{1,1′-[(2,2-Dimethyl­propane-1,3-di­yl)bis­(nitrilo­methyl­idyne)]di-2-naphthol­ato}dioxidomolybdenum(VI) dichloro­methane 1.75-solvate

Niaz Monadi; Iran Sheikhshoaie; Abdoreza Rezaeifard; Helen Stoeckli-Evans

doi:10.1107/S1600536809032759

. 2009 Aug 22;65(Pt 9):m1124–m1125. doi: 10.1107/S1600536809032759

{1,1′-[(2,2-Dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]di-2-naphtholato}dioxidomolybdenum(VI) dichloromethane 1.75-solvate

Niaz Monadi ^a, Iran Sheikhshoaie ^a,^*, Abdoreza Rezaeifard ^b, Helen Stoeckli-Evans ^c

PMCID: PMC2969995 PMID: 21577465

Abstract

In the crystal structure of the title compound, [Mo(C₂₇H₂₄N₂O₂)O₂]·1.75CH₂Cl₂, the Mo^VI ion is coordinated by two oxide O atoms and by two O and two N atoms of the tetradentate 1,1′-[(2,2-dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]di-2-naphtholate Schiff base ligand in a distorted octahedral configuration. The compound crystallizes with 1.75 molecules of dichloromethane per complex molecule. In the crystal, symmetry-related molecules are linked by a number of C—H⋯O interactions involving both the Schiff base ligand and the partly disordered dichloromethane solvent molecules, leading to the formation of a two-dimensional network extending parallel to (101).

Related literature

For the chemistry of molybdenum(VI)–Schiff base complexes and related structures with O=Mo=O units (metal oxidation state +VI), see: Abbasi et al. (2008 ▶); Arnaiz et al. (2000 ▶); Holm et al. (1996 ▶); Maurya et al. (1997 ▶); Nakayima et al. (1998 ▶); Rao et al. (1998 ▶); Sheikhshoaie et al. (2009 ▶); Syamal & Maurya (1989 ▶).

Experimental

Crystal data

[Mo(C₂₇H₂₄N₂O₂)O₂]·1.75CH₂Cl₂
M _r = 685.04
Monoclinic,
a = 27.6049 (18) Å
b = 10.7743 (8) Å
c = 21.6474 (14) Å
β = 112.861 (7)°
V = 5932.7 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 173 K
0.38 × 0.23 × 0.18 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009 ▶) T _min = 0.833, T _max = 0.864
21863 measured reflections
5537 independent reflections
4789 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.106
S = 1.12
5537 reflections
372 parameters
H-atom parameters constrained
Δρ_max = 1.08 e Å⁻³
Δρ_min = −0.83 e Å⁻³

Data collection: EXPOSE in IPDS-I (Stoe & Cie, 2000 ▶); cell refinement: CELL in IPDS-I (Stoe & Cie, 2000 ▶); data reduction: INTEGRATE in IPDS-I (Stoe & Cie, 2000 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809032759/wm2248sup1.cif

e-65-m1124-sup1.cif^{(28.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032759/wm2248Isup2.hkl

e-65-m1124-Isup2.hkl^{(271.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mo1—O1	2.0888 (19)
Mo1—O2	1.957 (2)
Mo1—O3	1.702 (2)
Mo1—O4	1.713 (2)
Mo1—N1	2.118 (2)
Mo1—N2	2.297 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O3ⁱ	0.95	2.43	3.328 (5)	159
C11—H11⋯O4ⁱⁱ	0.95	2.38	3.297 (3)	161
C12—H12A⋯O4	0.99	2.47	2.974 (4)	111
C27—H27A⋯O3ⁱⁱ	0.98	2.55	3.490 (4)	161
C28—H28A⋯O2ⁱⁱⁱ	0.99	2.40	3.213 (5)	139
C28—H28A⋯O4ⁱⁱⁱ	0.99	2.53	3.429 (6)	151

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

supplementary crystallographic information

Comment

Numerous molybdenum(VI) Schiff base complexes have been extensively investigated for over the past twenty years, due to their importance in the domains of stereochemistry (Maurya et al., 1997), structural chemistry (Nakayima, et al., 1998; Syamal & Maurya, 1989), analytical chemistry (Rao et al., 1998), bioinorganic chemistry (Holm et al., 1996), and oxidation catalysis (Abbasi et al., 2008; Arnaiz et al., 2000; Sheikhshoaie et al., 2009). Continuing our interest in the structural chemistry of dioxidomolybdenum(VI) Schiff base complexes, we have synthesized and structurally characterized the title compound.

The molecular structure of the title complex is illustrated in Fig. 1, and geometrical parameters are available in the archived CIF. The Mo^VI atom is in a distorted octahedral environment being coordinated by two oxido O atoms (O1 and O2) and four atoms (two oxygen and two nitrogen atoms) of the tetradentate Schiff base ligand 1,1'-[(2,2-dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]di-2-naphtholate. The Mo—O distances of the oxido ligands (Mo1O3 and Mo1O4) are significantly shorter [1.702 (2) and 1.713 (2) Å, respectively] than the corresponding Mo—O distances to the O-atoms (O2 and O1) of the tetradentate Schiff base ligand, 1.957 (2) and 2.0888 (19) Å, respectively. The Mo—N distances, to atoms N1 and N2, are even longer being 2.118 (2) and 2.297 (2) Å, respectively.

In the crystal, molecules are linked by a number of C—H···O interactions, involving both the Schiff base ligand and the solvent molecules of crystallization, leading to the formation of a two-dimensional network extending in the (101) plane (Table 1 and Fig. 2).

Experimental

The title dioxidomolybdenum (VI) complex was prepared by mixing MoO₂(acac)₂ with the ligand, 2,2'-[(2,2-dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]-dinaphtholate, in a 1:1 molar ratio using 25 ml of dry methanol as solvent, followed by refluxing the solution for 3 h. The small reddish crystals that formed were filtered off and recrystallized from dichloromethane.