[N,N'-Bis(3-carboxy­salicyl­idene)-1,2-di­phenyl-(RR,SS)-1,2-ethanediyl­diaminato-O,N,N',O']­(methanol-O)oxovanadium(IV) and [N,N'-bis(3-carboxy­salicyl­idene)-2,3-di­methyl-2,3-butanediyl­diaminato-O,N,N',O']oxo­vanadium(IV) mono­hydrate

The two title mononuclear oxovanadium (IV) complexes, [VO(C₃₀H₂₂N₂O₆)(CH₃OH)] and [VO(C₂₂H₂₂N₂O₆)]·H₂O, respectively, have distorted square-pyramidal coordination and the 3-carboxy groups form intramolecular hydrogen bonds with the coordinated salicyl O atoms. In (I), methanol coordinates to the vanadium atom trans with respect to the oxo ligand.

S1. Comment

The structures of dinuclear metal complexes containing the 3-COOH-salen ligand have been reported for homonuclear Cu–Cu (Galy et al., 1979; Gawron et al., 1986) and Ni–Ni (Morgenstern-Badarau et al., 1982) complexes, as well as for heteronuclear Cu–Mg (Beale et al., 1979), Cu–V (Kahn et al., 1982), Cu–Fe (Journaux et al., 1983), Cu–Co (Mikuriya et al., 1978; Galy et al., 1980) and Cu–Ni (Morgenstern-Badarau et al., 1982) complexes, where the inside N₂O₂ coordination site is occupied by the Cu^II atom.

The structures of mononuclear metal complexes with 3-COOH-salen were also reported for Fe, which occupies an O₄ coordination site (Zarembowitch et al., 1982), and for Co which occupies N₂O₂ coordination site (Charpin et al., 1988).

The structures of [VO{H₂(fsa)₂-rac-stien}(MeOH)], (I), and [VO{H₂(fsa)₂tmen}]·H₂O, (II), are reported here [H₄(fsa)₂-rac-stien is N,N'-bis(3-carboxysalicylidene)-1,2-diphenyl-1,2-ethanediyldiamine and H₄(fsa)₂tmen is N,N'-bis(3-carboxysalicylidene)-1,1,2,2-tetramethyl-1,2-ethanediyldiamine].

S2. Experimental

For the preparation of (I), 3-aldehydesalicylic acid was prepared according to the literature method of Duff & Bills (1932). The H₄(fsa)₂-rac-stien ligand was prepared by the reaction of 3-aldehydesalicylic acid (2 mmol) with 1,2-(±)-diphenylethylenediamine (1 mmol) in ethanol (yield 94%). The oxovanadium(IV) complex was prepared by the reaction of H₄(fsa)₂-rac-stien (0.5 mmol) with vanadyl sulfate (0.5 mmol) in methanol containing pyridine (yield 92%). Crystals of (I) were grown from a DMSO solution. For the preparation of (II), H₄(fsa)₂tmen was prepared by the reaction of 3-aldehydesalicylic acid (2 mmol) with 1,1,2,2-tetramethyl-1,2-ethylenediamine (1 mmol) in ethanol (yield 88%). The oxovanadium(IV) complex was prepared by the reaction of H₄(fsa)₂tmen (0.5 mmol) with vanadyl sulfate (0.5 mmol) in methanol containing pyridine (yield 83%). Crystals of (II) were grown from an acetone solution.

S3. Refinement

In (I), there is a positional disorder of the C19 and C26 atoms of the five-membered chelate ring moiety. The site-occupancy factors of the C19–C26 and C19*–C26* pairs were estimated to be 81 and 19%, respectively. Namely, the SS– and RR– complexes share the same site with occupancy factors of 81 and 19%, respectively (and vice versa in the centrosymmetric crystal structure). The disorder in the phenyl groups was not taken into account. This caused artificial bond angles, C19*—C20—C21 of 145.4 (6)°, for example. The hydroxyl H atoms were located in difference syntheses and their positional parameters were refined. All the other H-atom positional parameters were calculated geometrically and fixed with U_iso(H) = 1.2U_eq(parent atom). The O—H distances are in the range 0.96 (2)–0.98 (3) Å. In (II), all the H atoms were refined isotropically. The O—H and C—H distances are im the ranges 0.76 (4)–0.91 (4) and 0.83 (3)–1.04 (3) Å, respectively. The relatively large R_int value of 0.085 might be due to absorption by a thin glass rod.

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

[VO(C30H22N2O6)(CH3OH)]	Dx = 1.431 Mg m^−3
Mr = 605.50	Mo Kα radiation, λ = 0.71073 Å
Monoclinic, P21/c	Cell parameters from 24 reflections
a = 9.681 (2) Å	θ = 12.8–14.8°
b = 18.474 (2) Å	µ = 0.41 mm^−1
c = 15.786 (2) Å	T = 298 K
β = 95.27 (1)°	Prismatic, red
V = 2811.1 (7) Å^3	0.4 × 0.3 × 0.1 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.014
θ–2θ scans	θmax = 30°
Absorption correction: ψ scan (North et al., 1968)	h = 0→13
Tmin = 0.901, Tmax = 0.960	k = 0→25
8471 measured reflections	l = −22→22
8202 independent reflections	3 standard reflections every 150 reflections
4703 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H atoms: see text
R[F^2 > 2σ(F^2)] = 0.056	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 1P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.167	(Δ/σ)max = 0.001
S = 1.31	Δρmax = 0.50 e Å^−3
8202 reflections	Δρmin = −0.44 e Å^−3
397 parameters

Special details

Refinement. Refinement using reflections with F² > 0.0 σ(F²). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
V1	0.07892 (5)	0.13577 (3)	0.46521 (3)	0.0360 (1)
O2	0.1567 (3)	0.0675 (1)	0.5074 (1)	0.0634 (7)
O3	−0.0439 (2)	0.1662 (1)	0.5514 (1)	0.0509 (6)
O4	0.2123 (2)	0.2118 (1)	0.4987 (1)	0.0439 (5)
O5	−0.2142 (3)	0.2502 (2)	0.7538 (2)	0.0660 (7)
O6	−0.0353 (3)	0.2445 (2)	0.6791 (2)	0.0668 (7)
O7	0.4932 (3)	0.3365 (2)	0.6390 (2)	0.0718 (8)
O8	0.3009 (3)	0.2736 (2)	0.6349 (2)	0.0644 (7)
O41	−0.0355 (3)	0.2363 (1)	0.3973 (2)	0.0672 (7)
N9	−0.0845 (3)	0.0838 (1)	0.4001 (2)	0.0437 (6)
N10	0.1526 (3)	0.1296 (1)	0.3479 (1)	0.0390 (5)
C11	−0.1752 (3)	0.1494 (2)	0.5592 (2)	0.0388 (6)
C12	−0.2384 (3)	0.1777 (2)	0.6303 (2)	0.0393 (6)
C13	−0.1642 (3)	0.2259 (2)	0.6925 (2)	0.0456 (7)
C14	−0.3745 (3)	0.1575 (2)	0.6423 (2)	0.0481 (8)
C15	−0.4518 (3)	0.1133 (2)	0.5860 (2)	0.0510 (8)
C16	−0.3921 (3)	0.0884 (2)	0.5151 (2)	0.0457 (7)
C17	−0.2563 (3)	0.1049 (2)	0.5002 (2)	0.0386 (6)
C18	−0.2056 (3)	0.0748 (2)	0.4243 (2)	0.0461 (7)
C19	−0.0340 (4)	0.0409 (2)	0.3288 (2)	0.037 (1)	0.81
C19*	−0.063 (2)	0.0774 (10)	0.299 (1)	0.03559 (5)*	0.19
C20	−0.1477 (3)	0.0066 (2)	0.2679 (2)	0.0487 (8)
C21	−0.1484 (4)	−0.0666 (2)	0.2673 (3)	0.068 (1)
C22	−0.2440 (6)	−0.1038 (3)	0.2134 (4)	0.101 (2)
C23	−0.3378 (5)	−0.0664 (3)	0.1604 (4)	0.092 (2)
C24	−0.3396 (5)	0.0061 (3)	0.1624 (3)	0.081 (1)
C25	−0.2454 (4)	0.0437 (2)	0.2167 (3)	0.065 (1)
C26	0.0562 (4)	0.0928 (2)	0.2812 (2)	0.0357 (10)	0.81
C26*	0.090 (2)	0.0588 (10)	0.306 (1)	0.03287 (5)*	0.19
C27	0.1318 (3)	0.0519 (2)	0.2152 (2)	0.0452 (7)
C28	0.2270 (4)	−0.0023 (2)	0.2337 (3)	0.068 (1)
C29	0.2883 (5)	−0.0365 (3)	0.1704 (4)	0.084 (1)
C30	0.2565 (5)	−0.0175 (3)	0.0878 (3)	0.084 (1)
C31	0.1634 (5)	0.0363 (3)	0.0668 (2)	0.087 (1)
C32	0.1001 (4)	0.0714 (2)	0.1314 (2)	0.064 (1)
C33	0.2638 (3)	0.1594 (2)	0.3272 (2)	0.0432 (7)
C34	0.3562 (3)	0.2043 (2)	0.3819 (2)	0.0375 (6)
C35	0.4805 (3)	0.2256 (2)	0.3495 (2)	0.0477 (8)
C36	0.5748 (3)	0.2688 (2)	0.3960 (2)	0.0511 (8)
C37	0.5485 (3)	0.2923 (2)	0.4756 (2)	0.0490 (8)
C38	0.4265 (3)	0.2734 (2)	0.5102 (2)	0.0378 (6)
C39	0.4106 (4)	0.2980 (2)	0.5994 (2)	0.0493 (8)
C40	0.3281 (3)	0.2298 (2)	0.4640 (2)	0.0354 (6)
C42	−0.0304 (5)	0.3085 (3)	0.4263 (3)	0.091 (2)
H6	−0.013 (4)	0.214 (2)	0.632 (2)	0.0685*
H8	0.245 (3)	0.242 (2)	0.595 (2)	0.0685*
H14	−0.4159	0.1762	0.6914	0.0572*
H15	−0.5464	0.1006	0.5957	0.0608*
H16	−0.4462	0.0575	0.4744	0.0557*
H18	−0.2680	0.0438	0.3894	0.0535*
H19	0.0244	0.0026	0.3528	0.0449*	0.81
H19*	−0.0871	0.1214	0.2656	0.0423*	0.19
H21	−0.0780	−0.0929	0.3035	0.0797*
H22	−0.2459	−0.1568	0.2152	0.1216*
H23	−0.4042	−0.0924	0.1227	0.1105*
H24	−0.4077	0.0339	0.1250	0.0954*
H25	−0.2485	0.0961	0.2192	0.0766*
H26	−0.0026	0.1286	0.2525	0.0426*	0.81
H26*	0.1135	0.0149	0.3414	0.0386*	0.19
H28	0.2528	−0.0152	0.2920	0.0793*
H29	0.3563	−0.0745	0.1849	0.0988*
H30	0.3002	−0.0421	0.0433	0.0982*
H31	0.1411	0.0494	0.0084	0.1021*
H32	0.0313	0.1088	0.1168	0.0772*
H33	0.2875	0.1511	0.2700	0.0511*
H35	0.4993	0.2097	0.2936	0.0568*
H36	0.6597	0.2824	0.3732	0.0643*
H37	0.6153	0.3232	0.5083	0.0582*
H41	−0.092 (3)	0.241 (2)	0.344 (1)	0.0685*
H42A	−0.0134	0.3095	0.4872	0.1101*
H42B	0.0440	0.3340	0.4032	0.1101*
H42C	−0.1147	0.3333	0.4104	0.1101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0427 (3)	0.0414 (3)	0.0242 (2)	−0.0058 (2)	0.0046 (2)	−0.0008 (2)
O2	0.088 (2)	0.059 (2)	0.041 (1)	0.007 (1)	−0.004 (1)	0.008 (1)
O3	0.051 (1)	0.063 (1)	0.041 (1)	−0.019 (1)	0.0148 (9)	−0.018 (1)
O4	0.041 (1)	0.062 (1)	0.0300 (9)	−0.0106 (10)	0.0072 (8)	−0.0093 (9)
O5	0.060 (2)	0.097 (2)	0.042 (1)	0.000 (1)	0.012 (1)	−0.024 (1)
O6	0.070 (2)	0.078 (2)	0.056 (1)	−0.024 (1)	0.025 (1)	−0.032 (1)
O7	0.080 (2)	0.079 (2)	0.055 (1)	−0.031 (2)	0.000 (1)	−0.021 (1)
O8	0.064 (2)	0.088 (2)	0.043 (1)	−0.023 (1)	0.012 (1)	−0.025 (1)
O41	0.092 (2)	0.050 (2)	0.054 (1)	0.020 (1)	−0.022 (1)	−0.008 (1)
N9	0.048 (1)	0.048 (2)	0.036 (1)	−0.012 (1)	0.009 (1)	−0.010 (1)
N10	0.047 (1)	0.044 (1)	0.026 (1)	−0.007 (1)	0.0049 (9)	−0.006 (1)
C11	0.042 (2)	0.041 (2)	0.034 (1)	−0.002 (1)	0.007 (1)	0.001 (1)
C12	0.045 (2)	0.041 (2)	0.033 (1)	0.004 (1)	0.006 (1)	0.004 (1)
C13	0.054 (2)	0.048 (2)	0.036 (1)	0.000 (1)	0.008 (1)	−0.003 (1)
C14	0.043 (2)	0.061 (2)	0.042 (2)	0.010 (2)	0.010 (1)	0.003 (1)
C15	0.039 (2)	0.061 (2)	0.055 (2)	−0.001 (1)	0.010 (1)	0.005 (2)
C16	0.045 (2)	0.041 (2)	0.051 (2)	−0.007 (1)	0.005 (1)	−0.002 (1)
C17	0.045 (2)	0.032 (1)	0.039 (1)	−0.004 (1)	0.007 (1)	0.001 (1)
C18	0.049 (2)	0.049 (2)	0.041 (2)	−0.012 (1)	0.006 (1)	−0.010 (1)
C19	0.052 (2)	0.029 (2)	0.029 (2)	0.000 (2)	0.001 (1)	−0.002 (1)
C20	0.047 (2)	0.057 (2)	0.042 (2)	−0.010 (2)	0.006 (1)	−0.020 (2)
C21	0.073 (3)	0.054 (2)	0.076 (3)	−0.001 (2)	−0.003 (2)	0.004 (2)
C22	0.098 (4)	0.054 (3)	0.151 (5)	−0.018 (3)	0.013 (4)	−0.039 (3)
C23	0.072 (3)	0.099 (4)	0.101 (4)	−0.014 (3)	−0.015 (3)	−0.055 (3)
C24	0.068 (3)	0.102 (4)	0.069 (3)	0.000 (3)	−0.017 (2)	−0.005 (3)
C25	0.060 (2)	0.054 (2)	0.082 (3)	−0.002 (2)	0.004 (2)	−0.003 (2)
C26	0.044 (2)	0.037 (2)	0.025 (2)	0.000 (2)	0.001 (1)	0.000 (1)
C27	0.049 (2)	0.053 (2)	0.033 (1)	−0.007 (1)	0.006 (1)	−0.012 (1)
C28	0.068 (2)	0.075 (3)	0.060 (2)	0.015 (2)	0.010 (2)	0.010 (2)
C29	0.084 (3)	0.065 (3)	0.108 (4)	0.022 (2)	0.031 (3)	0.000 (3)
C30	0.091 (3)	0.079 (3)	0.089 (3)	−0.005 (3)	0.042 (3)	−0.040 (3)
C31	0.104 (4)	0.120 (4)	0.037 (2)	−0.004 (3)	0.013 (2)	−0.008 (2)
C32	0.077 (3)	0.071 (3)	0.044 (2)	0.016 (2)	0.010 (2)	0.005 (2)
C33	0.051 (2)	0.053 (2)	0.026 (1)	−0.005 (1)	0.009 (1)	−0.001 (1)
C34	0.041 (2)	0.043 (2)	0.029 (1)	−0.001 (1)	0.006 (1)	0.004 (1)
C35	0.045 (2)	0.064 (2)	0.035 (1)	−0.003 (2)	0.011 (1)	0.006 (1)
C36	0.043 (2)	0.060 (2)	0.052 (2)	−0.010 (2)	0.011 (1)	0.006 (2)
C37	0.045 (2)	0.052 (2)	0.048 (2)	−0.011 (1)	−0.002 (1)	0.004 (2)
C38	0.039 (2)	0.039 (2)	0.035 (1)	−0.001 (1)	0.000 (1)	0.004 (1)
C39	0.055 (2)	0.053 (2)	0.039 (2)	−0.008 (2)	0.000 (1)	−0.007 (1)
C40	0.037 (1)	0.040 (2)	0.029 (1)	0.000 (1)	0.001 (1)	0.005 (1)
C42	0.099 (4)	0.054 (3)	0.112 (4)	0.009 (2)	−0.032 (3)	−0.010 (3)

Geometric parameters (Å, º)

V1—O2	1.584 (3)	C20—C25	1.370 (5)
V1—O3	1.969 (2)	C21—C22	1.380 (7)
V1—O4	1.948 (2)	C21—H21	0.977
V1—O41	2.368 (3)	C22—C23	1.365 (8)
V1—N9	2.045 (3)	C22—H22	0.980
V1—N10	2.048 (2)	C23—C24	1.340 (8)
O3—C11	1.325 (4)	C23—H23	0.962
O4—C40	1.334 (4)	C24—C25	1.381 (6)
O5—C13	1.208 (4)	C24—H24	0.988
O6—C13	1.330 (4)	C25—H25	0.971
O6—H6	0.97 (3)	C26—C27	1.527 (5)
O7—C39	1.201 (4)	C26—H26	0.959
O8—C39	1.325 (4)	C26*—C27	1.54 (2)
O8—H8	0.98 (3)	C26*—H26*	1.00
O41—C42	1.409 (5)	C27—C28	1.373 (5)
O41—H41	0.96 (2)	C27—C32	1.378 (4)
N9—C18	1.276 (4)	C28—C29	1.364 (7)
N9—C19	1.495 (4)	C28—H28	0.961
N9—C19*	1.64 (2)	C29—C30	1.357 (8)
N10—C26	1.504 (4)	C29—H29	0.975
N10—C26*	1.56 (2)	C30—C31	1.362 (7)
N10—C33	1.277 (4)	C30—H30	0.967
C11—C12	1.426 (4)	C31—C32	1.398 (6)
C11—C17	1.423 (4)	C31—H31	0.957
C12—C13	1.464 (4)	C32—H32	0.973
C12—C14	1.398 (4)	C33—C34	1.446 (4)
C14—C15	1.378 (5)	C33—H33	0.964
C14—H14	0.969	C34—C35	1.406 (4)
C15—C16	1.384 (5)	C34—C40	1.428 (4)
C15—H15	0.971	C35—C36	1.373 (5)
C16—C17	1.391 (4)	C35—H35	0.963
C16—H16	0.974	C36—C37	1.376 (5)
C17—C18	1.447 (4)	C36—H36	0.960
C18—H18	0.967	C37—C38	1.390 (4)
C19—C20	1.529 (5)	C37—H37	0.973
C19—C26	1.539 (6)	C38—C39	1.502 (4)
C19—H19	0.961	C38—C40	1.400 (4)
C19*—C20	1.60 (2)	C42—H42A	0.961
C19*—C26*	1.51 (2)	C42—H42B	0.960
C19*—H19*	0.984	C42—H42C	0.950
C20—C21	1.354 (5)
O2—V1—O3	103.3 (1)	C22—C21—H21	120.3
O2—V1—O4	100.5 (1)	C21—C22—C23	119.8 (5)
O2—V1—O41	178.0 (1)	C21—C22—H22	119.6
O2—V1—N9	98.9 (1)	C23—C22—H22	120.6
O2—V1—N10	98.3 (1)	C22—C23—C24	120.0 (5)
O3—V1—O4	91.94 (9)	C22—C23—H23	119.7
O3—V1—N9	89.59 (10)	C24—C23—H23	120.2
O3—V1—O41	78.59 (10)	C23—C24—C25	120.5 (4)
O3—V1—N10	157.40 (10)	C23—C24—H24	121.1
O4—V1—N9	159.68 (10)	C25—C24—H24	118.4
O4—V1—O41	80.10 (9)	C20—C25—C24	119.8 (4)
O4—V1—N10	90.47 (9)	C20—C25—H25	119.8
N9—V1—N10	80.63 (10)	C24—C25—H25	120.4
O41—V1—N9	80.35 (10)	N10—C26—C19	106.5 (3)
O41—V1—N10	79.71 (10)	N10—C26—C27	113.3 (3)
V1—O3—C11	130.0 (2)	C19—C26—C27	110.7 (3)
V1—O4—C40	128.9 (2)	C19—C26—H26	108.8
C13—O6—H6	104 (2)	C27—C26—H26	108.6
C39—O8—H8	111 (2)	N10—C26*—C19*	100 (1)
V1—O41—C42	126.4 (3)	N10—C26*—C27	109 (1)
V1—O41—H41	132 (2)	N10—C26*—H26*	113.0
C42—O41—H41	101 (2)	C19*—C26*—C27	106 (1)
V1—N9—C18	126.8 (2)	C19*—C26*—H26*	113.6
V1—N9—C19	109.6 (2)	C27—C26*—H26*	112.8
V1—N9—C19*	111.1 (6)	C26—C27—C28	124.7 (3)
C18—N9—C19	121.9 (3)	C26—C27—C32	116.5 (3)
C18—N9—C19*	119.3 (6)	C26*—C27—C28	95.1 (7)
V1—N10—C26	114.4 (2)	C26*—C27—C32	145.4 (7)
V1—N10—C26*	105.8 (6)	C28—C27—C32	118.8 (3)
V1—N10—C33	125.3 (2)	C27—C28—C29	120.7 (4)
C26—N10—C33	120.0 (2)	C27—C28—H28	119.7
C26*—N10—C33	123.9 (6)	C29—C28—H28	119.7
O3—C11—C12	118.2 (3)	C28—C29—C30	120.6 (4)
O3—C11—C17	123.4 (3)	C28—C29—H29	119.4
C12—C11—C17	118.4 (3)	C30—C29—H29	120.0
C11—C12—C13	122.0 (3)	C29—C30—C31	120.6 (5)
C11—C12—C14	119.1 (3)	C29—C30—H30	120.0
C13—C12—C14	118.8 (3)	C31—C30—H30	119.3
O5—C13—O6	118.8 (3)	C30—C31—C32	119.0 (4)
O5—C13—C12	123.7 (3)	C30—C31—H31	120.4
O6—C13—C12	117.5 (3)	C32—C31—H31	120.6
C12—C14—C15	122.2 (3)	C27—C32—C31	120.4 (4)
C12—C14—H14	118.6	C27—C32—H32	120.1
C15—C14—H14	119.2	C31—C32—H32	119.6
C14—C15—C16	118.5 (3)	N10—C33—C34	125.8 (3)
C14—C15—H15	120.3	N10—C33—H33	116.7
C16—C15—H15	121.2	C34—C33—H33	117.6
C15—C16—C17	122.3 (3)	C33—C34—C35	116.6 (3)
C15—C16—H16	119.2	C33—C34—C40	124.8 (3)
C17—C16—H16	118.5	C35—C34—C40	118.6 (3)
C11—C17—C16	119.3 (3)	C34—C35—C36	121.2 (3)
C11—C17—C18	123.7 (3)	C34—C35—H35	119.2
C16—C17—C18	117.0 (3)	C36—C35—H35	119.6
N9—C18—C17	126.1 (3)	C35—C36—C37	120.1 (3)
N9—C18—H18	116.7	C35—C36—H36	120.2
C17—C18—H18	117.2	C37—C36—H36	119.7
N9—C19—C20	115.2 (3)	C36—C37—C38	120.9 (3)
N9—C19—C26	106.0 (3)	C36—C37—H37	119.9
N9—C19—H19	108.3	C38—C37—H37	119.1
C20—C19—C26	111.0 (3)	C37—C38—C39	117.1 (3)
C20—C19—H19	107.9	C37—C38—C40	120.2 (3)
C26—C19—H19	108.1	C39—C38—C40	122.6 (3)
N9—C19*—C20	104.3 (10)	O7—C39—O8	120.2 (3)
N9—C19*—C26*	98 (1)	O7—C39—C38	123.1 (3)
N9—C19*—H19*	114.5	O8—C39—C38	116.6 (3)
C20—C19*—C26*	108 (1)	O4—C40—C34	121.9 (2)
C20—C19*—H19*	114.8	O4—C40—C38	119.1 (2)
C26*—C19*—H19*	114.7	C34—C40—C38	119.0 (3)
C19—C20—C21	114.9 (3)	O41—C42—H42A	109.9
C19—C20—C25	125.6 (3)	O41—C42—H42B	110.4
C19*—C20—C21	145.4 (6)	O41—C42—H42C	111.5
C19*—C20—C25	94.6 (6)	H42A—C42—H42B	107.7
C21—C20—C25	119.5 (3)	H42A—C42—H42C	108.6
C20—C21—C22	120.3 (4)	H42B—C42—H42C	108.6
C20—C21—H21	119.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O3	0.97 (4)	1.56 (4)	2.476 (3)	156 (3)
O8—H8···O4	0.98 (3)	1.63 (3)	2.514 (3)	148 (3)
O41—H41···O5^i	0.96 (4)	1.78 (2)	2.732 (3)	172 (3)

Symmetry code: (i) x, −y+1/2, z−1/2.

(II)

Crystal data

[VO(C22H22N2O6)]·H2O	Z = 2
Mr = 495.37	Dx = 1.487 Mg m^−3
Triclinic, P1	Mo Kα radiation, λ = 0.71073 Å
a = 10.508 (3) Å	Cell parameters from 25 reflections
b = 11.728 (2) Å	θ = 14.9–15.0°
c = 9.726 (2) Å	µ = 0.50 mm^−1
α = 107.66 (2)°	T = 298 K
β = 96.21 (2)°	Prismatic, green
γ = 100.45 (2)°	0.5 × 0.4 × 0.3 mm
V = 1106.1 (5) Å^3

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.085
θ–2θ scans	θmax = 30°
Absorption correction: integration (Coppens et al., 1965)	h = 0→14
Tmin = 0.860, Tmax = 0.915	k = −16→16
6772 measured reflections	l = −13→13
6445 independent reflections	3 standard reflections every 150 reflections
5528 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0742P)^2 + 0.2356P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.116	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.70 e Å^−3
6445 reflections	Δρmin = −0.64 e Å^−3
394 parameters

Special details

Refinement. Refinement using reflections with F² > 0.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
V1	0.93844 (2)	0.23532 (2)	0.43953 (2)	0.02608 (8)
O2	1.0036 (1)	0.3126 (1)	0.3462 (1)	0.0416 (3)
O3	1.0678 (1)	0.2498 (1)	0.6074 (1)	0.0326 (2)
O4	0.9638 (1)	0.0696 (1)	0.3530 (1)	0.0355 (2)
O5	1.4343 (1)	0.2904 (1)	0.8360 (2)	0.0545 (4)
O6	1.2818 (2)	0.1782 (1)	0.6463 (2)	0.0536 (4)
O7	1.1604 (2)	−0.1782 (1)	0.1322 (2)	0.0585 (4)
O8	1.1578 (2)	−0.0317 (2)	0.3342 (2)	0.0669 (5)
O33	0.5718 (2)	0.1209 (2)	0.9139 (3)	0.0841 (7)
N9	0.8510 (1)	0.3552 (1)	0.5793 (1)	0.0267 (2)
N10	0.7439 (1)	0.1686 (1)	0.3478 (1)	0.0299 (2)
C11	1.1152 (1)	0.3485 (1)	0.7264 (2)	0.0264 (2)
C12	1.2410 (1)	0.3641 (1)	0.8077 (2)	0.0295 (3)
C13	1.3267 (2)	0.2754 (2)	0.7658 (2)	0.0373 (3)
C14	1.2919 (2)	0.4686 (2)	0.9299 (2)	0.0367 (3)
C15	1.2216 (2)	0.5585 (2)	0.9752 (2)	0.0383 (3)
C16	1.0979 (2)	0.5422 (1)	0.8990 (2)	0.0337 (3)
C17	1.0425 (1)	0.4390 (1)	0.7751 (2)	0.0275 (2)
C18	0.9116 (1)	0.4323 (1)	0.7037 (2)	0.0294 (3)
C19	0.7170 (1)	0.3616 (1)	0.5147 (2)	0.0290 (3)
C20	0.7378 (2)	0.4369 (2)	0.4117 (2)	0.0439 (4)
C21	0.6416 (2)	0.4238 (2)	0.6310 (2)	0.0421 (4)
C22	0.6454 (1)	0.2253 (1)	0.4301 (2)	0.0314 (3)
C23	0.5195 (2)	0.2162 (2)	0.3277 (2)	0.0510 (5)
C24	0.6139 (2)	0.1548 (2)	0.5361 (3)	0.0486 (4)
C25	0.7050 (1)	0.0797 (2)	0.2253 (2)	0.0350 (3)
C26	0.7870 (1)	0.0043 (1)	0.1483 (2)	0.0326 (3)
C27	0.7338 (2)	−0.0738 (2)	0.0052 (2)	0.0414 (4)
C28	0.8010 (2)	−0.1537 (2)	−0.0740 (2)	0.0452 (4)
C29	0.9215 (2)	−0.1611 (2)	−0.0074 (2)	0.0389 (3)
C30	0.9760 (2)	−0.0880 (1)	0.1365 (2)	0.0324 (3)
C31	1.1044 (2)	−0.1032 (2)	0.1997 (2)	0.0416 (4)
C32	0.9104 (1)	−0.0016 (1)	0.2160 (2)	0.0294 (3)
H6	1.209 (3)	0.175 (3)	0.623 (4)	0.0900 (1)*
H8	1.100 (4)	0.015 (3)	0.369 (4)	0.0985 (1)*
H14	1.374 (2)	0.481 (2)	0.981 (2)	0.04735 (7)*
H15	1.260 (2)	0.630 (2)	1.060 (3)	0.05258 (8)*
H16	1.047 (2)	0.599 (2)	0.924 (3)	0.05054 (8)*
H18	0.872 (2)	0.489 (2)	0.753 (2)	0.03272 (6)*
H20A	0.795 (3)	0.520 (2)	0.464 (3)	0.05827 (9)*
H20B	0.774 (2)	0.401 (2)	0.337 (3)	0.05209 (8)*
H20C	0.657 (3)	0.448 (2)	0.366 (3)	0.06366 (9)*
H21A	0.641 (2)	0.396 (2)	0.710 (3)	0.05008 (8)*
H21B	0.685 (3)	0.515 (3)	0.667 (3)	0.06448 (9)*
H21C	0.551 (3)	0.411 (2)	0.581 (3)	0.06145 (9)*
H23A	0.470 (3)	0.268 (2)	0.377 (3)	0.06091 (9)*
H23B	0.473 (3)	0.142 (2)	0.297 (3)	0.05343 (8)*
H23C	0.537 (3)	0.242 (2)	0.244 (3)	0.06223 (9)*
H24A	0.541 (2)	0.179 (2)	0.583 (3)	0.05292 (8)*
H24B	0.682 (3)	0.173 (3)	0.610 (3)	0.0667 (1)*
H24C	0.587 (3)	0.061 (3)	0.482 (3)	0.06793 (10)*
H25	0.615 (2)	0.052 (2)	0.185 (3)	0.05270 (8)*
H27	0.661 (3)	−0.069 (3)	−0.032 (3)	0.06791 (10)*
H28	0.768 (3)	−0.206 (3)	−0.173 (3)	0.06824 (10)*
H29	0.969 (2)	−0.206 (2)	−0.055 (3)	0.05341 (8)*
H33A	0.532 (4)	0.157 (3)	0.881 (4)	0.0904 (1)*
H33B	0.645 (3)	0.138 (3)	0.897 (3)	0.0748 (1)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0208 (1)	0.0271 (1)	0.0269 (1)	0.00825 (8)	0.00056 (8)	0.00353 (8)
O2	0.0388 (6)	0.0450 (6)	0.0425 (6)	0.0103 (5)	0.0119 (5)	0.0146 (5)
O3	0.0294 (5)	0.0295 (5)	0.0326 (5)	0.0117 (4)	−0.0050 (4)	0.0017 (4)
O4	0.0314 (5)	0.0338 (5)	0.0334 (5)	0.0158 (4)	−0.0059 (4)	−0.0013 (4)
O5	0.0329 (6)	0.0609 (8)	0.0643 (9)	0.0211 (6)	−0.0079 (6)	0.0124 (7)
O6	0.0424 (7)	0.0525 (8)	0.0564 (8)	0.0265 (6)	−0.0051 (6)	−0.0003 (6)
O7	0.0472 (7)	0.0524 (8)	0.0652 (9)	0.0313 (6)	0.0021 (6)	−0.0050 (7)
O8	0.0520 (8)	0.0667 (10)	0.0601 (9)	0.0397 (8)	−0.0188 (7)	−0.0161 (7)
O33	0.0426 (9)	0.077 (1)	0.157 (2)	0.0212 (9)	0.016 (1)	0.070 (1)
N9	0.0229 (5)	0.0283 (5)	0.0293 (5)	0.0104 (4)	0.0021 (4)	0.0081 (4)
N10	0.0220 (5)	0.0311 (6)	0.0335 (6)	0.0096 (4)	−0.0004 (4)	0.0058 (5)
C11	0.0247 (6)	0.0266 (6)	0.0271 (6)	0.0060 (5)	0.0009 (5)	0.0088 (5)
C12	0.0248 (6)	0.0322 (7)	0.0305 (6)	0.0073 (5)	−0.0006 (5)	0.0102 (5)
C13	0.0281 (7)	0.0423 (8)	0.0428 (8)	0.0137 (6)	0.0015 (6)	0.0142 (7)
C14	0.0288 (7)	0.0398 (8)	0.0347 (7)	0.0057 (6)	−0.0053 (6)	0.0075 (6)
C15	0.0371 (8)	0.0347 (7)	0.0329 (7)	0.0058 (6)	−0.0044 (6)	0.0014 (6)
C16	0.0357 (7)	0.0298 (7)	0.0304 (7)	0.0095 (6)	0.0003 (5)	0.0030 (5)
C17	0.0257 (6)	0.0287 (6)	0.0262 (6)	0.0076 (5)	0.0011 (5)	0.0066 (5)
C18	0.0278 (6)	0.0305 (6)	0.0291 (6)	0.0115 (5)	0.0033 (5)	0.0065 (5)
C19	0.0254 (6)	0.0323 (6)	0.0309 (6)	0.0127 (5)	0.0015 (5)	0.0101 (5)
C20	0.0438 (9)	0.0475 (10)	0.0509 (10)	0.0163 (8)	0.0054 (8)	0.0289 (8)
C21	0.0340 (8)	0.0512 (10)	0.0403 (8)	0.0234 (7)	0.0060 (6)	0.0061 (7)
C22	0.0215 (6)	0.0328 (7)	0.0380 (7)	0.0101 (5)	0.0023 (5)	0.0077 (6)
C23	0.0281 (7)	0.057 (1)	0.054 (1)	0.0193 (8)	−0.0094 (7)	−0.0017 (9)
C24	0.0424 (9)	0.0442 (10)	0.069 (1)	0.0128 (8)	0.0233 (9)	0.0269 (9)
C25	0.0253 (6)	0.0354 (7)	0.0367 (7)	0.0099 (5)	−0.0041 (5)	0.0025 (6)
C26	0.0286 (6)	0.0308 (7)	0.0316 (7)	0.0093 (5)	−0.0027 (5)	0.0018 (5)
C27	0.0375 (8)	0.0405 (8)	0.0355 (8)	0.0124 (7)	−0.0087 (6)	0.0001 (6)
C28	0.0498 (10)	0.0411 (9)	0.0335 (8)	0.0145 (7)	−0.0053 (7)	−0.0019 (7)
C29	0.0446 (9)	0.0331 (7)	0.0350 (7)	0.0156 (6)	0.0040 (6)	0.0026 (6)
C30	0.0320 (7)	0.0271 (6)	0.0354 (7)	0.0111 (5)	0.0029 (5)	0.0048 (5)
C31	0.0354 (8)	0.0367 (8)	0.0469 (9)	0.0168 (6)	0.0005 (7)	0.0026 (7)
C32	0.0276 (6)	0.0256 (6)	0.0305 (6)	0.0078 (5)	−0.0003 (5)	0.0037 (5)

Geometric parameters (Å, º)

V1—O2	1.588 (2)	C18—H18	0.89 (2)
V1—O3	1.952 (1)	C19—C20	1.532 (3)
V1—O4	1.950 (1)	C19—C21	1.531 (2)
V1—N9	2.061 (1)	C19—C22	1.558 (2)
V1—N10	2.047 (1)	C20—H20A	1.00 (2)
O3—C11	1.335 (2)	C20—H20B	0.88 (3)
O4—C32	1.334 (2)	C20—H20C	0.96 (3)
O5—C13	1.210 (2)	C21—H21A	0.92 (3)
O6—C13	1.324 (2)	C21—H21B	1.02 (3)
O6—H6	0.77 (4)	C21—H21C	0.99 (3)
O7—C31	1.213 (3)	C22—C23	1.534 (3)
O8—C31	1.317 (2)	C22—C24	1.532 (3)
O8—H8	0.91 (4)	C23—H23A	0.93 (3)
O33—H33A	0.76 (4)	C23—H23B	0.86 (2)
O33—H33B	0.81 (4)	C23—H23C	0.97 (3)
N9—C18	1.284 (2)	C24—H24A	0.97 (3)
N9—C19	1.503 (2)	C24—H24B	0.90 (3)
N10—C22	1.504 (2)	C24—H24C	1.04 (3)
N10—C25	1.289 (2)	C25—C26	1.449 (2)
C11—C12	1.416 (2)	C25—H25	0.94 (2)
C11—C17	1.415 (2)	C26—C27	1.401 (2)
C12—C13	1.490 (2)	C26—C32	1.412 (2)
C12—C14	1.393 (2)	C27—C28	1.375 (3)
C14—C15	1.387 (3)	C27—H27	0.83 (3)
C14—H14	0.91 (2)	C28—C29	1.388 (3)
C15—C16	1.375 (2)	C28—H28	0.96 (2)
C15—H15	0.96 (2)	C29—C30	1.393 (2)
C16—C17	1.402 (2)	C29—H29	0.86 (3)
C16—H16	0.92 (3)	C30—C31	1.485 (3)
C17—C18	1.449 (2)	C30—C32	1.412 (2)
O2—V1—O3	109.44 (6)	C19—C20—H20C	113 (2)
O2—V1—O4	105.60 (6)	H20A—C20—H20B	108 (2)
O2—V1—N9	103.98 (6)	H20A—C20—H20C	107 (2)
O2—V1—N10	107.38 (6)	H20B—C20—H20C	104 (2)
O3—V1—O4	86.82 (5)	C19—C21—H21A	115 (2)
O3—V1—N9	88.75 (5)	C19—C21—H21B	106 (2)
O3—V1—N10	142.90 (6)	C19—C21—H21C	107 (2)
O4—V1—N9	149.87 (5)	H21A—C21—H21B	109 (2)
O4—V1—N10	87.72 (5)	H21A—C21—H21C	110 (2)
N9—V1—N10	78.08 (5)	H21B—C21—H21C	110 (2)
V1—O3—C11	127.1 (1)	N10—C22—C19	105.5 (1)
V1—O4—C32	123.2 (1)	N10—C22—C23	112.2 (1)
C13—O6—H6	108 (2)	N10—C22—C24	106.1 (1)
C31—O8—H8	108 (2)	C19—C22—C23	111.6 (2)
H33A—O33—H33B	106 (4)	C19—C22—C24	111.1 (1)
V1—N9—C18	123.4 (1)	C23—C22—C24	110.2 (2)
V1—N9—C19	114.75 (8)	C22—C23—H23A	110 (2)
C18—N9—C19	121.1 (1)	C22—C23—H23B	110 (2)
V1—N10—C22	117.64 (8)	C22—C23—H23C	113 (2)
V1—N10—C25	122.1 (1)	H23A—C23—H23B	109 (2)
C22—N10—C25	120.2 (1)	H23A—C23—H23C	106 (3)
O3—C11—C12	119.9 (1)	H23B—C23—H23C	109 (2)
O3—C11—C17	121.7 (1)	C22—C24—H24A	111 (2)
C12—C11—C17	118.4 (1)	C22—C24—H24B	111 (2)
C11—C12—C13	123.0 (1)	C22—C24—H24C	111 (2)
C11—C12—C14	119.9 (1)	H24A—C24—H24B	106 (2)
C13—C12—C14	117.0 (1)	H24A—C24—H24C	107 (2)
O5—C13—O6	120.1 (2)	H24B—C24—H24C	111 (3)
O5—C13—C12	122.2 (1)	N10—C25—C26	125.4 (1)
O6—C13—C12	117.7 (1)	N10—C25—H25	120 (1)
C12—C14—C15	121.5 (1)	C26—C25—H25	113 (1)
C12—C14—H14	121 (1)	C25—C26—C27	117.2 (1)
C15—C14—H14	118 (1)	C25—C26—C32	122.8 (1)
C14—C15—C16	118.9 (1)	C27—C26—C32	119.8 (1)
C14—C15—H15	119 (2)	C26—C27—C28	121.6 (2)
C16—C15—H15	122 (2)	C26—C27—H27	118 (2)
C15—C16—C17	121.9 (2)	C28—C27—H27	120 (2)
C15—C16—H16	122 (1)	C27—C28—C29	118.9 (1)
C17—C16—H16	116 (1)	C27—C28—H28	123 (2)
C11—C17—C16	119.5 (1)	C29—C28—H28	118 (2)
C11—C17—C18	123.8 (1)	C28—C29—C30	121.3 (2)
C16—C17—C18	116.8 (1)	C28—C29—H29	121 (2)
N9—C18—C17	126.4 (1)	C30—C29—H29	117 (2)
N9—C18—H18	119 (1)	C29—C30—C31	117.7 (2)
C17—C18—H18	115 (1)	C29—C30—C32	120.0 (2)
N9—C19—C20	106.7 (1)	C31—C30—C32	122.3 (1)
N9—C19—C21	112.7 (1)	O7—C31—O8	119.8 (2)
N9—C19—C22	104.8 (1)	O7—C31—C30	122.4 (1)
C20—C19—C21	108.9 (2)	O8—C31—C30	117.8 (2)
C20—C19—C22	112.0 (1)	O4—C32—C26	121.8 (1)
C21—C19—C22	111.6 (1)	O4—C32—C30	119.9 (1)
C19—C20—H20A	112 (2)	C26—C32—C30	118.3 (1)
C19—C20—H20B	113 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O3	0.77 (4)	1.87 (4)	2.569 (2)	152 (3)
O8—H8···O4	0.91 (4)	1.68 (4)	2.535 (2)	154 (3)
O33—H33A···O5^i	0.76 (4)	2.11 (4)	2.886 (3)	167 (3)
O33—H33B···O7^ii	0.81 (4)	2.08 (4)	2.888 (3)	175 (4)

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