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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): m1594–m1595.
Published online 2010 November 17. doi:  10.1107/S1600536810046763
PMCID: PMC3011543

(4,4′-Dimethyl-2,2′-bipyridine-κ2 N,N′)(dimethyl sulfoxide-κO)diiodidozinc(II)

Abstract

In the title compound, [ZnI2(C12H12N2)(C2H6OS)], the ZnII ion is coordinated by two N atoms from a 4,4′-dimethyl-2,2′-bipyridine ligand, one O atom from a dimethyl sulfoxide mol­ecule and two I atoms in a distorted trigonal-bipyramidal geometry. Intra­molecular C—H(...)O hydrogen bonds and inter­molecular π–π stacking inter­actions between the pyridine rings [centroid–centroid distances = 3.637 (4) and 3.818 (4) Å] are present in the crystal structure.

Related literature

For metal complexes of 4,4′-dimethyl-2,2′-bipyridine, see: Ahmadi et al. (2008 [triangle]); Alizadeh et al. (2010 [triangle]); Amani et al. (2009 [triangle]); Bellusci et al. (2008 [triangle]); Hojjat Kashani et al. (2008 [triangle]); Kalateh et al. (2008 [triangle], 2010 [triangle]); Sakamoto et al. (2004 [triangle]); Sofetis et al. (2006 [triangle]); Willett et al. (2001 [triangle]); Yoshikawa et al. (2003 [triangle]); Yousefi et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1594-scheme1.jpg

Experimental

Crystal data

  • [ZnI2(C12H12N2)(C2H6OS)]
  • M r = 581.56
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1594-efi1.jpg
  • a = 8.6173 (7) Å
  • b = 15.5424 (11) Å
  • c = 14.8976 (10) Å
  • β = 102.908 (6)°
  • V = 1944.9 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 4.54 mm−1
  • T = 298 K
  • 0.40 × 0.20 × 0.10 mm

Data collection

  • Bruker APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.350, T max = 0.636
  • 21034 measured reflections
  • 5243 independent reflections
  • 4246 reflections with I > 2σ(I)
  • R int = 0.113

Refinement

  • R[F 2 > 2σ(F 2)] = 0.076
  • wR(F 2) = 0.202
  • S = 1.20
  • 5243 reflections
  • 191 parameters
  • H-atom parameters constrained
  • Δρmax = 2.11 e Å−3
  • Δρmin = −2.87 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. DOI: 10.1107/S1600536810046763/hy2375sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046763/hy2375Isup2.hkl

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

Acknowledgments

The author is grateful to the Islamic Azad University, Shahr-e-Rey Branch, for financial support.

supplementary crystallographic information

Comment

4,4'-Dimethyl-2,2'-bipyridine (4,4'-dmbipy) is a good bidentate ligand and numerous complexes with 4,4'-dmbipy have been prepared, such as that of mercury (Kalateh et al., 2008; Yousefi et al., 2008), indium (Ahmadi et al., 2008), iron (Amani et al., 2009), platinum (Hojjat Kashani et al., 2008), manganese (Sakamoto et al., 2004), silver (Bellusci et al., 2008), gallium (Sofetis et al., 2006), copper (Willett et al., 2001), zinc (Alizadeh et al., 2010), cadmium (Kalateh et al., 2010) and iridium (Yoshikawa et al., 2003). Here, we report the synthesis and structure of the title compound.

In the title compound (Fig. 1), the ZnII ion is coordinated by two N atoms from a 4,4'-dmbipy ligand, one O atom from a dimethyl sulfoxide molecule and two I- anions in a distorted trigonal-bipyramidal geometry. The Zn—I, Zn—O and Zn—N bond lengths are collected in Table 1. In the crystal structure, intramolecular C—H···O hydrogen bonds (Table 2) and intermolecular π–π stacking interactions (Fig. 2) between the pyridine rings, Cg2···Cg2i and Cg2···Cg3ii [symmetry codes: (i) 1-x, -y, 1-z; (ii) -x, -y, 1-z; Cg2 and Cg3 are the centroids of the N1, C1, C2, C3, C5, C6 ring and N2, C7, C8, C9, C11, C12 ring, respectively] may stabilize the structure, with centroid–centroid distances of 3.637 (4) and 3.818 (4) Å.

Experimental

For the preparation of the title compound, a solution of 4,4'-dmbipy (0.15 g, 0.80 mmol) in methanol (10 ml) was added to a solution of ZnI2 (0.25 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 after one week (yield: 0.34 g, 73.1%).

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) and 0.96 (methyl) Å and with Uiso(H) = 1.2Ueq(C). The highest residual electron density was found 0.81 Å from I2 and the deepest hole 0.86 Å from I1.

Figures

Fig. 1.
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
Crystal packing diagram for the title compound.

Crystal data

[ZnI2(C12H12N2)(C2H6OS)]F(000) = 1104
Mr = 581.56Dx = 1.986 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 21034 reflections
a = 8.6173 (7) Åθ = 2.4–29.2°
b = 15.5424 (11) ŵ = 4.54 mm1
c = 14.8976 (10) ÅT = 298 K
β = 102.908 (6)°Block, colorless
V = 1944.9 (3) Å30.40 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker APEX CCD diffractometer5243 independent reflections
Radiation source: fine-focus sealed tube4246 reflections with I > 2σ(I)
graphiteRint = 0.113
[var phi] and ω scansθmax = 29.2°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −11→11
Tmin = 0.350, Tmax = 0.636k = −21→21
21034 measured reflectionsl = −20→19

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)] = 0.076Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.202H-atom parameters constrained
S = 1.20w = 1/[σ2(Fo2) + (0.1105P)2 + 1.119P] where P = (Fo2 + 2Fc2)/3
5243 reflections(Δ/σ)max = 0.006
191 parametersΔρmax = 2.11 e Å3
0 restraintsΔρmin = −2.87 e Å3

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

xyzUiso*/Ueq
C10.3959 (9)0.0849 (4)0.5994 (5)0.0499 (15)
H10.44910.11100.65370.060*
C20.4035 (10)0.1229 (5)0.5175 (5)0.0558 (18)
H20.46130.17340.51710.067*
C30.3249 (8)0.0859 (4)0.4355 (5)0.0434 (13)
C40.3297 (12)0.1243 (6)0.3445 (5)0.060 (2)
H4C0.29990.08160.29720.072*
H4B0.43560.14420.34560.072*
H4A0.25680.17180.33200.072*
C50.2391 (8)0.0114 (4)0.4415 (4)0.0404 (12)
H50.1819−0.01460.38800.049*
C60.2382 (7)−0.0246 (4)0.5263 (4)0.0348 (11)
C70.1490 (7)−0.1048 (4)0.5361 (4)0.0371 (11)
C80.0708 (8)−0.1531 (5)0.4614 (4)0.0444 (13)
H80.0759−0.13630.40220.053*
C9−0.0137 (9)−0.2252 (5)0.4731 (5)0.0520 (16)
C10−0.0965 (13)−0.2786 (6)0.3928 (7)0.072 (2)
H10C−0.1468−0.32690.41460.087*
H10B−0.0202−0.29870.35950.087*
H10A−0.1755−0.24430.35280.087*
C11−0.0155 (10)−0.2477 (5)0.5633 (6)0.0578 (18)
H11−0.0723−0.29570.57490.069*
C120.0667 (11)−0.1988 (5)0.6351 (5)0.0563 (18)
H120.0660−0.21570.69490.068*
C130.573 (3)0.1599 (8)0.8800 (9)0.148 (9)
H13A0.48260.18820.84280.178*
H13B0.66320.16650.85230.178*
H13C0.59750.18490.94040.178*
C140.7238 (12)0.0134 (10)0.9372 (7)0.093 (4)
H14A0.79770.03730.90440.112*
H14B0.7258−0.04820.93340.112*
H14C0.75310.03071.00060.112*
N10.3148 (6)0.0114 (3)0.6051 (3)0.0390 (10)
N20.1480 (7)−0.1279 (4)0.6227 (3)0.0408 (11)
O10.4955 (6)0.0209 (4)0.7891 (3)0.0512 (11)
Zn10.28482 (9)−0.04667 (5)0.72994 (5)0.0401 (2)
I10.07682 (6)0.04536 (4)0.79226 (3)0.05824 (19)
I20.37974 (8)−0.18094 (4)0.84331 (4)0.0642 (2)
S10.5317 (2)0.05061 (13)0.88831 (11)0.0482 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.057 (4)0.047 (3)0.043 (3)−0.012 (3)0.005 (3)−0.002 (3)
C20.070 (5)0.052 (4)0.046 (4)−0.016 (3)0.013 (3)0.003 (3)
C30.045 (3)0.046 (3)0.039 (3)−0.005 (3)0.010 (2)0.005 (2)
C40.079 (5)0.064 (4)0.042 (4)−0.011 (4)0.021 (4)0.012 (3)
C50.046 (3)0.049 (3)0.027 (2)0.001 (3)0.009 (2)0.000 (2)
C60.035 (3)0.040 (3)0.030 (2)−0.001 (2)0.009 (2)−0.002 (2)
C70.038 (3)0.044 (3)0.030 (3)0.001 (2)0.009 (2)0.004 (2)
C80.046 (3)0.052 (3)0.036 (3)−0.009 (3)0.012 (2)−0.001 (3)
C90.050 (4)0.057 (4)0.049 (4)−0.012 (3)0.009 (3)0.001 (3)
C100.075 (6)0.073 (5)0.068 (5)−0.025 (5)0.014 (4)−0.009 (4)
C110.058 (4)0.052 (4)0.064 (5)−0.010 (3)0.016 (3)0.012 (3)
C120.065 (5)0.057 (4)0.048 (4)−0.007 (3)0.014 (3)0.018 (3)
C130.29 (3)0.070 (7)0.058 (6)−0.031 (11)−0.023 (10)−0.004 (5)
C140.048 (4)0.171 (12)0.055 (5)0.020 (6)0.000 (4)−0.011 (7)
N10.038 (2)0.046 (3)0.032 (2)−0.004 (2)0.0059 (19)0.000 (2)
N20.041 (3)0.051 (3)0.031 (2)−0.002 (2)0.0088 (19)0.006 (2)
O10.045 (2)0.078 (3)0.030 (2)−0.008 (2)0.0059 (18)−0.003 (2)
Zn10.0420 (4)0.0511 (4)0.0273 (3)0.0043 (3)0.0079 (3)0.0021 (3)
I10.0498 (3)0.0841 (4)0.0397 (3)0.0204 (2)0.00761 (19)−0.0118 (2)
I20.0731 (4)0.0624 (3)0.0512 (3)0.0118 (2)0.0009 (2)0.0195 (2)
S10.0445 (8)0.0693 (11)0.0297 (7)0.0026 (7)0.0062 (6)0.0014 (6)

Geometric parameters (Å, °)

C1—N11.352 (9)C10—H10B0.9600
C1—C21.370 (10)C10—H10A0.9600
C1—H10.9300C11—C121.372 (12)
C2—C31.383 (10)C11—H110.9300
C2—H20.9300C12—N21.341 (9)
C3—C51.388 (9)C12—H120.9300
C3—C41.490 (9)C13—S11.746 (12)
C4—H4C0.9600C13—H13A0.9600
C4—H4B0.9600C13—H13B0.9600
C4—H4A0.9600C13—H13C0.9600
C5—C61.384 (8)C14—S11.751 (10)
C5—H50.9300C14—H14A0.9600
C6—N11.334 (7)C14—H14B0.9600
C6—C71.488 (8)C14—H14C0.9600
C7—N21.341 (7)Zn1—N12.135 (5)
C7—C81.387 (9)Zn1—N22.167 (6)
C8—C91.368 (10)O1—S11.513 (5)
C8—H80.9300Zn1—O12.112 (5)
C9—C111.392 (11)Zn1—I12.6199 (9)
C9—C101.498 (12)Zn1—I22.6944 (9)
C10—H10C0.9600
N1—C1—C2123.3 (7)C12—C11—H11120.0
N1—C1—H1118.3C9—C11—H11120.0
C2—C1—H1118.3N2—C12—C11122.8 (7)
C1—C2—C3119.7 (7)N2—C12—H12118.6
C1—C2—H2120.2C11—C12—H12118.6
C3—C2—H2120.2S1—C13—H13A109.5
C2—C3—C5117.0 (6)S1—C13—H13B109.5
C2—C3—C4122.0 (6)H13A—C13—H13B109.5
C5—C3—C4121.1 (6)S1—C13—H13C109.5
C3—C4—H4C109.5H13A—C13—H13C109.5
C3—C4—H4B109.5H13B—C13—H13C109.5
H4C—C4—H4B109.5S1—C14—H14A109.5
C3—C4—H4A109.5S1—C14—H14B109.5
H4C—C4—H4A109.5H14A—C14—H14B109.5
H4B—C4—H4A109.5S1—C14—H14C109.5
C6—C5—C3120.5 (6)H14A—C14—H14C109.5
C6—C5—H5119.7H14B—C14—H14C109.5
C3—C5—H5119.7C6—N1—C1117.4 (5)
N1—C6—C5122.1 (6)C6—N1—Zn1117.2 (4)
N1—C6—C7115.5 (5)C1—N1—Zn1125.2 (4)
C5—C6—C7122.4 (5)C12—N2—C7117.9 (6)
N2—C7—C8121.4 (6)C12—N2—Zn1126.3 (5)
N2—C7—C6115.7 (5)C7—N2—Zn1115.7 (4)
C8—C7—C6123.0 (5)S1—O1—Zn1122.0 (3)
C9—C8—C7121.3 (6)O1—Zn1—N183.89 (19)
C9—C8—H8119.4O1—Zn1—N2150.80 (19)
C7—C8—H8119.4N1—Zn1—N275.84 (19)
C8—C9—C11116.7 (7)O1—Zn1—I199.96 (15)
C8—C9—C10121.6 (7)N1—Zn1—I1107.68 (15)
C11—C9—C10121.8 (7)N2—Zn1—I1106.06 (15)
C9—C10—H10C109.5O1—Zn1—I290.64 (15)
C9—C10—H10B109.5N1—Zn1—I2142.63 (15)
H10C—C10—H10B109.5N2—Zn1—I292.86 (14)
C9—C10—H10A109.5I1—Zn1—I2109.67 (3)
H10C—C10—H10A109.5O1—S1—C13103.2 (5)
H10B—C10—H10A109.5O1—S1—C14106.0 (4)
C12—C11—C9119.9 (7)C13—S1—C1499.2 (9)
N1—C1—C2—C30.3 (13)C8—C7—N2—C12−1.0 (10)
C1—C2—C3—C50.9 (12)C6—C7—N2—C12178.8 (6)
C1—C2—C3—C4−179.7 (8)C8—C7—N2—Zn1177.7 (5)
C2—C3—C5—C6−1.9 (10)C6—C7—N2—Zn1−2.6 (7)
C4—C3—C5—C6178.7 (7)S1—O1—Zn1—N1151.4 (4)
C3—C5—C6—N11.8 (10)S1—O1—Zn1—N2−162.7 (3)
C3—C5—C6—C7−179.5 (6)S1—O1—Zn1—I144.4 (4)
N1—C6—C7—N24.2 (8)S1—O1—Zn1—I2−65.7 (4)
C5—C6—C7—N2−174.5 (6)C6—N1—Zn1—O1160.7 (5)
N1—C6—C7—C8−176.1 (6)C1—N1—Zn1—O1−24.2 (6)
C5—C6—C7—C85.2 (10)C6—N1—Zn1—N21.9 (4)
N2—C7—C8—C91.6 (11)C1—N1—Zn1—N2177.0 (6)
C6—C7—C8—C9−178.1 (7)C6—N1—Zn1—I1−100.8 (4)
C7—C8—C9—C11−0.6 (12)C1—N1—Zn1—I174.3 (6)
C7—C8—C9—C10−179.1 (8)C6—N1—Zn1—I277.7 (5)
C8—C9—C11—C12−0.8 (13)C1—N1—Zn1—I2−107.2 (6)
C10—C9—C11—C12177.6 (9)C12—N2—Zn1—O1131.6 (6)
C9—C11—C12—N21.5 (14)C7—N2—Zn1—O1−46.9 (7)
C5—C6—N1—C1−0.5 (9)C12—N2—Zn1—N1179.0 (7)
C7—C6—N1—C1−179.3 (6)C7—N2—Zn1—N10.5 (4)
C5—C6—N1—Zn1174.9 (5)C12—N2—Zn1—I1−76.3 (6)
C7—C6—N1—Zn1−3.8 (7)C7—N2—Zn1—I1105.2 (4)
C2—C1—N1—C6−0.5 (11)C12—N2—Zn1—I235.1 (6)
C2—C1—N1—Zn1−175.6 (6)C7—N2—Zn1—I2−143.4 (4)
C11—C12—N2—C7−0.5 (12)Zn1—O1—S1—C13−127.7 (9)
C11—C12—N2—Zn1−179.0 (6)Zn1—O1—S1—C14128.5 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1···O10.932.412.938 (9)116

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2375).

References

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