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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): m1236.
Published online 2008 September 6. doi:  10.1107/S1600536808027773
PMCID: PMC2959326

Bis[μ-1,3-bis(4,5-dihydroimidazol-2-yl)benzene-κ2 N:N′]bis[dichloridozinc(II)] N,N′-dimethylformamide disolvate

Abstract

The title compound, [Zn2Cl4(C12H14N4)2]·2C3H7NO, is located on a centre of inversion with one half of a complex mol­ecule and one dimethyl­formamide solvent mol­ecule in the asymmetric unit. The ZnII ion is tetra­hedrally coordinated by two organic ligands and two chloride ions. Each organic ligand acts as a bidentate ligand, connecting two ZnII ions, resulting in a dimeric [2:2] metallamacrocyclic structure. Adjacent mol­ecules are further linked by N—H(...)Cl hydrogen bonds and the solvent is linked to the complex by N—H(...)O hydrogen bonds.

Related literature

For related structures, see: Ren et al. (2004 [triangle], 2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1236-scheme1.jpg

Experimental

Crystal data

  • [Zn2Cl4(C12H14N4)2]·2C3H7NO
  • M r = 847.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1236-efi1.jpg
  • a = 8.1774 (11) Å
  • b = 8.5032 (12) Å
  • c = 27.097 (4) Å
  • β = 92.890 (2)°
  • V = 1881.8 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.60 mm−1
  • T = 123 (2) K
  • 0.43 × 0.27 × 0.20 mm

Data collection

  • Bruker APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2000 [triangle]) T min = 0.546, T max = 0.740
  • 13375 measured reflections
  • 3659 independent reflections
  • 3215 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.087
  • S = 1.05
  • 3659 reflections
  • 217 parameters
  • H-atom parameters constrained
  • Δρmax = 0.54 e Å−3
  • Δρmin = −0.48 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SMART; data reduction: SAINT (Bruker, 2000 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808027773/bt2778sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027773/bt2778Isup2.hkl

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

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

Recently, the photophysical properties of coordination compounds of d10 monovalent ions of the coinage metals have been of great interests. And metallomacrocyclic compounds are a rapidly growing field concerning due to their rich luminescent properties (Ren et al. 2004). Here, we present the syntheses and structural characterization of a dimeric [2:2] metallomacrocyclic compound [Zn2(bib)2Cl2].2DMF (bib = 1,3-bis(4,5-Dihydro-1H-imidazol-2-yl)benzene).

The asymmetric unit of the title compound, [Zn2(bib)2Cl2].2DMF, contains one Zn(II) cation, one bib ligand, two chloride ions and one DMF molecule. In the compound, the Zn(II) ion displays a tetrahedral geometry, being surrounded by two bib ligands and two chloride ions. Each bib acts as a bidentate ligand and every two bib ligands ligate a pair of Zn(II) ions resulting in a dimeric [2:2] metallomacrocyclic structure. Adjacent molecules are further linked by the N-H···Cl hyrogen bonds and the solvent is linked to the complex by N-H···O hydrogen bonds.

Experimental

To a solution of ZnCl2.2H2O (0.172 g, 1 mmol) in CH3OH (5 ml), an aqueous solution (5 ml) of bib (0.214 g, 1 mmol) was added. After the mixture was stirred for half an hour, white precipitate was filtrated, dried and collected. Then the white solids were completely dissolved into 2 ml DMF by heating. The DMF solution are placed into a glass test tube, and ether vapors were slowly diffused into the solution. After four weeks, colorless block crystals were obtained [yield 10% (8.5 mg) based on Zn(II)].

Refinement

All H atoms were positioned geometrically and refined using a riding model with C—H = 0.95 and 0.99 Å with Uiso(H) = 1.2 Uiso(C), and N —H = 0.88 Å with Uiso(H) = 1.2 Uiso(N).

Figures

Fig. 1.
The title compound with 30% thermal ellipsoids. Symmetry code: a: 1 - x, 1 - y, -z.
Fig. 2.
Partial packing diagram of the title compound. The H atoms bonded to C atoms are omitted for clarity.

Crystal data

[Zn2Cl4(C12H14N4)2]·2C3H7NOF(000) = 872
Mr = 847.28Dx = 1.495 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 781 reflections
a = 8.1774 (11) Åθ = 2.4–28.0°
b = 8.5032 (12) ŵ = 1.60 mm1
c = 27.097 (4) ÅT = 123 K
β = 92.890 (2)°Block, colorless
V = 1881.8 (4) Å30.43 × 0.27 × 0.20 mm
Z = 2

Data collection

Bruker APEX CCD diffractometer3659 independent reflections
Radiation source: fine-focus sealed tube3215 reflections with I > 2σ(I)
graphiteRint = 0.043
phi and ω scanθmax = 26.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)h = −10→9
Tmin = 0.546, Tmax = 0.740k = −10→10
13375 measured reflectionsl = −31→33

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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0445P)2 + 0.1856P] where P = (Fo2 + 2Fc2)/3
3659 reflections(Δ/σ)max = 0.001
217 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = −0.48 e Å3

Special details

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)

xyzUiso*/Ueq
Zn10.48008 (3)0.59217 (3)0.126447 (9)0.01901 (11)
Cl10.75119 (7)0.59787 (7)0.12124 (2)0.03078 (16)
Cl20.39514 (8)0.76920 (7)0.18274 (2)0.03058 (17)
N10.3153 (3)0.1342 (2)0.15690 (7)0.0258 (5)
H1C0.26810.04670.14620.031*
N20.4140 (2)0.3782 (2)0.15104 (7)0.0207 (4)
N30.8313 (2)0.3109 (2)−0.00124 (7)0.0229 (4)
H3A0.85150.29810.03070.028*
N40.6803 (2)0.3684 (2)−0.06974 (7)0.0204 (4)
C10.3390 (4)0.1829 (3)0.20863 (9)0.0317 (6)
H1A0.43480.13000.22510.038*
H1B0.24060.16170.22740.038*
C20.3685 (3)0.3594 (3)0.20290 (9)0.0287 (6)
H2A0.26810.41980.20910.034*
H2B0.45810.39550.22610.034*
C30.3786 (3)0.2473 (3)0.12837 (8)0.0196 (5)
C40.3941 (3)0.2201 (3)0.07490 (8)0.0190 (5)
C50.2771 (3)0.1283 (3)0.04869 (9)0.0211 (5)
H5A0.18970.08170.06530.025*
C60.2896 (3)0.1059 (3)−0.00154 (9)0.0221 (5)
H6A0.20910.0454−0.01950.026*
C70.4181 (3)0.1707 (3)−0.02578 (8)0.0200 (5)
H7A0.42550.1550−0.06030.024*
C80.5371 (3)0.2590 (2)0.00036 (8)0.0185 (5)
C90.5245 (3)0.2843 (3)0.05072 (8)0.0190 (5)
H9A0.60480.34530.06860.023*
C100.6822 (3)0.3157 (3)−0.02469 (8)0.0188 (5)
C110.9542 (3)0.3309 (3)−0.03839 (8)0.0248 (5)
H11A0.99630.2285−0.04960.030*
H11B1.04690.3971−0.02590.030*
C120.8515 (3)0.4138 (3)−0.07927 (9)0.0256 (5)
H12A0.86590.5292−0.07720.031*
H12B0.88190.3774−0.11230.031*
N50.8751 (3)0.1284 (3)0.16839 (8)0.0381 (6)
C130.8524 (5)0.2201 (5)0.21257 (12)0.0666 (11)
H13A0.85090.33220.20420.100*
H13B0.94260.19900.23690.100*
H13C0.74830.19110.22650.100*
C140.8795 (7)−0.0394 (5)0.17315 (14)0.0913 (17)
H14A0.8958−0.08690.14080.137*
H14B0.7758−0.07660.18550.137*
H14C0.9698−0.06970.19630.137*
C150.8906 (3)0.1948 (3)0.12484 (10)0.0328 (6)
H15A0.89020.30640.12390.039*
O10.9055 (2)0.1264 (2)0.08571 (6)0.0313 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.02203 (17)0.02012 (16)0.01476 (16)0.00103 (10)−0.00025 (11)0.00084 (10)
Cl10.0216 (3)0.0318 (3)0.0388 (4)−0.0006 (2)−0.0008 (3)0.0019 (3)
Cl20.0501 (4)0.0242 (3)0.0176 (3)0.0052 (3)0.0033 (3)−0.0022 (2)
N10.0358 (12)0.0240 (10)0.0179 (10)−0.0066 (9)0.0033 (9)0.0009 (8)
N20.0265 (11)0.0222 (10)0.0135 (10)0.0017 (8)0.0020 (8)0.0011 (7)
N30.0216 (11)0.0327 (11)0.0144 (10)−0.0011 (9)−0.0005 (8)0.0020 (8)
N40.0194 (10)0.0252 (10)0.0167 (10)0.0023 (8)0.0026 (8)0.0006 (8)
C10.0473 (17)0.0289 (13)0.0194 (13)−0.0010 (12)0.0065 (11)0.0035 (10)
C20.0439 (16)0.0279 (13)0.0145 (12)0.0012 (11)0.0038 (11)0.0021 (10)
C30.0179 (12)0.0227 (11)0.0180 (12)0.0022 (9)0.0003 (9)0.0033 (9)
C40.0210 (12)0.0178 (11)0.0182 (12)0.0022 (9)0.0009 (9)−0.0002 (9)
C50.0190 (12)0.0204 (11)0.0240 (13)0.0017 (9)0.0014 (10)0.0028 (9)
C60.0215 (13)0.0194 (11)0.0245 (13)0.0020 (9)−0.0065 (10)−0.0011 (9)
C70.0235 (13)0.0201 (11)0.0160 (11)0.0045 (9)−0.0021 (9)0.0007 (9)
C80.0212 (12)0.0184 (11)0.0159 (11)0.0028 (9)−0.0006 (9)0.0015 (9)
C90.0210 (12)0.0186 (11)0.0171 (12)0.0018 (9)−0.0010 (9)−0.0009 (9)
C100.0233 (13)0.0169 (10)0.0161 (12)0.0019 (9)−0.0002 (9)−0.0024 (9)
C110.0198 (12)0.0338 (13)0.0208 (12)0.0004 (10)0.0008 (10)0.0015 (10)
C120.0217 (13)0.0340 (14)0.0211 (13)0.0005 (10)0.0017 (10)0.0049 (10)
N50.0468 (15)0.0488 (15)0.0192 (12)−0.0060 (11)0.0050 (10)−0.0011 (10)
C130.071 (3)0.096 (3)0.0334 (19)0.009 (2)0.0134 (17)−0.0192 (18)
C140.184 (5)0.052 (2)0.038 (2)−0.034 (3)0.008 (3)0.0071 (18)
C150.0330 (16)0.0336 (14)0.0318 (15)0.0057 (12)0.0013 (11)0.0033 (12)
O10.0307 (10)0.0468 (11)0.0163 (9)0.0015 (8)−0.0001 (7)0.0016 (8)

Geometric parameters (Å, °)

Zn1—N4i1.9978 (19)C5—H5A0.9500
Zn1—N22.0205 (19)C6—C71.382 (3)
Zn1—Cl12.2291 (7)C6—H6A0.9500
Zn1—Cl22.2764 (7)C7—C81.394 (3)
N1—C31.353 (3)C7—H7A0.9500
N1—C11.465 (3)C8—C91.390 (3)
N1—H1C0.8800C8—C101.477 (3)
N2—C31.298 (3)C9—H9A0.9500
N2—C21.480 (3)C11—C121.528 (3)
N3—C101.347 (3)C11—H11A0.9900
N3—C111.468 (3)C11—H11B0.9900
N3—H3A0.8800C12—H12A0.9900
N4—C101.300 (3)C12—H12B0.9900
N4—C121.487 (3)N5—C151.320 (3)
N4—Zn1i1.9978 (19)N5—C141.433 (4)
C1—C21.529 (3)N5—C131.449 (4)
C1—H1A0.9900C13—H13A0.9800
C1—H1B0.9900C13—H13B0.9800
C2—H2A0.9900C13—H13C0.9800
C2—H2B0.9900C14—H14A0.9800
C3—C41.479 (3)C14—H14B0.9800
C4—C91.391 (3)C14—H14C0.9800
C4—C51.400 (3)C15—O11.221 (3)
C5—C61.383 (3)C15—H15A0.9500
N4i—Zn1—N2103.21 (8)C6—C7—C8120.1 (2)
N4i—Zn1—Cl1124.35 (6)C6—C7—H7A120.0
N2—Zn1—Cl1108.90 (6)C8—C7—H7A120.0
N4i—Zn1—Cl2101.17 (6)C9—C8—C7119.9 (2)
N2—Zn1—Cl2106.18 (6)C9—C8—C10120.1 (2)
Cl1—Zn1—Cl2111.47 (3)C7—C8—C10119.9 (2)
C3—N1—C1108.03 (19)C8—C9—C4119.9 (2)
C3—N1—H1C126.0C8—C9—H9A120.1
C1—N1—H1C126.0C4—C9—H9A120.1
C3—N2—C2107.20 (19)N4—C10—N3114.9 (2)
C3—N2—Zn1132.35 (16)N4—C10—C8124.9 (2)
C2—N2—Zn1119.66 (14)N3—C10—C8120.2 (2)
C10—N3—C11107.93 (18)N3—C11—C12100.39 (18)
C10—N3—H3A126.0N3—C11—H11A111.7
C11—N3—H3A126.0C12—C11—H11A111.7
C10—N4—C12106.62 (19)N3—C11—H11B111.7
C10—N4—Zn1i139.15 (17)C12—C11—H11B111.7
C12—N4—Zn1i114.22 (14)H11A—C11—H11B109.5
N1—C1—C2101.20 (19)N4—C12—C11104.02 (19)
N1—C1—H1A111.5N4—C12—H12A111.0
C2—C1—H1A111.5C11—C12—H12A111.0
N1—C1—H1B111.5N4—C12—H12B111.0
C2—C1—H1B111.5C11—C12—H12B111.0
H1A—C1—H1B109.3H12A—C12—H12B109.0
N2—C2—C1104.55 (19)C15—N5—C14120.2 (3)
N2—C2—H2A110.8C15—N5—C13122.1 (3)
C1—C2—H2A110.8C14—N5—C13117.7 (3)
N2—C2—H2B110.8N5—C13—H13A109.5
C1—C2—H2B110.8N5—C13—H13B109.5
H2A—C2—H2B108.9H13A—C13—H13B109.5
N2—C3—N1115.0 (2)N5—C13—H13C109.5
N2—C3—C4124.7 (2)H13A—C13—H13C109.5
N1—C3—C4120.2 (2)H13B—C13—H13C109.5
C9—C4—C5120.0 (2)N5—C14—H14A109.5
C9—C4—C3120.4 (2)N5—C14—H14B109.5
C5—C4—C3119.6 (2)H14A—C14—H14B109.5
C6—C5—C4119.6 (2)N5—C14—H14C109.5
C6—C5—H5A120.2H14A—C14—H14C109.5
C4—C5—H5A120.2H14B—C14—H14C109.5
C7—C6—C5120.5 (2)O1—C15—N5126.3 (3)
C7—C6—H6A119.7O1—C15—H15A116.9
C5—C6—H6A119.7N5—C15—H15A116.9

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···Cl2ii0.882.743.241 (2)117.
N3—H3A···O10.882.122.870 (3)143.

Symmetry codes: (ii) x, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2778).

References

  • Bruker (2000). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ren, C.-X., Cheng, L., Ye, B.-H. & Chen, X.-M. (2007). Inorg. Chim. Acta, 360, 3741–3747.
  • Ren, C.-X., Ye, B.-H., He, F., Cheng, L. & Chen, X.-M. (2004). CrystEngComm, 6, 200–206.
  • Sheldrick, G. M. (2000). SADABS University of Göttingen.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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