Dioxidobis(2-oxo-1,2-dihydropyridin-3-olato)-molybdenum(VI).

In the title compound, [Mo(C(5)H(4)NO(2))(2)O(2)], the Mo(VI) atom exhibits a distorted octa-hedral coordination geometry formed by two terminal oxo ligands and two monoanionic O,O-bidentate pyridinone ligands. The two terminal oxo ligands lie in a cis arrangement, the ketonic O atoms of the pyridinone ligands are coordinated trans to the oxo ligands and the deprotonated hydroxyl O atoms are located trans to each other. The crystal structure contains inter-molecular N-H⋯O hydrogen bonds, C-H⋯O contacts and face-to-face π-π stacking inter-actions with an inter-planar separation of 3.25 (1) Å.

Related literature

For general background, see: Veiros et al. (2006 ▶); Tucci et al. (1998 ▶); Collison et al. (1996 ▶); Hille (1996 ▶). For related structures, see: Brown et al. (2004 ▶); Hanna et al. (2000 ▶); Thompson et al. (1999 ▶); Zhang et al. (1992 ▶). For related literature, see: Braga et al. (1997 ▶); Grasselli (1999 ▶); Hozba et al. (1997 ▶); Ranganathan et al. (1998 ▶); Schrock (1998 ▶); Schultz et al. (1993 ▶).

Experimental

Crystal data

[Mo(C5H4NO2)2O2]

M = 348.12

Monoclinic,

a = 13.263 (3) Å

b = 7.2470 (14) Å

c = 13.264 (3) Å

β = 118.540 (9)°

V = 1120.0 (4) Å3

Z = 4

Mo Kα radiation

μ = 1.20 mm−1

T = 100 (2) K

0.29 × 0.16 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.723, T max = 0.899

37847 measured reflections

3123 independent reflections

2772 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.058

S = 1.08

3123 reflections

172 parameters

H-atom parameters constrained

Δρmax = 0.70 e Å−3

Δρmin = −0.52 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808007782/bi2282sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007782/bi2282Isup2.hkl

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

[Mo(C5H4NO2)2O2]	F000 = 688
Mr = 348.12	Dx = 2.065 Mg m−3Dm = no Mg m−3Dm measured by not measured
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9899 reflections
a = 13.263 (3) Å	θ = 1.8–29.6º
b = 7.2470 (14) Å	µ = 1.20 mm−1
c = 13.264 (3) Å	T = 100 (2) K
β = 118.540 (9)º	Needle, orange
V = 1120.0 (4) Å3	0.29 × 0.16 × 0.09 mm
Z = 4

Bruker APEXII CCD diffractometer	3123 independent reflections
Radiation source: fine-focus sealed tube	2772 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.045
T = 100(2) K	θmax = 29.6º
φ and ω scans	θmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 2007)	h = −18→18
Tmin = 0.723, Tmax = 0.899	k = −10→10
37847 measured reflections	l = −18→18

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)] = 0.025	H-atom parameters constrained
wR(F2) = 0.058	w = 1/[σ2(Fo2) + (0.0224P)2 + 1.1984P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.001
3123 reflections	Δρmax = 0.70 e Å−3
172 parameters	Δρmin = −0.52 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	0.248605 (14)	0.91497 (2)	0.414412 (14)	0.01513 (6)
O1	0.08144 (11)	0.8541 (2)	0.33241 (11)	0.0172 (3)
O2	0.20602 (12)	0.8648 (2)	0.55242 (12)	0.0176 (3)
O3	0.40951 (12)	0.8995 (2)	0.53830 (12)	0.0173 (3)
O4	0.27660 (12)	0.6185 (2)	0.44705 (12)	0.0177 (3)
O5	0.25461 (12)	0.8903 (2)	0.28946 (12)	0.0196 (3)
O6	0.25285 (12)	1.1491 (2)	0.43339 (12)	0.0204 (3)
N1	0.06163 (14)	0.7521 (2)	0.58314 (14)	0.0166 (3)
H1N	0.1075	0.7516	0.6578	0.020*
N2	0.41302 (15)	0.4130 (2)	0.56670 (15)	0.0181 (3)
H2N	0.3655	0.3201	0.5347	0.022*
C1	−0.04904 (17)	0.6950 (3)	0.54263 (18)	0.0185 (4)
H1	−0.0754	0.6548	0.5942	0.022*
C2	−0.12129 (17)	0.6964 (3)	0.42750 (18)	0.0206 (4)
H2	−0.1989	0.6594	0.3987	0.025*
C3	−0.08198 (17)	0.7519 (3)	0.35098 (17)	0.0189 (4)
H3	−0.1325	0.7526	0.2706	0.023*
C4	0.02965 (17)	0.8049 (3)	0.39344 (16)	0.0160 (4)
C5	0.10352 (16)	0.8086 (3)	0.51457 (16)	0.0148 (4)
C6	0.37661 (17)	0.5850 (3)	0.52910 (16)	0.0157 (4)
C7	0.45352 (17)	0.7346 (3)	0.58207 (16)	0.0166 (4)
C8	0.56213 (17)	0.7023 (3)	0.66842 (17)	0.0203 (4)
H8	0.6140	0.8016	0.7037	0.024*
C9	0.59590 (18)	0.5190 (3)	0.70425 (18)	0.0231 (5)
H9	0.6710	0.4941	0.7645	0.028*
C10	0.52126 (18)	0.3776 (3)	0.65289 (18)	0.0218 (4)
H10	0.5444	0.2542	0.6770	0.026*

	U11	U22	U33	U12	U13	U23
Mo1	0.01552 (9)	0.01402 (9)	0.01085 (9)	0.00111 (6)	0.00226 (6)	0.00057 (6)
O1	0.0157 (6)	0.0197 (7)	0.0102 (6)	0.0007 (6)	0.0014 (5)	0.0007 (5)
O2	0.0159 (6)	0.0189 (7)	0.0120 (6)	−0.0009 (6)	0.0019 (5)	−0.0005 (5)
O3	0.0148 (6)	0.0167 (7)	0.0146 (7)	−0.0010 (5)	0.0023 (5)	0.0004 (5)
O4	0.0166 (6)	0.0152 (7)	0.0150 (7)	0.0016 (5)	0.0025 (5)	0.0001 (5)
O5	0.0200 (7)	0.0226 (8)	0.0122 (7)	0.0020 (6)	0.0045 (6)	0.0012 (6)
O6	0.0233 (7)	0.0158 (7)	0.0198 (7)	0.0012 (6)	0.0084 (6)	0.0010 (6)
N1	0.0181 (8)	0.0156 (8)	0.0113 (7)	0.0011 (7)	0.0031 (6)	−0.0005 (7)
N2	0.0213 (8)	0.0172 (8)	0.0168 (8)	0.0037 (7)	0.0099 (7)	0.0026 (7)
C1	0.0205 (10)	0.0137 (9)	0.0201 (10)	0.0017 (8)	0.0086 (8)	−0.0009 (8)
C2	0.0162 (9)	0.0193 (10)	0.0217 (10)	0.0000 (8)	0.0053 (8)	−0.0043 (8)
C3	0.0155 (9)	0.0184 (10)	0.0143 (9)	0.0021 (8)	0.0003 (7)	−0.0031 (8)
C4	0.0183 (9)	0.0122 (9)	0.0120 (9)	0.0028 (7)	0.0028 (7)	−0.0011 (7)
C5	0.0166 (9)	0.0089 (8)	0.0131 (9)	0.0017 (7)	0.0025 (7)	−0.0016 (7)
C6	0.0168 (9)	0.0183 (10)	0.0117 (9)	0.0024 (8)	0.0066 (7)	0.0016 (7)
C7	0.0172 (9)	0.0209 (10)	0.0112 (9)	0.0016 (8)	0.0065 (7)	0.0003 (8)
C8	0.0168 (9)	0.0312 (12)	0.0114 (9)	0.0001 (8)	0.0055 (8)	0.0001 (8)
C9	0.0178 (9)	0.0384 (13)	0.0115 (9)	0.0088 (9)	0.0057 (8)	0.0072 (9)
C10	0.0236 (10)	0.0270 (11)	0.0158 (10)	0.0114 (9)	0.0103 (8)	0.0091 (8)

Mo1—O1	1.9972 (14)	N2—H2N	0.880
Mo1—O2	2.1886 (15)	C1—C2	1.361 (3)
Mo1—O3	1.9790 (14)	C1—H1	0.950
Mo1—O4	2.1882 (15)	C2—C3	1.403 (3)
Mo1—O5	1.7062 (15)	C2—H2	0.950
Mo1—O6	1.7124 (16)	C3—C4	1.364 (3)
O1—C4	1.336 (3)	C3—H3	0.950
O2—C5	1.270 (2)	C4—C5	1.427 (3)
O3—C7	1.335 (2)	C6—C7	1.423 (3)
O4—C6	1.274 (2)	C7—C8	1.366 (3)
N1—C5	1.337 (3)	C8—C9	1.410 (3)
N1—C1	1.364 (3)	C8—H8	0.950
N1—H1N	0.880	C9—C10	1.360 (3)
N2—C6	1.344 (3)	C9—H9	0.950
N2—C10	1.366 (3)	C10—H10	0.950
O5—Mo1—O6	103.48 (7)	C1—C2—C3	120.52 (19)
O5—Mo1—O3	105.57 (7)	C1—C2—H2	119.7
O6—Mo1—O3	89.27 (6)	C3—C2—H2	119.7
O5—Mo1—O1	90.16 (6)	C4—C3—C2	119.16 (18)
O6—Mo1—O1	104.40 (6)	C4—C3—H3	120.4
O3—Mo1—O1	156.33 (6)	C2—C3—H3	120.4
O5—Mo1—O4	90.40 (6)	O1—C4—C3	126.57 (18)
O6—Mo1—O4	162.43 (6)	O1—C4—C5	113.69 (17)
O3—Mo1—O4	76.49 (6)	C3—C4—C5	119.74 (19)
O1—Mo1—O4	86.00 (6)	O2—C5—N1	122.93 (17)
O5—Mo1—O2	161.00 (6)	O2—C5—C4	118.70 (18)
O6—Mo1—O2	92.59 (6)	N1—C5—C4	118.37 (18)
O3—Mo1—O2	84.43 (6)	O4—C6—N2	122.44 (19)
O1—Mo1—O2	75.87 (6)	O4—C6—C7	119.02 (18)
O4—Mo1—O2	76.04 (5)	N2—C6—C7	118.53 (18)
C4—O1—Mo1	119.16 (12)	O3—C7—C8	125.8 (2)
C5—O2—Mo1	112.20 (12)	O3—C7—C6	113.95 (17)
C7—O3—Mo1	119.05 (12)	C8—C7—C6	120.3 (2)
C6—O4—Mo1	111.40 (13)	C7—C8—C9	118.8 (2)
C5—N1—C1	122.94 (17)	C7—C8—H8	120.6
C5—N1—H1N	118.5	C9—C8—H8	120.6
C1—N1—H1N	118.5	C10—C9—C8	120.20 (19)
C6—N2—C10	122.19 (19)	C10—C9—H9	119.9
C6—N2—H2N	118.9	C8—C9—H9	119.9
C10—N2—H2N	118.9	C9—C10—N2	120.0 (2)
C2—C1—N1	119.2 (2)	C9—C10—H10	120.0
C2—C1—H1	120.4	N2—C10—H10	120.0
N1—C1—H1	120.4
O5—Mo1—O1—C4	162.99 (15)	C2—C3—C4—O1	177.13 (19)
O6—Mo1—O1—C4	−93.04 (15)	C2—C3—C4—C5	−1.9 (3)
O3—Mo1—O1—C4	30.6 (2)	Mo1—O2—C5—N1	173.36 (15)
O4—Mo1—O1—C4	72.60 (14)	Mo1—O2—C5—C4	−6.4 (2)
O2—Mo1—O1—C4	−3.99 (13)	C1—N1—C5—O2	178.72 (18)
O5—Mo1—O2—C5	−38.2 (3)	C1—N1—C5—C4	−1.5 (3)
O6—Mo1—O2—C5	109.76 (14)	O1—C4—C5—O2	3.4 (3)
O3—Mo1—O2—C5	−161.22 (14)	C3—C4—C5—O2	−177.45 (18)
O1—Mo1—O2—C5	5.55 (13)	O1—C4—C5—N1	−176.45 (17)
O4—Mo1—O2—C5	−83.79 (13)	C3—C4—C5—N1	2.7 (3)
O5—Mo1—O3—C7	−88.95 (15)	Mo1—O4—C6—N2	178.53 (15)
O6—Mo1—O3—C7	167.25 (15)	Mo1—O4—C6—C7	−2.4 (2)
O1—Mo1—O3—C7	41.0 (2)	C10—N2—C6—O4	178.42 (19)
O4—Mo1—O3—C7	−2.36 (14)	C10—N2—C6—C7	−0.6 (3)
O2—Mo1—O3—C7	74.58 (14)	Mo1—O3—C7—C8	−179.11 (16)
O5—Mo1—O4—C6	108.44 (14)	Mo1—O3—C7—C6	1.9 (2)
O6—Mo1—O4—C6	−34.2 (3)	O4—C6—C7—O3	0.6 (3)
O3—Mo1—O4—C6	2.52 (13)	N2—C6—C7—O3	179.69 (17)
O1—Mo1—O4—C6	−161.43 (14)	O4—C6—C7—C8	−178.48 (19)
O2—Mo1—O4—C6	−85.01 (14)	N2—C6—C7—C8	0.6 (3)
C5—N1—C1—C2	−0.6 (3)	O3—C7—C8—C9	−179.41 (19)
N1—C1—C2—C3	1.4 (3)	C6—C7—C8—C9	−0.4 (3)
C1—C2—C3—C4	−0.1 (3)	C7—C8—C9—C10	0.3 (3)
Mo1—O1—C4—C3	−177.08 (16)	C8—C9—C10—N2	−0.3 (3)
Mo1—O1—C4—C5	2.0 (2)	C6—N2—C10—C9	0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O5i	0.88	2.16	2.900 (2)	142
N2—H2N···O6ii	0.88	1.91	2.776 (3)	167
C3—H3···O6iii	0.95	2.51	3.428 (3)	162
C9—H9···O2iv	0.95	2.38	3.235 (3)	150

Mo1—O1	1.9972 (14)
Mo1—O2	2.1886 (15)
Mo1—O3	1.9790 (14)
Mo1—O4	2.1882 (15)
Mo1—O5	1.7062 (15)
Mo1—O6	1.7124 (16)

O5—Mo1—O6

103.48 (7)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O5i	0.88	2.16	2.900 (2)	142
N2—H2N⋯O6ii	0.88	1.91	2.776 (3)	167
C3—H3⋯O6iii	0.95	2.51	3.428 (3)	162
C9—H9⋯O2iv	0.95	2.38	3.235 (3)	150

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .