Crystal structure of aqua-[(E)-N'-(5-bromo-2-oxido-benzyl-idene-κO)benzohydrazidato-κ(2) O,N']dioxidomolybdenum(VI) di-methyl-formamide monosolvate.

The title compound, [Mo(C14H9BrN2O2)O2(H2O)]·C3H7NO, has a distorted octa-hedral geometry around the Mo atom, with the two terminal oxide groups lying cis to each other. The two aromatic rings present in the mol-ecule 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 mol-ecules are linked by O-H⋯N hydrogen bonds. An O-H⋯O hydrogen bond connects the water ligand to the di-methyl-formamide solvent mol-ecule. The crystal packing also features π-π [centroid-centroid distance of 3.688 (2) Å] and C-H⋯O inter-actions.

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 ▸).

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)°.

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 ▸.

Figure 2

Hydrogen-bonding inter­actions in the title compound.

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C7H7O5i	0.93	2.51	3.421(5)	168
C17H17O4ii	0.93	2.63	3.404(5)	141
O6H6AN2iii	0.86(1)	2.04(1)	2.891(3)	173(3)
O6H6BO5iv	0.86(1)	1.85(1)	2.701(4)	171(4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

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.

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) νmax: 3400, 3194, 1657, 1546, 1345, 937, 810.

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 ( 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 ()	10.8581(8), 7.1145(5), 25.998(2)
()	93.900(3)
V (3)	2003.7(3)
Z	4
Radiation type	Mo K
(mm1)	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 > 2(I)] reflections	14880, 4957, 3710
R int	0.027
(sin /)max (1)	0.667
Refinement
R[F 2 > 2(F 2)], wR(F 2), 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
max, min (e 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 ▸).

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

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

CCDC reference: 1401828

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Mo(C14H9BrN2O2)O2(H2O)]·C3H7NO	F(000) = 1064
Mr = 536.19	Dx = 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

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

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(Fo2) + (0.0418P)2 + 1.3003P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.096	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 1.31 e Å−3
4957 reflections	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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···O5iv	0.86 (1)	1.85 (1)	2.701 (4)	171 (4)