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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1036.
Published online 2008 July 19. doi:  10.1107/S160053680802182X
PMCID: PMC2961957

{2,2′-[(2,2-Dimethyl­propane-1,3-di­yl)­bis­(nitrilo­methyl­idyne)]­diphenolato}­dioxidomolybdenum(VI)

Abstract

In the structure of the title compound, [Mo(C19H20N2O2)O2], the Mo atom exhibits oxidation state +VI and is surrounded by two O atoms and the tetra­dentate Schiff base ligand 2,2′-[(2,2-dimethyl­propane-1,3-di­yl)bis­(nitrilo­methyl­idyne)]diphenolate in a distorted octa­hedral configuration. An intra­molecular C—H(...)O hydrogen bond between a methyl­ene group and one O atom of the O=MoVI=O unit, as well as additional inter­molecular hydrogen bonds between neighboring mol­ecules, 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 [triangle]); Holm et al. (1996 [triangle]); Syamal & Maurya (1989 [triangle]). 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 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1036-scheme1.jpg

Experimental

Crystal data

  • [Mo(C19H20N2O2)O2]
  • M r = 436.31
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1036-efi1.jpg
  • 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 [triangle]); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2001 [triangle]); software used to prepare material for publication: PLATON (Spek, 2003 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

This work was supported by grants from the University of Kerman and the University of Tehran.

supplementary crystallographic information

Comment

Numerous chemical reactions are catalyzed by compounds containing complexes with the dioxidomolybdenum(VI) unit O═MoVI═O (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). Therefore we are interested in the structural chemistry of dioxidomolybdenum(VI) complexes and have synthesized and structurally characterized the title compound, MoO2(C19H20N2O2), (I).

The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. The molybdenum(VI) atom is in a distorted octahedral coordination by two oxygen atoms and one tetradentate ligand L, where L is N,N'-bis(2-hydroxybenzylidene)-2,2-dimethyl-1,3-propanediamine. The Mo–O distances of the oxido ligands are significantly shorter (average 1.71 Å) than the corresponding distances to the O atoms of the tetradentate ligand (average 2.02 Å). The Mo–N distances are the longest (average 2.24 Å). An intramolecular hydrogen bond is present between the methylene group and one O atom from the O═Mo═O group (C4—H41···O2, 2.985 Å). Much weaker intermolecular hydrogen bonds exist between neighboring molecules, leading to an dimer structure (see hydrogen bond Table and Fig. 2). For a packing plot of the structure, see Fig. 3. Resulting from the coordination of the tetradentate L ligand to the molybdenum ion, the chelate ligand is more twisted than the free ligand, with a larger dihedral angle between two phenyl rings of 75.2 (1)° compared to the free ligand with 68.7 (1)° (Corden et al., 1996).

Experimental

The title compound was prepared by adding MoO2(acac)2 and the ligand H2L (Corden et al., 1996) in the molar ratio 1:1 to 30 mL dry methanol, followed by refluxing the solution for 1 h. Small prismatic, yellowish crystals precipitated which were filtered off and recrystallized from acetonitrile to get a better crystal quality.

Refinement

All H atoms were placed in calculated positions with C—H = 0.93 Å for H atoms bonded to sp2 C atoms, and C—H = 0.97 Å for H atoms bonded to sp3 C atoms, and constrained to ride on their parent atoms with Uiso(H) = 1.2 and 1.5 Ueq(C), respectively.

Figures

Fig. 1.
Molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as circles of arbitrary radius. Hydrogen bonds are represented as dotted lines.
Fig. 2.
The inversion-symmetric dimeric structure of (I). Hydrogen bonds are represented as dotted lines.
Fig. 3.
Packing plot of (I) along [001].

Crystal data

[Mo(C19H20N2O2)O2]Z = 2
Mr = 436.31F000 = 444
Triclinic, P1Dx = 1.666 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 9.3875 (10) ÅCell parameters from 8420 reflections
b = 9.5597 (10) Åθ = 2.5–26.0º
c = 11.0422 (11) ŵ = 0.78 mm1
α = 104.6790 (17)ºT = 100 (2) K
β = 108.1939 (17)ºPrism, light yellow
γ = 101.1218 (17)º0.18 × 0.12 × 0.06 mm
V = 869.87 (16) Å3

Data collection

Bruker APEXII CCD diffractometer3204 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
Monochromator: graphiteθmax = 26.0º
T = 100(2) Kθmin = 2.1º
ω scansh = −11→11
Absorption correction: nonek = −11→11
8420 measured reflectionsl = −13→13
3413 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021H-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 reflectionsΔρmax = 0.42 e Å3
237 parametersΔρmin = −0.53 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
Mo10.742950 (19)0.625366 (18)0.282813 (16)0.01031 (6)
O10.70502 (16)0.74204 (15)0.19043 (14)0.0161 (3)
O20.84039 (16)0.52119 (16)0.20730 (14)0.0167 (3)
O30.59172 (16)0.68583 (15)0.37734 (13)0.0135 (3)
O40.90918 (16)0.76348 (15)0.44982 (13)0.0146 (3)
N10.75678 (18)0.46531 (18)0.41243 (16)0.0115 (3)
N20.52861 (19)0.44879 (18)0.15515 (16)0.0112 (3)
C10.3927 (2)0.4737 (2)0.11735 (19)0.0127 (4)
H10.31110.39810.04430.015*
C20.7108 (2)0.3002 (2)0.34369 (19)0.0122 (4)
H2A0.71900.25120.41150.015*
H2B0.78550.27820.30320.015*
C30.8231 (2)0.5116 (2)0.5423 (2)0.0121 (4)
H30.82290.43820.58380.014*
C40.5301 (2)0.2902 (2)0.11404 (19)0.0131 (4)
H4A0.61770.28360.08630.016*
H4B0.43390.22890.03750.016*
C50.4553 (2)0.7013 (2)0.3131 (2)0.0127 (4)
C60.3575 (2)0.6066 (2)0.1779 (2)0.0132 (4)
C70.2101 (2)0.6264 (2)0.1145 (2)0.0156 (4)
H70.14670.56430.02620.019*
C80.1596 (2)0.7357 (2)0.1811 (2)0.0188 (4)
H80.06310.74860.13800.023*
C90.2546 (3)0.8278 (2)0.3146 (2)0.0189 (4)
H90.22040.90200.36000.023*
C100.3979 (2)0.8102 (2)0.3795 (2)0.0161 (4)
H100.45790.87130.46880.019*
C110.9390 (2)0.7870 (2)0.58181 (19)0.0122 (4)
C120.8984 (2)0.6685 (2)0.62999 (19)0.0120 (4)
C130.9480 (2)0.6997 (2)0.7706 (2)0.0139 (4)
H130.92550.62120.80350.017*
C141.0294 (2)0.8440 (2)0.8609 (2)0.0154 (4)
H141.05950.86330.95360.019*
C151.0658 (2)0.9608 (2)0.8110 (2)0.0156 (4)
H151.12041.05850.87120.019*
C161.0218 (2)0.9330 (2)0.6732 (2)0.0143 (4)
H161.04731.01180.64140.017*
C170.5230 (2)0.0591 (2)0.1785 (2)0.0166 (4)
H17A0.53560.01830.25090.025*
H17B0.59990.04280.14040.025*
H17C0.41970.00950.10980.025*
C180.4199 (2)0.2557 (2)0.2899 (2)0.0156 (4)
H18A0.31850.21630.21740.023*
H18B0.44080.36230.33290.023*
H18C0.42160.20510.35490.023*
C190.5451 (2)0.2294 (2)0.23343 (19)0.0119 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mo10.01067 (9)0.01016 (9)0.00976 (9)0.00212 (6)0.00322 (6)0.00433 (6)
O10.0185 (7)0.0120 (7)0.0142 (7)0.0015 (6)0.0028 (6)0.0051 (6)
O20.0143 (7)0.0182 (7)0.0193 (7)0.0037 (6)0.0090 (6)0.0064 (6)
O30.0135 (7)0.0145 (7)0.0121 (7)0.0054 (6)0.0038 (5)0.0046 (5)
O40.0148 (7)0.0147 (7)0.0117 (7)0.0006 (6)0.0026 (6)0.0058 (6)
N10.0081 (8)0.0116 (8)0.0149 (8)0.0030 (6)0.0043 (6)0.0046 (7)
N20.0139 (8)0.0106 (8)0.0093 (8)0.0031 (6)0.0052 (6)0.0032 (6)
C10.0132 (10)0.0134 (9)0.0099 (9)0.0013 (8)0.0031 (7)0.0047 (7)
C20.0116 (9)0.0116 (9)0.0150 (10)0.0042 (8)0.0053 (8)0.0059 (8)
C30.0086 (9)0.0135 (9)0.0167 (10)0.0037 (7)0.0048 (8)0.0090 (8)
C40.0152 (10)0.0106 (9)0.0114 (9)0.0030 (8)0.0045 (8)0.0014 (7)
C50.0145 (10)0.0123 (9)0.0150 (10)0.0036 (8)0.0069 (8)0.0088 (8)
C60.0137 (10)0.0142 (9)0.0148 (10)0.0041 (8)0.0070 (8)0.0082 (8)
C70.0133 (10)0.0184 (10)0.0157 (10)0.0035 (8)0.0047 (8)0.0083 (8)
C80.0161 (10)0.0238 (11)0.0253 (11)0.0111 (9)0.0100 (9)0.0163 (9)
C90.0248 (12)0.0181 (10)0.0244 (11)0.0123 (9)0.0156 (9)0.0121 (9)
C100.0220 (11)0.0143 (10)0.0141 (10)0.0066 (8)0.0084 (8)0.0058 (8)
C110.0075 (9)0.0169 (10)0.0124 (9)0.0052 (8)0.0023 (7)0.0059 (8)
C120.0078 (9)0.0142 (9)0.0148 (10)0.0044 (7)0.0041 (7)0.0056 (8)
C130.0119 (10)0.0173 (10)0.0163 (10)0.0060 (8)0.0068 (8)0.0091 (8)
C140.0140 (10)0.0207 (10)0.0110 (9)0.0054 (8)0.0045 (8)0.0046 (8)
C150.0129 (10)0.0139 (10)0.0160 (10)0.0035 (8)0.0032 (8)0.0019 (8)
C160.0127 (10)0.0131 (10)0.0181 (10)0.0044 (8)0.0043 (8)0.0083 (8)
C170.0173 (10)0.0122 (10)0.0175 (10)0.0026 (8)0.0047 (8)0.0042 (8)
C180.0131 (10)0.0190 (10)0.0168 (10)0.0049 (8)0.0067 (8)0.0083 (8)
C190.0117 (9)0.0098 (9)0.0139 (9)0.0021 (7)0.0054 (8)0.0035 (8)

Geometric parameters (Å, °)

Mo1—O11.7072 (14)C7—C81.370 (3)
Mo1—O21.7120 (14)C7—H70.9300
Mo1—O41.9373 (13)C8—C91.401 (3)
Mo1—O32.0917 (14)C8—H80.9300
Mo1—N22.1442 (16)C9—C101.378 (3)
Mo1—N12.3402 (16)C9—H90.9300
O3—C51.313 (2)C10—H100.9300
O4—C111.345 (2)C11—C161.395 (3)
N1—C31.286 (2)C11—C121.407 (3)
N1—C21.477 (2)C12—C131.406 (3)
N2—C11.301 (3)C13—C141.379 (3)
N2—C41.472 (2)C13—H130.9300
C1—C61.428 (3)C14—C151.395 (3)
C1—H10.9300C14—H140.9300
C2—C191.534 (3)C15—C161.385 (3)
C2—H2A0.9700C15—H150.9300
C2—H2B0.9700C16—H160.9300
C3—C121.454 (3)C17—C191.534 (3)
C3—H30.9300C17—H17A0.9600
C4—C191.549 (3)C17—H17B0.9600
C4—H4A0.9700C17—H17C0.9600
C4—H4B0.9700C18—C191.525 (3)
C5—C101.410 (3)C18—H18A0.9600
C5—C61.425 (3)C18—H18B0.9600
C6—C71.415 (3)C18—H18C0.9600
O1—Mo1—O2103.33 (7)C8—C7—H7119.5
O1—Mo1—O4101.99 (6)C6—C7—H7119.5
O2—Mo1—O4102.79 (6)C7—C8—C9119.36 (19)
O1—Mo1—O390.82 (6)C7—C8—H8120.3
O2—Mo1—O3161.79 (6)C9—C8—H8120.3
O4—Mo1—O385.05 (6)C10—C9—C8120.94 (19)
O1—Mo1—N293.87 (6)C10—C9—H9119.5
O2—Mo1—N288.54 (6)C8—C9—H9119.5
O4—Mo1—N2157.64 (6)C9—C10—C5121.24 (19)
O3—Mo1—N279.01 (6)C9—C10—H10119.4
O1—Mo1—N1170.94 (6)C5—C10—H10119.4
O2—Mo1—N184.17 (6)O4—C11—C16117.93 (17)
O4—Mo1—N180.95 (6)O4—C11—C12122.15 (17)
O3—Mo1—N180.84 (5)C16—C11—C12119.80 (18)
N2—Mo1—N181.12 (6)C13—C12—C11118.62 (18)
C5—O3—Mo1123.46 (12)C13—C12—C3117.94 (17)
C11—O4—Mo1134.29 (12)C11—C12—C3123.05 (17)
C3—N1—C2115.90 (16)C14—C13—C12121.52 (18)
C3—N1—Mo1124.12 (13)C14—C13—H13119.2
C2—N1—Mo1119.23 (12)C12—C13—H13119.2
C1—N2—C4117.18 (16)C13—C14—C15118.99 (18)
C1—N2—Mo1122.83 (13)C13—C14—H14120.5
C4—N2—Mo1119.87 (12)C15—C14—H14120.5
N2—C1—C6125.94 (18)C16—C15—C14120.85 (19)
N2—C1—H1117.0C16—C15—H15119.6
C6—C1—H1117.0C14—C15—H15119.6
N1—C2—C19115.73 (15)C15—C16—C11120.17 (18)
N1—C2—H2A108.3C15—C16—H16119.9
C19—C2—H2A108.3C11—C16—H16119.9
N1—C2—H2B108.3C19—C17—H17A109.5
C19—C2—H2B108.3C19—C17—H17B109.5
H2A—C2—H2B107.4H17A—C17—H17B109.5
N1—C3—C12125.78 (17)C19—C17—H17C109.5
N1—C3—H3117.1H17A—C17—H17C109.5
C12—C3—H3117.1H17B—C17—H17C109.5
N2—C4—C19110.04 (15)C19—C18—H18A109.5
N2—C4—H4A109.7C19—C18—H18B109.5
C19—C4—H4A109.7H18A—C18—H18B109.5
N2—C4—H4B109.7C19—C18—H18C109.5
C19—C4—H4B109.7H18A—C18—H18C109.5
H4A—C4—H4B108.2H18B—C18—H18C109.5
O3—C5—C10120.15 (18)C18—C19—C2111.61 (16)
O3—C5—C6122.19 (18)C18—C19—C17109.71 (16)
C10—C5—C6117.62 (18)C2—C19—C17106.47 (16)
C7—C6—C5119.77 (18)C18—C19—C4110.70 (16)
C7—C6—C1119.37 (18)C2—C19—C4110.88 (15)
C5—C6—C1119.60 (17)C17—C19—C4107.29 (15)
C8—C7—C6121.04 (19)
O1—Mo1—O3—C541.55 (15)Mo1—O3—C5—C10−146.68 (14)
O2—Mo1—O3—C5−99.9 (2)Mo1—O3—C5—C635.9 (2)
O4—Mo1—O3—C5143.51 (15)O3—C5—C6—C7178.78 (17)
N2—Mo1—O3—C5−52.23 (14)C10—C5—C6—C71.3 (3)
N1—Mo1—O3—C5−134.88 (15)O3—C5—C6—C111.6 (3)
O1—Mo1—O4—C11135.68 (17)C10—C5—C6—C1−165.83 (18)
O2—Mo1—O4—C11−117.46 (17)N2—C1—C6—C7171.47 (18)
O3—Mo1—O4—C1145.89 (17)N2—C1—C6—C5−21.3 (3)
N2—Mo1—O4—C111.4 (3)C5—C6—C7—C80.1 (3)
N1—Mo1—O4—C11−35.61 (17)C1—C6—C7—C8167.25 (19)
O2—Mo1—N1—C3121.32 (16)C6—C7—C8—C9−0.8 (3)
O4—Mo1—N1—C317.34 (15)C7—C8—C9—C100.1 (3)
O3—Mo1—N1—C3−69.06 (15)C8—C9—C10—C51.3 (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—C2121.32 (13)Mo1—O4—C11—C1233.8 (3)
N2—Mo1—N1—C241.12 (13)O4—C11—C12—C13173.48 (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—C30.8 (3)
O4—Mo1—N2—C187.3 (2)C16—C11—C12—C3−175.13 (18)
O3—Mo1—N2—C142.02 (15)N1—C3—C12—C13172.40 (18)
N1—Mo1—N2—C1124.33 (15)N1—C3—C12—C11−14.9 (3)
O1—Mo1—N2—C4136.02 (13)C11—C12—C13—C142.7 (3)
O2—Mo1—N2—C432.75 (14)C3—C12—C13—C14175.75 (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—C110.4 (3)
C4—N2—C1—C6159.34 (18)O4—C11—C16—C15−175.12 (17)
Mo1—N2—C1—C6−16.7 (3)C12—C11—C16—C151.0 (3)
C3—N1—C2—C19133.97 (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—C12170.57 (17)N1—C2—C19—C464.4 (2)
Mo1—N1—C3—C120.6 (3)N2—C4—C19—C1852.6 (2)
C1—N2—C4—C19−100.26 (19)N2—C4—C19—C2−71.82 (19)
Mo1—N2—C4—C1975.87 (17)N2—C4—C19—C17172.30 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4A···O20.972.492.986 (2)112
C1—H1···O1i0.932.543.227 (2)131
C4—H4B···O1i0.972.563.294 (2)132
C7—H7···O2i0.932.553.315 (2)140

Symmetry codes: (i) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2183).

References

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