(Acetyl­acetone isonicotinoylhydrazonato-κ3O,N′,O′)dioxidovanadate(V) monohydrate

Wong, H.W.; Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536810028886

metal-organic compounds

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Volume 66| Part 8| August 2010| Page m1020

https://doi.org/10.1107/S1600536810028886

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(Acetylacetone isonicotinoylhydrazonato-κ³O,N′,O′)dioxidovanadate(V) monohydrate

Hon Wee Wong,^a Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 15 July 2010; accepted 20 July 2010; online 24 July 2010)

The hydrazone anion in the title compound, [V(C₁₁H₁₂N₃O₂)O₂]·H₂O, is zwitterionic as its pyridyl N atom is protonated; the O, N and O′ atoms span the axial–equatorial–axial positions of the trigonal-bipyramidal coordination polyhedron of the metal atom. All non-H atoms lie on a crystallographic mirror plane apart from the oxide ligands, which are related by mirror symmetry. The pyridinium N atom acts as a hydrogen-bond donor to the solvent water molecule, which is in turn a hydrogen-bond donor to the both oxide ligands. These hydrogen-bonding interactions give rise to a three-dimensional network motif.

Related literature

For related vanadium(V) structures, see: Shao et al. (1988 ). The reaction of oxidovanadium(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 ).

Experimental

Crystal data

[V(C₁₁H₁₂N₃O₂)O₂]·H₂O
M_r = 319.19
Orthorhombic, P n m a
a = 13.9848 (10) Å
b = 6.6630 (4) Å
c = 13.8904 (10) Å
V = 1294.32 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 100 K
0.35 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.770, T_max = 0.858
11995 measured reflections
1610 independent reflections
1416 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.121
S = 1.11
1610 reflections
125 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1w⋯O1	0.84 (1)	1.91 (1)	2.732 (2)	168 (3)
N3—H3⋯O1wⁱ	0.86 (1)	1.87 (3)	2.683 (4)	158 (6)
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810028886/nk2049sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028886/nk2049Isup2.hkl

checkCIF report

Comment top

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 isonicotinic acid hydrazide yields the expected vanadium(V) complex of the mono-deprotonated Schiff base as a negatively-charged zwitterion as the pyridyl N-atom is protonated (Scheme I). The metal atom shows trigonal bipyramidal coordination, with the O,N,O'-atoms of the Schiff base spanning the axial sites (Fig. 1).

All non-hydrogen atoms lie on a crystallographic mirror plane other than the oxo ligands, which are related by mirror symmetry. The pyridinium N atom acts as a hydrogen-bond donor to the solvate water molecule, which is in turn a hydrogen bond donor to the both oxo ligands. Hydrogen bonding gives rise to a three-dimensional network motif.

Related literature top

For related vanadium(V) structures, see: Shao et al. (1988). 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).

Experimental top

Bis(acetylacetonato)oxovanadium(IV) (0.13 g, 0.5 mmol) and isonicotinic acid hydrazide (0.07 g, 0.75 mmol) heated in methanol (50 ml) for one hour. The brown solution was filtered; slow evaporation of the filtrate afforded brown crystals.

Structure description top

Computing details top

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

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of VO₂(C₁₁H₁₂N₃O₂)^.H₂O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry transformation: i = x, 1/2 – y, z.

(Acetylacetone isonicotinoylhydrazonato- κ³O,N',O')dioxidovanadate(V) monohydrate top

Crystal data top

[V(C₁₁H₁₂N₃O₂)O₂]·H₂O	F(000) = 656
M_r = 319.19	D_x = 1.638 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3731 reflections
a = 13.9848 (10) Å	θ = 2.9–27.6°
b = 6.6630 (4) Å	µ = 0.79 mm⁻¹
c = 13.8904 (10) Å	T = 100 K
V = 1294.32 (15) Å³	Prism, brown
Z = 4	0.35 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEX diffractometer	1610 independent reflections
Radiation source: fine-focus sealed tube	1416 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
T_min = 0.770, T_max = 0.858	k = −8→8
11995 measured reflections	l = −17→18

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0616P)² + 2.2562P] where P = (F_o² + 2F_c²)/3
1610 reflections	(Δ/σ)_max = 0.001
125 parameters	Δρ_max = 0.75 e Å⁻³
2 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

[V(C₁₁H₁₂N₃O₂)O₂]·H₂O	V = 1294.32 (15) Å³
M_r = 319.19	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 13.9848 (10) Å	µ = 0.79 mm⁻¹
b = 6.6630 (4) Å	T = 100 K
c = 13.8904 (10) Å	0.35 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEX diffractometer	1610 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1416 reflections with I > 2σ(I)
T_min = 0.770, T_max = 0.858	R_int = 0.033
11995 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	2 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.75 e Å⁻³
1610 reflections	Δρ_min = −0.72 e Å⁻³
125 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
V1	0.41194 (4)	0.2500	0.31526 (4)	0.01205 (19)
O1	0.41890 (11)	0.0504 (3)	0.24747 (12)	0.0191 (4)
O2	0.27403 (16)	0.2500	0.32874 (16)	0.0204 (5)
O3	0.54634 (16)	0.2500	0.35590 (16)	0.0189 (5)
O1W	0.47876 (17)	−0.2500	0.12798 (18)	0.0194 (5)
H1W	0.467 (2)	−0.148 (3)	0.161 (2)	0.040 (10)*
N1	0.40746 (18)	0.2500	0.46744 (19)	0.0138 (5)
N2	0.49679 (19)	0.2500	0.51358 (19)	0.0139 (5)
N3	0.84943 (19)	0.2500	0.5420 (2)	0.0155 (5)
H3	0.9099 (11)	0.2500	0.554 (4)	0.059 (18)*
C1	0.1102 (2)	0.2500	0.3685 (3)	0.0218 (7)
H1A	0.1065	0.2500	0.2981	0.033*
H1B	0.0784	0.3701	0.3937	0.033*	0.50
H1C	0.0784	0.1299	0.3937	0.033*	0.50
C2	0.2135 (2)	0.2500	0.3993 (2)	0.0163 (6)
C3	0.2387 (2)	0.2500	0.4946 (2)	0.0165 (6)
H3A	0.1889	0.2500	0.5412	0.020*
C4	0.3340 (2)	0.2500	0.5277 (2)	0.0137 (6)
C5	0.3508 (2)	0.2500	0.6351 (2)	0.0198 (7)
H5A	0.4197	0.2500	0.6480	0.030*
H5B	0.3218	0.1299	0.6635	0.030*	0.50
H5C	0.3218	0.3701	0.6635	0.030*	0.50
C6	0.5624 (2)	0.2500	0.4488 (2)	0.0140 (6)
C7	0.6634 (2)	0.2500	0.4810 (2)	0.0133 (6)
C8	0.7378 (2)	0.2500	0.4146 (2)	0.0156 (6)
H8	0.7246	0.2500	0.3475	0.019*
C9	0.8314 (2)	0.2500	0.4473 (2)	0.0165 (6)
H9	0.8828	0.2500	0.4025	0.020*
C10	0.7787 (2)	0.2500	0.6080 (2)	0.0166 (6)
H10	0.7941	0.2500	0.6746	0.020*
C11	0.6845 (2)	0.2500	0.5800 (2)	0.0153 (6)
H11	0.6347	0.2500	0.6265	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.0111 (3)	0.0163 (3)	0.0087 (3)	0.000	0.00041 (18)	0.000
O1	0.0180 (8)	0.0203 (8)	0.0192 (8)	0.0007 (6)	−0.0002 (6)	−0.0048 (7)
O2	0.0131 (11)	0.0351 (14)	0.0129 (11)	0.000	−0.0001 (9)	0.000
O3	0.0127 (11)	0.0333 (14)	0.0108 (11)	0.000	−0.0004 (8)	0.000
O1W	0.0188 (12)	0.0193 (12)	0.0201 (12)	0.000	0.0066 (10)	0.000
N1	0.0109 (12)	0.0183 (13)	0.0121 (13)	0.000	−0.0012 (9)	0.000
N2	0.0121 (12)	0.0171 (12)	0.0124 (12)	0.000	−0.0019 (10)	0.000
N3	0.0126 (12)	0.0192 (13)	0.0146 (13)	0.000	−0.0021 (10)	0.000
C1	0.0122 (15)	0.035 (2)	0.0187 (16)	0.000	−0.0006 (13)	0.000
C2	0.0128 (14)	0.0195 (15)	0.0165 (16)	0.000	0.0011 (12)	0.000
C3	0.0144 (15)	0.0194 (15)	0.0158 (15)	0.000	0.0010 (12)	0.000
C4	0.0154 (15)	0.0141 (14)	0.0115 (14)	0.000	0.0005 (11)	0.000
C5	0.0178 (15)	0.0314 (19)	0.0102 (15)	0.000	0.0025 (12)	0.000
C6	0.0143 (14)	0.0150 (14)	0.0126 (14)	0.000	−0.0013 (12)	0.000
C7	0.0140 (14)	0.0131 (14)	0.0128 (14)	0.000	−0.0016 (11)	0.000
C8	0.0170 (15)	0.0180 (15)	0.0117 (14)	0.000	−0.0009 (12)	0.000
C9	0.0154 (15)	0.0195 (15)	0.0145 (15)	0.000	0.0010 (12)	0.000
C10	0.0185 (15)	0.0191 (15)	0.0123 (15)	0.000	−0.0015 (12)	0.000
C11	0.0156 (15)	0.0181 (15)	0.0122 (14)	0.000	0.0021 (12)	0.000

Geometric parameters (Å, º) top

V1—O1	1.6323 (17)	C1—H1C	0.9800
V1—O1ⁱ	1.6323 (17)	C2—C3	1.369 (5)
V1—O2	1.938 (2)	C3—C4	1.411 (4)
V1—O3	1.962 (2)	C3—H3A	0.9500
V1—N1	2.115 (3)	C4—C5	1.510 (4)
O2—C2	1.295 (4)	C5—H5A	0.9800
O3—C6	1.310 (4)	C5—H5B	0.9800
O1W—H1W	0.838 (10)	C5—H5C	0.9800
N1—C4	1.325 (4)	C6—C7	1.481 (4)
N1—N2	1.404 (4)	C7—C8	1.391 (4)
N2—C6	1.286 (4)	C7—C11	1.407 (4)
N3—C9	1.340 (4)	C8—C9	1.385 (4)
N3—C10	1.349 (4)	C8—H8	0.9500
N3—H3	0.861 (10)	C9—H9	0.9500
C1—C2	1.507 (4)	C10—C11	1.373 (5)
C1—H1A	0.9800	C10—H10	0.9500
C1—H1B	0.9800	C11—H11	0.9500

O1—V1—O1ⁱ	109.11 (13)	C2—C3—H3A	118.1
O1—V1—O2	96.61 (7)	C4—C3—H3A	118.1
O1ⁱ—V1—O2	96.61 (7)	N1—C4—C3	121.8 (3)
O1—V1—O3	96.25 (7)	N1—C4—C5	120.3 (3)
O1ⁱ—V1—O3	96.25 (7)	C3—C4—C5	117.9 (3)
O2—V1—O3	157.73 (10)	C4—C5—H5A	109.5
O1—V1—N1	125.34 (6)	C4—C5—H5B	109.5
O1ⁱ—V1—N1	125.34 (6)	H5A—C5—H5B	109.5
O2—V1—N1	82.75 (10)	C4—C5—H5C	109.5
O3—V1—N1	74.98 (10)	H5A—C5—H5C	109.5
C2—O2—V1	136.3 (2)	H5B—C5—H5C	109.5
C6—O3—V1	116.6 (2)	N2—C6—O3	124.5 (3)
C4—N1—N2	113.6 (3)	N2—C6—C7	118.0 (3)
C4—N1—V1	130.9 (2)	O3—C6—C7	117.5 (3)
N2—N1—V1	115.46 (19)	C8—C7—C11	119.4 (3)
C6—N2—N1	108.4 (3)	C8—C7—C6	120.9 (3)
C9—N3—C10	122.0 (3)	C11—C7—C6	119.7 (3)
C9—N3—H3	112 (4)	C9—C8—C7	119.3 (3)
C10—N3—H3	126 (4)	C9—C8—H8	120.3
C2—C1—H1A	109.5	C7—C8—H8	120.3
C2—C1—H1B	109.5	N3—C9—C8	120.0 (3)
H1A—C1—H1B	109.5	N3—C9—H9	120.0
C2—C1—H1C	109.5	C8—C9—H9	120.0
H1A—C1—H1C	109.5	N3—C10—C11	120.7 (3)
H1B—C1—H1C	109.5	N3—C10—H10	119.7
O2—C2—C3	124.3 (3)	C11—C10—H10	119.7
O2—C2—C1	114.3 (3)	C10—C11—C7	118.6 (3)
C3—C2—C1	121.4 (3)	C10—C11—H11	120.7
C2—C3—C4	123.9 (3)	C7—C11—H11	120.7

O1—V1—O2—C2	124.90 (6)	N2—N1—C4—C3	180.0
O1ⁱ—V1—O2—C2	−124.90 (6)	V1—N1—C4—C3	0.0
O3—V1—O2—C2	0.0	N2—N1—C4—C5	0.0
N1—V1—O2—C2	0.0	V1—N1—C4—C5	180.0
O1—V1—O3—C6	−124.96 (6)	C2—C3—C4—N1	0.0
O1ⁱ—V1—O3—C6	124.96 (6)	C2—C3—C4—C5	180.0
O2—V1—O3—C6	0.0	N1—N2—C6—O3	0.0
N1—V1—O3—C6	0.0	N1—N2—C6—C7	180.0
O1—V1—N1—C4	−92.98 (9)	V1—O3—C6—N2	0.0
O1ⁱ—V1—N1—C4	92.98 (9)	V1—O3—C6—C7	180.0
O2—V1—N1—C4	0.0	N2—C6—C7—C8	180.0
O3—V1—N1—C4	180.0	O3—C6—C7—C8	0.0
O1—V1—N1—N2	87.02 (9)	N2—C6—C7—C11	0.0
O1ⁱ—V1—N1—N2	−87.02 (9)	O3—C6—C7—C11	180.0
O2—V1—N1—N2	180.0	C11—C7—C8—C9	0.0
O3—V1—N1—N2	0.0	C6—C7—C8—C9	180.0
C4—N1—N2—C6	180.0	C10—N3—C9—C8	0.0
V1—N1—N2—C6	0.0	C7—C8—C9—N3	0.0
V1—O2—C2—C3	0.0	C9—N3—C10—C11	0.0
V1—O2—C2—C1	180.0	N3—C10—C11—C7	0.0
O2—C2—C3—C4	0.0	C8—C7—C11—C10	0.0
C1—C2—C3—C4	180.0	C6—C7—C11—C10	180.0

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1w···O1	0.84 (1)	1.91 (1)	2.732 (2)	168 (3)
N3—H3···O1wⁱⁱ	0.86 (1)	1.87 (3)	2.683 (4)	158 (6)

Symmetry code: (ii) −x+3/2, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	[V(C₁₁H₁₂N₃O₂)O₂]·H₂O
M_r	319.19
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	100
a, b, c (Å)	13.9848 (10), 6.6630 (4), 13.8904 (10)
V (Å³)	1294.32 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.35 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.770, 0.858
No. of measured, independent and observed [I > 2σ(I)] reflections	11995, 1610, 1416
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.121, 1.11
No. of reflections	1610
No. of parameters	125
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.72

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1w···O1	0.84 (1)	1.91 (1)	2.732 (2)	168 (3)
N3—H3···O1wⁱ	0.86 (1)	1.87 (3)	2.683 (4)	158 (6)

Symmetry code: (i) −x+3/2, −y, z+1/2.

Acknowledgements

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

References

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