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Acta Cryst. (2009). E65, m1422    [ doi:10.1107/S1600536809042810 ]

{2-Hydroxy-N'-[1-(2-oxidophenyl)ethylidene]benzohydrazidato}morpholinecopper(II)

S.-Z. Lin, R.-K. Jia, Y.-L. Yuan and P. Zhan

Abstract top

The CuII ion in the title complex, [Cu(C15H12N2O3)(C4H9NO)], is coordinated by one carbonyl O atom, one hydrazine N atom and one phenolate O atom from the doubly deprotonated tridentate ligand and one N atom from a morpholine molecule, forming a distorted trans-CuN2O2 square-planar coordination geometry. An intramolecular O-H...N hydrogen bond occurs within the ligand, generating an S(6) ring.

Comment top

In the past decade, much attention has been focused on the study of aroylhydrazones derivative with aryl, aroyl and heteroaroyl Schiff bases due to their coordination abilities to metal ions (Singh et al., 1992; Liu et al., 2003; Bai et al., 2005). Ongoing the study of aroylhydrazone complexes, we report here the synthesis and crystal structure of a new complex with 2-hydroxy-N'- (2-oxyphenyl-ethylidene)benzohydrazidate(2-) ligand (Fig. 1).

The title complex, (I), contains one copper(II) center having distorted quadrilateral coordination environment, one O,N,O'-tridentate ligand molecule and one coordinated morpholine molecule. There exists one intramolecular phenol-hydrazone O—H···N hydrogen bond in each ligand, forming a six-membered ring.

Related literature top

For background to aroylhydrazone derivatives, see: Singh et al. (1992); Liu et al. (2003); Bai et al. (2005). For related structures, see: Gatto et al. (2004); Huo et al. (2004); Chen et al. (2009).

Experimental top

The ligand was prepared by the reaction of 2-hydroxyacetophenone and salicylhydrazine in a molar ratio of 1:1 under reflux in ethanol for 2 h. The white precipitate was collected, washed several times with ethanol and dried in vacuo (yield 79%). Morpholine (3 ml) was dropped into the mixture of 2-hydroxy-N'-(2-oxyphenyl- ethylidene)benzohydrazide (27 mg, 0.1 mmol) and Cu(Ac)2.2H2O (21 mg, 0.1 mmol) in methanol (10 ml). After stirring for 5 h, the reaction mixture was filtered and left to stand at room temperature. Green prisms of (I) were obtained by slow evaporation after 10 d. Analysis calculated for C19H21N3O4Cu: C 54.47, H 5.05, N 10.03%; found: C 53.99, H 5.01, N 10.29%.

Refinement top

H atoms bouded to phenolate O and morpholine N atoms were located in difference Fourier maps and were refined isotropically with O—H and N—H distance restraints of 0.82 and 0.91 Å, respectively. All other H atoms were placed in idealized positions and refined using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms and C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for the methylene H atoms].

Computing details top

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY (Molecular Structure Corporation, 1999); data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms. Dashed lines indicate hydrogen bonding. Only H atoms involved in hydrogen bonds have been included.
{2-Hydroxy-N'-[1-(2- oxidophenyl)ethylidene]benzohydrazidato}morpholinecopper(II) top
Crystal data top
[Cu(C15H12N2O3)(C4H9NO)]F(000) = 868
Mr = 418.93Dx = 1.540 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4032 reflections
a = 9.220 (4) Åθ = 3.3–27.5°
b = 17.616 (9) ŵ = 1.24 mm−1
c = 12.023 (6) ÅT = 293 K
β = 112.257 (14)°Prism, green
V = 1807.4 (15) Å30.26 × 0.17 × 0.14 mm
Z = 4
Data collection top
Rigaku Weissenberg IP
diffractometer		4032 independent reflections
Radiation source: fine-focus sealed tube3273 reflections with I > 2σ(I)
graphiteRint = 0.049
ω scansθmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan
(TEXRAY; Molecular Structure Corporation, 1999)		h = −11→10
Tmin = 0.769, Tmax = 0.837k = −22→22
16528 measured reflectionsl = −14→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.042P)2 + 0.6843P]
where P = (Fo2 + 2Fc2)/3
4032 reflections(Δ/σ)max = 0.001
246 parametersΔρmax = 0.35 e Å−3
0 restraintsΔρmin = −0.47 e Å−3
Crystal data top
[Cu(C15H12N2O3)(C4H9NO)]V = 1807.4 (15) Å3
Mr = 418.93Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.220 (4) ŵ = 1.24 mm−1
b = 17.616 (9) ÅT = 293 K
c = 12.023 (6) Å0.26 × 0.17 × 0.14 mm
β = 112.257 (14)°
Data collection top
Rigaku Weissenberg IP
diffractometer		3273 reflections with I > 2σ(I)
Absorption correction: multi-scan
(TEXRAY; Molecular Structure Corporation, 1999)		Rint = 0.049
Tmin = 0.769, Tmax = 0.837θmax = 27.5°
16528 measured reflectionsStandard reflections: ?
4032 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.089Δρmax = 0.35 e Å−3
S = 1.05Δρmin = −0.47 e Å−3
4032 reflectionsAbsolute structure: ?
246 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cu10.35584 (3)0.512750 (15)0.55888 (2)0.03343 (10)
O1−0.2016 (2)0.39749 (11)0.30393 (17)0.0635 (5)
H1A−0.14040.43300.31470.064 (9)*
O20.24346 (16)0.42406 (8)0.57392 (13)0.0392 (4)
O30.46114 (18)0.59329 (10)0.52104 (14)0.0479 (4)
O40.7081 (2)0.51533 (12)0.97389 (16)0.0626 (5)
N10.06587 (19)0.46639 (10)0.39142 (17)0.0373 (4)
N20.17322 (19)0.52585 (9)0.41154 (16)0.0334 (4)
N30.5322 (2)0.49568 (9)0.72070 (16)0.0343 (4)
H3B0.59800.46180.70680.042 (6)*
C1−0.1317 (3)0.34097 (13)0.3828 (2)0.0438 (5)
C20.0206 (2)0.34834 (12)0.4699 (2)0.0369 (5)
C30.0825 (3)0.28792 (13)0.5489 (2)0.0428 (5)
H3A0.18290.29210.60750.051*
C4−0.0011 (3)0.22263 (14)0.5418 (3)0.0534 (6)
H4A0.04280.18270.59460.064*
C5−0.1511 (3)0.21633 (16)0.4560 (3)0.0618 (7)
H5A−0.20850.17220.45130.074*
C6−0.2160 (3)0.27518 (16)0.3775 (3)0.0583 (7)
H6A−0.31740.27070.32050.070*
C70.1169 (2)0.41671 (12)0.4806 (2)0.0356 (5)
C80.1354 (2)0.58214 (12)0.33475 (19)0.0362 (5)
C90.2478 (2)0.64281 (12)0.34607 (19)0.0361 (5)
C100.4016 (3)0.64486 (12)0.43607 (19)0.0370 (5)
C110.5022 (3)0.70507 (13)0.4351 (2)0.0482 (6)
H11A0.60180.70720.49520.058*
C120.4580 (3)0.76027 (14)0.3488 (3)0.0570 (7)
H12A0.52750.79870.34940.068*
C130.3082 (4)0.75849 (15)0.2602 (3)0.0619 (7)
H13A0.27710.79580.20110.074*
C140.2067 (3)0.70213 (14)0.2596 (2)0.0503 (6)
H14A0.10650.70250.20020.060*
C15−0.0237 (3)0.58277 (16)0.2353 (2)0.0536 (6)
H15A−0.04900.53260.20240.080*
H15B−0.02350.61720.17350.080*
H15C−0.10040.59890.26650.080*
C160.6283 (3)0.56298 (15)0.7719 (2)0.0539 (7)
H16A0.56260.60220.78490.065*
H16B0.67060.58240.71490.065*
C170.7606 (3)0.5460 (2)0.8884 (2)0.0656 (8)
H17A0.83190.51040.87400.079*
H17B0.81820.59240.92000.079*
C180.6243 (4)0.44769 (19)0.9289 (2)0.0773 (10)
H18A0.58810.42680.98850.093*
H18B0.69410.41080.91530.093*
C190.4852 (3)0.46037 (18)0.8129 (2)0.0630 (8)
H19A0.43480.41210.78320.076*
H19B0.40980.49280.82820.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02910 (14)0.03649 (15)0.02903 (15)−0.00266 (10)0.00461 (11)0.00205 (10)
O10.0410 (9)0.0587 (11)0.0667 (12)−0.0113 (8)−0.0069 (9)0.0105 (9)
O20.0315 (8)0.0406 (8)0.0368 (8)−0.0046 (6)0.0032 (7)0.0024 (6)
O30.0385 (8)0.0521 (10)0.0427 (9)−0.0085 (7)0.0035 (7)0.0171 (7)
O40.0669 (12)0.0777 (13)0.0314 (9)−0.0159 (10)0.0053 (9)−0.0069 (8)
N10.0294 (9)0.0389 (10)0.0378 (10)−0.0020 (7)0.0060 (8)−0.0014 (8)
N20.0295 (8)0.0347 (10)0.0316 (9)0.0004 (7)0.0067 (7)−0.0024 (7)
N30.0321 (9)0.0344 (9)0.0314 (9)0.0001 (7)0.0065 (8)−0.0045 (7)
C10.0394 (12)0.0444 (13)0.0434 (13)−0.0061 (9)0.0111 (10)−0.0073 (10)
C20.0326 (10)0.0384 (11)0.0383 (11)−0.0029 (8)0.0118 (9)−0.0091 (9)
C30.0402 (12)0.0424 (12)0.0438 (13)−0.0020 (9)0.0138 (11)−0.0039 (10)
C40.0618 (16)0.0403 (13)0.0558 (15)−0.0078 (11)0.0197 (13)−0.0032 (11)
C50.0701 (18)0.0481 (15)0.0636 (17)−0.0251 (13)0.0212 (15)−0.0121 (13)
C60.0494 (15)0.0606 (16)0.0532 (15)−0.0206 (12)0.0063 (13)−0.0138 (13)
C70.0297 (10)0.0382 (11)0.0377 (11)0.0000 (8)0.0115 (9)−0.0047 (9)
C80.0335 (11)0.0416 (12)0.0304 (10)0.0084 (8)0.0087 (9)−0.0003 (8)
C90.0391 (11)0.0350 (11)0.0341 (11)0.0086 (8)0.0139 (9)0.0012 (8)
C100.0416 (11)0.0356 (11)0.0345 (11)0.0025 (8)0.0151 (10)0.0017 (9)
C110.0489 (13)0.0413 (13)0.0524 (14)−0.0024 (10)0.0170 (12)0.0038 (10)
C120.0651 (17)0.0374 (13)0.0692 (17)−0.0018 (11)0.0262 (15)0.0089 (12)
C130.0736 (18)0.0452 (15)0.0617 (17)0.0103 (13)0.0196 (15)0.0198 (13)
C140.0526 (14)0.0436 (14)0.0478 (14)0.0109 (11)0.0112 (12)0.0126 (11)
C150.0411 (13)0.0613 (16)0.0451 (14)0.0045 (11)0.0014 (11)0.0107 (11)
C160.0597 (15)0.0538 (15)0.0383 (12)−0.0212 (12)0.0072 (12)−0.0059 (10)
C170.0515 (15)0.092 (2)0.0416 (14)−0.0220 (15)0.0043 (13)−0.0141 (14)
C180.100 (2)0.068 (2)0.0369 (14)−0.0222 (17)−0.0044 (16)0.0128 (13)
C190.0653 (17)0.0730 (18)0.0367 (13)−0.0284 (14)0.0036 (13)0.0081 (12)
Geometric parameters (Å, °) top
Cu1—O31.8702 (17)C6—H6A0.9300
Cu1—O21.9208 (16)C8—C91.459 (3)
Cu1—N21.9409 (18)C8—C151.501 (3)
Cu1—N32.0308 (19)C9—C141.421 (3)
O1—C11.357 (3)C9—C101.421 (3)
O1—H1A0.8200C10—C111.412 (3)
O2—C71.283 (3)C11—C121.366 (3)
O3—C101.321 (3)C11—H11A0.9300
O4—C171.399 (4)C12—C131.389 (4)
O4—C181.412 (4)C12—H12A0.9300
N1—C71.325 (3)C13—C141.362 (4)
N1—N21.398 (2)C13—H13A0.9300
N2—C81.309 (3)C14—H14A0.9300
N3—C161.468 (3)C15—H15A0.9600
N3—C191.472 (3)C15—H15B0.9600
N3—H3B0.9100C15—H15C0.9600
C1—C61.384 (3)C16—C171.499 (4)
C1—C21.404 (3)C16—H16A0.9700
C2—C31.397 (3)C16—H16B0.9700
C2—C71.473 (3)C17—H17A0.9700
C3—C41.370 (3)C17—H17B0.9700
C3—H3A0.9300C18—C191.512 (4)
C4—C51.381 (4)C18—H18A0.9700
C4—H4A0.9300C18—H18B0.9700
C5—C61.377 (4)C19—H19A0.9700
C5—H5A0.9300C19—H19B0.9700
O3—Cu1—O2171.23 (7)C10—C9—C8123.93 (19)
O3—Cu1—N292.21 (7)O3—C10—C11116.2 (2)
O2—Cu1—N282.54 (7)O3—C10—C9125.0 (2)
O3—Cu1—N392.53 (7)C11—C10—C9118.8 (2)
O2—Cu1—N393.11 (7)C12—C11—C10122.2 (2)
N2—Cu1—N3174.38 (8)C12—C11—H11A118.9
C1—O1—H1A109.5C10—C11—H11A118.9
C7—O2—Cu1110.14 (14)C11—C12—C13119.4 (2)
C10—O3—Cu1127.42 (14)C11—C12—H12A120.3
C17—O4—C18109.6 (2)C13—C12—H12A120.3
C7—N1—N2110.10 (17)C14—C13—C12120.1 (2)
C8—N2—N1117.62 (17)C14—C13—H13A119.9
C8—N2—Cu1129.87 (15)C12—C13—H13A119.9
N1—N2—Cu1112.43 (13)C13—C14—C9122.7 (2)
C16—N3—C19109.2 (2)C13—C14—H14A118.7
C16—N3—Cu1114.77 (15)C9—C14—H14A118.7
C19—N3—Cu1115.24 (15)C8—C15—H15A109.5
C16—N3—H3B105.6C8—C15—H15B109.5
C19—N3—H3B105.6H15A—C15—H15B109.5
Cu1—N3—H3B105.6C8—C15—H15C109.5
O1—C1—C6118.2 (2)H15A—C15—H15C109.5
O1—C1—C2122.0 (2)H15B—C15—H15C109.5
C6—C1—C2119.8 (2)N3—C16—C17112.2 (2)
C3—C2—C1118.2 (2)N3—C16—H16A109.2
C3—C2—C7119.06 (19)C17—C16—H16A109.2
C1—C2—C7122.7 (2)N3—C16—H16B109.2
C4—C3—C2121.5 (2)C17—C16—H16B109.2
C4—C3—H3A119.3H16A—C16—H16B107.9
C2—C3—H3A119.3O4—C17—C16112.2 (2)
C3—C4—C5119.7 (3)O4—C17—H17A109.2
C3—C4—H4A120.2C16—C17—H17A109.2
C5—C4—H4A120.2O4—C17—H17B109.2
C6—C5—C4120.2 (2)C16—C17—H17B109.2
C6—C5—H5A119.9H17A—C17—H17B107.9
C4—C5—H5A119.9O4—C18—C19112.3 (2)
C5—C6—C1120.6 (2)O4—C18—H18A109.2
C5—C6—H6A119.7C19—C18—H18A109.2
C1—C6—H6A119.7O4—C18—H18B109.2
O2—C7—N1124.6 (2)C19—C18—H18B109.2
O2—C7—C2118.6 (2)H18A—C18—H18B107.9
N1—C7—C2116.84 (19)N3—C19—C18111.6 (2)
N2—C8—C9119.94 (18)N3—C19—H19A109.3
N2—C8—C15119.1 (2)C18—C19—H19A109.3
C9—C8—C15121.0 (2)N3—C19—H19B109.3
C14—C9—C10116.8 (2)C18—C19—H19B109.3
C14—C9—C8119.2 (2)H19A—C19—H19B108.0
O3—Cu1—O2—C7−49.8 (5)N2—N1—C7—C2−176.95 (18)
N2—Cu1—O2—C73.75 (14)C3—C2—C7—O2−11.5 (3)
N3—Cu1—O2—C7−179.83 (14)C1—C2—C7—O2168.8 (2)
O2—Cu1—O3—C1065.8 (5)C3—C2—C7—N1168.0 (2)
N2—Cu1—O3—C1012.8 (2)C1—C2—C7—N1−11.7 (3)
N3—Cu1—O3—C10−164.2 (2)N1—N2—C8—C9−175.30 (18)
C7—N1—N2—C8−176.03 (19)Cu1—N2—C8—C98.3 (3)
C7—N1—N2—Cu11.0 (2)N1—N2—C8—C154.2 (3)
O3—Cu1—N2—C8−13.1 (2)Cu1—N2—C8—C15−172.20 (17)
O2—Cu1—N2—C8173.9 (2)N2—C8—C9—C14177.9 (2)
N3—Cu1—N2—C8134.4 (7)C15—C8—C9—C14−1.6 (3)
O3—Cu1—N2—N1170.31 (14)N2—C8—C9—C101.1 (3)
O2—Cu1—N2—N1−2.64 (14)C15—C8—C9—C10−178.4 (2)
N3—Cu1—N2—N1−42.2 (8)Cu1—O3—C10—C11172.81 (17)
O3—Cu1—N3—C1625.97 (19)Cu1—O3—C10—C9−8.7 (3)
O2—Cu1—N3—C16−160.75 (18)C14—C9—C10—O3−177.8 (2)
N2—Cu1—N3—C16−121.6 (7)C8—C9—C10—O3−0.9 (4)
O3—Cu1—N3—C19154.11 (19)C14—C9—C10—C110.6 (3)
O2—Cu1—N3—C19−32.60 (19)C8—C9—C10—C11177.5 (2)
N2—Cu1—N3—C196.6 (8)O3—C10—C11—C12176.9 (2)
O1—C1—C2—C3178.8 (2)C9—C10—C11—C12−1.7 (4)
C6—C1—C2—C30.3 (4)C10—C11—C12—C131.4 (4)
O1—C1—C2—C7−1.4 (4)C11—C12—C13—C140.0 (4)
C6—C1—C2—C7−180.0 (2)C12—C13—C14—C9−1.0 (4)
C1—C2—C3—C40.6 (4)C10—C9—C14—C130.7 (4)
C7—C2—C3—C4−179.1 (2)C8—C9—C14—C13−176.3 (3)
C2—C3—C4—C5−0.9 (4)C19—N3—C16—C1751.4 (3)
C3—C4—C5—C60.3 (4)Cu1—N3—C16—C17−177.45 (19)
C4—C5—C6—C10.6 (5)C18—O4—C17—C1659.0 (4)
O1—C1—C6—C5−179.5 (3)N3—C16—C17—O4−56.9 (3)
C2—C1—C6—C5−0.9 (4)C17—O4—C18—C19−58.7 (4)
Cu1—O2—C7—N1−4.7 (3)C16—N3—C19—C18−50.8 (3)
Cu1—O2—C7—C2174.76 (15)Cu1—N3—C19—C18178.3 (2)
N2—N1—C7—O22.6 (3)O4—C18—C19—N355.9 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N10.821.872.588 (3)146
Table 1
Selected geometric parameters (Å) top
Cu1—O31.8702 (17)Cu1—N21.9409 (18)
Cu1—O21.9208 (16)Cu1—N32.0308 (19)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N10.821.872.588 (3)146
Acknowledgements top

We thank the Northeast Dianli University for supporting this study.

references
References top

Bai, Y., Dang, D. B., Duan, C. Y., Song, Y. & Meng, Q. J. (2005). Inorg. Chem. 44, 5972–5974.

Chen, X.-H., Wu, Q.-J., Liang, Z.-Y., Zhan, C.-R. & Liu, J.-B. (2009). Acta Cryst. C65, m190–m194.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Gatto, C. C., Schulz Lang, E., Kupfer, A., Hagenbach, A. & Abram, U. (2004). Z. Anorg. Allg. Chem. 630, 1286–1295.

Huo, L.-H., Lu, Z.-Z., Gao, S., Zhao, H. & Zhao, J.-G. (2004). Acta Cryst. E60, m1636–m1638.

Liu, L., Ji, Y.-L., Jia, D.-Z. & Yu, K.-B. (2003). Chin. J. Struct. Chem. 22, 568–572.

Molecular Structure Corporation (1999). TEXRAY and TEXSAN. MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Singh, G. (1992). Synth. React. Inorg. Met.-Org. Chem. 22, 1605–1618.