Crystal structure of aquadioxido(2-{[(2-oxido­ethyl)­imino]­meth­yl}phenol­ato-κ3O,N,O′)molybdenum(VI)

Parimala, S.; Selvam, P.

doi:10.1107/S2056989015001231

metal-organic compounds

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Volume 71| Part 2| February 2015| Pages m35-m36

doi:10.1107/S2056989015001231

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Crystal structure of aquadioxido(2-{[(2-oxidoethyl)imino]methyl}phenolato-κ³O,N,O′)molybdenum(VI)

Sowmianarayanan Parimala ^a and Parasuraman Selvam ^a,^b,^c ^*

^aNational Centre for Catalysis Research and Department of Chemistry, Indian Institute of Technology-Madras, Chennai 600 036, India, ^bNew Industry Creation Hatchery Center, Tohoku University, Sendai 980 8579, Japan, and ^cSchool of Science and Health, University of Western Australia, Sydney, Penrith, NSW 275, Australia
^*Correspondence e-mail: selvam@iitm.ac.in

Edited by M. Weil, Vienna University of Technology, Austria (Received 9 January 2015; accepted 20 January 2015; online 24 January 2015)

The mononuclear title complex, [Mo(C₉H₉NO₂)O₂(H₂O)], contains an Mo(VI) atom in a distorted octahedral coordination sphere defined by an Mo=O and an Mo—(OH₂) bond to the axial ligands and two Mo—O bonds to phenolate and alcoholate O atoms, another Mo=O bond and one Mo—N bond to the imino N atom in the equatorial plane. The five-membered metalla-ring shows an envelope conformation. In the crystal, individual molecules are connected into a layered arrangement parallel to (100) by means of O—H⋯O hydrogen bonds involving the water molecule as a donor group and the O atoms of neighbouring complexes as acceptor atoms. These interactions lead to the formation of a three-dimensional network.

Keywords: crystal structure; dioxidomolybdenum(VI) complex; hydrogen bonding.

CCDC reference: 1044382

1. Related literature

For dioxidomolybdenum complexes used as potential oxidation catalysts for the epoxidation of alkenes, see: Sakthivel et al. (2005 ); Masteri-Farahani et al. (2006 ). For chiral molybdenum complexes, see: Burke (2008 ); Kühn et al. (2005 ). These compounds are good catalysts for the oxidation of organic compounds, see: Rayati et al. (2012 ). For heterogenization of polymer-supported molybdenum complexes, see: Sherrington et al. (2000 ); Maurya (2012 ), and for molybdenum systems on silica supports, see: Tangestaninejad et al. (2008 ).

2. Experimental

2.1. Crystal data

[Mo(C₉H₉NO₂)O₂(H₂O)]
M_r = 309.13
Monoclinic, P 2₁ /c
a = 14.9710 (3) Å
b = 6.7026 (1) Å
c = 10.8673 (2) Å
β = 99.486 (1)°
V = 1075.56 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 296 K
0.25 × 0.16 × 0.10 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.813, T_max = 0.934
8837 measured reflections
2392 independent reflections
2263 reflections with I > 2σ(I)
R_int = 0.012

2.3. Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.042
S = 1.10
2392 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected bond lengths (Å)

Mo1—O5	1.6902 (14)
Mo1—O4	1.7160 (13)
Mo1—O1	1.9438 (12)
Mo1—O2	1.9446 (12)
Mo1—N1	2.2652 (14)
Mo1—O3	2.3259 (14)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1O⋯O1ⁱ	0.73 (2)	1.97 (3)	2.6656 (19)	161 (3)
O3—H2O⋯O4ⁱⁱ	0.78 (3)	2.07 (3)	2.8425 (19)	173 (3)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1044382

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015001231/wm5114sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015001231/wm5114Isup2.hkl

checkCIF report

Related literature top

For dioxidomolybdenum complexes used as potential oxidation catalysts for the epoxidation of alkenes, see: Sakthivel et al. (2005); Masteri-Farahani et al. (2006). For chiral molybdenum complexes, see: Burke (2008); Kühn et al. (2005). These compounds are good catalysts for the oxidation of organic compounds, see: Rayati et al. (2012). For heterogenization of polymer-supported molybdenum complexes, see: Sherrington et al. (2000); Maurya (2012), and for molybdenum systems on silica supports, see: Tangestaninejad et al. (2008).

Experimental top

Molybdenyl acetylacetone (MoO₂(acac)₂) (4.03 g, 0.012 mol) dissolved in methanol (20 ml) was added to a refluxing solution of salicylaldehyde (2.62 ml, 0.012 mol) and ethanolamine (1.5 ml, 0.012 mol) in ethanol (30 ml). The mixture was refluxed for five hours, and the solvent removed under vacuum at room temperature. The resulting yellow solution was filtered, evaporated slowly, to yield yellow crystals. The crystals were purified by washing with ethanol/methanol mixture and dried at room temperature. The obtained crystals have incorporated water. The used solvents ethanol and methanol have not been dried prior to the reaction and thus contain water. Another source of water is the condensation reaction between salicylaldehyde and ethanolamine.

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Unit-cell packing diagram of the title compound with hydrogen bonds shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

Aquadioxido(2-{[(2-oxidoethyl)imino]methyl}phenolato-κ³O,N,O')molybdenum(VI) top

Crystal data top

[Mo(C₉H₉NO₂)O₂(H₂O)]	F(000) = 616
M_r = 309.13	D_x = 1.909 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.9710 (3) Å	Cell parameters from 6907 reflections
b = 6.7026 (1) Å	θ = 2.8–27.2°
c = 10.8673 (2) Å	µ = 1.22 mm⁻¹
β = 99.486 (1)°	T = 296 K
V = 1075.56 (3) Å³	Block, yellow
Z = 4	0.25 × 0.16 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	2263 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.012
Absorption correction: multi-scan (SADABS; Bruker, 2012)	θ_max = 27.2°, θ_min = 1.4°
T_min = 0.813, T_max = 0.934	h = −19→18
8837 measured reflections	k = −8→8
2392 independent reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.016	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.042	w = 1/[σ²(F_o²) + (0.0163P)² + 0.8254P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2392 reflections	Δρ_max = 0.31 e Å⁻³
153 parameters	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Mo(C₉H₉NO₂)O₂(H₂O)]	V = 1075.56 (3) Å³
M_r = 309.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.9710 (3) Å	µ = 1.22 mm⁻¹
b = 6.7026 (1) Å	T = 296 K
c = 10.8673 (2) Å	0.25 × 0.16 × 0.10 mm
β = 99.486 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2392 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	2263 reflections with I > 2σ(I)
T_min = 0.813, T_max = 0.934	R_int = 0.012
8837 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	0 restraints
wR(F²) = 0.042	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.31 e Å⁻³
2392 reflections	Δρ_min = −0.30 e Å⁻³
153 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.37800 (15)	−0.3126 (3)	0.4461 (2)	0.0394 (5)
H1A	0.3281	−0.3758	0.4778	0.047*
H1B	0.4281	−0.4060	0.4541	0.047*
C2	0.34936 (14)	−0.2553 (3)	0.31132 (19)	0.0384 (5)
H2A	0.4018	−0.2223	0.2734	0.046*
H2B	0.3169	−0.3641	0.2649	0.046*
C3	0.22629 (12)	−0.0467 (3)	0.22157 (16)	0.0288 (4)
H3	0.2174	−0.1379	0.1562	0.035*
C4	0.16677 (11)	0.1238 (3)	0.21392 (16)	0.0267 (4)
C5	0.09354 (13)	0.1343 (3)	0.11473 (18)	0.0371 (4)
H5	0.0846	0.0313	0.0567	0.044*
C6	0.03507 (13)	0.2930 (4)	0.10178 (19)	0.0427 (5)
H6	−0.0136	0.2961	0.0365	0.051*
C7	0.04887 (13)	0.4486 (4)	0.1865 (2)	0.0404 (5)
H7	0.0090	0.5561	0.1780	0.049*
C8	0.12118 (13)	0.4458 (3)	0.28334 (18)	0.0331 (4)
H8	0.1304	0.5525	0.3387	0.040*
C9	0.18051 (11)	0.2837 (3)	0.29870 (15)	0.0244 (3)
Mo1	0.32157 (2)	0.08935 (2)	0.49415 (2)	0.02134 (5)
N1	0.29025 (10)	−0.0807 (2)	0.31202 (14)	0.0254 (3)
O1	0.40476 (8)	−0.13539 (19)	0.51476 (12)	0.0286 (3)
O2	0.25056 (8)	0.29088 (18)	0.39282 (11)	0.0275 (3)
O3	0.42590 (10)	0.2153 (2)	0.37755 (13)	0.0306 (3)
O4	0.37757 (10)	0.2275 (2)	0.61586 (12)	0.0372 (3)
O5	0.23417 (9)	−0.0248 (2)	0.54594 (13)	0.0392 (3)
H1O	0.4715 (17)	0.176 (4)	0.395 (2)	0.037 (7)*
H2O	0.4144 (17)	0.221 (4)	0.305 (3)	0.048 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0454 (11)	0.0219 (9)	0.0463 (12)	0.0080 (8)	−0.0058 (9)	−0.0057 (8)
C2	0.0417 (11)	0.0331 (10)	0.0382 (11)	0.0118 (8)	−0.0003 (8)	−0.0154 (8)
C3	0.0325 (9)	0.0312 (9)	0.0219 (8)	−0.0039 (7)	0.0024 (7)	−0.0059 (7)
C4	0.0239 (8)	0.0331 (9)	0.0223 (8)	−0.0025 (7)	0.0019 (6)	0.0033 (7)
C5	0.0344 (10)	0.0460 (12)	0.0274 (9)	−0.0061 (9)	−0.0045 (8)	0.0021 (9)
C6	0.0301 (10)	0.0601 (14)	0.0341 (10)	−0.0005 (9)	−0.0064 (8)	0.0154 (10)
C7	0.0325 (10)	0.0508 (13)	0.0384 (11)	0.0142 (9)	0.0068 (8)	0.0183 (10)
C8	0.0351 (10)	0.0363 (10)	0.0286 (9)	0.0097 (8)	0.0075 (7)	0.0061 (8)
C9	0.0231 (8)	0.0295 (9)	0.0207 (8)	0.0010 (7)	0.0038 (6)	0.0059 (7)
Mo1	0.02586 (8)	0.02184 (8)	0.01569 (8)	0.00375 (5)	0.00161 (5)	−0.00128 (5)
N1	0.0283 (7)	0.0234 (7)	0.0241 (7)	0.0011 (6)	0.0031 (6)	−0.0047 (6)
O1	0.0297 (6)	0.0241 (6)	0.0295 (6)	0.0054 (5)	−0.0023 (5)	−0.0007 (5)
O2	0.0306 (6)	0.0243 (6)	0.0247 (6)	0.0054 (5)	−0.0035 (5)	−0.0023 (5)
O3	0.0250 (7)	0.0404 (8)	0.0251 (7)	0.0017 (6)	0.0007 (5)	0.0052 (6)
O4	0.0479 (8)	0.0381 (8)	0.0219 (6)	0.0062 (6)	−0.0049 (6)	−0.0085 (6)
O5	0.0370 (7)	0.0451 (8)	0.0382 (8)	0.0037 (6)	0.0144 (6)	0.0072 (7)

Geometric parameters (Å, º) top

C1—O1	1.425 (2)	C6—H6	0.9300
C1—C2	1.507 (3)	C7—C8	1.380 (3)
C1—H1A	0.9700	C7—H7	0.9300
C1—H1B	0.9700	C8—C9	1.396 (2)
C2—N1	1.468 (2)	C8—H8	0.9300
C2—H2A	0.9700	C9—O2	1.3397 (19)
C2—H2B	0.9700	Mo1—O5	1.6902 (14)
C3—N1	1.275 (2)	Mo1—O4	1.7160 (13)
C3—C4	1.443 (3)	Mo1—O1	1.9438 (12)
C3—H3	0.9300	Mo1—O2	1.9446 (12)
C4—C9	1.406 (3)	Mo1—N1	2.2652 (14)
C4—C5	1.407 (2)	Mo1—O3	2.3259 (14)
C5—C6	1.370 (3)	O3—H1O	0.73 (2)
C5—H5	0.9300	O3—H2O	0.78 (3)
C6—C7	1.384 (3)

O1—C1—C2	107.86 (16)	C7—C8—H8	119.8
O1—C1—H1A	110.1	C9—C8—H8	119.8
C2—C1—H1A	110.1	O2—C9—C8	117.79 (16)
O1—C1—H1B	110.1	O2—C9—C4	122.62 (15)
C2—C1—H1B	110.1	C8—C9—C4	119.56 (16)
H1A—C1—H1B	108.4	O5—Mo1—O4	107.11 (7)
N1—C2—C1	105.88 (15)	O5—Mo1—O1	97.32 (6)
N1—C2—H2A	110.6	O4—Mo1—O1	96.15 (6)
C1—C2—H2A	110.6	O5—Mo1—O2	97.01 (6)
N1—C2—H2B	110.6	O4—Mo1—O2	102.33 (6)
C1—C2—H2B	110.6	O1—Mo1—O2	152.09 (5)
H2A—C2—H2B	108.7	O5—Mo1—N1	90.18 (6)
N1—C3—C4	124.35 (16)	O4—Mo1—N1	161.73 (6)
N1—C3—H3	117.8	O1—Mo1—N1	75.35 (5)
C4—C3—H3	117.8	O2—Mo1—N1	80.78 (5)
C9—C4—C5	118.37 (17)	O5—Mo1—O3	166.38 (6)
C9—C4—C3	122.93 (15)	O4—Mo1—O3	86.41 (6)
C5—C4—C3	118.66 (17)	O1—Mo1—O3	82.47 (5)
C6—C5—C4	121.4 (2)	O2—Mo1—O3	78.05 (5)
C6—C5—H5	119.3	N1—Mo1—O3	76.56 (5)
C4—C5—H5	119.3	C3—N1—C2	121.04 (15)
C5—C6—C7	119.60 (18)	C3—N1—Mo1	127.21 (12)
C5—C6—H6	120.2	C2—N1—Mo1	111.56 (11)
C7—C6—H6	120.2	C1—O1—Mo1	117.80 (11)
C8—C7—C6	120.62 (19)	C9—O2—Mo1	133.92 (11)
C8—C7—H7	119.7	Mo1—O3—H1O	114.5 (19)
C6—C7—H7	119.7	Mo1—O3—H2O	120.8 (18)
C7—C8—C9	120.37 (19)	H1O—O3—H2O	109 (3)

O1—C1—C2—N1	−46.2 (2)	C3—C4—C9—O2	0.6 (3)
N1—C3—C4—C9	8.2 (3)	C5—C4—C9—C8	0.8 (3)
N1—C3—C4—C5	−174.14 (18)	C3—C4—C9—C8	178.44 (16)
C9—C4—C5—C6	−1.7 (3)	C4—C3—N1—C2	−178.44 (18)
C3—C4—C5—C6	−179.50 (19)	C4—C3—N1—Mo1	7.0 (3)
C4—C5—C6—C7	1.2 (3)	C1—C2—N1—C3	−149.68 (18)
C5—C6—C7—C8	0.3 (3)	C1—C2—N1—Mo1	25.66 (19)
C6—C7—C8—C9	−1.3 (3)	C2—C1—O1—Mo1	51.2 (2)
C7—C8—C9—O2	178.67 (17)	C8—C9—O2—Mo1	152.01 (14)
C7—C8—C9—C4	0.7 (3)	C4—C9—O2—Mo1	−30.1 (2)
C5—C4—C9—O2	−177.10 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O···O1ⁱ	0.73 (2)	1.97 (3)	2.6656 (19)	161 (3)
O3—H2O···O4ⁱⁱ	0.78 (3)	2.07 (3)	2.8425 (19)	173 (3)

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

Selected bond lengths (Å) top

Mo1—O5	1.6902 (14)	Mo1—O2	1.9446 (12)
Mo1—O4	1.7160 (13)	Mo1—N1	2.2652 (14)
Mo1—O1	1.9438 (12)	Mo1—O3	2.3259 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O···O1ⁱ	0.73 (2)	1.97 (3)	2.6656 (19)	161 (3)
O3—H2O···O4ⁱⁱ	0.78 (3)	2.07 (3)	2.8425 (19)	173 (3)

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

Acknowledgements

The authors thank the Department of Science and Technology (DST), Government of India, for funding the National Centre for Catalysis Research (NCCR), IIT-Madras. They also thank Mr V. Ramkumar and Dr R. Jagan for the data collection and technical assistance in the preparation of the manuscript.

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