Synthesis and crystal structure of a new hybrid organic–inorganic material containing neutral mol­ecules, cations and hepta­molybdate anions

Sarr, B.; Mbaye, A.; Diallo, W.; Diop, C.A.K.; Sidibe, M.; Michaud, F.

doi:10.1107/S2056989019008454

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 7| July 2019| Pages 1001-1004

https://doi.org/10.1107/S2056989019008454

Open

access

Synthesis and crystal structure of a new hybrid organic–inorganic material containing neutral molecules, cations and heptamolybdate anions

Bougar Sarr,^a ^* Abdou Mbaye,^b Wally Diallo,^a Cheikh Abdoul Khadir Diop,^a Mamadou Sidibe ^a and Francois Michaud ^c

^aLaboratoire de Chimie Minérale et Analytique, Département de Chimie, Faculté des Sciences et Téchniques, Université Cheikh Anta Diop, Dakar, Senegal, ^bLaboratoire de Chimie et de Physique des Matériaux (LCPM) de l'Université Assane Seck de Ziguinchor (UASZ), BP 523 Ziguinchor, Senegal, and ^cService Commun d'Analyse par Diffraction des Rayons X, Universite de Bretagne Occidentale, 6, avenue Victor Le Gorgeu, CS 93837, F-29238 Brest cedex 3, France
^*Correspondence e-mail: bouks89@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 31 May 2019; accepted 14 June 2019; online 21 June 2019)

The title compound, hexakis(2-methyl-1H-imidazol-3-ium) heptamolybdate 2-methyl-1H-imidazole disolvate dihydrate, (C₄H₇N₂)₆[Mo₇O₂₄]·2C₄H₆N₂·2H₂O, was prepared from 2-methylimidazole and ammonium heptamolybdate tetrahydrate in acid solution. The [Mo₇O₂₄]⁶⁻ heptamolybdate cluster anion is accompanied by six protonated (C₄H₇N₂)⁺ 2-methylimidazolium cations, two neutral C₄H₆N₂ 2-methylimidazole molecules and two water molecules of crystallization. The cluster consists of seven distorted MoO₆ octahedra sharing edges or vertices. In the crystal, the components are linked by N—H⋯N, N—H⋯O, O—H⋯O, N—H⋯(O,O) and O—H⋯(O,O) hydrogen bonds, generating a three-dimensional network. Weak C—H⋯O interactions consolidate the packing.

Keywords: crystal structure; polyoxomolybdates; IR spectroscopic study; hydrogen bonding.

CCDC reference: 1922927

1. Chemical context

Polyoxometalates (POMs) are clusters of transition metals (M = V, Nb, Ta, Mo, W, ⋯) and oxygen atoms with a structural and compositional diversity that lead to numerous applications because of their electrochemical, optical, catalytic and photochromic properties as well as their antiviral and antitumor activities (Katsoulis, 1998 ; Hasenknopf, 2005 ; Gerth et al., 2005 ; Coué et al., 2007 ). In this context, the [Mo₇O₂₄]⁶⁻ heptamolybdate anion has been isolated with numerous different counter-cations such as 4-aminopyridinium, N-pentylammonium, diethylenetriammonium, N,N,N′,N′-tetramethylethylenediammonium, tetramethylammonium, guanidinium, hexanediammonium, butan-1-aminium, ammonium, potassium and sodium (Román et al., 1985 , 1988 , 1990 , 1992 ; Don & Weakly, 1981 ; Gatehouse & Leverett, 1968 ; Sjöbom & Hedman, 1973 ; Niu et al., 1996 ; Himeno et al., 1997 ; Reinoso et al., 2008 ; Ftini, 2015 ; Khandolkar et al., 2016 ). As a continuation of our work in this area (Sarr et al., 2018 ), we now describe the synthesis and structure of the title compound (I), which is notable for the incorporation of both protonated [C₄H₇N₂]⁺ 2-methylimidazolium cations and neutral C₄H₆N₂ 2-methylimidazole molecules in the crystal.

2. Structural commentary

The title compound is characterized by the presence of the familiar [Mo₇O₂₄]⁶⁻ heptamolybdate cluster anion (Fig. 1).

Figure 1
Molecular structure of the [Mo₇O₂₄]⁶⁻ heptamolybdate cluster anion in (I)

There are four categories of oxygen atoms within the polyanion: O_t (terminal oxygen atoms), μ²-O (oxygen atoms bridging two molybdenum atoms), μ³-O (oxygen atoms bridging three molybdenum atoms) and μ⁴-O (oxygen atoms bridging four molybdenum atoms). All of the Mo atoms are bound to two terminal oxygen atoms except for Mo7, which is located in the `core' of the cluster. The geometrical data for the cluster in (I) are consistent with those found in previous studies (Román et al., 1992; Reinoso et al., 2008): the Mo—O bond lengths vary between 1.707 (2) and 1.726 (2) Å for O_t, 1.754 (2)—2.453 (2) Å for μ²-O, 1.8945 (19)–2.3057 (19) Å for μ³-O and 2.1329 (19)–2.3011 (18) Å for μ⁴-O. The variations of Mo—O bond lengths and O—Mo—O angles indicate that all seven octahedra (MoO₆) within the cluster are highly distorted. As in the compound (H₃dien)₂[Mo₇O₂₄]·4H₂O (Román et al., 1988), we note that the longest Mo—O bond length derives from an oxygen atom bridging two molybdenum atoms (μ²-O). As well as the [Mo₇O₂₄]⁶⁻ anion, six (C₄H₇N₂)⁺ cations, two neutral C₄H₆N₂ molecules and two water molecules of crystallization are present in the asymmetric unit (Fig. 2).

Figure 2
The asymmetric unit of (I)

with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

In the crystal, each heptamolybdate anion interacts with six neighbours via the water molecules, (C₄H₇N₂)⁺ cations and/or neutral 2-methylimidazole molecules (Fig. 3). These interactions occur through simple O—H⋯O, N—H⋯O and N—H⋯N and bifurcated N—H⋯(O,O) and O—H⋯(O,O) hydrogen bonds (Table 1) involving three categories of oxygen atoms of the polyanion: O_t, μ²-O and μ³-O. The N—H⋯N hydrogen bonds from N9 and N12 link (C₄H₇N₂)⁺ cations to neutral molecules. The packing is consolidated by weak C—H⋯O links (Table 1). The overall hydrogen-bonding topology is an infinite three-dimensional network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O22ⁱ	0.88 (2)	1.85 (2)	2.710 (3)	167 (2)
N2—H2N⋯O20	0.87 (2)	1.79 (2)	2.655 (3)	172 (2)
N3—H3N⋯O18ⁱ	0.88 (2)	1.87 (2)	2.743 (4)	171 (5)
N4—H4N⋯O9	0.88 (2)	1.79 (2)	2.662 (4)	171 (5)
N5—H5N⋯O12	0.89 (2)	1.77 (3)	2.644 (4)	168 (4)
N6—H6N⋯O3ⁱⁱ	0.90 (2)	1.80 (3)	2.684 (4)	168 (5)
N7—H7N⋯O1ⁱⁱⁱ	0.89 (3)	1.83 (3)	2.697 (4)	167 (3)
N8—H8N⋯O25	0.89 (3)	1.78 (3)	2.659 (4)	172 (5)
N9—H9N⋯N14^iv	0.89 (2)	1.81 (2)	2.698 (4)	177 (3)
N10—H10N⋯O15	0.88 (2)	1.98 (2)	2.852 (3)	174 (3)
N11—H11N⋯O6	0.88 (2)	1.78 (2)	2.636 (3)	166 (3)
N12—H12N⋯N16^v	0.88 (2)	1.87 (2)	2.725 (4)	165 (3)
N13—H13N⋯O5	0.88 (4)	2.32 (4)	3.186 (5)	167 (3)
N13—H13N⋯O8	0.88 (4)	2.55 (4)	3.043 (5)	116 (2)
N15—H15N⋯O14	0.87 (3)	2.22 (3)	2.953 (4)	142 (3)
N15—H15N⋯O17	0.87 (3)	2.27 (3)	2.917 (4)	132 (3)
O25—H25V⋯O19	0.86 (2)	2.00 (2)	2.788 (3)	154 (5)
O25—H25W⋯O26^vi	0.86 (3)	1.85 (3)	2.702 (4)	176 (5)
O26—H26V⋯O10	0.83 (4)	2.50 (6)	2.999 (4)	119 (5)
O26—H26V⋯O13	0.83 (4)	2.25 (5)	3.009 (4)	151 (6)
O26—H26W⋯O7	0.83 (4)	1.99 (6)	2.737 (4)	149 (6)
C4—H4A⋯O8	0.98	2.35	3.228 (5)	149
C8—H8B⋯O2ⁱ	0.98	2.54	3.517 (6)	176
C8—H8C⋯O8	0.98	2.49	3.386 (5)	152
C10—H10⋯O26^vii	0.95	2.45	3.318 (5)	151
C12—H12A⋯O5ⁱⁱ	0.98	2.44	3.407 (5)	167
C13—H13⋯O4ⁱⁱⁱ	0.95	2.50	3.297 (6)	141
C17—H17⋯O2^viii	0.95	2.46	3.154 (4)	130
C18—H18⋯O26	0.95	2.58	3.522 (5)	172
C21—H21⋯O16	0.95	2.46	3.302 (4)	147
C22—H22⋯O11^ix	0.95	2.22	3.113 (4)	156
C24—H24B⋯O7	0.98	2.50	3.346 (5)	145
C25—H25⋯O8	0.95	2.59	3.055 (5)	110
C32—H32B⋯O14	0.98	2.55	3.234 (5)	126
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) -x+1, -y+1, -z+1; (viii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ix) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 3
Detail of the structure of (I)

showing the interconnections of the [Mo₇O₂₄]⁶⁻ anion with its neighbours.

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.40, update November 2018; Groom et al., 2016 ) resulted in 35 hits for the heptamolybdate anion and 90 hits for the 2-methylimidazolium cation.

5. Synthesis and crystallization

Sulfuric acid (2.1 g, 21.7 mmol), 2-methylimidazole (3.5 g, 43.4 mmol) and ammonium heptamolybdate tetrahydrate (2.2 g, 1.8 mmol) in a ratio of 1:2:1/12 were dissolved in water (60 ml). The solution was stirred for one h and evaporated in the oven at 333 K to yield a whitish precipitate. The precipitate was recrystallized from methanol solution: after two weeks at room temperature, colourless prisms of (I) were recovered.

The IR spectrum of (I) is included in the supporting information. The absorption bands at 3400 and 3395 cm⁻¹ correspond to ν(O—H) stretches and indicate the presence of water molecules and those at 1621 and 1564 cm⁻¹ to the deformation vibrations δ(O—H). The bands centered at 3132 and 1431 cm⁻¹ with shoulders are respectively attributed to the stretching and deformation vibrations of the N—H bonds of the protonated and/or non-protonated entities of 2-methylimidazole (Jinnah et al., 2004 ). The bands between 2904–2686 cm⁻¹ are attributed to the stretching vibrations of the C—H bonds, while that at 1291 cm⁻¹ is a δ(C—H) deformation vibration (Jinnah et al., 2004). The two bands at 929 and 900 cm⁻¹ correspond to ν(Mo—Ot) stretching vibrations while the bands between 838 and 650 cm⁻¹ are typical for the vibrations of ν(Mo—O—Mo) and ν[Mo—(μ-O)] groupings (Dey et al., 2011 ).

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms treated by a mixture of independent and constrained refinement were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N—H distances of 0.87 (2), 0.88 (2) and 0.89 (2) Å, Cmethyl—H = 0.97/0.98 Å and Cmethine—H = 0.94/0.95 Å, and with U_iso (H) = 1.2U_eq(C,N) or 1.5U_eq(C-methyl).

Table 2
Experimental details

Crystal data
Chemical formula	(C₄H₇N₂)₆[Mo₇O₂₄]·2C₄H₆N₂·2H₂O
M_r	1754.52
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	170
a, b, c (Å)	16.5325 (2), 17.5842 (2), 19.8873 (2)
β (°)	90.653 (1)
V (Å³)	5781.08 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.56
Crystal size (mm)	0.38 × 0.28 × 0.19

Data collection
Diffractometer	Agilent Xcalibur, Sapphire2
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.476, 0.756
No. of measured, independent and observed [I > 2σ(I)] reflections	104921, 27993, 21593
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.833

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.120, 1.15
No. of reflections	27993
No. of parameters	792
No. of restraints	58
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.83, −2.87
Computer programs: CrysAlis PRO (Agilent, 2014), SIR92 (Altomare et al., 1992 ), SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1922927

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019008454/hb7831sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019008454/hb7831Isup2.hkl

The IR spectrum of compound (I). DOI: https://doi.org/10.1107/S2056989019008454/hb7831sup3.tif

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR92 (Altomare et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Hexakis(2-methyl-1H-imidazol-3-ium) heptamolybdate 2-methyl-1H-imidazole disolvate dihydrate top

Crystal data top

(C₄H₇N₂)₆[Mo₇O₂₄]·2C₄H₆N₂·2H₂O	F(000) = 3456
M_r = 1754.52	D_x = 2.016 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 38522 reflections
a = 16.5325 (2) Å	θ = 3.5–37.4°
b = 17.5842 (2) Å	µ = 1.56 mm⁻¹
c = 19.8873 (2) Å	T = 170 K
β = 90.653 (1)°	Fragment of prism, colourless
V = 5781.08 (11) Å³	0.38 × 0.28 × 0.19 mm
Z = 4

Data collection top

Agilent Xcalibur, Sapphire2, large Be window diffractometer	27993 independent reflections
Radiation source: Enhance (Mo) X-ray Source	21593 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 8.3622 pixels mm^-1	θ_max = 36.3°, θ_min = 3.3°
ω scans	h = −24→27
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −29→29
T_min = 0.476, T_max = 0.756	l = −33→33
104921 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.0397P)² + 11.2859P] where P = (F_o² + 2F_c²)/3
27993 reflections	(Δ/σ)_max = 0.011
792 parameters	Δρ_max = 1.83 e Å⁻³
58 restraints	Δρ_min = −2.87 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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) top

	x	y	z	U_iso*/U_eq
O1	−0.04305 (13)	0.24793 (14)	0.39565 (12)	0.0280 (4)
O2	0.00551 (14)	0.27946 (14)	0.26843 (11)	0.0284 (5)
O3	0.07596 (13)	0.15830 (12)	0.34241 (10)	0.0230 (4)
O4	0.07336 (14)	0.12579 (14)	0.48407 (11)	0.0269 (4)
O5	0.15457 (15)	0.03530 (13)	0.39571 (12)	0.0295 (5)
O6	0.23807 (12)	0.13563 (11)	0.47918 (9)	0.0185 (3)
O7	0.40034 (14)	0.12283 (14)	0.50582 (12)	0.0284 (5)
O8	0.33831 (15)	0.04054 (13)	0.40157 (12)	0.0280 (4)
O9	0.42573 (14)	0.16391 (13)	0.36926 (12)	0.0268 (4)
O10	0.52563 (15)	0.25984 (16)	0.44633 (15)	0.0364 (6)
O11	0.50709 (16)	0.28585 (17)	0.31122 (14)	0.0393 (6)
O12	0.41549 (13)	0.37036 (12)	0.40412 (11)	0.0223 (4)
O13	0.39387 (13)	0.34235 (15)	0.54308 (11)	0.0277 (4)
O14	0.32385 (14)	0.46326 (12)	0.47845 (11)	0.0246 (4)
O15	0.23109 (12)	0.33656 (12)	0.51719 (9)	0.0197 (3)
O16	0.06318 (13)	0.33595 (15)	0.52098 (11)	0.0278 (5)
O17	0.13927 (14)	0.45859 (13)	0.46625 (11)	0.0251 (4)
O18	0.06704 (13)	0.36491 (12)	0.37905 (10)	0.0213 (4)
O19	0.16800 (13)	0.28094 (12)	0.28601 (10)	0.0227 (4)
O20	0.24914 (12)	0.16416 (11)	0.35550 (9)	0.0191 (3)
O21	0.33322 (14)	0.28445 (13)	0.29412 (11)	0.0253 (4)
O22	0.24226 (12)	0.36427 (11)	0.39099 (9)	0.0171 (3)
O23	0.14447 (11)	0.25197 (11)	0.41666 (9)	0.0164 (3)
O24	0.33781 (11)	0.25392 (11)	0.42940 (9)	0.0172 (3)
Mo1	0.042356 (14)	0.264056 (14)	0.348758 (11)	0.01907 (5)
Mo2	0.142420 (14)	0.128403 (13)	0.420960 (11)	0.01805 (4)
Mo3	0.342279 (14)	0.130828 (14)	0.434127 (12)	0.01888 (4)
Mo4	0.454713 (15)	0.269540 (15)	0.383726 (13)	0.02328 (5)
Mo5	0.333156 (14)	0.365314 (13)	0.475739 (11)	0.01745 (4)
Mo6	0.134696 (14)	0.360541 (13)	0.463691 (11)	0.01669 (4)
Mo7	0.248954 (14)	0.271359 (12)	0.343147 (10)	0.01554 (4)
C1	0.2405 (3)	0.0776 (2)	0.1309 (2)	0.0436 (9)
H1	0.235	0.0891	0.0844	0.052*
C2	0.2374 (3)	0.1281 (2)	0.18283 (19)	0.0366 (8)
H2	0.2294	0.1814	0.1794	0.044*
C3	0.25571 (18)	0.01393 (18)	0.22512 (16)	0.0243 (5)
C4	0.2682 (3)	−0.0505 (2)	0.2726 (2)	0.0466 (10)
H4A	0.2705	−0.031	0.3188	0.07*
H4B	0.3192	−0.0763	0.2623	0.07*
H4C	0.2233	−0.0865	0.2681	0.07*
N1	0.25288 (17)	0.00771 (16)	0.15858 (13)	0.0265 (5)
N2	0.24786 (16)	0.08720 (15)	0.24065 (13)	0.0236 (5)
H1N	0.255 (2)	−0.0354 (12)	0.1362 (13)	0.028*
H2N	0.248 (2)	0.1084 (15)	0.2801 (10)	0.028*
C5	0.4466 (3)	0.0710 (3)	0.1457 (2)	0.0472 (10)
H5	0.4409	0.0769	0.0984	0.057*
C6	0.4432 (3)	0.1273 (3)	0.1927 (2)	0.0429 (9)
H6	0.4352	0.1801	0.1847	0.051*
C7	0.46291 (19)	0.0184 (2)	0.2452 (2)	0.0338 (7)
C8	0.4797 (3)	−0.0370 (3)	0.3006 (2)	0.0458 (10)
H8A	0.5322	−0.0253	0.3215	0.069*
H8B	0.4807	−0.0887	0.2822	0.069*
H8C	0.4372	−0.0333	0.3344	0.069*
N3	0.45995 (18)	0.00367 (19)	0.18011 (18)	0.0356 (7)
N4	0.45352 (17)	0.09260 (18)	0.25376 (18)	0.0343 (6)
H3N	0.457 (3)	−0.0409 (12)	0.1597 (14)	0.041*
H4N	0.450 (3)	0.1166 (16)	0.2926 (10)	0.041*
C9	0.4628 (3)	0.5730 (2)	0.3839 (2)	0.0417 (9)
H9	0.4661	0.5816	0.431	0.05*
C10	0.4672 (2)	0.6261 (2)	0.3346 (2)	0.0389 (8)
H10	0.4739	0.6794	0.3407	0.047*
C11	0.45236 (19)	0.5147 (2)	0.28609 (19)	0.0308 (7)
C12	0.4469 (3)	0.4532 (3)	0.2355 (2)	0.0536 (12)
H12A	0.4124	0.4697	0.1979	0.08*
H12B	0.4235	0.4077	0.2561	0.08*
H12C	0.5011	0.4413	0.219	0.08*
N5	0.45244 (17)	0.50405 (18)	0.35196 (16)	0.0316 (6)
N6	0.46028 (17)	0.58857 (17)	0.27414 (16)	0.0316 (6)
H5N	0.446 (3)	0.4604 (12)	0.3735 (13)	0.038*
H6N	0.456 (3)	0.6126 (15)	0.2346 (10)	0.038*
C13	0.4092 (3)	0.3119 (4)	0.0588 (3)	0.0606 (14)
H13	0.4644	0.327	0.0599	0.073*
C14	0.3540 (3)	0.3234 (3)	0.1070 (3)	0.0549 (12)
H14	0.363	0.3476	0.1492	0.066*
C15	0.2921 (3)	0.2642 (2)	0.02298 (19)	0.0364 (8)
C16	0.2296 (4)	0.2267 (3)	−0.0190 (3)	0.0564 (12)
H16A	0.2271	0.1726	−0.0075	0.085*
H16B	0.2433	0.2323	−0.0666	0.085*
H16C	0.177	0.2503	−0.0108	0.085*
N7	0.3698 (2)	0.2740 (2)	0.00784 (19)	0.0475 (9)
N8	0.2818 (2)	0.2935 (2)	0.08359 (17)	0.0398 (7)
H7N	0.3920 (18)	0.263 (3)	−0.0313 (13)	0.048*
H8N	0.2341 (13)	0.301 (3)	0.1029 (17)	0.048*
C17	0.3403 (2)	0.3084 (2)	0.75070 (18)	0.0319 (7)
H17	0.3787	0.2916	0.7834	0.038*
C18	0.34305 (19)	0.2954 (2)	0.68388 (18)	0.0300 (6)
H18	0.3836	0.2681	0.6606	0.036*
C19	0.23323 (18)	0.36274 (19)	0.70469 (15)	0.0251 (5)
C20	0.1568 (2)	0.4053 (3)	0.6948 (2)	0.0404 (9)
H20A	0.119	0.392	0.7305	0.061*
H20B	0.1328	0.392	0.651	0.061*
H20C	0.1679	0.46	0.6962	0.061*
N9	0.27156 (17)	0.35055 (18)	0.76280 (14)	0.0292 (5)
N10	0.27544 (16)	0.32947 (17)	0.65606 (13)	0.0260 (5)
H9N	0.2597 (19)	0.369 (2)	0.8029 (10)	0.031*
H10N	0.2612 (19)	0.328 (2)	0.6133 (9)	0.031*
C21	0.1295 (2)	0.2036 (2)	0.62572 (16)	0.0294 (6)
H21	0.0909	0.2298	0.5985	0.035*
C22	0.12795 (19)	0.1954 (2)	0.69351 (15)	0.0289 (6)
H22	0.0878	0.2144	0.7228	0.035*
C23	0.23697 (19)	0.13713 (18)	0.65689 (14)	0.0241 (5)
C24	0.3139 (2)	0.0943 (2)	0.6550 (2)	0.0356 (7)
H24A	0.3575	0.1257	0.6739	0.053*
H24B	0.3264	0.0813	0.6083	0.053*
H24C	0.3088	0.0476	0.6815	0.053*
N11	0.19766 (16)	0.16674 (17)	0.60401 (12)	0.0262 (5)
N12	0.19571 (16)	0.15416 (17)	0.71190 (12)	0.0257 (5)
H11N	0.2134 (19)	0.164 (2)	0.5621 (9)	0.031*
H12N	0.2122 (19)	0.145 (2)	0.7531 (9)	0.031*
C25	0.3331 (3)	−0.0694 (3)	0.5204 (2)	0.0543 (12)
H25	0.3753	−0.0638	0.4888	0.065*
C26	0.3380 (3)	−0.1023 (3)	0.5821 (2)	0.0498 (11)
H26	0.3853	−0.1248	0.6009	0.06*
C27	0.2140 (3)	−0.0632 (2)	0.5699 (2)	0.0439 (10)
C28	0.1286 (4)	−0.0448 (3)	0.5815 (3)	0.0625 (14)
H28A	0.0994	−0.0912	0.5938	0.094*
H28B	0.1046	−0.0234	0.5404	0.094*
H28C	0.1248	−0.0077	0.618	0.094*
N13	0.2543 (3)	−0.0461 (2)	0.51329 (18)	0.0523 (10)
N14	0.2641 (2)	−0.0981 (2)	0.61320 (16)	0.0421 (8)
H13N	0.2347 (18)	−0.022 (3)	0.4779 (15)	0.05*
C29	0.1459 (2)	0.5736 (2)	0.59154 (18)	0.0331 (7)
H29	0.0966	0.5697	0.5669	0.04*
C30	0.1591 (2)	0.6127 (2)	0.64964 (18)	0.0325 (7)
H30	0.1195	0.6411	0.673	0.039*
C31	0.2732 (2)	0.5611 (2)	0.62385 (16)	0.0289 (6)
C32	0.3600 (2)	0.5372 (3)	0.6246 (2)	0.0472 (11)
H32A	0.3916	0.5723	0.6526	0.071*
H32B	0.3807	0.5378	0.5786	0.071*
H32C	0.3645	0.4856	0.643	0.071*
N15	0.21866 (17)	0.54082 (17)	0.57597 (14)	0.0287 (5)
N16	0.23894 (17)	0.60467 (18)	0.66955 (14)	0.0302 (6)
H15N	0.2266 (18)	0.511 (2)	0.5419 (15)	0.036*
O25	0.14267 (16)	0.30433 (19)	0.14871 (12)	0.0369 (6)
H25V	0.134 (3)	0.300 (3)	0.1909 (10)	0.055*
H25W	0.0957 (17)	0.302 (3)	0.130 (2)	0.055*
O26	0.4963 (2)	0.2100 (2)	0.58818 (17)	0.0519 (8)
H26V	0.482 (4)	0.248 (2)	0.566 (3)	0.078*
H26W	0.482 (4)	0.172 (2)	0.566 (3)	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0214 (9)	0.0333 (12)	0.0294 (11)	−0.0021 (8)	0.0030 (8)	0.0072 (9)
O2	0.0330 (11)	0.0339 (12)	0.0182 (9)	−0.0065 (9)	−0.0104 (8)	0.0047 (8)
O3	0.0288 (10)	0.0217 (9)	0.0183 (9)	−0.0051 (8)	−0.0051 (7)	0.0004 (7)
O4	0.0258 (10)	0.0345 (12)	0.0206 (9)	−0.0030 (9)	0.0017 (8)	0.0070 (8)
O5	0.0382 (12)	0.0218 (10)	0.0285 (11)	−0.0060 (9)	−0.0035 (9)	−0.0020 (8)
O6	0.0218 (8)	0.0208 (9)	0.0129 (7)	−0.0003 (7)	0.0016 (6)	0.0024 (6)
O7	0.0255 (10)	0.0328 (12)	0.0268 (11)	0.0018 (9)	−0.0034 (8)	0.0067 (9)
O8	0.0375 (12)	0.0221 (10)	0.0247 (10)	0.0050 (9)	0.0080 (9)	0.0008 (8)
O9	0.0295 (10)	0.0258 (10)	0.0253 (10)	0.0044 (8)	0.0119 (8)	0.0025 (8)
O10	0.0240 (11)	0.0398 (14)	0.0452 (15)	0.0009 (10)	−0.0018 (10)	0.0059 (12)
O11	0.0371 (13)	0.0433 (15)	0.0379 (14)	0.0011 (11)	0.0227 (11)	0.0077 (11)
O12	0.0239 (9)	0.0206 (9)	0.0223 (9)	−0.0029 (7)	0.0041 (7)	0.0025 (7)
O13	0.0233 (10)	0.0389 (13)	0.0206 (9)	−0.0016 (9)	−0.0060 (8)	0.0031 (9)
O14	0.0312 (10)	0.0204 (9)	0.0222 (9)	−0.0040 (8)	−0.0020 (8)	−0.0034 (7)
O15	0.0219 (9)	0.0257 (9)	0.0116 (7)	−0.0001 (7)	−0.0011 (6)	0.0004 (7)
O16	0.0256 (10)	0.0402 (13)	0.0177 (9)	0.0037 (9)	0.0059 (8)	0.0036 (8)
O17	0.0310 (11)	0.0228 (10)	0.0215 (9)	0.0033 (8)	−0.0038 (8)	−0.0032 (7)
O18	0.0242 (9)	0.0206 (9)	0.0189 (9)	0.0013 (7)	−0.0031 (7)	0.0008 (7)
O19	0.0306 (10)	0.0237 (9)	0.0137 (8)	−0.0029 (8)	−0.0038 (7)	0.0018 (7)
O20	0.0283 (9)	0.0160 (8)	0.0129 (7)	−0.0013 (7)	0.0032 (7)	−0.0007 (6)
O21	0.0321 (11)	0.0255 (10)	0.0186 (9)	0.0004 (8)	0.0110 (8)	0.0020 (7)
O22	0.0229 (8)	0.0167 (8)	0.0117 (7)	−0.0007 (6)	0.0003 (6)	−0.0007 (6)
O23	0.0187 (8)	0.0189 (8)	0.0117 (7)	−0.0014 (6)	0.0007 (6)	0.0008 (6)
O24	0.0198 (8)	0.0175 (8)	0.0143 (7)	0.0004 (6)	0.0029 (6)	0.0014 (6)
Mo1	0.01912 (9)	0.02215 (10)	0.01584 (9)	−0.00268 (8)	−0.00351 (7)	0.00174 (7)
Mo2	0.02159 (10)	0.01762 (9)	0.01494 (9)	−0.00348 (7)	−0.00019 (7)	0.00209 (7)
Mo3	0.02075 (10)	0.01832 (10)	0.01763 (9)	0.00146 (8)	0.00352 (7)	0.00293 (7)
Mo4	0.01970 (10)	0.02472 (11)	0.02561 (11)	0.00006 (8)	0.00868 (8)	0.00360 (9)
Mo5	0.01950 (9)	0.01916 (10)	0.01367 (9)	−0.00115 (7)	−0.00133 (7)	−0.00076 (7)
Mo6	0.01876 (9)	0.01945 (10)	0.01188 (8)	0.00120 (7)	0.00054 (7)	−0.00103 (7)
Mo7	0.02116 (9)	0.01513 (9)	0.01035 (8)	−0.00110 (7)	0.00168 (7)	−0.00035 (6)
C1	0.069 (3)	0.0360 (19)	0.0254 (16)	0.0063 (19)	−0.0037 (17)	−0.0048 (14)
C2	0.054 (2)	0.0268 (15)	0.0291 (16)	0.0069 (15)	−0.0016 (15)	−0.0060 (12)
C3	0.0225 (12)	0.0242 (13)	0.0263 (13)	0.0004 (10)	0.0014 (10)	−0.0075 (10)
C4	0.076 (3)	0.0280 (17)	0.036 (2)	−0.0038 (18)	0.002 (2)	−0.0050 (15)
N1	0.0293 (12)	0.0281 (12)	0.0222 (11)	0.0017 (10)	0.0000 (9)	−0.0128 (9)
N2	0.0248 (11)	0.0248 (11)	0.0211 (11)	0.0002 (9)	0.0014 (9)	−0.0092 (9)
C5	0.052 (2)	0.051 (3)	0.038 (2)	0.000 (2)	−0.0123 (18)	−0.0113 (18)
C6	0.047 (2)	0.041 (2)	0.041 (2)	0.0030 (17)	−0.0089 (17)	−0.0061 (17)
C7	0.0215 (13)	0.0335 (17)	0.047 (2)	−0.0041 (12)	0.0096 (13)	−0.0113 (14)
C8	0.045 (2)	0.046 (2)	0.046 (2)	0.0079 (18)	0.0100 (18)	−0.0030 (18)
N3	0.0256 (13)	0.0373 (16)	0.0439 (17)	−0.0015 (11)	0.0025 (12)	−0.0179 (13)
N4	0.0231 (12)	0.0330 (15)	0.0469 (18)	−0.0027 (11)	0.0027 (11)	−0.0127 (13)
C9	0.050 (2)	0.037 (2)	0.038 (2)	−0.0067 (17)	0.0036 (17)	0.0054 (15)
C10	0.043 (2)	0.0313 (17)	0.043 (2)	−0.0031 (15)	0.0023 (16)	0.0063 (15)
C11	0.0230 (13)	0.0311 (15)	0.0380 (17)	−0.0034 (11)	−0.0103 (12)	0.0118 (13)
C12	0.073 (3)	0.040 (2)	0.047 (2)	−0.004 (2)	−0.020 (2)	0.0017 (19)
N5	0.0250 (12)	0.0308 (14)	0.0389 (16)	−0.0056 (10)	−0.0032 (11)	0.0133 (12)
N6	0.0261 (12)	0.0306 (14)	0.0380 (15)	−0.0036 (10)	−0.0054 (11)	0.0120 (12)
C13	0.037 (2)	0.077 (4)	0.068 (3)	0.002 (2)	0.012 (2)	−0.008 (3)
C14	0.045 (2)	0.070 (3)	0.050 (3)	−0.003 (2)	0.005 (2)	−0.020 (2)
C15	0.047 (2)	0.0326 (17)	0.0296 (16)	0.0093 (15)	0.0081 (14)	0.0016 (13)
C16	0.077 (4)	0.044 (3)	0.047 (3)	0.002 (2)	−0.011 (2)	−0.005 (2)
N7	0.053 (2)	0.052 (2)	0.0381 (18)	0.0154 (17)	0.0202 (16)	0.0027 (16)
N8	0.0393 (16)	0.0454 (19)	0.0350 (16)	0.0044 (14)	0.0116 (13)	−0.0041 (14)
C17	0.0242 (13)	0.0393 (18)	0.0321 (16)	0.0027 (12)	−0.0053 (12)	0.0007 (13)
C18	0.0220 (13)	0.0359 (17)	0.0322 (16)	0.0035 (12)	0.0030 (11)	−0.0006 (13)
C19	0.0228 (12)	0.0309 (15)	0.0215 (12)	0.0022 (11)	0.0018 (10)	−0.0001 (10)
C20	0.0333 (17)	0.048 (2)	0.040 (2)	0.0146 (16)	−0.0022 (14)	0.0057 (17)
N9	0.0293 (13)	0.0380 (15)	0.0203 (11)	0.0040 (11)	−0.0012 (9)	−0.0007 (10)
N10	0.0266 (12)	0.0338 (13)	0.0177 (10)	−0.0006 (10)	0.0024 (9)	−0.0001 (9)
C21	0.0277 (14)	0.0417 (18)	0.0190 (12)	0.0009 (13)	0.0000 (10)	0.0026 (12)
C22	0.0268 (13)	0.0415 (18)	0.0187 (12)	−0.0004 (12)	0.0069 (10)	0.0002 (11)
C23	0.0288 (13)	0.0282 (14)	0.0155 (11)	−0.0015 (11)	0.0017 (10)	−0.0007 (9)
C24	0.0362 (17)	0.0365 (18)	0.0343 (17)	0.0089 (14)	0.0056 (14)	0.0012 (14)
N11	0.0289 (12)	0.0374 (14)	0.0124 (9)	−0.0002 (10)	0.0027 (8)	0.0008 (9)
N12	0.0293 (12)	0.0347 (14)	0.0132 (9)	−0.0017 (10)	0.0013 (8)	0.0037 (9)
C25	0.081 (3)	0.039 (2)	0.043 (2)	0.008 (2)	0.026 (2)	0.0121 (18)
C26	0.066 (3)	0.042 (2)	0.042 (2)	0.003 (2)	0.013 (2)	0.0089 (18)
C27	0.074 (3)	0.0266 (16)	0.0306 (17)	−0.0031 (18)	0.0014 (18)	0.0015 (13)
C28	0.075 (4)	0.054 (3)	0.058 (3)	−0.001 (3)	−0.006 (3)	0.005 (2)
N13	0.095 (3)	0.0330 (17)	0.0288 (16)	0.0064 (19)	0.0075 (18)	0.0112 (13)
N14	0.065 (2)	0.0348 (16)	0.0260 (14)	−0.0038 (15)	0.0053 (14)	0.0052 (12)
C29	0.0285 (15)	0.0419 (19)	0.0286 (15)	0.0052 (13)	−0.0094 (12)	−0.0013 (13)
C30	0.0307 (15)	0.0369 (17)	0.0298 (15)	0.0115 (13)	−0.0028 (12)	−0.0057 (13)
C31	0.0290 (14)	0.0355 (16)	0.0222 (13)	0.0043 (12)	−0.0059 (11)	−0.0094 (12)
C32	0.0322 (18)	0.068 (3)	0.041 (2)	0.0155 (19)	−0.0086 (15)	−0.019 (2)
N15	0.0315 (13)	0.0327 (14)	0.0217 (11)	0.0048 (11)	−0.0046 (10)	−0.0109 (10)
N16	0.0302 (13)	0.0364 (15)	0.0240 (12)	0.0088 (11)	−0.0057 (10)	−0.0092 (11)
O25	0.0344 (12)	0.0563 (17)	0.0199 (10)	0.0001 (12)	0.0025 (9)	0.0003 (11)
O26	0.066 (2)	0.0466 (18)	0.0422 (17)	−0.0038 (16)	−0.0272 (15)	0.0040 (14)

Geometric parameters (Å, º) top

O1—Mo1	1.724 (2)	C11—N6	1.328 (4)
O2—Mo1	1.725 (2)	C11—C12	1.479 (6)
O3—Mo1	1.945 (2)	C12—H12A	0.98
O3—Mo2	1.971 (2)	C12—H12B	0.98
O4—Mo2	1.707 (2)	C12—H12C	0.98
O5—Mo2	1.725 (2)	N5—H5N	0.886 (17)
O6—Mo3	1.9528 (19)	N6—H6N	0.895 (17)
O6—Mo2	1.953 (2)	C13—C14	1.347 (7)
O7—Mo3	1.715 (2)	C13—N7	1.372 (7)
O8—Mo3	1.716 (2)	C13—H13	0.95
O9—Mo4	1.939 (2)	C14—N8	1.379 (6)
O9—Mo3	1.987 (2)	C14—H14	0.95
O10—Mo4	1.709 (3)	C15—N8	1.324 (5)
O11—Mo4	1.715 (2)	C15—N7	1.333 (5)
O12—Mo4	1.932 (2)	C15—C16	1.476 (6)
O12—Mo5	1.983 (2)	C16—H16A	0.98
O13—Mo5	1.713 (2)	C16—H16B	0.98
O14—Mo5	1.730 (2)	C16—H16C	0.98
O15—Mo6	1.9521 (19)	N7—H7N	0.887 (17)
O15—Mo5	1.953 (2)	N8—H8N	0.893 (17)
O16—Mo6	1.707 (2)	C17—C18	1.350 (5)
O17—Mo6	1.726 (2)	C17—N9	1.380 (4)
O18—Mo1	1.916 (2)	C17—H17	0.95
O18—Mo6	2.012 (2)	C18—N10	1.379 (4)
O19—Mo7	1.754 (2)	C18—H18	0.95
O19—Mo1	2.453 (2)	C19—N9	1.329 (4)
O20—Mo7	1.901 (2)	C19—N10	1.334 (4)
O20—Mo3	2.259 (2)	C19—C20	1.480 (5)
O20—Mo2	2.292 (2)	C20—H20A	0.98
O21—Mo7	1.725 (2)	C20—H20B	0.98
O22—Mo7	1.8945 (19)	C20—H20C	0.98
O22—Mo5	2.2453 (19)	N9—H9N	0.886 (17)
O22—Mo6	2.3057 (19)	N10—H10N	0.880 (17)
O23—Mo6	2.1329 (19)	C21—C22	1.356 (4)
O23—Mo1	2.1604 (19)	C21—N11	1.374 (4)
O23—Mo2	2.1748 (19)	C21—H21	0.95
O23—Mo7	2.3011 (18)	C22—N12	1.380 (4)
O24—Mo4	2.1624 (19)	C22—H22	0.95
O24—Mo5	2.1665 (19)	C23—N12	1.330 (4)
O24—Mo3	2.1677 (19)	C23—N11	1.336 (4)
O24—Mo7	2.2665 (19)	C23—C24	1.479 (5)
Mo1—Mo6	3.2178 (3)	C24—H24A	0.98
Mo4—Mo5	3.2105 (3)	C24—H24B	0.98
C1—C2	1.362 (5)	C24—H24C	0.98
C1—N1	1.362 (5)	N11—H11N	0.877 (17)
C1—H1	0.95	N12—H12N	0.876 (17)
C2—N2	1.365 (5)	C25—C26	1.357 (6)
C2—H2	0.95	C25—N13	1.371 (7)
C3—N1	1.328 (4)	C25—H25	0.95
C3—N2	1.332 (4)	C26—N14	1.377 (6)
C3—C4	1.488 (5)	C26—H26	0.95
C4—H4A	0.98	C27—N14	1.338 (6)
C4—H4B	0.98	C27—N13	1.348 (6)
C4—H4C	0.98	C27—C28	1.470 (8)
N1—H1N	0.881 (17)	C28—H28A	0.98
N2—H2N	0.868 (17)	C28—H28B	0.98
C5—C6	1.363 (6)	C28—H28C	0.98
C5—N3	1.384 (6)	N13—H13N	0.880 (19)
C5—H5	0.95	C29—C30	1.360 (5)
C6—N4	1.367 (6)	C29—N15	1.372 (4)
C6—H6	0.95	C29—H29	0.95
C7—N3	1.321 (5)	C30—N16	1.380 (4)
C7—N4	1.325 (5)	C30—H30	0.95
C7—C8	1.493 (6)	C31—N16	1.321 (4)
C8—H8A	0.98	C31—N15	1.352 (4)
C8—H8B	0.98	C31—C32	1.495 (5)
C8—H8C	0.98	C32—H32A	0.98
N3—H3N	0.884 (17)	C32—H32B	0.98
N4—H4N	0.884 (17)	C32—H32C	0.98
C9—C10	1.357 (6)	N15—H15N	0.867 (19)
C9—N5	1.378 (5)	O25—H25V	0.857 (19)
C9—H9	0.95	O25—H25W	0.856 (18)
C10—N6	1.375 (5)	O26—H26V	0.842 (19)
C10—H10	0.95	O26—H26W	0.843 (19)
C11—N5	1.323 (5)

Mo1—O3—Mo2	111.13 (10)	C3—C4—H4A	109.5
Mo3—O6—Mo2	115.96 (9)	C3—C4—H4B	109.5
Mo4—O9—Mo3	110.89 (11)	H4A—C4—H4B	109.5
Mo4—O12—Mo5	110.14 (10)	C3—C4—H4C	109.5
Mo6—O15—Mo5	114.70 (9)	H4A—C4—H4C	109.5
Mo1—O18—Mo6	110.01 (10)	H4B—C4—H4C	109.5
Mo7—O19—Mo1	107.64 (9)	C3—N1—C1	109.4 (3)
Mo7—O20—Mo3	110.29 (9)	C3—N1—H1N	125.1 (19)
Mo7—O20—Mo2	110.20 (9)	C1—N1—H1N	125.4 (19)
Mo3—O20—Mo2	93.36 (7)	C3—N2—C2	109.0 (3)
Mo7—O22—Mo5	109.98 (9)	C3—N2—H2N	128.7 (19)
Mo7—O22—Mo6	109.89 (9)	C2—N2—H2N	122.3 (19)
Mo5—O22—Mo6	92.51 (7)	C6—C5—N3	106.9 (4)
Mo6—O23—Mo1	97.09 (8)	C6—C5—H5	126.6
Mo6—O23—Mo2	151.14 (9)	N3—C5—H5	126.6
Mo1—O23—Mo2	96.34 (7)	C5—C6—N4	106.2 (4)
Mo6—O23—Mo7	101.96 (8)	C5—C6—H6	126.9
Mo1—O23—Mo7	100.09 (7)	N4—C6—H6	126.9
Mo2—O23—Mo7	100.67 (7)	N3—C7—N4	108.4 (4)
Mo4—O24—Mo5	95.74 (8)	N3—C7—C8	126.8 (4)
Mo4—O24—Mo3	96.60 (8)	N4—C7—C8	124.7 (4)
Mo5—O24—Mo3	152.34 (9)	C7—C8—H8A	109.5
Mo4—O24—Mo7	103.86 (7)	C7—C8—H8B	109.5
Mo5—O24—Mo7	100.00 (8)	H8A—C8—H8B	109.5
Mo3—O24—Mo7	100.92 (8)	C7—C8—H8C	109.5
O1—Mo1—O2	104.12 (11)	H8A—C8—H8C	109.5
O1—Mo1—O18	98.92 (11)	H8B—C8—H8C	109.5
O2—Mo1—O18	102.57 (10)	C7—N3—C5	108.7 (3)
O1—Mo1—O3	96.55 (11)	C7—N3—H3N	129 (2)
O2—Mo1—O3	100.84 (10)	C5—N3—H3N	122 (2)
O18—Mo1—O3	147.73 (9)	C7—N4—C6	109.9 (3)
O1—Mo1—O23	106.54 (9)	C7—N4—H4N	126 (2)
O2—Mo1—O23	149.29 (10)	C6—N4—H4N	124 (2)
O18—Mo1—O23	74.47 (8)	C10—C9—N5	106.3 (4)
O3—Mo1—O23	74.03 (8)	C10—C9—H9	126.9
O1—Mo1—O19	176.53 (9)	N5—C9—H9	126.9
O2—Mo1—O19	78.58 (10)	C9—C10—N6	107.2 (4)
O18—Mo1—O19	82.49 (8)	C9—C10—H10	126.4
O3—Mo1—O19	80.71 (8)	N6—C10—H10	126.4
O23—Mo1—O19	70.72 (7)	N5—C11—N6	108.4 (3)
O1—Mo1—Mo6	95.01 (8)	N5—C11—C12	124.7 (3)
O2—Mo1—Mo6	137.30 (8)	N6—C11—C12	126.8 (4)
O18—Mo1—Mo6	35.98 (6)	C11—C12—H12A	109.5
O3—Mo1—Mo6	114.62 (6)	C11—C12—H12B	109.5
O23—Mo1—Mo6	41.13 (5)	H12A—C12—H12B	109.5
O19—Mo1—Mo6	84.26 (5)	C11—C12—H12C	109.5
O4—Mo2—O5	105.64 (12)	H12A—C12—H12C	109.5
O4—Mo2—O6	96.30 (9)	H12B—C12—H12C	109.5
O5—Mo2—O6	97.94 (10)	C11—N5—C9	109.3 (3)
O4—Mo2—O3	102.62 (10)	C11—N5—H5N	127.0 (19)
O5—Mo2—O3	95.05 (10)	C9—N5—H5N	123.7 (19)
O6—Mo2—O3	153.21 (8)	C11—N6—C10	108.7 (3)
O4—Mo2—O23	93.82 (10)	C11—N6—H6N	127.8 (19)
O5—Mo2—O23	159.22 (10)	C10—N6—H6N	123.1 (19)
O6—Mo2—O23	86.87 (8)	C14—C13—N7	106.2 (4)
O3—Mo2—O23	73.22 (8)	C14—C13—H13	126.9
O4—Mo2—O20	161.90 (10)	N7—C13—H13	126.9
O5—Mo2—O20	90.12 (10)	C13—C14—N8	107.0 (4)
O6—Mo2—O20	72.28 (7)	C13—C14—H14	126.5
O3—Mo2—O20	84.40 (8)	N8—C14—H14	126.5
O23—Mo2—O20	72.01 (7)	N8—C15—N7	106.8 (4)
O8—Mo3—O7	104.86 (12)	N8—C15—C16	126.4 (4)
O8—Mo3—O6	100.55 (10)	N7—C15—C16	126.8 (4)
O7—Mo3—O6	96.34 (10)	C15—C16—H16A	109.5
O8—Mo3—O9	92.85 (10)	C15—C16—H16B	109.5
O7—Mo3—O9	100.23 (11)	H16A—C16—H16B	109.5
O6—Mo3—O9	155.25 (9)	C15—C16—H16C	109.5
O8—Mo3—O24	155.03 (9)	H16A—C16—H16C	109.5
O7—Mo3—O24	97.84 (10)	H16B—C16—H16C	109.5
O6—Mo3—O24	86.96 (8)	C15—N7—C13	110.3 (4)
O9—Mo3—O24	72.72 (8)	C15—N7—H7N	125 (2)
O8—Mo3—O20	87.48 (10)	C13—N7—H7N	124 (2)
O7—Mo3—O20	165.23 (10)	C15—N8—C14	109.7 (4)
O6—Mo3—O20	73.05 (7)	C15—N8—H8N	125 (2)
O9—Mo3—O20	86.99 (9)	C14—N8—H8N	124 (2)
O24—Mo3—O20	71.84 (7)	C18—C17—N9	107.4 (3)
O10—Mo4—O11	106.30 (14)	C18—C17—H17	126.3
O10—Mo4—O12	99.66 (12)	N9—C17—H17	126.3
O11—Mo4—O12	101.36 (12)	C17—C18—N10	106.6 (3)
O10—Mo4—O9	100.30 (12)	C17—C18—H18	126.7
O11—Mo4—O9	99.31 (12)	N10—C18—H18	126.7
O12—Mo4—O9	145.80 (9)	N9—C19—N10	108.1 (3)
O10—Mo4—O24	106.87 (10)	N9—C19—C20	126.5 (3)
O11—Mo4—O24	146.81 (11)	N10—C19—C20	125.3 (3)
O12—Mo4—O24	74.02 (8)	C19—C20—H20A	109.5
O9—Mo4—O24	73.74 (8)	C19—C20—H20B	109.5
O10—Mo4—Mo5	93.77 (10)	H20A—C20—H20B	109.5
O11—Mo4—Mo5	135.81 (10)	C19—C20—H20C	109.5
O12—Mo4—Mo5	35.45 (6)	H20A—C20—H20C	109.5
O9—Mo4—Mo5	115.58 (6)	H20B—C20—H20C	109.5
O24—Mo4—Mo5	42.18 (5)	C19—N9—C17	108.7 (3)
O13—Mo5—O14	105.18 (11)	C19—N9—H9N	128.0 (19)
O13—Mo5—O15	96.34 (10)	C17—N9—H9N	123.0 (19)
O14—Mo5—O15	99.61 (10)	C19—N10—C18	109.2 (3)
O13—Mo5—O12	99.85 (10)	C19—N10—H10N	125.4 (19)
O14—Mo5—O12	92.28 (10)	C18—N10—H10N	125.4 (19)
O15—Mo5—O12	156.65 (9)	C22—C21—N11	106.6 (3)
O13—Mo5—O24	95.51 (10)	C22—C21—H21	126.7
O14—Mo5—O24	156.48 (9)	N11—C21—H21	126.7
O15—Mo5—O24	88.88 (8)	C21—C22—N12	107.2 (3)
O12—Mo5—O24	72.96 (8)	C21—C22—H22	126.4
O13—Mo5—O22	165.08 (10)	N12—C22—H22	126.4
O14—Mo5—O22	88.42 (9)	N12—C23—N11	108.1 (3)
O15—Mo5—O22	74.97 (7)	N12—C23—C24	125.8 (3)
O12—Mo5—O22	85.42 (8)	N11—C23—C24	126.1 (3)
O24—Mo5—O22	72.54 (7)	C23—C24—H24A	109.5
O13—Mo5—Mo4	87.53 (8)	C23—C24—H24B	109.5
O14—Mo5—Mo4	126.61 (8)	H24A—C24—H24B	109.5
O15—Mo5—Mo4	130.86 (6)	C23—C24—H24C	109.5
O12—Mo5—Mo4	34.41 (6)	H24A—C24—H24C	109.5
O24—Mo5—Mo4	42.08 (5)	H24B—C24—H24C	109.5
O22—Mo5—Mo4	89.18 (5)	C23—N11—C21	109.3 (2)
O16—Mo6—O17	105.29 (12)	C23—N11—H11N	125.3 (18)
O16—Mo6—O15	98.56 (10)	C21—N11—H11N	125.4 (18)
O17—Mo6—O15	99.46 (10)	C23—N12—C22	108.8 (2)
O16—Mo6—O18	100.69 (10)	C23—N12—H12N	124.9 (19)
O17—Mo6—O18	90.59 (9)	C22—N12—H12N	125.9 (19)
O15—Mo6—O18	155.08 (8)	C26—C25—N13	105.5 (4)
O16—Mo6—O23	97.03 (10)	C26—C25—H25	127.2
O17—Mo6—O23	154.60 (9)	N13—C25—H25	127.2
O15—Mo6—O23	88.86 (8)	C25—C26—N14	109.8 (5)
O18—Mo6—O23	73.23 (8)	C25—C26—H26	125.1
O16—Mo6—O22	166.13 (10)	N14—C26—H26	125.1
O17—Mo6—O22	87.49 (9)	N14—C27—N13	109.4 (4)
O15—Mo6—O22	73.58 (7)	N14—C27—C28	126.1 (4)
O18—Mo6—O22	84.24 (8)	N13—C27—C28	124.5 (4)
O23—Mo6—O22	71.80 (7)	C27—C28—H28A	109.5
O16—Mo6—Mo1	90.80 (8)	C27—C28—H28B	109.5
O17—Mo6—Mo1	124.59 (7)	H28A—C28—H28B	109.5
O15—Mo6—Mo1	130.62 (6)	C27—C28—H28C	109.5
O18—Mo6—Mo1	34.01 (6)	H28A—C28—H28C	109.5
O23—Mo6—Mo1	41.78 (5)	H28B—C28—H28C	109.5
O22—Mo6—Mo1	86.14 (5)	C27—N13—C25	108.9 (4)
O21—Mo7—O19	103.66 (11)	C27—N13—H13N	126 (2)
O21—Mo7—O22	102.76 (10)	C25—N13—H13N	125 (2)
O19—Mo7—O22	101.19 (9)	C27—N14—C26	106.3 (4)
O21—Mo7—O20	101.84 (10)	C30—C29—N15	105.7 (3)
O19—Mo7—O20	100.32 (9)	C30—C29—H29	127.1
O22—Mo7—O20	142.21 (8)	N15—C29—H29	127.1
O21—Mo7—O24	85.71 (9)	C29—C30—N16	109.6 (3)
O19—Mo7—O24	170.59 (8)	C29—C30—H30	125.2
O22—Mo7—O24	77.15 (8)	N16—C30—H30	125.2
O20—Mo7—O24	76.58 (8)	N16—C31—N15	110.4 (3)
O21—Mo7—O23	174.78 (9)	N16—C31—C32	125.2 (3)
O19—Mo7—O23	81.55 (8)	N15—C31—C32	124.4 (3)
O22—Mo7—O23	76.12 (8)	C31—C32—H32A	109.5
O20—Mo7—O23	76.77 (8)	C31—C32—H32B	109.5
O24—Mo7—O23	89.07 (6)	H32A—C32—H32B	109.5
C2—C1—N1	106.8 (3)	C31—C32—H32C	109.5
C2—C1—H1	126.6	H32A—C32—H32C	109.5
N1—C1—H1	126.6	H32B—C32—H32C	109.5
C1—C2—N2	106.9 (3)	C31—N15—C29	108.1 (3)
C1—C2—H2	126.6	C31—N15—H15N	127.1 (19)
N2—C2—H2	126.6	C29—N15—H15N	124.8 (19)
N1—C3—N2	108.0 (3)	C31—N16—C30	106.1 (3)
N1—C3—C4	125.0 (3)	H25V—O25—H25W	105 (3)
N2—C3—C4	127.0 (3)	H26V—O26—H26W	107 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O22ⁱ	0.88 (2)	1.85 (2)	2.710 (3)	167 (2)
N2—H2N···O20	0.87 (2)	1.79 (2)	2.655 (3)	172 (2)
N3—H3N···O18ⁱ	0.88 (2)	1.87 (2)	2.743 (4)	171 (5)
N4—H4N···O9	0.88 (2)	1.79 (2)	2.662 (4)	171 (5)
N5—H5N···O12	0.89 (2)	1.77 (3)	2.644 (4)	168 (4)
N6—H6N···O3ⁱⁱ	0.90 (2)	1.80 (3)	2.684 (4)	168 (5)
N7—H7N···O1ⁱⁱⁱ	0.89 (3)	1.83 (3)	2.697 (4)	167 (3)
N8—H8N···O25	0.89 (3)	1.78 (3)	2.659 (4)	172 (5)
N9—H9N···N14^iv	0.89 (2)	1.81 (2)	2.698 (4)	177 (3)
N10—H10N···O15	0.88 (2)	1.98 (2)	2.852 (3)	174 (3)
N11—H11N···O6	0.88 (2)	1.78 (2)	2.636 (3)	166 (3)
N12—H12N···N16^v	0.88 (2)	1.87 (2)	2.725 (4)	165 (3)
N13—H13N···O5	0.88 (4)	2.32 (4)	3.186 (5)	167 (3)
N13—H13N···O8	0.88 (4)	2.55 (4)	3.043 (5)	116 (2)
N15—H15N···O14	0.87 (3)	2.22 (3)	2.953 (4)	142 (3)
N15—H15N···O17	0.87 (3)	2.27 (3)	2.917 (4)	132 (3)
O25—H25V···O19	0.86 (2)	2.00 (2)	2.788 (3)	154 (5)
O25—H25W···O26^vi	0.86 (3)	1.85 (3)	2.702 (4)	176 (5)
O26—H26V···O10	0.83 (4)	2.50 (6)	2.999 (4)	119 (5)
O26—H26V···O13	0.83 (4)	2.25 (5)	3.009 (4)	151 (6)
O26—H26W···O7	0.83 (4)	1.99 (6)	2.737 (4)	149 (6)
C4—H4A···O8	0.98	2.35	3.228 (5)	149
C8—H8B···O2ⁱ	0.98	2.54	3.517 (6)	176
C8—H8C···O8	0.98	2.49	3.386 (5)	152
C10—H10···O26^vii	0.95	2.45	3.318 (5)	151
C12—H12A···O5ⁱⁱ	0.98	2.44	3.407 (5)	167
C13—H13···O4ⁱⁱⁱ	0.95	2.50	3.297 (6)	141
C17—H17···O2^viii	0.95	2.46	3.154 (4)	130
C18—H18···O26	0.95	2.58	3.522 (5)	172
C21—H21···O16	0.95	2.46	3.302 (4)	147
C22—H22···O11^ix	0.95	2.22	3.113 (4)	156
C24—H24B···O7	0.98	2.50	3.346 (5)	145
C25—H25···O8	0.95	2.59	3.055 (5)	110
C32—H32B···O14	0.98	2.55	3.234 (5)	126

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

Acknowledgements

The authors thank the Université Cheikh Anta Diop Dakar-Sénégal, the Laboratoire de Chimie et de Physique des Matériaux (LCPM) de l'Université Assane Seck de Ziguinchor, Sénégal and the service commun d'analyse par diffraction des rayons X, Universitée de Bretagne Occidentale, France for financial support. All measurements were performed in the institutes above quoted.

References

Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1992). J. Appl. Cryst. 27, 435. CrossRef IUCr Journals Google Scholar
Coué, V., Dessapt, R., Bujoli-Doeuff, M., Evain, M. & Jobic, S. (2007). Inorg. Chem. 46, 2824–2835. PubMed Google Scholar
Dey, C. D., Das, R., Pachfule, P., Poddar, P. & Banerjee, R. (2011). Cryst. Growth Des. 11, 139–146. CSD CrossRef CAS Google Scholar
Don, A. & Weakley, T. J. R. (1981). Acta Cryst. B37, 451–453. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ftini, M. M. (2015). J. Struct. Chem. 56, 1595–1601. CSD CrossRef CAS Google Scholar
Gatehouse, B. M. & Leverett, P. (1968). Chem. Commun. pp. 901–902. Google Scholar
Gerth, H. U. V., Rompel, A., Krebs, B., Boos, J. & Lanvers-Kaminsky, C. (2005). Anticancer Drugs, 16, 101–106. Web of Science CrossRef PubMed CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hasenknopf, B. (2005). Front. Biosci. 10, 275–287. Web of Science CrossRef PubMed CAS Google Scholar
Himeno, S., Niiya, H. & Ueda, T. (1997). Bull. Chem. Soc. Jpn, 70, 631–637. CrossRef CAS Web of Science Google Scholar
Jinnah, M. M. A., Umadevi, M. & Ramakrishnan, V. (2004). J. Raman Spectrosc. 35, 956–960. CrossRef CAS Google Scholar
Katsoulis, D. E. (1998). Chem. Rev. 98, 359–388. Web of Science CrossRef PubMed CAS Google Scholar
Khandolkar, S. S., Naik, A. R., Näther, C., Bensch, W. & Srinivasan, B. R. (2016). J. Chem. Sci. 128, 1737–1744. CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Niu, J.-Y., You, X.-Z., Fun, H.-K., Zhou, Z.-Y. & Yip, B.-C. (1996). Polyhedron, 15, 1003–1008. CAS Google Scholar
Reinoso, S., Dickman, M. H., Praetorius, A. & Kortz, U. (2008). Acta Cryst. E64, m614–m615. Web of Science CSD CrossRef IUCr Journals Google Scholar
Román, P., Gutiérrez-Zorrilla, J. M., Luque, A. & Martínez-Ripoll, M. (1988). J. Crystallogr. Spectrosc. Res. 18, 117–131. Google Scholar
Román, P., Gutiérrez-Zorrilla, J. M., Martínez-Ripoll, M. & García-Blanco, S. (1985). Z. Kristallogr. 173, 283–292. Google Scholar
Román, P., Luque, A., Aranzabe, A. & Gutiérrez-Zorrilla, J. M. (1992). Polyhedron, 11, 2027–2038. Google Scholar
Román, P., Luque, A., Gutiérrez-Zorrilla, J. M. & Zuniga, F. J. (1990). Z. Kristallogr. 190, 249–258. Google Scholar
Sarr, B., Diop, C. A. K., Melin, F., Sidibe, M., Hellwig, P., Michaud, F., Maury, F., Senocq, F., Mbaye, A. & Rousselin, Y. (2018). J. Mol. Struct. 1170, 44–50. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sjöbom, K. & Hedman, B. (1973). Acta Chem. Scand. A27, 3673–3691. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.