Crystal structure of aqua­[(E)-N′-(5-bromo-2-oxido­benzyl­idene-κO)benzohydrazidato-κ2O,N′]dioxidomolybdenum(VI) di­methyl­formamide monosolvate

Sudheer, R.; Sithambaresan, M.; Sajitha, N.R.; Manoj, E.; Kurup, M.R.P.

doi:10.1107/S2056989015009639

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ISSN: 2056-9890

Volume 71| Part 6| June 2015| Pages 702-705

doi:10.1107/S2056989015009639

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Crystal structure of aqua[(E)-N′-(5-bromo-2-oxidobenzylidene-κO)benzohydrazidato-κ²O,N′]dioxidomolybdenum(VI) dimethylformamide monosolvate

Radhika Sudheer,^a M. Sithambaresan,^b ^* N. R. Sajitha,^a E. Manoj ^c and M. R. Prathapachandra Kurup ^a

^aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, ^bDepartment of Chemistry, Faculty of Science, Eastern University, Chenkalady, Sri Lanka, and ^cDept. of Chemistry, Sree Krishna College, Guruvayur 680 102, Thrissur, Kerala, India
^*Correspondence e-mail: msithambaresan@gmail.com

Edited by S. Parkin, University of Kentucky, USA (Received 1 May 2015; accepted 19 May 2015; online 28 May 2015)

The title compound, [Mo(C₁₄H₉BrN₂O₂)O₂(H₂O)]·C₃H₇NO, has a distorted octahedral geometry around the Mo atom, with the two terminal oxide groups lying cis to each other. The two aromatic rings present in the molecule are almost coplanar, forming a dihedral angle of 1.4 (2)°. The five-membered ring involving the metal atom is puckered, with an amplitude Q = 0.358 (2) Å and φ = 204.1 (6)°. In the crystal, pairs of inversion-related molecules are linked by O—H⋯N hydrogen bonds. An O—H⋯O hydrogen bond connects the water ligand to the dimethylformamide solvent molecule. The crystal packing also features π–π [centroid–centroid distance of 3.688 (2) Å] and C—H⋯O interactions.

Keywords: crystal structure; aroyl hydrazone; supramolecular; hydrogen bonding; molybdenum complex.

CCDC reference: 1401828

1. Chemical context

Aroylhydrazones are unique organic compounds characterized by the azomethine group in their molecules (Sheeja et al., 2010 ). They exhibit a wide range of applications in the field of biology, optics, catalysis and analytical chemistry. Their broad spectrum of biological activities include antimicrobial (Sreeja et al., 2004 ), antifungal (Nfor et al., 2013 ), antiviral and antineoplastic (Nair et al., 2014 ) activities. Biocidal studies reveal that hydrazones can be used as fungicides (Rai, 2006 ). Hydrazones are also used as DNA photocleaving agents (Pal et al., 2014 ) and even as a reversible photochromic system (Li et al., 2014 ). Hydrazone-based molecular switches, metalloassemblies and sensors have also been developed (Su & Aprahamian, 2014 ).

Molybdenum is an important trace metal capable of forming various complexes with versatile organic ligands. Its flexibility in possessing a large number of stable and accessible oxidation states leads to applications in industrial and biological reactions. Molybdenum complexes play a major role in catalytic activity (Maurya et al., 2014 ). They are employed as catalysts in olefin epoxidation (Lei & Chelamalla, 2013 ), reduction of dinitrogen to ammonia (Sengupta et al., 2015 ) and oxidation of secondary alcohols (Maurya et al., 2015 ). The biological relevance of molybdenum complexes include their application in modelling active sites of molybdoenzymes (Pramanik et al., 2004 ) and also their antibacterial (Pasayat et al., 2012 ), cytotoxic and antiproliferative activities (Pasayat et al., 2014 ).

2. Structural commentary

The title complex [Mo(C₁₄H₉BrN₂O₂)O₂(H₂O)]·C₃H₇NO crystallizes in the monoclinic space group P2₁/n. The complex adopts a distorted octahedral geometry around the Mo atom (Fig. 1) in which the aroylhydrazone coordinates to the metal in a tridentate manner. One dimethylformamide solvent molecule is present without any coordination to the metal centre. Two oxygen atoms and one nitrogen atom of the aroylhydrazone and one of the terminal oxido atoms occupy equatorial positions in the complex. The axial positions are occupied by the other terminal oxygen and the oxygen atom of the water molecule. The two terminal oxido groups are cis to each other. The C8—O2 bond length [1.314 (3) Å] is close to the reported C—O single bond length (1.318 Å; Gupta et al., 2007 ). The Mo1—O4 and Mo1—O3 bonds of 1.693 (3) and 1.702 (2) Å, respectively, are very close to the reported Mo=O double bond [1.697 (1) Å], indicating that the complex has two Mo=O double bonds (Ebrahimipour et al., 2015 ).

Figure 1
The title compound drawn with 50% probability displacement ellipsoids for the non-H atoms.

The ligand adopts Z configurations with respect to the C7—N1 and C8—N2 bonds in the complex, which is clear from C1—C6—C7—N1 and N1—N2—C8—O2 torsion angles [9.8 (5) and −1.4 (4)°, respectively]. This configuration is similar to that of the metal-free ligand (Liu et al., 2006 ). The C1–C6 and C9–C14 rings make a dihedral angle of 1.4 (2)° with each other. Ring puckering analysis and least-squares plane calculations show that the Mo1/O1/C1/C6/C7/N1 ring is puckered with puckering amplitude Q = 0.358 (2)Å and φ = 204.1 (6)°.

3. Supramolecular features

The supramolecular arrangement of the complex is driven by various types of classical and non-classical hydrogen-bonding interactions, in which O4, O5 and N2 act as acceptor atoms (Fig. 2, Table 1). There are classical O—H⋯N and O—H⋯O hydrogen-bonding interactions with D⋯A distances 2.891 (4) and 2.701 (4) Å respectively, and a non-classical C—H⋯O interaction with a D⋯A distance of 3.421 (5) Å. These interactions connect pairs of molecules along with the solvent dimethylformamide. The complex molecule is stacked along the b axis through two different types of O—H⋯π interaction (Fig. 3), with H–centroid distances 2.67 (4) and 2.94 (5) Å and a π–π interaction between rings C1–C6 and C9–C14(2 − x, −y, −z) with a centroid-centroid distance of 3.688 (2) Å (Fig. 3). A view of the crystal packing along the a axis is given in Fig. 4.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O5ⁱ	0.93	2.51	3.421 (5)	168
C17—H17⋯O4ⁱⁱ	0.93	2.63	3.404 (5)	141
O6—H6A⋯N2ⁱⁱⁱ	0.86 (1)	2.04 (1)	2.891 (3)	173 (3)
O6—H6B⋯O5^iv	0.86 (1)	1.85 (1)	2.701 (4)	171 (4)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+2, -y, -z; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Hydrogen-bonding interactions in the title compound.

Figure 3
O—H⋯π and π–π interactions present in the molecule. Atom O6 is the water O atom.

Figure 4
Packing of the molecules, viewed along the a axis.

4. Synthesis and crystallization

The benzoyl hydrazone was synthesized by a reported procedure (Liu et al., 2006). A methanolic solution of benzhydrazide (0.0680 g, 0.5 mmol) was refluxed with a methanolic solution of 5-bromosalicylaldehyde (0.1005 g, 0.5 mmol) continuously for 3 h. The reaction mixture was kept aside for slow evaporation at room temperature. After 2–3 days, a pale-yellow compound formed, and was washed with methanol and dried under vacuum.

The complex was synthesized by refluxing a methanolic solution of benzoyl hydrazone (0.1595 g, 0.5 mmol) and MoCl₅ (0.1362 g, 0.5 mmol) for 3 h. The brown precipitate obtained was filtered, washed with methanol, dried and recrystallized from dimethylformamide (yield, 0.1688g, 63%). FT–IR (KBr, cm⁻¹) 3400, 3194, 1657, 1546, 1345, 937, 810.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All C-bound H atoms were placed in calculated positions, guided by difference Fourier maps, with C—H bond lengths of 0.93–0.96 Å and with U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl C). The O—H distances were restrained with 1,2 and 1,3 distance restraints of 0.86 (1) and 1.36 (2) Å. Reflections (0 0 2), (1 0 1) and ( $[\overline{1}]$ 0 1), which were obscured by the beam stop, were omitted.

Table 2
Experimental details

Crystal data
Chemical formula	[Mo(C₁₄H₉BrN₂O₂)O₂(H₂O)]·C₃H₇NO
M_r	536.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	10.8581 (8), 7.1145 (5), 25.998 (2)
β (°)	93.900 (3)
V (Å³)	2003.7 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.69
Crystal size (mm)	0.40 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.355, 0.447
No. of measured, independent and observed [I > 2σ(I)] reflections	14880, 4957, 3710
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.096, 1.08
No. of reflections	4957
No. of parameters	264
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.31, −0.89
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXS2014 and SHELXL97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 (Burnett & Johnson, 1996 ), DIAMOND (Brandenburg, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1401828

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015009639/pk2550sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015009639/pk2550Isup2.hkl

checkCIF report

Chemical context top

Aroylhydrazones are unique organic compounds characterized by the azomethine group in their molecules (Sheeja et al., 2010). They exhibit a wide range of applications in the field of biology, optics, catalysis and analytical chemistry. Their broad spectrum of biological activities include antimicrobial (Sreeja et al., 2004), antifungal (Nfor et al., 2013), antiviral and antineoplastic (Nair et al., 2014) activities. Biocidal studies reveal that hydrazones can be used as fungicides (Rai, 2006). Hydrazones are also used as DNA photocleaving agents (Pal et al., 2014)and even as a reversible photochromic system (Li et al., 2014). Hydrazone-based molecular switches, metalloassemblies and sensors have also been developed (Su & Aprahamian, 2014).

Molybdenum is an important trace metal capable of forming various complexes with versatile organic ligands. Its flexibility in possessing a large number of stable and accessible oxidation states leads to applications in industrial and biological reactions. Molybdenum complexes play a major role in catalytic activity (Maurya et al., 2014). They are employed as catalysts in olefin epoxidation (Lei & Chelamalla, 2013), reduction of dinitrogen to ammonia (Sengupta et al., 2015) and oxidation of secondary alcohols (Maurya et al., 2015). The biological relevance of molybdenum complexes include their application in modelling active sites of molybdoenzymes (Pramanik et al., 2004) and also their antibacterial (Pasayat et al., 2012), cytotoxic and antiproliferative activities (Pasayat et al., 2014).

Structural commentary top

The title complex [MoO₂(C₁₄H₉N₂O₂Br)H₂O]·C₃H₇NO crystallized in the monoclinic space group P2₁/n . The complex adopts a distorted octahedral geometry around the Mo atom (Fig. 1) in which the aroylhydrazone coordinates to the metal in a tridentate manner. One dimethylformamide solvent molecule is present without any coordination to the metal centre. Two oxygen atoms and one nitrogen atom of the aroylhydrazone and one of the terminal oxo atoms occupy equatorial positions in the complex. The axial positions are occupied by the other terminal oxygen and the oxygen atom of the water molecule. The two terminal oxo groups are cis to each other. The C8—O2 bond length [1.314 (3) Å] is close to the reported C—O single bond length (1.318 Å; Gupta et al., 2007). The Mo1—O4 and Mo1—O3 bonds of 1.693 (3) and 1.702 (2) Å, respectively, are very close to the reported Mo═O double bond [1.697 (1) Å], indicating that the complex has two Mo=O double bonds (Ebrahimipour et al., 2015).

The ligand adopts Z configurations with respect to the C7—N1 and C8—N2 bonds in the complex, which is clear from C1—C6—C7—N1 and N1—N2—C8—O2 torsion angles [9.8 (5) and -1.4 (4)°, respectively]. This configuration is similar to that of the metal in the free ligand (Liu et al., 2006). The C1–C6 and C9–C14 rings make a dihedral angle of 1.4 (2)° with each other. Ring puckering analysis and least-squares plane calculations show that the Mo1/O1/C1/C6/C7/N1 ring is puckered with puckering amplitude Q = 0.358 (2)Å and ϕ = 204.1 (6)°.

Supramolecular features top

The supramolecular arrangement of the complex is driven by various types of classical and non-classical hydrogen-bonding interactions, in which O4, O5 and N2 act as acceptor atoms (Fig. 2, Table 1). There are classical O—H···N and O—H···O hydrogen-bonding interactions with D···A distances 2.891 (4) and 2.701 (4) Å respectively, and a non-classical C—H···O interaction with a D···A distance of 3.421 (5) Å. These interactions connect pairs of molecules along with the solvent dimethylformamide. The complex molecule is stacked along the b axis through two different types of C—H···π interaction (Fig. 3), with H-centroid distances 2.67 (4) and 2.94 (5) Å and a π–π interaction between rings C1–C6 and C9–C14(2 - x, -y, -z) with a centroid-centroid distance of 3.688 (2) Å (Fig. 3). A view of the crystal packing along the a axis is given in Fig. 4.

Synthesis and crystallization top

The benzoyl hydrazone was synthesized by a reported procedure (Liu et al., 2006). A methanolic solution of benzhydrazide (0.0680g, 0.5mmol) was refluxed with a methanolic solution of 5-bromosalicylaldehyde (0.1005g, 0.5mmol) continuously for 3 hours. The reaction mixture was kept aside for slow evaporation at room temperature. After 2–3 days, a pale-yellow compound formed, and was washed with methanol and dried under vacuum.

The complex was synthesized by refluxing a methanolic solution of benzoyl hydrazone (0.1595g, 0.5 mmol) and MoCl₅ (0.1362g, 0.5 mmol) for 3 hours. The brown precipitate obtained was filtered, washed with methanol, dried and recrystallized from dimethylformamide (yield, 0.1688g, 63%). FT–IR (KBr, cm^-1) ν_max: 3400, 3194, 1657, 1546, 1345, 937, 810.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All C-bound H atoms were placed in calculated positions, guided by difference Fourier maps, with C—H bond lengths of 0.93–0.96 Å and with U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl C). The O—H distances were restrained with 1,2 and 1,3 distance restraints of 0.86 (1) and 1.36 (2) Å. Reflections (0 0 2), (1 0 1) and (1 0 1), which were obscured by the beam stop, were omitted.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 (Burnett & Johnson, 1996) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The title compound drawn with 50% probability displacement ellipsoids for the non-H atoms.
	Fig. 2. Hydrogen-bonding interactions in the title compound.
	Fig. 3. C—H···π and π–π interactions present in the molecule. Atom O6 is the water O atom.
	Fig. 4. Packing of the molecules, viewed along the a axis.

Aqua[(E)-N'-(5-bromo-2-oxidobenzylidene-κO)benzohydrazidato-κ²O,N']dioxidomolybdenum(VI) dimethylformamide monosolvate top

Crystal data top

[Mo(C₁₄H₉BrN₂O₂)O₂(H₂O)]·C₃H₇NO	F(000) = 1064
M_r = 536.19	D_x = 1.777 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.8581 (8) Å	Cell parameters from 5189 reflections
b = 7.1145 (5) Å	θ = 2.9–28.1°
c = 25.998 (2) Å	µ = 2.69 mm⁻¹
β = 93.900 (3)°	T = 296 K
V = 2003.7 (3) Å³	Needle, yellow
Z = 4	0.40 × 0.15 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	3710 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
ω and ϕ scan	θ_max = 28.3°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
T_min = 0.355, T_max = 0.447	k = −8→9
14880 measured reflections	l = −34→31
4957 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0418P)² + 1.3003P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.096	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 1.31 e Å⁻³
4957 reflections	Δρ_min = −0.88 e Å⁻³
264 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0007 (2)

Crystal data top

[Mo(C₁₄H₉BrN₂O₂)O₂(H₂O)]·C₃H₇NO	V = 2003.7 (3) Å³
M_r = 536.19	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.8581 (8) Å	µ = 2.69 mm⁻¹
b = 7.1145 (5) Å	T = 296 K
c = 25.998 (2) Å	0.40 × 0.15 × 0.10 mm
β = 93.900 (3)°

Data collection top

Bruker APEXII CCD diffractometer	4957 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3710 reflections with I > 2σ(I)
T_min = 0.355, T_max = 0.447	R_int = 0.027
14880 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	3 restraints
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 1.31 e Å⁻³
4957 reflections	Δρ_min = −0.88 e Å⁻³
264 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	0.6397 (3)	0.2038 (4)	0.03480 (13)	0.0315 (7)
C2	0.5256 (3)	0.2057 (5)	0.05560 (14)	0.0399 (8)
H2	0.4549	0.1793	0.0346	0.048*
C3	0.5153 (3)	0.2461 (5)	0.10676 (14)	0.0453 (9)
H3	0.4382	0.2497	0.1203	0.054*
C4	0.6213 (3)	0.2812 (5)	0.13790 (14)	0.0433 (8)
C5	0.7351 (3)	0.2765 (5)	0.11877 (13)	0.0402 (8)
H5	0.8051	0.2982	0.1406	0.048*
C6	0.7471 (3)	0.2391 (4)	0.06655 (12)	0.0312 (6)
C7	0.8694 (3)	0.2411 (4)	0.04814 (12)	0.0317 (6)
H7	0.9367	0.2462	0.0722	0.038*
C8	1.0185 (3)	0.2494 (4)	−0.06177 (12)	0.0299 (6)
C9	1.1389 (3)	0.2485 (4)	−0.08474 (12)	0.0315 (6)
C10	1.2469 (3)	0.2848 (5)	−0.05437 (13)	0.0354 (7)
H10	1.2436	0.3138	−0.0196	0.042*
C11	1.3591 (3)	0.2772 (5)	−0.07643 (15)	0.0443 (9)
H11	1.4315	0.3026	−0.0564	0.053*
C12	1.3649 (3)	0.2328 (6)	−0.12723 (16)	0.0524 (10)
H12	1.4410	0.2266	−0.1415	0.063*
C13	1.2584 (4)	0.1972 (7)	−0.15748 (16)	0.0620 (12)
H13	1.2624	0.1666	−0.1921	0.074*
C14	1.1456 (3)	0.2070 (6)	−0.13613 (14)	0.0498 (10)
H14	1.0735	0.1853	−0.1567	0.060*
C15	0.3158 (5)	1.0771 (9)	0.2643 (2)	0.105 (2)
H15A	0.2832	1.0438	0.2303	0.158*
H15B	0.3700	1.1831	0.2624	0.158*
H15C	0.2491	1.1090	0.2852	0.158*
C16	0.4848 (5)	0.8476 (8)	0.2605 (2)	0.0858 (16)
H16A	0.5059	0.7242	0.2732	0.129*
H16B	0.5547	0.9293	0.2661	0.129*
H16C	0.4614	0.8408	0.2243	0.129*
C17	0.3545 (4)	0.8450 (7)	0.33094 (16)	0.0553 (10)
H17	0.2877	0.8967	0.3465	0.066*
N1	0.8897 (2)	0.2360 (3)	0.00006 (10)	0.0284 (5)
N2	1.0134 (2)	0.2354 (4)	−0.01231 (10)	0.0308 (6)
N3	0.3835 (3)	0.9198 (5)	0.28720 (12)	0.0550 (8)
O1	0.64511 (18)	0.1587 (4)	−0.01536 (9)	0.0394 (5)
O2	0.92037 (18)	0.2583 (3)	−0.09418 (9)	0.0367 (5)
O3	0.6772 (2)	0.1701 (4)	−0.12470 (9)	0.0512 (7)
O4	0.7253 (2)	0.4738 (4)	−0.06416 (11)	0.0539 (7)
O5	0.4074 (3)	0.7140 (5)	0.35275 (12)	0.0743 (9)
O6	0.8105 (2)	−0.0693 (3)	−0.06282 (10)	0.0384 (5)
Br1	0.60802 (5)	0.33679 (9)	0.20859 (2)	0.07719 (18)
Mo1	0.75010 (2)	0.23944 (4)	−0.06785 (2)	0.03247 (10)
H6A	0.858 (3)	−0.117 (5)	−0.0387 (9)	0.046 (11)*
H6B	0.834 (4)	−0.118 (6)	−0.0907 (8)	0.092 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0296 (14)	0.0328 (18)	0.0324 (16)	0.0022 (12)	0.0037 (12)	0.0019 (13)
C2	0.0290 (15)	0.047 (2)	0.044 (2)	−0.0013 (13)	0.0035 (14)	0.0032 (16)
C3	0.0371 (16)	0.057 (2)	0.043 (2)	0.0015 (17)	0.0154 (15)	0.0038 (18)
C4	0.052 (2)	0.047 (2)	0.0325 (18)	−0.0001 (16)	0.0122 (15)	0.0028 (16)
C5	0.0396 (17)	0.048 (2)	0.0326 (17)	0.0010 (15)	0.0016 (13)	0.0010 (16)
C6	0.0303 (14)	0.0311 (16)	0.0322 (16)	0.0032 (13)	0.0022 (11)	0.0040 (14)
C7	0.0280 (13)	0.0354 (17)	0.0309 (16)	0.0003 (13)	−0.0030 (11)	−0.0033 (15)
C8	0.0270 (13)	0.0281 (16)	0.0346 (16)	−0.0016 (13)	0.0017 (11)	0.0037 (14)
C9	0.0262 (13)	0.0333 (17)	0.0352 (17)	0.0019 (13)	0.0033 (12)	0.0053 (15)
C10	0.0318 (15)	0.038 (2)	0.0363 (18)	−0.0015 (13)	0.0013 (13)	0.0070 (14)
C11	0.0276 (14)	0.056 (2)	0.049 (2)	−0.0003 (15)	0.0004 (14)	0.0156 (18)
C12	0.0327 (16)	0.074 (3)	0.052 (2)	0.0104 (18)	0.0146 (16)	0.014 (2)
C13	0.047 (2)	0.101 (4)	0.039 (2)	0.009 (2)	0.0117 (17)	0.000 (2)
C14	0.0346 (17)	0.077 (3)	0.038 (2)	−0.0012 (17)	0.0021 (15)	−0.0014 (19)
C15	0.102 (4)	0.099 (5)	0.116 (5)	0.026 (4)	0.017 (4)	0.044 (4)
C16	0.083 (4)	0.103 (4)	0.075 (4)	0.012 (3)	0.035 (3)	0.021 (3)
C17	0.056 (2)	0.069 (3)	0.042 (2)	−0.008 (2)	0.0081 (18)	−0.005 (2)
N1	0.0229 (11)	0.0293 (14)	0.0326 (14)	0.0023 (10)	0.0002 (9)	−0.0006 (12)
N2	0.0217 (11)	0.0353 (15)	0.0352 (14)	0.0005 (10)	0.0007 (10)	−0.0010 (12)
N3	0.060 (2)	0.062 (2)	0.0432 (19)	0.0035 (16)	0.0052 (15)	0.0134 (16)
O1	0.0249 (10)	0.0582 (15)	0.0347 (13)	−0.0035 (10)	0.0002 (9)	−0.0062 (12)
O2	0.0259 (9)	0.0533 (15)	0.0307 (11)	0.0017 (10)	−0.0001 (8)	0.0064 (11)
O3	0.0334 (12)	0.086 (2)	0.0321 (13)	0.0029 (12)	−0.0099 (10)	−0.0021 (13)
O4	0.0500 (15)	0.0474 (16)	0.0641 (18)	0.0155 (12)	0.0026 (13)	0.0089 (13)
O5	0.087 (2)	0.088 (3)	0.0481 (18)	−0.0023 (18)	0.0050 (16)	0.0220 (17)
O6	0.0417 (13)	0.0406 (14)	0.0323 (13)	0.0056 (10)	−0.0025 (10)	−0.0038 (12)
Br1	0.0820 (3)	0.1149 (5)	0.0373 (2)	−0.0145 (3)	0.0234 (2)	−0.0067 (3)
Mo1	0.02312 (13)	0.04399 (19)	0.02970 (15)	0.00441 (12)	−0.00257 (9)	0.00338 (13)

Geometric parameters (Å, º) top

C1—O1	1.348 (4)	C12—H12	0.9300
C1—C2	1.386 (4)	C13—C14	1.380 (5)
C1—C6	1.405 (4)	C13—H13	0.9300
C2—C3	1.373 (5)	C14—H14	0.9300
C2—H2	0.9300	C15—N3	1.445 (6)
C3—C4	1.384 (5)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C5	1.364 (5)	C15—H15C	0.9600
C4—Br1	1.895 (4)	C16—N3	1.435 (5)
C5—C6	1.398 (4)	C16—H16A	0.9600
C5—H5	0.9300	C16—H16B	0.9600
C6—C7	1.441 (4)	C16—H16C	0.9600
C7—N1	1.284 (4)	C17—O5	1.215 (5)
C7—H7	0.9300	C17—N3	1.313 (5)
C8—N2	1.295 (4)	C17—H17	0.9300
C8—O2	1.314 (3)	N1—N2	1.403 (3)
C8—C9	1.474 (4)	N1—Mo1	2.247 (2)
C9—C14	1.375 (5)	O1—Mo1	1.924 (2)
C9—C10	1.393 (4)	O2—Mo1	2.019 (2)
C10—C11	1.382 (4)	O3—Mo1	1.702 (2)
C10—H10	0.9300	O4—Mo1	1.693 (3)
C11—C12	1.363 (5)	O6—Mo1	2.293 (2)
C11—H11	0.9300	O6—H6A	0.857 (10)
C12—C13	1.377 (6)	O6—H6B	0.856 (10)

O1—C1—C2	118.6 (3)	N3—C15—H15A	109.5
O1—C1—C6	121.4 (3)	N3—C15—H15B	109.5
C2—C1—C6	119.9 (3)	H15A—C15—H15B	109.5
C3—C2—C1	120.9 (3)	N3—C15—H15C	109.5
C3—C2—H2	119.5	H15A—C15—H15C	109.5
C1—C2—H2	119.5	H15B—C15—H15C	109.5
C2—C3—C4	119.0 (3)	N3—C16—H16A	109.5
C2—C3—H3	120.5	N3—C16—H16B	109.5
C4—C3—H3	120.5	H16A—C16—H16B	109.5
C5—C4—C3	121.4 (3)	N3—C16—H16C	109.5
C5—C4—Br1	119.3 (3)	H16A—C16—H16C	109.5
C3—C4—Br1	119.3 (3)	H16B—C16—H16C	109.5
C4—C5—C6	120.4 (3)	O5—C17—N3	125.6 (4)
C4—C5—H5	119.8	O5—C17—H17	117.2
C6—C5—H5	119.8	N3—C17—H17	117.2
C5—C6—C1	118.4 (3)	C7—N1—N2	117.0 (2)
C5—C6—C7	118.0 (3)	C7—N1—Mo1	127.82 (19)
C1—C6—C7	123.6 (3)	N2—N1—Mo1	115.16 (18)
N1—C7—C6	123.1 (3)	C8—N2—N1	109.5 (2)
N1—C7—H7	118.5	C17—N3—C16	120.7 (4)
C6—C7—H7	118.5	C17—N3—C15	121.7 (4)
N2—C8—O2	123.6 (3)	C16—N3—C15	117.6 (4)
N2—C8—C9	120.0 (3)	C1—O1—Mo1	132.99 (19)
O2—C8—C9	116.3 (3)	C8—O2—Mo1	120.02 (19)
C14—C9—C10	119.5 (3)	Mo1—O6—H6A	126 (2)
C14—C9—C8	120.1 (3)	Mo1—O6—H6B	116 (3)
C10—C9—C8	120.4 (3)	H6A—O6—H6B	105 (2)
C11—C10—C9	119.3 (3)	O4—Mo1—O3	105.57 (13)
C11—C10—H10	120.3	O4—Mo1—O1	98.63 (11)
C9—C10—H10	120.3	O3—Mo1—O1	105.44 (11)
C12—C11—C10	120.7 (3)	O4—Mo1—O2	96.11 (11)
C12—C11—H11	119.7	O3—Mo1—O2	96.16 (10)
C10—C11—H11	119.7	O1—Mo1—O2	149.37 (9)
C11—C12—C13	120.3 (3)	O4—Mo1—N1	93.86 (11)
C11—C12—H12	119.9	O3—Mo1—N1	158.18 (11)
C13—C12—H12	119.9	O1—Mo1—N1	80.79 (9)
C12—C13—C14	119.6 (4)	O2—Mo1—N1	71.52 (9)
C12—C13—H13	120.2	O4—Mo1—O6	170.43 (11)
C14—C13—H13	120.2	O3—Mo1—O6	83.47 (11)
C9—C14—C13	120.6 (3)	O1—Mo1—O6	81.64 (10)
C9—C14—H14	119.7	O2—Mo1—O6	79.51 (9)
C13—C14—H14	119.7	N1—Mo1—O6	76.70 (9)

O1—C1—C2—C3	178.4 (3)	C8—C9—C10—C11	177.9 (3)
C6—C1—C2—C3	1.5 (5)	C9—C10—C11—C12	−0.7 (5)
C1—C2—C3—C4	−1.4 (5)	C10—C11—C12—C13	0.8 (6)
C2—C3—C4—C5	0.0 (6)	C11—C12—C13—C14	0.2 (7)
C2—C3—C4—Br1	−179.9 (3)	C10—C9—C14—C13	1.3 (6)
C3—C4—C5—C6	1.2 (5)	C8—C9—C14—C13	−177.0 (4)
Br1—C4—C5—C6	−178.8 (3)	C12—C13—C14—C9	−1.2 (7)
C4—C5—C6—C1	−1.0 (5)	C6—C7—N1—N2	−178.9 (3)
C4—C5—C6—C7	178.3 (3)	C6—C7—N1—Mo1	3.7 (4)
O1—C1—C6—C5	−177.1 (3)	O2—C8—N2—N1	−1.4 (4)
C2—C1—C6—C5	−0.3 (5)	C9—C8—N2—N1	−178.9 (3)
O1—C1—C6—C7	3.6 (5)	C7—N1—N2—C8	−173.6 (3)
C2—C1—C6—C7	−179.6 (3)	Mo1—N1—N2—C8	4.1 (3)
C5—C6—C7—N1	−169.5 (3)	O5—C17—N3—C16	0.4 (7)
C1—C6—C7—N1	9.8 (5)	O5—C17—N3—C15	−179.4 (5)
N2—C8—C9—C14	160.5 (3)	C2—C1—O1—Mo1	146.6 (3)
O2—C8—C9—C14	−17.2 (5)	C6—C1—O1—Mo1	−36.6 (4)
N2—C8—C9—C10	−17.8 (5)	N2—C8—O2—Mo1	−2.5 (4)
O2—C8—C9—C10	164.5 (3)	C9—C8—O2—Mo1	175.1 (2)
C14—C9—C10—C11	−0.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O5ⁱ	0.93	2.51	3.421 (5)	168
C17—H17···O4ⁱⁱ	0.93	2.63	3.404 (5)	141
O6—H6A···N2ⁱⁱⁱ	0.86 (1)	2.04 (1)	2.891 (3)	173 (3)
O6—H6B···O5^iv	0.86 (1)	1.85 (1)	2.701 (4)	171 (4)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+2, −y, −z; (iv) x+1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O5ⁱ	0.93	2.51	3.421 (5)	168.2
C17—H17···O4ⁱⁱ	0.93	2.63	3.404 (5)	141.2
O6—H6A···N2ⁱⁱⁱ	0.857 (10)	2.038 (11)	2.891 (3)	173 (3)
O6—H6B···O5^iv	0.856 (10)	1.852 (13)	2.701 (4)	171 (4)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+2, −y, −z; (iv) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Mo(C₁₄H₉BrN₂O₂)O₂(H₂O)]·C₃H₇NO
M_r	536.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	10.8581 (8), 7.1145 (5), 25.998 (2)
β (°)	93.900 (3)
V (Å³)	2003.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.69
Crystal size (mm)	0.40 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.355, 0.447
No. of measured, independent and observed [I > 2σ(I)] reflections	14880, 4957, 3710
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.096, 1.08
No. of reflections	4957
No. of parameters	264
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.31, −0.88

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS2014 (Sheldrick, 2015), SHELXL2014 (Sheldrick, 2015), ORTEP-3 (Burnett & Johnson, 1996) and DIAMOND (Brandenburg, 2010), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Acknowledgements

NRS thanks the Council of Scientific and Industrial Research (India) for a Junior Research Fellowship. MRPK is grateful to UGC, New Delhi, India, for a UGC–BSR one-time grant to Faculty. EM thanks UGC for the financial assistance in the form of a minor research project. We thank the Sophisticated Analytical Instruments Facility, Cochin University of Science and Technology, Kochi-22, India, for the diffraction measurements.

References

Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Ebrahimipour, S. Y., Khabazadeh, H., Castro, J., Sheikhshoaie, I., Crochet, A. & Fromm, K. M. (2015). Inorg. Chim. Acta, 427, 52–61. CSD CrossRef CAS Google Scholar
Gupta, S., Barik, A. K., Pal, S., Hazra, A., Roy, S., Butcher, R. J. & Kar, S. K. (2007). Polyhedron, 26, 133–141. CSD CrossRef CAS Google Scholar
Lei, X. & Chelamalla, N. (2013). Polyhedron, 49, 244–251. Web of Science CSD CrossRef CAS Google Scholar
Li, K., Xiang, Y., Wang, X., Li, J., Hu, R., Tong, A. & Tang, B. Z. (2014). J. Am. Chem. Soc. 136, 1643–1649. CrossRef CAS PubMed Google Scholar
Liu, H.-Y., Wang, H.-Y., Gao, F., Lu, Z.-S. & Niu, D.-Z. (2006). Acta Cryst. E62, o4495–o4496. Web of Science CSD CrossRef IUCr Journals Google Scholar
Maurya, M. R., Dhaka, S. & Avecilla, F. (2014). Polyhedron, 67, 145–159. CSD CrossRef CAS Google Scholar
Maurya, M. R., Dhaka, S. & Avecilla, F. (2015). New J. Chem. 39, 2130–2139. CSD CrossRef CAS Google Scholar
Nair, R. S., Kuriakose, M., Somasundaram, V., Shenoi, V., Kurup, M. R. P. & Srinivas, P. (2014). Life Sci. 116, 90–97. Web of Science CrossRef CAS PubMed Google Scholar
Nfor, E. N., Husian, A., Majoumo-Mbe, F., Njah, I. N., Offiong, O. E. & Bourne, S. A. (2013). Polyhedron, 63, 207–213. CSD CrossRef CAS Google Scholar
Pal, R., Kumar, V., Gupta, A. K. & Beniwal, V. (2014). Med. Chem. Res. 23, 3327–3335. CrossRef CAS Google Scholar
Pasayat, S., Dash, S. P., Majumder, S., Dinda, R., Sinn, E., Stoeckli-Evans, H., Mukhopadhyay, S., Bhutia, S. K. & Mitra, P. (2014). Polyhedron, 80, 198–205. CSD CrossRef CAS Google Scholar
Pasayat, S., Dash, S. P., Saswati, Majhi, P. K., Patil, Y. P., Nethaji, M., Dash, H. R., Das, S. & Dinda, R. (2012). Polyhedron, 38, 198–204. CSD CrossRef CAS Google Scholar
Pramanik, N. R., Ghosh, S., Raychaudhuri, T. K., Ray, S., Butcher, R. J. & Mandal, S. S. (2004). Polyhedron, 23, 1595–1603. CSD CrossRef CAS Google Scholar
Rai, B. K. (2006). J. Indian Council Chem. 23, 13–16. CAS Google Scholar
Sengupta, D., Gangopadhyay, S., Drew, M. G. B. & Gangopadhyay, P. K. (2015). Dalton Trans. 44, 1323–1331. CSD CrossRef CAS PubMed Google Scholar
Sheeja, S. R., Mangalam, N. A., Prathapachandra Kurup, M. R., Sheena Mary, Y., Raju, K., Varghese, H. T. & Panicker, C. Y. (2010). J. Mol. Struct. 973, 36–46. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sreeja, P. B., Prathapachandra Kurup, M. R., Kishore, A. & Jasmin, C. (2004). Polyhedron, 23, 575–581. Web of Science CSD CrossRef CAS Google Scholar
Su, X. & Aprahamian, I. (2014). Chem. Soc. Rev. 43, 1963–1981. Web of Science CrossRef CAS PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 71| Part 6| June 2015| Pages 702-705

doi:10.1107/S2056989015009639

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