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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): m1434–m1435.
Published online 2010 October 23. doi:  10.1107/S1600536810041681
PMCID: PMC3009326

Di-μ-iodido-bis{[hydroxy(methoxy)bis(2-pyridyl)methane-κ3 N,O,N′]iodidocadmium(II)}

Abstract

In the centrosymmetric dinuclear title compound, [Cd2I4(C12H12N2O2)2], two μ-I atoms bridge two CdII atoms and each CdII atom is also bonded to a terminal I atom and a hy­droxy-meth­oxy-bis­(2-pyrid­yl)methane ligand, which functions in an N,O,N′-tridentate mode, resulting in a distorted octa­hedral coordination environment. Inter­molecular O—H(...)I hydrogen bonds and π–π stacking inter­actions between the pyridine rings [centroid–centroid distance = 3.790 (2) Å] are present in the crystal structure.

Related literature

For general background to metal complexes with bis­(2-pyrid­yl)ketone or derivative ligands, see: Bandoli et al. (1994 [triangle]); Breeze et al. (1996 [triangle]); Crowder et al. (2004 [triangle]); Hemmert et al. (1999 [triangle]); Katsoulakou et al. (2002 [triangle]); Kavounis et al. (1996 [triangle]); Padhi & Sahu (2008 [triangle]); Papadopoulos et al. (1996 [triangle]); Rattanaphani & McWhinnie (1974 [triangle]); Serna et al. (2001 [triangle]); Sommerer et al. (1993 [triangle]); Tangoulis et al. (1997 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1434-scheme1.jpg

Experimental

Crystal data

  • [Cd2I4(C12H12N2O2)2]
  • M r = 1164.89
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1434-efi1.jpg
  • a = 9.6684 (6) Å
  • b = 10.1083 (7) Å
  • c = 16.4970 (13) Å
  • β = 105.365 (5)°
  • V = 1554.64 (19) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 5.38 mm−1
  • T = 298 K
  • 0.33 × 0.09 × 0.05 mm

Data collection

  • Bruker APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.560, T max = 0.760
  • 12218 measured reflections
  • 4186 independent reflections
  • 3589 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.027
  • wR(F 2) = 0.056
  • S = 1.08
  • 4186 reflections
  • 174 parameters
  • H-atom parameters constrained
  • Δρmax = 0.61 e Å−3
  • Δρmin = −0.69 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810041681/hy2362sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041681/hy2362Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We are grateful to the University of Urmiyeh and Shahid Beheshti University for financial support.

supplementary crystallographic information

Comment

Bis(2-pyridyl)ketone (bpk) is a molecule that can exhibit different modes of coordination. As a bidentate ligand, it may present an N,O-coordination giving a five-membered chelate ring or an N,N-coordination forming a three or six-membered ring (Crowder et al., 2004; Rattanaphani & McWhinnie, 1974; Sommerer et al., 1993). Frequently the coordinated bpk undergoes nucleophilic addition of water or an alcohol at the carbonylic carbon atom to form the diol or the corresponding hemiacetal, (pyridyl)2C(OR)(OH), which, deprotonated, acts as a mononegative, tridentate N,O,N-donor ligand. The three donor atoms may be coordinated to one metal atom (Bandoli et al., 1994; Crowder et al., 2004; Kavounis et al., 1996; Padhi & Sahu, 2008) or to two metal atoms in a bridging coordination (Breeze et al., 1996; Hemmert et al., 1999; Katsoulakou et al., 2002; Papadopoulos et al., 1996; Serna et al., 2001; Tangoulis et al., 1997). Here, we report the synthesis and structure of the title compound.

The asymmetric unit of the title compound contains a half of the molecule (Fig. 1). Two µ-I atoms bridge two CdII atoms, and each CdII atom is also bonded to a terminal I atom and an organic ligand which functions in an N,O,N'-tridentate mode, resulting in a distorted octahedral coordination environment. The Cd—I, Cd—O and Cd—N bond lengths are collected in Table 1.

In the crystal structure, intermolecular O—H···I hydrogen bonds (Table 2) and π–π interactions between the pyridine rings (Fig. 2), Cg···Cgi [symmetry code: (i) -x, 2-y,-z; Cg is the centroid of the N1, C1–C5 ring], stabilize the structure, with a centroid-centroid distance of 3.790 (2) Å.

Experimental

For the preparation of the title compound, a solution of bis(2-pyridyl)ketone (0.15 g, 0.80 mmol) in methanol (10 ml) was added to a solution of CdI2 (0.29 g, 0.80 mmol) in methanol (5 ml) at room temperature. Crystals suitable for X-ray diffraction experiment were obtained by methanol diffusion into a colorless solution in DMSO. The crystals were isolated after one week (yield: 0.34 g, 72.9%).

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) and 0.96 (methyl), O—H = 0.82 Å, and with Uiso(H) = 1.2(1.5 for methyl and hydroxyl)Ueq(C,O).

Figures

Fig. 1.
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (a) 1-x, 2-y, -z.]
Fig. 2.
Packing diagram of the title compound. Dashed lines denote hydrogen bonds.

Crystal data

[Cd2I4(C12H12N2O2)2]F(000) = 1072
Mr = 1164.89Dx = 2.489 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 998 reflections
a = 9.6684 (6) Åθ = 2.2–29.3°
b = 10.1083 (7) ŵ = 5.38 mm1
c = 16.4970 (13) ÅT = 298 K
β = 105.365 (5)°Needle, colorless
V = 1554.64 (19) Å30.33 × 0.09 × 0.05 mm
Z = 2

Data collection

Bruker APEX CCD diffractometer4186 independent reflections
Radiation source: fine-focus sealed tube3589 reflections with I > 2σ(I)
graphiteRint = 0.037
[var phi] and ω scansθmax = 29.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −13→13
Tmin = 0.560, Tmax = 0.760k = −13→13
12218 measured reflectionsl = −22→22

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0193P)2 + 1.4317P] where P = (Fo2 + 2Fc2)/3
4186 reflections(Δ/σ)max = 0.001
174 parametersΔρmax = 0.61 e Å3
0 restraintsΔρmin = −0.69 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.1500 (4)0.9278 (4)−0.0544 (2)0.0400 (8)
H10.20450.9914−0.07260.048*
C20.0103 (4)0.9080 (4)−0.1006 (2)0.0449 (9)
H2−0.02890.9575−0.14880.054*
C3−0.0696 (4)0.8134 (5)−0.0738 (2)0.0487 (10)
H3−0.16370.7970−0.10420.058*
C4−0.0093 (4)0.7425 (4)−0.0012 (2)0.0429 (8)
H4−0.06220.67900.01820.051*
C50.1307 (3)0.7683 (3)0.0414 (2)0.0321 (6)
C60.2084 (3)0.6988 (3)0.1231 (2)0.0333 (7)
C70.3574 (5)0.5630 (4)0.0613 (3)0.0546 (10)
H7A0.33760.47870.08250.082*
H7B0.45170.56190.05250.082*
H7C0.28780.58080.00900.082*
C80.2258 (3)0.7955 (3)0.1957 (2)0.0328 (7)
C90.1399 (4)0.7896 (4)0.2505 (2)0.0425 (8)
H90.07280.72220.24620.051*
C100.1556 (4)0.8853 (5)0.3119 (2)0.0499 (10)
H100.09830.88360.34920.060*
C110.2557 (5)0.9825 (4)0.3176 (2)0.0469 (9)
H110.26841.04730.35900.056*
C120.3383 (4)0.9825 (4)0.2602 (2)0.0409 (8)
H120.40661.04870.26400.049*
N10.2106 (3)0.8594 (3)0.01554 (17)0.0330 (6)
N20.3235 (3)0.8920 (3)0.20032 (18)0.0340 (6)
O10.3501 (2)0.6642 (2)0.12090 (16)0.0373 (5)
O20.1277 (3)0.5886 (3)0.13179 (18)0.0478 (6)
H2A0.16540.55130.17630.072*
Cd10.45074 (2)0.89825 (2)0.095665 (15)0.03330 (6)
I10.46360 (3)1.17684 (2)0.059856 (16)0.03945 (6)
I20.71540 (3)0.85526 (3)0.213660 (16)0.04384 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0416 (18)0.044 (2)0.0351 (17)0.0046 (16)0.0115 (14)0.0072 (15)
C20.0449 (19)0.057 (2)0.0317 (17)0.0187 (18)0.0077 (15)0.0028 (16)
C30.0281 (16)0.075 (3)0.0395 (19)0.0080 (18)0.0027 (14)−0.0097 (19)
C40.0319 (16)0.054 (2)0.0418 (18)−0.0047 (16)0.0080 (14)−0.0011 (17)
C50.0293 (15)0.0334 (16)0.0330 (15)0.0016 (13)0.0071 (12)−0.0014 (13)
C60.0292 (14)0.0314 (16)0.0383 (17)−0.0022 (13)0.0073 (13)0.0057 (14)
C70.061 (2)0.040 (2)0.061 (3)0.0116 (19)0.013 (2)−0.0058 (19)
C80.0308 (15)0.0351 (17)0.0314 (15)−0.0013 (13)0.0062 (12)0.0049 (13)
C90.0420 (18)0.048 (2)0.0395 (18)−0.0023 (17)0.0146 (15)0.0121 (17)
C100.051 (2)0.063 (3)0.041 (2)0.002 (2)0.0227 (17)0.0076 (19)
C110.061 (2)0.048 (2)0.0345 (18)0.0048 (19)0.0166 (17)0.0008 (16)
C120.0429 (19)0.0398 (19)0.0408 (18)−0.0067 (16)0.0127 (15)−0.0038 (16)
N10.0308 (13)0.0369 (14)0.0311 (13)0.0025 (12)0.0080 (11)0.0040 (12)
N20.0334 (13)0.0354 (15)0.0344 (14)−0.0026 (11)0.0109 (11)0.0015 (12)
O10.0343 (12)0.0350 (12)0.0400 (13)0.0055 (10)0.0054 (10)0.0005 (10)
O20.0493 (15)0.0385 (14)0.0524 (16)−0.0161 (12)0.0080 (12)0.0098 (12)
Cd10.02758 (11)0.03613 (13)0.03617 (12)−0.00235 (9)0.00842 (9)0.00239 (10)
I10.04378 (12)0.03060 (11)0.04923 (13)−0.00043 (9)0.02155 (10)−0.00408 (9)
I20.03782 (12)0.04460 (14)0.04293 (13)0.00002 (10)−0.00012 (9)0.00529 (10)

Geometric parameters (Å, °)

C1—N11.340 (4)C8—N21.346 (4)
C1—C21.378 (5)C8—C91.383 (5)
C1—H10.9300C9—C101.380 (6)
C2—C31.375 (6)C9—H90.9300
C2—H20.9300C10—C111.365 (6)
C3—C41.384 (6)C10—H100.9300
C3—H30.9300C11—C121.391 (5)
C4—C51.375 (5)C11—H110.9300
C4—H40.9300C12—N21.327 (4)
C5—N11.342 (4)C12—H120.9300
C5—C61.529 (5)Cd1—N12.381 (3)
C6—O21.389 (4)Cd1—N22.371 (3)
C6—O11.424 (4)Cd1—O12.633 (2)
C6—C81.520 (5)O2—H2A0.8200
C7—O11.433 (5)Cd1—I12.8868 (4)
C7—H7A0.9600Cd1—I1i2.9951 (4)
C7—H7B0.9600Cd1—I22.8082 (4)
C7—H7C0.9600
N1—C1—C2122.8 (4)C11—C10—H10120.2
N1—C1—H1118.6C9—C10—H10120.2
C2—C1—H1118.6C10—C11—C12118.5 (4)
C3—C2—C1118.4 (3)C10—C11—H11120.7
C3—C2—H2120.8C12—C11—H11120.7
C1—C2—H2120.8N2—C12—C11122.6 (3)
C2—C3—C4119.7 (3)N2—C12—H12118.7
C2—C3—H3120.2C11—C12—H12118.7
C4—C3—H3120.2C1—N1—C5118.1 (3)
C5—C4—C3118.5 (4)C1—N1—Cd1122.2 (2)
C5—C4—H4120.8C5—N1—Cd1119.7 (2)
C3—C4—H4120.8C12—N2—C8118.6 (3)
N1—C5—C4122.6 (3)C12—N2—Cd1123.3 (2)
N1—C5—C6114.0 (3)C8—N2—Cd1118.0 (2)
C4—C5—C6123.5 (3)C6—O1—C7114.5 (3)
O2—C6—O1112.1 (3)C6—O1—Cd1100.48 (18)
O2—C6—C8112.5 (3)C7—O1—Cd1116.5 (2)
O1—C6—C8105.7 (3)C6—O2—H2A109.5
O2—C6—C5107.5 (3)N2—Cd1—N177.41 (9)
O1—C6—C5110.0 (3)N2—Cd1—O164.93 (9)
C8—C6—C5108.9 (3)N1—Cd1—O165.95 (8)
O1—C7—H7A109.5N2—Cd1—I292.54 (7)
O1—C7—H7B109.5N1—Cd1—I2159.22 (7)
H7A—C7—H7B109.5O1—Cd1—I293.35 (5)
O1—C7—H7C109.5N2—Cd1—I1103.52 (7)
H7A—C7—H7C109.5N1—Cd1—I197.81 (7)
H7B—C7—H7C109.5O1—Cd1—I1161.21 (5)
N2—C8—C9121.9 (3)I2—Cd1—I1102.242 (11)
N2—C8—C6116.2 (3)N2—Cd1—I1i158.66 (7)
C9—C8—C6121.8 (3)N1—Cd1—I1i86.16 (7)
C10—C9—C8118.8 (4)O1—Cd1—I1i96.05 (5)
C10—C9—H9120.6I2—Cd1—I1i98.429 (11)
C8—C9—H9120.6I1—Cd1—I1i92.019 (9)
C11—C10—C9119.6 (3)Cd1—I1—Cd1i87.981 (9)
N1—C1—C2—C3−0.4 (6)C8—C6—O1—Cd1−60.1 (2)
C1—C2—C3—C41.0 (6)C5—C6—O1—Cd157.4 (3)
C2—C3—C4—C5−0.9 (6)C12—N2—Cd1—N1−131.9 (3)
C3—C4—C5—N10.2 (5)C8—N2—Cd1—N144.4 (2)
C3—C4—C5—C6178.8 (3)C12—N2—Cd1—O1159.0 (3)
N1—C5—C6—O2−166.4 (3)C8—N2—Cd1—O1−24.7 (2)
C4—C5—C6—O214.9 (5)C12—N2—Cd1—I266.5 (3)
N1—C5—C6—O1−44.1 (4)C8—N2—Cd1—I2−117.2 (2)
C4—C5—C6—O1137.2 (3)C12—N2—Cd1—I1−36.7 (3)
N1—C5—C6—C871.4 (3)C8—N2—Cd1—I1139.5 (2)
C4—C5—C6—C8−107.3 (4)C12—N2—Cd1—I1i−172.4 (2)
O2—C6—C8—N2168.1 (3)C8—N2—Cd1—I1i3.9 (4)
O1—C6—C8—N245.4 (4)C1—N1—Cd1—N2133.1 (3)
C5—C6—C8—N2−72.7 (4)C5—N1—Cd1—N2−45.4 (2)
O2—C6—C8—C9−15.8 (4)C1—N1—Cd1—O1−159.0 (3)
O1—C6—C8—C9−138.5 (3)C5—N1—Cd1—O122.5 (2)
C5—C6—C8—C9103.4 (4)C1—N1—Cd1—I2−164.33 (19)
N2—C8—C9—C10−0.2 (5)C5—N1—Cd1—I217.2 (4)
C6—C8—C9—C10−176.1 (3)C1—N1—Cd1—I130.9 (3)
C8—C9—C10—C11−0.6 (6)C5—N1—Cd1—I1−147.6 (2)
C9—C10—C11—C120.7 (6)C1—N1—Cd1—I1i−60.6 (3)
C10—C11—C12—N20.0 (6)C5—N1—Cd1—I1i120.9 (2)
C2—C1—N1—C5−0.3 (5)C6—O1—Cd1—N245.57 (19)
C2—C1—N1—Cd1−178.8 (3)C7—O1—Cd1—N2169.9 (3)
C4—C5—N1—C10.4 (5)C6—O1—Cd1—N1−41.29 (19)
C6—C5—N1—C1−178.3 (3)C7—O1—Cd1—N183.0 (2)
C4—C5—N1—Cd1179.0 (3)C6—O1—Cd1—I2136.82 (18)
C6—C5—N1—Cd10.3 (4)C7—O1—Cd1—I2−98.9 (2)
C11—C12—N2—C8−0.8 (5)C6—O1—Cd1—I1−9.4 (3)
C11—C12—N2—Cd1175.4 (3)C7—O1—Cd1—I1114.9 (3)
C9—C8—N2—C120.9 (5)C6—O1—Cd1—I1i−124.33 (18)
C6—C8—N2—C12177.0 (3)C7—O1—Cd1—I1i0.0 (2)
C9—C8—N2—Cd1−175.5 (3)N2—Cd1—I1—Cd1i−165.25 (7)
C6—C8—N2—Cd10.5 (4)N1—Cd1—I1—Cd1i−86.40 (7)
O2—C6—O1—C751.3 (4)O1—Cd1—I1—Cd1i−115.52 (17)
C8—C6—O1—C7174.3 (3)I2—Cd1—I1—Cd1i99.076 (12)
C5—C6—O1—C7−68.3 (4)I1i—Cd1—I1—Cd1i0.0
O2—C6—O1—Cd1176.9 (2)

Symmetry codes: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2A···I2ii0.822.733.509 (3)160

Symmetry codes: (ii) −x+1, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2362).

References

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