Crystal structure of {2,2′-[ethyl­enebis(nitrilo­methanylyl­idene)]diphenolato-κ4O,N,N′,O′}oxidovanadium(IV) methanol monosolvate

Hsuan, R.E.; Hughes, J.E.; Miller, T.H.; Shaikh, N.; Cunningham, P.H.M.; O'Connor, A.E.; Tidey, J.P.; Blake, A.J.

doi:10.1107/S1600536814023332

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages m380-m381

doi:10.1107/S1600536814023332

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Crystal structure of {2,2′-[ethylenebis(nitrilomethanylylidene)]diphenolato-κ⁴O,N,N′,O′}oxidovanadium(IV) methanol monosolvate

Rachel E. Hsuan,^a Jemma E. Hughes,^a Thomas H. Miller,^a Nabila Shaikh,^a Phoebe H. M. Cunningham,^a Alice E. O'Connor,^a Jeremiah P. Tidey ^a and Alexander J. Blake ^a ^*

^aSchool of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, England
^*Correspondence e-mail: a.j.blake@nottingham.ac.uk

Edited by J. F. Gallagher, Dublin City University, Ireland (Received 19 October 2014; accepted 22 October 2014; online 29 October 2014)

Two independent molecules of the title solvated complex, [V(C₁₆H₁₄N₂O₂)O]·CH₃OH, also known as [N,N′-bis(salicylidene)ethylenediamine]oxidovanadium(IV) or vanadyl salen, crystallize in the asymmetric unit. Each disordered methanol solvent molecule [occupancy ratios 0.678 (4):0.322 (4) and 0.750 (5):0.250 (5)] is linked to a [N,N′-bis(salicylidene)ethylenediamine]oxidovanadium(IV) molecule by an O—H⋯O hydrogen bond and to others by C—H⋯O hydrogen bonds. The resulting extended structure consists of a bilayer of molecules parallel to the ab plane. Despite the fact that solvates are common in complexes derived from substituted analogues of the N,N′-bis(salicylidene)ethylenediamine ligand, the title solvate is the first one of [N,N′-bis(salicylidene)ethylenediamine]oxidovanadium(IV) to be structurally characterized. The two vanadyl species have very similar internal geometries, which are best characterized as distorted square-based pyramidal with the vanadium atom displaced from the N₂O₂ basal plane by 0.5966 (9) Å in the direction of the doubly-bonded oxide ligand.

Keywords: crystal structure; oxidovanadium(IV); 2,2′-[ethylenebis(nitrilomethanylylidene)]diphenolate; N,N′-bis(salicylidene)ethylenediamine; hydrogen bonding.

CCDC reference: 1030592

1. Related literature

The literature reports three structure determinations on the unsolvated title complex, also known as [N,N′-bis(salicylidene)ethylenediamine]oxidovanadium(IV). The first was in the monoclinic space group P2₁/c by Riley et al. (1986 ), the second by Li et al. (2004 ) in the triclinic space group P $[\overline{1}]$ and the third in the monoclinic space group P2₁ (Wang et al., 2008 ). All three determinations were carried out at ambient temperature. According to the Cambridge Structural Database (Groom & Allen, 2014 ) no solvates of [N,N′-bis(salicylidene)ethylenediamine]oxidovanadium(IV) have been reported previously, although these are common for substituted analogues of the N,N′-bis(salicylidene)ethylenediamine ligand.

2. Experimental

2.1. Crystal data

[V(C₁₆H₁₄N₂O₂)O]·CH₄O
M_r = 365.27
Orthorhombic, P n a 2₁
a = 12.9597 (4) Å
b = 8.8616 (2) Å
c = 28.5426 (7) Å
V = 3277.92 (15) Å³
Z = 8
Cu Kα radiation
μ = 5.27 mm⁻¹
T = 120 K
0.31 × 0.14 × 0.05 mm

2.2. Data collection

Agilent GV1000 diffractometer with an Atlas CCD detector
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2013 ) T_min = 0.480, T_max = 0.959
7416 measured reflections
4634 independent reflections
4350 reflections with I > 2σ(I)
R_int = 0.025

2.3. Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.04
4634 reflections
479 parameters
32 restraints
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ). 1395 Friedel pairs
Absolute structure parameter: 0.066 (9)

Table 1
Selected geometric parameters (Å, °)

V1—O1	1.9155 (17)
V1—O2	1.9429 (16)
V1—O3	1.6070 (17)
V1—N1	2.0597 (19)
V1—N2	2.051 (2)
V2—O4	1.9164 (16)
V2—O5	1.6089 (16)
V2—O6	1.9314 (16)
V2—N3	2.062 (2)
V2—N4	2.060 (2)

O2—V1—N2	87.30 (8)
O2—V1—N1	150.78 (7)
O3—V1—O2	105.76 (8)
O3—V1—N2	107.35 (9)
O3—V1—O1	113.39 (8)
O3—V1—N1	102.90 (8)
N2—V1—N1	78.80 (8)
O1—V1—O2	86.60 (7)
O1—V1—N2	138.94 (8)
O1—V1—N1	87.26 (8)
O6—V2—N4	87.20 (8)
O6—V2—N3	150.79 (7)
O5—V2—O6	105.81 (8)
O5—V2—N4	107.66 (8)
O5—V2—O4	113.60 (8)
O5—V2—N3	102.81 (8)
N4—V2—N3	78.63 (8)
O4—V2—O6	86.66 (7)
O4—V2—N4	138.40 (8)
O4—V2—N3	87.25 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O8ⁱ	0.93	2.48	3.368 (4)	159
C14—H14⋯O8Aⁱ	0.93	2.48	3.299 (7)	147
C25—H25⋯O7ⁱⁱ	0.93	2.51	3.391 (4)	158
C25—H25⋯O7Aⁱⁱ	0.93	2.66	3.457 (9)	144
C13—H13⋯O3ⁱⁱⁱ	0.93	2.60	3.372 (3)	141
C23—H23⋯O5^iv	0.93	2.59	3.364 (3)	141
O8—H8A⋯O2	0.82	2.12	2.926 (4)	167
O7—H7A⋯O6	0.82	2.18	2.940 (3)	153
O7—H7A⋯O4	0.82	2.64	3.246 (4)	132
O8A—H8AA⋯O1	0.82	2.18	2.984 (6)	166
Symmetry codes: (i) x, y+1, z; (ii) x, y-1, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, z]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 1030592

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814023332/gg2143sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814023332/gg2143Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814023332/gg2143Isup3.cdx

checkCIF report

Related literature top

The literature reports three structure determinations on the unsolvated title complex, also known as [N,N'-bis(salicylidene)ethylenediamine]oxidovanadium(IV). The first was in the monoclinic space group P2₁/c by Riley et al. (1986), the second by Li et al. (2004) in the triclinic space group P1 and the third in the monoclinic space group P2₁ (Wang et al., 2008). All three determinations were carried out at ambient temperature. According to the Cambridge Structural Database (Groom & Allen, 2014) no solvates of [N,N'-bis(salicylidene)ethylenediamine]oxidovanadium(IV) have been reported previously, although these are common for substituted analogues of the N,N'-bis(salicylidene)ethylenediamine ligand.

Experimental top

Crystals of the title complex were obtained by slow cooling of a methanolic solution of {2,2'-[ethylenebis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N',O'}oxidovanadium(IV).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Fig. 1. One of the two independent solvated molecules in the asymmetric unit, with atom labels and 50% probability displacement ellipsoids for non-H atoms. Only one component of the disordered MeOH molecule is shown.

{2,2'-[Ethylenebis(nitrilomethanylylidene)]diphenolato-κ⁴O,N,N',O'}oxidovanadium(IV) methanol monosolvate top

Crystal data top

[V(C₁₆H₁₄N₂O₂)O]·CH₄O	D_x = 1.480 Mg m⁻³
M_r = 365.27	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pna2₁	Cell parameters from 3840 reflections
a = 12.9597 (4) Å	θ = 5.2–72.3°
b = 8.8616 (2) Å	µ = 5.27 mm⁻¹
c = 28.5426 (7) Å	T = 120 K
V = 3277.92 (15) Å³	Block, green
Z = 8	0.31 × 0.14 × 0.05 mm
F(000) = 1512

Data collection top

Agilent GV1000 diffractometer with an Atlas CCD detector	4634 independent reflections
Radiation source: Agilent GV1000 (Cu) X-ray Source	4350 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 10.3271 pixels mm^-1	θ_max = 74.4°, θ_min = 5.2°
ω scans	h = −15→15
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2013)	k = −10→6
T_min = 0.480, T_max = 0.959	l = −33→34
7416 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.065P)² + 1.252P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.105	(Δ/σ)_max = 0.02
S = 1.04	Δρ_max = 0.42 e Å⁻³
4634 reflections	Δρ_min = −0.29 e Å⁻³
479 parameters	Absolute structure: Flack (1983), 1395 Friedel pairs
32 restraints	Absolute structure parameter: 0.066 (9)
Primary atom site location: structure-invariant direct methods

Crystal data top

[V(C₁₆H₁₄N₂O₂)O]·CH₄O	V = 3277.92 (15) Å³
M_r = 365.27	Z = 8
Orthorhombic, Pna2₁	Cu Kα radiation
a = 12.9597 (4) Å	µ = 5.27 mm⁻¹
b = 8.8616 (2) Å	T = 120 K
c = 28.5426 (7) Å	0.31 × 0.14 × 0.05 mm

Data collection top

Agilent GV1000 diffractometer with an Atlas CCD detector	4634 independent reflections
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2013)	4350 reflections with I > 2σ(I)
T_min = 0.480, T_max = 0.959	R_int = 0.025
7416 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.105	Δρ_max = 0.42 e Å⁻³
S = 1.04	Δρ_min = −0.29 e Å⁻³
4634 reflections	Absolute structure: Flack (1983), 1395 Friedel pairs
479 parameters	Absolute structure parameter: 0.066 (9)
32 restraints

Special details top

Experimental. Absorption correction: CrysAlisPro version 1.171.36.32 (Agilent, 2013). Numerical absorption correction based on Gaussian integration over a multifaceted crystal model.

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	0.33525 (3)	1.13029 (4)	0.50170 (2)	0.02409 (8)
V2	0.57988 (3)	0.36777 (4)	0.18892 (2)	0.02364 (8)
O1	0.24854 (12)	0.95916 (19)	0.49027 (6)	0.0305 (4)
O2	0.41375 (12)	1.06657 (19)	0.44719 (6)	0.0277 (4)
O3	0.41104 (12)	1.1086 (2)	0.54575 (6)	0.0298 (4)
O4	0.49307 (12)	0.53856 (17)	0.20089 (6)	0.0292 (4)
O5	0.65555 (12)	0.39010 (19)	0.14477 (6)	0.0292 (4)
O6	0.65825 (12)	0.4296 (2)	0.24318 (6)	0.0294 (4)
N2	0.35312 (15)	1.3476 (2)	0.47830 (7)	0.0275 (4)
N4	0.59693 (16)	0.1492 (2)	0.21225 (7)	0.0289 (5)
C12	0.49325 (19)	1.1394 (3)	0.42862 (7)	0.0283 (6)
C14	0.42784 (18)	1.3949 (3)	0.45247 (8)	0.0295 (5)
H14	0.4327	1.4981	0.4471	0.035*
C30	0.73712 (18)	0.3563 (3)	0.26195 (8)	0.0306 (6)
C3	0.15814 (17)	0.9193 (3)	0.50810 (8)	0.0280 (5)
C25	0.6714 (2)	0.1024 (3)	0.23826 (8)	0.0322 (6)
H25	0.6761	−0.0010	0.2435	0.039*
N1	0.20834 (14)	1.2335 (2)	0.53104 (7)	0.0269 (4)
C26	0.8334 (2)	0.1282 (3)	0.28130 (9)	0.0409 (7)
H26	0.8397	0.0237	0.2803	0.049*
N3	0.45275 (15)	0.2651 (2)	0.15943 (7)	0.0278 (4)
C4	0.09719 (17)	1.0158 (3)	0.53631 (7)	0.0273 (5)
C10	0.6518 (2)	1.1282 (4)	0.38350 (9)	0.0423 (8)
H10	0.7005	1.0710	0.3674	0.051*
C8	0.5908 (2)	1.3668 (3)	0.40987 (8)	0.0396 (7)
H8	0.5986	1.4710	0.4113	0.048*
C15	0.2266 (2)	1.3957 (3)	0.53910 (9)	0.0326 (6)
H15A	0.2729	1.4102	0.5654	0.039*
H15B	0.1621	1.4470	0.5457	0.039*
C22	0.40338 (16)	0.5789 (3)	0.18283 (8)	0.0273 (5)
C17	0.36417 (19)	0.7228 (3)	0.19338 (10)	0.0352 (6)
H17	0.4014	0.7860	0.2132	0.042*
C24	0.74815 (18)	0.1970 (3)	0.26002 (8)	0.0316 (6)
C13	0.12347 (18)	1.1718 (3)	0.54445 (8)	0.0295 (5)
H13	0.0761	1.2316	0.5604	0.035*
C18	0.2719 (2)	0.7725 (3)	0.17509 (9)	0.0390 (6)
H18	0.2478	0.8680	0.1830	0.047*
C1	0.0269 (2)	0.7261 (3)	0.51707 (9)	0.0375 (6)
H1	0.0032	0.6295	0.5102	0.045*
C9	0.50432 (18)	1.2990 (3)	0.43126 (7)	0.0301 (6)
C7	0.6641 (2)	1.2817 (4)	0.38686 (9)	0.0451 (8)
H7	0.7215	1.3281	0.3737	0.054*
C20	0.34189 (17)	0.4834 (3)	0.15433 (7)	0.0278 (5)
C28	0.8976 (2)	0.3678 (4)	0.30590 (9)	0.0440 (8)
H28	0.9476	0.4251	0.3211	0.053*
C2	0.11882 (19)	0.7752 (3)	0.49797 (9)	0.0331 (6)
H2	0.1554	0.7117	0.4780	0.040*
C23	0.36811 (17)	0.3277 (3)	0.14619 (8)	0.0283 (5)
H23	0.3205	0.2683	0.1302	0.034*
C16	0.27463 (19)	1.4566 (3)	0.49437 (9)	0.0333 (6)
H16A	0.2220	1.4695	0.4705	0.040*
H16B	0.3064	1.5539	0.5003	0.040*
C5	0.00379 (18)	0.9625 (3)	0.55506 (8)	0.0323 (6)
H5	−0.0355	1.0263	0.5738	0.039*
C21	0.24831 (18)	0.5379 (3)	0.13563 (8)	0.0334 (6)
H21	0.2088	0.4753	0.1166	0.040*
C11	0.56715 (19)	1.0573 (3)	0.40398 (8)	0.0344 (6)
H11	0.5598	0.9533	0.4011	0.041*
C19	0.21417 (19)	0.6823 (3)	0.14501 (9)	0.0377 (6)
H19	0.1538	0.7186	0.1315	0.045*
C27	0.9082 (2)	0.2117 (4)	0.30372 (9)	0.0508 (8)
H27	0.9650	0.1644	0.3172	0.061*
C6	−0.03109 (19)	0.8186 (3)	0.54647 (9)	0.0362 (6)
H6	−0.0919	0.7839	0.5600	0.043*
C29	0.81364 (18)	0.4385 (4)	0.28575 (8)	0.0360 (6)
H29	0.8076	0.5429	0.2880	0.043*
C31	0.51874 (19)	0.0415 (3)	0.19582 (9)	0.0328 (6)
H31A	0.4662	0.0279	0.2196	0.039*
H31B	0.5505	−0.0555	0.1896	0.039*
C32	0.4706 (2)	0.1028 (3)	0.15151 (9)	0.0332 (6)
H32A	0.5165	0.0879	0.1251	0.040*
H32B	0.4059	0.0518	0.1451	0.040*
O8	0.3881 (3)	0.7530 (4)	0.41726 (11)	0.0533 (9)	0.678 (4)
H8A	0.3953	0.8354	0.4299	0.080*	0.678 (4)
O7	0.6257 (3)	0.7431 (3)	0.27352 (11)	0.0573 (9)	0.750 (5)
H7A	0.6295	0.6685	0.2566	0.086*	0.750 (5)
C33	0.5510 (3)	0.7185 (6)	0.30846 (13)	0.0506 (11)	0.750 (5)
H33A	0.4851	0.7011	0.2940	0.076*	0.750 (5)
H33B	0.5469	0.8056	0.3284	0.076*	0.750 (5)
H33C	0.5700	0.6320	0.3268	0.076*	0.750 (5)
C34	0.3009 (4)	0.7570 (6)	0.38743 (15)	0.0614 (14)	0.678 (4)
H34A	0.3138	0.6966	0.3602	0.092*	0.678 (4)
H34B	0.2876	0.8593	0.3781	0.092*	0.678 (4)
H34C	0.2419	0.7180	0.4038	0.092*	0.678 (4)
O7A	0.5715 (10)	0.7560 (9)	0.2706 (2)	0.068 (3)	0.250 (5)
H7AA	0.5107	0.7627	0.2629	0.103*	0.250 (5)
C33A	0.5784 (9)	0.6910 (16)	0.3163 (3)	0.073 (4)	0.250 (5)
H33D	0.6391	0.6293	0.3182	0.110*	0.250 (5)
H33E	0.5185	0.6302	0.3221	0.110*	0.250 (5)
H33F	0.5823	0.7700	0.3393	0.110*	0.250 (5)
C34A	0.3143 (7)	0.7847 (9)	0.37978 (19)	0.041 (2)	0.322 (4)
H34D	0.3315	0.7086	0.3572	0.061*	0.322 (4)
H34E	0.3511	0.8759	0.3726	0.061*	0.322 (4)
H34F	0.2414	0.8038	0.3788	0.061*	0.322 (4)
O8A	0.3422 (6)	0.7342 (7)	0.42510 (16)	0.0481 (19)	0.322 (4)
H8AA	0.3271	0.7990	0.4444	0.072*	0.322 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
V1	0.02276 (15)	0.02190 (17)	0.02763 (14)	0.00204 (14)	−0.00088 (14)	−0.00101 (14)
V2	0.02314 (15)	0.02248 (17)	0.02531 (14)	−0.00205 (14)	0.00061 (14)	−0.00063 (14)
O1	0.0274 (7)	0.0247 (8)	0.0394 (8)	0.0009 (6)	0.0042 (7)	−0.0034 (7)
O2	0.0263 (7)	0.0274 (8)	0.0295 (7)	−0.0023 (7)	0.0018 (6)	−0.0025 (6)
O3	0.0232 (7)	0.0338 (9)	0.0325 (7)	0.0038 (7)	−0.0038 (6)	0.0015 (7)
O4	0.0276 (7)	0.0246 (8)	0.0355 (7)	−0.0019 (6)	−0.0030 (7)	−0.0032 (7)
O5	0.0249 (7)	0.0318 (8)	0.0310 (7)	−0.0031 (7)	0.0021 (6)	0.0000 (7)
O6	0.0282 (7)	0.0312 (8)	0.0289 (6)	−0.0007 (7)	−0.0021 (6)	−0.0023 (7)
N2	0.0288 (8)	0.0239 (9)	0.0297 (8)	0.0006 (8)	−0.0091 (8)	−0.0023 (8)
N4	0.0326 (9)	0.0250 (9)	0.0290 (8)	0.0013 (8)	0.0067 (8)	0.0004 (8)
C12	0.0333 (11)	0.0334 (12)	0.0183 (8)	−0.0018 (10)	−0.0057 (9)	0.0025 (8)
C14	0.0329 (11)	0.0300 (11)	0.0255 (9)	−0.0055 (10)	−0.0071 (9)	0.0028 (9)
C30	0.0270 (10)	0.0426 (13)	0.0222 (8)	0.0018 (10)	0.0061 (9)	−0.0022 (9)
C3	0.0259 (9)	0.0266 (10)	0.0316 (9)	0.0010 (9)	−0.0035 (9)	0.0032 (9)
C25	0.0432 (12)	0.0287 (11)	0.0248 (9)	0.0079 (10)	0.0086 (10)	0.0029 (9)
N1	0.0230 (8)	0.0278 (9)	0.0301 (8)	0.0034 (7)	−0.0022 (7)	−0.0059 (8)
C26	0.0420 (13)	0.0542 (16)	0.0266 (10)	0.0179 (12)	0.0028 (11)	0.0024 (11)
N3	0.0285 (9)	0.0256 (9)	0.0294 (8)	−0.0043 (8)	0.0036 (8)	−0.0056 (8)
C4	0.0263 (10)	0.0307 (11)	0.0248 (8)	0.0021 (9)	−0.0051 (8)	0.0022 (9)
C10	0.0376 (13)	0.0658 (19)	0.0234 (9)	0.0038 (13)	0.0046 (10)	0.0017 (11)
C8	0.0449 (14)	0.0480 (15)	0.0260 (10)	−0.0143 (12)	−0.0023 (10)	0.0045 (10)
C15	0.0321 (11)	0.0289 (11)	0.0368 (11)	0.0081 (10)	−0.0023 (10)	−0.0079 (9)
C22	0.0228 (9)	0.0292 (11)	0.0300 (9)	0.0006 (9)	0.0034 (9)	0.0061 (9)
C17	0.0319 (10)	0.0290 (11)	0.0447 (12)	−0.0012 (10)	0.0053 (11)	0.0022 (11)
C24	0.0346 (11)	0.0369 (12)	0.0233 (8)	0.0073 (11)	0.0044 (9)	0.0012 (10)
C13	0.0254 (10)	0.0372 (12)	0.0257 (9)	0.0077 (10)	−0.0029 (9)	−0.0041 (9)
C18	0.0391 (12)	0.0319 (12)	0.0458 (12)	0.0081 (11)	0.0133 (11)	0.0098 (11)
C1	0.0357 (12)	0.0302 (11)	0.0468 (12)	−0.0025 (11)	−0.0094 (11)	0.0112 (11)
C9	0.0310 (10)	0.0420 (13)	0.0172 (8)	−0.0051 (11)	−0.0043 (9)	0.0023 (9)
C7	0.0394 (13)	0.0687 (19)	0.0272 (10)	−0.0097 (13)	0.0092 (10)	0.0072 (12)
C20	0.0225 (9)	0.0351 (12)	0.0258 (9)	−0.0038 (9)	0.0030 (8)	−0.0002 (9)
C28	0.0322 (12)	0.075 (2)	0.0250 (10)	−0.0029 (13)	−0.0005 (10)	−0.0022 (11)
C2	0.0306 (11)	0.0276 (11)	0.0411 (11)	−0.0002 (10)	−0.0026 (10)	0.0023 (10)
C23	0.0230 (9)	0.0349 (12)	0.0269 (9)	−0.0054 (10)	0.0001 (8)	−0.0029 (9)
C16	0.0349 (11)	0.0237 (11)	0.0412 (11)	0.0045 (10)	−0.0115 (10)	−0.0012 (9)
C5	0.0268 (10)	0.0438 (14)	0.0262 (9)	0.0024 (10)	−0.0019 (9)	0.0028 (10)
C21	0.0265 (10)	0.0468 (14)	0.0269 (9)	−0.0018 (11)	0.0017 (9)	0.0081 (10)
C11	0.0348 (11)	0.0461 (14)	0.0223 (8)	0.0024 (11)	−0.0023 (9)	−0.0005 (10)
C19	0.0292 (11)	0.0481 (14)	0.0358 (10)	0.0045 (11)	0.0040 (10)	0.0134 (11)
C27	0.0431 (13)	0.079 (2)	0.0301 (11)	0.0202 (15)	−0.0037 (11)	0.0057 (13)
C6	0.0263 (10)	0.0466 (14)	0.0356 (10)	−0.0044 (11)	−0.0024 (10)	0.0126 (11)
C29	0.0291 (10)	0.0553 (15)	0.0238 (9)	−0.0055 (11)	0.0001 (9)	−0.0019 (10)
C31	0.0377 (11)	0.0225 (11)	0.0383 (11)	−0.0061 (9)	0.0077 (10)	−0.0031 (10)
C32	0.0340 (11)	0.0263 (11)	0.0394 (11)	−0.0039 (10)	0.0084 (10)	−0.0086 (10)
O8	0.0693 (19)	0.0407 (16)	0.0501 (15)	0.0048 (15)	−0.0044 (16)	−0.0062 (14)
O7	0.0792 (19)	0.0308 (13)	0.0618 (16)	−0.0094 (14)	0.0178 (16)	−0.0105 (13)
C33	0.055 (2)	0.058 (2)	0.0383 (16)	0.006 (2)	−0.0047 (17)	−0.0122 (16)
C34	0.086 (3)	0.057 (3)	0.0412 (19)	−0.025 (2)	−0.008 (2)	0.0187 (19)
O7A	0.122 (8)	0.028 (4)	0.055 (4)	0.017 (5)	−0.020 (4)	−0.016 (3)
C33A	0.043 (5)	0.105 (9)	0.071 (5)	0.049 (5)	−0.002 (4)	0.009 (5)
C34A	0.076 (5)	0.028 (4)	0.019 (3)	−0.025 (4)	0.012 (3)	0.000 (3)
O8A	0.090 (5)	0.029 (3)	0.025 (2)	0.008 (3)	−0.002 (3)	−0.003 (2)

Geometric parameters (Å, º) top

V1—O1	1.9155 (17)	C13—H13	0.9300
V1—O2	1.9429 (16)	C18—H18	0.9300
V1—O3	1.6070 (17)	C18—C19	1.392 (4)
V1—N1	2.0597 (19)	C1—H1	0.9300
V1—N2	2.051 (2)	C1—C2	1.381 (4)
V2—O4	1.9164 (16)	C1—C6	1.393 (4)
V2—O5	1.6089 (16)	C7—H7	0.9300
V2—O6	1.9314 (16)	C20—C23	1.440 (4)
V2—N3	2.062 (2)	C20—C21	1.410 (3)
V2—N4	2.060 (2)	C28—H28	0.9300
O6—C30	1.324 (3)	C28—C27	1.392 (5)
O2—C12	1.326 (3)	C28—C29	1.381 (4)
N4—C25	1.286 (3)	C2—H2	0.9300
N4—C31	1.469 (3)	C23—H23	0.9300
N2—C14	1.287 (3)	C16—H16A	0.9700
N2—C16	1.476 (3)	C16—H16B	0.9700
O1—C3	1.325 (3)	C5—H5	0.9300
C12—C9	1.424 (4)	C5—C6	1.375 (4)
C12—C11	1.393 (4)	C21—H21	0.9300
O4—C22	1.321 (3)	C21—C19	1.380 (4)
C14—H14	0.9300	C11—H11	0.9300
C14—C9	1.439 (3)	C19—H19	0.9300
C30—C24	1.420 (4)	C27—H27	0.9300
C30—C29	1.406 (4)	C6—H6	0.9300
C3—C4	1.415 (3)	C29—H29	0.9300
C3—C2	1.405 (4)	C31—H31A	0.9700
C25—H25	0.9300	C31—H31B	0.9700
C25—C24	1.442 (4)	C31—C32	1.511 (4)
N1—C15	1.474 (3)	C32—H32A	0.9700
N1—C13	1.286 (3)	C32—H32B	0.9700
C26—H26	0.9300	O8—H8A	0.8200
C26—C24	1.401 (4)	O8—C34	1.416 (6)
C26—C27	1.377 (4)	O7—H7A	0.8200
N3—C23	1.286 (3)	O7—C33	1.407 (5)
N3—C32	1.474 (3)	C33—H33A	0.9600
C4—C13	1.443 (4)	C33—H33B	0.9600
C4—C5	1.405 (3)	C33—H33C	0.9600
C10—H10	0.9300	C34—H34A	0.9600
C10—C7	1.373 (5)	C34—H34B	0.9600
C10—C11	1.393 (4)	C34—H34C	0.9600
C8—H8	0.9300	O7A—H7AA	0.8200
C8—C9	1.411 (4)	O7A—C33A	1.428 (9)
C8—C7	1.379 (4)	C33A—H33D	0.9600
C15—H15A	0.9700	C33A—H33E	0.9600
C15—H15B	0.9700	C33A—H33F	0.9600
C15—C16	1.520 (4)	C34A—H34D	0.9600
C22—C17	1.405 (4)	C34A—H34E	0.9600
C22—C20	1.419 (3)	C34A—H34F	0.9600
C17—H17	0.9300	C34A—O8A	1.416 (7)
C17—C18	1.376 (4)	O8A—H8AA	0.8200

O2—V1—N2	87.30 (8)	C6—C1—H1	119.4
O2—V1—N1	150.78 (7)	C12—C9—C14	122.6 (2)
O3—V1—O2	105.76 (8)	C8—C9—C12	118.7 (2)
O3—V1—N2	107.35 (9)	C8—C9—C14	118.6 (2)
O3—V1—O1	113.39 (8)	C10—C7—C8	119.7 (3)
O3—V1—N1	102.90 (8)	C10—C7—H7	120.2
N2—V1—N1	78.80 (8)	C8—C7—H7	120.2
O1—V1—O2	86.60 (7)	C22—C20—C23	122.1 (2)
O1—V1—N2	138.94 (8)	C21—C20—C22	119.7 (2)
O1—V1—N1	87.26 (8)	C21—C20—C23	118.1 (2)
O6—V2—N4	87.20 (8)	C27—C28—H28	119.6
O6—V2—N3	150.79 (7)	C29—C28—H28	119.6
O5—V2—O6	105.81 (8)	C29—C28—C27	120.7 (3)
O5—V2—N4	107.66 (8)	C3—C2—H2	119.4
O5—V2—O4	113.60 (8)	C1—C2—C3	121.2 (2)
O5—V2—N3	102.81 (8)	C1—C2—H2	119.4
N4—V2—N3	78.63 (8)	N3—C23—C20	124.6 (2)
O4—V2—O6	86.66 (7)	N3—C23—H23	117.7
O4—V2—N4	138.40 (8)	C20—C23—H23	117.7
O4—V2—N3	87.25 (7)	N2—C16—C15	108.1 (2)
C30—O6—V2	126.23 (15)	N2—C16—H16A	110.1
C12—O2—V1	125.84 (15)	N2—C16—H16B	110.1
C25—N4—V2	124.78 (18)	C15—C16—H16A	110.1
C25—N4—C31	119.5 (2)	C15—C16—H16B	110.1
C31—N4—V2	115.70 (15)	H16A—C16—H16B	108.4
C14—N2—V1	125.24 (17)	C4—C5—H5	119.1
C14—N2—C16	118.9 (2)	C6—C5—C4	121.8 (2)
C16—N2—V1	115.82 (15)	C6—C5—H5	119.1
C3—O1—V1	131.62 (15)	C20—C21—H21	119.3
O2—C12—C9	122.7 (2)	C19—C21—C20	121.3 (2)
O2—C12—C11	118.8 (2)	C19—C21—H21	119.3
C11—C12—C9	118.4 (2)	C12—C11—C10	121.2 (3)
C22—O4—V2	131.37 (15)	C12—C11—H11	119.4
N2—C14—H14	117.7	C10—C11—H11	119.4
N2—C14—C9	124.5 (2)	C18—C19—H19	120.7
C9—C14—H14	117.7	C21—C19—C18	118.7 (2)
O6—C30—C24	123.4 (2)	C21—C19—H19	120.7
O6—C30—C29	119.0 (2)	C26—C27—C28	119.0 (3)
C29—C30—C24	117.6 (2)	C26—C27—H27	120.5
O1—C3—C4	123.5 (2)	C28—C27—H27	120.5
O1—C3—C2	118.9 (2)	C1—C6—H6	120.8
C2—C3—C4	117.6 (2)	C5—C6—C1	118.4 (2)
N4—C25—H25	117.3	C5—C6—H6	120.8
N4—C25—C24	125.4 (2)	C30—C29—H29	119.3
C24—C25—H25	117.3	C28—C29—C30	121.4 (3)
C15—N1—V1	111.60 (15)	C28—C29—H29	119.3
C13—N1—V1	127.96 (17)	N4—C31—H31A	110.0
C13—N1—C15	120.3 (2)	N4—C31—H31B	110.0
C24—C26—H26	119.2	N4—C31—C32	108.60 (19)
C27—C26—H26	119.2	H31A—C31—H31B	108.4
C27—C26—C24	121.5 (3)	C32—C31—H31A	110.0
C23—N3—V2	127.69 (17)	C32—C31—H31B	110.0
C23—N3—C32	120.6 (2)	N3—C32—C31	106.66 (19)
C32—N3—V2	111.60 (15)	N3—C32—H32A	110.4
C3—C4—C13	122.6 (2)	N3—C32—H32B	110.4
C5—C4—C3	119.7 (2)	C31—C32—H32A	110.4
C5—C4—C13	117.6 (2)	C31—C32—H32B	110.4
C7—C10—H10	119.7	H32A—C32—H32B	108.6
C7—C10—C11	120.5 (3)	C34—O8—H8A	109.5
C11—C10—H10	119.7	C33—O7—H7A	109.5
C9—C8—H8	119.3	O7—C33—H33A	109.5
C7—C8—H8	119.3	O7—C33—H33B	109.5
C7—C8—C9	121.4 (3)	O7—C33—H33C	109.5
N1—C15—H15A	110.5	H33A—C33—H33B	109.5
N1—C15—H15B	110.5	H33A—C33—H33C	109.5
N1—C15—C16	106.33 (19)	H33B—C33—H33C	109.5
H15A—C15—H15B	108.7	O8—C34—H34A	109.5
C16—C15—H15A	110.5	O8—C34—H34B	109.5
C16—C15—H15B	110.5	O8—C34—H34C	109.5
O4—C22—C17	118.7 (2)	H34A—C34—H34B	109.5
O4—C22—C20	123.8 (2)	H34A—C34—H34C	109.5
C17—C22—C20	117.5 (2)	H34B—C34—H34C	109.5
C22—C17—H17	119.2	C33A—O7A—H7AA	109.5
C18—C17—C22	121.5 (2)	O7A—C33A—H33D	109.5
C18—C17—H17	119.2	O7A—C33A—H33E	109.5
C30—C24—C25	121.7 (2)	O7A—C33A—H33F	109.5
C26—C24—C30	119.7 (2)	H33D—C33A—H33E	109.5
C26—C24—C25	118.6 (2)	H33D—C33A—H33F	109.5
N1—C13—C4	124.1 (2)	H33E—C33A—H33F	109.5
N1—C13—H13	117.9	H34D—C34A—H34E	109.5
C4—C13—H13	117.9	H34D—C34A—H34F	109.5
C17—C18—H18	119.4	H34E—C34A—H34F	109.5
C17—C18—C19	121.2 (3)	O8A—C34A—H34D	109.5
C19—C18—H18	119.4	O8A—C34A—H34E	109.5
C2—C1—H1	119.4	O8A—C34A—H34F	109.5
C2—C1—C6	121.2 (3)	C34A—O8A—H8AA	109.5

V2—O6—C30—C24	−29.7 (3)	C4—C5—C6—C1	−2.1 (4)
V2—O6—C30—C29	151.31 (17)	C15—N1—C13—C4	177.3 (2)
V2—N4—C25—C24	7.9 (3)	C22—C17—C18—C19	−0.6 (4)
V2—N4—C31—C32	22.2 (2)	C22—C20—C23—N3	−7.4 (4)
V2—O4—C22—C17	−170.69 (17)	C22—C20—C21—C19	−1.0 (3)
V2—O4—C22—C20	11.4 (3)	C17—C22—C20—C23	−172.0 (2)
V2—N3—C23—C20	−7.0 (3)	C17—C22—C20—C21	3.7 (3)
V2—N3—C32—C31	46.0 (2)	C17—C18—C19—C21	3.4 (4)
V1—O2—C12—C9	−29.3 (3)	C24—C30—C29—C28	1.1 (3)
V1—O2—C12—C11	153.17 (16)	C24—C26—C27—C28	1.1 (4)
V1—N2—C14—C9	7.7 (3)	C13—N1—C15—C16	−137.4 (2)
V1—N2—C16—C15	22.8 (2)	C13—C4—C5—C6	175.5 (2)
V1—O1—C3—C4	10.4 (3)	C9—C12—C11—C10	1.9 (3)
V1—O1—C3—C2	−170.93 (17)	C9—C8—C7—C10	1.7 (4)
V1—N1—C15—C16	46.5 (2)	C7—C10—C11—C12	−0.5 (4)
V1—N1—C13—C4	−7.2 (3)	C7—C8—C9—C12	−0.2 (4)
O6—C30—C24—C25	−1.8 (3)	C7—C8—C9—C14	−176.6 (2)
O6—C30—C24—C26	−179.2 (2)	C20—C22—C17—C18	−3.0 (4)
O6—C30—C29—C28	−179.9 (2)	C20—C21—C19—C18	−2.6 (4)
O2—C12—C9—C14	−2.8 (3)	C2—C3—C4—C13	−172.5 (2)
O2—C12—C9—C8	−179.1 (2)	C2—C3—C4—C5	3.4 (3)
O2—C12—C11—C10	179.6 (2)	C2—C1—C6—C5	1.9 (4)
N4—C25—C24—C30	12.3 (4)	C23—N3—C32—C31	−137.4 (2)
N4—C25—C24—C26	−170.2 (2)	C23—C20—C21—C19	174.9 (2)
N4—C31—C32—N3	−42.8 (2)	C16—N2—C14—C9	−174.5 (2)
N2—C14—C9—C12	13.4 (3)	C5—C4—C13—N1	176.9 (2)
N2—C14—C9—C8	−170.3 (2)	C21—C20—C23—N3	176.9 (2)
O1—C3—C4—C13	6.2 (3)	C11—C12—C9—C14	174.7 (2)
O1—C3—C4—C5	−177.9 (2)	C11—C12—C9—C8	−1.6 (3)
O1—C3—C2—C1	177.6 (2)	C11—C10—C7—C8	−1.3 (4)
O4—C22—C17—C18	179.0 (2)	C27—C26—C24—C30	−0.8 (4)
O4—C22—C20—C23	5.9 (3)	C27—C26—C24—C25	−178.4 (2)
O4—C22—C20—C21	−178.4 (2)	C27—C28—C29—C30	−0.8 (4)
C14—N2—C16—C15	−155.1 (2)	C6—C1—C2—C3	1.1 (4)
C3—C4—C13—N1	−7.1 (4)	C29—C30—C24—C25	177.2 (2)
C3—C4—C5—C6	−0.6 (3)	C29—C30—C24—C26	−0.3 (3)
C25—N4—C31—C32	−155.7 (2)	C29—C28—C27—C26	−0.3 (4)
N1—C15—C16—N2	−43.4 (2)	C31—N4—C25—C24	−174.5 (2)
C4—C3—C2—C1	−3.7 (4)	C32—N3—C23—C20	177.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O8ⁱ	0.93	2.48	3.368 (4)	159
C14—H14···O8Aⁱ	0.93	2.48	3.299 (7)	147
C25—H25···O7ⁱⁱ	0.93	2.51	3.391 (4)	158
C25—H25···O7Aⁱⁱ	0.93	2.66	3.457 (9)	144
C13—H13···O3ⁱⁱⁱ	0.93	2.60	3.372 (3)	141
C23—H23···O5^iv	0.93	2.59	3.364 (3)	141
O8—H8A···O2	0.82	2.12	2.926 (4)	167
O7—H7A···O6	0.82	2.18	2.940 (3)	153
O7—H7A···O4	0.82	2.64	3.246 (4)	132
O8A—H8AA···O1	0.82	2.18	2.984 (6)	166

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) x−1/2, −y+5/2, z; (iv) x−1/2, −y+1/2, z.

Selected geometric parameters (Å, º) top

V1—O1	1.9155 (17)	V2—O4	1.9164 (16)
V1—O2	1.9429 (16)	V2—O5	1.6089 (16)
V1—O3	1.6070 (17)	V2—O6	1.9314 (16)
V1—N1	2.0597 (19)	V2—N3	2.062 (2)
V1—N2	2.051 (2)	V2—N4	2.060 (2)

O2—V1—N2	87.30 (8)	O6—V2—N4	87.20 (8)
O2—V1—N1	150.78 (7)	O6—V2—N3	150.79 (7)
O3—V1—O2	105.76 (8)	O5—V2—O6	105.81 (8)
O3—V1—N2	107.35 (9)	O5—V2—N4	107.66 (8)
O3—V1—O1	113.39 (8)	O5—V2—O4	113.60 (8)
O3—V1—N1	102.90 (8)	O5—V2—N3	102.81 (8)
N2—V1—N1	78.80 (8)	N4—V2—N3	78.63 (8)
O1—V1—O2	86.60 (7)	O4—V2—O6	86.66 (7)
O1—V1—N2	138.94 (8)	O4—V2—N4	138.40 (8)
O1—V1—N1	87.26 (8)	O4—V2—N3	87.25 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O8ⁱ	0.93	2.48	3.368 (4)	159
C14—H14···O8Aⁱ	0.93	2.48	3.299 (7)	147
C25—H25···O7ⁱⁱ	0.93	2.51	3.391 (4)	158
C25—H25···O7Aⁱⁱ	0.93	2.66	3.457 (9)	144
C13—H13···O3ⁱⁱⁱ	0.93	2.60	3.372 (3)	141
C23—H23···O5^iv	0.93	2.59	3.364 (3)	141
O8—H8A···O2	0.82	2.12	2.926 (4)	167
O7—H7A···O6	0.82	2.18	2.940 (3)	153
O7—H7A···O4	0.82	2.64	3.246 (4)	132
O8A—H8AA···O1	0.82	2.18	2.984 (6)	166

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) x−1/2, −y+5/2, z; (iv) x−1/2, −y+1/2, z.

Acknowledgements

We thank Professor A. N. Khlobystov for the sample of unsolvated {2,2′-[ethylenebis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N′,O′}oxidovanadium(IV). We thank EPSRC (UK) for support.

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