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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): m1021.
Published online 2010 July 24. doi:  10.1107/S1600536810028898
PMCID: PMC3007558

(Acetyl­acetone 3-hy­droxy-2-naphtho­yl­hydrazonato-κ3 O,N′,O′)(methoxo-κO)oxidovanadate(V)

Abstract

The tridentate Schiff base ligand in the title compound, [V(C16H14N2O3)(CH3O)O], has its O, N and O′ atoms spanning three basal positions of the square-based-pyrimidally VV atom. The fourth basal site is occupied by a methoxo ligand, which results from a deprotonated methanol solvent molecule, and the oxido ligand occupies the apical position. The hy­droxy H atom forms an intra­molecular O—H(...)N hydrogen bond with an N-atom acceptor site.

Related literature

For related vanadium(V) structures, see: Shao et al. (1988 [triangle]). The reaction of oxovanadium(IV) bis­(acetyl­acetonate), VO(acac)2, with aroylhydrazines in methanol yields Schiff-base complexes having the dinuclear [V(=O)(μ-OMe)2V(=O)]4+ core, see: Sarkari & Pal (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1021-scheme1.jpg

Experimental

Crystal data

  • [V(C16H14N2O3)(CH3O)O]
  • M r = 380.27
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1021-efi1.jpg
  • a = 7.7379 (8) Å
  • b = 9.7753 (10) Å
  • c = 11.4411 (11) Å
  • α = 86.618 (1)°
  • β = 70.821 (1)°
  • γ = 85.974 (1)°
  • V = 814.77 (14) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.64 mm−1
  • T = 100 K
  • 0.30 × 0.10 × 0.10 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.831, T max = 0.939
  • 7840 measured reflections
  • 3716 independent reflections
  • 3013 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.102
  • S = 1.03
  • 3716 reflections
  • 233 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.75 e Å−3
  • Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810028898/nk2050sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028898/nk2050Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the University of Malaya (RG020/09AFR) for supporting this study.

supplementary crystallographic information

Comment

The reaction of oxovanadium(IV) bis(acetylacetonate), VO(acac)2, with aroylhydrazines in acetonitrile yields vanadium(V) compounds of the formulation V2O3L2 (where L represents the doubly-deprotonated Schiff base). In methanol, the reaction yields Schiff-base complexes having the dinuclear [V(=O)(µ-OMe)2V(=O)]4+ core (Sarkari & Pal, 2009). In the present study, the reaction with a hydroxy-substituted naphthanoic acid hydrazide yields the expected vanadium(V) complex of the doubly-deprotonated Schiff base but a molecule of the solvent is reduced to a methoxide ion (Scheme I). The metal center has square-based pyramidal coordination geometry, with the O,N,O'-atoms of the Schiff base spanning the basal sites, the fourth basal site is occupied by a methoxy ligand and the apical site is occupied by an oxo ligand.

Experimental

Bis(acetylacetonato)oxovanadium(IV) (0.20 g, 0.75 mmol) and 3-hydroxy-2-naphthoyl hydrazide (0.15 g, 0.75 mmol) were heated in methanol (100 ml) for one hour. The brown solution was filtered; slow evaporation of the filtrate afforded brown crystals.

Refinement

C-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The hydroxyl H-atom was located in a difference Fourier map, and was refined with a distance restraint of O–H 0.84 (1) Å; its isotropic displacement parameter was freely refined. There is no residual electron density near the methoxido O-atom.

Figures

Fig. 1.
Displacement ellipsoid plot of VO(CH3O)(C16H14N2O3) at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

[V(C16H14N2O3)(CH3O)O]Z = 2
Mr = 380.27F(000) = 392
Triclinic, P1Dx = 1.550 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7379 (8) ÅCell parameters from 2783 reflections
b = 9.7753 (10) Åθ = 2.8–28.1°
c = 11.4411 (11) ŵ = 0.64 mm1
α = 86.618 (1)°T = 100 K
β = 70.821 (1)°Prism, brown
γ = 85.974 (1)°0.30 × 0.10 × 0.10 mm
V = 814.77 (14) Å3

Data collection

Bruker SMART APEX diffractometer3716 independent reflections
Radiation source: fine-focus sealed tube3013 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −9→10
Tmin = 0.831, Tmax = 0.939k = −12→12
7840 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0499P)2 + 0.2795P] where P = (Fo2 + 2Fc2)/3
3716 reflections(Δ/σ)max = 0.001
233 parametersΔρmax = 0.75 e Å3
1 restraintΔρmin = −0.42 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
V11.03271 (5)0.59868 (4)0.20412 (3)0.01980 (12)
O11.23385 (19)0.48290 (15)0.12970 (13)0.0226 (3)
O20.90127 (19)0.68028 (15)0.35967 (13)0.0215 (3)
O30.5685 (2)0.44133 (16)0.65797 (15)0.0270 (4)
H30.642 (3)0.413 (3)0.5925 (17)0.052 (9)*
O40.8957 (2)0.58562 (17)0.12891 (14)0.0268 (4)
O51.1345 (2)0.75747 (15)0.15366 (13)0.0242 (3)
N10.9533 (2)0.43490 (19)0.32837 (15)0.0200 (4)
N20.8269 (2)0.46643 (18)0.44290 (15)0.0197 (4)
C11.4016 (3)0.3021 (2)0.0049 (2)0.0262 (5)
H1A1.51570.33900.00560.039*
H1B1.37640.3345−0.07090.039*
H1C1.41380.20160.00770.039*
C21.2480 (3)0.3493 (2)0.11473 (19)0.0226 (5)
C31.1325 (3)0.2624 (2)0.1970 (2)0.0237 (5)
H3a1.14400.16810.17860.028*
C40.9969 (3)0.3040 (2)0.30769 (19)0.0211 (4)
C50.9049 (3)0.1972 (2)0.4039 (2)0.0246 (5)
H5A0.77160.21230.42630.037*
H5B0.94130.20400.47760.037*
H5C0.94180.10570.37040.037*
C60.8042 (3)0.5988 (2)0.45013 (18)0.0197 (4)
C70.6691 (3)0.6619 (2)0.55786 (18)0.0191 (4)
C80.5524 (3)0.5805 (2)0.65770 (19)0.0202 (4)
C90.4232 (3)0.6431 (2)0.75423 (19)0.0213 (4)
H90.34740.58830.81990.026*
C100.3994 (3)0.7875 (2)0.75869 (19)0.0197 (4)
C110.2617 (3)0.8555 (2)0.8555 (2)0.0240 (5)
H110.18390.80290.92210.029*
C120.2394 (3)0.9953 (2)0.8542 (2)0.0262 (5)
H120.14591.03860.91970.031*
C130.3529 (3)1.0762 (2)0.7572 (2)0.0257 (5)
H130.33561.17330.75720.031*
C140.4881 (3)1.0143 (2)0.6631 (2)0.0227 (5)
H140.56531.06920.59820.027*
C150.5148 (3)0.8695 (2)0.66085 (18)0.0187 (4)
C160.6479 (3)0.8029 (2)0.56254 (18)0.0194 (4)
H160.72590.85690.49720.023*
C171.2231 (3)0.8381 (2)0.2134 (2)0.0286 (5)
H17A1.13330.87410.28890.043*
H17B1.27890.91460.15770.043*
H17C1.31850.78130.23500.043*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
V10.01469 (19)0.0299 (2)0.01415 (19)−0.00336 (14)−0.00424 (14)0.00440 (14)
O10.0149 (7)0.0334 (8)0.0186 (8)−0.0038 (6)−0.0041 (6)0.0014 (6)
O20.0170 (7)0.0285 (8)0.0160 (7)−0.0034 (6)−0.0019 (6)0.0047 (6)
O30.0288 (9)0.0262 (8)0.0201 (8)−0.0047 (7)0.0000 (7)0.0030 (6)
O40.0197 (8)0.0417 (9)0.0203 (8)−0.0049 (7)−0.0089 (6)0.0057 (7)
O50.0217 (8)0.0306 (8)0.0167 (8)−0.0047 (6)−0.0013 (6)0.0030 (6)
N10.0127 (8)0.0318 (10)0.0147 (9)−0.0022 (7)−0.0037 (7)0.0017 (7)
N20.0134 (8)0.0310 (10)0.0138 (8)−0.0012 (7)−0.0036 (7)0.0019 (7)
C10.0187 (11)0.0391 (13)0.0203 (11)−0.0008 (9)−0.0058 (9)−0.0006 (9)
C20.0183 (11)0.0336 (12)0.0185 (11)−0.0018 (9)−0.0096 (9)−0.0002 (9)
C30.0213 (11)0.0293 (11)0.0218 (11)−0.0009 (9)−0.0083 (9)−0.0029 (9)
C40.0165 (10)0.0297 (11)0.0200 (11)−0.0032 (8)−0.0100 (8)0.0012 (9)
C50.0225 (11)0.0292 (12)0.0208 (11)−0.0035 (9)−0.0055 (9)0.0021 (9)
C60.0140 (10)0.0319 (12)0.0146 (10)−0.0035 (8)−0.0072 (8)0.0048 (8)
C70.0140 (10)0.0296 (11)0.0140 (10)−0.0031 (8)−0.0053 (8)0.0044 (8)
C80.0183 (10)0.0272 (11)0.0175 (10)−0.0042 (8)−0.0095 (8)0.0045 (8)
C90.0179 (10)0.0305 (11)0.0157 (10)−0.0068 (9)−0.0059 (8)0.0066 (8)
C100.0157 (10)0.0312 (11)0.0148 (10)−0.0045 (8)−0.0085 (8)0.0038 (8)
C110.0164 (10)0.0373 (13)0.0175 (11)−0.0034 (9)−0.0049 (8)0.0043 (9)
C120.0192 (11)0.0370 (13)0.0206 (11)0.0031 (9)−0.0049 (9)−0.0019 (9)
C130.0259 (12)0.0280 (11)0.0250 (12)−0.0006 (9)−0.0110 (9)−0.0002 (9)
C140.0211 (11)0.0293 (11)0.0190 (11)−0.0053 (9)−0.0083 (9)0.0061 (9)
C150.0153 (10)0.0271 (11)0.0157 (10)−0.0022 (8)−0.0082 (8)0.0029 (8)
C160.0139 (10)0.0300 (11)0.0152 (10)−0.0064 (8)−0.0065 (8)0.0073 (8)
C170.0321 (13)0.0277 (12)0.0227 (12)−0.0055 (10)−0.0032 (10)−0.0023 (9)

Geometric parameters (Å, °)

V1—O41.5850 (15)C5—H5C0.9800
V1—O51.7693 (15)C6—C71.465 (3)
V1—O11.8504 (15)C7—C161.378 (3)
V1—O21.9242 (15)C7—C81.439 (3)
V1—N12.0632 (17)C8—C91.365 (3)
O1—C21.319 (3)C9—C101.412 (3)
O2—C61.322 (2)C9—H90.9500
O3—C81.357 (3)C10—C111.420 (3)
O3—H30.828 (10)C10—C151.425 (3)
O5—C171.416 (3)C11—C121.365 (3)
N1—C41.315 (3)C11—H110.9500
N1—N21.390 (2)C12—C131.408 (3)
N2—C61.297 (3)C12—H120.9500
C1—C21.488 (3)C13—C141.367 (3)
C1—H1A0.9800C13—H130.9500
C1—H1B0.9800C14—C151.417 (3)
C1—H1C0.9800C14—H140.9500
C2—C31.366 (3)C15—C161.408 (3)
C3—C41.414 (3)C16—H160.9500
C3—H3a0.9500C17—H17A0.9800
C4—C51.504 (3)C17—H17B0.9800
C5—H5A0.9800C17—H17C0.9800
C5—H5B0.9800
O4—V1—O5105.62 (8)N2—C6—O2120.77 (19)
O4—V1—O1105.47 (8)N2—C6—C7121.02 (18)
O5—V1—O198.56 (7)O2—C6—C7118.20 (18)
O4—V1—O2108.97 (7)C16—C7—C8118.74 (19)
O5—V1—O287.78 (6)C16—C7—C6119.59 (18)
O1—V1—O2141.78 (6)C8—C7—C6121.63 (19)
O4—V1—N198.68 (7)O3—C8—C9118.97 (19)
O5—V1—N1153.82 (7)O3—C8—C7121.06 (19)
O1—V1—N183.93 (7)C9—C8—C7120.0 (2)
O2—V1—N175.08 (7)C8—C9—C10121.51 (19)
C2—O1—V1131.01 (13)C8—C9—H9119.2
C6—O2—V1117.27 (13)C10—C9—H9119.2
C8—O3—H3112 (2)C9—C10—C11122.76 (19)
C17—O5—V1128.78 (13)C9—C10—C15119.14 (19)
C4—N1—N2116.69 (17)C11—C10—C15118.09 (19)
C4—N1—V1127.25 (14)C12—C11—C10120.9 (2)
N2—N1—V1115.79 (13)C12—C11—H11119.5
C6—N2—N1108.95 (17)C10—C11—H11119.5
C2—C1—H1A109.5C11—C12—C13121.0 (2)
C2—C1—H1B109.5C11—C12—H12119.5
H1A—C1—H1B109.5C13—C12—H12119.5
C2—C1—H1C109.5C14—C13—C12119.7 (2)
H1A—C1—H1C109.5C14—C13—H13120.1
H1B—C1—H1C109.5C12—C13—H13120.1
O1—C2—C3121.7 (2)C13—C14—C15120.9 (2)
O1—C2—C1114.88 (19)C13—C14—H14119.5
C3—C2—C1123.4 (2)C15—C14—H14119.5
C2—C3—C4124.2 (2)C16—C15—C14122.15 (19)
C2—C3—H3a117.9C16—C15—C10118.45 (19)
C4—C3—H3a117.9C14—C15—C10119.37 (19)
N1—C4—C3120.71 (19)C7—C16—C15122.19 (18)
N1—C4—C5119.81 (19)C7—C16—H16118.9
C3—C4—C5119.47 (19)C15—C16—H16118.9
C4—C5—H5A109.5O5—C17—H17A109.5
C4—C5—H5B109.5O5—C17—H17B109.5
H5A—C5—H5B109.5H17A—C17—H17B109.5
C4—C5—H5C109.5O5—C17—H17C109.5
H5A—C5—H5C109.5H17A—C17—H17C109.5
H5B—C5—H5C109.5H17B—C17—H17C109.5
O4—V1—O1—C2−60.18 (18)N1—N2—C6—O2−3.3 (2)
O5—V1—O1—C2−169.10 (17)N1—N2—C6—C7175.95 (16)
O2—V1—O1—C293.57 (19)V1—O2—C6—N213.9 (2)
N1—V1—O1—C237.18 (17)V1—O2—C6—C7−165.34 (13)
O4—V1—O2—C681.17 (14)N2—C6—C7—C16−179.81 (18)
O5—V1—O2—C6−173.06 (14)O2—C6—C7—C16−0.5 (3)
O1—V1—O2—C6−72.03 (17)N2—C6—C7—C8−2.0 (3)
N1—V1—O2—C6−13.05 (13)O2—C6—C7—C8177.25 (17)
O4—V1—O5—C17159.55 (17)C16—C7—C8—O3−179.55 (18)
O1—V1—O5—C17−91.66 (18)C6—C7—C8—O32.6 (3)
O2—V1—O5—C1750.46 (17)C16—C7—C8—C90.4 (3)
N1—V1—O5—C172.0 (3)C6—C7—C8—C9−177.42 (18)
O4—V1—N1—C477.84 (18)O3—C8—C9—C10−179.64 (18)
O5—V1—N1—C4−124.0 (2)C7—C8—C9—C100.4 (3)
O1—V1—N1—C4−26.94 (17)C8—C9—C10—C11177.58 (19)
O2—V1—N1—C4−174.72 (18)C8—C9—C10—C15−0.8 (3)
O4—V1—N1—N2−95.99 (14)C9—C10—C11—C12−177.81 (19)
O5—V1—N1—N262.2 (2)C15—C10—C11—C120.6 (3)
O1—V1—N1—N2159.23 (13)C10—C11—C12—C13−0.3 (3)
O2—V1—N1—N211.45 (12)C11—C12—C13—C14−0.3 (3)
C4—N1—N2—C6177.68 (17)C12—C13—C14—C150.7 (3)
V1—N1—N2—C6−7.82 (19)C13—C14—C15—C16177.35 (19)
V1—O1—C2—C3−29.6 (3)C13—C14—C15—C10−0.4 (3)
V1—O1—C2—C1152.33 (15)C9—C10—C15—C160.4 (3)
O1—C2—C3—C4−4.0 (3)C11—C10—C15—C16−178.07 (18)
C1—C2—C3—C4173.90 (19)C9—C10—C15—C14178.22 (18)
N2—N1—C4—C3−176.11 (17)C11—C10—C15—C14−0.3 (3)
V1—N1—C4—C310.1 (3)C8—C7—C16—C15−0.8 (3)
N2—N1—C4—C52.5 (3)C6—C7—C16—C15177.05 (18)
V1—N1—C4—C5−171.27 (14)C14—C15—C16—C7−177.34 (19)
C2—C3—C4—N111.5 (3)C10—C15—C16—C70.4 (3)
C2—C3—C4—C5−167.2 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···N20.83 (1)1.91 (2)2.623 (2)144 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NK2050).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sarkari, A. & Pal, S. (2009). Inorg. Chim. Acta, 362, 3807–3812.
  • Shao, M.-C., Zhang, Y.-J., Zhang, Z.-Y. & Tang, Y.-Q. (1988). Sci. Chin. Ser. B (Engl. Ed.), 31, 781–788.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

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