metal-organic compounds
Dichlorido{2-[2-(piperidin-1-yl)ethyliminomethyl]phenolato}zinc(II) monohydrate
aSchool of Pharmaceutical Sciences, China Medical University, Shenyang 110001, People's Republic of China, and bNortheast Pharmaceutical Group Co. Ltd, Shenyang 110026, People's Republic of China
*Correspondence e-mail: lnsyzdf@sohu.com
In the title mononuclear zinc(II) complex, [ZnCl2(C14H20N2O)]·H2O, the ZnII atom is four-coordinated by the phenolate O and imine N atoms of the Schiff base ligand and by two Cl atoms in a tetrahedral geometry. In the O—H⋯Cl, O—H⋯O and N—H⋯O hydrogen bonds involving the water molecules bridge adjacent complexes into a ladder-like structure running along the c axis.
Related literature
For general background on Schiff base complexes, see: Kawamoto et al. (2008); Tomat et al. (2007). For biological properties of Schiff base compounds, see: Abd-Elzaher (2004); Iqbal et al. (2005); Osowole et al. (2005); Raman & Thangaraja (2005). For related structures, see: Ali et al. (2008); Li (2007); Tatar et al. (2002); Wang (2007).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); 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
10.1107/S1600536808014311/ci2598sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808014311/ci2598Isup2.hkl
A mixture of salicylaldehyde (0.1 mmol, 12.2 mg), 2-piperidin-1-ylethylamine (0.1 mmol, 12.8 mg) and ZnCl2 (0.1 mmol, 13.6 mg) in methanol was stirred for 30 min at room temperature to give a yellow solution. After keeping the solution in air for 12 d, yellow block-shaped crystals were formed.
Atoms H2A, H2B and H2C were located from a difference Fourier map and refined isotropically, with O-H, N-H, and H···H distances restrained to 0.85 (1), 0.90 (1), and 1.37 (2) Å, respectively. The remaining H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C-H = 0.93 or 0.97 Å and Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).[ZnCl2(C14H20N2O)]·H2O | F(000) = 800 |
Mr = 386.61 | Dx = 1.504 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2461 reflections |
a = 9.1860 (18) Å | θ = 2.4–25.0° |
b = 19.875 (4) Å | µ = 1.76 mm−1 |
c = 9.966 (2) Å | T = 298 K |
β = 110.20 (3)° | Block, yellow |
V = 1707.6 (7) Å3 | 0.20 × 0.18 × 0.17 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3882 independent reflections |
Radiation source: fine-focus sealed tube | 2685 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −11→11 |
Tmin = 0.720, Tmax = 0.755 | k = −25→25 |
14151 measured reflections | l = −12→12 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0472P)2] where P = (Fo2 + 2Fc2)/3 |
3882 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.49 e Å−3 |
4 restraints | Δρmin = −0.59 e Å−3 |
[ZnCl2(C14H20N2O)]·H2O | V = 1707.6 (7) Å3 |
Mr = 386.61 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.1860 (18) Å | µ = 1.76 mm−1 |
b = 19.875 (4) Å | T = 298 K |
c = 9.966 (2) Å | 0.20 × 0.18 × 0.17 mm |
β = 110.20 (3)° |
Bruker SMART CCD area-detector diffractometer | 3882 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2685 reflections with I > 2σ(I) |
Tmin = 0.720, Tmax = 0.755 | Rint = 0.056 |
14151 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 4 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.49 e Å−3 |
3882 reflections | Δρmin = −0.59 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 | 0.30417 (4) | 0.444609 (17) | 0.67776 (4) | 0.03531 (13) | |
Cl1 | 0.53819 (11) | 0.40618 (5) | 0.68728 (10) | 0.0547 (3) | |
Cl2 | 0.13426 (12) | 0.36691 (5) | 0.68208 (10) | 0.0566 (3) | |
O1 | 0.3309 (3) | 0.51454 (10) | 0.8185 (2) | 0.0466 (6) | |
O2 | 0.2673 (3) | 0.48851 (13) | 0.0627 (3) | 0.0540 (7) | |
N1 | 0.2172 (3) | 0.50529 (13) | 0.5054 (2) | 0.0330 (6) | |
N2 | 0.1661 (3) | 0.38887 (13) | 0.1946 (3) | 0.0322 (6) | |
C6 | 0.2940 (3) | 0.60705 (15) | 0.6525 (3) | 0.0349 (7) | |
C1 | 0.3412 (4) | 0.57904 (16) | 0.7920 (3) | 0.0360 (7) | |
C2 | 0.3972 (4) | 0.62356 (17) | 0.9080 (3) | 0.0423 (8) | |
H2 | 0.4311 | 0.6063 | 1.0004 | 0.051* | |
C3 | 0.4035 (4) | 0.69155 (18) | 0.8893 (4) | 0.0494 (9) | |
H3 | 0.4404 | 0.7197 | 0.9684 | 0.059* | |
C4 | 0.3549 (4) | 0.71867 (18) | 0.7520 (4) | 0.0553 (10) | |
H4 | 0.3586 | 0.7649 | 0.7392 | 0.066* | |
C5 | 0.3019 (4) | 0.67719 (17) | 0.6368 (4) | 0.0481 (9) | |
H5 | 0.2702 | 0.6956 | 0.5454 | 0.058* | |
C7 | 0.2314 (4) | 0.56952 (15) | 0.5204 (3) | 0.0351 (7) | |
H7 | 0.1976 | 0.5948 | 0.4367 | 0.042* | |
C8 | 0.1417 (4) | 0.48009 (16) | 0.3607 (3) | 0.0420 (8) | |
H8A | 0.1519 | 0.5126 | 0.2919 | 0.050* | |
H8B | 0.0321 | 0.4730 | 0.3428 | 0.050* | |
C9 | 0.2177 (4) | 0.41441 (16) | 0.3450 (3) | 0.0379 (8) | |
H9A | 0.3293 | 0.4206 | 0.3789 | 0.045* | |
H9B | 0.1945 | 0.3807 | 0.4051 | 0.045* | |
C10 | 0.2450 (4) | 0.32330 (17) | 0.1916 (3) | 0.0414 (8) | |
H10A | 0.2136 | 0.2904 | 0.2482 | 0.050* | |
H10B | 0.3564 | 0.3292 | 0.2339 | 0.050* | |
C11 | 0.2048 (4) | 0.29752 (17) | 0.0403 (3) | 0.0454 (9) | |
H11A | 0.2538 | 0.2542 | 0.0419 | 0.054* | |
H11B | 0.2446 | 0.3284 | −0.0141 | 0.054* | |
C12 | 0.0304 (4) | 0.29045 (18) | −0.0318 (4) | 0.0507 (9) | |
H12A | 0.0064 | 0.2773 | −0.1308 | 0.061* | |
H12B | −0.0082 | 0.2558 | 0.0158 | 0.061* | |
C13 | −0.0471 (4) | 0.35675 (18) | −0.0247 (3) | 0.0476 (9) | |
H13A | −0.1587 | 0.3514 | −0.0667 | 0.057* | |
H13B | −0.0156 | 0.3900 | −0.0805 | 0.057* | |
C14 | −0.0063 (4) | 0.38173 (17) | 0.1267 (3) | 0.0422 (8) | |
H14A | −0.0555 | 0.4249 | 0.1267 | 0.051* | |
H14B | −0.0442 | 0.3503 | 0.1814 | 0.051* | |
H2C | 0.198 (5) | 0.4214 (14) | 0.148 (4) | 0.080* | |
H2B | 0.295 (4) | 0.492 (2) | −0.009 (2) | 0.080* | |
H2A | 0.330 (4) | 0.5124 (18) | 0.128 (3) | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0448 (3) | 0.0329 (2) | 0.0281 (2) | 0.00015 (17) | 0.01246 (17) | 0.00067 (15) |
Cl1 | 0.0473 (6) | 0.0665 (6) | 0.0490 (5) | 0.0112 (5) | 0.0150 (4) | 0.0005 (5) |
Cl2 | 0.0635 (6) | 0.0507 (5) | 0.0599 (6) | −0.0155 (5) | 0.0266 (5) | 0.0007 (4) |
O1 | 0.0800 (18) | 0.0341 (13) | 0.0296 (12) | −0.0072 (12) | 0.0238 (12) | −0.0028 (10) |
O2 | 0.0692 (19) | 0.0562 (16) | 0.0411 (14) | −0.0195 (13) | 0.0248 (14) | −0.0026 (12) |
N1 | 0.0398 (16) | 0.0353 (14) | 0.0255 (13) | 0.0008 (12) | 0.0132 (12) | −0.0010 (11) |
N2 | 0.0331 (15) | 0.0381 (14) | 0.0252 (13) | 0.0002 (12) | 0.0099 (11) | 0.0004 (11) |
C6 | 0.0319 (18) | 0.0368 (17) | 0.0374 (18) | 0.0024 (14) | 0.0138 (15) | 0.0022 (14) |
C1 | 0.0355 (19) | 0.0385 (17) | 0.0386 (19) | 0.0004 (14) | 0.0187 (15) | −0.0065 (14) |
C2 | 0.046 (2) | 0.047 (2) | 0.0370 (19) | −0.0021 (16) | 0.0183 (16) | −0.0113 (15) |
C3 | 0.037 (2) | 0.045 (2) | 0.068 (3) | −0.0056 (16) | 0.0200 (19) | −0.0248 (19) |
C4 | 0.050 (2) | 0.0339 (19) | 0.080 (3) | 0.0040 (17) | 0.020 (2) | −0.0045 (19) |
C5 | 0.049 (2) | 0.0342 (18) | 0.060 (2) | 0.0049 (16) | 0.0171 (19) | 0.0042 (17) |
C7 | 0.0336 (18) | 0.0404 (19) | 0.0336 (18) | 0.0073 (14) | 0.0145 (15) | 0.0088 (14) |
C8 | 0.047 (2) | 0.048 (2) | 0.0294 (17) | 0.0098 (17) | 0.0113 (16) | 0.0019 (15) |
C9 | 0.043 (2) | 0.0495 (19) | 0.0190 (16) | 0.0072 (16) | 0.0082 (14) | −0.0001 (13) |
C10 | 0.039 (2) | 0.0447 (19) | 0.0378 (19) | 0.0078 (16) | 0.0102 (16) | 0.0010 (15) |
C11 | 0.045 (2) | 0.045 (2) | 0.045 (2) | 0.0031 (16) | 0.0135 (17) | −0.0076 (16) |
C12 | 0.049 (2) | 0.053 (2) | 0.047 (2) | −0.0069 (18) | 0.0124 (18) | −0.0116 (17) |
C13 | 0.036 (2) | 0.063 (2) | 0.0363 (19) | −0.0028 (17) | 0.0029 (16) | −0.0081 (17) |
C14 | 0.0313 (19) | 0.050 (2) | 0.041 (2) | 0.0048 (16) | 0.0077 (15) | −0.0008 (16) |
Zn1—O1 | 1.929 (2) | C4—H4 | 0.93 |
Zn1—N1 | 2.024 (2) | C5—H5 | 0.93 |
Zn1—Cl2 | 2.2066 (10) | C7—H7 | 0.93 |
Zn1—Cl1 | 2.2523 (10) | C8—C9 | 1.514 (4) |
O1—C1 | 1.319 (4) | C8—H8A | 0.97 |
O2—H2B | 0.84 (3) | C8—H8B | 0.97 |
O2—H2A | 0.85 (3) | C9—H9A | 0.97 |
N1—C7 | 1.287 (4) | C9—H9B | 0.97 |
N1—C8 | 1.457 (4) | C10—C11 | 1.512 (4) |
N2—C9 | 1.496 (4) | C10—H10A | 0.97 |
N2—C10 | 1.496 (4) | C10—H10B | 0.97 |
N2—C14 | 1.499 (4) | C11—C12 | 1.520 (5) |
N2—H2C | 0.90 (4) | C11—H11A | 0.97 |
C6—C5 | 1.407 (4) | C11—H11B | 0.97 |
C6—C1 | 1.420 (4) | C12—C13 | 1.511 (5) |
C6—C7 | 1.448 (4) | C12—H12A | 0.97 |
C1—C2 | 1.404 (4) | C12—H12B | 0.97 |
C2—C3 | 1.368 (5) | C13—C14 | 1.507 (4) |
C2—H2 | 0.93 | C13—H13A | 0.97 |
C3—C4 | 1.393 (5) | C13—H13B | 0.97 |
C3—H3 | 0.93 | C14—H14A | 0.97 |
C4—C5 | 1.360 (5) | C14—H14B | 0.97 |
O1—Zn1—N1 | 95.83 (10) | C9—C8—H8A | 110.0 |
O1—Zn1—Cl2 | 113.80 (8) | N1—C8—H8B | 110.0 |
N1—Zn1—Cl2 | 111.04 (8) | C9—C8—H8B | 110.0 |
O1—Zn1—Cl1 | 109.48 (8) | H8A—C8—H8B | 108.3 |
N1—Zn1—Cl1 | 109.22 (8) | N2—C9—C8 | 113.5 (2) |
Cl2—Zn1—Cl1 | 115.66 (4) | N2—C9—H9A | 108.9 |
C1—O1—Zn1 | 123.71 (18) | C8—C9—H9A | 108.9 |
H2B—O2—H2A | 106 (2) | N2—C9—H9B | 108.9 |
C7—N1—C8 | 116.8 (3) | C8—C9—H9B | 108.9 |
C7—N1—Zn1 | 119.9 (2) | H9A—C9—H9B | 107.7 |
C8—N1—Zn1 | 123.31 (19) | N2—C10—C11 | 111.2 (2) |
C9—N2—C10 | 109.1 (2) | N2—C10—H10A | 109.4 |
C9—N2—C14 | 113.8 (2) | C11—C10—H10A | 109.4 |
C10—N2—C14 | 110.6 (2) | N2—C10—H10B | 109.4 |
C9—N2—H2C | 103 (3) | C11—C10—H10B | 109.4 |
C10—N2—H2C | 112 (3) | H10A—C10—H10B | 108.0 |
C14—N2—H2C | 108 (3) | C10—C11—C12 | 110.9 (3) |
C5—C6—C1 | 119.1 (3) | C10—C11—H11A | 109.4 |
C5—C6—C7 | 115.4 (3) | C12—C11—H11A | 109.4 |
C1—C6—C7 | 125.4 (3) | C10—C11—H11B | 109.4 |
O1—C1—C2 | 118.6 (3) | C12—C11—H11B | 109.4 |
O1—C1—C6 | 123.9 (3) | H11A—C11—H11B | 108.0 |
C2—C1—C6 | 117.4 (3) | C13—C12—C11 | 109.5 (3) |
C3—C2—C1 | 122.1 (3) | C13—C12—H12A | 109.8 |
C3—C2—H2 | 119.0 | C11—C12—H12A | 109.8 |
C1—C2—H2 | 119.0 | C13—C12—H12B | 109.8 |
C2—C3—C4 | 120.1 (3) | C11—C12—H12B | 109.8 |
C2—C3—H3 | 120.0 | H12A—C12—H12B | 108.2 |
C4—C3—H3 | 120.0 | C12—C13—C14 | 112.1 (3) |
C5—C4—C3 | 119.7 (3) | C12—C13—H13A | 109.2 |
C5—C4—H4 | 120.2 | C14—C13—H13A | 109.2 |
C3—C4—H4 | 120.2 | C12—C13—H13B | 109.2 |
C4—C5—C6 | 121.6 (3) | C14—C13—H13B | 109.2 |
C4—C5—H5 | 119.2 | H13A—C13—H13B | 107.9 |
C6—C5—H5 | 119.2 | N2—C14—C13 | 110.0 (3) |
N1—C7—C6 | 127.5 (3) | N2—C14—H14A | 109.7 |
N1—C7—H7 | 116.2 | C13—C14—H14A | 109.7 |
C6—C7—H7 | 116.2 | N2—C14—H14B | 109.7 |
N1—C8—C9 | 108.6 (2) | C13—C14—H14B | 109.7 |
N1—C8—H8A | 110.0 | H14A—C14—H14B | 108.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···O2 | 0.90 (4) | 1.81 (4) | 2.712 (3) | 177 (4) |
O2—H2B···O1i | 0.84 (3) | 1.91 (3) | 2.741 (3) | 168 (4) |
O2—H2A···Cl1ii | 0.85 (3) | 2.44 (3) | 3.272 (3) | 168 (4) |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C14H20N2O)]·H2O |
Mr | 386.61 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.1860 (18), 19.875 (4), 9.966 (2) |
β (°) | 110.20 (3) |
V (Å3) | 1707.6 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.76 |
Crystal size (mm) | 0.20 × 0.18 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.720, 0.755 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14151, 3882, 2685 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.104, 0.97 |
No. of reflections | 3882 |
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) | 0.49, −0.59 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).
Zn1—O1 | 1.929 (2) | Zn1—Cl2 | 2.2066 (10) |
Zn1—N1 | 2.024 (2) | Zn1—Cl1 | 2.2523 (10) |
O1—Zn1—N1 | 95.83 (10) | O1—Zn1—Cl1 | 109.48 (8) |
O1—Zn1—Cl2 | 113.80 (8) | N1—Zn1—Cl1 | 109.22 (8) |
N1—Zn1—Cl2 | 111.04 (8) | Cl2—Zn1—Cl1 | 115.66 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···O2 | 0.90 (4) | 1.81 (4) | 2.712 (3) | 177 (4) |
O2—H2B···O1i | 0.84 (3) | 1.91 (3) | 2.741 (3) | 168 (4) |
O2—H2A···Cl1ii | 0.85 (3) | 2.44 (3) | 3.272 (3) | 168 (4) |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1. |
Acknowledgements
The authors acknowledge China Medical University for support of this research.
References
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Zinc(II) complexes with Schiff base ligands have received much attention in recent years (Tomat et al., 2007; Kawamoto et al., 2008). Some of the complexes have been found to have biological properties (Osowole et al., 2005; Iqbal et al., 2005; Raman & Thangaraja, 2005; Abd-Elzaher, 2004). In this paper, the crystal structure of the title new zinc(II) complex with the Schiff base ligand 2-[(2-piperidin-1-ylethylimino)methyl]phenol is reported.
The title compound consists of a mononuclear Schiff base zinc(II) complex molecule and a water of hydration (Fig. 1). The ZnII atom in the complex is four-coordinate in a tetrahedral geometry with one phenolate O and one imine N atoms of the Schiff base ligand, and with two Cl atoms. Bond lengths and angles (Table 1) about the ZnII centre are comparable with the values observed in other Schiff base zinc(II) complexes (Wang, 2007; Ali et al., 2008; Li, 2007; Tatar et al., 2002). The crystal structure is stabilized by intermolecular O–H···Cl, O–H···O and N—H···O hydrogen bonds (Table 2 and Fig. 2).