{4-Bromo-2-[3-(diethyl-ammonio)propyl-imino-meth-yl]phenolato}diiodidozinc(II) methanol solvate.

In the title complex, [ZnI(2)(C(14)H(21)BrN(2)O)]·CH(3)OH, the asymmetric unit consists of a mononuclear zinc(II) complex mol-ecule and a methanol solvent mol-ecule. The compound was derived from the zwitterionic form of the Schiff base 4-bromo-2-[3-(diethyl-amino)propyl-imino-meth-yl]phenol. The Zn(II) atom is four-coordinated by the imine N and phenolate O atoms of the Schiff base ligand and by two iodide ions in a distorted tetra-hedral coordination. In the crystal structure, the methanol mol-ecules are linked to the Schiff base mol-ecules through N-H⋯O and O-H⋯O hydrogen bonds. One I atom is disordered over two positions in a 0.702 (19):0.298 (19) ratio.

Related literature

For background to 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 (2008 ▶); Zhu & Yang (2008a ▶,b ▶,c ▶); Qiu (2006a ▶,b ▶); Wei et al. (2007 ▶); Zhu et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[ZnI2(C14H21BrN2O)]·CH4O

M = 664.45

Monoclinic,

a = 10.869 (2) Å

b = 17.562 (3) Å

c = 11.377 (2) Å

β = 94.358 (3)°

V = 2165.4 (7) Å3

Z = 4

Mo Kα radiation

μ = 5.84 mm−1

T = 298 K

0.20 × 0.20 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.388, T max = 0.437

14106 measured reflections

4664 independent reflections

3499 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.105

S = 1.06

4664 reflections

225 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.75 e Å−3

Δρmin = −0.85 e Å−3

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/S1600536809038446/bx2241sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038446/bx2241Isup2.hkl

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

[ZnI2(C14H21BrN2O)]·CH4O	F(000) = 1264
Mr = 664.45	Dx = 2.038 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3253 reflections
a = 10.869 (2) Å	θ = 2.2–24.5°
b = 17.562 (3) Å	µ = 5.84 mm−1
c = 11.377 (2) Å	T = 298 K
β = 94.358 (3)°	Block, colorless
V = 2165.4 (7) Å3	0.20 × 0.20 × 0.17 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	4664 independent reflections
Radiation source: fine-focus sealed tube	3499 reflections with I > 2σ(I)
graphite	Rint = 0.041
ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→13
Tmin = 0.388, Tmax = 0.437	k = −22→22
14106 measured reflections	l = −14→13

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) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0298P)2 + 7.4538P] where P = (Fo2 + 2Fc2)/3
4664 reflections	(Δ/σ)max = 0.001
225 parameters	Δρmax = 0.75 e Å−3
8 restraints	Δρmin = −0.85 e Å−3

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	0.17105 (6)	0.26943 (4)	−0.06556 (7)	0.0380 (2)
I1	0.13989 (4)	0.14098 (3)	−0.17051 (4)	0.05239 (16)
I2	0.1766 (2)	0.39343 (11)	−0.1861 (2)	0.0541 (8)	0.702 (19)
I2'	0.1771 (8)	0.3793 (9)	−0.2109 (16)	0.118 (2)	0.298 (19)
Br1	0.19879 (8)	0.49547 (5)	0.46762 (7)	0.0630 (2)
O1	0.0560 (4)	0.2904 (3)	0.0548 (4)	0.0443 (11)
O2	0.8239 (4)	0.2628 (3)	−0.0180 (5)	0.0546 (13)
H2	0.8982	0.2714	−0.0142	0.082*
N1	0.3188 (4)	0.2626 (3)	0.0547 (4)	0.0311 (11)
N2	0.6505 (5)	0.3665 (3)	−0.0945 (5)	0.0383 (12)
C1	0.2134 (5)	0.3368 (3)	0.1971 (5)	0.0301 (13)
C2	0.0899 (5)	0.3330 (4)	0.1466 (5)	0.0338 (14)
C3	0.0011 (6)	0.3764 (4)	0.2014 (6)	0.0414 (16)
H3	−0.0810	0.3733	0.1723	0.050*
C4	0.0311 (6)	0.4231 (4)	0.2955 (6)	0.0431 (16)
H4	−0.0297	0.4516	0.3284	0.052*
C5	0.1523 (6)	0.4276 (4)	0.3417 (6)	0.0400 (15)
C6	0.2417 (6)	0.3841 (3)	0.2958 (5)	0.0355 (14)
H6	0.3220	0.3857	0.3302	0.043*
C7	0.3161 (5)	0.2950 (3)	0.1550 (5)	0.0340 (14)
H7	0.3870	0.2914	0.2059	0.041*
C8	0.4322 (5)	0.2223 (3)	0.0264 (6)	0.0369 (14)
H8A	0.4115	0.1707	0.0018	0.044*
H8B	0.4888	0.2195	0.0965	0.044*
C9	0.4942 (5)	0.2625 (3)	−0.0704 (6)	0.0349 (14)
H9A	0.4367	0.2659	−0.1397	0.042*
H9B	0.5644	0.2326	−0.0911	0.042*
C10	0.5383 (5)	0.3429 (4)	−0.0348 (6)	0.0395 (15)
H10A	0.4722	0.3789	−0.0547	0.047*
H10B	0.5568	0.3446	0.0499	0.047*
C11	0.6305 (6)	0.3689 (4)	−0.2268 (6)	0.0506 (18)
H11A	0.5991	0.3198	−0.2544	0.061*
H11B	0.7096	0.3766	−0.2591	0.061*
C12	0.5423 (8)	0.4303 (5)	−0.2747 (8)	0.074 (3)
H12A	0.4639	0.4237	−0.2425	0.111*
H12B	0.5320	0.4265	−0.3590	0.111*
H12C	0.5753	0.4794	−0.2528	0.111*
C13	0.7034 (6)	0.4385 (4)	−0.0402 (7)	0.0545 (19)
H13A	0.7097	0.4334	0.0450	0.065*
H13B	0.6478	0.4804	−0.0608	0.065*
C14	0.8299 (7)	0.4567 (5)	−0.0810 (8)	0.064 (2)
H14A	0.8834	0.4137	−0.0666	0.096*
H14B	0.8637	0.5000	−0.0384	0.096*
H14C	0.8225	0.4679	−0.1638	0.096*
C15	0.7989 (8)	0.2122 (6)	0.0666 (8)	0.075 (3)
H15A	0.8652	0.1762	0.0773	0.113*
H15B	0.7236	0.1858	0.0433	0.113*
H15C	0.7900	0.2387	0.1393	0.113*
H2A	0.705 (6)	0.329 (3)	−0.073 (7)	0.080*

	U11	U22	U33	U12	U13	U23
Zn1	0.0302 (4)	0.0493 (4)	0.0342 (4)	0.0016 (3)	0.0001 (3)	−0.0028 (3)
I1	0.0523 (3)	0.0513 (3)	0.0513 (3)	0.0029 (2)	−0.0108 (2)	−0.0073 (2)
I2	0.0678 (10)	0.0487 (8)	0.0474 (9)	0.0168 (6)	0.0150 (8)	0.0091 (5)
I2'	0.130 (4)	0.100 (4)	0.115 (5)	−0.016 (3)	−0.036 (3)	0.035 (4)
Br1	0.0832 (6)	0.0568 (5)	0.0503 (5)	0.0002 (4)	0.0141 (4)	−0.0192 (4)
O1	0.026 (2)	0.065 (3)	0.042 (3)	−0.005 (2)	0.0035 (19)	−0.009 (2)
O2	0.032 (2)	0.059 (3)	0.071 (4)	−0.006 (2)	−0.006 (2)	0.006 (3)
N1	0.024 (2)	0.035 (3)	0.035 (3)	0.0020 (19)	0.005 (2)	−0.002 (2)
N2	0.034 (3)	0.040 (3)	0.042 (3)	−0.003 (2)	0.009 (2)	0.002 (3)
C1	0.025 (3)	0.032 (3)	0.033 (3)	−0.003 (2)	0.009 (2)	0.003 (3)
C2	0.029 (3)	0.041 (4)	0.032 (3)	−0.002 (2)	0.010 (3)	0.005 (3)
C3	0.030 (3)	0.048 (4)	0.047 (4)	0.005 (3)	0.010 (3)	0.009 (3)
C4	0.051 (4)	0.040 (4)	0.041 (4)	0.008 (3)	0.020 (3)	0.008 (3)
C5	0.055 (4)	0.034 (3)	0.032 (4)	0.000 (3)	0.011 (3)	−0.003 (3)
C6	0.038 (3)	0.042 (4)	0.027 (3)	−0.003 (3)	0.006 (3)	−0.002 (3)
C7	0.024 (3)	0.041 (3)	0.036 (4)	−0.003 (2)	−0.003 (3)	0.005 (3)
C8	0.030 (3)	0.032 (3)	0.049 (4)	0.004 (2)	0.006 (3)	−0.003 (3)
C9	0.024 (3)	0.038 (3)	0.043 (4)	0.003 (2)	0.007 (3)	−0.011 (3)
C10	0.035 (3)	0.045 (4)	0.040 (4)	0.000 (3)	0.013 (3)	−0.006 (3)
C11	0.049 (4)	0.058 (5)	0.045 (4)	−0.006 (3)	0.011 (3)	0.003 (4)
C12	0.070 (5)	0.076 (6)	0.074 (6)	−0.002 (4)	−0.003 (5)	0.026 (5)
C13	0.051 (4)	0.043 (4)	0.069 (5)	−0.009 (3)	0.005 (4)	−0.007 (4)
C14	0.054 (4)	0.061 (5)	0.077 (6)	−0.019 (4)	0.008 (4)	0.011 (4)
C15	0.055 (5)	0.098 (7)	0.071 (6)	−0.005 (5)	−0.002 (4)	0.008 (5)

Zn1—O1	1.958 (4)	C7—H7	0.9300
Zn1—N1	2.032 (5)	C8—C9	1.510 (9)
Zn1—I2'	2.545 (6)	C8—H8A	0.9700
Zn1—I1	2.5627 (9)	C8—H8B	0.9700
Zn1—I2	2.5768 (18)	C9—C10	1.536 (8)
Br1—C5	1.902 (6)	C9—H9A	0.9700
O1—C2	1.315 (7)	C9—H9B	0.9700
O2—C15	1.353 (9)	C10—H10A	0.9700
O2—H2	0.8200	C10—H10B	0.9700
N1—C7	1.278 (7)	C11—C12	1.516 (10)
N1—C8	1.478 (7)	C11—H11A	0.9700
N2—C10	1.499 (8)	C11—H11B	0.9700
N2—C13	1.503 (8)	C12—H12A	0.9600
N2—C11	1.506 (9)	C12—H12B	0.9600
N2—H2A	0.91 (6)	C12—H12C	0.9600
C1—C6	1.412 (8)	C13—C14	1.519 (9)
C1—C2	1.421 (8)	C13—H13A	0.9700
C1—C7	1.447 (8)	C13—H13B	0.9700
C2—C3	1.411 (8)	C14—H14A	0.9600
C3—C4	1.368 (9)	C14—H14B	0.9600
C3—H3	0.9300	C14—H14C	0.9600
C4—C5	1.383 (9)	C15—H15A	0.9600
C4—H4	0.9300	C15—H15B	0.9600
C5—C6	1.370 (8)	C15—H15C	0.9600
C6—H6	0.9300
O1—Zn1—N1	93.11 (18)	N1—C8—H8B	109.4
O1—Zn1—I2'	111.2 (5)	C9—C8—H8B	109.4
N1—Zn1—I2'	115.1 (3)	H8A—C8—H8B	108.0
O1—Zn1—I1	115.00 (13)	C8—C9—C10	112.7 (5)
N1—Zn1—I1	109.36 (14)	C8—C9—H9A	109.1
I2'—Zn1—I1	111.9 (5)	C10—C9—H9A	109.1
O1—Zn1—I2	104.79 (15)	C8—C9—H9B	109.1
N1—Zn1—I2	111.03 (15)	C10—C9—H9B	109.1
I2'—Zn1—I2	8.4 (5)	H9A—C9—H9B	107.8
I1—Zn1—I2	120.23 (7)	N2—C10—C9	112.5 (5)
C2—O1—Zn1	120.5 (4)	N2—C10—H10A	109.1
C15—O2—H2	109.5	C9—C10—H10A	109.1
C7—N1—C8	118.9 (5)	N2—C10—H10B	109.1
C7—N1—Zn1	120.3 (4)	C9—C10—H10B	109.1
C8—N1—Zn1	120.7 (4)	H10A—C10—H10B	107.8
C10—N2—C13	110.2 (5)	N2—C11—C12	114.7 (6)
C10—N2—C11	113.6 (5)	N2—C11—H11A	108.6
C13—N2—C11	114.2 (5)	C12—C11—H11A	108.6
C10—N2—H2A	103 (5)	N2—C11—H11B	108.6
C13—N2—H2A	106 (5)	C12—C11—H11B	108.6
C11—N2—H2A	109 (5)	H11A—C11—H11B	107.6
C6—C1—C2	119.4 (5)	C11—C12—H12A	109.5
C6—C1—C7	115.8 (5)	C11—C12—H12B	109.5
C2—C1—C7	124.9 (5)	H12A—C12—H12B	109.5
O1—C2—C3	119.9 (5)	C11—C12—H12C	109.5
O1—C2—C1	123.1 (5)	H12A—C12—H12C	109.5
C3—C2—C1	116.9 (6)	H12B—C12—H12C	109.5
C4—C3—C2	122.6 (6)	N2—C13—C14	112.2 (6)
C4—C3—H3	118.7	N2—C13—H13A	109.2
C2—C3—H3	118.7	C14—C13—H13A	109.2
C3—C4—C5	119.7 (6)	N2—C13—H13B	109.2
C3—C4—H4	120.2	C14—C13—H13B	109.2
C5—C4—H4	120.2	H13A—C13—H13B	107.9
C6—C5—C4	120.4 (6)	C13—C14—H14A	109.5
C6—C5—Br1	118.8 (5)	C13—C14—H14B	109.5
C4—C5—Br1	120.8 (5)	H14A—C14—H14B	109.5
C5—C6—C1	120.9 (6)	C13—C14—H14C	109.5
C5—C6—H6	119.5	H14A—C14—H14C	109.5
C1—C6—H6	119.5	H14B—C14—H14C	109.5
N1—C7—C1	126.3 (5)	O2—C15—H15A	109.5
N1—C7—H7	116.9	O2—C15—H15B	109.5
C1—C7—H7	116.9	H15A—C15—H15B	109.5
N1—C8—C9	111.1 (5)	O2—C15—H15C	109.5
N1—C8—H8A	109.4	H15A—C15—H15C	109.5
C9—C8—H8A	109.4	H15B—C15—H15C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1i	0.82	1.86	2.640 (6)	158
N2—H2A···O2	0.91 (6)	1.81 (6)	2.716 (7)	173 (8)

Table 1

Selected geometric parameters (Å, °)

Zn1—O1	1.958 (4)
Zn1—N1	2.032 (5)
Zn1—I2′	2.545 (6)
Zn1—I1	2.5627 (9)
Zn1—I2	2.5768 (18)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1i	0.82	1.86	2.640 (6)	158
N2—H2A⋯O2	0.91 (6)	1.81 (6)	2.716 (7)	173 (8)

Symmetry code: (i) .