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Acta Cryst. (2009). E65, m435    [ doi:10.1107/S1600536809009003 ]

Bis[[mu]-N'-isobutyryl-1-oxidonaphthalene-2-carbohydrazidato(3-)]dipyridinetricopper(II)

X.-F. Shi, D. Li, P.-Y. Li and D.-Q. Wang

Abstract top

The complete molecule of the title complex, [Cu3(C15H13N2O3)2(C5H5N)2], is generated by crystallographic twofold symmetry, with the central Cu atom lying on the rotation axis: it is coordinated by two N,O-bidentate ligands in a trans-CuN2O2 distorted square-planar arrangement. The other Cu atom is coordinated by an N,O,O'-tridentate ligand and a pyridine molecule in a distorted trans-CuN2O2 arrangement. In the crystal structure, a C-H...[pi] interaction occurs.

Comment top

A large number of aroylhydrazine complexes have been prepared and studied due to their diverse molecular architectures and quite interesting chemical properties (Patole et al., 2003; Pouralimardan et al., 2007). However, researches on the copper(II) complexes with N-isobutyryl-1-hydroxy-2-naphthalenecarbohydrazide have not reported. So we have synthesized a new complex, (I), (Fig. 1), which has been characterized by X-ray diffraction and elemental analysis. The molecule of (I) contains three copper(II), two ligand molecules, and two pyridine molecules. Both copper centres adopt distorted square planar trans-CuN2O2 arrangements. The triple-deprotonated N-isobutyryl-1-hydroxy-2-naphthalenecarbohydrazide bridges the metal ions using a hydrazide N—N group and formed the trinuclear copper complex. In the crystal packing, the complex molecules are linked into two-dimensional network by intermolecular C—H···π interactions (Fig. 2) (Saalfrank & Bernt, 1998; Nishio, 2004).

Related literature top

For related structures, see: Patole et al. (2003); Pouralimardan et al. (2007). For background on C—H···π interactions, see: Nishio (2004); Saalfrank & Bernt (1998). Cg1 is the centroid of the C2–C7 ring.

Experimental top

Isobutyric anhydride (0.632 g, 4 mmol) and 1-hydroxy-2-naphthalenecarbohydrazide (0.808 g, 4 mmol) were added to 40 ml of chloroform at ice-water bath. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After overnight refrigeration, the resulting white precipitate was filtered and rinsed with chloroform and diethyl ether (1.02 g, 93.57% yield). A solution of CuNO3(0.04 g,0.2 mmol) in methanol (10 ml) was added to a mixture of N-isobutyryl-1-hydroxy-2-naphthalenecarbohydrazide (0.055 g, 0.2 mmol) and sodium methylate (0.0324 g, 0.6 mmol) in pyridine (10 ml). A green solution was obtained after refluxing for 3 h. After being filtrated, dimethyl ether was slowly diffused into the filtrate, and green blocks of (I) were obtained after two weeks. Elemental analysis calculated for C40H36N6O6Cu3: C, 54.09; H, 4.05; O, 10.78; N, 9.43. Found (%): C, 54.12; H, 4.06; O, 10.82; N, 9.47

Refinement top

The C-bound H atoms were positioned with idealized geometry (C—H = 0.93–0.98Å) and refined as riding with Uiso(H) = 1.2 Ueq(C) or 1.5Ueq(methyl C).

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 (I) showing 40% probability displacement ellipsoids. H atoms have been omitted for clarity. Symmetry code: (i) 1–x, y, 1/2–z.
[Figure 2] Fig. 2. View of the two-dimensional network structure in (I). Intermolecular C—H···π are shown as dashed lines. Most of H atoms are omitted.
Bis[µ-N'-isobutyryl-1-oxidonaphthalene-2- carbohydrazidato(3-)]dipyridinetricopper(II) top
Crystal data top
[Cu3(C15H13N2O3)2(C5H5N)2]F(000) = 1812
Mr = 887.37Dx = 1.565 Mg m−3
Dm = 1.565 Mg m−3
Dm measured by not measured
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3140 reflections
a = 23.661 (2) Åθ = 2.7–26.3°
b = 13.0521 (18) ŵ = 1.74 mm−1
c = 13.3142 (15) ÅT = 298 K
β = 113.684 (2)°Block, green
V = 3765.5 (7) Å30.37 × 0.35 × 0.31 mm
Z = 4
Data collection top
Siemens SMART CCD
diffractometer		3310 independent reflections
Radiation source: fine-focus sealed tube2319 reflections with I > 2σ(I)
graphiteRint = 0.050
ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Siemens, 1996)		h = −28→27
Tmin = 0.566, Tmax = 0.615k = −14→15
9477 measured reflectionsl = −13→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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.079P)2 + 4.0071P]
where P = (Fo2 + 2Fc2)/3
3310 reflections(Δ/σ)max = 0.001
251 parametersΔρmax = 0.82 e Å−3
0 restraintsΔρmin = −0.33 e Å−3
Crystal data top
[Cu3(C15H13N2O3)2(C5H5N)2]V = 3765.5 (7) Å3
Mr = 887.37Z = 4
Monoclinic, C2/cMo Kα radiation
a = 23.661 (2) ŵ = 1.74 mm−1
b = 13.0521 (18) ÅT = 298 K
c = 13.3142 (15) Å0.37 × 0.35 × 0.31 mm
β = 113.684 (2)°
Data collection top
Siemens SMART CCD
diffractometer		3310 independent reflections
Absorption correction: multi-scan
(SADABS; Siemens, 1996)		2319 reflections with I > 2σ(I)
Tmin = 0.566, Tmax = 0.615Rint = 0.050
9477 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.135Δρmax = 0.82 e Å−3
S = 1.00Δρmin = −0.33 e Å−3
3310 reflectionsAbsolute structure: ?
251 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50000.86302 (6)0.25000.0410 (2)
Cu20.68569 (2)0.80745 (4)0.23216 (4)0.0404 (2)
N10.62147 (15)0.8496 (3)0.2723 (3)0.0401 (8)
N20.56137 (15)0.8380 (3)0.1900 (3)0.0425 (9)
N30.74587 (15)0.7504 (3)0.1787 (3)0.0386 (8)
O10.57183 (12)0.8896 (2)0.3816 (2)0.0446 (7)
O20.74777 (12)0.8431 (2)0.3698 (2)0.0442 (7)
O30.61596 (13)0.7851 (3)0.0920 (2)0.0523 (8)
C10.62281 (18)0.8758 (3)0.3692 (3)0.0363 (9)
C20.73934 (18)0.8742 (3)0.4567 (3)0.0361 (9)
C30.68203 (18)0.8912 (3)0.4623 (3)0.0341 (9)
C40.68036 (19)0.9281 (3)0.5618 (3)0.0399 (10)
H40.64210.93860.56450.048*
C50.7314 (2)0.9484 (3)0.6518 (3)0.0440 (11)
H50.72780.97330.71440.053*
C60.7909 (2)0.9322 (3)0.6522 (3)0.0421 (10)
C70.79500 (19)0.8936 (3)0.5546 (3)0.0398 (10)
C80.85377 (19)0.8776 (4)0.5545 (4)0.0503 (11)
H80.85700.85220.49190.060*
C90.9059 (2)0.8990 (5)0.6448 (4)0.0674 (15)
H90.94430.88850.64260.081*
C100.9026 (2)0.9367 (4)0.7415 (4)0.0655 (15)
H100.93850.95070.80290.079*
C110.8464 (2)0.9522 (4)0.7439 (4)0.0559 (13)
H110.84430.97670.80800.067*
C120.56432 (19)0.8035 (4)0.0990 (4)0.0451 (11)
C130.5056 (2)0.7872 (4)−0.0027 (4)0.0548 (13)
H130.47030.79440.01760.066*
C140.5046 (3)0.6793 (5)−0.0479 (5)0.090 (2)
H14A0.53180.6765−0.08540.135*
H14B0.46340.6627−0.09820.135*
H14C0.51800.63100.01140.135*
C150.5004 (3)0.8681 (5)−0.0879 (5)0.0862 (19)
H15A0.50840.9344−0.05390.129*
H15B0.45950.8668−0.14490.129*
H15C0.52990.8541−0.11880.129*
C160.7284 (2)0.6777 (3)0.0995 (3)0.0414 (10)
H160.68720.65770.06890.050*
C170.7684 (2)0.6324 (3)0.0624 (4)0.0468 (11)
H170.75480.58220.00840.056*
C180.8288 (2)0.6624 (4)0.1064 (4)0.0585 (13)
H180.85710.63240.08290.070*
C190.8476 (2)0.7379 (5)0.1861 (4)0.0604 (13)
H190.88830.76050.21600.072*
C200.8046 (2)0.7787 (4)0.2200 (4)0.0489 (11)
H200.81740.82850.27450.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0270 (4)0.0562 (5)0.0400 (4)0.0000.0138 (3)0.000
Cu20.0282 (3)0.0537 (4)0.0391 (3)−0.0004 (2)0.0133 (2)−0.0070 (2)
N10.0243 (17)0.058 (2)0.0350 (19)−0.0019 (16)0.0083 (15)−0.0053 (17)
N20.0269 (18)0.062 (2)0.0371 (19)−0.0036 (17)0.0110 (16)−0.0097 (18)
N30.0349 (19)0.044 (2)0.0392 (19)0.0012 (16)0.0175 (16)−0.0024 (17)
O10.0286 (15)0.0644 (19)0.0435 (17)−0.0017 (14)0.0172 (13)−0.0100 (15)
O20.0308 (15)0.0602 (19)0.0417 (17)−0.0003 (14)0.0146 (13)−0.0083 (15)
O30.0291 (16)0.088 (2)0.0386 (17)0.0002 (16)0.0123 (13)−0.0135 (16)
C10.031 (2)0.039 (2)0.041 (2)−0.0013 (18)0.0161 (18)−0.0011 (19)
C20.034 (2)0.032 (2)0.040 (2)−0.0022 (17)0.0121 (18)0.0006 (18)
C30.029 (2)0.034 (2)0.037 (2)−0.0010 (17)0.0120 (17)−0.0024 (18)
C40.039 (2)0.042 (2)0.040 (2)−0.0004 (19)0.016 (2)−0.0016 (19)
C50.057 (3)0.041 (2)0.034 (2)−0.003 (2)0.017 (2)−0.0002 (19)
C60.046 (3)0.032 (2)0.041 (2)−0.0017 (19)0.011 (2)0.0039 (19)
C70.040 (2)0.032 (2)0.043 (2)−0.0017 (18)0.013 (2)0.0008 (19)
C80.034 (2)0.059 (3)0.053 (3)0.002 (2)0.012 (2)−0.008 (2)
C90.037 (3)0.089 (4)0.066 (3)0.001 (3)0.009 (3)−0.006 (3)
C100.041 (3)0.072 (4)0.058 (3)−0.002 (3)−0.007 (2)−0.004 (3)
C110.057 (3)0.054 (3)0.043 (3)−0.003 (2)0.006 (2)−0.002 (2)
C120.031 (2)0.064 (3)0.040 (2)−0.001 (2)0.0130 (19)−0.001 (2)
C130.031 (2)0.088 (4)0.038 (2)0.001 (2)0.008 (2)−0.009 (3)
C140.078 (4)0.082 (4)0.070 (4)−0.011 (3)−0.012 (3)−0.016 (3)
C150.074 (4)0.084 (4)0.064 (4)−0.006 (3)−0.009 (3)0.004 (3)
C160.042 (2)0.038 (2)0.044 (2)−0.0023 (19)0.018 (2)0.001 (2)
C170.056 (3)0.040 (3)0.046 (3)0.004 (2)0.022 (2)−0.002 (2)
C180.057 (3)0.070 (3)0.055 (3)0.024 (3)0.031 (3)0.002 (3)
C190.035 (3)0.089 (4)0.056 (3)0.005 (3)0.017 (2)−0.003 (3)
C200.035 (2)0.062 (3)0.047 (3)0.000 (2)0.014 (2)−0.008 (2)
Geometric parameters (Å, °) top
Cu1—O11.920 (3)C8—C91.361 (6)
Cu1—O1i1.920 (3)C8—H80.9300
Cu1—N21.946 (3)C9—C101.409 (7)
Cu1—N2i1.946 (3)C9—H90.9300
Cu2—N11.884 (3)C10—C111.360 (7)
Cu2—O21.890 (3)C10—H100.9300
Cu2—O31.953 (3)C11—H110.9300
Cu2—N31.975 (3)C12—C131.516 (6)
N1—C11.323 (5)C13—C151.518 (8)
N1—N21.412 (5)C13—C141.529 (8)
N2—C121.320 (5)C13—H130.9800
N3—C201.326 (5)C14—H14A0.9600
N3—C161.354 (5)C14—H14B0.9600
O1—C11.294 (5)C14—H14C0.9600
O2—C21.315 (5)C15—H15A0.9600
O3—C121.285 (5)C15—H15B0.9600
C1—C31.465 (5)C15—H15C0.9600
C2—C31.405 (5)C16—C171.365 (6)
C2—C71.455 (6)C16—H160.9300
C3—C41.425 (6)C17—C181.367 (7)
C4—C51.342 (6)C17—H170.9300
C4—H40.9300C18—C191.384 (7)
C5—C61.423 (6)C18—H180.9300
C5—H50.9300C19—C201.374 (6)
C6—C111.412 (6)C19—H190.9300
C6—C71.433 (6)C20—H200.9300
C7—C81.406 (6)
O1—Cu1—O1i159.21 (19)C7—C8—H8119.5
O1—Cu1—N282.65 (13)C8—C9—C10121.0 (5)
O1i—Cu1—N2100.87 (13)C8—C9—H9119.5
O1—Cu1—N2i100.87 (13)C10—C9—H9119.5
O1i—Cu1—N2i82.65 (13)C11—C10—C9119.2 (4)
N2—Cu1—N2i160.7 (2)C11—C10—H10120.4
N1—Cu2—O293.11 (13)C9—C10—H10120.4
N1—Cu2—O381.17 (13)C10—C11—C6122.0 (5)
O2—Cu2—O3173.00 (13)C10—C11—H11119.0
N1—Cu2—N3172.94 (14)C6—C11—H11119.0
O2—Cu2—N392.88 (13)O3—C12—N2122.2 (4)
O3—Cu2—N393.10 (13)O3—C12—C13117.8 (4)
C1—N1—N2114.0 (3)N2—C12—C13120.0 (4)
C1—N1—Cu2130.2 (3)C12—C13—C15109.9 (4)
N2—N1—Cu2115.1 (3)C12—C13—C14110.1 (4)
C12—N2—N1109.9 (3)C15—C13—C14111.2 (5)
C12—N2—Cu1139.2 (3)C12—C13—H13108.5
N1—N2—Cu1110.4 (2)C15—C13—H13108.5
C20—N3—C16117.3 (4)C14—C13—H13108.5
C20—N3—Cu2122.2 (3)C13—C14—H14A109.5
C16—N3—Cu2120.4 (3)C13—C14—H14B109.5
C1—O1—Cu1112.8 (3)H14A—C14—H14B109.5
C2—O2—Cu2126.6 (3)C13—C14—H14C109.5
C12—O3—Cu2111.4 (3)H14A—C14—H14C109.5
O1—C1—N1120.1 (4)H14B—C14—H14C109.5
O1—C1—C3119.8 (4)C13—C15—H15A109.5
N1—C1—C3120.1 (3)C13—C15—H15B109.5
O2—C2—C3125.9 (4)H15A—C15—H15B109.5
O2—C2—C7116.0 (4)C13—C15—H15C109.5
C3—C2—C7118.1 (4)H15A—C15—H15C109.5
C2—C3—C4119.4 (4)H15B—C15—H15C109.5
C2—C3—C1123.3 (4)N3—C16—C17123.1 (4)
C4—C3—C1117.3 (3)N3—C16—H16118.5
C5—C4—C3123.1 (4)C17—C16—H16118.5
C5—C4—H4118.5C16—C17—C18118.6 (4)
C3—C4—H4118.5C16—C17—H17120.7
C4—C5—C6120.6 (4)C18—C17—H17120.7
C4—C5—H5119.7C17—C18—C19119.4 (4)
C6—C5—H5119.7C17—C18—H18120.3
C11—C6—C5123.4 (4)C19—C18—H18120.3
C11—C6—C7118.2 (4)C20—C19—C18118.4 (5)
C5—C6—C7118.4 (4)C20—C19—H19120.8
C8—C7—C6118.6 (4)C18—C19—H19120.8
C8—C7—C2120.9 (4)N3—C20—C19123.2 (4)
C6—C7—C2120.5 (4)N3—C20—H20118.4
C9—C8—C7121.0 (5)C19—C20—H20118.4
C9—C8—H8119.5
O2—Cu2—N1—C1−10.5 (4)N1—C1—C3—C4174.6 (4)
O3—Cu2—N1—C1173.6 (4)C2—C3—C4—C50.4 (6)
O2—Cu2—N1—N2179.6 (3)C1—C3—C4—C5−177.8 (4)
O3—Cu2—N1—N23.6 (3)C3—C4—C5—C6−0.9 (7)
C1—N1—N2—C12−174.6 (4)C4—C5—C6—C11179.9 (4)
Cu2—N1—N2—C12−3.0 (5)C4—C5—C6—C7−0.1 (6)
C1—N1—N2—Cu1−0.9 (5)C11—C6—C7—C8−0.1 (6)
Cu2—N1—N2—Cu1170.69 (17)C5—C6—C7—C8179.8 (4)
O1—Cu1—N2—C12172.5 (5)C11—C6—C7—C2−178.4 (4)
O1i—Cu1—N2—C12−28.3 (5)C5—C6—C7—C21.6 (6)
N2i—Cu1—N2—C1270.6 (5)O2—C2—C7—C8−1.0 (6)
O1—Cu1—N2—N11.6 (3)C3—C2—C7—C8179.8 (4)
O1i—Cu1—N2—N1160.8 (3)O2—C2—C7—C6177.1 (4)
N2i—Cu1—N2—N1−100.4 (3)C3—C2—C7—C6−2.1 (6)
O2—Cu2—N3—C20−23.5 (4)C6—C7—C8—C9−0.4 (7)
O3—Cu2—N3—C20152.8 (4)C2—C7—C8—C9177.8 (5)
O2—Cu2—N3—C16154.6 (3)C7—C8—C9—C100.7 (8)
O3—Cu2—N3—C16−29.1 (3)C8—C9—C10—C11−0.3 (9)
O1i—Cu1—O1—C1−103.3 (3)C9—C10—C11—C6−0.3 (8)
N2—Cu1—O1—C1−2.0 (3)C5—C6—C11—C10−179.4 (5)
N2i—Cu1—O1—C1158.7 (3)C7—C6—C11—C100.5 (7)
N1—Cu2—O2—C26.4 (3)Cu2—O3—C12—N23.1 (6)
N3—Cu2—O2—C2−169.9 (3)Cu2—O3—C12—C13−178.6 (3)
N1—Cu2—O3—C12−3.6 (3)N1—N2—C12—O3−0.2 (6)
N3—Cu2—O3—C12172.2 (3)Cu1—N2—C12—O3−171.2 (3)
Cu1—O1—C1—N12.2 (5)N1—N2—C12—C13−178.4 (4)
Cu1—O1—C1—C3−179.0 (3)Cu1—N2—C12—C1310.7 (8)
N2—N1—C1—O1−0.8 (6)O3—C12—C13—C15−69.6 (6)
Cu2—N1—C1—O1−170.8 (3)N2—C12—C13—C15108.6 (5)
N2—N1—C1—C3−179.6 (3)O3—C12—C13—C1453.2 (6)
Cu2—N1—C1—C310.4 (6)N2—C12—C13—C14−128.5 (5)
Cu2—O2—C2—C3−3.0 (6)C20—N3—C16—C170.9 (6)
Cu2—O2—C2—C7177.9 (3)Cu2—N3—C16—C17−177.3 (3)
O2—C2—C3—C4−178.1 (4)N3—C16—C17—C18−0.7 (7)
C7—C2—C3—C41.1 (6)C16—C17—C18—C19−0.5 (7)
O2—C2—C3—C10.1 (7)C17—C18—C19—C201.4 (8)
C7—C2—C3—C1179.2 (4)C16—N3—C20—C190.0 (7)
O1—C1—C3—C2177.6 (4)Cu2—N3—C20—C19178.2 (4)
N1—C1—C3—C2−3.6 (6)C18—C19—C20—N3−1.2 (8)
O1—C1—C3—C4−4.3 (6)
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C17—H17···Cg1ii0.932.533.362 (4)150
Symmetry codes: (ii) −x+3/2, y−1/2, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.920 (3)Cu2—N11.884 (3)
Cu1—O1i1.920 (3)Cu2—O21.890 (3)
Cu1—N21.946 (3)Cu2—O31.953 (3)
Cu1—N2i1.946 (3)Cu2—N31.975 (3)
Symmetry codes: (i) −x+1, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C17—H17···Cg1ii0.932.533.362 (4)150
Symmetry codes: (ii) −x+3/2, y−1/2, −z+1/2.
Acknowledgements top

We acknowledge financial support from the National Natural science Foundation of China (grant No. 20671048).

references
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