metal-organic compounds
Dibromido{2-[2-(piperidinium-1-yl)ethyliminomethyl]phenolato}zinc(II) monohydrate
aDepartment of Chemistry, Huainan Normal College, Huainan 232001, People's Republic of China
*Correspondence e-mail: huainanweiyijun@163.com
The 2(C14H20N2O)]·H2O, consists of a mononuclear Schiff base zinc(II) complex molecule and a solvent water molecule. The ZnII 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 molecules are linked through intermolecular O—H⋯Br and O—H⋯O hydrogen bonds, forming chains running along the b axis.
of the title compound, [ZnBrRelated literature
For the background to 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).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); 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.
Supporting information
10.1107/S1600536808015730/sj2508sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808015730/sj2508Isup2.hkl
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.
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 Uiso(H) values set at 1.2Ueq(C).
Data collection: SMART (Bruker, 2002); cell
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).[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) Å3 |
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 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0405P)2 + 0.3508P] where P = (Fo2 + 2Fc2)/3 |
3983 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.72 e Å−3 |
4 restraints | Δρmin = −0.55 e Å−3 |
[ZnBr2(C14H20N2O)]·H2O | γ = 67.571 (2)° |
Mr = 475.53 | V = 901.8 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2997 (18) Å | Mo Kα radiation |
b = 10.1776 (17) Å | µ = 5.80 mm−1 |
c = 11.1667 (18) Å | T = 298 K |
α = 71.510 (2)° | 0.20 × 0.20 × 0.18 mm |
β = 71.215 (2)° |
Bruker SMART 1000 CCD area-detector diffractometer | 3983 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2891 reflections with I > 2σ(I) |
Tmin = 0.390, Tmax = 0.422 | Rint = 0.016 |
5468 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 4 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.72 e Å−3 |
3983 reflections | Δρmin = −0.55 e Å−3 |
199 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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 |
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···Br2i | 0.85 (4) | 2.57 (4) | 3.399 (3) | 165 (4) |
O2—H2B···O1ii | 0.86 (3) | 1.93 (4) | 2.762 (4) | 165 (5) |
Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [ZnBr2(C14H20N2O)]·H2O |
Mr | 475.53 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 9.2997 (18), 10.1776 (17), 11.1667 (18) |
α, β, γ (°) | 71.510 (2), 71.215 (2), 67.571 (2) |
V (Å3) | 901.8 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 5.80 |
Crystal size (mm) | 0.20 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.390, 0.422 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5468, 3983, 2891 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.091, 1.03 |
No. of reflections | 3983 |
No. of parameters | 199 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.72, −0.55 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Zn1—O1 | 1.936 (2) | Zn1—Br1 | 2.3417 (7) |
Zn1—N1 | 2.024 (3) | Zn1—Br2 | 2.3991 (7) |
O1—Zn1—N1 | 93.91 (11) | O1—Zn1—Br2 | 109.78 (8) |
O1—Zn1—Br1 | 116.12 (8) | N1—Zn1—Br2 | 108.84 (9) |
N1—Zn1—Br1 | 113.04 (8) | Br1—Zn1—Br2 | 113.42 (2) |
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···Br2i | 0.85 (4) | 2.57 (4) | 3.399 (3) | 165 (4) |
O2—H2B···O1ii | 0.86 (3) | 1.93 (4) | 2.762 (4) | 165 (5) |
Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y, −z. |
Acknowledgements
The authors thank the Education Office of Anhui Province, People's Republic of China, for research grant No. KJ2007A126ZC.
References
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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 ZnII 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).