PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): m1137.
Published online 2010 August 21. doi:  10.1107/S1600536810032836
PMCID: PMC3008093

Dioxidobis{2-[(E)-p-tolyl­imino­meth­yl]phenolato}molybdenum(VI)

Abstract

The asymmetric unit of the title compound, [Mo(C14H12NO)2O2], comprises half of the complex with the full mol­ecule generated by the application of twofold symmetry. The MoVI atom is surrounded by two oxide O atoms and the two sets of N,O-donor atoms of the bidentate Schiff base ligands. The resulting N2O4 donor set defines a distorted octa­hedral coordination geometry. Inter­molecular C—H(...)O contacts link mol­ecules into chains along the b axis. The crystal structure is further stabilized by inter­molecular π–π inter­actions [ring centroid–centroid distance = 3.724 (6) Å].

Related literature

For related structures with MoO2 units and for the synthesis, see: Arnaiz et al. (2000 [triangle]); Holm et al. (1996 [triangle]); Syamal & Maurya (1989 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1137-scheme1.jpg

Experimental

Crystal data

  • [Mo(C14H12NO)2O2]
  • M r = 548.43
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1137-efi2.jpg
  • a = 26.375 (8) Å
  • b = 6.8095 (8) Å
  • c = 15.648 (10) Å
  • β = 116.94 (2)°
  • V = 2505.4 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.56 mm−1
  • T = 296 K
  • 0.21 × 0.11 × 0.08 mm

Data collection

  • Stoe IPDS II diffractometer
  • Absorption correction: multi-scan [MULABS in PLATON (Spek, 2009 [triangle]; Blessing, 1995 [triangle])] T min = 0.892, T max = 0.957
  • 4305 measured reflections
  • 2006 independent reflections
  • 761 reflections with I > 2σ(I)
  • R int = 0.144

Refinement

  • R[F 2 > 2σ(F 2)] = 0.079
  • wR(F 2) = 0.168
  • S = 0.83
  • 2006 reflections
  • 124 parameters
  • H-atom parameters constrained
  • Δρmax = 0.55 e Å−3
  • Δρmin = −0.81 e Å−3

Data collection: X-AREA (Stoe & Cie, 2005 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032836/tk2696sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032836/tk2696Isup2.hkl

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

Acknowledgments

This work was supported by grants from the University of Kerman and the University of Tehran. RK thanks the Islamic Azad University for the X-ray diffractometer facility.

supplementary crystallographic information

Comment

Numerous chemical reactions are catalyzed by complexes containing the dioxomolybdenum(VI) unit, MoO2 (Arnaiz et al. 2000). Moreover, Schiff base compounds containing molybdenum play a significant role in the chemistry of molybdoenzymes (Holm et al. 1996; Syamal & Maurya, 1989).

The asymmetric unit of the title compound, Fig. 1, comprises half of the complex. The Mo atom is located on a crystallographic 2-fold axis. The MoVI atom is surrounded by two oxo-O atoms and the N2O2 donor atoms of two bidentate Schiff base ligands to define a distorted octahedral coordination geometry. Intermolecular C—H···O contacts link molecules into chains along the b axis, Table 1 and Fig. 2. The crystal structure is further stabilized by intermolecular π–π interactions with the ring centroid(C1– C6) to centroid(C8–C13)i distance being 3.724 (6) Å for i: -x, y, 1/2-z.

Experimental

The title complex was prepared by adding MoO2(acac)2 and the ligand (molar ratio 1:1) to dry methanol (30 ml), followed by refluxing for 1 h. Small, light-yellow crystals were filtered off and recrystallized from acetonitrile. The quality of the crystal was not optimal and it was weakly diffracting. Although recrystallization was attempted repeatedly, better crystals were not obtained.

Refinement

All H atoms were positioned geometrically (C–H = 0.93–0.96 Å) and constrained to refine with the parent atoms with Uiso (H) = 1.2–1.5 Ueq (C).

Figures

Fig. 1.
The molecular structure of the title complex showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level. Symmetry code for the unlabeled atoms: -x, y, 1/2 - z.
Fig. 2.
A view of the crystal packing of the title compound down the a axis showing connections of molecules through C—H···O interactions (shown as dashed lines) along the b axis.

Crystal data

[Mo(C14H12NO)2O2]F(000) = 1120
Mr = 548.43Dx = 1.454 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2560 reflections
a = 26.375 (8) Åθ = 1.7–29.6°
b = 6.8095 (8) ŵ = 0.56 mm1
c = 15.648 (10) ÅT = 296 K
β = 116.94 (2)°Block, colourless
V = 2505.4 (18) Å30.21 × 0.11 × 0.08 mm
Z = 4

Data collection

Stoe IPDS II diffractometer2006 independent reflections
Radiation source: fine-focus sealed tube761 reflections with I > 2σ(I)
graphiteRint = 0.144
Detector resolution: 0.15 mm pixels mm-1θmax = 25.5°, θmin = 2.6°
[var phi] and ω scansh = −31→22
Absorption correction: multi-scan (MULABS in PLATON; Blessing, 1995)k = −7→8
Tmin = 0.892, Tmax = 0.957l = −18→18
4305 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.079Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168H-atom parameters constrained
S = 0.83w = 1/[σ2(Fo2) + (0.0476P)2] where P = (Fo2 + 2Fc2)/3
2006 reflections(Δ/σ)max < 0.001
124 parametersΔρmax = 0.55 e Å3
0 restraintsΔρmin = −0.81 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Mo10.0000−0.2892 (2)0.25000.0502 (7)
O1−0.0423 (3)−0.2223 (11)0.3209 (4)0.053 (2)
O2−0.0486 (4)−0.4409 (11)0.1680 (6)0.079 (3)
N10.0559 (5)−0.0212 (13)0.3428 (5)0.037 (3)
C1−0.0533 (6)−0.061 (2)0.3573 (8)0.0479 (18)
C2−0.1029 (5)−0.0625 (17)0.3693 (7)0.0479 (18)
H2A−0.1260−0.17330.35410.057*
C3−0.1165 (5)0.1058 (16)0.4047 (7)0.0479 (18)
H3A−0.14930.10520.41270.057*
C4−0.0846 (5)0.2697 (19)0.4278 (6)0.0479 (18)
H4A−0.09570.37980.45030.057*
C5−0.0345 (5)0.2726 (19)0.4176 (6)0.054 (4)
H5A−0.01180.38450.43330.065*
C6−0.0187 (5)0.1007 (18)0.3827 (6)0.037 (3)
C70.0360 (5)0.1081 (16)0.3804 (6)0.041 (3)
H7A0.05890.21670.40870.049*
C80.1129 (6)0.013 (2)0.3551 (7)0.044 (3)
C90.1308 (6)0.198 (2)0.3415 (7)0.063 (2)
H9A0.10630.30490.32530.075*
C100.1856 (6)0.219 (2)0.3524 (7)0.067 (4)
H10A0.19720.34290.34290.081*
C110.2243 (6)0.063 (2)0.3771 (8)0.063 (2)
C120.2048 (6)−0.115 (2)0.3891 (7)0.063 (2)
H12A0.2294−0.22170.40540.075*
C130.1500 (5)−0.144 (2)0.3781 (7)0.063 (2)
H13A0.1384−0.26900.38610.075*
C140.2838 (6)0.095 (3)0.3862 (11)0.120 (6)
H14A0.3085−0.00830.42390.181*
H14B0.29840.21930.41690.181*
H14C0.28210.09550.32360.181*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mo10.0830 (15)0.0203 (8)0.0809 (12)0.0000.0666 (11)0.000
O10.056 (6)0.046 (5)0.080 (5)0.015 (5)0.050 (5)0.018 (5)
O20.110 (10)0.039 (5)0.138 (8)−0.036 (6)0.099 (7)−0.043 (5)
N10.045 (9)0.033 (6)0.037 (6)0.027 (6)0.022 (6)0.014 (4)
C10.043 (5)0.055 (4)0.049 (4)0.005 (4)0.024 (4)0.007 (3)
C20.043 (5)0.055 (4)0.049 (4)0.005 (4)0.024 (4)0.007 (3)
C30.043 (5)0.055 (4)0.049 (4)0.005 (4)0.024 (4)0.007 (3)
C40.043 (5)0.055 (4)0.049 (4)0.005 (4)0.024 (4)0.007 (3)
C50.064 (10)0.060 (9)0.034 (6)0.006 (9)0.018 (6)−0.006 (6)
C60.031 (9)0.064 (9)0.017 (6)0.010 (7)0.012 (6)0.002 (6)
C70.053 (11)0.037 (7)0.029 (6)0.010 (7)0.015 (7)0.018 (5)
C80.029 (9)0.075 (10)0.034 (7)0.010 (8)0.020 (6)0.004 (6)
C90.053 (6)0.079 (5)0.062 (4)0.031 (6)0.031 (4)0.015 (4)
C100.072 (11)0.063 (9)0.073 (8)−0.010 (10)0.038 (8)−0.020 (8)
C110.053 (6)0.079 (5)0.062 (4)0.031 (6)0.031 (4)0.015 (4)
C120.053 (6)0.079 (5)0.062 (4)0.031 (6)0.031 (4)0.015 (4)
C130.053 (6)0.079 (5)0.062 (4)0.031 (6)0.031 (4)0.015 (4)
C140.070 (14)0.165 (18)0.150 (14)−0.014 (12)0.071 (11)−0.031 (12)

Geometric parameters (Å, °)

Mo1—O21.694 (9)C5—H5A0.9300
Mo1—O2i1.694 (9)C6—C71.459 (14)
Mo1—O1i1.950 (6)C7—H7A0.9300
Mo1—O11.950 (6)C8—C131.385 (15)
Mo1—N12.382 (9)C8—C91.394 (17)
Mo1—N1i2.382 (9)C9—C101.384 (15)
O1—C11.330 (12)C9—H9A0.9300
N1—C71.293 (12)C10—C111.400 (16)
N1—C81.446 (14)C10—H10A0.9300
C1—C61.367 (15)C11—C121.363 (17)
C1—C21.405 (16)C11—C141.528 (18)
C2—C31.388 (14)C12—C131.391 (16)
C2—H2A0.9300C12—H12A0.9300
C3—C41.344 (14)C13—H13A0.9300
C3—H3A0.9300C14—H14A0.9600
C4—C51.402 (14)C14—H14B0.9600
C4—H4A0.9300C14—H14C0.9600
C5—C61.432 (14)
O2—Mo1—O2i104.8 (6)C4—C5—H5A120.5
O2—Mo1—O1i98.2 (3)C6—C5—H5A120.5
O2i—Mo1—O1i98.2 (4)C1—C6—C5119.7 (12)
O2—Mo1—O198.2 (4)C1—C6—C7123.9 (11)
O2i—Mo1—O198.2 (3)C5—C6—C7116.3 (12)
O1i—Mo1—O1153.0 (4)N1—C7—C6126.5 (11)
O2—Mo1—N1167.6 (4)N1—C7—H7A116.7
O2i—Mo1—N187.6 (3)C6—C7—H7A116.7
O1i—Mo1—N179.2 (3)C13—C8—C9119.4 (13)
O1—Mo1—N180.2 (3)C13—C8—N1118.7 (12)
O2—Mo1—N1i87.6 (3)C9—C8—N1121.9 (12)
O2i—Mo1—N1i167.6 (4)C10—C9—C8118.9 (14)
O1i—Mo1—N1i80.2 (3)C10—C9—H9A120.5
O1—Mo1—N1i79.2 (3)C8—C9—H9A120.5
N1—Mo1—N1i80.0 (4)C9—C10—C11122.9 (14)
C1—O1—Mo1136.7 (7)C9—C10—H10A118.6
C7—N1—C8116.2 (10)C11—C10—H10A118.6
C7—N1—Mo1122.2 (9)C12—C11—C10116.2 (14)
C8—N1—Mo1121.5 (7)C12—C11—C14123.3 (15)
O1—C1—C6122.9 (12)C10—C11—C14120.5 (14)
O1—C1—C2116.5 (12)C11—C12—C13123.1 (14)
C6—C1—C2120.6 (12)C11—C12—H12A118.4
C3—C2—C1118.0 (12)C13—C12—H12A118.4
C3—C2—H2A121.0C8—C13—C12119.5 (13)
C1—C2—H2A121.0C8—C13—H13A120.2
C4—C3—C2123.4 (12)C12—C13—H13A120.2
C4—C3—H3A118.3C11—C14—H14A109.5
C2—C3—H3A118.3C11—C14—H14B109.5
C3—C4—C5119.2 (12)H14A—C14—H14B109.5
C3—C4—H4A120.4C11—C14—H14C109.5
C5—C4—H4A120.4H14A—C14—H14C109.5
C4—C5—C6119.0 (12)H14B—C14—H14C109.5
O2—Mo1—O1—C1−136.1 (11)C2—C1—C6—C5−3.0 (15)
O2i—Mo1—O1—C1117.6 (11)O1—C1—C6—C7−5.2 (16)
O1i—Mo1—O1—C1−9.2 (10)C2—C1—C6—C7174.4 (9)
N1—Mo1—O1—C131.5 (11)C4—C5—C6—C11.9 (14)
N1i—Mo1—O1—C1−50.1 (11)C4—C5—C6—C7−175.7 (8)
O2—Mo1—N1—C762 (2)C8—N1—C7—C6−176.2 (9)
O2i—Mo1—N1—C7−119.5 (8)Mo1—N1—C7—C67.8 (13)
O1i—Mo1—N1—C7141.7 (8)C1—C6—C7—N110.1 (16)
O1—Mo1—N1—C7−20.8 (7)C5—C6—C7—N1−172.5 (9)
N1i—Mo1—N1—C759.9 (7)C7—N1—C8—C13137.6 (10)
O2—Mo1—N1—C8−113.4 (19)Mo1—N1—C8—C13−46.3 (11)
O2i—Mo1—N1—C864.6 (8)C7—N1—C8—C9−44.5 (13)
O1i—Mo1—N1—C8−34.2 (7)Mo1—N1—C8—C9131.6 (9)
O1—Mo1—N1—C8163.4 (8)C13—C8—C9—C10−0.7 (15)
N1i—Mo1—N1—C8−116.0 (8)N1—C8—C9—C10−178.7 (8)
Mo1—O1—C1—C6−25.2 (17)C8—C9—C10—C11−0.3 (16)
Mo1—O1—C1—C2155.2 (7)C9—C10—C11—C120.8 (16)
O1—C1—C2—C3−178.3 (9)C9—C10—C11—C14178.8 (10)
C6—C1—C2—C32.1 (16)C10—C11—C12—C13−0.2 (17)
C1—C2—C3—C40.0 (16)C14—C11—C12—C13−178.1 (11)
C2—C3—C4—C5−1.0 (15)C9—C8—C13—C121.3 (15)
C3—C4—C5—C60.1 (14)N1—C8—C13—C12179.3 (9)
O1—C1—C6—C5177.4 (9)C11—C12—C13—C8−0.9 (16)

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9A···O2ii0.932.343.237 (18)163
C13—H13A···O2iii0.932.423.164 (17)136

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2696).

References

  • Arnaiz, F. J., Aguado, R., Pedrosa, M. R., De Cian, A. & Fischer, A. (2000). Polyhedron, 19, 2141–2147.
  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • Holm, R. H., Kennepohl, P. & Solomon, E. I. (1996). Chem. Rev.96, 2239–2314. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Stoe & Cie (2005). X-AREA. Stoe & Cie, Darmstadt, Germany.
  • Syamal, A. & Maurya, M. R. (1989). Coord. Chem. Rev.95, 183–238.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography