metal-organic compounds
A dinuclear zinc complex with (E)-4-dimethylamino-N′-(2-hydroxybenzylidene)benzohydrazide
aDepartment of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China
*Correspondence e-mail: linlr@xmu.edu.cn
The title compound, bis[μ-(E)-2-({2-[4-(dimethylamino)benzoyl]hydrazinylidene}methyl)phenolato]bis[formatozinc], [Zn2(C16H16N3O2)2(CHO2)2], is a dinuclear ZnII complex containing two ZnII cations, two monovalent anions of a Schiff base ligand, 4-dimethylamino-N′-(2-hydroxybenzylidene)benzohydrazide (L), and two formate ions. Each ZnII atom chelates with the hydroxy O atom of salicylaldehyde, the imine N atom, the carbonyl O atom, the formate carboxylate O atom and the hydroxy O atom of the salicylaldehyde moiety in a symmetry-related unit. The five-coordinate ZnII atoms form a dimeric centrosymmetric unit with a central parallelepiped Zn2O2 core and parallel faces derived from the Schiff base ligands. The crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds between the amide N atom and the formate carboxylate O atom.
Related literature
For details of Zn complexes and related applications, see: Shamsipur et al. (2001); Cametti et al. (2008); Winter et al. (2009); Shi et al. (2009); Rai et al. (2009). For potential applications in luminescence materials, see: Erxleben (2001). For recent advances in biosensory and medicinal therapeutic applications of ZnII complexes, see: Drewry & Gunning (2011). For other applications of Schiff base–zinc complexes, see: Costamagna et al. (1992); Sunatsuki et al. (2002); Jiang et al. (2010); Li et al. (2010). For details of the synthesis of the Schiff base ligand, see: Pouralimardan et al. (2007). For related literature on zinc complex applications, see: Consiglio et al. (2010); Kwok et al. (2004).
Experimental
Crystal data
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Refinement
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Data collection: RAPID-AUTO (Rigaku, 2004); cell RAPID-AUTO; data reduction: RAPID-AUTO; 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: SHELXL97.
Supporting information
10.1107/S1600536811014462/jj2088sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811014462/jj2088Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811014462/jj2088Isup3.cdx
A mixture of ethyl-4-(dimethylamino) benzoate(10 mmol) and hydrazinium hydroxide (50%, 70ml) was stirred at 120 °C for 3h and then filtered. The resulting white residues were recrystallization by ethanol. Then, 2-hydroxybenzaldehyde (2 mmol) was added to the solution of the above powder (2 mmol) in 50 ml ethanol and refluxed for 3h to obtain the crude product. The crude product was purified by recrystallization with the ethanol and dichloromethane mixed solvent(v/v=2:1) to give white solid Schiff base ligand (N-(2-hydroxybenzylidene)-4-(dimethylamino)benzohydrazide, HL) with 85% yield. A DMF solution containing HL (0.2 mmol) and Zn(ClO4)2.6H2O (0.1 mmol) was stirred at room temperature for 5h and then was sealed in a 20 ml Teflon-lined stainless-steel autoclave, which was heated to 110o and kept at this temperature for 35h. Yellow block crystals were obtained after the reactor was cooled to room temperature in about 40h.
H atoms were placed at calculated positions with C—H = 0.95 (aromatic), 0.98 (methyl) Å and were refined with Uiso(H)= 1.5 Ueq(C) for methyl H atoms and 1.2 Ueq(C) for aromatic moieties.
Data collection: RAPID-AUTO (Rigaku, 2004); cell
RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); 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: SHELXL97 (Sheldrick, 2008).Fig. 1. Thermal ellipsoid plot of the title compound at the 30% probability level. Hydrogen atoms are removed for clarity. |
[Zn2(C16H16N3O2)2(CHO2)2] | F(000) = 808 |
Mr = 785.41 | Dx = 1.584 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 11481 reflections |
a = 14.556 (3) Å | θ = 6.1–55.0° |
b = 6.7607 (14) Å | µ = 1.52 mm−1 |
c = 17.085 (3) Å | T = 173 K |
β = 101.63 (3)° | Block, yellow |
V = 1646.8 (6) Å3 | 0.10 × 0.10 × 0.08 mm |
Z = 2 |
Rigaku R-AXIS RAPID diffractometer | 3213 independent reflections |
Radiation source: Rotating anode | 2679 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 26.0°, θmin = 3.3° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −17→17 |
Tmin = 0.863, Tmax = 0.888 | k = −8→8 |
13433 measured reflections | l = −21→21 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.0838P] where P = (Fo2 + 2Fc2)/3 |
3213 reflections | (Δ/σ)max = 0.002 |
228 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
[Zn2(C16H16N3O2)2(CHO2)2] | V = 1646.8 (6) Å3 |
Mr = 785.41 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.556 (3) Å | µ = 1.52 mm−1 |
b = 6.7607 (14) Å | T = 173 K |
c = 17.085 (3) Å | 0.10 × 0.10 × 0.08 mm |
β = 101.63 (3)° |
Rigaku R-AXIS RAPID diffractometer | 3213 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2679 reflections with I > 2σ(I) |
Tmin = 0.863, Tmax = 0.888 | Rint = 0.032 |
13433 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.33 e Å−3 |
3213 reflections | Δρmin = −0.30 e Å−3 |
228 parameters |
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 | ||
Zn1 | 0.604524 (15) | 0.57545 (3) | 0.527904 (16) | 0.03564 (10) | |
O1 | 0.47575 (10) | 0.5761 (2) | 0.56269 (10) | 0.0401 (4) | |
N2 | 0.68239 (11) | 0.9705 (2) | 0.53175 (12) | 0.0381 (4) | |
H8 | 0.6959 | 1.0948 | 0.5444 | 0.046* | |
N1 | 0.60914 (11) | 0.8734 (2) | 0.55588 (11) | 0.0344 (4) | |
O2 | 0.71192 (10) | 0.6870 (2) | 0.47370 (10) | 0.0436 (4) | |
C11 | 0.90778 (14) | 1.2366 (3) | 0.44114 (14) | 0.0418 (5) | |
H11 | 0.9247 | 1.3710 | 0.4520 | 0.050* | |
C9 | 0.80890 (13) | 0.9595 (3) | 0.45818 (13) | 0.0339 (5) | |
C12 | 0.95679 (14) | 1.1247 (3) | 0.39372 (14) | 0.0378 (5) | |
C13 | 0.92810 (15) | 0.9259 (3) | 0.37917 (15) | 0.0419 (5) | |
H13 | 0.9591 | 0.8446 | 0.3472 | 0.050* | |
C8 | 0.73176 (13) | 0.8649 (3) | 0.48804 (13) | 0.0347 (5) | |
C6 | 0.48425 (14) | 0.8912 (3) | 0.62988 (14) | 0.0378 (5) | |
N3 | 1.02861 (13) | 1.2013 (3) | 0.36293 (13) | 0.0476 (5) | |
C10 | 0.83602 (14) | 1.1570 (3) | 0.47224 (14) | 0.0385 (5) | |
H10 | 0.8042 | 1.2374 | 0.5039 | 0.046* | |
C1 | 0.44444 (13) | 0.7007 (3) | 0.61235 (13) | 0.0355 (5) | |
C7 | 0.56179 (15) | 0.9695 (3) | 0.59851 (15) | 0.0414 (5) | |
H7 | 0.5789 | 1.1034 | 0.6106 | 0.050* | |
C14 | 0.85623 (15) | 0.8488 (3) | 0.41056 (15) | 0.0418 (5) | |
H14 | 0.8383 | 0.7151 | 0.3993 | 0.050* | |
C15 | 1.08257 (17) | 1.0784 (4) | 0.31949 (17) | 0.0560 (7) | |
H15A | 1.1347 | 1.1554 | 0.3068 | 0.084* | |
H15B | 1.0422 | 1.0322 | 0.2699 | 0.084* | |
H15C | 1.1074 | 0.9642 | 0.3524 | 0.084* | |
C16 | 1.06386 (17) | 1.3985 (3) | 0.38441 (18) | 0.0547 (6) | |
H16A | 1.0112 | 1.4911 | 0.3788 | 0.082* | |
H16B | 1.1058 | 1.4389 | 0.3490 | 0.082* | |
H16C | 1.0985 | 1.3987 | 0.4399 | 0.082* | |
C2 | 0.37002 (15) | 0.6489 (4) | 0.64826 (15) | 0.0461 (6) | |
H2 | 0.3428 | 0.5212 | 0.6387 | 0.055* | |
C3 | 0.33486 (16) | 0.7778 (4) | 0.69733 (16) | 0.0540 (6) | |
H3 | 0.2835 | 0.7380 | 0.7202 | 0.065* | |
C5 | 0.44609 (16) | 1.0176 (4) | 0.68003 (16) | 0.0504 (6) | |
H5 | 0.4723 | 1.1458 | 0.6909 | 0.060* | |
C4 | 0.37272 (17) | 0.9632 (4) | 0.71382 (16) | 0.0559 (7) | |
H4 | 0.3483 | 1.0512 | 0.7479 | 0.067* | |
O3 | 0.68177 (10) | 0.3641 (2) | 0.58935 (10) | 0.0429 (4) | |
O4 | 0.71583 (15) | 0.5810 (3) | 0.68721 (13) | 0.0722 (6) | |
C17 | 0.72061 (16) | 0.4179 (3) | 0.65971 (16) | 0.0455 (6) | |
H17 | 0.7563 | 0.3216 | 0.6933 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.03384 (15) | 0.02593 (14) | 0.04950 (19) | −0.00573 (9) | 0.01398 (11) | −0.00385 (10) |
O1 | 0.0353 (7) | 0.0404 (8) | 0.0478 (10) | −0.0092 (6) | 0.0162 (7) | −0.0117 (7) |
N2 | 0.0372 (9) | 0.0266 (8) | 0.0540 (13) | −0.0070 (7) | 0.0180 (9) | −0.0025 (8) |
N1 | 0.0336 (8) | 0.0281 (8) | 0.0432 (11) | −0.0063 (7) | 0.0117 (8) | 0.0007 (7) |
O2 | 0.0469 (8) | 0.0292 (7) | 0.0604 (11) | −0.0115 (6) | 0.0246 (8) | −0.0085 (7) |
C11 | 0.0446 (11) | 0.0323 (10) | 0.0517 (15) | −0.0104 (9) | 0.0171 (10) | −0.0037 (10) |
C9 | 0.0335 (10) | 0.0320 (10) | 0.0368 (13) | −0.0043 (8) | 0.0084 (9) | 0.0010 (8) |
C12 | 0.0349 (10) | 0.0399 (11) | 0.0396 (14) | −0.0026 (9) | 0.0097 (9) | 0.0037 (9) |
C13 | 0.0449 (11) | 0.0382 (11) | 0.0469 (15) | −0.0002 (9) | 0.0194 (11) | −0.0060 (10) |
C8 | 0.0329 (9) | 0.0319 (10) | 0.0389 (13) | −0.0036 (8) | 0.0067 (9) | 0.0014 (9) |
C6 | 0.0371 (10) | 0.0364 (10) | 0.0416 (14) | −0.0006 (9) | 0.0124 (9) | −0.0042 (9) |
N3 | 0.0465 (10) | 0.0476 (10) | 0.0548 (14) | −0.0094 (9) | 0.0250 (10) | −0.0018 (9) |
C10 | 0.0410 (11) | 0.0333 (10) | 0.0443 (14) | −0.0055 (9) | 0.0159 (10) | −0.0053 (9) |
C1 | 0.0315 (9) | 0.0402 (11) | 0.0347 (13) | −0.0008 (9) | 0.0065 (9) | −0.0020 (9) |
C7 | 0.0427 (11) | 0.0305 (10) | 0.0536 (16) | −0.0054 (9) | 0.0161 (11) | −0.0061 (10) |
C14 | 0.0459 (11) | 0.0307 (10) | 0.0511 (15) | −0.0066 (9) | 0.0150 (11) | −0.0037 (10) |
C15 | 0.0486 (13) | 0.0675 (16) | 0.0584 (18) | −0.0044 (12) | 0.0259 (13) | −0.0030 (13) |
C16 | 0.0475 (12) | 0.0561 (14) | 0.0650 (19) | −0.0153 (11) | 0.0220 (12) | −0.0036 (13) |
C2 | 0.0411 (11) | 0.0556 (13) | 0.0436 (15) | −0.0127 (10) | 0.0138 (10) | −0.0057 (11) |
C3 | 0.0392 (11) | 0.0807 (18) | 0.0466 (16) | −0.0074 (12) | 0.0191 (11) | −0.0078 (13) |
C5 | 0.0490 (13) | 0.0467 (12) | 0.0576 (17) | −0.0018 (11) | 0.0154 (12) | −0.0139 (12) |
C4 | 0.0472 (13) | 0.0709 (17) | 0.0537 (17) | 0.0033 (12) | 0.0196 (12) | −0.0178 (13) |
O3 | 0.0489 (8) | 0.0299 (7) | 0.0510 (11) | −0.0020 (6) | 0.0125 (8) | −0.0009 (7) |
O4 | 0.1017 (16) | 0.0525 (11) | 0.0617 (14) | −0.0037 (10) | 0.0148 (12) | −0.0154 (9) |
C17 | 0.0452 (12) | 0.0419 (12) | 0.0513 (17) | −0.0026 (10) | 0.0144 (11) | 0.0063 (11) |
Zn1—O3 | 1.9829 (16) | C6—C7 | 1.444 (3) |
Zn1—O1i | 2.0204 (16) | N3—C15 | 1.447 (3) |
Zn1—N1 | 2.0681 (17) | N3—C16 | 1.449 (3) |
Zn1—O1 | 2.0776 (15) | C10—H10 | 0.9500 |
Zn1—O2 | 2.1104 (15) | C1—C2 | 1.393 (3) |
O1—C1 | 1.339 (2) | C7—H7 | 0.9500 |
O1—Zn1i | 2.0204 (16) | C14—H14 | 0.9500 |
N2—C8 | 1.342 (3) | C15—H15A | 0.9800 |
N2—N1 | 1.384 (2) | C15—H15B | 0.9800 |
N2—H8 | 0.8800 | C15—H15C | 0.9800 |
N1—C7 | 1.277 (3) | C16—H16A | 0.9800 |
O2—C8 | 1.250 (2) | C16—H16B | 0.9800 |
C11—C10 | 1.374 (3) | C16—H16C | 0.9800 |
C11—C12 | 1.404 (3) | C2—C3 | 1.378 (3) |
C11—H11 | 0.9500 | C2—H2 | 0.9500 |
C9—C14 | 1.387 (3) | C3—C4 | 1.375 (4) |
C9—C10 | 1.399 (3) | C3—H3 | 0.9500 |
C9—C8 | 1.470 (3) | C5—C4 | 1.363 (3) |
C12—N3 | 1.364 (3) | C5—H5 | 0.9500 |
C12—C13 | 1.415 (3) | C4—H4 | 0.9500 |
C13—C14 | 1.371 (3) | O3—C17 | 1.274 (3) |
C13—H13 | 0.9500 | O4—C17 | 1.206 (3) |
C6—C5 | 1.402 (3) | C17—H17 | 0.9500 |
C6—C1 | 1.419 (3) | ||
O3—Zn1—O1i | 102.64 (7) | C11—C10—C9 | 121.2 (2) |
O3—Zn1—N1 | 126.22 (7) | C11—C10—H10 | 119.4 |
O1i—Zn1—N1 | 131.13 (7) | C9—C10—H10 | 119.4 |
O3—Zn1—O1 | 107.34 (6) | O1—C1—C2 | 120.97 (18) |
O1i—Zn1—O1 | 78.72 (7) | O1—C1—C6 | 121.88 (18) |
N1—Zn1—O1 | 85.47 (6) | C2—C1—C6 | 117.1 (2) |
O3—Zn1—O2 | 95.66 (6) | N1—C7—C6 | 125.24 (19) |
O1i—Zn1—O2 | 102.13 (6) | N1—C7—H7 | 117.4 |
N1—Zn1—O2 | 76.17 (6) | C6—C7—H7 | 117.4 |
O1—Zn1—O2 | 156.30 (6) | C13—C14—C9 | 122.20 (19) |
C1—O1—Zn1i | 125.90 (12) | C13—C14—H14 | 118.9 |
C1—O1—Zn1 | 128.65 (12) | C9—C14—H14 | 118.9 |
Zn1i—O1—Zn1 | 101.28 (7) | N3—C15—H15A | 109.5 |
C8—N2—N1 | 116.42 (16) | N3—C15—H15B | 109.5 |
C8—N2—H8 | 121.8 | H15A—C15—H15B | 109.5 |
N1—N2—H8 | 121.8 | N3—C15—H15C | 109.5 |
C7—N1—N2 | 117.73 (17) | H15A—C15—H15C | 109.5 |
C7—N1—Zn1 | 129.16 (14) | H15B—C15—H15C | 109.5 |
N2—N1—Zn1 | 112.60 (12) | N3—C16—H16A | 109.5 |
C8—O2—Zn1 | 114.85 (13) | N3—C16—H16B | 109.5 |
C10—C11—C12 | 121.76 (19) | H16A—C16—H16B | 109.5 |
C10—C11—H11 | 119.1 | N3—C16—H16C | 109.5 |
C12—C11—H11 | 119.1 | H16A—C16—H16C | 109.5 |
C14—C9—C10 | 117.34 (18) | H16B—C16—H16C | 109.5 |
C14—C9—C8 | 118.27 (18) | C3—C2—C1 | 121.7 (2) |
C10—C9—C8 | 124.35 (19) | C3—C2—H2 | 119.1 |
N3—C12—C11 | 122.44 (19) | C1—C2—H2 | 119.1 |
N3—C12—C13 | 121.0 (2) | C4—C3—C2 | 121.3 (2) |
C11—C12—C13 | 116.57 (18) | C4—C3—H3 | 119.4 |
C14—C13—C12 | 120.9 (2) | C2—C3—H3 | 119.4 |
C14—C13—H13 | 119.5 | C4—C5—C6 | 122.4 (2) |
C12—C13—H13 | 119.5 | C4—C5—H5 | 118.8 |
O2—C8—N2 | 119.51 (18) | C6—C5—H5 | 118.8 |
O2—C8—C9 | 120.87 (19) | C5—C4—C3 | 118.3 (2) |
N2—C8—C9 | 119.62 (17) | C5—C4—H4 | 120.8 |
C5—C6—C1 | 119.1 (2) | C3—C4—H4 | 120.8 |
C5—C6—C7 | 116.03 (19) | C17—O3—Zn1 | 112.98 (14) |
C1—C6—C7 | 124.82 (19) | O4—C17—O3 | 125.4 (2) |
C12—N3—C15 | 121.18 (19) | O4—C17—H17 | 117.3 |
C12—N3—C16 | 120.76 (19) | O3—C17—H17 | 117.3 |
C15—N3—C16 | 117.20 (18) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H8···O3ii | 0.88 | 2.00 | 2.838 (2) | 158 |
Symmetry code: (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C16H16N3O2)2(CHO2)2] |
Mr | 785.41 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 14.556 (3), 6.7607 (14), 17.085 (3) |
β (°) | 101.63 (3) |
V (Å3) | 1646.8 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.52 |
Crystal size (mm) | 0.10 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.863, 0.888 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13433, 3213, 2679 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.077, 1.07 |
No. of reflections | 3213 |
No. of parameters | 228 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.30 |
Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick,2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H8···O3i | 0.88 | 2.00 | 2.838 (2) | 158.0 |
Symmetry code: (i) x, y+1, z. |
Acknowledgements
This work was supported financially by the Natural Science Foundation of Fujian Province (grant Nos. 2009S0063 and 2010J01048).
References
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Zinc(II) Schiff base compounds, which are thermally stable, structurally diverse and easily modified, have attracted great interest due to their potential applications in luminescence materials (Andrea, 2001), biosensory and medicinal therapeutic (Drewry & Gunning, 2011). As part of our ongoing work in the biosensory area, the title Zn-Schiff base complex was synthesized by solvothermal methods and the crystal structure is herein reported. The title molecule consists of two subparallel, tridentate Schiff base ligands, two five coodinate zinc cations and two formyl groups (from the decomposion of dimethylformamide (DMF)). The center plane assumes a parallelogram geometry which is comprised of the alternate atoms of Zn and O atoms (Fig. 1). Crystal packing is stabilized by weak N—H···O intermolecular hydrogen bonds between the amide nitrogen atom and the formate carboxyl oxygen atom (Table 1).