Acta Cryst. (2007). E63, m1930 [ doi:10.1107/S1600536807028322 ]
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N]bis(salicylato-O)zinc(II)The reaction of Zn(CH3COO)2 with 4-(dimethylamino)pyridine (DMAP) and salicylic acid in a 1:2:2 molar ratio affords the title complex, [Zn(C7H5O3)2(C7H10N2)2]. The ZnII atom resides on a twofold rotation axis and is tetrahedrally coordinated by two DMAP ligands and two salicylate anions in a distorted tetrahedral geometry.
An aqueous solution (10 ml) containing salicylic acid (0.1381 g, 1.0 mmol) and Zn(CH3COO)2·2H2O (0.1098 g, 0.5 mmol) was mixed and refluxed for 1 h. Then another ethanol solution (5 ml) of DMAP (0.1222 g, 1 mmol) was added dropwise into the above solution. The resulted mixture was refluxed for 4 h. The solution was filtered after cooling to room temperature. Colorless single crystals suitable for X-ray diffraction were obtained from the filtrate after 4 d.
The H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances = 0.93Å and Uiso(H) = 1.2Ueq(C), O—H distance = 0.8156 Å and Uiso(H) = 1.2Ueq(O)
Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./om2121fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. |
| [Zn(C7H5O3)2(C7H10N2)2] | F000 = 1216 |
| Mr = 583.93 | Dx = 1.404 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| a = 19.961 (2) Å | Cell parameters from 2692 reflections |
| b = 7.5009 (9) Å | θ = 2.2–23.7º |
| c = 18.488 (2) Å | µ = 0.94 mm−1 |
| β = 93.583 (8)º | T = 293 (2) K |
| V = 2762.7 (5) Å3 | Block, colourless |
| Z = 4 | 0.30 × 0.20 × 0.20 mm |
| Bruker SMART APEXII diffractometer | 2032 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.020 |
| Monochromator: graphite | θmax = 25.0º |
| T = 293(2) K | θmin = 2.2º |
| φ and ω scans | h = −23→20 |
| Absorption correction: none | k = −8→8 |
| 6850 measured reflections | l = −21→21 |
| 2419 independent reflections |
| 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)] = 0.042 | H-atom parameters constrained |
| wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0463P)2 + 3.8555P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 2419 reflections | Δρmax = 0.58 e Å−3 |
| 177 parameters | Δρmin = −0.29 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Zn(C7H5O3)2(C7H10N2)2] | V = 2762.7 (5) Å3 |
| Mr = 583.93 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 19.961 (2) Å | µ = 0.94 mm−1 |
| b = 7.5009 (9) Å | T = 293 (2) K |
| c = 18.488 (2) Å | 0.30 × 0.20 × 0.20 mm |
| β = 93.583 (8)º |
| Bruker SMART APEXII diffractometer | 2419 independent reflections |
| Absorption correction: none | 2032 reflections with I > 2σ(I) |
| 6850 measured reflections | Rint = 0.020 |
| R[F2 > 2σ(F2)] = 0.042 | 177 parameters |
| wR(F2) = 0.107 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.58 e Å−3 |
| 2419 reflections | Δρmin = −0.29 e Å−3 |
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 | 0.0000 | 0.58617 (6) | 0.2500 | 0.05591 (19) | |
| C1 | 0.15627 (14) | 0.2514 (4) | 0.31399 (16) | 0.0536 (7) | |
| C2 | 0.19655 (18) | 0.2440 (5) | 0.37794 (17) | 0.0682 (9) | |
| C3 | 0.24291 (17) | 0.1075 (5) | 0.38911 (19) | 0.0709 (9) | |
| H3 | 0.2699 | 0.1028 | 0.4319 | 0.085* | |
| C4 | 0.24888 (16) | −0.0184 (5) | 0.3378 (2) | 0.0734 (9) | |
| H4 | 0.2803 | −0.1091 | 0.3456 | 0.088* | |
| C5 | 0.20952 (17) | −0.0147 (5) | 0.2746 (2) | 0.0783 (10) | |
| H5 | 0.2138 | −0.1026 | 0.2397 | 0.094* | |
| C6 | 0.16372 (15) | 0.1199 (4) | 0.26335 (18) | 0.0642 (8) | |
| H6 | 0.1370 | 0.1223 | 0.2203 | 0.077* | |
| C7 | 0.10649 (19) | 0.3990 (5) | 0.3030 (3) | 0.0789 (10) | |
| C8 | −0.01148 (16) | 0.9075 (4) | 0.15743 (17) | 0.0649 (8) | |
| H8 | −0.0528 | 0.9157 | 0.1778 | 0.078* | |
| C9 | 0.00609 (16) | 1.0410 (4) | 0.11356 (16) | 0.0625 (8) | |
| H9 | −0.0228 | 1.1372 | 0.1051 | 0.075* | |
| C10 | 0.06755 (15) | 1.0362 (4) | 0.08056 (14) | 0.0532 (7) | |
| C11 | 0.10614 (15) | 0.8820 (4) | 0.09559 (16) | 0.0566 (7) | |
| H11 | 0.1466 | 0.8665 | 0.0740 | 0.068* | |
| C12 | 0.08467 (14) | 0.7553 (4) | 0.14149 (15) | 0.0543 (7) | |
| H12 | 0.1122 | 0.6570 | 0.1510 | 0.065* | |
| C13 | 0.0484 (2) | 1.3291 (5) | 0.0261 (2) | 0.0835 (11) | |
| H13A | 0.0519 | 1.4051 | 0.0670 | 0.100* | |
| H13B | 0.0638 | 1.3916 | −0.0158 | 0.100* | |
| H13C | 0.0013 | 1.2988 | 0.0151 | 0.100* | |
| C14 | 0.1501 (2) | 1.1575 (6) | 0.0028 (2) | 0.0967 (13) | |
| H14A | 0.1476 | 1.0874 | −0.0415 | 0.116* | |
| H14B | 0.1679 | 1.2744 | −0.0092 | 0.116* | |
| H14C | 0.1871 | 1.1006 | 0.0343 | 0.116* | |
| N1 | 0.02661 (12) | 0.7628 (3) | 0.17384 (12) | 0.0555 (6) | |
| N2 | 0.08845 (14) | 1.1690 (4) | 0.03907 (14) | 0.0683 (7) | |
| O1 | 0.07388 (13) | 0.4073 (3) | 0.24406 (18) | 0.0930 (8) | |
| O2 | 0.09803 (19) | 0.5057 (5) | 0.3525 (2) | 0.1405 (14) | |
| O3 | 0.1925 (2) | 0.3681 (5) | 0.43048 (16) | 0.1324 (13) | |
| H3A | 0.1616 | 0.4356 | 0.4193 | 0.159* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0570 (3) | 0.0546 (3) | 0.0565 (3) | 0.000 | 0.0065 (2) | 0.000 |
| C1 | 0.0468 (15) | 0.0503 (17) | 0.0651 (18) | −0.0040 (13) | 0.0138 (13) | 0.0031 (14) |
| C2 | 0.079 (2) | 0.069 (2) | 0.0574 (19) | −0.0070 (8) | 0.0153 (16) | −0.0098 (16) |
| C3 | 0.065 (2) | 0.083 (2) | 0.063 (2) | −0.0058 (18) | −0.0032 (15) | 0.0084 (18) |
| C4 | 0.0552 (19) | 0.071 (2) | 0.094 (3) | 0.0100 (17) | 0.0049 (18) | 0.003 (2) |
| C5 | 0.070 (2) | 0.075 (2) | 0.089 (3) | 0.0123 (19) | 0.0035 (19) | −0.027 (2) |
| C6 | 0.0551 (18) | 0.075 (2) | 0.0624 (18) | −0.0047 (16) | 0.0005 (14) | −0.0051 (16) |
| C7 | 0.064 (2) | 0.065 (2) | 0.109 (3) | 0.0015 (18) | 0.017 (2) | 0.016 (2) |
| C8 | 0.0542 (17) | 0.075 (2) | 0.0675 (19) | 0.0148 (16) | 0.0160 (14) | 0.0046 (17) |
| C9 | 0.0636 (19) | 0.0623 (19) | 0.0620 (19) | 0.0193 (15) | 0.0068 (15) | 0.0026 (15) |
| C10 | 0.0603 (17) | 0.0541 (17) | 0.0449 (15) | 0.0057 (13) | 0.0027 (13) | −0.0044 (13) |
| C11 | 0.0536 (16) | 0.0557 (18) | 0.0617 (17) | 0.0072 (13) | 0.0126 (13) | 0.0016 (14) |
| C12 | 0.0521 (16) | 0.0525 (17) | 0.0583 (17) | 0.0098 (13) | 0.0047 (13) | −0.0018 (13) |
| C13 | 0.108 (3) | 0.061 (2) | 0.083 (2) | 0.018 (2) | 0.011 (2) | 0.0116 (19) |
| C14 | 0.097 (3) | 0.086 (3) | 0.111 (3) | 0.005 (2) | 0.039 (2) | 0.029 (2) |
| N1 | 0.0513 (13) | 0.0581 (15) | 0.0575 (14) | 0.0068 (11) | 0.0074 (11) | 0.0015 (11) |
| N2 | 0.0818 (18) | 0.0587 (16) | 0.0663 (16) | 0.0107 (14) | 0.0193 (14) | 0.0111 (13) |
| O1 | 0.0681 (15) | 0.0830 (18) | 0.127 (2) | 0.0055 (13) | −0.0008 (16) | 0.0269 (16) |
| O2 | 0.159 (3) | 0.104 (2) | 0.081 (3) | 0.043 (3) | 0.006 (3) | −0.030 (2) |
| O3 | 0.187 (4) | 0.121 (3) | 0.087 (2) | 0.036 (2) | −0.008 (2) | −0.0484 (19) |
| Zn1—O1i | 2.002 (3) | C8—C9 | 1.349 (4) |
| Zn1—O1 | 2.002 (3) | C8—H8 | 0.9300 |
| Zn1—N1 | 2.028 (2) | C9—C10 | 1.404 (4) |
| Zn1—N1i | 2.028 (2) | C9—H9 | 0.9300 |
| C1—C6 | 1.375 (4) | C10—N2 | 1.340 (4) |
| C1—C2 | 1.389 (4) | C10—C11 | 1.408 (4) |
| C1—C7 | 1.493 (5) | C11—C12 | 1.361 (4) |
| C2—O3 | 1.351 (4) | C11—H11 | 0.9300 |
| C2—C3 | 1.387 (5) | C12—N1 | 1.338 (3) |
| C3—C4 | 1.349 (5) | C12—H12 | 0.9300 |
| C3—H3 | 0.9300 | C13—N2 | 1.454 (4) |
| C4—C5 | 1.367 (5) | C13—H13A | 0.9460 |
| C4—H4 | 0.9300 | C13—H13B | 0.9719 |
| C5—C6 | 1.369 (5) | C13—H13C | 0.9775 |
| C5—H5 | 0.9300 | C14—N2 | 1.440 (4) |
| C6—H6 | 0.9300 | C14—H14A | 0.9714 |
| C7—O1 | 1.235 (5) | C14—H14B | 0.9769 |
| C7—O2 | 1.236 (5) | C14—H14C | 1.0073 |
| C8—N1 | 1.349 (4) | O3—H3A | 0.8156 |
| O1i—Zn1—O1 | 95.82 (15) | C8—C9—H9 | 119.7 |
| O1i—Zn1—N1 | 134.57 (12) | C10—C9—H9 | 119.7 |
| O1—Zn1—N1 | 100.02 (10) | N2—C10—C9 | 122.8 (3) |
| O1i—Zn1—N1i | 100.02 (10) | N2—C10—C11 | 122.5 (3) |
| O1—Zn1—N1i | 134.57 (12) | C9—C10—C11 | 114.7 (3) |
| N1—Zn1—N1i | 98.43 (14) | C12—C11—C10 | 120.5 (3) |
| C6—C1—C2 | 118.0 (3) | C12—C11—H11 | 119.8 |
| C6—C1—C7 | 122.6 (3) | C10—C11—H11 | 119.8 |
| C2—C1—C7 | 119.4 (3) | N1—C12—C11 | 124.4 (3) |
| O3—C2—C3 | 118.1 (3) | N1—C12—H12 | 117.8 |
| O3—C2—C1 | 121.8 (3) | C11—C12—H12 | 117.8 |
| C3—C2—C1 | 120.1 (3) | N2—C13—H13A | 110.7 |
| C4—C3—C2 | 120.0 (3) | N2—C13—H13B | 109.4 |
| C4—C3—H3 | 120.0 | H13A—C13—H13B | 109.7 |
| C2—C3—H3 | 120.0 | N2—C13—H13C | 110.7 |
| C3—C4—C5 | 121.1 (3) | H13A—C13—H13C | 109.2 |
| C3—C4—H4 | 119.5 | H13B—C13—H13C | 107.1 |
| C5—C4—H4 | 119.5 | N2—C14—H14A | 115.1 |
| C4—C5—C6 | 119.1 (3) | N2—C14—H14B | 112.7 |
| C4—C5—H5 | 120.4 | H14A—C14—H14B | 107.2 |
| C6—C5—H5 | 120.4 | N2—C14—H14C | 111.9 |
| C5—C6—C1 | 121.7 (3) | H14A—C14—H14C | 104.8 |
| C5—C6—H6 | 119.1 | H14B—C14—H14C | 104.4 |
| C1—C6—H6 | 119.1 | C12—N1—C8 | 115.2 (3) |
| O1—C7—O2 | 122.1 (4) | C12—N1—Zn1 | 123.7 (2) |
| O1—C7—C1 | 117.9 (4) | C8—N1—Zn1 | 120.88 (19) |
| O2—C7—C1 | 120.0 (4) | C10—N2—C14 | 121.9 (3) |
| N1—C8—C9 | 124.6 (3) | C10—N2—C13 | 121.4 (3) |
| N1—C8—H8 | 117.7 | C14—N2—C13 | 116.7 (3) |
| C9—C8—H8 | 117.7 | C7—O1—Zn1 | 109.6 (3) |
| C8—C9—C10 | 120.6 (3) | C2—O3—H3A | 108.9 |
| Symmetry codes: (i) −x, y, −z+1/2. |
Bruker (2000). APEX2 (Version 1.27) and SAINT (Version?). Bruker AXS Inc., Madison, Wisconsin, USA.
Fu, G.-C. (2000). Acc. Chem. Res. 33, 412–420.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Sheldrick, G. M. (2000). SHELXTL. Version 6.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Tyrra, W., Naumann, D. & Pantenburg, I. (2003). J. Fluorine Chem. 120, 13–19.
Wang, H., Li, M.-X., Shao, M. & He, X. (2006). Acta Cryst. E62, m3309–m3311.
In preparing metal complexes, carboxylate and pyridine ligands have been frequently employed (Wang et al., 2006). Although 4-dimethylaminopyridine (DMAP) has good coordination ability, there are few reports on its complexes (Tyrra et al., 2003) except a lot of reports on its nucleophilic catalytic properties (Fu, 2000). We report here the synthesis and crystal structure of a new DMAP mononuclear zinc(II) complex.
The asymmetric unit contains one-half molecule of [Zn(C7H10N2)2(C7H5O3)2] (Fig. 1). The Zn atom resides on a site of 2-fold symmetry and is in a tetrahedral environment with the Zn1—O1 and Zn1—N1 bond lengths 2.002 (3) and 2.028 (2) Å, respectively. The DMAP ligands coordinate to zinc through the pyridyl N atoms while the salicylate anions bond through a single carboxyl O atom. The non-coordinated carboxyl O atom is involved in an intramolecular hydrogen bond to the non-coordinated hydroxyl group (Table 1).