Dibromido{2-[2-(piperidinium-1-yl)ethyl­imino­meth­yl]phenolato}zinc(II) monohydrate

The asymmetric unit of the title compound, [ZnBr₂(C₁₄H₂₀N₂O)]·H₂O, consists of a mononuclear Schiff base zinc(II) complex mol­ecule and a solvent water mol­ecule. The Zn^II atom is four-coordinated in an approximately tetra­hedral geometry, binding to the imine N and phenolate O atoms of the neutral zwitterionic Schiff base ligand and to two terminal Br⁻ anions. In the crystal structure, mol­ecules are linked through inter­molecular O—H...Br and O—H...O hydrogen bonds, forming chains running along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.038
• wR factor = 0.091
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.53 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.83
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.835
            Tmax scaled      0.352 Tmin scaled      0.326
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Zinc(II) complexes derived from Schiff base ligands have been studied extensively due to their interesting structures and wide applications (Lacroix et al., 1996; Chisholm et al., 2001; Jian et al., 2004; Tatar et al., 2002; Bhosekar et al., 2006). Recently, we have reported two Schiff base zinc(II) complexes with bromide ligands (Wei et al., 2007; Zhu et al., 2007). As a continuation of our work on the structures of such complexes, we report herein the crystal structure of the new title complex, (I), which is isostructural with the zinc(II) complex with chloride ligands (Zhang et al., 2008).

The tetrahedral coordination sphere of Zn^II atom in (I) is formed by the imine N and phenolate O atoms of the Schiff base ligand and by two terminal Br^- anions (Fig. 1). The coordinate bond distances (Table 1) are typical and comparable with the values in other similar zinc(II) complexes (Peng & Hou, 2006; Peng et al., 2006; Ma, Gu et al., 2006; Ma, Lv et al., 2006). The O1—Zn1—N1 and O1—Zn1—Br1 bond angles deviate most from ideal tetrahedral geometry with values of 93.91 (11) and 116.12 (8)°, respectively. The other angles in the coordination sphere are in the range 108.84 (9)–113.42 (2)° (Table 1).

In the crystal structure of (I), molecules are linked through intermolecular O—H···Br and O—H···O hydrogen bonds (Table 2), forming chains running along the b axis (Fig. 2).

Related literature

For the background of Schiff base zinc(II) complexes, see: Bhosekar et al. (2006); Chisholm et al. (2001); Jian et al. (2004); Lacroix et al. (1996); Tatar et al. (2002). For related structures, see: Ma, Gu et al. (2006); Ma, Lv et al. (2006); Peng & Hou (2006); Peng et al. (2006); Wei et al. (2007); Zhang et al. (2008); Zhu et al. (2007).

S2. Experimental

Compound (I) was obtained by stirring of salicylaldehyde (0.1 mmol, 12.2 mg), 2-piperidin-1-ylethylamine (0.1 mmol, 12.8 mg), and zinc(II) bromide (0.1 mmol, 22.5 mg) in methanol (20 ml) for 30 min at room temperature. The reaction mixture was fitered. Yellow block-shaped single crystals suitable for X-ray diffraction formed from the filtrate after one day.

S3. Refinement

Atoms H2, H2A and H2B were located in a difference Fourier map and refined isotropically, with the N—H, O—H, and H···H distances restrained to 0.90 (1), 0.85 (1), and 1.37 (2) Å, respectively. Other H atom positions were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding, with U_iso(H) values set at 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), shown with 30% probability displacement ellipsoids.
	Fig. 2. Molecular packing of (I), viewed along the a axis. Intermolecular hydrogen bonds are shown as dashed lines.

Dibromido{2-[2-(piperidinium-1-yl)ethyliminomethyl]phenolato}zinc(II) monohydrate

Crystal data

[ZnBr2(C14H20N2O)]·H2O	Z = 2
Mr = 475.53	F(000) = 472
Triclinic, P1	Dx = 1.751 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2997 (18) Å	Cell parameters from 1797 reflections
b = 10.1776 (17) Å	θ = 2.2–25.4°
c = 11.1667 (18) Å	µ = 5.80 mm^−1
α = 71.510 (2)°	T = 298 K
β = 71.215 (2)°	Block, yellow
γ = 67.571 (2)°	0.20 × 0.20 × 0.18 mm
V = 901.8 (3) Å^3

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	3983 independent reflections
Radiation source: fine-focus sealed tube	2891 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→9
Tmin = 0.390, Tmax = 0.422	k = −13→12
5468 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0405P)^2 + 0.3508P] where P = (Fo^2 + 2Fc^2)/3
3983 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 0.72 e Å^−3
4 restraints	Δρmin = −0.55 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.82333 (5)	−0.20793 (4)	0.11443 (4)	0.03909 (13)
Br1	0.93736 (6)	−0.24561 (5)	0.28619 (4)	0.06059 (15)
Br2	0.56849 (5)	−0.24885 (5)	0.18395 (4)	0.05682 (14)
O1	0.9582 (3)	−0.3089 (3)	−0.0226 (2)	0.0451 (6)
O2	0.7190 (3)	0.4568 (3)	0.0481 (3)	0.0515 (7)
N1	0.8013 (4)	−0.0074 (3)	−0.0039 (3)	0.0406 (7)
N2	0.5644 (4)	0.2574 (3)	0.2120 (3)	0.0420 (7)
C1	0.8738 (4)	−0.1069 (4)	−0.1951 (3)	0.0378 (8)
C2	0.9415 (4)	−0.2555 (4)	−0.1434 (3)	0.0379 (8)
C3	0.9993 (5)	−0.3518 (4)	−0.2277 (4)	0.0451 (9)
H3	1.0451	−0.4508	−0.1960	0.054*
C4	0.9897 (5)	−0.3031 (5)	−0.3550 (4)	0.0555 (11)
H4	1.0283	−0.3696	−0.4077	0.067*
C5	0.9234 (6)	−0.1561 (5)	−0.4069 (4)	0.0594 (12)
H5	0.9176	−0.1236	−0.4935	0.071*
C6	0.8668 (5)	−0.0600 (5)	−0.3273 (4)	0.0513 (10)
H6	0.8225	0.0387	−0.3611	0.062*
C7	0.8178 (4)	0.0091 (4)	−0.1258 (4)	0.0409 (8)
H7	0.7915	0.1043	−0.1745	0.049*
C8	0.7581 (5)	0.1241 (4)	0.0443 (4)	0.0552 (11)
H8A	0.7560	0.2080	−0.0279	0.066*
H8B	0.8374	0.1140	0.0884	0.066*
C9	0.5982 (5)	0.1467 (5)	0.1357 (5)	0.0633 (12)
H9A	0.5928	0.0547	0.1952	0.076*
H9B	0.5166	0.1790	0.0870	0.076*
C10	0.3889 (5)	0.3298 (5)	0.2454 (5)	0.0594 (11)
H10A	0.3359	0.2573	0.2962	0.071*
H10B	0.3502	0.3761	0.1664	0.071*
C11	0.3486 (6)	0.4435 (6)	0.3223 (6)	0.0836 (17)
H11A	0.3915	0.5216	0.2677	0.100*
H11B	0.2334	0.4848	0.3476	0.100*
C12	0.4153 (7)	0.3795 (7)	0.4409 (6)	0.094 (2)
H12A	0.3925	0.4556	0.4853	0.113*
H12B	0.3651	0.3077	0.4997	0.113*
C13	0.5908 (6)	0.3095 (7)	0.4042 (5)	0.0835 (17)
H13A	0.6325	0.2653	0.4819	0.100*
H13B	0.6414	0.3830	0.3510	0.100*
C14	0.6302 (6)	0.1951 (5)	0.3306 (5)	0.0701 (13)
H14A	0.7453	0.1528	0.3059	0.084*
H14B	0.5862	0.1179	0.3862	0.084*
H2B	0.8210 (13)	0.423 (5)	0.029 (5)	0.080*
H2A	0.699 (4)	0.524 (4)	0.086 (4)	0.080*
H2	0.611 (5)	0.327 (4)	0.168 (4)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0453 (3)	0.0381 (2)	0.0358 (2)	−0.01543 (19)	−0.00516 (18)	−0.01193 (18)
Br1	0.0684 (3)	0.0803 (3)	0.0459 (2)	−0.0337 (3)	−0.0178 (2)	−0.0131 (2)
Br2	0.0462 (3)	0.0559 (3)	0.0720 (3)	−0.0217 (2)	−0.0069 (2)	−0.0184 (2)
O1	0.0509 (16)	0.0409 (14)	0.0377 (14)	−0.0066 (12)	−0.0070 (12)	−0.0138 (11)
O2	0.0503 (17)	0.0479 (16)	0.0572 (18)	−0.0181 (14)	−0.0049 (14)	−0.0170 (13)
N1	0.0497 (19)	0.0346 (16)	0.0412 (17)	−0.0198 (14)	−0.0023 (14)	−0.0134 (13)
N2	0.0438 (19)	0.0411 (18)	0.0415 (17)	−0.0163 (15)	−0.0001 (14)	−0.0157 (14)
C1	0.041 (2)	0.041 (2)	0.0329 (18)	−0.0188 (17)	−0.0024 (15)	−0.0099 (15)
C2	0.033 (2)	0.044 (2)	0.0387 (19)	−0.0167 (16)	−0.0012 (15)	−0.0128 (16)
C3	0.046 (2)	0.044 (2)	0.049 (2)	−0.0169 (18)	−0.0028 (18)	−0.0200 (18)
C4	0.059 (3)	0.071 (3)	0.049 (2)	−0.030 (2)	0.001 (2)	−0.031 (2)
C5	0.071 (3)	0.081 (3)	0.034 (2)	−0.040 (3)	−0.002 (2)	−0.013 (2)
C6	0.057 (3)	0.054 (2)	0.042 (2)	−0.023 (2)	−0.0084 (19)	−0.0033 (18)
C7	0.039 (2)	0.0348 (19)	0.047 (2)	−0.0154 (16)	−0.0043 (17)	−0.0070 (16)
C8	0.064 (3)	0.043 (2)	0.059 (3)	−0.022 (2)	0.001 (2)	−0.0222 (19)
C9	0.061 (3)	0.063 (3)	0.076 (3)	−0.026 (2)	0.001 (2)	−0.037 (2)
C10	0.046 (3)	0.062 (3)	0.074 (3)	−0.018 (2)	−0.011 (2)	−0.022 (2)
C11	0.040 (3)	0.071 (3)	0.140 (5)	−0.011 (2)	0.002 (3)	−0.056 (4)
C12	0.083 (4)	0.141 (5)	0.084 (4)	−0.056 (4)	0.023 (3)	−0.073 (4)
C13	0.077 (4)	0.140 (5)	0.050 (3)	−0.045 (4)	−0.013 (3)	−0.030 (3)
C14	0.055 (3)	0.074 (3)	0.065 (3)	−0.011 (3)	−0.019 (2)	−0.002 (3)

Geometric parameters (Å, º)

Zn1—O1	1.936 (2)	C5—H5	0.9300
Zn1—N1	2.024 (3)	C6—H6	0.9300
Zn1—Br1	2.3417 (7)	C7—H7	0.9300
Zn1—Br2	2.3991 (7)	C8—C9	1.488 (6)
O1—C2	1.321 (4)	C8—H8A	0.9700
O2—H2B	0.86 (3)	C8—H8B	0.9700
O2—H2A	0.85 (4)	C9—H9A	0.9700
N1—C7	1.282 (5)	C9—H9B	0.9700
N1—C8	1.467 (4)	C10—C11	1.519 (6)
N2—C10	1.487 (5)	C10—H10A	0.9700
N2—C14	1.491 (5)	C10—H10B	0.9700
N2—C9	1.503 (5)	C11—C12	1.496 (8)
N2—H2	0.90 (4)	C11—H11A	0.9700
C1—C2	1.404 (5)	C11—H11B	0.9700
C1—C6	1.415 (5)	C12—C13	1.485 (7)
C1—C7	1.454 (5)	C12—H12A	0.9700
C2—C3	1.411 (5)	C12—H12B	0.9700
C3—C4	1.370 (6)	C13—C14	1.502 (7)
C3—H3	0.9300	C13—H13A	0.9700
C4—C5	1.389 (6)	C13—H13B	0.9700
C4—H4	0.9300	C14—H14A	0.9700
C5—C6	1.371 (6)	C14—H14B	0.9700
O1—Zn1—N1	93.91 (11)	C9—C8—H8A	109.7
O1—Zn1—Br1	116.12 (8)	N1—C8—H8B	109.7
N1—Zn1—Br1	113.04 (8)	C9—C8—H8B	109.7
O1—Zn1—Br2	109.78 (8)	H8A—C8—H8B	108.2
N1—Zn1—Br2	108.84 (9)	C8—C9—N2	112.2 (3)
Br1—Zn1—Br2	113.42 (2)	C8—C9—H9A	109.2
C2—O1—Zn1	121.6 (2)	N2—C9—H9A	109.2
H2B—O2—H2A	105 (2)	C8—C9—H9B	109.2
C7—N1—C8	117.3 (3)	N2—C9—H9B	109.2
C7—N1—Zn1	119.8 (2)	H9A—C9—H9B	107.9
C8—N1—Zn1	122.8 (2)	N2—C10—C11	110.8 (3)
C10—N2—C14	111.0 (3)	N2—C10—H10A	109.5
C10—N2—C9	108.7 (3)	C11—C10—H10A	109.5
C14—N2—C9	113.6 (3)	N2—C10—H10B	109.5
C10—N2—H2	108 (3)	C11—C10—H10B	109.5
C14—N2—H2	102 (3)	H10A—C10—H10B	108.1
C9—N2—H2	113 (3)	C12—C11—C10	111.6 (4)
C2—C1—C6	119.5 (3)	C12—C11—H11A	109.3
C2—C1—C7	125.2 (3)	C10—C11—H11A	109.3
C6—C1—C7	115.1 (3)	C12—C11—H11B	109.3
O1—C2—C1	123.9 (3)	C10—C11—H11B	109.3
O1—C2—C3	118.6 (3)	H11A—C11—H11B	108.0
C1—C2—C3	117.4 (3)	C13—C12—C11	110.0 (4)
C4—C3—C2	121.6 (4)	C13—C12—H12A	109.7
C4—C3—H3	119.2	C11—C12—H12A	109.7
C2—C3—H3	119.2	C13—C12—H12B	109.7
C3—C4—C5	121.2 (4)	C11—C12—H12B	109.7
C3—C4—H4	119.4	H12A—C12—H12B	108.2
C5—C4—H4	119.4	C12—C13—C14	110.9 (4)
C6—C5—C4	118.4 (4)	C12—C13—H13A	109.5
C6—C5—H5	120.8	C14—C13—H13A	109.5
C4—C5—H5	120.8	C12—C13—H13B	109.5
C5—C6—C1	121.8 (4)	C14—C13—H13B	109.5
C5—C6—H6	119.1	H13A—C13—H13B	108.0
C1—C6—H6	119.1	N2—C14—C13	111.4 (4)
N1—C7—C1	126.2 (3)	N2—C14—H14A	109.4
N1—C7—H7	116.9	C13—C14—H14A	109.4
C1—C7—H7	116.9	N2—C14—H14B	109.4
N1—C8—C9	109.9 (3)	C13—C14—H14B	109.4
N1—C8—H8A	109.7	H14A—C14—H14B	108.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.90 (4)	1.89 (4)	2.777 (4)	169 (4)
O2—H2A···Br2^i	0.85 (4)	2.57 (4)	3.399 (3)	165 (4)
O2—H2B···O1^ii	0.86 (3)	1.93 (4)	2.762 (4)	165 (5)

Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y, −z.