{2,2'-[(2,2-Dimethyl-propane-1,3-di-yl)-bis-(nitrilo-methyl-idyne)]-diphenolato}-dioxidomolybdenum(VI).

In the structure of the title compound, [Mo(C(19)H(20)N(2)O(2))O(2)], the Mo atom exhibits oxidation state +VI and is surrounded by two O atoms and the tetra-dentate Schiff base ligand 2,2'-[(2,2-dimethyl-propane-1,3-di-yl)bis-(nitrilo-methyl-idyne)]diphenolate in a distorted octa-hedral configuration. An intra-molecular C-H⋯O hydrogen bond between a methyl-ene group and one O atom of the O=Mo(VI)=O unit, as well as additional inter-molecular hydrogen bonds between neighboring mol-ecules, lead to a weakly bonded inversion-symmetric dimeric structure.

Related literature

For related structures with O=MoVI=O units and for synthesis, see: Arnaiz et al. (2000 ▶); Holm et al. (1996 ▶); Syamal & Maurya (1989 ▶). The crystal structure of the free ligand N,N′-bis­(2-hydroxy­benzyl­idene)-2,2-dimethyl-1,3-propane­diamine was described by Corden et al. (1996 ▶).

Experimental

Crystal data

[Mo(C19H20N2O2)O2]

M = 436.31

Triclinic,

a = 9.3875 (10) Å

b = 9.5597 (10) Å

c = 11.0422 (11) Å

α = 104.6790 (17)°

β = 108.1939 (17)°

γ = 101.1218 (17)°

V = 869.87 (16) Å3

Z = 2

Mo Kα radiation

μ = 0.78 mm−1

T = 100 (2) K

0.18 × 0.12 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: none

8420 measured reflections

3413 independent reflections

3204 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.051

S = 1.07

3413 reflections

237 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.53 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680802182X/wm2183sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802182X/wm2183Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mo(C19H20N2O2)O2]	Z = 2
Mr = 436.31	F000 = 444
Triclinic, P1	Dx = 1.666 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 9.3875 (10) Å	Cell parameters from 8420 reflections
b = 9.5597 (10) Å	θ = 2.5–26.0º
c = 11.0422 (11) Å	µ = 0.78 mm−1
α = 104.6790 (17)º	T = 100 (2) K
β = 108.1939 (17)º	Prism, light yellow
γ = 101.1218 (17)º	0.18 × 0.12 × 0.06 mm
V = 869.87 (16) Å3

Bruker APEXII CCD diffractometer	3204 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Monochromator: graphite	θmax = 26.0º
T = 100(2) K	θmin = 2.1º
ω scans	h = −11→11
Absorption correction: none	k = −11→11
8420 measured reflections	l = −13→13
3413 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021	H-atom parameters constrained
wR(F2) = 0.051	w = 1/[σ2(Fo2) + (0.0184P)2 + 0.8169P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
3413 reflections	Δρmax = 0.42 e Å−3
237 parameters	Δρmin = −0.53 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Mo1	0.742950 (19)	0.625366 (18)	0.282813 (16)	0.01031 (6)
O1	0.70502 (16)	0.74204 (15)	0.19043 (14)	0.0161 (3)
O2	0.84039 (16)	0.52119 (16)	0.20730 (14)	0.0167 (3)
O3	0.59172 (16)	0.68583 (15)	0.37734 (13)	0.0135 (3)
O4	0.90918 (16)	0.76348 (15)	0.44982 (13)	0.0146 (3)
N1	0.75678 (18)	0.46531 (18)	0.41243 (16)	0.0115 (3)
N2	0.52861 (19)	0.44879 (18)	0.15515 (16)	0.0112 (3)
C1	0.3927 (2)	0.4737 (2)	0.11735 (19)	0.0127 (4)
H1	0.3111	0.3981	0.0443	0.015*
C2	0.7108 (2)	0.3002 (2)	0.34369 (19)	0.0122 (4)
H2A	0.7190	0.2512	0.4115	0.015*
H2B	0.7855	0.2782	0.3032	0.015*
C3	0.8231 (2)	0.5116 (2)	0.5423 (2)	0.0121 (4)
H3	0.8229	0.4382	0.5838	0.014*
C4	0.5301 (2)	0.2902 (2)	0.11404 (19)	0.0131 (4)
H4A	0.6177	0.2836	0.0863	0.016*
H4B	0.4339	0.2289	0.0375	0.016*
C5	0.4553 (2)	0.7013 (2)	0.3131 (2)	0.0127 (4)
C6	0.3575 (2)	0.6066 (2)	0.1779 (2)	0.0132 (4)
C7	0.2101 (2)	0.6264 (2)	0.1145 (2)	0.0156 (4)
H7	0.1467	0.5643	0.0262	0.019*
C8	0.1596 (2)	0.7357 (2)	0.1811 (2)	0.0188 (4)
H8	0.0631	0.7486	0.1380	0.023*
C9	0.2546 (3)	0.8278 (2)	0.3146 (2)	0.0189 (4)
H9	0.2204	0.9020	0.3600	0.023*
C10	0.3979 (2)	0.8102 (2)	0.3795 (2)	0.0161 (4)
H10	0.4579	0.8713	0.4688	0.019*
C11	0.9390 (2)	0.7870 (2)	0.58181 (19)	0.0122 (4)
C12	0.8984 (2)	0.6685 (2)	0.62999 (19)	0.0120 (4)
C13	0.9480 (2)	0.6997 (2)	0.7706 (2)	0.0139 (4)
H13	0.9255	0.6212	0.8035	0.017*
C14	1.0294 (2)	0.8440 (2)	0.8609 (2)	0.0154 (4)
H14	1.0595	0.8633	0.9536	0.019*
C15	1.0658 (2)	0.9608 (2)	0.8110 (2)	0.0156 (4)
H15	1.1204	1.0585	0.8712	0.019*
C16	1.0218 (2)	0.9330 (2)	0.6732 (2)	0.0143 (4)
H16	1.0473	1.0118	0.6414	0.017*
C17	0.5230 (2)	0.0591 (2)	0.1785 (2)	0.0166 (4)
H17A	0.5356	0.0183	0.2509	0.025*
H17B	0.5999	0.0428	0.1404	0.025*
H17C	0.4197	0.0095	0.1098	0.025*
C18	0.4199 (2)	0.2557 (2)	0.2899 (2)	0.0156 (4)
H18A	0.3185	0.2163	0.2174	0.023*
H18B	0.4408	0.3623	0.3329	0.023*
H18C	0.4216	0.2051	0.3549	0.023*
C19	0.5451 (2)	0.2294 (2)	0.23343 (19)	0.0119 (4)

	U11	U22	U33	U12	U13	U23
Mo1	0.01067 (9)	0.01016 (9)	0.00976 (9)	0.00212 (6)	0.00322 (6)	0.00433 (6)
O1	0.0185 (7)	0.0120 (7)	0.0142 (7)	0.0015 (6)	0.0028 (6)	0.0051 (6)
O2	0.0143 (7)	0.0182 (7)	0.0193 (7)	0.0037 (6)	0.0090 (6)	0.0064 (6)
O3	0.0135 (7)	0.0145 (7)	0.0121 (7)	0.0054 (6)	0.0038 (5)	0.0046 (5)
O4	0.0148 (7)	0.0147 (7)	0.0117 (7)	0.0006 (6)	0.0026 (6)	0.0058 (6)
N1	0.0081 (8)	0.0116 (8)	0.0149 (8)	0.0030 (6)	0.0043 (6)	0.0046 (7)
N2	0.0139 (8)	0.0106 (8)	0.0093 (8)	0.0031 (6)	0.0052 (6)	0.0032 (6)
C1	0.0132 (10)	0.0134 (9)	0.0099 (9)	0.0013 (8)	0.0031 (7)	0.0047 (7)
C2	0.0116 (9)	0.0116 (9)	0.0150 (10)	0.0042 (8)	0.0053 (8)	0.0059 (8)
C3	0.0086 (9)	0.0135 (9)	0.0167 (10)	0.0037 (7)	0.0048 (8)	0.0090 (8)
C4	0.0152 (10)	0.0106 (9)	0.0114 (9)	0.0030 (8)	0.0045 (8)	0.0014 (7)
C5	0.0145 (10)	0.0123 (9)	0.0150 (10)	0.0036 (8)	0.0069 (8)	0.0088 (8)
C6	0.0137 (10)	0.0142 (9)	0.0148 (10)	0.0041 (8)	0.0070 (8)	0.0082 (8)
C7	0.0133 (10)	0.0184 (10)	0.0157 (10)	0.0035 (8)	0.0047 (8)	0.0083 (8)
C8	0.0161 (10)	0.0238 (11)	0.0253 (11)	0.0111 (9)	0.0100 (9)	0.0163 (9)
C9	0.0248 (12)	0.0181 (10)	0.0244 (11)	0.0123 (9)	0.0156 (9)	0.0121 (9)
C10	0.0220 (11)	0.0143 (10)	0.0141 (10)	0.0066 (8)	0.0084 (8)	0.0058 (8)
C11	0.0075 (9)	0.0169 (10)	0.0124 (9)	0.0052 (8)	0.0023 (7)	0.0059 (8)
C12	0.0078 (9)	0.0142 (9)	0.0148 (10)	0.0044 (7)	0.0041 (7)	0.0056 (8)
C13	0.0119 (10)	0.0173 (10)	0.0163 (10)	0.0060 (8)	0.0068 (8)	0.0091 (8)
C14	0.0140 (10)	0.0207 (10)	0.0110 (9)	0.0054 (8)	0.0045 (8)	0.0046 (8)
C15	0.0129 (10)	0.0139 (10)	0.0160 (10)	0.0035 (8)	0.0032 (8)	0.0019 (8)
C16	0.0127 (10)	0.0131 (10)	0.0181 (10)	0.0044 (8)	0.0043 (8)	0.0083 (8)
C17	0.0173 (10)	0.0122 (10)	0.0175 (10)	0.0026 (8)	0.0047 (8)	0.0042 (8)
C18	0.0131 (10)	0.0190 (10)	0.0168 (10)	0.0049 (8)	0.0067 (8)	0.0083 (8)
C19	0.0117 (9)	0.0098 (9)	0.0139 (9)	0.0021 (7)	0.0054 (8)	0.0035 (8)

Mo1—O1	1.7072 (14)	C7—C8	1.370 (3)
Mo1—O2	1.7120 (14)	C7—H7	0.9300
Mo1—O4	1.9373 (13)	C8—C9	1.401 (3)
Mo1—O3	2.0917 (14)	C8—H8	0.9300
Mo1—N2	2.1442 (16)	C9—C10	1.378 (3)
Mo1—N1	2.3402 (16)	C9—H9	0.9300
O3—C5	1.313 (2)	C10—H10	0.9300
O4—C11	1.345 (2)	C11—C16	1.395 (3)
N1—C3	1.286 (2)	C11—C12	1.407 (3)
N1—C2	1.477 (2)	C12—C13	1.406 (3)
N2—C1	1.301 (3)	C13—C14	1.379 (3)
N2—C4	1.472 (2)	C13—H13	0.9300
C1—C6	1.428 (3)	C14—C15	1.395 (3)
C1—H1	0.9300	C14—H14	0.9300
C2—C19	1.534 (3)	C15—C16	1.385 (3)
C2—H2A	0.9700	C15—H15	0.9300
C2—H2B	0.9700	C16—H16	0.9300
C3—C12	1.454 (3)	C17—C19	1.534 (3)
C3—H3	0.9300	C17—H17A	0.9600
C4—C19	1.549 (3)	C17—H17B	0.9600
C4—H4A	0.9700	C17—H17C	0.9600
C4—H4B	0.9700	C18—C19	1.525 (3)
C5—C10	1.410 (3)	C18—H18A	0.9600
C5—C6	1.425 (3)	C18—H18B	0.9600
C6—C7	1.415 (3)	C18—H18C	0.9600
O1—Mo1—O2	103.33 (7)	C8—C7—H7	119.5
O1—Mo1—O4	101.99 (6)	C6—C7—H7	119.5
O2—Mo1—O4	102.79 (6)	C7—C8—C9	119.36 (19)
O1—Mo1—O3	90.82 (6)	C7—C8—H8	120.3
O2—Mo1—O3	161.79 (6)	C9—C8—H8	120.3
O4—Mo1—O3	85.05 (6)	C10—C9—C8	120.94 (19)
O1—Mo1—N2	93.87 (6)	C10—C9—H9	119.5
O2—Mo1—N2	88.54 (6)	C8—C9—H9	119.5
O4—Mo1—N2	157.64 (6)	C9—C10—C5	121.24 (19)
O3—Mo1—N2	79.01 (6)	C9—C10—H10	119.4
O1—Mo1—N1	170.94 (6)	C5—C10—H10	119.4
O2—Mo1—N1	84.17 (6)	O4—C11—C16	117.93 (17)
O4—Mo1—N1	80.95 (6)	O4—C11—C12	122.15 (17)
O3—Mo1—N1	80.84 (5)	C16—C11—C12	119.80 (18)
N2—Mo1—N1	81.12 (6)	C13—C12—C11	118.62 (18)
C5—O3—Mo1	123.46 (12)	C13—C12—C3	117.94 (17)
C11—O4—Mo1	134.29 (12)	C11—C12—C3	123.05 (17)
C3—N1—C2	115.90 (16)	C14—C13—C12	121.52 (18)
C3—N1—Mo1	124.12 (13)	C14—C13—H13	119.2
C2—N1—Mo1	119.23 (12)	C12—C13—H13	119.2
C1—N2—C4	117.18 (16)	C13—C14—C15	118.99 (18)
C1—N2—Mo1	122.83 (13)	C13—C14—H14	120.5
C4—N2—Mo1	119.87 (12)	C15—C14—H14	120.5
N2—C1—C6	125.94 (18)	C16—C15—C14	120.85 (19)
N2—C1—H1	117.0	C16—C15—H15	119.6
C6—C1—H1	117.0	C14—C15—H15	119.6
N1—C2—C19	115.73 (15)	C15—C16—C11	120.17 (18)
N1—C2—H2A	108.3	C15—C16—H16	119.9
C19—C2—H2A	108.3	C11—C16—H16	119.9
N1—C2—H2B	108.3	C19—C17—H17A	109.5
C19—C2—H2B	108.3	C19—C17—H17B	109.5
H2A—C2—H2B	107.4	H17A—C17—H17B	109.5
N1—C3—C12	125.78 (17)	C19—C17—H17C	109.5
N1—C3—H3	117.1	H17A—C17—H17C	109.5
C12—C3—H3	117.1	H17B—C17—H17C	109.5
N2—C4—C19	110.04 (15)	C19—C18—H18A	109.5
N2—C4—H4A	109.7	C19—C18—H18B	109.5
C19—C4—H4A	109.7	H18A—C18—H18B	109.5
N2—C4—H4B	109.7	C19—C18—H18C	109.5
C19—C4—H4B	109.7	H18A—C18—H18C	109.5
H4A—C4—H4B	108.2	H18B—C18—H18C	109.5
O3—C5—C10	120.15 (18)	C18—C19—C2	111.61 (16)
O3—C5—C6	122.19 (18)	C18—C19—C17	109.71 (16)
C10—C5—C6	117.62 (18)	C2—C19—C17	106.47 (16)
C7—C6—C5	119.77 (18)	C18—C19—C4	110.70 (16)
C7—C6—C1	119.37 (18)	C2—C19—C4	110.88 (15)
C5—C6—C1	119.60 (17)	C17—C19—C4	107.29 (15)
C8—C7—C6	121.04 (19)
O1—Mo1—O3—C5	41.55 (15)	Mo1—O3—C5—C10	−146.68 (14)
O2—Mo1—O3—C5	−99.9 (2)	Mo1—O3—C5—C6	35.9 (2)
O4—Mo1—O3—C5	143.51 (15)	O3—C5—C6—C7	178.78 (17)
N2—Mo1—O3—C5	−52.23 (14)	C10—C5—C6—C7	1.3 (3)
N1—Mo1—O3—C5	−134.88 (15)	O3—C5—C6—C1	11.6 (3)
O1—Mo1—O4—C11	135.68 (17)	C10—C5—C6—C1	−165.83 (18)
O2—Mo1—O4—C11	−117.46 (17)	N2—C1—C6—C7	171.47 (18)
O3—Mo1—O4—C11	45.89 (17)	N2—C1—C6—C5	−21.3 (3)
N2—Mo1—O4—C11	1.4 (3)	C5—C6—C7—C8	0.1 (3)
N1—Mo1—O4—C11	−35.61 (17)	C1—C6—C7—C8	167.25 (19)
O2—Mo1—N1—C3	121.32 (16)	C6—C7—C8—C9	−0.8 (3)
O4—Mo1—N1—C3	17.34 (15)	C7—C8—C9—C10	0.1 (3)
O3—Mo1—N1—C3	−69.06 (15)	C8—C9—C10—C5	1.3 (3)
N2—Mo1—N1—C3	−149.25 (16)	O3—C5—C10—C9	−179.54 (18)
O2—Mo1—N1—C2	−48.30 (13)	C6—C5—C10—C9	−2.0 (3)
O4—Mo1—N1—C2	−152.29 (13)	Mo1—O4—C11—C16	−150.25 (15)
O3—Mo1—N1—C2	121.32 (13)	Mo1—O4—C11—C12	33.8 (3)
N2—Mo1—N1—C2	41.12 (13)	O4—C11—C12—C13	173.48 (17)
O1—Mo1—N2—C1	−48.07 (15)	C16—C11—C12—C13	−2.4 (3)
O2—Mo1—N2—C1	−151.34 (15)	O4—C11—C12—C3	0.8 (3)
O4—Mo1—N2—C1	87.3 (2)	C16—C11—C12—C3	−175.13 (18)
O3—Mo1—N2—C1	42.02 (15)	N1—C3—C12—C13	172.40 (18)
N1—Mo1—N2—C1	124.33 (15)	N1—C3—C12—C11	−14.9 (3)
O1—Mo1—N2—C4	136.02 (13)	C11—C12—C13—C14	2.7 (3)
O2—Mo1—N2—C4	32.75 (14)	C3—C12—C13—C14	175.75 (18)
O4—Mo1—N2—C4	−88.6 (2)	C12—C13—C14—C15	−1.4 (3)
O3—Mo1—N2—C4	−133.89 (14)	C13—C14—C15—C16	−0.2 (3)
N1—Mo1—N2—C4	−51.57 (13)	C14—C15—C16—C11	0.4 (3)
C4—N2—C1—C6	159.34 (18)	O4—C11—C16—C15	−175.12 (17)
Mo1—N2—C1—C6	−16.7 (3)	C12—C11—C16—C15	1.0 (3)
C3—N1—C2—C19	133.97 (18)	N1—C2—C19—C18	−59.5 (2)
Mo1—N1—C2—C19	−55.57 (19)	N1—C2—C19—C17	−179.21 (16)
C2—N1—C3—C12	170.57 (17)	N1—C2—C19—C4	64.4 (2)
Mo1—N1—C3—C12	0.6 (3)	N2—C4—C19—C18	52.6 (2)
C1—N2—C4—C19	−100.26 (19)	N2—C4—C19—C2	−71.82 (19)
Mo1—N2—C4—C19	75.87 (17)	N2—C4—C19—C17	172.30 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2	0.97	2.49	2.986 (2)	112
C1—H1···O1i	0.93	2.54	3.227 (2)	131
C4—H4B···O1i	0.97	2.56	3.294 (2)	132
C7—H7···O2i	0.93	2.55	3.315 (2)	140

Table 1

Selected bond lengths (Å)

Mo1—O1	1.7072 (14)
Mo1—O2	1.7120 (14)
Mo1—O4	1.9373 (13)
Mo1—O3	2.0917 (14)
Mo1—N2	2.1442 (16)
Mo1—N1	2.3402 (16)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O2	0.97	2.49	2.986 (2)	112
C1—H1⋯O1i	0.93	2.54	3.227 (2)	131
C4—H4B⋯O1i	0.97	2.56	3.294 (2)	132
C7—H7⋯O2i	0.93	2.55	3.315 (2)	140

Symmetry code: (i) .