Crystal structure of (2-formyl­phenolato-κ2O,O′)oxido(2-{[(2-oxidoeth­yl)imino]­meth­yl}phenolato-κ3O,N,O′)vanadium(V)

Parimala, S.; Selvam, P.

doi:10.1107/S2056989015006477

metal-organic compounds

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages m104-m105

https://doi.org/10.1107/S2056989015006477

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Crystal structure of (2-formylphenolato-κ²O,O′)oxido(2-{[(2-oxidoethyl)imino]methyl}phenolato-κ³O,N,O′)vanadium(V)

Sowmianarayanan Parimala ^a and Parasuraman Selvam ^a,^b,^c ^*

^aNational Centre for Catalysis Research, Chemistry Department, Indian Institute of Technology-Madras, Chennai 600 032, India, ^bNew Industry Creation Hatchery Center, Tohoku University, Sendai 980 8579, Japan, and ^cSchool of Science and Health, University of Western, Sydney, Penrith, NSW 275, Australia
^*Correspondence e-mail: selvam@iitm.ac.in

Edited by R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 5 January 2015; accepted 30 March 2015; online 9 April 2015)

In the unsymmetrical title vanadyl complex, [V(C₉H₉NO₂)(C₇H₅O₂)O], one of the ligands (2-formylphenol) is disordered over two sets of sites, with an occupancy ratio of 0.55 (2):0.45 (2). The metal atom is hexacoordinated, with a distorted octahedral geometry. The vanadyl O atom (which subtends the shortest V—O bond) occupies one of the apical positions and the remaining axial bond (the longest in the polyhedron) is provided by the (disordered) formyl O atoms. The basal plane is defined by the two phenoxide O atoms, the iminoalcoholic O and the imino N atom. The planes of the two benzene rings are almost perpendicular to each other, subtending an interplanar angle of 84.1 (2)° between the major parts. The crystal structure features weak C—H⋯O and C—H⋯π interactions, forming a lateral arrangement of adjacent molecules.

Keywords: crystal structure; vanadyl complex; catalyst; hydrogen bonding; C—H⋯π interactions.

CCDC reference: 1057002

1. Related literature

For general background to catalysis, see: Forzatti et al. (1987 ); Harding et al. (1994 ); Xia et al. (2012 ); Salavati-Niasari et al. (2004 ). For C—H oxidation reactions, see: Grivani et al. (2013 ); Maurya et al. (2011 ); Talsi et al. (1993 ); Zhang et al. (2005 ).

2. Experimental

2.1. Crystal data

[V(C₉H₉NO₂)(C₇H₅O₂)O]
M_r = 351.22
Monoclinic, P 2₁ /c
a = 6.6915 (2) Å
b = 7.6542 (4) Å
c = 29.1847 (9) Å
β = 95.126 (3)°
V = 1488.81 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 293 K
0.25 × 0.25 × 0.20 mm

2.2. Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.846, T_max = 0.880
18824 measured reflections
3249 independent reflections
2918 reflections with I > 2σ(I)
R_int = 0.025

2.3. Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.102
S = 1.22
3249 reflections
290 parameters
143 restraints
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected bond lengths (Å)

V1—O5	1.5886 (19)
V1—O3	1.859 (3)
V1—O2	1.8333 (18)
V1—O1	1.8957 (17)
V1—O3′	1.859 (3)
V1—N1	2.0966 (19)
V1—O4′	2.269 (4)
V1—O4	2.275 (3)

Table 2
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O5ⁱ	0.93	2.56	3.352 (4)	143
C5—H5⋯O4ⁱⁱ	0.93	2.50	3.220 (13)	134
C2—H2⋯Cgⁱ	0.93	2.84	3.615 (3)	141
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL2014/7.

Supporting information

CCDC reference: 1057002

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015006477/bg2547sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015006477/bg2547Isup2.hkl

checkCIF report

Introduction top

Vanadyl complexes are good catalysts for oxidation of organic compounds as they have the ability to transfer an oxygen atom for epoxidation and C—H oxidation reactions by hydrogen peroxide and tertiary butyl hydroperoxide. In the presence of peroxides they are readily converted into oxoperoxovanadium(V) complexes or alkylhydroperoxideVanadium(V) complex.

Experimental top

Synthesis and crystallization top

The title complex was synthesized by the reaction of Vanadylsulphate ( 4.52g, 0.025mol) in 20ml of methanol with 2-formylphenol ( 5.24ml, 0.05mol) in 20ml of methanol and the mixture was refluxed for 1 hr. To the above mixture, 10ml of methanol containing 2-aminoethanol (1.5ml, 0.025mol) was added and the reflux was continued for 6 hr. The resulting dark brown crystalline solid was filtered, washed quickly with cold methanol and recrystallized from methanol to get pure blackish brown crystals.

Refinement top

All the hydrogen atoms in the molecule were identified from the difference electron density map, further idealized and treated as riding with a distance d(C—H)=0.93Å (for aromatic C—H) and d(C—H)=0.97 for (CH₂)respectively. In all cases Uiso(H)=-1.2Ueq.

The 2-formylphenyl moeity is disordered over two sites, with site occupancies 0.55:0.452 (2). C—C and C—O bond distances in the disordered moieties were restrained using similarity restraints (SAME command in SHELXL2014), while continuity restraints were applied to the anisotropic displacement parameters Uij for all atoms (RIGU command in SHELXL2014).

Results and discussion top

Crystal data, data collection and structure refinement details for the title compound C₁₆H₁₄NO₅V (I) are summarized in Table 1, while bond distances are summarized in Table 2. An ORTEP diagram of the molecule with 30% probability displacement factors is shown in Figure 1.

The molecule consists of a vanadyl moiety with (O,O') 2-formylphenol and (O,N,O') ((2-hydroxyethylimino)methyl)phenol ligands bound to vanadium and defining a distorted octahedral geometry around the cation. The (2-formylphenol) group is disordered over two sites with occupancies of 55:45 (2). The basal plane of the (distorted) vanadium octahedral environment is defined by phenoxide oxygens O1 (C1—C6) and O3 (C11—C16), the imino N1 and the iminoalcoholic O2. The vanadyl oxygen O5 (which subtends the shortest V—O bond, see Table 2) occupies one of the apical positions; this axial oxygen atom is suitable for the formation of a cyclic V—O—O intermediate which is an important step in the mechanism of peroxidative oxidation of organic compounds. The remaining axial bond is provided by O4 from the formyl group belonging to the phenyl ring C11—C16, and which displays the longest V—O distance in the molecule. The planes of the two phenyl rings are almost perpendicular to each other, subtending an interplanar angle of 84.1 (2)^ο^. between major parts.

The crystal structure is stabilized by some weak C—H···O and C—H···π contacts presented in Table 3.

Related literature top

For general background to catalysis, see: Forzatti et al. (1987); Harding et al. (1994); Xia et al. (2012); Salavati-Niasari et al. (2004). For C—H oxidation reactions, see: Grivani et al. (2013); Maurya et al. (2011); Talsi et al. (1993); Zhang et al. (2005).

Structure description top

The crystal structure is stabilized by some weak C—H···O and C—H···π contacts presented in Table 3.

For general background to catalysis, see: Forzatti et al. (1987); Harding et al. (1994); Xia et al. (2012); Salavati-Niasari et al. (2004). For C—H oxidation reactions, see: Grivani et al. (2013); Maurya et al. (2011); Talsi et al. (1993); Zhang et al. (2005).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015).

Figures top

Fig. 1. Molecular structure of the title compound with atom labelling. Displacement ellipsoids are drawn at 30% probability level. (The minor component of the disordered 2-formylphenol moiety is not shown).

(2-formylphenolato-κ²O,O')oxido(2-{[(2-oxidoethyl)imino]methyl}phenolato-κ³O,N,O')vanadium(V) top

Crystal data top

[V(C₉H₉NO₂)(C₇H₅O₂)O]	F(000) = 720
M_r = 351.22	D_x = 1.567 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.6915 (2) Å	Cell parameters from 7573 reflections
b = 7.6542 (4) Å	θ = 2.8–29.9°
c = 29.1847 (9) Å	µ = 0.69 mm⁻¹
β = 95.126 (3)°	T = 293 K
V = 1488.81 (10) Å³	Blocks, black
Z = 4	0.25 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2918 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
ω and φ scan	θ_max = 27.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→8
T_min = 0.846, T_max = 0.880	k = −9→9
18824 measured reflections	l = −37→37
3249 independent reflections

Refinement top

Refinement on F²	143 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0298P)² + 1.478P] where P = (F_o² + 2F_c²)/3
S = 1.22	(Δ/σ)_max = 0.001
3249 reflections	Δρ_max = 0.29 e Å⁻³
290 parameters	Δρ_min = −0.35 e Å⁻³

Crystal data top

[V(C₉H₉NO₂)(C₇H₅O₂)O]	V = 1488.81 (10) Å³
M_r = 351.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6915 (2) Å	µ = 0.69 mm⁻¹
b = 7.6542 (4) Å	T = 293 K
c = 29.1847 (9) Å	0.25 × 0.25 × 0.20 mm
β = 95.126 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3249 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2918 reflections with I > 2σ(I)
T_min = 0.846, T_max = 0.880	R_int = 0.025
18824 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	143 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.22	Δρ_max = 0.29 e Å⁻³
3249 reflections	Δρ_min = −0.35 e Å⁻³
290 parameters

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
V1	0.26635 (5)	0.25635 (6)	0.12647 (2)	0.02941 (13)
N1	0.5270 (3)	0.2221 (3)	0.17101 (7)	0.0309 (4)
O1	0.1761 (2)	0.3678 (2)	0.17886 (5)	0.0335 (4)
O2	0.4526 (3)	0.2057 (3)	0.08602 (6)	0.0441 (5)
O5	0.1870 (3)	0.0660 (3)	0.13678 (7)	0.0430 (4)
C1	0.1947 (3)	0.3159 (3)	0.22234 (8)	0.0283 (5)
C2	0.0450 (4)	0.3559 (3)	0.25122 (9)	0.0353 (5)
H2	−0.0677	0.4184	0.2398	0.042*
C3	0.0638 (4)	0.3033 (4)	0.29651 (9)	0.0430 (6)
H3	−0.0391	0.3274	0.3150	0.052*
C4	0.2328 (5)	0.2150 (4)	0.31514 (9)	0.0450 (7)
H4	0.2430	0.1793	0.3457	0.054*
C5	0.3843 (4)	0.1810 (4)	0.28796 (9)	0.0392 (6)
H5	0.5002	0.1259	0.3006	0.047*
C6	0.3684 (3)	0.2278 (3)	0.24135 (8)	0.0315 (5)
C7	0.5346 (3)	0.1987 (3)	0.21439 (9)	0.0334 (5)
H7	0.6550	0.1606	0.2295	0.040*
C8	0.7059 (4)	0.1994 (4)	0.14621 (10)	0.0395 (6)
H8A	0.8031	0.1246	0.1633	0.047*
H8B	0.7682	0.3111	0.1409	0.047*
C9	0.6286 (4)	0.1157 (4)	0.10163 (10)	0.0438 (6)
H9A	0.7273	0.1248	0.0793	0.053*
H9B	0.5998	−0.0069	0.1063	0.053*
O3	0.0652 (12)	0.3279 (8)	0.0824 (4)	0.0280 (19)	0.55 (2)
O4	0.3721 (14)	0.5368 (8)	0.1196 (5)	0.035 (2)	0.55 (2)
C10	0.2794 (14)	0.6543 (7)	0.0990 (4)	0.0368 (19)	0.55 (2)
H10	0.3396	0.7639	0.1000	0.044*	0.55 (2)
C11	0.0863 (13)	0.6404 (7)	0.0732 (3)	0.0310 (16)	0.55 (2)
C12	0.0013 (15)	0.7914 (8)	0.0525 (3)	0.043 (2)	0.55 (2)
H12	0.0660	0.8983	0.0572	0.052*	0.55 (2)
C13	−0.1765 (14)	0.7829 (11)	0.0252 (3)	0.044 (2)	0.55 (2)
H13	−0.2320	0.8833	0.0114	0.053*	0.55 (2)
C14	−0.2714 (11)	0.6253 (12)	0.0186 (3)	0.0386 (18)	0.55 (2)
H14	−0.3922	0.6200	0.0002	0.046*	0.55 (2)
C15	−0.1924 (9)	0.4741 (11)	0.0386 (3)	0.0338 (17)	0.55 (2)
H15	−0.2611	0.3690	0.0340	0.041*	0.55 (2)
C16	−0.0087 (11)	0.4785 (8)	0.0657 (4)	0.0262 (16)	0.55 (2)
O3'	0.0547 (14)	0.3519 (9)	0.0891 (5)	0.028 (2)	0.45 (2)
O4'	0.4058 (16)	0.5227 (10)	0.1170 (6)	0.039 (3)	0.45 (2)
C10'	0.3244 (16)	0.6488 (8)	0.0978 (5)	0.041 (3)	0.45 (2)
H10'	0.3946	0.7538	0.1001	0.050*	0.45 (2)
C11'	0.1309 (15)	0.6516 (8)	0.0720 (5)	0.037 (2)	0.45 (2)
C12'	0.0638 (18)	0.8090 (8)	0.0514 (4)	0.043 (2)	0.45 (2)
H12'	0.1444	0.9080	0.0547	0.052*	0.45 (2)
C13'	−0.1199 (18)	0.8183 (11)	0.0266 (4)	0.045 (2)	0.45 (2)
H13'	−0.1619	0.9218	0.0121	0.054*	0.45 (2)
C14'	−0.2409 (14)	0.6738 (14)	0.0234 (4)	0.043 (2)	0.45 (2)
H14'	−0.3661	0.6809	0.0069	0.052*	0.45 (2)
C15'	−0.1817 (13)	0.5178 (13)	0.0441 (4)	0.039 (2)	0.45 (2)
H15'	−0.2659	0.4211	0.0410	0.047*	0.45 (2)
C16'	0.0050 (13)	0.5050 (10)	0.0697 (5)	0.031 (2)	0.45 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.0230 (2)	0.0370 (2)	0.0279 (2)	−0.00340 (17)	0.00052 (14)	0.00299 (17)
N1	0.0210 (9)	0.0339 (11)	0.0381 (11)	0.0003 (8)	0.0031 (8)	0.0045 (9)
O1	0.0282 (8)	0.0432 (10)	0.0289 (8)	0.0098 (7)	0.0016 (6)	0.0045 (7)
O2	0.0359 (9)	0.0629 (13)	0.0347 (9)	0.0014 (9)	0.0096 (8)	−0.0020 (9)
O5	0.0384 (10)	0.0422 (11)	0.0479 (11)	−0.0069 (8)	0.0020 (8)	0.0045 (9)
C1	0.0277 (11)	0.0292 (11)	0.0275 (11)	−0.0026 (9)	−0.0002 (9)	−0.0030 (9)
C2	0.0324 (13)	0.0342 (13)	0.0398 (13)	0.0035 (10)	0.0056 (10)	−0.0041 (11)
C3	0.0520 (16)	0.0416 (15)	0.0376 (14)	−0.0031 (13)	0.0153 (12)	−0.0097 (12)
C4	0.0621 (18)	0.0452 (16)	0.0273 (12)	−0.0051 (14)	0.0025 (12)	−0.0001 (11)
C5	0.0418 (14)	0.0405 (14)	0.0336 (13)	0.0004 (12)	−0.0058 (11)	0.0037 (11)
C6	0.0299 (11)	0.0329 (13)	0.0306 (12)	−0.0031 (10)	−0.0024 (9)	0.0016 (10)
C7	0.0226 (11)	0.0355 (13)	0.0407 (13)	0.0017 (9)	−0.0057 (9)	0.0059 (11)
C8	0.0230 (11)	0.0460 (15)	0.0508 (16)	0.0018 (11)	0.0102 (10)	0.0048 (12)
C9	0.0386 (14)	0.0441 (15)	0.0513 (16)	0.0002 (12)	0.0186 (12)	−0.0007 (13)
O3	0.030 (3)	0.036 (2)	0.017 (3)	−0.0034 (18)	−0.002 (2)	−0.002 (2)
O4	0.026 (3)	0.040 (3)	0.036 (3)	−0.007 (2)	−0.003 (3)	−0.002 (2)
C10	0.034 (3)	0.038 (3)	0.037 (3)	−0.0057 (17)	−0.005 (3)	−0.004 (2)
C11	0.031 (3)	0.037 (2)	0.024 (3)	−0.0048 (15)	0.000 (2)	−0.0031 (16)
C12	0.042 (4)	0.036 (3)	0.048 (3)	−0.007 (2)	−0.013 (3)	0.000 (2)
C13	0.041 (4)	0.038 (3)	0.048 (3)	−0.004 (2)	−0.014 (3)	0.000 (2)
C14	0.040 (3)	0.040 (3)	0.033 (3)	−0.005 (2)	−0.012 (2)	0.000 (2)
C15	0.032 (2)	0.039 (3)	0.028 (3)	−0.0076 (19)	−0.0067 (19)	0.001 (3)
C16	0.028 (2)	0.035 (2)	0.015 (3)	−0.0042 (15)	0.0015 (18)	−0.0029 (19)
O3'	0.026 (3)	0.035 (3)	0.022 (4)	−0.005 (2)	0.001 (2)	−0.002 (3)
O4'	0.029 (4)	0.048 (4)	0.039 (4)	−0.009 (3)	0.005 (3)	0.003 (3)
C10'	0.037 (4)	0.045 (4)	0.041 (4)	−0.011 (2)	−0.001 (3)	0.000 (3)
C11'	0.038 (3)	0.039 (3)	0.034 (4)	−0.008 (2)	0.003 (3)	−0.002 (2)
C12'	0.048 (4)	0.038 (3)	0.042 (4)	−0.009 (2)	−0.005 (4)	−0.001 (3)
C13'	0.049 (4)	0.039 (3)	0.046 (4)	−0.008 (3)	−0.007 (3)	−0.004 (3)
C14'	0.040 (4)	0.039 (3)	0.048 (5)	−0.004 (3)	−0.013 (3)	−0.001 (3)
C15'	0.040 (3)	0.038 (3)	0.037 (4)	−0.003 (2)	−0.008 (3)	−0.004 (3)
C16'	0.034 (3)	0.037 (3)	0.020 (4)	−0.0031 (19)	0.001 (2)	−0.001 (3)

Geometric parameters (Å, º) top

V1—O5	1.5886 (19)	O3—C16	1.330 (4)
V1—O3	1.859 (3)	O4—C10	1.220 (4)
V1—O2	1.8333 (18)	C10—C11	1.439 (5)
V1—O1	1.8957 (17)	C10—H10	0.9300
V1—O3'	1.859 (3)	C11—C12	1.402 (4)
V1—N1	2.0966 (19)	C11—C16	1.401 (5)
V1—O4'	2.269 (4)	C12—C13	1.372 (6)
V1—O4	2.275 (3)	C12—H12	0.9300
N1—C7	1.275 (3)	C13—C14	1.369 (7)
N1—C8	1.464 (3)	C13—H13	0.9300
O1—C1	1.325 (3)	C14—C15	1.379 (5)
O2—C9	1.404 (3)	C14—H14	0.9300
C1—C2	1.400 (3)	C15—C16	1.401 (4)
C1—C6	1.413 (3)	C15—H15	0.9300
C2—C3	1.377 (4)	O3'—C16'	1.330 (4)
C2—H2	0.9300	O4'—C10'	1.220 (4)
C3—C4	1.386 (4)	C10'—C11'	1.439 (5)
C3—H3	0.9300	C10'—H10'	0.9300
C4—C5	1.367 (4)	C11'—C12'	1.402 (4)
C4—H4	0.9300	C11'—C16'	1.401 (5)
C5—C6	1.401 (3)	C12'—C13'	1.372 (6)
C5—H5	0.9300	C12'—H12'	0.9300
C6—C7	1.436 (3)	C13'—C14'	1.369 (7)
C7—H7	0.9300	C13'—H13'	0.9300
C8—C9	1.500 (4)	C14'—C15'	1.380 (5)
C8—H8A	0.9700	C14'—H14'	0.9300
C8—H8B	0.9700	C15'—C16'	1.402 (4)
C9—H9A	0.9700	C15'—H15'	0.9300
C9—H9B	0.9700

O5—V1—O3	99.65 (14)	C9—C8—H8B	110.9
O5—V1—O2	100.72 (10)	H8A—C8—H8B	108.9
O3—V1—O2	96.2 (5)	O2—C9—C8	106.6 (2)
O5—V1—O1	97.12 (9)	O2—C9—H9A	110.4
O3—V1—O1	99.3 (5)	C8—C9—H9A	110.4
O2—V1—O1	153.94 (8)	O2—C9—H9B	110.4
O5—V1—O3'	102.82 (18)	C8—C9—H9B	110.4
O2—V1—O3'	103.4 (6)	H9A—C9—H9B	108.6
O1—V1—O3'	90.9 (6)	C16—O3—V1	137.1 (4)
O5—V1—N1	92.39 (9)	C10—O4—V1	126.2 (3)
O3—V1—N1	167.5 (2)	O4—C10—C11	126.6 (3)
O2—V1—N1	78.28 (8)	O4—C10—H10	116.7
O1—V1—N1	82.15 (7)	C11—C10—H10	116.7
O3'—V1—N1	164.0 (2)	C12—C11—C16	120.1 (4)
O5—V1—O4'	174.29 (18)	C12—C11—C10	118.4 (4)
O2—V1—O4'	78.5 (5)	C16—C11—C10	121.4 (3)
O1—V1—O4'	81.8 (5)	C13—C12—C11	120.5 (4)
O3'—V1—O4'	82.83 (15)	C13—C12—H12	119.7
N1—V1—O4'	81.91 (16)	C11—C12—H12	119.7
O5—V1—O4	173.8 (4)	C12—C13—C14	119.4 (4)
O3—V1—O4	82.66 (13)	C12—C13—H13	120.3
O2—V1—O4	84.7 (4)	C14—C13—H13	120.3
O1—V1—O4	76.8 (4)	C13—C14—C15	121.6 (4)
N1—V1—O4	85.69 (13)	C13—C14—H14	119.2
C7—N1—C8	120.8 (2)	C15—C14—H14	119.2
C7—N1—V1	126.16 (16)	C14—C15—C16	120.1 (4)
C8—N1—V1	112.34 (16)	C14—C15—H15	119.9
C1—O1—V1	128.93 (15)	C16—C15—H15	119.9
C9—O2—V1	119.57 (16)	O3—C16—C15	117.7 (4)
O1—C1—C2	120.0 (2)	O3—C16—C11	124.1 (3)
O1—C1—C6	121.5 (2)	C15—C16—C11	118.2 (3)
C2—C1—C6	118.4 (2)	C16'—O3'—V1	138.1 (2)
C3—C2—C1	120.4 (2)	C10'—O4'—V1	126.5 (3)
C3—C2—H2	119.8	O4'—C10'—C11'	126.6 (3)
C1—C2—H2	119.8	O4'—C10'—H10'	116.7
C2—C3—C4	121.3 (3)	C11'—C10'—H10'	116.7
C2—C3—H3	119.3	C12'—C11'—C16'	120.0 (4)
C4—C3—H3	119.3	C12'—C11'—C10'	118.4 (4)
C5—C4—C3	119.1 (2)	C16'—C11'—C10'	121.4 (3)
C5—C4—H4	120.4	C13'—C12'—C11'	120.5 (4)
C3—C4—H4	120.4	C13'—C12'—H12'	119.7
C4—C5—C6	121.2 (2)	C11'—C12'—H12'	119.7
C4—C5—H5	119.4	C12'—C13'—C14'	119.4 (4)
C6—C5—H5	119.4	C12'—C13'—H13'	120.3
C5—C6—C1	119.5 (2)	C14'—C13'—H13'	120.3
C5—C6—C7	119.8 (2)	C13'—C14'—C15'	121.6 (4)
C1—C6—C7	120.6 (2)	C13'—C14'—H14'	119.2
N1—C7—C6	123.9 (2)	C15'—C14'—H14'	119.2
N1—C7—H7	118.0	C14'—C15'—C16'	120.1 (4)
C6—C7—H7	118.0	C14'—C15'—H15'	119.9
N1—C8—C9	104.2 (2)	C16'—C15'—H15'	119.9
N1—C8—H8A	110.9	O3'—C16'—C15'	117.7 (4)
C9—C8—H8A	110.9	O3'—C16'—C11'	124.0 (3)
N1—C8—H8B	110.9	C15'—C16'—C11'	118.2 (3)

O5—V1—O1—C1	46.7 (2)	O4—V1—O3—C16	−16.3 (14)
O3—V1—O1—C1	147.7 (2)	V1—O4—C10—C11	−2.3 (18)
O2—V1—O1—C1	−86.3 (3)	O4—C10—C11—C12	178.8 (12)
O3'—V1—O1—C1	149.7 (3)	O4—C10—C11—C16	−6.3 (16)
N1—V1—O1—C1	−44.75 (19)	C16—C11—C12—C13	1.0 (14)
O4'—V1—O1—C1	−127.6 (2)	C10—C11—C12—C13	176.0 (8)
O4—V1—O1—C1	−132.1 (2)	C11—C12—C13—C14	0.4 (12)
O5—V1—O2—C9	−68.2 (2)	C12—C13—C14—C15	−0.2 (12)
O3—V1—O2—C9	−169.3 (2)	C13—C14—C15—C16	−1.3 (13)
O1—V1—O2—C9	64.2 (3)	V1—O3—C16—C15	−166.8 (12)
O3'—V1—O2—C9	−174.3 (3)	V1—O3—C16—C11	14 (2)
N1—V1—O2—C9	22.07 (19)	C14—C15—C16—O3	−177.1 (11)
O4'—V1—O2—C9	106.1 (3)	C14—C15—C16—C11	2.5 (13)
O4—V1—O2—C9	108.7 (2)	C12—C11—C16—O3	177.2 (12)
V1—O1—C1—C2	−147.23 (18)	C10—C11—C16—O3	2.3 (15)
V1—O1—C1—C6	36.1 (3)	C12—C11—C16—C15	−2.4 (13)
O1—C1—C2—C3	−179.7 (2)	C10—C11—C16—C15	−177.2 (9)
C6—C1—C2—C3	−2.9 (4)	O5—V1—O3'—C16'	174.4 (17)
C1—C2—C3—C4	2.1 (4)	O2—V1—O3'—C16'	−81.1 (18)
C2—C3—C4—C5	0.6 (4)	O1—V1—O3'—C16'	76.9 (18)
C3—C4—C5—C6	−2.5 (4)	N1—V1—O3'—C16'	13 (4)
C4—C5—C6—C1	1.7 (4)	O4'—V1—O3'—C16'	−4.7 (17)
C4—C5—C6—C7	176.7 (3)	V1—O4'—C10'—C11'	−8 (2)
O1—C1—C6—C5	177.7 (2)	O4'—C10'—C11'—C12'	−178.7 (16)
C2—C1—C6—C5	1.0 (4)	O4'—C10'—C11'—C16'	6 (2)
O1—C1—C6—C7	2.8 (4)	C16'—C11'—C12'—C13'	−4.1 (17)
C2—C1—C6—C7	−173.9 (2)	C10'—C11'—C12'—C13'	−179.8 (10)
C8—N1—C7—C6	176.5 (2)	C11'—C12'—C13'—C14'	2.4 (15)
V1—N1—C7—C6	−13.5 (4)	C12'—C13'—C14'—C15'	−0.8 (14)
C5—C6—C7—N1	173.2 (2)	C13'—C14'—C15'—C16'	1.0 (16)
C1—C6—C7—N1	−11.9 (4)	V1—O3'—C16'—C15'	−178.2 (15)
C7—N1—C8—C9	141.9 (2)	V1—O3'—C16'—C11'	4 (2)
V1—N1—C8—C9	−29.4 (2)	C14'—C15'—C16'—O3'	179.8 (13)
V1—O2—C9—C8	−45.1 (3)	C14'—C15'—C16'—C11'	−2.6 (17)
N1—C8—C9—O2	44.1 (3)	C12'—C11'—C16'—O3'	−178.5 (15)
O5—V1—O3—C16	157.8 (14)	C10'—C11'—C16'—O3'	−2.9 (19)
O2—V1—O3—C16	−100.1 (14)	C12'—C11'—C16'—C15'	4.1 (17)
O1—V1—O3—C16	58.9 (15)	C10'—C11'—C16'—C15'	179.7 (12)
N1—V1—O3—C16	−37 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5ⁱ	0.93	2.56	3.352 (4)	143
C5—H5···O4ⁱⁱ	0.93	2.50	3.220 (13)	134
C2—H2···Cgⁱ	0.93	2.84	3.615 (3)	141

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.

Selected bond lengths (Å) top

V1—O5	1.5886 (19)	V1—O3'	1.859 (3)
V1—O3	1.859 (3)	V1—N1	2.0966 (19)
V1—O2	1.8333 (18)	V1—O4'	2.269 (4)
V1—O1	1.8957 (17)	V1—O4	2.275 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5ⁱ	0.93	2.56	3.352 (4)	143
C5—H5···O4ⁱⁱ	0.93	2.50	3.220 (13)	134
C2—H2···Cgⁱ	0.93	2.84	3.615 (3)	141

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors thank the Department of Science and Technology (DST), Government of India, for funding the National Centre for Catalysis Research (NCCR), IIT-Madras. The authors also thank Dr Babu Varghese and Dr P. K. Sudhadevi Antharjanam, SAIF, IIT-Madras, for the X-ray data collection and technical assistance in the preparation of the manuscript.

References

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Volume 71| Part 5| May 2015| Pages m104-m105

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