PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): m869.
Published online 2008 June 7. doi:  10.1107/S1600536808016255
PMCID: PMC2961892

{(E)-2-Bromo-4-chloro-6-[3-(dimethyl­ammonio)propyl­imino­meth­yl]­phenol­ato}­dichloridozinc(II)

Abstract

The title compound, [ZnCl2(C12H16BrClN2O)], is a mononuclear zinc(II) complex. The ZnII atom is four-coordinate in a tetra­hedral geometry, binding to the phenolate O and imine N atoms of the zwitterionic Schiff base ligand and to two Cl ions. In the crystal structure, mol­ecules are linked through inter­molecular N—H(...)Cl hydrogen bonds to form chains running along the a axis.

Related literature

For related structures, see: Ali et al. (2008 [triangle]); Wang (2007 [triangle]); You (2005 [triangle]). For our recent investigations of metal complex systems, see: Ye & You (2007a [triangle],b [triangle],c [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m869-scheme1.jpg

Experimental

Crystal data

  • [ZnCl2(C12H16BrClN2O)]
  • M r = 455.90
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m869-efi1.jpg
  • a = 7.522 (4) Å
  • b = 26.808 (15) Å
  • c = 8.354 (4) Å
  • β = 90.921 (9)°
  • V = 1684.3 (16) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 4.30 mm−1
  • T = 298 (2) K
  • 0.32 × 0.30 × 0.30 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.261, T max = 0.275
  • 9470 measured reflections
  • 3633 independent reflections
  • 2283 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.126
  • S = 1.04
  • 3633 reflections
  • 186 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.58 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

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

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016255/sj2511sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016255/sj2511Isup2.hkl

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

Acknowledgments

Financial support from the Hunan Provincial Natural Sciences Foundation of China (grant No. 03JJY3019) and the Hunan Provincial Educational Ministry Foundation of China (grant No. 05 C627) is acknowledged.

supplementary crystallographic information

Comment

Recently, we have reported thiocyanate coordinated zinc(II) (Ye & You, 2007a), and copper(II) complexes (Ye & You, 2007b), and a chlorido-bridged polynuclear copper(II) complex (Ye & You, 2007c). As an extension of the work on the crystal structures of such complexes, we report herein the crystal structure of the title compound, (I), Fig. 1.

Compound (I) is a mononuclear zinc(II) complex. The ZnII atom is four-coordinate in a tetrahedral geometry, binding to the phenolate O and imine N atoms of the zwitterionic Schiff base ligand and two Cl- ions. The coordinate bond values (Table 1) are comparable to those reported in other similar zinc(II) complexes (Wang, 2007; Ali et al., 2008; You, 2005).

In the crystal structure, molecules are linked through intermolecular N–H···Cl hydrogen bonds, Table 2, to form chains running along the a axis (Fig. 2).

Experimental

3-Bromo-5-chlorosalicylaldehyde (0.1 mmol, 23.5 mg), N,N-dimethylpropane-1,3-diamine (0.1 mmol, 10.2 mg), and zinc(II) chloride (0.1 mmol, 13.6 mg) were dissolved in a methanol solution (10 ml). The mixture was stirred at room temperature for 30 min to give a clear colorless solution. Crystals of the compound were formed by slow evaporation of the solvent over a week at room temperature.

Refinement

Atom H2 on the amine N2 atom was located from a difference Fourier map and refined isotropically, with the N–H distance restrained to 0.90 (1) Å, and with Uiso(H) fixed at 0.08 Å2. The remaining H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C–H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2 or 1.5Ueq(C).

Figures

Fig. 1.
Molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
Molecular packing of (I). Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

[ZnCl2(C12H16BrClN2O)]F000 = 904
Mr = 455.90Dx = 1.798 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1372 reflections
a = 7.522 (4) Åθ = 2.3–25.3º
b = 26.808 (15) ŵ = 4.30 mm1
c = 8.354 (4) ÅT = 298 (2) K
β = 90.921 (9)ºBlock, colorless
V = 1684.3 (16) Å30.32 × 0.30 × 0.30 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer3633 independent reflections
Radiation source: fine-focus sealed tube2283 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.037
T = 298(2) Kθmax = 27.0º
ω scansθmin = 1.5º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.261, Tmax = 0.275k = −32→34
9470 measured reflectionsl = −10→7

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.126  w = 1/[σ2(Fo2) + (0.0506P)2 + 2.1641P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3633 reflectionsΔρmax = 0.58 e Å3
186 parametersΔρmin = −0.36 e Å3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods

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
Zn10.25129 (8)0.59843 (2)0.53367 (8)0.0531 (2)
Br1−0.09048 (7)0.73965 (3)0.73104 (8)0.0691 (2)
Cl10.4472 (2)0.86120 (6)0.5360 (2)0.0868 (6)
Cl20.1025 (2)0.56893 (7)0.32087 (19)0.0748 (5)
Cl30.2609 (2)0.54111 (6)0.7302 (2)0.0718 (4)
O10.1550 (5)0.66062 (14)0.6102 (5)0.0592 (10)
N10.4876 (5)0.62653 (18)0.4750 (5)0.0485 (10)
N20.8671 (7)0.5717 (2)0.8271 (6)0.0708 (15)
C10.3975 (6)0.7126 (2)0.5273 (6)0.0465 (12)
C20.2268 (6)0.7039 (2)0.5936 (6)0.0464 (12)
C30.1364 (6)0.7472 (2)0.6440 (6)0.0499 (13)
C40.2038 (7)0.7947 (2)0.6301 (6)0.0554 (14)
H40.14080.82210.66750.066*
C50.3661 (7)0.8009 (2)0.5599 (7)0.0561 (14)
C60.4609 (7)0.7608 (2)0.5106 (7)0.0545 (14)
H60.57120.76580.46450.065*
C70.5140 (6)0.6730 (2)0.4739 (6)0.0501 (13)
H70.62260.68320.43350.060*
C80.6332 (7)0.5932 (2)0.4223 (7)0.0566 (14)
H8A0.72810.61310.37760.068*
H8B0.58860.57090.33940.068*
C90.7047 (7)0.5631 (2)0.5607 (7)0.0562 (14)
H9A0.80070.54200.52450.067*
H9B0.61150.54180.60120.067*
C100.7721 (7)0.5967 (2)0.6924 (6)0.0557 (14)
H10A0.85150.62110.64620.067*
H10B0.67170.61470.73530.067*
C110.9452 (10)0.6088 (3)0.9358 (8)0.094 (2)
H11A1.01310.63230.87550.140*
H11B1.02160.59241.01250.140*
H11C0.85220.62590.99060.140*
C120.7535 (10)0.5353 (3)0.9111 (9)0.092 (2)
H12A0.81450.52361.00580.137*
H12B0.72830.50750.84170.137*
H12C0.64420.55100.94040.137*
H20.957 (6)0.5538 (19)0.785 (7)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0387 (3)0.0640 (4)0.0565 (4)0.0016 (3)0.0037 (3)0.0026 (3)
Br10.0423 (3)0.0841 (5)0.0814 (5)0.0067 (3)0.0171 (3)−0.0044 (4)
Cl10.0821 (12)0.0638 (10)0.1152 (15)−0.0146 (9)0.0261 (10)0.0035 (10)
Cl20.0598 (9)0.1019 (13)0.0625 (10)−0.0042 (9)−0.0082 (7)−0.0015 (9)
Cl30.0628 (9)0.0818 (11)0.0713 (10)0.0011 (8)0.0118 (7)0.0115 (9)
O10.045 (2)0.056 (2)0.077 (3)0.0007 (18)0.0174 (18)0.005 (2)
N10.033 (2)0.062 (3)0.051 (3)0.009 (2)0.0019 (18)0.003 (2)
N20.057 (3)0.095 (4)0.061 (3)0.035 (3)0.007 (2)0.016 (3)
C10.033 (2)0.064 (3)0.042 (3)0.002 (2)−0.002 (2)0.001 (3)
C20.034 (2)0.062 (4)0.043 (3)0.006 (2)−0.002 (2)0.005 (3)
C30.036 (3)0.067 (4)0.046 (3)0.006 (2)0.000 (2)0.006 (3)
C40.056 (3)0.058 (4)0.052 (3)0.009 (3)−0.004 (3)−0.001 (3)
C50.050 (3)0.060 (4)0.058 (4)−0.002 (3)0.001 (3)0.004 (3)
C60.039 (3)0.070 (4)0.055 (3)−0.003 (3)−0.002 (2)0.004 (3)
C70.032 (2)0.077 (4)0.041 (3)0.008 (3)0.006 (2)0.008 (3)
C80.040 (3)0.072 (4)0.058 (4)0.014 (3)0.006 (2)−0.004 (3)
C90.040 (3)0.061 (3)0.068 (4)0.014 (3)0.011 (3)0.000 (3)
C100.041 (3)0.072 (4)0.054 (3)0.011 (3)0.002 (2)0.012 (3)
C110.081 (5)0.155 (7)0.044 (4)0.008 (5)−0.010 (3)−0.003 (4)
C120.109 (6)0.084 (5)0.083 (5)0.028 (4)0.034 (4)0.031 (4)

Geometric parameters (Å, °)

Zn1—O11.931 (4)C4—H40.9300
Zn1—N11.999 (4)C5—C61.359 (8)
Zn1—Cl22.2303 (19)C6—H60.9300
Zn1—Cl32.2489 (19)C7—H70.9300
Br1—C31.877 (5)C8—C91.502 (8)
Cl1—C51.740 (6)C8—H8A0.9700
O1—C21.288 (6)C8—H8B0.9700
N1—C71.261 (7)C9—C101.504 (8)
N1—C81.485 (6)C9—H9A0.9700
N2—C111.464 (9)C9—H9B0.9700
N2—C121.482 (8)C10—H10A0.9700
N2—C101.483 (7)C10—H10B0.9700
N2—H20.91 (5)C11—H11A0.9600
C1—C61.385 (8)C11—H11B0.9600
C1—C21.425 (7)C11—H11C0.9600
C1—C71.451 (7)C12—H12A0.9600
C2—C31.413 (7)C12—H12B0.9600
C3—C41.375 (8)C12—H12C0.9600
C4—C51.372 (8)
O1—Zn1—N195.48 (17)N1—C7—C1128.6 (5)
O1—Zn1—Cl2112.60 (13)N1—C7—H7115.7
N1—Zn1—Cl2112.04 (14)C1—C7—H7115.7
O1—Zn1—Cl3110.85 (13)N1—C8—C9110.6 (4)
N1—Zn1—Cl3114.71 (13)N1—C8—H8A109.5
Cl2—Zn1—Cl3110.45 (8)C9—C8—H8A109.5
C2—O1—Zn1125.6 (3)N1—C8—H8B109.5
C7—N1—C8118.4 (4)C9—C8—H8B109.5
C7—N1—Zn1121.0 (3)H8A—C8—H8B108.1
C8—N1—Zn1120.6 (4)C8—C9—C10110.7 (5)
C11—N2—C12112.5 (6)C8—C9—H9A109.5
C11—N2—C10110.3 (5)C10—C9—H9A109.5
C12—N2—C10112.5 (5)C8—C9—H9B109.5
C11—N2—H2108 (4)C10—C9—H9B109.5
C12—N2—H2106 (4)H9A—C9—H9B108.1
C10—N2—H2107 (4)N2—C10—C9115.9 (5)
C6—C1—C2120.3 (5)N2—C10—H10A108.3
C6—C1—C7116.1 (5)C9—C10—H10A108.3
C2—C1—C7123.6 (5)N2—C10—H10B108.3
O1—C2—C3120.3 (4)C9—C10—H10B108.3
O1—C2—C1124.7 (5)H10A—C10—H10B107.4
C3—C2—C1115.0 (5)N2—C11—H11A109.5
C4—C3—C2123.7 (5)N2—C11—H11B109.5
C4—C3—Br1118.2 (4)H11A—C11—H11B109.5
C2—C3—Br1118.1 (4)N2—C11—H11C109.5
C5—C4—C3118.7 (5)H11A—C11—H11C109.5
C5—C4—H4120.7H11B—C11—H11C109.5
C3—C4—H4120.7N2—C12—H12A109.5
C6—C5—C4120.5 (5)N2—C12—H12B109.5
C6—C5—Cl1121.0 (4)H12A—C12—H12B109.5
C4—C5—Cl1118.5 (5)N2—C12—H12C109.5
C5—C6—C1121.7 (5)H12A—C12—H12C109.5
C5—C6—H6119.2H12B—C12—H12C109.5
C1—C6—H6119.2

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···Cl3i0.91 (5)2.37 (3)3.190 (5)152 (5)

Symmetry codes: (i) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2511).

References

  • Ali, H. M., Mohamed Mustafa, M. I., Rizal, M. R. & Ng, S. W. (2008). Acta Cryst. E64, m718–m719. [PMC free article] [PubMed]
  • Bruker (2002). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, S.-X. (2007). Acta Cryst. E63, m706–m707.
  • Ye, L.-J. & You, Z. (2007a). Acta Cryst. E63, m523–m525.
  • Ye, L.-J. & You, Z. (2007b). Acta Cryst. E63, m1837.
  • Ye, L.-J. & You, Z. (2007c). Acta Cryst. E63, m3137.
  • You, Z.-L. (2005). Acta Cryst. E61, m2416–m2418.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography