metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

aDepartment of Chemistry and Life Sciences, Xiangnan University, Chenzhou 423000, People's Republic of China, and bDepartment of Chemistry, Liaoning Teachers' University, Dalian 116029, People's Republic of China
*Correspondence e-mail: lijuan_ye@163.com

(Received 27 May 2008; accepted 29 May 2008; online 7 June 2008)

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[Ali, H. M., Mohamed Mustafa, M. I., Rizal, M. R. & Ng, S. W. (2008). Acta Cryst. E64, m718-m719.]); Wang (2007[Wang, S.-X. (2007). Acta Cryst. E63, m706-m707.]); You (2005[You, Z.-L. (2005). Acta Cryst. E61, m2416-m2418.]). For our recent investigations of metal complex systems, see: Ye & You (2007a[Ye, L.-J. & You, Z. (2007a). Acta Cryst. E63, m523-m525.],b[Ye, L.-J. & You, Z. (2007b). Acta Cryst. E63, m1837.],c[Ye, L.-J. & You, Z. (2007c). Acta Cryst. E63, m3137.]).

[Scheme 1]

Experimental

Crystal data
  • [ZnCl2(C12H16BrClN2O)]

  • Mr = 455.90

  • Monoclinic, P 21 /c

  • 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.261, Tmax = 0.275

  • 9470 measured reflections

  • 3633 independent reflections

  • 2283 reflections with I > 2σ(I)

  • Rint = 0.037

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 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

Table 1
Selected geometric parameters (Å, °)

Zn1—O1 1.931 (4)
Zn1—N1 1.999 (4)
Zn1—Cl2 2.2303 (19)
Zn1—Cl3 2.2489 (19)
O1—Zn1—N1 95.48 (17)
O1—Zn1—Cl2 112.60 (13)
N1—Zn1—Cl2 112.04 (14)
O1—Zn1—Cl3 110.85 (13)
N1—Zn1—Cl3 114.71 (13)
Cl2—Zn1—Cl3 110.45 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2⋯Cl3i 0.91 (5) 2.37 (3) 3.190 (5) 152 (5)
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Bruker, 2002[Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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).

Computing details top

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

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. Molecular packing of (I). Intermolecular hydrogen bonds are shown as dashed lines.
{(E)-2-Bromo-4-chloro-6-[3- (dimethylammonio)propyliminomethyl]phenolato}dichloridozinc(II) top
Crystal data top
[ZnCl2(C12H16BrClN2O)]F(000) = 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 = 2.3–25.3°
b = 26.808 (15) ŵ = 4.30 mm1
c = 8.354 (4) ÅT = 298 K
β = 90.921 (9)°Block, colorless
V = 1684.3 (16) Å30.32 × 0.30 × 0.30 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3633 independent reflections
Radiation source: fine-focus sealed tube2283 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω scansθmax = 27.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.261, Tmax = 0.275k = 3234
9470 measured reflectionsl = 107
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0506P)2 + 2.1641P]
where P = (Fo2 + 2Fc2)/3
3633 reflections(Δ/σ)max = 0.001
186 parametersΔρmax = 0.58 e Å3
1 restraintΔρmin = 0.36 e Å3
Crystal data top
[ZnCl2(C12H16BrClN2O)]V = 1684.3 (16) Å3
Mr = 455.90Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.522 (4) ŵ = 4.30 mm1
b = 26.808 (15) ÅT = 298 K
c = 8.354 (4) Å0.32 × 0.30 × 0.30 mm
β = 90.921 (9)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3633 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2283 reflections with I > 2σ(I)
Tmin = 0.261, Tmax = 0.275Rint = 0.037
9470 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0481 restraint
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.58 e Å3
3633 reflectionsΔρmin = 0.36 e Å3
186 parameters
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
Zn10.25129 (8)0.59843 (2)0.53367 (8)0.0531 (2)
Br10.09048 (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) top
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, º) top
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, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl3i0.91 (5)2.37 (3)3.190 (5)152 (5)
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula[ZnCl2(C12H16BrClN2O)]
Mr455.90
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)7.522 (4), 26.808 (15), 8.354 (4)
β (°) 90.921 (9)
V3)1684.3 (16)
Z4
Radiation typeMo Kα
µ (mm1)4.30
Crystal size (mm)0.32 × 0.30 × 0.30
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.261, 0.275
No. of measured, independent and
observed [I > 2σ(I)] reflections
9470, 3633, 2283
Rint0.037
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.126, 1.04
No. of reflections3633
No. of parameters186
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.58, 0.36

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Zn1—O11.931 (4)Zn1—Cl22.2303 (19)
Zn1—N11.999 (4)Zn1—Cl32.2489 (19)
O1—Zn1—N195.48 (17)O1—Zn1—Cl3110.85 (13)
O1—Zn1—Cl2112.60 (13)N1—Zn1—Cl3114.71 (13)
N1—Zn1—Cl2112.04 (14)Cl2—Zn1—Cl3110.45 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl3i0.91 (5)2.37 (3)3.190 (5)152 (5)
Symmetry code: (i) x+1, y, z.
 

Acknowledgements

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.

References

First citationAli, H. M., Mohamed Mustafa, M. I., Rizal, M. R. & Ng, S. W. (2008). Acta Cryst. E64, m718–m719.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationBruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWang, S.-X. (2007). Acta Cryst. E63, m706–m707.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationYe, L.-J. & You, Z. (2007a). Acta Cryst. E63, m523–m525.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationYe, L.-J. & You, Z. (2007b). Acta Cryst. E63, m1837.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationYe, L.-J. & You, Z. (2007c). Acta Cryst. E63, m3137.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationYou, Z.-L. (2005). Acta Cryst. E61, m2416–m2418.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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