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Acta Cryst. (2009). E65, m794    [ doi:10.1107/S160053680902234X ]

{N'-[(E)-1-(5-Bromo-2-oxidophenyl)ethylidene]-4-chlorobenzohydrazidato}pyridinenickel(II)

X.-L. Chang, B. Xie, C.-Y. Ji, Y.-G. Xiang and L.-K. Zou

Abstract top

The title complex, [Ni(C15H10BrClN2O2)(C5H5N)], displays a square-planar coordination geometry around the NiII ion, formed by the tridentate hydrazone and monodentate pyridine ligands, with the N atoms in a trans arrangement about the Ni center.

Comment top

The chemistry of aroylhydrazones continues to attract much attention due to their coordination ability to metal ions (Singh et al., 1982; Salem, 1998; Ali et al., 2004) and their biological activity (Singh et al., 1982; Carcelli et al., 1995). As an extension of work on the structural characterization of aroylhydrazone derivatives, the title compound was synthesized and its crystal structure is reported.

Related literature top

For the coordination properties of aroylhydrazones, see: Ali et al. (2004); Carcelli et al. (1995); Salem (1998); Singh et al. (1982).

Experimental top

A DMF solution (5 ml) of N'-[(E)-(5-bromo-2-hydroxyphenyl)ethylidene]-4-chlorobenzo-hydrazide (0.25 mmol, 0.092 g) was mixed with a methanol solution (5 ml) of NiCl2.6H2O (0.25 mmol, 0.059 g). The mixture was stirred at 298 K for 4 h and then filtered. A green precipitate was produced after about 10 d. A pyridine mixture (5 ml) was used to dissolve the precipitate at 330 K. Dark green block-shaped crystals were obtained after one month (yield 30%).

Refinement top

H atoms were placed in calculated positions, with C—H bond lengths fixed to 0.93 (aromatic CH) or 0.96 Å (methyl CH3). Isotropic displacement parameters for H atoms were computed as Uiso(H) =xUeq(carrier C) with x = 1.2 (aromatic CH) or 1.5 (methyl CH3).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted.
{N'-[(E)-1-(5-Bromo-2-oxidophenyl)ethylidene]-4- chlorobenzohydrazidato}pyridinenickel(II) top
Crystal data top
[Ni(C15H10BrClNO2)(C5H5N)]F(000) = 2016
Mr = 503.42Dx = 1.738 Mg m−3
Monoclinic, C2/cMelting point: 330 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 32.430 (4) ÅCell parameters from 2958 reflections
b = 6.0816 (8) Åθ = 2.6–25.0°
c = 22.865 (3) ŵ = 3.25 mm−1
β = 121.422 (2)°T = 278 K
V = 3848.3 (9) Å3Block, green
Z = 80.18 × 0.13 × 0.10 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		3401 independent reflections
Radiation source: fine-focus sealed tube2651 reflections with I > 2σ(I)
graphiteRint = 0.028
φ and ω scansθmax = 25.1°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −37→38
Tmin = 0.581, Tmax = 0.723k = −7→7
9680 measured reflectionsl = −24→27
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0383P)2 + 2.3403P]
where P = (Fo2 + 2Fc2)/3
3401 reflections(Δ/σ)max < 0.001
253 parametersΔρmax = 0.48 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
0 constraints
Crystal data top
[Ni(C15H10BrClNO2)(C5H5N)]V = 3848.3 (9) Å3
Mr = 503.42Z = 8
Monoclinic, C2/cMo Kα radiation
a = 32.430 (4) ŵ = 3.25 mm−1
b = 6.0816 (8) ÅT = 278 K
c = 22.865 (3) Å0.18 × 0.13 × 0.10 mm
β = 121.422 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer		3401 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2651 reflections with I > 2σ(I)
Tmin = 0.581, Tmax = 0.723Rint = 0.028
9680 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.080Δρmax = 0.48 e Å−3
S = 1.02Δρmin = −0.27 e Å−3
3401 reflectionsAbsolute structure: ?
253 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.041268 (13)0.23786 (6)0.156018 (18)0.04192 (13)
Br1−0.211124 (13)−0.09987 (7)−0.01369 (2)0.07519 (15)
Cl10.26998 (4)−0.39055 (19)0.14682 (6)0.0893 (3)
O10.09933 (7)0.1537 (3)0.16792 (10)0.0483 (5)
O2−0.01644 (7)0.3235 (3)0.14192 (11)0.0532 (5)
N10.05323 (9)−0.1250 (4)0.09609 (12)0.0460 (6)
N20.01755 (9)−0.0048 (4)0.09955 (11)0.0418 (6)
N30.07253 (9)0.4809 (4)0.22016 (12)0.0449 (6)
C10.21951 (12)−0.2894 (6)0.14580 (16)0.0572 (9)
C20.22207 (12)−0.0906 (6)0.17554 (17)0.0647 (9)
H20.2510−0.01290.19800.078*
C30.18122 (12)−0.0071 (6)0.17171 (16)0.0578 (8)
H30.18270.12850.19150.069*
C40.13809 (11)−0.1220 (5)0.13888 (14)0.0454 (7)
C50.13736 (13)−0.3249 (5)0.11103 (18)0.0595 (9)
H50.1089−0.40650.08990.071*
C60.17748 (13)−0.4080 (6)0.11382 (18)0.0646 (9)
H60.1763−0.54370.09420.077*
C70.09448 (11)−0.0276 (5)0.13425 (14)0.0437 (7)
C8−0.02649 (11)−0.0808 (5)0.06426 (13)0.0417 (7)
C9−0.03642 (12)−0.2861 (5)0.02193 (16)0.0539 (8)
H9A−0.0094−0.31640.01690.081*
H9B−0.0649−0.2649−0.02250.081*
H9C−0.0413−0.40770.04440.081*
C10−0.06526 (10)0.0294 (5)0.06629 (13)0.0415 (7)
C11−0.05843 (11)0.2266 (5)0.10261 (15)0.0456 (7)
C12−0.09895 (12)0.3312 (5)0.09768 (16)0.0545 (8)
H12−0.09470.46490.11980.065*
C13−0.14427 (12)0.2416 (6)0.06125 (17)0.0564 (8)
H13−0.17060.31380.05820.068*
C14−0.15003 (11)0.0428 (6)0.02932 (15)0.0516 (8)
C15−0.11213 (11)−0.0603 (5)0.03060 (14)0.0487 (7)
H15−0.1174−0.19260.00740.058*
C160.12054 (12)0.4904 (6)0.25973 (16)0.0600 (9)
H160.13870.37680.25710.072*
C170.14431 (14)0.6615 (6)0.30425 (19)0.0701 (10)
H170.17790.66280.33110.084*
C180.11809 (15)0.8293 (6)0.30861 (17)0.0655 (10)
H180.13350.94820.33750.079*
C190.06898 (14)0.8192 (5)0.26974 (17)0.0589 (9)
H190.05030.92940.27270.071*
C200.04720 (12)0.6437 (5)0.22580 (15)0.0525 (8)
H200.01360.63880.19920.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0420 (2)0.0397 (2)0.0444 (2)−0.00392 (17)0.02273 (18)−0.00596 (17)
Br10.0486 (2)0.0968 (3)0.0797 (3)−0.0210 (2)0.0332 (2)−0.0084 (2)
Cl10.0596 (6)0.1029 (8)0.1085 (8)0.0179 (6)0.0461 (6)−0.0134 (6)
O10.0456 (12)0.0462 (12)0.0522 (12)−0.0061 (9)0.0248 (10)−0.0130 (10)
O20.0433 (13)0.0501 (12)0.0657 (13)−0.0055 (10)0.0281 (11)−0.0161 (11)
N10.0454 (15)0.0431 (15)0.0514 (15)0.0007 (12)0.0265 (13)−0.0048 (12)
N20.0445 (15)0.0388 (13)0.0440 (13)−0.0011 (11)0.0245 (12)−0.0025 (11)
N30.0486 (16)0.0436 (14)0.0464 (14)−0.0058 (12)0.0275 (12)−0.0051 (11)
C10.047 (2)0.067 (2)0.058 (2)0.0122 (17)0.0272 (17)0.0007 (17)
C20.044 (2)0.074 (3)0.074 (2)−0.0059 (17)0.0297 (18)−0.0151 (19)
C30.054 (2)0.057 (2)0.067 (2)−0.0062 (17)0.0347 (18)−0.0163 (17)
C40.0454 (18)0.0493 (19)0.0432 (16)0.0000 (14)0.0242 (15)−0.0001 (14)
C50.050 (2)0.054 (2)0.072 (2)−0.0075 (16)0.0299 (18)−0.0163 (17)
C60.065 (2)0.056 (2)0.078 (2)0.0055 (18)0.040 (2)−0.0129 (18)
C70.0457 (18)0.0448 (17)0.0423 (16)0.0001 (14)0.0241 (15)0.0003 (14)
C80.0465 (18)0.0381 (16)0.0388 (15)−0.0049 (13)0.0210 (14)0.0000 (13)
C90.055 (2)0.0444 (19)0.0595 (19)−0.0082 (15)0.0274 (17)−0.0105 (15)
C100.0414 (17)0.0421 (17)0.0425 (15)−0.0046 (13)0.0229 (14)0.0012 (13)
C110.0441 (18)0.0476 (18)0.0494 (17)−0.0047 (14)0.0274 (15)0.0001 (14)
C120.053 (2)0.0525 (19)0.064 (2)−0.0029 (16)0.0350 (17)−0.0048 (16)
C130.047 (2)0.066 (2)0.066 (2)0.0010 (17)0.0358 (17)0.0043 (18)
C140.0421 (18)0.063 (2)0.0496 (18)−0.0102 (16)0.0239 (15)0.0023 (16)
C150.0504 (19)0.0510 (18)0.0465 (17)−0.0095 (15)0.0266 (15)−0.0020 (14)
C160.048 (2)0.064 (2)0.070 (2)−0.0108 (17)0.0320 (18)−0.0193 (18)
C170.059 (2)0.075 (2)0.074 (2)−0.025 (2)0.033 (2)−0.028 (2)
C180.085 (3)0.059 (2)0.062 (2)−0.028 (2)0.045 (2)−0.0210 (18)
C190.079 (3)0.0463 (19)0.059 (2)−0.0047 (18)0.042 (2)−0.0088 (16)
C200.056 (2)0.0511 (19)0.0510 (18)−0.0009 (16)0.0288 (17)−0.0042 (15)
Geometric parameters (Å, °) top
Ni1—O21.802 (2)C8—C101.447 (4)
Ni1—O11.830 (2)C8—C91.508 (4)
Ni1—N21.844 (2)C9—H9A0.9600
Ni1—N31.953 (2)C9—H9B0.9600
Br1—C141.901 (3)C9—H9C0.9600
Cl1—C11.737 (3)C10—C151.407 (4)
O1—C71.306 (3)C10—C111.409 (4)
O2—C111.317 (3)C11—C121.410 (4)
N1—C71.298 (4)C12—C131.369 (4)
N1—N21.405 (3)C12—H120.9300
N2—C81.305 (4)C13—C141.374 (4)
N3—C161.333 (4)C13—H130.9300
N3—C201.335 (4)C14—C151.366 (4)
C1—C21.368 (5)C15—H150.9300
C1—C61.369 (5)C16—C171.377 (4)
C2—C31.378 (4)C16—H160.9300
C2—H20.9300C17—C181.364 (5)
C3—C41.383 (4)C17—H170.9300
C3—H30.9300C18—C191.362 (5)
C4—C51.383 (4)C18—H180.9300
C4—C71.478 (4)C19—C201.381 (4)
C5—C61.366 (5)C19—H190.9300
C5—H50.9300C20—H200.9300
C6—H60.9300
O2—Ni1—O1178.39 (9)C8—C9—H9A109.5
O2—Ni1—N295.20 (10)C8—C9—H9B109.5
O1—Ni1—N284.35 (9)H9A—C9—H9B109.5
O2—Ni1—N389.99 (10)C8—C9—H9C109.5
O1—Ni1—N390.52 (9)H9A—C9—H9C109.5
N2—Ni1—N3174.43 (11)H9B—C9—H9C109.5
C7—O1—Ni1110.50 (18)C15—C10—C11117.5 (3)
C11—O2—Ni1126.92 (19)C15—C10—C8119.7 (3)
C7—N1—N2108.4 (2)C11—C10—C8122.7 (3)
C8—N2—N1116.7 (2)O2—C11—C10124.9 (3)
C8—N2—Ni1129.7 (2)O2—C11—C12116.2 (3)
N1—N2—Ni1113.61 (18)C10—C11—C12118.9 (3)
C16—N3—C20117.5 (3)C13—C12—C11122.0 (3)
C16—N3—Ni1120.5 (2)C13—C12—H12119.0
C20—N3—Ni1122.0 (2)C11—C12—H12119.0
C2—C1—C6121.1 (3)C12—C13—C14118.6 (3)
C2—C1—Cl1119.6 (3)C12—C13—H13120.7
C6—C1—Cl1119.3 (3)C14—C13—H13120.7
C1—C2—C3119.1 (3)C15—C14—C13121.4 (3)
C1—C2—H2120.4C15—C14—Br1119.0 (3)
C3—C2—H2120.4C13—C14—Br1119.5 (2)
C2—C3—C4121.0 (3)C14—C15—C10121.5 (3)
C2—C3—H3119.5C14—C15—H15119.3
C4—C3—H3119.5C10—C15—H15119.3
C3—C4—C5118.1 (3)N3—C16—C17122.7 (3)
C3—C4—C7120.1 (3)N3—C16—H16118.6
C5—C4—C7121.8 (3)C17—C16—H16118.6
C6—C5—C4121.4 (3)C18—C17—C16119.3 (4)
C6—C5—H5119.3C18—C17—H17120.4
C4—C5—H5119.3C16—C17—H17120.4
C5—C6—C1119.2 (3)C19—C18—C17118.7 (3)
C5—C6—H6120.4C19—C18—H18120.7
C1—C6—H6120.4C17—C18—H18120.7
N1—C7—O1123.1 (3)C18—C19—C20119.4 (3)
N1—C7—C4118.9 (3)C18—C19—H19120.3
O1—C7—C4118.0 (3)C20—C19—H19120.3
N2—C8—C10120.4 (3)N3—C20—C19122.4 (3)
N2—C8—C9119.3 (3)N3—C20—H20118.8
C10—C8—C9120.4 (3)C19—C20—H20118.8
N2—Ni1—O1—C7−2.06 (18)N1—N2—C8—C10178.4 (2)
N3—Ni1—O1—C7175.76 (18)Ni1—N2—C8—C10−0.2 (4)
N2—Ni1—O2—C110.0 (2)N1—N2—C8—C9−1.0 (4)
N3—Ni1—O2—C11−178.0 (2)Ni1—N2—C8—C9−179.5 (2)
C7—N1—N2—C8−179.6 (2)N2—C8—C10—C15−177.0 (2)
C7—N1—N2—Ni1−0.8 (3)C9—C8—C10—C152.4 (4)
O2—Ni1—N2—C8−1.3 (3)N2—C8—C10—C113.4 (4)
O1—Ni1—N2—C8−179.8 (3)C9—C8—C10—C11−177.3 (3)
O2—Ni1—N2—N1−179.92 (18)Ni1—O2—C11—C102.9 (4)
O1—Ni1—N2—N11.62 (17)Ni1—O2—C11—C12−177.3 (2)
O2—Ni1—N3—C16168.9 (2)C15—C10—C11—O2175.5 (3)
O1—Ni1—N3—C16−12.6 (2)C8—C10—C11—O2−4.9 (4)
O2—Ni1—N3—C20−11.7 (2)C15—C10—C11—C12−4.3 (4)
O1—Ni1—N3—C20166.7 (2)C8—C10—C11—C12175.4 (3)
C6—C1—C2—C3−1.5 (5)O2—C11—C12—C13−176.7 (3)
Cl1—C1—C2—C3177.0 (3)C10—C11—C12—C133.1 (5)
C1—C2—C3—C40.5 (5)C11—C12—C13—C140.7 (5)
C2—C3—C4—C51.1 (5)C12—C13—C14—C15−3.2 (5)
C2—C3—C4—C7−178.9 (3)C12—C13—C14—Br1173.6 (2)
C3—C4—C5—C6−1.9 (5)C13—C14—C15—C101.9 (5)
C7—C4—C5—C6178.1 (3)Br1—C14—C15—C10−175.0 (2)
C4—C5—C6—C11.0 (5)C11—C10—C15—C142.0 (4)
C2—C1—C6—C50.7 (5)C8—C10—C15—C14−177.7 (3)
Cl1—C1—C6—C5−177.8 (3)C20—N3—C16—C17−1.3 (5)
N2—N1—C7—O1−1.1 (4)Ni1—N3—C16—C17178.0 (3)
N2—N1—C7—C4−179.6 (2)N3—C16—C17—C180.0 (5)
Ni1—O1—C7—N12.4 (3)C16—C17—C18—C191.5 (5)
Ni1—O1—C7—C4−179.08 (19)C17—C18—C19—C20−1.8 (5)
C3—C4—C7—N1171.6 (3)C16—N3—C20—C191.0 (4)
C5—C4—C7—N1−8.4 (4)Ni1—N3—C20—C19−178.3 (2)
C3—C4—C7—O1−7.0 (4)C18—C19—C20—N30.5 (5)
C5—C4—C7—O1173.0 (3)
Acknowledgements top

This project was supported by the Postgraduate Foundation of Sichuan University of Science and Engineering (No.Y05–2–09).

references
References top

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