Dichlorido{2-[3-(dimethyl-ammonio)-propyl-imino-meth-yl]phenolato}zinc(II) hemihydrate.

The title complex, [ZnCl(2)(C(12)H(18)N(2)O)]·0.5H(2)O, is a mononuclear zinc(II) compound derived from the zwitterionic form of the Schiff base 2-[3-(dimethyl-amino)propyl-imino-meth-yl]-phenol. The Zn(II) atom is four-coordinated by the imine N and the phenolate O atoms of the Schiff base ligand, and by two chloride ions, in a distorted tetra-hedral coordination geometry. The dimethyl-ammonio group is disordered over two positions with site occupancies of 0.51 (3) and 0.49 (3). In the asymmetric unit, there is also a disordered water mol-ecule with a partial occupancy of 0.5. In the crystal structure, the water mol-ecules are linked to the Schiff base complex mol-ecules through inter-molecular N-H⋯O hydrogen bonds. Mol-ecules are further linked through additional inter-molecular N-H⋯O hydrogen bonds, forming chains running along the b axis.

Related literature

For a general background on the chemistry of Schiff base complexes, see: Ali et al. (2008 ▶); Biswas et al. (2008 ▶); Chen et al. (2008 ▶); Darensbourg & Frantz (2007 ▶); Habibi et al. (2007 ▶); Kawamoto et al. (2008 ▶); Lipscomb & Sträter (1996 ▶); Tomat et al. (2007 ▶); Wu et al. (2008 ▶); Yuan et al. (2007 ▶). For related structures, see: Zhu & Yang (2008a ▶,b ▶,c ▶,d ▶); Qiu (2006a ▶,b ▶); Wei et al. (2007 ▶); Zhu et al. (2007 ▶).

Experimental

Crystal data

[ZnCl2(C12H18N2O)]·0.5H2O

M = 351.58

Orthorhombic,

a = 13.335 (2) Å

b = 16.384 (2) Å

c = 7.212 (1) Å

V = 1575.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 1.89 mm−1

T = 298 (2) K

0.23 × 0.23 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.650, T max = 0.661

12635 measured reflections

3426 independent reflections

2915 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.103

S = 1.08

3426 reflections

206 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.40 e Å−3

Absolute structure: Flack (1983 ▶), 1569 Friedel pairs

Flack parameter: 0.03 (2)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033977/rz2256sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033977/rz2256Isup2.hkl

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

[ZnCl2(C12H18N2O)]·0.5H2O	F(000) = 724
Mr = 351.58	Dx = 1.482 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3872 reflections
a = 13.335 (2) Å	θ = 2.4–25.3°
b = 16.384 (2) Å	µ = 1.89 mm−1
c = 7.212 (1) Å	T = 298 K
V = 1575.7 (4) Å3	Block, colorless
Z = 4	0.23 × 0.23 × 0.22 mm

Bruker APEXII CCD area-detector diffractometer	3426 independent reflections
Radiation source: fine-focus sealed tube	2915 reflections with I > 2σ(I)
graphite	Rint = 0.035
ω scans	θmax = 27.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −17→17
Tmin = 0.650, Tmax = 0.661	k = −20→20
12635 measured reflections	l = −9→9

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103	w = 1/[σ2(Fo2) + (0.0381P)2 + 0.643P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.001
3426 reflections	Δρmax = 0.42 e Å−3
206 parameters	Δρmin = −0.40 e Å−3
4 restraints	Absolute structure: Flack (1983), 1569 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.03 (2)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.73458 (3)	1.10664 (2)	1.00222 (10)	0.04900 (15)
Cl1	0.59091 (11)	1.09513 (7)	1.1550 (2)	0.0746 (4)
Cl2	0.86270 (14)	1.03257 (11)	1.1229 (3)	0.1022 (5)
N1	0.7159 (3)	1.0824 (2)	0.7323 (5)	0.0449 (7)
O1	0.7749 (2)	1.21988 (16)	0.9610 (4)	0.0563 (8)
O2	0.9856 (5)	0.9368 (4)	0.1435 (12)	0.0704 (18)	0.50
C1	0.8128 (3)	1.2011 (2)	0.6371 (6)	0.0488 (9)
C2	0.8218 (3)	1.2425 (2)	0.8055 (6)	0.0464 (9)
C3	0.8817 (4)	1.3118 (3)	0.8081 (9)	0.0656 (13)
H3	0.8897	1.3401	0.9189	0.079*
C4	0.9288 (4)	1.3393 (3)	0.6546 (10)	0.0783 (16)
H4	0.9668	1.3868	0.6615	0.094*
C5	0.9217 (4)	1.2989 (3)	0.4892 (11)	0.0835 (17)
H5	0.9564	1.3172	0.3853	0.100*
C6	0.8631 (4)	1.2317 (3)	0.4807 (8)	0.0736 (14)
H6	0.8558	1.2049	0.3678	0.088*
C7	0.7537 (3)	1.1280 (3)	0.6068 (6)	0.0506 (10)
H7	0.7423	1.1129	0.4843	0.061*
C8	0.6601 (3)	1.0080 (2)	0.6728 (7)	0.0575 (11)
H8A	0.5968	1.0053	0.7389	0.069*
H8B	0.6455	1.0117	0.5413	0.069*
C9	0.7184 (4)	0.9327 (3)	0.7093 (7)	0.0674 (13)
H9A	0.6748	0.8858	0.6947	0.081*
H9B	0.7419	0.9335	0.8365	0.081*
N2	0.8576 (13)	0.8452 (7)	0.543 (2)	0.055 (4)	0.51 (3)
H2C	0.8090	0.8071	0.5247	0.066*	0.51 (3)
C10	0.8059 (4)	0.9240 (3)	0.5831 (9)	0.0800 (18)	0.51 (3)
H10A	0.8570	0.9608	0.6296	0.096*	0.51 (3)
H10B	0.7849	0.9456	0.4641	0.096*	0.51 (3)
C11	0.9122 (17)	0.8214 (9)	0.713 (4)	0.091 (8)	0.51 (3)
H11A	0.8683	0.8257	0.8176	0.137*	0.51 (3)
H11B	0.9687	0.8569	0.7296	0.137*	0.51 (3)
H11C	0.9351	0.7661	0.7008	0.137*	0.51 (3)
C12	0.9244 (10)	0.8403 (9)	0.389 (3)	0.082 (6)	0.51 (3)
H12A	0.9523	0.7864	0.3816	0.123*	0.51 (3)
H12B	0.9775	0.8793	0.4036	0.123*	0.51 (3)
H12C	0.8883	0.8519	0.2765	0.123*	0.51 (3)
N2'	0.8443 (12)	0.8327 (9)	0.641 (4)	0.071 (5)	0.49 (3)
H2'A	0.7970	0.7970	0.5998	0.085*	0.49 (3)
C10'	0.8059 (4)	0.9240 (3)	0.5831 (9)	0.0800 (18)	0.49 (3)
H10C	0.8566	0.9650	0.6072	0.096*	0.49 (3)
H10D	0.7860	0.9265	0.4538	0.096*	0.49 (3)
C11'	0.8661 (16)	0.8106 (11)	0.824 (4)	0.101 (8)	0.49 (3)
H11D	0.8812	0.7534	0.8288	0.152*	0.49 (3)
H11E	0.8091	0.8220	0.9010	0.152*	0.49 (3)
H11F	0.9228	0.8413	0.8668	0.152*	0.49 (3)
C12'	0.9351 (17)	0.8164 (14)	0.534 (6)	0.139 (12)	0.49 (3)
H12D	0.9592	0.7626	0.5629	0.209*	0.49 (3)
H12E	0.9855	0.8559	0.5658	0.209*	0.49 (3)
H12F	0.9203	0.8199	0.4044	0.209*	0.49 (3)
H2A	0.984 (7)	0.973 (5)	0.228 (11)	0.080*	0.50
H2B	0.930 (4)	0.911 (5)	0.146 (15)	0.080*	0.50

	U11	U22	U33	U12	U13	U23
Zn1	0.0640 (3)	0.0390 (2)	0.0440 (2)	−0.00734 (18)	0.0112 (3)	−0.0061 (3)
Cl1	0.0750 (8)	0.0720 (8)	0.0768 (8)	−0.0113 (6)	0.0324 (7)	−0.0094 (6)
Cl2	0.1140 (13)	0.1004 (11)	0.0921 (11)	−0.0145 (9)	−0.0136 (10)	0.0143 (9)
N1	0.0476 (18)	0.0393 (16)	0.0478 (18)	0.0030 (14)	0.0062 (15)	−0.0058 (14)
O1	0.0774 (18)	0.0361 (12)	0.055 (2)	−0.0102 (12)	0.0190 (14)	−0.0142 (12)
O2	0.056 (4)	0.054 (4)	0.102 (6)	0.011 (3)	0.005 (4)	0.015 (4)
C1	0.052 (2)	0.0417 (19)	0.053 (2)	0.0019 (17)	0.0052 (18)	0.0038 (18)
C2	0.051 (2)	0.0308 (17)	0.058 (2)	−0.0004 (16)	0.0125 (19)	0.0006 (16)
C3	0.067 (3)	0.042 (2)	0.088 (4)	−0.008 (2)	0.011 (3)	−0.014 (2)
C4	0.064 (3)	0.048 (2)	0.123 (5)	−0.009 (2)	0.031 (3)	0.009 (3)
C5	0.079 (3)	0.072 (3)	0.100 (4)	0.002 (2)	0.041 (4)	0.019 (4)
C6	0.088 (3)	0.070 (3)	0.063 (3)	0.001 (2)	0.030 (3)	0.010 (3)
C7	0.062 (3)	0.049 (2)	0.041 (2)	−0.0007 (18)	0.0022 (19)	−0.0092 (19)
C8	0.059 (3)	0.046 (2)	0.068 (3)	−0.0111 (19)	0.001 (2)	−0.018 (2)
C9	0.098 (4)	0.043 (2)	0.061 (3)	−0.021 (2)	−0.006 (3)	−0.010 (2)
N2	0.070 (7)	0.026 (3)	0.069 (9)	−0.004 (3)	−0.020 (7)	−0.001 (5)
C10	0.078 (3)	0.037 (2)	0.124 (5)	−0.002 (2)	−0.008 (3)	−0.020 (3)
C11	0.085 (14)	0.052 (7)	0.136 (19)	0.000 (7)	−0.051 (14)	0.024 (9)
C12	0.072 (8)	0.049 (7)	0.125 (14)	0.020 (5)	0.017 (9)	−0.028 (7)
N2'	0.067 (8)	0.044 (7)	0.101 (14)	0.004 (5)	−0.006 (9)	−0.029 (8)
C10'	0.078 (3)	0.037 (2)	0.124 (5)	−0.002 (2)	−0.008 (3)	−0.020 (3)
C11'	0.094 (12)	0.051 (8)	0.16 (2)	0.014 (8)	−0.054 (13)	−0.027 (10)
C12'	0.094 (12)	0.127 (16)	0.20 (4)	0.010 (12)	0.068 (19)	−0.002 (19)

Zn1—O1	1.954 (3)	C9—C10	1.487 (8)
Zn1—N1	2.003 (4)	C9—H9A	0.9700
Zn1—Cl1	2.2182 (13)	C9—H9B	0.9700
Zn1—Cl2	2.2692 (18)	N2—C12	1.430 (19)
N1—C7	1.277 (6)	N2—C11	1.47 (2)
N1—C8	1.491 (5)	N2—C10	1.491 (15)
O1—C2	1.336 (5)	N2—H2C	0.9100
O2—H2A	0.852 (10)	C10—H10A	0.9700
O2—H2B	0.848 (10)	C10—H10B	0.9700
C1—C2	1.396 (6)	C11—H11A	0.9600
C1—C6	1.405 (6)	C11—H11B	0.9600
C1—C7	1.451 (6)	C11—H11C	0.9600
C2—C3	1.389 (6)	C12—H12A	0.9600
C3—C4	1.350 (8)	C12—H12B	0.9600
C3—H3	0.9300	C12—H12C	0.9600
C4—C5	1.368 (9)	N2'—C11'	1.40 (3)
C4—H4	0.9300	N2'—C12'	1.46 (2)
C5—C6	1.352 (7)	N2'—H2'A	0.9100
C5—H5	0.9300	C11'—H11D	0.9600
C6—H6	0.9300	C11'—H11E	0.9600
C7—H7	0.9300	C11'—H11F	0.9600
C8—C9	1.481 (7)	C12'—H12D	0.9600
C8—H8A	0.9700	C12'—H12E	0.9600
C8—H8B	0.9700	C12'—H12F	0.9600
O1—Zn1—N1	94.29 (13)	C10—C9—H9B	109.1
O1—Zn1—Cl1	113.19 (9)	H9A—C9—H9B	107.8
N1—Zn1—Cl1	111.04 (11)	C12—N2—C11	108.9 (14)
O1—Zn1—Cl2	111.03 (11)	C12—N2—C10	119.2 (9)
N1—Zn1—Cl2	111.10 (11)	C11—N2—C10	107.3 (12)
Cl1—Zn1—Cl2	114.48 (7)	C12—N2—H2C	106.9
C7—N1—C8	118.1 (4)	C11—N2—H2C	106.9
C7—N1—Zn1	121.6 (3)	C10—N2—H2C	106.9
C8—N1—Zn1	120.3 (3)	C9—C10—N2	124.4 (8)
C2—O1—Zn1	121.3 (2)	C9—C10—H10A	106.2
H2A—O2—H2B	108 (3)	N2—C10—H10A	106.2
C2—C1—C6	119.0 (4)	C9—C10—H10B	106.2
C2—C1—C7	125.4 (4)	N2—C10—H10B	106.2
C6—C1—C7	115.6 (4)	H10A—C10—H10B	106.4
O1—C2—C3	119.0 (4)	N2—C11—H11A	109.5
O1—C2—C1	123.7 (3)	N2—C11—H11B	109.5
C3—C2—C1	117.2 (4)	H11A—C11—H11B	109.5
C4—C3—C2	122.0 (5)	N2—C11—H11C	109.5
C4—C3—H3	119.0	H11A—C11—H11C	109.5
C2—C3—H3	119.0	H11B—C11—H11C	109.5
C3—C4—C5	121.4 (5)	N2—C12—H12A	109.5
C3—C4—H4	119.3	N2—C12—H12B	109.5
C5—C4—H4	119.3	H12A—C12—H12B	109.5
C6—C5—C4	118.3 (5)	N2—C12—H12C	109.5
C6—C5—H5	120.8	H12A—C12—H12C	109.5
C4—C5—H5	120.8	H12B—C12—H12C	109.5
C5—C6—C1	122.0 (6)	C11'—N2'—C12'	106.1 (19)
C5—C6—H6	119.0	C11'—N2'—H2'A	106.6
C1—C6—H6	119.0	C12'—N2'—H2'A	106.6
N1—C7—C1	126.2 (4)	N2'—C11'—H11D	109.5
N1—C7—H7	116.9	N2'—C11'—H11E	109.5
C1—C7—H7	116.9	H11D—C11'—H11E	109.5
C9—C8—N1	111.5 (4)	N2'—C11'—H11F	109.5
C9—C8—H8A	109.3	H11D—C11'—H11F	109.5
N1—C8—H8A	109.3	H11E—C11'—H11F	109.5
C9—C8—H8B	109.3	N2'—C12'—H12D	109.5
N1—C8—H8B	109.3	N2'—C12'—H12E	109.5
H8A—C8—H8B	108.0	H12D—C12'—H12E	109.5
C8—C9—C10	112.6 (4)	N2'—C12'—H12F	109.5
C8—C9—H9A	109.1	H12D—C12'—H12F	109.5
C10—C9—H9A	109.1	H12E—C12'—H12F	109.5
C8—C9—H9B	109.1

D—H···A	D—H	H···A	D···A	D—H···A
N2'—H2'A···O1i	0.91	1.88	2.762 (14)	164
N2—H2C···O1i	0.91	1.87	2.773 (12)	170

Table 1

Selected bond lengths (Å)

Zn1—O1	1.954 (3)
Zn1—N1	2.003 (4)
Zn1—Cl1	2.2182 (13)
Zn1—Cl2	2.2692 (18)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2′—H2′A⋯O1i	0.91	1.88	2.762 (14)	164
N2—H2C⋯O1i	0.91	1.87	2.773 (12)	170

Symmetry code: (i) .