 (2)−0.00834 (19)−0.00098 (16)
I30.0673 (3)0.0548 (3)0.0524 (2)0.0105 (2)0.01750 (19)−0.00039 (17)
I10.0624 (3)0.0576 (3)0.0635 (3)−0.0183 (2)−0.0058 (2)0.00984 (19)
Ag10.0715 (4)0.0658 (4)0.0631 (3)0.0075 (3)0.0083 (3)0.0091 (2)
N30.048 (3)0.041 (3)0.050 (2)0.006 (2)0.016 (2)0.0011 (19)
N40.058 (3)0.048 (3)0.043 (2)0.002 (2)0.006 (2)0.005 (2)
N20.045 (3)0.072 (4)0.057 (3)0.015 (3)0.000 (2)−0.011 (3)
N10.070 (3)0.044 (3)0.056 (3)0.002 (3)−0.004 (3)0.002 (2)
C150.063 (4)0.036 (3)0.041 (2)−0.011 (3)0.010 (2)0.002 (2)
C60.074 (4)0.051 (4)0.056 (3)0.025 (3)−0.017 (3)−0.021 (3)
C200.059 (3)0.037 (3)0.052 (3)−0.003 (3)0.024 (3)0.003 (2)
C10.084 (5)0.037 (3)0.056 (3)0.008 (3)−0.028 (3)−0.004 (3)
C160.048 (3)0.052 (4)0.076 (4)0.004 (3)0.003 (3)0.000 (3)
C140.083 (5)0.066 (5)0.047 (3)−0.015 (4)0.011 (3)−0.001 (3)
C190.090 (6)0.052 (4)0.066 (4)−0.001 (4)0.037 (4)−0.005 (3)
C110.063 (4)0.064 (4)0.059 (3)−0.001 (3)−0.004 (3)0.007 (3)
C180.066 (5)0.060 (5)0.103 (6)0.007 (4)0.044 (4)−0.003 (4)
C170.058 (4)0.054 (4)0.104 (6)0.007 (3)0.022 (4)−0.003 (4)
C120.068 (4)0.086 (6)0.060 (4)−0.029 (4)−0.004 (3)0.015 (4)
C50.084 (5)0.071 (5)0.082 (5)−0.020 (4)0.017 (4)0.003 (4)
C130.098 (6)0.077 (5)0.043 (3)−0.036 (5)0.002 (4)−0.002 (3)
C100.060 (4)0.094 (7)0.089 (5)0.014 (4)0.019 (4)−0.018 (5)
C70.106 (7)0.079 (6)0.093 (6)0.053 (6)−0.027 (6)−0.036 (5)
C20.104 (7)0.039 (4)0.107 (6)0.011 (4)−0.051 (6)0.003 (4)
C90.054 (5)0.160 (12)0.107 (7)0.014 (6)0.018 (5)−0.053 (8)
C80.114 (9)0.102 (9)0.106 (7)0.049 (7)0.007 (6)−0.035 (6)
C30.129 (9)0.072 (7)0.124 (8)−0.042 (7)−0.056 (7)0.032 (6)
C40.125 (9)0.081 (7)0.086 (6)−0.036 (6)−0.011 (6)0.027 (5)
Geometric parameters (Å, °) top
Cd1—N12.407 (6)C11—C121.391 (10)
Cd1—N22.331 (5)C18—C171.344 (12)
Cd1—N32.339 (4)C12—C131.359 (12)
Cd1—N42.399 (5)C5—C41.381 (12)
Cd1—I22.8352 (6)C10—C91.397 (12)
Cd1—I12.9368 (6)C7—C81.362 (16)
I2—Ag12.9058 (8)C2—C31.325 (15)
I3—Ag12.8036 (7)C9—C81.358 (17)
I3—Ag1i2.8155 (7)C3—C41.353 (17)
I1—Ag12.8784 (7)C1—H1A0.930
Ag1—I3i2.8155 (7)C2—H2A0.930
Ag1—Ag1i3.2260 (11)C3—H3A0.930
N3—C201.332 (7)C4—H4A0.930
N3—C161.341 (8)C5—H5A0.930
N4—C111.317 (8)C6—H6A0.930
N4—C151.337 (8)C7—H7A0.930
N2—C101.328 (9)C8—H8A0.930
N2—C61.341 (9)C9—H9A0.930
N1—C11.316 (9)C10—H10A0.930
N1—C51.332 (9)C11—H11A0.930
C15—C141.376 (9)C12—H12A0.930
C15—C201.489 (9)C13—H13A0.930
C6—C71.365 (10)C14—H14A0.930
C6—C11.503 (11)C15—H15A0.930
C20—C191.412 (9)C16—H16A0.930
C1—C21.400 (11)C17—H17A0.930
C16—C171.369 (10)C18—H18A0.930
C14—C131.374 (11)C19—H19A0.930
C19—C181.364 (12)C20—H20A0.930
N2—Cd1—N3155.03 (18)N1—C1—C6116.4 (6)
N2—Cd1—N490.75 (18)C2—C1—C6123.2 (7)
N3—Cd1—N469.61 (17)N3—C16—C17121.4 (7)
N2—Cd1—N169.7 (2)C13—C14—C15119.3 (7)
N3—Cd1—N192.37 (19)C18—C19—C20118.0 (7)
N4—Cd1—N184.32 (17)N4—C11—C12123.3 (8)
N2—Cd1—I296.99 (13)C17—C18—C19120.4 (7)
N3—Cd1—I2101.70 (12)C18—C17—C16119.8 (8)
N4—Cd1—I2171.04 (13)C13—C12—C11117.7 (8)
N1—Cd1—I294.10 (13)N1—C5—C4123.2 (10)
N2—Cd1—I199.88 (16)C12—C13—C14119.6 (6)
N3—Cd1—I194.44 (12)N2—C10—C9120.7 (10)
N4—Cd1—I186.86 (12)C8—C7—C6117.7 (11)
N1—Cd1—I1166.23 (14)C3—C2—C1120.5 (9)
I2—Cd1—I196.217 (17)C8—C9—C10117.8 (10)
Cd1—I2—Ag181.934 (18)C9—C8—C7121.8 (10)
Ag1—I3—Ag1i70.08 (2)C2—C3—C4119.9 (9)
Ag1—I1—Cd180.672 (18)C3—C4—C5117.6 (11)
I3—Ag1—I3i109.92 (2)H2A—C2—C1118.70
I3—Ag1—I1109.69 (2)H2A—C2—C3120.25
I3i—Ag1—I1116.74 (2)H3A—C3—C2118.67
I3—Ag1—I2118.40 (2)H3A—C3—C4118.70
I3i—Ag1—I2105.86 (2)H4A—C4—C3120.25
I1—Ag1—I295.96 (2)H4A—C4—C5120.22
I3—Ag1—Ag1i55.135 (19)H5A—C5—C4120.69
I3i—Ag1—Ag1i54.790 (19)H5A—C5—N1120.71
I1—Ag1—Ag1i133.27 (3)H7A—C7—C6118.22
I2—Ag1—Ag1i130.68 (3)H7A—C7—C8118.28
C20—N3—C16119.5 (5)H8A—C8—C7118.38
C20—N3—Cd1118.8 (4)H8A—C8—C9118.39
C16—N3—Cd1121.8 (4)H9A—C9—C8120.51
C11—N4—C15118.6 (6)H9A—C9—C10120.52
C11—N4—Cd1124.2 (4)H10A—C10—C9120.59
C15—N4—Cd1115.9 (4)H10A—C10—N2120.64
C10—N2—C6120.0 (7)H11A—C11—N4120.53
C10—N2—Cd1121.3 (6)H11A—C11—C12120.57
C6—N2—Cd1118.7 (5)H12A—C12—C11118.34
C1—N1—C5118.3 (7)H12A—C12—C13118.41
C1—N1—Cd1117.6 (5)H13A—C13—C12118.67
C5—N1—Cd1124.1 (5)H13A—C13—C14118.70
N4—C15—C14121.4 (6)H14A—C14—C13120.25
N4—C15—C20116.5 (5)H14A—C14—C15120.22
C14—C15—C20122.1 (6)H16A—C16—N3120.69
N2—C6—C7121.9 (9)H16A—C16—C17120.71
N2—C6—C1117.5 (5)H17A—C17—C16118.22
C7—C6—C1120.5 (9)H17A—C17—C18118.28
N3—C20—C19120.9 (6)H18A—C18—C17118.38
N3—C20—C15117.0 (5)H18A—C18—C19118.39
C19—C20—C15122.1 (6)H19A—C19—C18120.51
N1—C1—C2120.3 (8)H19A—C19—C20120.52
Symmetry codes: (i) −x+2, −y, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cd1—N12.407 (6)Cd1—I12.9368 (6)
Cd1—N22.331 (5)I2—Ag12.9058 (8)
Cd1—N32.339 (4)I3—Ag12.8036 (7)
Cd1—N42.399 (5)I1—Ag12.8784 (7)
Cd1—I22.8352 (6)Ag1—Ag1i3.2260 (11)
N2—Cd1—N3155.03 (18)N4—Cd1—I186.86 (12)
N2—Cd1—N490.75 (18)I2—Cd1—I196.217 (17)
N3—Cd1—N469.61 (17)Ag1—I3—Ag1i70.08 (2)
N2—Cd1—N169.7 (2)I3—Ag1—I1109.69 (2)
N3—Cd1—N192.37 (19)I3—Ag1—I2118.40 (2)
N4—Cd1—N184.32 (17)I1—Ag1—I295.96 (2)
N4—Cd1—I2171.04 (13)
Symmetry codes: (i) −x+2, −y, −z+1.
Acknowledgements top

We thank the Natural Science Foundation of China for financially supporting this work (20671015).

references
References top

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