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

Ye, L.-J.; You, Z.

doi:10.1107/S1600536808016255

metal-organic compounds

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Volume 64| Part 7| July 2008| Page m869

doi:10.1107/S1600536808016255

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

Li-Juan Ye ^a ^* and Zhonglu You ^b

^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 Zn^II 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 ); Wang (2007 ); You (2005 ). For our recent investigations of metal complex systems, see: Ye & You (2007a ,b ,c ).

Experimental

Crystal data

[ZnCl₂(C₁₂H₁₆BrClN₂O)]
M_r = 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 ) 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[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
Δρ_max = 0.58 e Å⁻³
Δρ_min = −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	D⋯A	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 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

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

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

checkCIF report

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 Zn^II 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.

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

	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.

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

Crystal data top

[ZnCl₂(C₁₂H₁₆BrClN₂O)]	F(000) = 904
M_r = 455.90	D_x = 1.798 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1372 reflections
a = 7.522 (4) Å	θ = 2.3–25.3°
b = 26.808 (15) Å	µ = 4.30 mm⁻¹
c = 8.354 (4) Å	T = 298 K
β = 90.921 (9)°	Block, colorless
V = 1684.3 (16) Å³	0.32 × 0.30 × 0.30 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3633 independent reflections
Radiation source: fine-focus sealed tube	2283 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 27.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.261, T_max = 0.275	k = −32→34
9470 measured reflections	l = −10→7

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0506P)² + 2.1641P] where P = (F_o² + 2F_c²)/3
3633 reflections	(Δ/σ)_max = 0.001
186 parameters	Δρ_max = 0.58 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

[ZnCl₂(C₁₂H₁₆BrClN₂O)]	V = 1684.3 (16) Å³
M_r = 455.90	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.522 (4) Å	µ = 4.30 mm⁻¹
b = 26.808 (15) Å	T = 298 K
c = 8.354 (4) Å	0.32 × 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)
T_min = 0.261, T_max = 0.275	R_int = 0.037
9470 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	1 restraint
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.58 e Å⁻³
3633 reflections	Δρ_min = −0.36 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Zn1	0.25129 (8)	0.59843 (2)	0.53367 (8)	0.0531 (2)
Br1	−0.09048 (7)	0.73965 (3)	0.73104 (8)	0.0691 (2)
Cl1	0.4472 (2)	0.86120 (6)	0.5360 (2)	0.0868 (6)
Cl2	0.1025 (2)	0.56893 (7)	0.32087 (19)	0.0748 (5)
Cl3	0.2609 (2)	0.54111 (6)	0.7302 (2)	0.0718 (4)
O1	0.1550 (5)	0.66062 (14)	0.6102 (5)	0.0592 (10)
N1	0.4876 (5)	0.62653 (18)	0.4750 (5)	0.0485 (10)
N2	0.8671 (7)	0.5717 (2)	0.8271 (6)	0.0708 (15)
C1	0.3975 (6)	0.7126 (2)	0.5273 (6)	0.0465 (12)
C2	0.2268 (6)	0.7039 (2)	0.5936 (6)	0.0464 (12)
C3	0.1364 (6)	0.7472 (2)	0.6440 (6)	0.0499 (13)
C4	0.2038 (7)	0.7947 (2)	0.6301 (6)	0.0554 (14)
H4	0.1408	0.8221	0.6675	0.066*
C5	0.3661 (7)	0.8009 (2)	0.5599 (7)	0.0561 (14)
C6	0.4609 (7)	0.7608 (2)	0.5106 (7)	0.0545 (14)
H6	0.5712	0.7658	0.4645	0.065*
C7	0.5140 (6)	0.6730 (2)	0.4739 (6)	0.0501 (13)
H7	0.6226	0.6832	0.4335	0.060*
C8	0.6332 (7)	0.5932 (2)	0.4223 (7)	0.0566 (14)
H8A	0.7281	0.6131	0.3776	0.068*
H8B	0.5886	0.5709	0.3394	0.068*
C9	0.7047 (7)	0.5631 (2)	0.5607 (7)	0.0562 (14)
H9A	0.8007	0.5420	0.5245	0.067*
H9B	0.6115	0.5418	0.6012	0.067*
C10	0.7721 (7)	0.5967 (2)	0.6924 (6)	0.0557 (14)
H10A	0.8515	0.6211	0.6462	0.067*
H10B	0.6717	0.6147	0.7353	0.067*
C11	0.9452 (10)	0.6088 (3)	0.9358 (8)	0.094 (2)
H11A	1.0131	0.6323	0.8755	0.140*
H11B	1.0216	0.5924	1.0125	0.140*
H11C	0.8522	0.6259	0.9906	0.140*
C12	0.7535 (10)	0.5353 (3)	0.9111 (9)	0.092 (2)
H12A	0.8145	0.5236	1.0058	0.137*
H12B	0.7283	0.5075	0.8417	0.137*
H12C	0.6442	0.5510	0.9404	0.137*
H2	0.957 (6)	0.5538 (19)	0.785 (7)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0387 (3)	0.0640 (4)	0.0565 (4)	0.0016 (3)	0.0037 (3)	0.0026 (3)
Br1	0.0423 (3)	0.0841 (5)	0.0814 (5)	0.0067 (3)	0.0171 (3)	−0.0044 (4)
Cl1	0.0821 (12)	0.0638 (10)	0.1152 (15)	−0.0146 (9)	0.0261 (10)	0.0035 (10)
Cl2	0.0598 (9)	0.1019 (13)	0.0625 (10)	−0.0042 (9)	−0.0082 (7)	−0.0015 (9)
Cl3	0.0628 (9)	0.0818 (11)	0.0713 (10)	0.0011 (8)	0.0118 (7)	0.0115 (9)
O1	0.045 (2)	0.056 (2)	0.077 (3)	0.0007 (18)	0.0174 (18)	0.005 (2)
N1	0.033 (2)	0.062 (3)	0.051 (3)	0.009 (2)	0.0019 (18)	0.003 (2)
N2	0.057 (3)	0.095 (4)	0.061 (3)	0.035 (3)	0.007 (2)	0.016 (3)
C1	0.033 (2)	0.064 (3)	0.042 (3)	0.002 (2)	−0.002 (2)	0.001 (3)
C2	0.034 (2)	0.062 (4)	0.043 (3)	0.006 (2)	−0.002 (2)	0.005 (3)
C3	0.036 (3)	0.067 (4)	0.046 (3)	0.006 (2)	0.000 (2)	0.006 (3)
C4	0.056 (3)	0.058 (4)	0.052 (3)	0.009 (3)	−0.004 (3)	−0.001 (3)
C5	0.050 (3)	0.060 (4)	0.058 (4)	−0.002 (3)	0.001 (3)	0.004 (3)
C6	0.039 (3)	0.070 (4)	0.055 (3)	−0.003 (3)	−0.002 (2)	0.004 (3)
C7	0.032 (2)	0.077 (4)	0.041 (3)	0.008 (3)	0.006 (2)	0.008 (3)
C8	0.040 (3)	0.072 (4)	0.058 (4)	0.014 (3)	0.006 (2)	−0.004 (3)
C9	0.040 (3)	0.061 (3)	0.068 (4)	0.014 (3)	0.011 (3)	0.000 (3)
C10	0.041 (3)	0.072 (4)	0.054 (3)	0.011 (3)	0.002 (2)	0.012 (3)
C11	0.081 (5)	0.155 (7)	0.044 (4)	0.008 (5)	−0.010 (3)	−0.003 (4)
C12	0.109 (6)	0.084 (5)	0.083 (5)	0.028 (4)	0.034 (4)	0.031 (4)

Geometric parameters (Å, º) top

Zn1—O1	1.931 (4)	C4—H4	0.9300
Zn1—N1	1.999 (4)	C5—C6	1.359 (8)
Zn1—Cl2	2.2303 (19)	C6—H6	0.9300
Zn1—Cl3	2.2489 (19)	C7—H7	0.9300
Br1—C3	1.877 (5)	C8—C9	1.502 (8)
Cl1—C5	1.740 (6)	C8—H8A	0.9700
O1—C2	1.288 (6)	C8—H8B	0.9700
N1—C7	1.261 (7)	C9—C10	1.504 (8)
N1—C8	1.485 (6)	C9—H9A	0.9700
N2—C11	1.464 (9)	C9—H9B	0.9700
N2—C12	1.482 (8)	C10—H10A	0.9700
N2—C10	1.483 (7)	C10—H10B	0.9700
N2—H2	0.91 (5)	C11—H11A	0.9600
C1—C6	1.385 (8)	C11—H11B	0.9600
C1—C2	1.425 (7)	C11—H11C	0.9600
C1—C7	1.451 (7)	C12—H12A	0.9600
C2—C3	1.413 (7)	C12—H12B	0.9600
C3—C4	1.375 (8)	C12—H12C	0.9600
C4—C5	1.372 (8)

O1—Zn1—N1	95.48 (17)	N1—C7—C1	128.6 (5)
O1—Zn1—Cl2	112.60 (13)	N1—C7—H7	115.7
N1—Zn1—Cl2	112.04 (14)	C1—C7—H7	115.7
O1—Zn1—Cl3	110.85 (13)	N1—C8—C9	110.6 (4)
N1—Zn1—Cl3	114.71 (13)	N1—C8—H8A	109.5
Cl2—Zn1—Cl3	110.45 (8)	C9—C8—H8A	109.5
C2—O1—Zn1	125.6 (3)	N1—C8—H8B	109.5
C7—N1—C8	118.4 (4)	C9—C8—H8B	109.5
C7—N1—Zn1	121.0 (3)	H8A—C8—H8B	108.1
C8—N1—Zn1	120.6 (4)	C8—C9—C10	110.7 (5)
C11—N2—C12	112.5 (6)	C8—C9—H9A	109.5
C11—N2—C10	110.3 (5)	C10—C9—H9A	109.5
C12—N2—C10	112.5 (5)	C8—C9—H9B	109.5
C11—N2—H2	108 (4)	C10—C9—H9B	109.5
C12—N2—H2	106 (4)	H9A—C9—H9B	108.1
C10—N2—H2	107 (4)	N2—C10—C9	115.9 (5)
C6—C1—C2	120.3 (5)	N2—C10—H10A	108.3
C6—C1—C7	116.1 (5)	C9—C10—H10A	108.3
C2—C1—C7	123.6 (5)	N2—C10—H10B	108.3
O1—C2—C3	120.3 (4)	C9—C10—H10B	108.3
O1—C2—C1	124.7 (5)	H10A—C10—H10B	107.4
C3—C2—C1	115.0 (5)	N2—C11—H11A	109.5
C4—C3—C2	123.7 (5)	N2—C11—H11B	109.5
C4—C3—Br1	118.2 (4)	H11A—C11—H11B	109.5
C2—C3—Br1	118.1 (4)	N2—C11—H11C	109.5
C5—C4—C3	118.7 (5)	H11A—C11—H11C	109.5
C5—C4—H4	120.7	H11B—C11—H11C	109.5
C3—C4—H4	120.7	N2—C12—H12A	109.5
C6—C5—C4	120.5 (5)	N2—C12—H12B	109.5
C6—C5—Cl1	121.0 (4)	H12A—C12—H12B	109.5
C4—C5—Cl1	118.5 (5)	N2—C12—H12C	109.5
C5—C6—C1	121.7 (5)	H12A—C12—H12C	109.5
C5—C6—H6	119.2	H12B—C12—H12C	109.5
C1—C6—H6	119.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl3ⁱ	0.91 (5)	2.37 (3)	3.190 (5)	152 (5)

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

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₂H₁₆BrClN₂O)]
M_r	455.90
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.522 (4), 26.808 (15), 8.354 (4)
β (°)	90.921 (9)
V (Å³)	1684.3 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.30
Crystal size (mm)	0.32 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.261, 0.275
No. of measured, independent and observed [I > 2σ(I)] reflections	9470, 3633, 2283
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.126, 1.04
No. of reflections	3633
No. of parameters	186
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.36

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

Selected geometric parameters (Å, º) top

Zn1—O1	1.931 (4)	Zn1—Cl2	2.2303 (19)
Zn1—N1	1.999 (4)	Zn1—Cl3	2.2489 (19)

O1—Zn1—N1	95.48 (17)	O1—Zn1—Cl3	110.85 (13)
O1—Zn1—Cl2	112.60 (13)	N1—Zn1—Cl3	114.71 (13)
N1—Zn1—Cl2	112.04 (14)	Cl2—Zn1—Cl3	110.45 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl3ⁱ	0.91 (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

Ali, 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
Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Ye, L.-J. & You, Z. (2007a). Acta Cryst. E63, m523–m525. Web of Science CSD CrossRef IUCr Journals Google Scholar
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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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