exo-[N,N'-Bis(3-tert-butyl­salicyl­idene)-1,2-di­phenyl-(RS,SR)-1,2-ethane­diyl­diaminato]­oxovanadium(IV)

The title mononuclear oxovanadium(IV) complex, [VO(C₃₆H₃₈N₂O₂)], has a distorted square-pyramidal coordination. The complex was shown to be the exo isomer.

S1. Comment

The crystal structure and the thermal isomerization of [VO(3-EtO-sal-meso-stien)] have been investigated by the authors (Hoshina et al., 1999), together with the thermal dehydrogenation in the solid state (Hoshina et al., 1998, 2000).

In the crystals of [VO(3-^tBu,5-Me-salen)], (I), the complex has an asymmetric distortion with a ^tBu—C···C—^tBu torsion angle of 25.1° (Cornman et al., 1997). Distortion of the title compound in the crystal is moderate and the C9—C8···C37—C38 torsion angle is 10.1 (3)°°.

S2. Experimental

To a hot methanol solution (50 ml) of vanadium(IV) oxide sulfate (0.25 g, 1 mmol) were added H₂(3-^tBu-sal-meso-stien) (0.53 g, 1 mmol) and pyridine (2 ml), and the mixture was stirred for 1 h at 333 K. The resulting green precipitate was collected by filtration and washed with ether (yield 80%). Found: C 72.34, H 6.52, N 4.72%; calculated for C₃₆H₃₈N₂O₃V: C 72.35, H 6.41, N 4.69%. An analysis of the product by high-performance liquid reverse-phase chromatography suggested that only one of two possible geometrical isomers had been obtained. Crystals of the title compound, exo-[VO(3-^tBu-sal-meso-stien)], were grown from an acetonitrile solution.

S3. Refinement

All H-atom positional parameters were calculated geometrically, and fixed with U_iso(H) = 1.2U_eq(parent atom).

Computing details

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(C36H38N2O2)]	Dx = 1.268 Mg m^−3
Mr = 597.65	Mo Kα radiation, λ = 0.71073 Å
Monoclinic, C2/c	Cell parameters from 25 reflections
a = 32.529 (4) Å	θ = 14.8–15.0°
b = 11.877 (5) Å	µ = 0.35 mm^−1
c = 18.909 (7) Å	T = 297 K
β = 121.01 (1)°	Prismatic, green
V = 6261 (3) Å^3	0.5 × 0.3 × 0.1 mm
Z = 8

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.045
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = −42→42
Tmin = 0.866, Tmax = 0.979	k = 0→15
7427 measured reflections	l = −25→0
7203 independent reflections	3 standard reflections every 150 reflections
3823 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.061	w = 1/[σ^2(Fo^2) + (0.1616P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.219	(Δ/σ)max = 0.0001
S = 1.18	Δρmax = 0.81 e Å^−3
7203 reflections	Δρmin = −0.73 e Å^−3
379 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
V1	−0.21722 (2)	−0.13575 (6)	−0.69752 (4)	0.0278 (2)
O2	−0.2192 (1)	−0.0058 (3)	−0.7218 (2)	0.0431 (8)
O3	−0.1792 (1)	−0.1420 (3)	−0.5794 (2)	0.0360 (7)
O4	−0.1653 (1)	−0.2075 (3)	−0.7006 (2)	0.0374 (7)
N5	−0.2750 (1)	−0.1740 (3)	−0.6837 (2)	0.0324 (8)
N6	−0.2623 (1)	−0.2212 (3)	−0.8053 (2)	0.0307 (8)
C7	−0.1902 (2)	−0.1033 (4)	−0.5255 (3)	0.0328 (9)
C8	−0.1539 (2)	−0.0567 (4)	−0.4502 (3)	0.0336 (10)
C9	−0.1023 (2)	−0.0449 (4)	−0.4313 (3)	0.038 (1)
C10	−0.1023 (2)	0.0336 (5)	−0.4959 (4)	0.060 (2)
C11	−0.0683 (2)	0.0068 (5)	−0.3465 (3)	0.058 (1)
C12	−0.0829 (2)	−0.1609 (5)	−0.4333 (4)	0.062 (2)
C13	−0.1673 (2)	−0.0197 (4)	−0.3946 (3)	0.043 (1)
C14	−0.2140 (2)	−0.0315 (5)	−0.4097 (3)	0.050 (1)
C15	−0.2487 (2)	−0.0779 (5)	−0.4819 (3)	0.045 (1)
C16	−0.2381 (2)	−0.1124 (4)	−0.5421 (3)	0.036 (1)
C17	−0.2755 (2)	−0.1593 (4)	−0.6165 (3)	0.039 (1)
C18	−0.3156 (2)	−0.2385 (3)	−0.7512 (3)	0.0326 (9)
C19	−0.3649 (1)	−0.2139 (4)	−0.7657 (3)	0.0354 (10)
C20	−0.3795 (2)	−0.1071 (4)	−0.7592 (3)	0.046 (1)
C21	−0.4268 (2)	−0.0896 (5)	−0.7788 (4)	0.063 (2)
C22	−0.4594 (2)	−0.1775 (6)	−0.8074 (4)	0.074 (2)
C23	−0.4452 (2)	−0.2824 (6)	−0.8158 (4)	0.072 (2)
C24	−0.3979 (2)	−0.3008 (4)	−0.7933 (4)	0.055 (1)
C25	−0.3137 (2)	−0.2259 (3)	−0.8319 (3)	0.0339 (9)
C26	−0.3430 (1)	−0.1313 (4)	−0.8904 (3)	0.0298 (9)
C27	−0.3249 (2)	−0.0250 (4)	−0.8886 (3)	0.041 (1)
C28	−0.3528 (2)	0.0566 (4)	−0.9459 (3)	0.045 (1)
C29	−0.3987 (2)	0.0329 (5)	−1.0044 (3)	0.049 (1)
C30	−0.4184 (2)	−0.0708 (5)	−1.0072 (3)	0.054 (1)
C31	−0.3904 (2)	−0.1525 (4)	−0.9506 (3)	0.043 (1)
C32	−0.2494 (2)	−0.2722 (4)	−0.8513 (3)	0.036 (1)
C33	−0.2018 (2)	−0.2803 (4)	−0.8372 (3)	0.0370 (10)
C34	−0.1967 (2)	−0.3265 (5)	−0.9012 (3)	0.050 (1)
C35	−0.1533 (2)	−0.3366 (5)	−0.8929 (3)	0.053 (1)
C36	−0.1124 (2)	−0.3030 (4)	−0.8179 (3)	0.044 (1)
C37	−0.1145 (2)	−0.2602 (4)	−0.7517 (3)	0.0324 (9)
C38	−0.0690 (2)	−0.2289 (4)	−0.6702 (3)	0.0353 (10)
C39	−0.0700 (2)	−0.1052 (4)	−0.6490 (3)	0.046 (1)
C40	−0.0233 (2)	−0.2471 (5)	−0.6740 (3)	0.048 (1)
C41	−0.0646 (2)	−0.3041 (5)	−0.6004 (3)	0.050 (1)
C42	−0.1613 (2)	−0.2476 (4)	−0.7622 (3)	0.0334 (10)
H10A	−0.1147	0.1074	−0.4945	0.0693*
H10B	−0.0712	0.0444	−0.4882	0.0693*
H10C	−0.1230	0.0051	−0.5513	0.0693*
H11A	−0.0797	0.0815	−0.3435	0.0657*
H11B	−0.0680	−0.0378	−0.3044	0.0657*
H11C	−0.0366	0.0147	−0.3357	0.0657*
H12A	−0.1015	−0.1958	−0.4860	0.0672*
H12B	−0.0500	−0.1556	−0.4224	0.0672*
H12C	−0.0820	−0.2085	−0.3923	0.0672*
H13	−0.1443	0.0142	−0.3447	0.0596*
H14	−0.2229	−0.0077	−0.3716	0.0618*
H15	−0.2808	−0.0848	−0.4931	0.0540*
H17	−0.3028	−0.1840	−0.6164	0.0479*
H18	−0.3092	−0.3149	−0.7360	0.0423*
H20	−0.3565	−0.0454	−0.7392	0.0585*
H21	−0.4370	−0.0190	−0.7753	0.0830*
H22	−0.4914	−0.1662	−0.8201	0.0914*
H23	−0.4669	−0.3436	−0.8369	0.0840*
H24	−0.3876	−0.3745	−0.7977	0.0675*
H25	−0.3264	−0.2929	−0.8620	0.0427*
H27	−0.2923	−0.0086	−0.8492	0.0542*
H28	−0.3404	0.1294	−0.9424	0.0535*
H29	−0.4173	0.0878	−1.0452	0.0569*
H30	−0.4504	−0.0852	−1.0485	0.0641*
H31	−0.4033	−0.2247	−0.9538	0.0508*
H32	−0.2740	−0.3097	−0.8986	0.0464*
H34	−0.2260	−0.3509	−0.9523	0.0579*
H35	−0.1509	−0.3696	−0.9366	0.0672*
H36	−0.0835	−0.3134	−0.8161	0.0570*
H39A	−0.0980	−0.0886	−0.6437	0.0568*
H39B	−0.0725	−0.0552	−0.6908	0.0568*
H39C	−0.0425	−0.0820	−0.5972	0.0568*
H40A	0.0060	−0.2285	−0.6215	0.0631*
H40B	−0.0195	−0.3254	−0.6843	0.0631*
H40C	−0.0229	−0.2028	−0.7153	0.0631*
H41A	−0.0613	−0.3821	−0.6097	0.0599*
H41B	−0.0916	−0.2965	−0.5937	0.0599*
H41C	−0.0362	−0.2848	−0.5471	0.0599*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0286 (4)	0.0281 (4)	0.0294 (4)	−0.0022 (3)	0.0168 (3)	−0.0044 (3)
O2	0.056 (2)	0.029 (2)	0.044 (2)	−0.005 (1)	0.026 (2)	0.001 (1)
O3	0.030 (1)	0.047 (2)	0.033 (2)	0.002 (1)	0.018 (1)	−0.007 (1)
O4	0.034 (2)	0.048 (2)	0.036 (2)	0.003 (1)	0.023 (1)	−0.007 (1)
N5	0.032 (2)	0.030 (2)	0.036 (2)	−0.001 (1)	0.018 (2)	−0.001 (2)
N6	0.032 (2)	0.028 (2)	0.031 (2)	0.002 (1)	0.015 (2)	−0.003 (2)
C7	0.040 (2)	0.029 (2)	0.034 (2)	0.005 (2)	0.023 (2)	0.000 (2)
C8	0.043 (2)	0.028 (2)	0.031 (2)	0.003 (2)	0.020 (2)	−0.001 (2)
C9	0.031 (2)	0.043 (3)	0.035 (2)	−0.001 (2)	0.012 (2)	−0.008 (2)
C10	0.058 (3)	0.072 (4)	0.054 (3)	−0.019 (3)	0.031 (3)	−0.003 (3)
C11	0.051 (3)	0.066 (4)	0.042 (3)	−0.009 (3)	0.013 (3)	−0.019 (3)
C12	0.037 (3)	0.062 (4)	0.065 (4)	0.011 (2)	0.010 (3)	−0.015 (3)
C13	0.048 (3)	0.046 (3)	0.031 (2)	0.000 (2)	0.017 (2)	−0.007 (2)
C14	0.062 (3)	0.058 (3)	0.041 (3)	0.009 (3)	0.034 (3)	−0.003 (2)
C15	0.041 (3)	0.062 (3)	0.044 (3)	0.011 (2)	0.029 (2)	0.007 (2)
C16	0.042 (2)	0.037 (3)	0.036 (2)	0.004 (2)	0.025 (2)	0.000 (2)
C17	0.040 (2)	0.040 (3)	0.049 (3)	0.000 (2)	0.032 (2)	0.004 (2)
C18	0.032 (2)	0.026 (2)	0.039 (2)	−0.005 (2)	0.018 (2)	−0.001 (2)
C19	0.025 (2)	0.041 (3)	0.038 (2)	−0.006 (2)	0.015 (2)	0.004 (2)
C20	0.038 (3)	0.041 (3)	0.063 (3)	−0.002 (2)	0.028 (2)	−0.003 (2)
C21	0.051 (3)	0.062 (4)	0.083 (4)	0.013 (3)	0.040 (3)	0.005 (3)
C22	0.020 (2)	0.096 (5)	0.101 (5)	0.000 (3)	0.028 (3)	0.014 (4)
C23	0.034 (3)	0.066 (4)	0.103 (5)	−0.008 (3)	0.025 (3)	0.019 (4)
C24	0.034 (3)	0.042 (3)	0.079 (4)	−0.009 (2)	0.023 (3)	0.005 (3)
C25	0.032 (2)	0.026 (2)	0.040 (2)	−0.005 (2)	0.016 (2)	−0.008 (2)
C26	0.026 (2)	0.033 (2)	0.032 (2)	0.004 (2)	0.016 (2)	−0.002 (2)
C27	0.030 (2)	0.041 (3)	0.052 (3)	0.000 (2)	0.021 (2)	0.000 (2)
C28	0.042 (3)	0.031 (2)	0.062 (3)	0.005 (2)	0.026 (3)	0.005 (2)
C29	0.055 (3)	0.048 (3)	0.042 (3)	0.017 (2)	0.024 (3)	0.005 (2)
C30	0.047 (3)	0.056 (3)	0.038 (3)	0.004 (2)	0.007 (2)	−0.009 (2)
C31	0.035 (2)	0.038 (3)	0.044 (3)	0.001 (2)	0.012 (2)	−0.004 (2)
C32	0.035 (2)	0.034 (2)	0.037 (2)	0.001 (2)	0.017 (2)	−0.009 (2)
C33	0.043 (3)	0.034 (2)	0.038 (2)	0.003 (2)	0.024 (2)	−0.005 (2)
C34	0.054 (3)	0.055 (3)	0.041 (3)	0.005 (2)	0.024 (2)	−0.013 (2)
C35	0.061 (3)	0.060 (4)	0.050 (3)	0.006 (3)	0.038 (3)	−0.011 (3)
C36	0.050 (3)	0.043 (3)	0.056 (3)	0.012 (2)	0.038 (3)	0.005 (2)
C37	0.039 (2)	0.029 (2)	0.039 (2)	0.005 (2)	0.027 (2)	0.005 (2)
C38	0.030 (2)	0.039 (2)	0.041 (2)	0.006 (2)	0.021 (2)	0.008 (2)
C39	0.045 (3)	0.044 (3)	0.050 (3)	−0.003 (2)	0.025 (2)	−0.004 (2)
C40	0.033 (2)	0.062 (3)	0.060 (3)	0.009 (2)	0.032 (2)	0.016 (3)
C41	0.046 (3)	0.063 (3)	0.043 (3)	0.003 (2)	0.024 (2)	0.019 (3)
C42	0.042 (2)	0.029 (2)	0.040 (2)	0.007 (2)	0.029 (2)	0.001 (2)

Geometric parameters (Å, º)

V1—O2	1.601 (3)	C21—H21	0.918
V1—O3	1.917 (3)	C22—C23	1.37 (1)
V1—O4	1.918 (4)	C22—H22	0.949
V1—N5	2.077 (5)	C23—C24	1.387 (9)
V1—N6	2.063 (3)	C23—H23	0.946
O3—C7	1.325 (7)	C24—H24	0.956
O4—C42	1.326 (7)	C25—C26	1.519 (6)
N5—C17	1.291 (8)	C25—H25	0.942
N5—C18	1.491 (5)	C26—C27	1.386 (7)
N6—C25	1.480 (6)	C26—C31	1.388 (5)
N6—C32	1.294 (7)	C27—C28	1.388 (6)
C7—C8	1.412 (5)	C27—H27	0.949
C7—C16	1.428 (8)	C28—C29	1.351 (6)
C8—C9	1.533 (8)	C28—H28	0.943
C8—C13	1.400 (9)	C29—C30	1.376 (8)
C9—C10	1.536 (9)	C29—H29	0.952
C9—C11	1.531 (7)	C30—C31	1.383 (7)
C9—C12	1.525 (8)	C30—H30	0.942
C10—H10A	0.972	C31—H31	0.944
C10—H10B	0.953	C32—C33	1.433 (8)
C10—H10C	0.969	C32—H32	0.948
C11—H11A	0.975	C33—C34	1.415 (9)
C11—H11B	0.953	C33—C42	1.405 (5)
C11—H11C	0.946	C34—C35	1.342 (10)
C12—H12A	0.954	C34—H34	0.989
C12—H12B	0.980	C35—C36	1.413 (6)
C12—H12C	0.948	C35—H35	0.953
C13—C14	1.401 (9)	C36—C37	1.384 (9)
C13—H13	0.940	C36—H36	0.932
C14—C15	1.361 (6)	C37—C38	1.533 (5)
C14—H14	0.947	C37—C42	1.438 (8)
C15—C16	1.411 (9)	C38—C39	1.529 (7)
C15—H15	0.953	C38—C40	1.542 (8)
C16—C17	1.416 (6)	C38—C41	1.538 (8)
C17—H17	0.937	C39—H39A	0.987
C18—C19	1.510 (7)	C39—H39B	0.958
C18—C25	1.564 (8)	C39—H39C	0.967
C18—H18	0.942	C40—H40A	0.983
C19—C20	1.383 (7)	C40—H40B	0.971
C19—C24	1.384 (7)	C40—H40C	0.946
C20—C21	1.398 (9)	C41—H41A	0.959
C20—H20	0.975	C41—H41B	0.956
C21—C22	1.385 (9)	C41—H41C	0.980
O2—V1—O3	106.1 (1)	C21—C22—C23	119.7 (6)
O2—V1—O4	109.0 (2)	C21—C22—H22	120.8
O2—V1—N5	109.9 (2)	C23—C22—H22	119.4
O2—V1—N6	106.7 (1)	C22—C23—C24	119.7 (5)
O3—V1—O4	88.2 (1)	C22—C23—H23	121.8
O3—V1—N5	85.9 (1)	C24—C23—H23	118.5
O3—V1—N6	146.6 (1)	C19—C24—C23	121.4 (5)
O4—V1—N5	140.7 (1)	C19—C24—H24	118.4
O4—V1—N6	86.6 (1)	C23—C24—H24	120.1
N5—V1—N6	77.8 (2)	N6—C25—C18	106.1 (3)
V1—O3—C7	127.9 (2)	N6—C25—C26	113.2 (4)
V1—O4—C42	132.3 (2)	N6—C25—H25	107.7
V1—N5—C17	124.4 (3)	C18—C25—C26	117.2 (4)
V1—N5—C18	117.6 (4)	C18—C25—H25	106.5
C17—N5—C18	117.3 (4)	C26—C25—H25	105.6
V1—N6—C25	117.3 (3)	C25—C26—C27	123.9 (3)
V1—N6—C32	125.6 (3)	C25—C26—C31	118.5 (4)
C25—N6—C32	117.1 (3)	C27—C26—C31	117.6 (4)
O3—C7—C8	119.8 (5)	C26—C27—C28	121.2 (4)
O3—C7—C16	120.1 (3)	C26—C27—H27	119.6
C8—C7—C16	120.1 (5)	C28—C27—H27	119.1
C7—C8—C9	121.1 (5)	C27—C28—C29	119.7 (5)
C7—C8—C13	117.3 (5)	C27—C28—H28	120.0
C9—C8—C13	121.6 (4)	C29—C28—H28	120.1
C8—C9—C10	108.6 (4)	C28—C29—C30	120.9 (4)
C8—C9—C11	113.2 (5)	C28—C29—H29	119.6
C8—C9—C12	109.2 (4)	C30—C29—H29	119.5
C10—C9—C11	107.1 (4)	C29—C30—C31	119.3 (4)
C10—C9—C12	111.0 (6)	C29—C30—H30	119.4
C11—C9—C12	107.6 (4)	C31—C30—H30	121.3
C9—C10—H10A	110.8	C26—C31—C30	121.2 (5)
C9—C10—H10B	113.3	C26—C31—H31	119.2
C9—C10—H10C	111.3	C30—C31—H31	119.6
H10A—C10—H10B	107.4	N6—C32—C33	126.8 (4)
H10A—C10—H10C	106.1	N6—C32—H32	116.5
H10B—C10—H10C	107.7	C33—C32—H32	116.6
C9—C11—H11A	109.6	C32—C33—C34	117.3 (4)
C9—C11—H11B	110.1	C32—C33—C42	122.1 (5)
C9—C11—H11C	112.6	C34—C33—C42	120.6 (5)
H11A—C11—H11B	107.2	C33—C34—C35	121.0 (4)
H11A—C11—H11C	107.7	C33—C34—H34	117.9
H11B—C11—H11C	109.5	C35—C34—H34	121.0
C9—C12—H12A	111.7	C34—C35—C36	118.7 (6)
C9—C12—H12B	110.9	C34—C35—H35	119.1
C9—C12—H12C	110.9	C36—C35—H35	122.1
H12A—C12—H12B	106.6	C35—C36—C37	123.6 (6)
H12A—C12—H12C	109.3	C35—C36—H36	114.1
H12B—C12—H12C	107.2	C37—C36—H36	122.3
C8—C13—C14	122.6 (4)	C36—C37—C38	121.8 (5)
C8—C13—H13	119.4	C36—C37—C42	117.1 (4)
C14—C13—H13	117.9	C38—C37—C42	121.2 (5)
C13—C14—C15	119.9 (6)	C37—C38—C39	110.9 (3)
C13—C14—H14	122.6	C37—C38—C40	112.0 (5)
C15—C14—H14	117.6	C37—C38—C41	109.7 (4)
C14—C15—C16	120.3 (6)	C39—C38—C40	107.3 (4)
C14—C15—H15	120.4	C39—C38—C41	109.8 (5)
C16—C15—H15	119.2	C40—C38—C41	107.0 (4)
C7—C16—C15	119.6 (4)	C38—C39—H39A	111.4
C7—C16—C17	122.0 (5)	C38—C39—H39B	112.6
C15—C16—C17	118.3 (5)	C38—C39—H39C	114.0
N5—C17—C16	126.3 (5)	H39A—C39—H39B	105.8
N5—C17—H17	116.9	H39A—C39—H39C	105.2
C16—C17—H17	116.8	H39B—C39—H39C	107.4
N5—C18—C19	116.4 (4)	C38—C40—H40A	112.1
N5—C18—C25	108.9 (4)	C38—C40—H40B	111.6
N5—C18—H18	106.0	C38—C40—H40C	112.5
C19—C18—C25	112.0 (3)	H40A—C40—H40B	105.1
C19—C18—H18	106.7	H40A—C40—H40C	107.1
C25—C18—H18	106.1	H40B—C40—H40C	108.0
C18—C19—C20	123.0 (4)	C38—C41—H41A	111.8
C18—C19—C24	118.0 (4)	C38—C41—H41B	111.9
C20—C19—C24	118.8 (5)	C38—C41—H41C	111.7
C19—C20—C21	119.6 (5)	H41A—C41—H41B	108.2
C19—C20—H20	119.5	H41A—C41—H41C	106.3
C21—C20—H20	120.8	H41B—C41—H41C	106.5
C20—C21—C22	120.6 (6)	O4—C42—C33	121.4 (5)
C20—C21—H21	120.5	O4—C42—C37	119.6 (3)
C22—C21—H21	118.8	C33—C42—C37	119.1 (5)