Crystal structures and hydrogen-bonding analysis of a series of solvated ammonium salts of molybdenum(II) chloride clusters

Johnston, D.H.; Agho, I.

doi:10.1107/S205698901901380X

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1705-1711

https://doi.org/10.1107/S205698901901380X

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Crystal structures and hydrogen-bonding analysis of a series of solvated ammonium salts of molybdenum(II) chloride clusters

Dean H. Johnston ^a ^* and Ikponmwosa Agho ^a

^aDepartment of Chemistry, Otterbein University, Westerville, OH 43081, USA
^*Correspondence e-mail: djohnston@otterbein.edu

Edited by E. V. Boldyreva, Russian Academy of Sciences, Russia (Received 18 July 2019; accepted 9 October 2019; online 22 October 2019)

Charge-assisted hydrogen bonding plays a significant role in the crystal structures of solvates of ionic compounds, especially when the cation or cations are primary ammonium salts. We report the crystal structures of four ammonium salts of molybdenum halide cluster solvates where we observe significant hydrogen bonding between the solvent molecules and cations. The crystal structures of bis(anilinium) octa-μ₃-chlorido-hexachlorido-octahedro-hexamolybdate N,N-dimethylformamide tetrasolvate, (C₆H₈N)₂[Mo₆Cl₈Cl₆]·4C₃H₇NO, (I), p-phenylenediammonium octa-μ₃-chlorido-hexachlorido-octahedro-hexamolybdate N,N-dimethylformamide hexasolvate, (C₆H₁₀N₂)[Mo₆Cl₈Cl₆]·6C₃H₇NO, (II), N,N′-(1,4-phenylene)bis(propan-2-iminium) octa-μ₃-chlorido-hexachlorido-octahedro-hexamolybdate acetone trisolvate, (C₁₂H₁₈N₂)[Mo₆Cl₈Cl₆]·3C₃H₆O, (III), and 1,1′-dimethyl-4,4′-bipyridinium octa-μ₃-chlorido-hexachlorido-octahedro-hexamolybdate N,N-dimethylformamide tetrasolvate, (C₁₂H₁₄N₂)[Mo₆Cl₈Cl₆]·4C₃H₇NO, (IV), are reported and described. In (I), the anilinium cations and N,N-dimethylformamide (DMF) solvent molecules form a cyclic R₄²(8) hydrogen-bonded motif centered on a crystallographic inversion center with an additional DMF molecule forming a D(2) interaction. The p-phenylenediammonium cation in (II) forms three D(2) interactions between the three N—H bonds and three independent N,N-dimethylformamide molecules. The dication in (III) is a protonated Schiff base solvated by acetone molecules. Compound (IV) contains a methyl viologen dication with N,N-dimethylformamide molecules forming close contacts with both aromatic and methyl H atoms.

Keywords: metal–halide cluster; charge-assisted hydrogen bonds; primary ammonium salt; quaternary ammonium salt; Hirshfeld surface; crystal structure.

CCDC references: 1907244; 1907230; 1907249; 1907231; 1907230; 1907231; 1907244; 1907249

1. Chemical context

The unique photochemistry of the molybdenum and tungsten halide clusters [M₆X₈Y₆]²⁻ (M = Mo, W; X, Y = Cl, Br, I) has been known for over 30 years (Maverick et al., 1983 ) and researchers continue to explore the tunabilty of the redox potentials, crystal structures and photochemical properties of cluster-containing compounds via variation of the bridging and terminal ligands and the counter-ion (Mikhailov et al., 2016 ; Saito et al., 2017 ; Akagi et al., 2018 ). Metal clusters, such as molybdenum halides, consist of an inner [Mo₆X₈]⁴⁺ core surrounded by six axial ligands which are more labile than the core ligands, making the preparation of mixed-ligand cluster complexes relatively straightforward.

Charge-assisted hydrogen bonds (CAHBs) are particularly strong among hydrogen bonds (Gilli & Gilli, 2009 ) and can be a significant factor in the design and formation of supramolecular complexes. CAHBs have been exploited in the formation of supramolecular organic–inorganic uranyl materials (de Groot et al., 2014 ), noncovalent macrocycles and catenanes (Pop et al., 2016 ), molecular switches (Gurbanov et al., 2017 ), and CAHB networks (Ward, 2009 ). Protonated diamines are a common motif found in hydrogen-bonded materials (Brozdowska & Chojnacki, 2017 ; Zick & Geiger, 2018 ). Examination of the nature and range of hydrogen bonding for solvates can provide information about the stability and physical properties of molecular solids (Brychczynska et al., 2012 ).

We have prepared a series of ammonium salts of the [Mo₆Cl₈Cl₆]²⁻ complex anion, each containing cations `solvated' by either dimethylformamide or acetone through strong CAHBs.

2. Structural commentary

The asymmetric unit of dianilinium salt (I) (Fig. 1) contains half a cluster unit, one anilinium cation, and two independent N,N-dimethylformamide (DMF) molecules. The structure with the atom-numbering scheme is shown in Fig. 2. The [Mo₆Cl₈Cl₆]²⁻ cluster unit resides on a crystallographic inversion center, as it does in all four structures. In compound (II), the asymmetric unit contains half a cluster unit, half a p-phenylenediammonium cation, and three independent DMF molecules. The p-phenylenediammonium cation is disordered over two positions (rotation of 70.6° about the N—N axis), with a refined occupancy of 0.918 (4) for the primary orientation. The structure with the atom-numbering scheme is shown in Fig. 3.

Figure 1
The structures of (I)–(IV).

Figure 2
Displacement ellipsoid plot and atom-numbering scheme for (I), with ellipsoids drawn at the 50% probability level.

Figure 3
Displacement ellipsoid plot and atom-numbering scheme for (II), with ellipsoids drawn at the 50% probability level. The minor component of the disordered p-phenylenediammonium cation is not shown for clarity.

The asymmetric unit of Schiff base salt (III) contains half a cluster unit, half a Schiff base cation, and two independent acetone molecules. The structure with the atom-numbering scheme is shown in Fig. 4. One acetone molecule is disordered over an inversion center. The Schiff base cation, presumably formed from the reaction between a p-phenylenediammonium cation and two acetone molecules, shows strong similarities to the cation found in the bismuthate structure reported by Shestimerova et al. (2018 ).

Figure 4
Displacement ellipsoid plot and atom-numbering scheme for (III), with ellipsoids drawn at the 50% probability level.

For comparison, a dicationic salt incapable of conventional hydrogen bonding (methyl viologen) was prepared and structurally characterized. The asymmetric unit of (IV), as in the other structures, contains half of the cluster unit, half of the methyl viologen dication, and two independent DMF molecules. The structure with the atom-numbering scheme is shown in Fig. 5.

Figure 5
Displacement ellipsoid plot and atom-numbering scheme for (IV), with ellipsoids drawn at the 50% probability level.

3. Hydrogen-bonding analysis

In compound (I), the anilinium cation and DMF molecules form a cyclic R₄²(8) hydrogen-bonded motif centered on a crystallographic inversion center, with an additional DMF forming a D(2) interaction, as illustrated in Fig. 6. Although similar to some motifs discussed by Loehlin & Okasako (2007 ), the hydrogen-bonding network in (I) does not represent an example of saturated hydrogen bonding, as one DMF molecule has an additional lone pair that is not involved in hydrogen bonding (Table 1). The DMF molecules in compound (II) form three unique D(2) interactions with the three N—H bonds on each end of the p-phenylenediammonium cations, as shown in Fig. 7 (Table 2). In compound (III), one acetone molecule forms a hydrogen-bonding interaction with the N—H group of the Schiff base, as shown in Fig. 8 (Table 3).

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89 (3)	2.01 (3)	2.827 (3)	152 (2)
N1—H1B⋯O2ⁱⁱ	0.91 (3)	1.94 (3)	2.833 (3)	168 (3)
N1—H1C⋯O1ⁱⁱⁱ	0.91 (3)	1.82 (3)	2.715 (3)	166 (3)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x-1, y, z; (iii) x, y, z-1.

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.92 (2)	1.76 (2)	2.672 (4)	171 (4)
N1—H1B⋯O3ⁱⁱ	0.93 (2)	1.79 (2)	2.710 (4)	173 (4)
N1—H1C⋯O1ⁱⁱⁱ	0.92 (2)	1.81 (2)	2.727 (4)	175 (4)
Symmetry codes: (i) x, y+1, z-1; (ii) -x+2, -y+1, -z; (iii) -x+1, -y+1, -z+1.

Table 3
Hydrogen-bond geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.87 (2)	1.93 (2)	2.791 (4)	172 (3)
Symmetry code: (i) x, y-1, z.

Figure 6
The cationic hydrogen-bonded dimer formed by anilinium cations and DMF molecules in (I).

Figure 7
Hydrogen bonding in the DMF-solvated p-phenylenediammonium dication in (II). The minor component of the disordered p-phenylenediammonium cation is not shown for clarity.

Figure 8
Hydrogen bonding in the acetone-solvated Schiff base dication in (III).

In spite of the lack of conventional hydrogen bonding in compound (IV), the methyl viologen cation forms several C—H⋯O contacts, with the O atoms of the two independent DMF molecules forming close contacts with the H atoms of the aromatic ring (O⋯H = 2.23 Å) and the methyl group (O⋯H = 2.31 Å) (Table 4).

Table 4
Hydrogen-bond geometry (Å, °) for (IV)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O1ⁱ	0.95	2.23	3.063 (4)	145
C6—H6C⋯O2ⁱⁱ	0.98	2.31	3.088 (4)	136
Symmetry codes: (i) x, y+1, z; (ii) -x, -y+2, -z+1.

Analysis of the hydrogen bonding and close contacts via Hirshfeld surfaces and fingerprint plots was conducted using CrystalExplorer (Spackman & Jayatilaka, 2009 ) and the results are shown in Fig. 9. Compound (II) has the strongest hydrogen-bonding interactions, with similar, but slightly weaker, interactions for (I) and (III). All four compounds show very similar H(cation)⋯Cl(cluster anion) interactions. The C—H⋯O contacts in (IV), especially with the aromatic C—H group of the methyl viologen, can be clearly identified on the Hirshfeld surface.

Figure 9
Fingerprint plots and Hirshfeld surfaces for (I)–(IV). For (II), only the major component of the disordered p-phenylenediammonium cation was included in the generation of the fingerprint plot.

4. Database survey

Interest in molybdenum(II) halide clusters and related compounds have led to numerous structural studies, with 45 entries in the Cambridge Structural Database (CSD, Version 5.40; Groom et al., 2016 ) containing the [Mo₆Cl₁₄]²⁻ dianion and almost 200 structures containing the [Mo₆X₈]⁴⁺ core. Similarly, one can find over 50 structures in the Inorganic Crystal Structure Database (ICSD, Version 4.2.0; Hellenbrandt, 2004 ) containing the same molybdenum halide core structure. The structures of the [Mo₆Cl₁₄]²⁻ cluster anions in this study are unremarkable and do not differ significantly from previous studies.

The anilinium cluster dihydrate structure published by Flemström (2003 ) has some similarities to (I). In that structure, the three N—H bonds of the anilinium cation serve as hydrogen-bond donors to one water molecule (hydrate) and two terminal Cl atoms on two discrete cluster anions. The N—H⋯Cl interactions create C₄⁴(15) chains. The water molecules create R₄⁴(14) rings involving two water molecules and two cluster units, as well as C₂²(8) and C₂²(7) chains.

While DMF-solvated ammonium salts appear to be relatively uncommon, a series of molybdenum halide cluster salts have been prepared with dimethylformamide-coordinated metal cations serving as the counter-cation (Khutornoi et al., 2002 ; Kozhomuratova et al., 2007 ; Liu et al., 2006 ). The complexes prepared and characterized include the [Mo₆Cl₈Cl₆]²⁻, [Mo₆Br₈Cl₆]²⁻, and [Mo₆Br₈(NCS)₆]²⁻ cluster anions as salts with [M(DMF)]²⁺ cations, where M = Ca²⁺, Mn²⁺, and Co²⁺. A similar set of rhenium chalcogenide cluster salts with DMF-solvated calcium and a series of lanthanides has been prepared by Perruchas et al. (2002 ) and Yarovoi et al. (2006 ).

A separate search of the CSD for structures with similar hydrogen-bonded networks containing anilinium and p-phenylenediammonium cations yielded a large number of hits due to their propensity for forming significant hydrogen-bonding networks. In the structure of anilinium dihydrogen phosphate (Kaman et al., 2012 ), each of the three independent ammonium groups forms four different hydrogen bonds to the O atoms of nearby dihydrogen phosphate moieties. A very similar set of hydrogen-bonding interactions and layered organic/inorganic structural arrangements are found in the structures of p-phenylenediammonium bis(dihydrogen phosphate) (Mrad et al., 2006a ) and p-phenylenediammonium dihydrogen diphosphate (Mrad et al., 2006b ). While less closely related to the current report, the structure of p-phenylenediammonium tetrachloridozincate(II) (Bringley & Rajeswaran, 2006 ) also displays alternating organic and inorganic layers and strong hydrogen bonding between the tetrachloridozinc(II) anions and the p-phenylenediammonium cations.

A dimethyl sulfoxide (DMSO)-solvated p-phenylenediammonium salt of an iodidobismuthate reported by Shestimerova et al. (2018) displays strong structural similarities to (II) in the way the DMSO solvates the p-phenylenediammonium cation. Three unique DMSO molecules also form D(2) interactions with each end of the p-phenylenediammonium. One of the three DMSO molecules simultaneously coordinates to one of the Bi atoms.

5. Synthesis and crystallization

All reagents were used as received from the manufacturer.

5.1. Cluster synthesis, metathesis, and crystallization of (I), (II), and (IV)

The hydronium salt of the [Mo₆Cl₈Cl₆]²⁻ anion was prepared by the method of Hay et al. (2004 ) and then metathesized to the appropriate ammonium salt by combining an ethanolic solution of (H₃O)₂[Mo₆Cl₈Cl₆]·6H₂O with a slight stoichiometric excess (∼2.5 times) of the respective ammonium chloride salt (anilinium chloride, p-phenylenediamine hydrochloride, and methyl viologen dichloride). The bright-yellow precipitate that formed was isolated by filtration and the product was recrystallized by vapor diffusion of diethyl ether into a dimethylformamide solution of the cluster salt.

5.2. Synthesis and crystallization of Schiff base salt (III)

The cluster in compound (III) was prepared and metathesized to the diammonium salt via the same procedure as above using the p-phenylenediammonium chloride to isolate a yellow precipitate. The salt was then redissolved in acetone and allowed to evaporate. The acetone inadvertently formed a Schiff base dication in a reaction with the p-phenylenediammonium cation (Kolb & Bahadir, 1994 ).

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 5. All H atoms were located in a difference map. All carbon-bonded H atoms were placed in idealized positions using a riding model, with aromatic and amide C—H = 0.95 Å and methyl C—H = 0.98 Å, and with U_iso(H) = 1.2U_eq(C) (aromatic and amide) or U_iso(H) = 1.5U_eq(C) (methyl). The positions of all H atoms bonded to N atoms were refined with N—H distances restrained to 0.91 (2) (NH₃) or 0.88 (2) Å (Schiff base), and with U_iso(H) = 1.5U_eq(N).

Table 5
Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	(C₆H₈N)₂[Mo₆Cl₈Cl₆]·4C₃H₇NO	(C₆H₁₀N₂)[Mo₆Cl₈Cl₆]·6C₃H₇NO	(C₁₂H₁₈N₂)[Mo₆Cl₈Cl₆]·3C₃H₆O	(C₁₂H₁₄N₂)[Mo₆Cl₈Cl₆]·4C₃H₇NO
M_r	1552.59	1620.67	1436.46	1550.57
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	200	200	200	200
a, b, c (Å)	9.9813 (11), 10.6074 (13), 12.1686 (15)	10.1752 (16), 10.3227 (16), 13.736 (2)	9.451 (2), 11.236 (3), 11.712 (3)	9.8252 (11), 10.0933 (11), 12.6319 (15)
α, β, γ (°)	104.606 (3), 90.709 (3), 103.146 (3)	95.204 (4), 111.483 (4), 101.973 (4)	64.933 (6), 71.174 (6), 75.440 (6)	107.395 (3), 91.881 (3), 93.309 (3)
V (Å³)	1210.7 (3)	1291.1 (3)	1056.7 (5)	1191.8 (2)
Z	1	1	1	1
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	2.32	2.18	2.64	2.35
Crystal size (mm)	0.48 × 0.46 × 0.12	0.50 × 0.13 × 0.13	0.55 × 0.33 × 0.20	0.32 × 0.30 × 0.28

Data collection
Diffractometer	Bruker SMART X2S benchtop	Bruker SMART X2S benchtop	Bruker SMART X2S benchtop	Bruker SMART X2S benchtop
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )	Multi-scan (SADABS; Bruker, 2012)	Multi-scan (SADABS; Bruker, 2012)	Multi-scan (SADABS; Bruker, 2012)
T_min, T_max	0.498, 0.745	0.552, 0.745	0.490, 0.745	0.815, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11709, 4245, 3834	12459, 4504, 3666	10036, 3692, 3220	11498, 4187, 3743
R_int	0.026	0.035	0.030	0.024
(sin θ/λ)_max (Å⁻¹)	0.597	0.595	0.598	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.046, 1.07	0.026, 0.062, 1.03	0.025, 0.068, 1.05	0.020, 0.049, 1.02
No. of reflections	4245	4504	3692	4187
No. of parameters	258	285	235	250
No. of restraints	0	144	13	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.54	0.66, −0.56	0.96, −0.82	0.42, −0.44
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), CrystalMaker (Palmer, 2019 ), CrystalExplorer (Spackman & Jayatilaka, 2009), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

All four structures were refined in the space group P $[\overline{1}]$ and the [Mo₆Cl₁₄]²⁻ dianion sits on an inversion center in every case. The dications in (II), (III), and (IV) are also each located on an inversion center. The p-phenylenediammonium cation in (II) is disordered over two orientations with an occupancy of 0.918 (4) for the major component. One of the two acetone molecules in (III) is disordered over an inversion center.

Supporting information

CCDC references: 1907244; 1907230; 1907249; 1907231; 1907230; 1907231; 1907244; 1907249

Crystal structure: contains datablocks global, 1, 2, 3, 4. DOI: https://doi.org/10.1107/S205698901901380X/eb2023sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S205698901901380X/eb20231sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S205698901901380X/eb20232sup3.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S205698901901380X/eb20233sup4.hkl

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S205698901901380X/eb20234sup5.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901901380X/eb20231sup6.mol

Supporting information file. DOI: https://doi.org/10.1107/S205698901901380X/eb20232sup7.mol

Supporting information file. DOI: https://doi.org/10.1107/S205698901901380X/eb20233sup8.mol

Supporting information file. DOI: https://doi.org/10.1107/S205698901901380X/eb20234sup9.mol

checkCIF report

Computing details top

For all structures, data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: CrystalMaker (Palmer, 2019) and CrystalExplorer (Spackman & Jayatilaka, 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Bis(anilinium) octa-µ₃-chlorido-hexachlorido-octahedro-hexamolybdate N,N-dimethylformamide tetrasolvate (1) top

Crystal data top

(C₆H₈N)₂[Mo₆Cl₈Cl₆]·4C₃H₇NO	Z = 1
M_r = 1552.59	F(000) = 752
Triclinic, P1	D_x = 2.129 Mg m⁻³
a = 9.9813 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6074 (13) Å	Cell parameters from 7006 reflections
c = 12.1686 (15) Å	θ = 2.3–25.1°
α = 104.606 (3)°	µ = 2.32 mm⁻¹
β = 90.709 (3)°	T = 200 K
γ = 103.146 (3)°	Plate, clear orangish yellow
V = 1210.7 (3) Å³	0.48 × 0.46 × 0.12 mm

Data collection top

Bruker SMART X2S benchtop diffractometer	4245 independent reflections
Radiation source: sealed microfocus source, XOS X-beam microfocus source	3834 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 8.3330 pixels mm^-1	θ_max = 25.1°, θ_min = 2.3°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −12→12
T_min = 0.498, T_max = 0.745	l = −14→14
11709 measured 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)] = 0.019	w = 1/[σ²(F_o²) + (0.0123P)² + 0.5808P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.046	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.36 e Å⁻³
4245 reflections	Δρ_min = −0.54 e Å⁻³
258 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0096 (3)
Primary atom site location: structure-invariant direct methods

Special details top

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

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

	x	y	z	U_iso*/U_eq
Mo1	0.33000 (2)	0.50142 (2)	0.43962 (2)	0.01755 (7)
Mo2	0.42505 (2)	0.33816 (2)	0.52988 (2)	0.01753 (7)
Mo3	0.45872 (2)	0.58737 (2)	0.64151 (2)	0.01766 (7)
Cl1	0.30660 (6)	0.26453 (5)	0.33717 (5)	0.02208 (12)
Cl2	0.44848 (6)	0.57046 (5)	0.27978 (5)	0.02298 (13)
Cl3	0.37196 (6)	0.73926 (5)	0.55008 (5)	0.02352 (13)
Cl4	0.22876 (5)	0.43149 (5)	0.60532 (5)	0.02318 (13)
Cl5	0.32774 (6)	0.12583 (6)	0.57003 (5)	0.03234 (15)
Cl6	0.39836 (6)	0.69501 (6)	0.82888 (5)	0.03331 (15)
Cl7	0.10839 (6)	0.50315 (6)	0.35713 (5)	0.03118 (14)
N1	0.1138 (2)	0.6861 (2)	−0.02394 (19)	0.0291 (5)
H1A	0.144 (3)	0.612 (3)	−0.048 (2)	0.044*
H1B	0.026 (3)	0.651 (3)	−0.010 (2)	0.044*
H1C	0.111 (3)	0.732 (3)	−0.078 (2)	0.044*
C1	0.1999 (2)	0.7715 (2)	0.0778 (2)	0.0262 (5)
C2	0.1890 (3)	0.7327 (3)	0.1777 (2)	0.0352 (6)
H2	0.125907	0.652029	0.180955	0.042*
C3	0.2713 (3)	0.8128 (3)	0.2728 (2)	0.0439 (7)
H3	0.264848	0.787222	0.342295	0.053*
C4	0.3621 (3)	0.9288 (3)	0.2678 (3)	0.0454 (7)
H4	0.418475	0.983410	0.333788	0.055*
C5	0.2894 (3)	0.8879 (2)	0.0709 (2)	0.0326 (6)
H5	0.294613	0.913873	0.001580	0.039*
C6	0.3718 (3)	0.9666 (3)	0.1671 (2)	0.0411 (7)
H6	0.435330	1.046973	0.163742	0.049*
O1	0.0921 (2)	0.85206 (19)	0.84303 (16)	0.0431 (5)
N2	0.0472 (2)	0.88716 (19)	0.67193 (17)	0.0287 (5)
C7	0.0074 (3)	1.0112 (3)	0.7195 (2)	0.0408 (7)
H7A	0.004355	1.025920	0.802189	0.061*
H7B	−0.083924	1.006277	0.685843	0.061*
H7C	0.074846	1.085755	0.702938	0.061*
C8	0.0860 (2)	0.8186 (3)	0.7380 (2)	0.0325 (6)
H8	0.111034	0.737608	0.702115	0.039*
C9	0.0410 (3)	0.8403 (3)	0.5486 (2)	0.0364 (6)
H9A	0.057014	0.749801	0.526886	0.055*
H9B	0.111888	0.901063	0.519142	0.055*
H9C	−0.050269	0.838466	0.516599	0.055*
O2	0.85598 (19)	0.57853 (18)	0.05179 (17)	0.0418 (5)
N3	0.7318 (2)	0.7329 (2)	0.05377 (17)	0.0320 (5)
C10	0.7698 (3)	0.6417 (3)	0.0921 (2)	0.0397 (7)
H10	0.727510	0.621423	0.157083	0.048*
C11	0.6338 (3)	0.8071 (3)	0.1095 (2)	0.0460 (7)
H11A	0.607218	0.779492	0.178708	0.069*
H11B	0.551612	0.788223	0.057583	0.069*
H11C	0.676785	0.903485	0.129568	0.069*
C12	0.7879 (4)	0.7684 (4)	−0.0466 (3)	0.0621 (10)
H12A	0.866691	0.846144	−0.023497	0.093*
H12B	0.716767	0.790546	−0.089431	0.093*
H12C	0.818232	0.692417	−0.094617	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01465 (11)	0.01876 (11)	0.01888 (11)	0.00353 (8)	0.00272 (8)	0.00463 (8)
Mo2	0.01627 (11)	0.01691 (10)	0.01871 (11)	0.00234 (8)	0.00337 (8)	0.00474 (8)
Mo3	0.01646 (12)	0.01852 (11)	0.01703 (11)	0.00379 (8)	0.00436 (8)	0.00307 (8)
Cl1	0.0205 (3)	0.0202 (3)	0.0218 (3)	0.0011 (2)	0.0008 (2)	0.0022 (2)
Cl2	0.0233 (3)	0.0256 (3)	0.0208 (3)	0.0045 (2)	0.0022 (2)	0.0086 (2)
Cl3	0.0231 (3)	0.0211 (3)	0.0272 (3)	0.0086 (2)	0.0041 (2)	0.0046 (2)
Cl4	0.0169 (3)	0.0267 (3)	0.0247 (3)	0.0029 (2)	0.0066 (2)	0.0066 (2)
Cl5	0.0345 (3)	0.0242 (3)	0.0369 (3)	−0.0020 (3)	0.0024 (3)	0.0134 (3)
Cl6	0.0350 (4)	0.0359 (3)	0.0241 (3)	0.0078 (3)	0.0112 (3)	−0.0010 (3)
Cl7	0.0199 (3)	0.0356 (3)	0.0397 (3)	0.0061 (3)	−0.0019 (3)	0.0132 (3)
N1	0.0306 (12)	0.0255 (11)	0.0341 (12)	0.0094 (10)	0.0055 (10)	0.0104 (10)
C1	0.0273 (13)	0.0252 (12)	0.0296 (13)	0.0132 (11)	0.0041 (11)	0.0072 (10)
C2	0.0437 (16)	0.0307 (13)	0.0379 (15)	0.0162 (12)	0.0069 (13)	0.0142 (12)
C3	0.063 (2)	0.0469 (17)	0.0309 (15)	0.0328 (16)	0.0019 (14)	0.0097 (13)
C4	0.0505 (18)	0.0396 (16)	0.0433 (17)	0.0259 (15)	−0.0084 (14)	−0.0073 (13)
C5	0.0372 (15)	0.0263 (13)	0.0383 (15)	0.0145 (11)	0.0117 (12)	0.0089 (11)
C6	0.0412 (17)	0.0277 (14)	0.0495 (18)	0.0115 (12)	0.0063 (14)	−0.0016 (13)
O1	0.0496 (12)	0.0479 (11)	0.0392 (11)	0.0149 (10)	0.0045 (9)	0.0219 (9)
N2	0.0270 (11)	0.0275 (11)	0.0326 (11)	0.0065 (9)	0.0007 (9)	0.0094 (9)
C7	0.0462 (17)	0.0355 (15)	0.0465 (17)	0.0170 (13)	0.0084 (14)	0.0144 (13)
C8	0.0248 (14)	0.0313 (13)	0.0428 (16)	0.0048 (11)	0.0040 (12)	0.0140 (12)
C9	0.0334 (15)	0.0362 (14)	0.0332 (14)	−0.0008 (12)	−0.0040 (12)	0.0062 (12)
O2	0.0359 (11)	0.0345 (10)	0.0614 (13)	0.0134 (9)	0.0149 (10)	0.0192 (9)
N3	0.0309 (12)	0.0407 (12)	0.0301 (11)	0.0169 (10)	0.0066 (10)	0.0120 (10)
C10	0.0391 (16)	0.0390 (15)	0.0470 (17)	0.0112 (13)	0.0145 (13)	0.0197 (13)
C11	0.0527 (19)	0.0527 (18)	0.0427 (17)	0.0301 (15)	0.0149 (15)	0.0142 (14)
C12	0.073 (2)	0.099 (3)	0.0438 (18)	0.053 (2)	0.0248 (17)	0.0425 (19)

Geometric parameters (Å, º) top

Mo1—Mo2ⁱ	2.6034 (4)	C3—H3	0.9500
Mo1—Mo2	2.6051 (3)	C3—C4	1.368 (4)
Mo1—Mo3ⁱ	2.6068 (3)	C4—H4	0.9500
Mo1—Mo3	2.6032 (4)	C4—C6	1.381 (4)
Mo1—Cl1	2.4636 (6)	C5—H5	0.9500
Mo1—Cl2	2.4697 (6)	C5—C6	1.383 (4)
Mo1—Cl3	2.4782 (6)	C6—H6	0.9500
Mo1—Cl4	2.4700 (6)	O1—C8	1.234 (3)
Mo1—Cl7	2.4235 (6)	N2—C7	1.444 (3)
Mo2—Mo3	2.5922 (4)	N2—C8	1.319 (3)
Mo2—Mo3ⁱ	2.6065 (3)	N2—C9	1.453 (3)
Mo2—Cl1	2.4687 (6)	C7—H7A	0.9800
Mo2—Cl2ⁱ	2.4772 (6)	C7—H7B	0.9800
Mo2—Cl3ⁱ	2.4756 (6)	C7—H7C	0.9800
Mo2—Cl4	2.4758 (6)	C8—H8	0.9500
Mo2—Cl5	2.4138 (6)	C9—H9A	0.9800
Mo3—Cl1ⁱ	2.4754 (6)	C9—H9B	0.9800
Mo3—Cl2ⁱ	2.4639 (6)	C9—H9C	0.9800
Mo3—Cl3	2.4695 (6)	O2—C10	1.239 (3)
Mo3—Cl4	2.4652 (6)	N3—C10	1.299 (3)
Mo3—Cl6	2.4288 (6)	N3—C11	1.461 (3)
N1—H1A	0.89 (3)	N3—C12	1.449 (3)
N1—H1B	0.91 (3)	C10—H10	0.9500
N1—H1C	0.91 (3)	C11—H11A	0.9800
N1—C1	1.465 (3)	C11—H11B	0.9800
C1—C2	1.376 (3)	C11—H11C	0.9800
C1—C5	1.371 (3)	C12—H12A	0.9800
C2—H2	0.9500	C12—H12B	0.9800
C2—C3	1.378 (4)	C12—H12C	0.9800

Mo2ⁱ—Mo1—Mo2	89.753 (11)	Cl3—Mo3—Mo1ⁱ	118.261 (15)
Mo2—Mo1—Mo3ⁱ	60.013 (9)	Cl3—Mo3—Mo2ⁱ	58.306 (14)
Mo2ⁱ—Mo1—Mo3ⁱ	59.675 (10)	Cl3—Mo3—Mo2	118.588 (17)
Mo3—Mo1—Mo2ⁱ	60.080 (8)	Cl3—Mo3—Cl1ⁱ	89.67 (2)
Mo3—Mo1—Mo2	59.698 (9)	Cl4—Mo3—Mo1ⁱ	118.636 (17)
Mo3—Mo1—Mo3ⁱ	89.786 (11)	Cl4—Mo3—Mo1	58.254 (14)
Cl1—Mo1—Mo2ⁱ	118.020 (15)	Cl4—Mo3—Mo2	58.556 (14)
Cl1—Mo1—Mo2	58.214 (16)	Cl4—Mo3—Mo2ⁱ	118.205 (16)
Cl1—Mo1—Mo3	117.899 (15)	Cl4—Mo3—Cl1ⁱ	175.592 (19)
Cl1—Mo1—Mo3ⁱ	58.365 (14)	Cl4—Mo3—Cl3	89.93 (2)
Cl1—Mo1—Cl2	89.683 (19)	Cl6—Mo3—Mo1	134.228 (19)
Cl1—Mo1—Cl3	175.251 (19)	Cl6—Mo3—Mo1ⁱ	135.485 (18)
Cl1—Mo1—Cl4	89.963 (19)	Cl6—Mo3—Mo2ⁱ	137.228 (18)
Cl2—Mo1—Mo2ⁱ	58.387 (15)	Cl6—Mo3—Mo2	132.798 (17)
Cl2—Mo1—Mo2	117.999 (16)	Cl6—Mo3—Cl1ⁱ	94.40 (2)
Cl2—Mo1—Mo3	118.444 (17)	Cl6—Mo3—Cl2ⁱ	90.84 (2)
Cl2—Mo1—Mo3ⁱ	57.995 (14)	Cl6—Mo3—Cl3	93.06 (2)
Cl2—Mo1—Cl3	90.38 (2)	Cl6—Mo3—Cl4	90.01 (2)
Cl2—Mo1—Cl4	175.624 (19)	Mo1—Cl1—Mo2	63.764 (15)
Cl3—Mo1—Mo2ⁱ	58.247 (14)	Mo1—Cl1—Mo3ⁱ	63.713 (15)
Cl3—Mo1—Mo2	117.771 (17)	Mo2—Cl1—Mo3ⁱ	63.630 (15)
Cl3—Mo1—Mo3ⁱ	117.898 (15)	Mo1—Cl2—Mo2ⁱ	63.507 (16)
Cl3—Mo1—Mo3	58.092 (14)	Mo3ⁱ—Cl2—Mo1	63.792 (15)
Cl4—Mo1—Mo2ⁱ	118.144 (16)	Mo3ⁱ—Cl2—Mo2ⁱ	63.287 (16)
Cl4—Mo1—Mo2	58.325 (14)	Mo2ⁱ—Cl3—Mo1	63.408 (14)
Cl4—Mo1—Mo3ⁱ	118.319 (15)	Mo3—Cl3—Mo1	63.489 (16)
Cl4—Mo1—Mo3	58.077 (16)	Mo3—Cl3—Mo2ⁱ	63.616 (15)
Cl4—Mo1—Cl3	89.62 (2)	Mo1—Cl4—Mo2	63.569 (15)
Cl7—Mo1—Mo2	135.582 (17)	Mo3—Cl4—Mo1	63.669 (15)
Cl7—Mo1—Mo2ⁱ	134.650 (17)	Mo3—Cl4—Mo2	63.286 (16)
Cl7—Mo1—Mo3	135.962 (17)	H1A—N1—H1B	101 (2)
Cl7—Mo1—Mo3ⁱ	134.249 (18)	H1A—N1—H1C	114 (3)
Cl7—Mo1—Cl1	92.00 (2)	H1B—N1—H1C	109 (2)
Cl7—Mo1—Cl2	91.25 (2)	C1—N1—H1A	108.4 (18)
Cl7—Mo1—Cl3	92.75 (2)	C1—N1—H1B	113.6 (18)
Cl7—Mo1—Cl4	93.12 (2)	C1—N1—H1C	111.0 (18)
Mo1ⁱ—Mo2—Mo1	90.246 (11)	C2—C1—N1	119.1 (2)
Mo1ⁱ—Mo2—Mo3ⁱ	59.955 (8)	C5—C1—N1	119.1 (2)
Mo1—Mo2—Mo3ⁱ	60.026 (9)	C5—C1—C2	121.8 (2)
Mo3—Mo2—Mo1ⁱ	60.228 (8)	C1—C2—H2	120.6
Mo3—Mo2—Mo1	60.114 (10)	C1—C2—C3	118.8 (3)
Mo3—Mo2—Mo3ⁱ	90.033 (11)	C3—C2—H2	120.6
Cl1—Mo2—Mo1	58.022 (15)	C2—C3—H3	119.7
Cl1—Mo2—Mo1ⁱ	118.250 (15)	C4—C3—C2	120.5 (3)
Cl1—Mo2—Mo3ⁱ	58.310 (15)	C4—C3—H3	119.7
Cl1—Mo2—Mo3	118.122 (15)	C3—C4—H4	120.0
Cl1—Mo2—Cl2ⁱ	175.448 (18)	C3—C4—C6	120.0 (3)
Cl1—Mo2—Cl3ⁱ	89.68 (2)	C6—C4—H4	120.0
Cl1—Mo2—Cl4	89.71 (2)	C1—C5—H5	120.7
Cl2ⁱ—Mo2—Mo1ⁱ	58.106 (14)	C1—C5—C6	118.6 (3)
Cl2ⁱ—Mo2—Mo1	118.200 (16)	C6—C5—H5	120.7
Cl2ⁱ—Mo2—Mo3	58.105 (14)	C4—C6—C5	120.2 (3)
Cl2ⁱ—Mo2—Mo3ⁱ	118.038 (16)	C4—C6—H6	119.9
Cl3ⁱ—Mo2—Mo1ⁱ	58.346 (16)	C5—C6—H6	119.9
Cl3ⁱ—Mo2—Mo1	118.097 (16)	C7—N2—C9	117.3 (2)
Cl3ⁱ—Mo2—Mo3	118.549 (15)	C8—N2—C7	121.2 (2)
Cl3ⁱ—Mo2—Mo3ⁱ	58.076 (14)	C8—N2—C9	121.5 (2)
Cl3ⁱ—Mo2—Cl2ⁱ	90.26 (2)	N2—C7—H7A	109.5
Cl3ⁱ—Mo2—Cl4	175.629 (18)	N2—C7—H7B	109.5
Cl4—Mo2—Mo1	58.105 (15)	N2—C7—H7C	109.5
Cl4—Mo2—Mo1ⁱ	118.367 (16)	H7A—C7—H7B	109.5
Cl4—Mo2—Mo3	58.157 (14)	H7A—C7—H7C	109.5
Cl4—Mo2—Mo3ⁱ	118.112 (15)	H7B—C7—H7C	109.5
Cl4—Mo2—Cl2ⁱ	90.00 (2)	O1—C8—N2	124.7 (2)
Cl5—Mo2—Mo1ⁱ	134.531 (18)	O1—C8—H8	117.6
Cl5—Mo2—Mo1	135.222 (19)	N2—C8—H8	117.6
Cl5—Mo2—Mo3ⁱ	135.276 (17)	N2—C9—H9A	109.5
Cl5—Mo2—Mo3	134.689 (19)	N2—C9—H9B	109.5
Cl5—Mo2—Cl1	92.63 (2)	N2—C9—H9C	109.5
Cl5—Mo2—Cl2ⁱ	91.92 (2)	H9A—C9—H9B	109.5
Cl5—Mo2—Cl3ⁱ	92.04 (2)	H9A—C9—H9C	109.5
Cl5—Mo2—Cl4	92.31 (2)	H9B—C9—H9C	109.5
Mo1—Mo3—Mo1ⁱ	90.214 (10)	C10—N3—C11	122.7 (2)
Mo1—Mo3—Mo2ⁱ	59.965 (10)	C10—N3—C12	121.0 (2)
Mo2—Mo3—Mo1ⁱ	60.098 (8)	C12—N3—C11	116.3 (2)
Mo2ⁱ—Mo3—Mo1ⁱ	59.961 (8)	O2—C10—N3	126.1 (3)
Mo2—Mo3—Mo1	60.188 (8)	O2—C10—H10	116.9
Mo2—Mo3—Mo2ⁱ	89.968 (10)	N3—C10—H10	116.9
Cl1ⁱ—Mo3—Mo1ⁱ	57.923 (15)	N3—C11—H11A	109.5
Cl1ⁱ—Mo3—Mo1	118.008 (15)	N3—C11—H11B	109.5
Cl1ⁱ—Mo3—Mo2	118.001 (15)	N3—C11—H11C	109.5
Cl1ⁱ—Mo3—Mo2ⁱ	58.058 (14)	H11A—C11—H11B	109.5
Cl2ⁱ—Mo3—Mo1ⁱ	58.214 (14)	H11A—C11—H11C	109.5
Cl2ⁱ—Mo3—Mo1	118.777 (16)	H11B—C11—H11C	109.5
Cl2ⁱ—Mo3—Mo2	58.608 (16)	N3—C12—H12A	109.5
Cl2ⁱ—Mo3—Mo2ⁱ	118.165 (15)	N3—C12—H12B	109.5
Cl2ⁱ—Mo3—Cl1ⁱ	89.55 (2)	N3—C12—H12C	109.5
Cl2ⁱ—Mo3—Cl3	176.071 (19)	H12A—C12—H12B	109.5
Cl2ⁱ—Mo3—Cl4	90.56 (2)	H12A—C12—H12C	109.5
Cl3—Mo3—Mo1	58.419 (15)	H12B—C12—H12C	109.5

N1—C1—C2—C3	179.4 (2)	C3—C4—C6—C5	0.4 (4)
N1—C1—C5—C6	−178.9 (2)	C5—C1—C2—C3	−0.5 (4)
C1—C2—C3—C4	0.0 (4)	C7—N2—C8—O1	0.0 (4)
C1—C5—C6—C4	−0.8 (4)	C9—N2—C8—O1	−179.2 (2)
C2—C1—C5—C6	0.9 (4)	C11—N3—C10—O2	−177.1 (3)
C2—C3—C4—C6	0.1 (4)	C12—N3—C10—O2	1.5 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱ	0.89 (3)	2.01 (3)	2.827 (3)	152 (2)
N1—H1B···O2ⁱⁱⁱ	0.91 (3)	1.94 (3)	2.833 (3)	168 (3)
N1—H1C···O1^iv	0.91 (3)	1.82 (3)	2.715 (3)	166 (3)

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

p-Phenylenediammonium octa-µ₃-chlorido-hexachlorido-octahedro-hexamolybdate N,N-dimethylformamide hexasolvate (2) top

Crystal data top

(C₆H₁₀N₂)[Mo₆Cl₈Cl₆]·6C₃H₇NO	Z = 1
M_r = 1620.67	F(000) = 790
Triclinic, P1	D_x = 2.084 Mg m⁻³
a = 10.1752 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3227 (16) Å	Cell parameters from 4690 reflections
c = 13.736 (2) Å	θ = 2.2–25.0°
α = 95.204 (4)°	µ = 2.18 mm⁻¹
β = 111.483 (4)°	T = 200 K
γ = 101.973 (4)°	Needle, yellow
V = 1291.1 (3) Å³	0.50 × 0.13 × 0.13 mm

Data collection top

Bruker SMART X2S benchtop diffractometer	4504 independent reflections
Radiation source: sealed microfocus source, XOS X-beam microfocus source	3666 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 8.3330 pixels mm^-1	θ_max = 25.0°, θ_min = 2.4°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −12→12
T_min = 0.552, T_max = 0.745	l = −16→16
12459 measured 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)] = 0.026	w = 1/[σ²(F_o²) + (0.0182P)² + 0.7035P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.062	(Δ/σ)_max = 0.002
S = 1.03	Δρ_max = 0.66 e Å⁻³
4504 reflections	Δρ_min = −0.56 e Å⁻³
285 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
144 restraints	Extinction coefficient: 0.0019 (2)
Primary atom site location: structure-invariant direct methods

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	0.38576 (3)	0.32569 (3)	0.46504 (2)	0.01984 (9)
Mo2	0.38226 (3)	0.53457 (3)	0.37203 (2)	0.01942 (9)
Mo3	0.61719 (3)	0.44772 (3)	0.43759 (2)	0.01961 (9)
Cl1	0.39098 (9)	0.31721 (8)	0.28606 (6)	0.02470 (19)
Cl2	0.16889 (8)	0.41769 (8)	0.40411 (7)	0.02485 (19)
Cl3	0.61432 (9)	0.25211 (8)	0.52889 (7)	0.02446 (19)
Cl4	0.39296 (9)	0.35261 (8)	0.64765 (6)	0.02436 (19)
Cl5	0.23637 (10)	0.09538 (8)	0.42076 (7)	0.0329 (2)
Cl6	0.22927 (9)	0.58540 (9)	0.20362 (7)	0.0303 (2)
Cl7	0.77350 (10)	0.38668 (9)	0.35511 (7)	0.0340 (2)
N1	0.6572 (4)	0.7709 (3)	0.0311 (3)	0.0349 (8)
H1A	0.593 (4)	0.816 (4)	−0.008 (3)	0.052*
H1B	0.735 (3)	0.773 (4)	0.010 (3)	0.052*
H1C	0.702 (4)	0.814 (4)	0.1013 (17)	0.052*
C1	0.5771 (4)	0.6310 (4)	0.0161 (3)	0.0300 (8)
C2	0.4838 (4)	0.5982 (4)	0.0660 (3)	0.0346 (10)	0.918 (4)
H2	0.473071	0.666286	0.111672	0.041*	0.918 (4)
C2A	0.614 (4)	0.562 (3)	0.098 (2)	0.0346 (10)	0.082 (4)
H2A	0.690135	0.603414	0.164923	0.041*	0.082 (4)
C3	0.5946 (4)	0.5334 (4)	−0.0500 (3)	0.0368 (11)	0.918 (4)
H3	0.659871	0.556614	−0.084221	0.044*	0.918 (4)
C3A	0.465 (2)	0.570 (3)	−0.0792 (18)	0.0368 (11)	0.082 (4)
H3A	0.440687	0.620672	−0.134626	0.044*	0.082 (4)
O1	0.2262 (3)	0.1030 (3)	0.7614 (2)	0.0397 (7)
N2	0.0590 (3)	0.1987 (3)	0.6536 (2)	0.0345 (7)
C4	−0.0193 (4)	0.2197 (4)	0.5464 (3)	0.0471 (11)
H4A	0.012128	0.173444	0.496723	0.071*
H4B	0.001881	0.316351	0.544827	0.071*
H4C	−0.124667	0.183480	0.525552	0.071*
C5	0.0344 (6)	0.2671 (6)	0.7385 (4)	0.089 (2)
H5A	0.105377	0.355397	0.767114	0.133*
H5B	0.045962	0.213536	0.795020	0.133*
H5C	−0.064912	0.279168	0.711359	0.133*
C6	0.1511 (4)	0.1229 (3)	0.6738 (3)	0.0310 (9)
H6	0.160825	0.078393	0.614092	0.037*
O2	0.4557 (3)	−0.1235 (3)	0.9024 (2)	0.0528 (8)
N3	0.5360 (3)	−0.0093 (3)	0.7928 (2)	0.0365 (8)
C7	0.6841 (5)	0.0426 (5)	0.8704 (4)	0.0737 (16)
H7A	0.742668	−0.019070	0.863107	0.111*
H7B	0.684310	0.050996	0.942109	0.111*
H7C	0.726072	0.131344	0.858773	0.111*
C8	0.5004 (5)	0.0294 (4)	0.6892 (3)	0.0521 (12)
H8A	0.516051	0.127409	0.697400	0.078*
H8B	0.397800	−0.014548	0.643792	0.078*
H8C	0.563372	0.001622	0.656359	0.078*
C9	0.4359 (4)	−0.0854 (4)	0.8172 (4)	0.0401 (10)
H9	0.339326	−0.113538	0.763903	0.048*
O3	1.1120 (3)	0.2000 (3)	0.0265 (2)	0.0531 (8)
N4	0.9538 (3)	0.2480 (3)	0.0950 (2)	0.0348 (7)
C10	0.8672 (5)	0.3384 (4)	0.1084 (4)	0.0542 (12)
H10A	0.910401	0.386797	0.182173	0.081*
H10B	0.767006	0.286161	0.091710	0.081*
H10C	0.865666	0.403223	0.060362	0.081*
C11	0.9567 (5)	0.1356 (4)	0.1512 (3)	0.0513 (11)
H11A	0.986243	0.066079	0.116745	0.077*
H11B	0.859138	0.097880	0.149607	0.077*
H11C	1.026857	0.166773	0.225219	0.077*
C12	1.0327 (4)	0.2695 (4)	0.0379 (3)	0.0415 (10)
H12	1.027845	0.344630	0.002820	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01844 (16)	0.01776 (16)	0.02281 (18)	0.00192 (12)	0.00933 (13)	0.00253 (12)
Mo2	0.01778 (16)	0.01982 (16)	0.02082 (18)	0.00380 (12)	0.00849 (13)	0.00326 (12)
Mo3	0.01810 (16)	0.01988 (16)	0.02220 (18)	0.00434 (12)	0.01006 (13)	0.00274 (12)
Cl1	0.0253 (4)	0.0231 (4)	0.0234 (5)	0.0034 (3)	0.0097 (4)	−0.0003 (3)
Cl2	0.0174 (4)	0.0274 (4)	0.0279 (5)	0.0026 (3)	0.0088 (4)	0.0041 (4)
Cl3	0.0252 (4)	0.0212 (4)	0.0287 (5)	0.0079 (3)	0.0115 (4)	0.0047 (4)
Cl4	0.0249 (4)	0.0248 (4)	0.0264 (5)	0.0041 (3)	0.0142 (4)	0.0067 (4)
Cl5	0.0336 (5)	0.0222 (4)	0.0385 (5)	−0.0019 (4)	0.0151 (4)	0.0018 (4)
Cl6	0.0290 (5)	0.0361 (5)	0.0254 (5)	0.0108 (4)	0.0087 (4)	0.0072 (4)
Cl7	0.0331 (5)	0.0407 (5)	0.0373 (5)	0.0137 (4)	0.0223 (4)	0.0051 (4)
N1	0.0345 (19)	0.039 (2)	0.0338 (19)	0.0056 (16)	0.0181 (16)	0.0081 (16)
C1	0.028 (2)	0.036 (2)	0.029 (2)	0.0097 (17)	0.0132 (17)	0.0136 (17)
C2	0.039 (2)	0.038 (2)	0.032 (2)	0.015 (2)	0.018 (2)	0.0055 (19)
C2A	0.039 (2)	0.038 (2)	0.032 (2)	0.015 (2)	0.018 (2)	0.0055 (19)
C3	0.035 (2)	0.049 (3)	0.033 (2)	0.010 (2)	0.021 (2)	0.012 (2)
C3A	0.035 (2)	0.049 (3)	0.033 (2)	0.010 (2)	0.021 (2)	0.012 (2)
O1	0.0426 (16)	0.0405 (16)	0.0385 (17)	0.0171 (13)	0.0145 (14)	0.0111 (13)
N2	0.0296 (17)	0.0395 (19)	0.040 (2)	0.0109 (15)	0.0191 (15)	0.0086 (15)
C4	0.030 (2)	0.060 (3)	0.054 (3)	0.013 (2)	0.015 (2)	0.027 (2)
C5	0.109 (5)	0.126 (5)	0.065 (4)	0.083 (4)	0.045 (3)	0.016 (4)
C6	0.032 (2)	0.0247 (19)	0.039 (2)	0.0027 (17)	0.0197 (19)	0.0024 (17)
O2	0.0527 (19)	0.0526 (19)	0.052 (2)	0.0122 (15)	0.0172 (16)	0.0249 (16)
N3	0.0329 (18)	0.0305 (18)	0.040 (2)	0.0080 (15)	0.0073 (15)	0.0089 (15)
C7	0.048 (3)	0.060 (3)	0.082 (4)	−0.008 (3)	−0.001 (3)	0.027 (3)
C8	0.076 (3)	0.054 (3)	0.041 (3)	0.032 (3)	0.029 (2)	0.016 (2)
C9	0.033 (2)	0.027 (2)	0.051 (3)	0.0096 (18)	0.007 (2)	0.003 (2)
O3	0.0490 (18)	0.0476 (18)	0.071 (2)	0.0059 (15)	0.0388 (17)	0.0033 (16)
N4	0.0308 (17)	0.0370 (19)	0.0326 (19)	0.0017 (15)	0.0122 (15)	0.0045 (15)
C10	0.047 (3)	0.057 (3)	0.064 (3)	0.012 (2)	0.028 (2)	0.008 (2)
C11	0.051 (3)	0.055 (3)	0.048 (3)	0.009 (2)	0.021 (2)	0.020 (2)
C12	0.039 (2)	0.040 (2)	0.037 (2)	−0.004 (2)	0.014 (2)	0.0043 (19)

Geometric parameters (Å, º) top

Mo1—Mo2ⁱ	2.6065 (5)	C3A—H3A	0.9500
Mo1—Mo2	2.6040 (5)	O1—C6	1.229 (4)
Mo1—Mo3	2.6039 (5)	N2—C4	1.456 (5)
Mo1—Mo3ⁱ	2.5984 (5)	N2—C5	1.435 (5)
Mo1—Cl1	2.4724 (9)	N2—C6	1.312 (4)
Mo1—Cl2	2.4764 (9)	C4—H4A	0.9800
Mo1—Cl3	2.4727 (9)	C4—H4B	0.9800
Mo1—Cl4	2.4708 (9)	C4—H4C	0.9800
Mo1—Cl5	2.4277 (9)	C5—H5A	0.9800
Mo2—Mo3ⁱ	2.6027 (5)	C5—H5B	0.9800
Mo2—Mo3	2.6055 (5)	C5—H5C	0.9800
Mo2—Cl1	2.4729 (9)	C6—H6	0.9500
Mo2—Cl2	2.4644 (9)	O2—C9	1.228 (5)
Mo2—Cl3ⁱ	2.4682 (9)	N3—C7	1.442 (5)
Mo2—Cl4ⁱ	2.4629 (9)	N3—C8	1.450 (5)
Mo2—Cl6	2.4436 (9)	N3—C9	1.316 (5)
Mo3—Cl1	2.4781 (9)	C7—H7A	0.9800
Mo3—Cl2ⁱ	2.4751 (9)	C7—H7B	0.9800
Mo3—Cl3	2.4724 (9)	C7—H7C	0.9800
Mo3—Cl4ⁱ	2.4632 (9)	C8—H8A	0.9800
Mo3—Cl7	2.4116 (9)	C8—H8B	0.9800
N1—H1A	0.922 (18)	C8—H8C	0.9800
N1—H1B	0.927 (18)	C9—H9	0.9500
N1—H1C	0.924 (18)	O3—C12	1.227 (5)
N1—C1	1.458 (5)	N4—C10	1.453 (5)
C1—C2	1.367 (5)	N4—C11	1.450 (5)
C1—C2A	1.361 (16)	N4—C12	1.314 (5)
C1—C3	1.377 (5)	C10—H10A	0.9800
C1—C3A	1.366 (16)	C10—H10B	0.9800
C2—H2	0.9500	C10—H10C	0.9800
C2—C3ⁱⁱ	1.378 (5)	C11—H11A	0.9800
C2A—H2A	0.9500	C11—H11B	0.9800
C2A—C3Aⁱⁱ	1.380 (15)	C11—H11C	0.9800
C3—H3	0.9500	C12—H12	0.9500

Mo2—Mo1—Mo2ⁱ	90.126 (16)	Cl4ⁱ—Mo3—Cl3	175.60 (3)
Mo3—Mo1—Mo2ⁱ	59.936 (14)	Cl7—Mo3—Mo1	136.77 (3)
Mo3—Mo1—Mo2	60.038 (12)	Cl7—Mo3—Mo1ⁱ	133.17 (3)
Mo3ⁱ—Mo1—Mo2ⁱ	60.074 (13)	Cl7—Mo3—Mo2ⁱ	135.56 (3)
Mo3ⁱ—Mo1—Mo2	60.036 (15)	Cl7—Mo3—Mo2	134.21 (3)
Mo3ⁱ—Mo1—Mo3	89.946 (14)	Cl7—Mo3—Cl1	92.98 (3)
Cl1—Mo1—Mo2ⁱ	118.30 (2)	Cl7—Mo3—Cl2ⁱ	91.41 (3)
Cl1—Mo1—Mo2	58.24 (2)	Cl7—Mo3—Cl3	93.96 (3)
Cl1—Mo1—Mo3ⁱ	118.26 (2)	Cl7—Mo3—Cl4ⁱ	90.44 (3)
Cl1—Mo1—Mo3	58.37 (2)	Mo1—Cl1—Mo2	63.55 (2)
Cl1—Mo1—Cl2	89.61 (3)	Mo1—Cl1—Mo3	63.47 (2)
Cl1—Mo1—Cl3	90.01 (3)	Mo2—Cl1—Mo3	63.50 (2)
Cl2—Mo1—Mo2	57.97 (2)	Mo2—Cl2—Mo1	63.61 (2)
Cl2—Mo1—Mo2ⁱ	118.37 (2)	Mo2—Cl2—Mo3ⁱ	63.59 (2)
Cl2—Mo1—Mo3ⁱ	58.32 (2)	Mo3ⁱ—Cl2—Mo1	63.31 (2)
Cl2—Mo1—Mo3	117.99 (2)	Mo2ⁱ—Cl3—Mo1	63.68 (2)
Cl3—Mo1—Mo2ⁱ	58.08 (2)	Mo2ⁱ—Cl3—Mo3	63.58 (2)
Cl3—Mo1—Mo2	118.24 (2)	Mo3—Cl3—Mo1	63.55 (2)
Cl3—Mo1—Mo3ⁱ	118.13 (2)	Mo2ⁱ—Cl4—Mo1	63.78 (2)
Cl3—Mo1—Mo3	58.22 (2)	Mo2ⁱ—Cl4—Mo3ⁱ	63.86 (2)
Cl3—Mo1—Cl2	175.50 (3)	Mo3ⁱ—Cl4—Mo1	63.56 (2)
Cl4—Mo1—Mo2ⁱ	57.96 (2)	H1A—N1—H1B	112 (4)
Cl4—Mo1—Mo2	118.09 (2)	H1A—N1—H1C	110 (4)
Cl4—Mo1—Mo3	117.88 (2)	H1B—N1—H1C	103 (3)
Cl4—Mo1—Mo3ⁱ	58.08 (2)	C1—N1—H1A	108 (3)
Cl4—Mo1—Cl1	175.46 (3)	C1—N1—H1B	109 (3)
Cl4—Mo1—Cl2	90.28 (3)	C1—N1—H1C	114 (3)
Cl4—Mo1—Cl3	89.74 (3)	C2—C1—N1	119.9 (3)
Cl5—Mo1—Mo2ⁱ	134.38 (3)	C2—C1—C3	120.7 (4)
Cl5—Mo1—Mo2	135.49 (3)	C2A—C1—N1	119.6 (15)
Cl5—Mo1—Mo3	135.18 (2)	C2A—C1—C3A	120.3 (10)
Cl5—Mo1—Mo3ⁱ	134.87 (3)	C3—C1—N1	119.4 (3)
Cl5—Mo1—Cl1	92.58 (3)	C3A—C1—N1	120.1 (16)
Cl5—Mo1—Cl2	92.57 (3)	C1—C2—H2	119.9
Cl5—Mo1—Cl3	91.93 (3)	C1—C2—C3ⁱⁱ	120.1 (4)
Cl5—Mo1—Cl4	91.96 (3)	C3ⁱⁱ—C2—H2	119.9
Mo1—Mo2—Mo1ⁱ	89.873 (16)	C1—C2A—H2A	121.4
Mo1—Mo2—Mo3	59.978 (12)	C1—C2A—C3Aⁱⁱ	117 (3)
Mo3ⁱ—Mo2—Mo1ⁱ	59.981 (14)	C3Aⁱⁱ—C2A—H2A	121.4
Mo3ⁱ—Mo2—Mo1	59.875 (13)	C1—C3—C2ⁱⁱ	119.2 (4)
Mo3—Mo2—Mo1ⁱ	59.809 (14)	C1—C3—H3	120.4
Mo3ⁱ—Mo2—Mo3	89.819 (14)	C2ⁱⁱ—C3—H3	120.4
Cl1—Mo2—Mo1ⁱ	118.14 (2)	C1—C3A—C2Aⁱⁱ	122 (3)
Cl1—Mo2—Mo1	58.22 (2)	C1—C3A—H3A	118.8
Cl1—Mo2—Mo3ⁱ	118.08 (2)	C2Aⁱⁱ—C3A—H3A	118.8
Cl1—Mo2—Mo3	58.34 (2)	C5—N2—C4	117.3 (3)
Cl2—Mo2—Mo1ⁱ	118.37 (2)	C6—N2—C4	122.3 (3)
Cl2—Mo2—Mo1	58.42 (2)	C6—N2—C5	120.4 (3)
Cl2—Mo2—Mo3	118.38 (2)	N2—C4—H4A	109.5
Cl2—Mo2—Mo3ⁱ	58.40 (2)	N2—C4—H4B	109.5
Cl2—Mo2—Cl1	89.88 (3)	N2—C4—H4C	109.5
Cl2—Mo2—Cl3ⁱ	89.95 (3)	H4A—C4—H4B	109.5
Cl3ⁱ—Mo2—Mo1ⁱ	58.25 (2)	H4A—C4—H4C	109.5
Cl3ⁱ—Mo2—Mo1	118.15 (2)	H4B—C4—H4C	109.5
Cl3ⁱ—Mo2—Mo3ⁱ	58.29 (2)	N2—C5—H5A	109.5
Cl3ⁱ—Mo2—Mo3	118.04 (2)	N2—C5—H5B	109.5
Cl3ⁱ—Mo2—Cl1	175.56 (3)	N2—C5—H5C	109.5
Cl4ⁱ—Mo2—Mo1	118.04 (2)	H5A—C5—H5B	109.5
Cl4ⁱ—Mo2—Mo1ⁱ	58.26 (2)	H5A—C5—H5C	109.5
Cl4ⁱ—Mo2—Mo3	58.07 (2)	H5B—C5—H5C	109.5
Cl4ⁱ—Mo2—Mo3ⁱ	118.22 (2)	O1—C6—N2	127.2 (4)
Cl4ⁱ—Mo2—Cl1	89.81 (3)	O1—C6—H6	116.4
Cl4ⁱ—Mo2—Cl2	175.77 (3)	N2—C6—H6	116.4
Cl4ⁱ—Mo2—Cl3ⁱ	90.03 (3)	C7—N3—C8	117.8 (4)
Cl6—Mo2—Mo1ⁱ	133.87 (3)	C9—N3—C7	120.7 (4)
Cl6—Mo2—Mo1	136.26 (3)	C9—N3—C8	121.5 (4)
Cl6—Mo2—Mo3ⁱ	134.96 (3)	N3—C7—H7A	109.5
Cl6—Mo2—Mo3	135.19 (2)	N3—C7—H7B	109.5
Cl6—Mo2—Cl1	93.14 (3)	N3—C7—H7C	109.5
Cl6—Mo2—Cl2	92.74 (3)	H7A—C7—H7B	109.5
Cl6—Mo2—Cl3ⁱ	91.30 (3)	H7A—C7—H7C	109.5
Cl6—Mo2—Cl4ⁱ	91.49 (3)	H7B—C7—H7C	109.5
Mo1ⁱ—Mo3—Mo1	90.053 (14)	N3—C8—H8A	109.5
Mo1ⁱ—Mo3—Mo2ⁱ	60.086 (12)	N3—C8—H8B	109.5
Mo1—Mo3—Mo2	59.984 (14)	N3—C8—H8C	109.5
Mo1ⁱ—Mo3—Mo2	60.116 (12)	H8A—C8—H8B	109.5
Mo2ⁱ—Mo3—Mo1	60.082 (11)	H8A—C8—H8C	109.5
Mo2ⁱ—Mo3—Mo2	90.179 (13)	H8B—C8—H8C	109.5
Cl1—Mo3—Mo1ⁱ	118.25 (2)	O2—C9—N3	126.1 (4)
Cl1—Mo3—Mo1	58.16 (2)	O2—C9—H9	116.9
Cl1—Mo3—Mo2	58.15 (2)	N3—C9—H9	116.9
Cl1—Mo3—Mo2ⁱ	118.23 (2)	C11—N4—C10	117.9 (3)
Cl2ⁱ—Mo3—Mo1	118.07 (2)	C12—N4—C10	121.7 (3)
Cl2ⁱ—Mo3—Mo1ⁱ	58.37 (2)	C12—N4—C11	120.3 (4)
Cl2ⁱ—Mo3—Mo2	118.46 (2)	N4—C10—H10A	109.5
Cl2ⁱ—Mo3—Mo2ⁱ	58.00 (2)	N4—C10—H10B	109.5
Cl2ⁱ—Mo3—Cl1	175.60 (3)	N4—C10—H10C	109.5
Cl3—Mo3—Mo1	58.23 (2)	H10A—C10—H10B	109.5
Cl3—Mo3—Mo1ⁱ	118.20 (2)	H10A—C10—H10C	109.5
Cl3—Mo3—Mo2	118.20 (2)	H10B—C10—H10C	109.5
Cl3—Mo3—Mo2ⁱ	58.13 (2)	N4—C11—H11A	109.5
Cl3—Mo3—Cl1	89.89 (3)	N4—C11—H11B	109.5
Cl3—Mo3—Cl2ⁱ	89.61 (3)	N4—C11—H11C	109.5
Cl4ⁱ—Mo3—Mo1	118.03 (2)	H11A—C11—H11B	109.5
Cl4ⁱ—Mo3—Mo1ⁱ	58.36 (2)	H11A—C11—H11C	109.5
Cl4ⁱ—Mo3—Mo2ⁱ	118.43 (2)	H11B—C11—H11C	109.5
Cl4ⁱ—Mo3—Mo2	58.06 (2)	O3—C12—N4	125.0 (4)
Cl4ⁱ—Mo3—Cl1	89.68 (3)	O3—C12—H12	117.5
Cl4ⁱ—Mo3—Cl2ⁱ	90.48 (3)	N4—C12—H12	117.5

N1—C1—C2—C3ⁱⁱ	178.5 (3)	C3A—C1—C2A—C3Aⁱⁱ	1.0 (17)
N1—C1—C2A—C3Aⁱⁱ	−179.7 (9)	C4—N2—C6—O1	177.0 (4)
N1—C1—C3—C2ⁱⁱ	−178.5 (3)	C5—N2—C6—O1	−1.6 (6)
N1—C1—C3A—C2Aⁱⁱ	179.7 (9)	C7—N3—C9—O2	−2.6 (6)
C2—C1—C3—C2ⁱⁱ	0.3 (6)	C8—N3—C9—O2	179.8 (4)
C2A—C1—C3A—C2Aⁱⁱ	−1.1 (18)	C10—N4—C12—O3	177.3 (4)
C3—C1—C2—C3ⁱⁱ	−0.3 (6)	C11—N4—C12—O3	0.4 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱⁱ	0.92 (2)	1.76 (2)	2.672 (4)	171 (4)
N1—H1B···O3^iv	0.93 (2)	1.79 (2)	2.710 (4)	173 (4)
N1—H1C···O1ⁱ	0.92 (2)	1.81 (2)	2.727 (4)	175 (4)

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

N,N'-(1,4-Phenylene)bis(propan-2-iminium) octa-µ₃-chlorido-hexachlorido-octahedro-hexamolybdate acetone trisolvate (3) top

Crystal data top

(C₁₂H₁₈N₂)[Mo₆Cl₈Cl₆]·3C₃H₆O	Z = 1
M_r = 1436.46	F(000) = 690
Triclinic, P1	D_x = 2.257 Mg m⁻³
a = 9.451 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.236 (3) Å	Cell parameters from 5309 reflections
c = 11.712 (3) Å	θ = 2.2–25.1°
α = 64.933 (6)°	µ = 2.64 mm⁻¹
β = 71.174 (6)°	T = 200 K
γ = 75.440 (6)°	Block, clear light orange
V = 1056.7 (5) Å³	0.55 × 0.33 × 0.20 mm

Data collection top

Bruker SMART X2S benchtop diffractometer	3692 independent reflections
Radiation source: sealed microfocus source, XOS X-beam microfocus source	3220 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 8.3330 pixels mm^-1	θ_max = 25.2°, θ_min = 2.6°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −13→13
T_min = 0.490, T_max = 0.745	l = −13→13
10036 measured reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0347P)² + 0.3989P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3692 reflections	Δρ_max = 0.96 e Å⁻³
235 parameters	Δρ_min = −0.82 e Å⁻³
13 restraints

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	0.54044 (3)	0.46936 (2)	0.65449 (2)	0.01669 (9)
Mo2	0.46251 (3)	0.32776 (2)	0.56169 (2)	0.01681 (9)
Mo3	0.29965 (3)	0.55064 (2)	0.56544 (2)	0.01718 (9)
Cl1	0.41212 (10)	0.10003 (8)	0.64118 (8)	0.0324 (2)
Cl2	0.76390 (8)	0.58538 (7)	0.52537 (7)	0.02273 (17)
Cl3	0.69229 (9)	0.25958 (7)	0.64379 (7)	0.02413 (18)
Cl4	0.59212 (10)	0.43277 (8)	0.85707 (7)	0.0303 (2)
Cl5	0.38283 (9)	0.68264 (7)	0.65005 (7)	0.02236 (17)
Cl6	0.31409 (9)	0.35417 (8)	0.76707 (7)	0.02377 (18)
Cl7	0.03772 (9)	0.61748 (9)	0.65222 (9)	0.0360 (2)
N1	0.2062 (3)	0.0615 (3)	0.2565 (3)	0.0242 (6)
H1	0.196 (4)	0.021 (3)	0.211 (3)	0.036*
C1	0.4140 (4)	0.1369 (4)	0.0787 (3)	0.0382 (9)
H1A	0.431717	0.228439	0.022574	0.057*
H1B	0.366916	0.102550	0.037660	0.057*
H1C	0.510355	0.081919	0.091601	0.057*
C2	0.3131 (4)	0.1337 (3)	0.2058 (3)	0.0265 (7)
C3	0.3406 (4)	0.2109 (3)	0.2704 (4)	0.0370 (9)
H3A	0.424810	0.163487	0.311157	0.056*
H3B	0.249770	0.222227	0.337134	0.056*
H3C	0.365572	0.298048	0.205817	0.056*
C4	0.1507 (4)	−0.0037 (3)	0.4928 (3)	0.0281 (7)
H4	0.253881	−0.006002	0.486934	0.034*
C5	0.1019 (4)	0.0328 (3)	0.3819 (3)	0.0227 (7)
C6	−0.0482 (4)	0.0368 (3)	0.3885 (3)	0.0274 (7)
H6	−0.079966	0.062241	0.311317	0.033*
O1	0.1737 (3)	0.9573 (3)	0.0897 (2)	0.0440 (7)
C7	0.0245 (5)	0.7839 (4)	0.1942 (4)	0.0502 (11)
H7A	0.012696	0.802221	0.271696	0.075*
H7B	0.067673	0.691137	0.209401	0.075*
H7C	−0.074289	0.800190	0.175911	0.075*
C8	0.1262 (4)	0.8717 (4)	0.0818 (4)	0.0345 (8)
C9	0.1705 (5)	0.8501 (4)	−0.0432 (4)	0.0468 (10)
H9A	0.205823	0.930184	−0.115350	0.070*
H9B	0.083109	0.830392	−0.056688	0.070*
H9C	0.251527	0.775370	−0.039653	0.070*
O2	0.0767 (6)	0.3001 (5)	0.0578 (5)	0.0461 (13)	0.5
C10	0.0375 (9)	0.4167 (7)	0.0246 (6)	0.0351 (17)	0.5
C11	0.143 (2)	0.512 (2)	−0.011 (2)	0.049 (5)	0.5
H11A	0.117815	0.548863	0.056809	0.073*	0.5
H11B	0.134909	0.584134	−0.094095	0.073*	0.5
H11C	0.246860	0.466249	−0.018685	0.073*	0.5
C12	−0.1156 (17)	0.473 (2)	0.006 (2)	0.044 (5)	0.5
H12A	−0.114886	0.495968	−0.085108	0.067*	0.5
H12B	−0.148442	0.553655	0.026059	0.067*	0.5
H12C	−0.185388	0.408443	0.063119	0.067*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01921 (17)	0.01543 (15)	0.01644 (15)	−0.00245 (12)	−0.00747 (11)	−0.00459 (11)
Mo2	0.01936 (17)	0.01344 (15)	0.01826 (15)	−0.00251 (11)	−0.00714 (11)	−0.00450 (11)
Mo3	0.01548 (17)	0.01715 (15)	0.01989 (15)	−0.00117 (11)	−0.00588 (11)	−0.00728 (12)
Cl1	0.0385 (5)	0.0179 (4)	0.0390 (5)	−0.0077 (4)	−0.0110 (4)	−0.0057 (3)
Cl2	0.0208 (4)	0.0243 (4)	0.0272 (4)	−0.0053 (3)	−0.0092 (3)	−0.0098 (3)
Cl3	0.0278 (4)	0.0172 (4)	0.0286 (4)	0.0030 (3)	−0.0158 (3)	−0.0065 (3)
Cl4	0.0429 (5)	0.0301 (4)	0.0223 (4)	−0.0098 (4)	−0.0159 (4)	−0.0053 (3)
Cl5	0.0248 (4)	0.0208 (4)	0.0247 (4)	−0.0008 (3)	−0.0075 (3)	−0.0118 (3)
Cl6	0.0266 (4)	0.0245 (4)	0.0186 (4)	−0.0084 (3)	−0.0029 (3)	−0.0057 (3)
Cl7	0.0189 (4)	0.0453 (5)	0.0457 (5)	0.0015 (4)	−0.0055 (4)	−0.0237 (4)
N1	0.0263 (16)	0.0219 (14)	0.0257 (14)	−0.0046 (12)	−0.0068 (12)	−0.0090 (11)
C1	0.040 (2)	0.036 (2)	0.0310 (19)	−0.0163 (18)	−0.0023 (16)	−0.0037 (16)
C2	0.0241 (19)	0.0158 (16)	0.0354 (18)	0.0018 (14)	−0.0126 (15)	−0.0045 (14)
C3	0.037 (2)	0.0235 (18)	0.054 (2)	−0.0030 (16)	−0.0155 (18)	−0.0152 (17)
C4	0.0213 (18)	0.0312 (18)	0.0346 (18)	−0.0018 (15)	−0.0099 (15)	−0.0136 (15)
C5	0.0251 (19)	0.0163 (15)	0.0275 (16)	0.0008 (13)	−0.0074 (14)	−0.0102 (13)
C6	0.028 (2)	0.0311 (18)	0.0265 (17)	−0.0021 (15)	−0.0113 (14)	−0.0115 (15)
O1	0.0565 (18)	0.0433 (16)	0.0429 (15)	−0.0198 (14)	−0.0152 (13)	−0.0166 (13)
C7	0.038 (2)	0.047 (2)	0.063 (3)	−0.012 (2)	−0.013 (2)	−0.014 (2)
C8	0.031 (2)	0.0322 (19)	0.043 (2)	0.0004 (16)	−0.0204 (17)	−0.0105 (16)
C9	0.057 (3)	0.043 (2)	0.050 (2)	−0.001 (2)	−0.028 (2)	−0.018 (2)
O2	0.051 (4)	0.037 (3)	0.052 (3)	−0.007 (3)	−0.016 (3)	−0.015 (3)
C10	0.046 (5)	0.038 (5)	0.020 (3)	−0.006 (4)	−0.003 (3)	−0.013 (3)
C11	0.048 (8)	0.054 (10)	0.061 (10)	−0.010 (7)	−0.008 (8)	−0.040 (8)
C12	0.043 (7)	0.042 (8)	0.036 (8)	0.000 (6)	0.006 (5)	−0.017 (7)

Geometric parameters (Å, º) top

Mo1—Mo2ⁱ	2.5943 (6)	C2—C3	1.480 (5)
Mo1—Mo2	2.6126 (5)	C3—H3A	0.9800
Mo1—Mo3	2.6038 (6)	C3—H3B	0.9800
Mo1—Mo3ⁱ	2.6031 (7)	C3—H3C	0.9800
Mo1—Cl2	2.4695 (9)	C4—H4	0.9500
Mo1—Cl3	2.4627 (9)	C4—C5	1.381 (4)
Mo1—Cl4	2.4202 (9)	C4—C6ⁱⁱ	1.372 (5)
Mo1—Cl5	2.4727 (9)	C5—C6	1.386 (4)
Mo1—Cl6	2.4729 (9)	C6—H6	0.9500
Mo2—Mo3ⁱ	2.6069 (6)	O1—C8	1.206 (4)
Mo2—Mo3	2.5989 (7)	C7—H7A	0.9800
Mo2—Cl1	2.4391 (10)	C7—H7B	0.9800
Mo2—Cl2ⁱ	2.4668 (9)	C7—H7C	0.9800
Mo2—Cl3	2.4727 (9)	C7—C8	1.480 (5)
Mo2—Cl5ⁱ	2.4738 (9)	C8—C9	1.494 (5)
Mo2—Cl6	2.4616 (9)	C9—H9A	0.9800
Mo3—Cl2ⁱ	2.4655 (8)	C9—H9B	0.9800
Mo3—Cl3ⁱ	2.4680 (9)	C9—H9C	0.9800
Mo3—Cl5	2.4767 (8)	O2—C10	1.193 (8)
Mo3—Cl6	2.4714 (9)	C10—C11	1.488 (13)
Mo3—Cl7	2.4110 (10)	C10—C12	1.475 (13)
N1—H1	0.870 (18)	C11—H11A	0.9800
N1—C2	1.284 (4)	C11—H11B	0.9800
N1—C5	1.434 (4)	C11—H11C	0.9800
C1—H1A	0.9800	C12—H12A	0.9800
C1—H1B	0.9800	C12—H12B	0.9800
C1—H1C	0.9800	C12—H12C	0.9800
C1—C2	1.477 (5)

Mo2ⁱ—Mo1—Mo2	89.98 (2)	Cl3ⁱ—Mo3—Cl5	89.98 (3)
Mo2ⁱ—Mo1—Mo3ⁱ	60.005 (19)	Cl3ⁱ—Mo3—Cl6	175.12 (3)
Mo2ⁱ—Mo1—Mo3	60.202 (14)	Cl5—Mo3—Mo1	58.18 (2)
Mo3ⁱ—Mo1—Mo2	59.977 (16)	Cl5—Mo3—Mo1ⁱ	118.35 (2)
Mo3—Mo1—Mo2	59.763 (15)	Cl5—Mo3—Mo2ⁱ	58.17 (2)
Mo3ⁱ—Mo1—Mo3	89.98 (2)	Cl5—Mo3—Mo2	118.46 (3)
Cl2—Mo1—Mo2	118.05 (2)	Cl6—Mo3—Mo1	58.25 (2)
Cl2—Mo1—Mo2ⁱ	58.24 (2)	Cl6—Mo3—Mo1ⁱ	117.84 (3)
Cl2—Mo1—Mo3ⁱ	58.09 (2)	Cl6—Mo3—Mo2	58.02 (2)
Cl2—Mo1—Mo3	118.42 (3)	Cl6—Mo3—Mo2ⁱ	117.94 (2)
Cl2—Mo1—Cl5	90.29 (3)	Cl6—Mo3—Cl5	90.12 (3)
Cl2—Mo1—Cl6	175.36 (2)	Cl7—Mo3—Mo1	134.62 (3)
Cl3—Mo1—Mo2	58.22 (2)	Cl7—Mo3—Mo1ⁱ	135.36 (2)
Cl3—Mo1—Mo2ⁱ	118.22 (2)	Cl7—Mo3—Mo2ⁱ	134.89 (3)
Cl3—Mo1—Mo3ⁱ	58.23 (2)	Cl7—Mo3—Mo2	135.11 (3)
Cl3—Mo1—Mo3	117.98 (2)	Cl7—Mo3—Cl2ⁱ	92.39 (3)
Cl3—Mo1—Cl2	89.80 (3)	Cl7—Mo3—Cl3ⁱ	92.59 (3)
Cl3—Mo1—Cl5	175.65 (2)	Cl7—Mo3—Cl5	91.72 (3)
Cl3—Mo1—Cl6	89.39 (3)	Cl7—Mo3—Cl6	92.28 (3)
Cl4—Mo1—Mo2ⁱ	134.02 (3)	Mo2ⁱ—Cl2—Mo1	63.41 (2)
Cl4—Mo1—Mo2	136.00 (2)	Mo3ⁱ—Cl2—Mo1	63.67 (2)
Cl4—Mo1—Mo3ⁱ	135.46 (3)	Mo3ⁱ—Cl2—Mo2ⁱ	63.59 (2)
Cl4—Mo1—Mo3	134.55 (2)	Mo1—Cl3—Mo2	63.92 (2)
Cl4—Mo1—Cl2	91.90 (3)	Mo1—Cl3—Mo3ⁱ	63.73 (2)
Cl4—Mo1—Cl3	93.21 (3)	Mo3ⁱ—Cl3—Mo2	63.69 (2)
Cl4—Mo1—Cl5	91.13 (3)	Mo1—Cl5—Mo2ⁱ	63.26 (2)
Cl4—Mo1—Cl6	92.71 (3)	Mo1—Cl5—Mo3	63.48 (2)
Cl5—Mo1—Mo2ⁱ	58.39 (2)	Mo2ⁱ—Cl5—Mo3	63.55 (2)
Cl5—Mo1—Mo2	118.08 (2)	Mo2—Cl6—Mo1	63.94 (2)
Cl5—Mo1—Mo3	58.33 (2)	Mo2—Cl6—Mo3	63.58 (3)
Cl5—Mo1—Mo3ⁱ	118.37 (2)	Mo3—Cl6—Mo1	63.56 (2)
Cl5—Mo1—Cl6	90.17 (3)	C2—N1—H1	117 (2)
Cl6—Mo1—Mo2ⁱ	118.37 (2)	C2—N1—C5	129.1 (3)
Cl6—Mo1—Mo2	57.82 (2)	C5—N1—H1	114 (2)
Cl6—Mo1—Mo3	58.19 (2)	H1A—C1—H1B	109.5
Cl6—Mo1—Mo3ⁱ	117.79 (2)	H1A—C1—H1C	109.5
Mo1ⁱ—Mo2—Mo1	90.02 (2)	H1B—C1—H1C	109.5
Mo1ⁱ—Mo2—Mo3	60.165 (17)	C2—C1—H1A	109.5
Mo1ⁱ—Mo2—Mo3ⁱ	60.081 (15)	C2—C1—H1B	109.5
Mo3—Mo2—Mo1	59.951 (17)	C2—C1—H1C	109.5
Mo3ⁱ—Mo2—Mo1	59.830 (17)	N1—C2—C1	118.1 (3)
Mo3—Mo2—Mo3ⁱ	90.00 (2)	N1—C2—C3	122.8 (3)
Cl1—Mo2—Mo1	135.83 (3)	C1—C2—C3	119.1 (3)
Cl1—Mo2—Mo1ⁱ	134.15 (2)	C2—C3—H3A	109.5
Cl1—Mo2—Mo3	134.88 (3)	C2—C3—H3B	109.5
Cl1—Mo2—Mo3ⁱ	135.11 (2)	C2—C3—H3C	109.5
Cl1—Mo2—Cl2ⁱ	91.56 (3)	H3A—C3—H3B	109.5
Cl1—Mo2—Cl3	93.08 (3)	H3A—C3—H3C	109.5
Cl1—Mo2—Cl5ⁱ	91.61 (3)	H3B—C3—H3C	109.5
Cl1—Mo2—Cl6	92.55 (3)	C5—C4—H4	120.4
Cl2ⁱ—Mo2—Mo1ⁱ	58.35 (2)	C6ⁱⁱ—C4—H4	120.4
Cl2ⁱ—Mo2—Mo1	118.11 (2)	C6ⁱⁱ—C4—C5	119.1 (3)
Cl2ⁱ—Mo2—Mo3ⁱ	118.40 (2)	C4—C5—N1	121.0 (3)
Cl2ⁱ—Mo2—Mo3	58.18 (2)	C4—C5—C6	121.2 (3)
Cl2ⁱ—Mo2—Cl3	175.35 (2)	C6—C5—N1	117.7 (3)
Cl2ⁱ—Mo2—Cl5ⁱ	90.33 (3)	C4ⁱⁱ—C6—C5	119.6 (3)
Cl3—Mo2—Mo1	57.85 (2)	C4ⁱⁱ—C6—H6	120.2
Cl3—Mo2—Mo1ⁱ	118.13 (2)	C5—C6—H6	120.2
Cl3—Mo2—Mo3ⁱ	58.07 (2)	H7A—C7—H7B	109.5
Cl3—Mo2—Mo3	117.79 (2)	H7A—C7—H7C	109.5
Cl3—Mo2—Cl5ⁱ	89.93 (3)	H7B—C7—H7C	109.5
Cl5ⁱ—Mo2—Mo1	118.09 (2)	C8—C7—H7A	109.5
Cl5ⁱ—Mo2—Mo1ⁱ	58.35 (2)	C8—C7—H7B	109.5
Cl5ⁱ—Mo2—Mo3ⁱ	58.28 (2)	C8—C7—H7C	109.5
Cl5ⁱ—Mo2—Mo3	118.49 (2)	O1—C8—C7	121.9 (4)
Cl6—Mo2—Mo1	58.24 (2)	O1—C8—C9	120.5 (3)
Cl6—Mo2—Mo1ⁱ	118.54 (3)	C7—C8—C9	117.7 (3)
Cl6—Mo2—Mo3ⁱ	118.06 (2)	C8—C9—H9A	109.5
Cl6—Mo2—Mo3	58.39 (2)	C8—C9—H9B	109.5
Cl6—Mo2—Cl2ⁱ	89.98 (3)	C8—C9—H9C	109.5
Cl6—Mo2—Cl3	89.42 (3)	H9A—C9—H9B	109.5
Cl6—Mo2—Cl5ⁱ	175.82 (2)	H9A—C9—H9C	109.5
Mo1ⁱ—Mo3—Mo1	90.025 (19)	H9B—C9—H9C	109.5
Mo1—Mo3—Mo2ⁱ	59.719 (18)	O2—C10—C11	122.1 (9)
Mo1ⁱ—Mo3—Mo2ⁱ	60.193 (13)	O2—C10—C12	120.8 (9)
Mo2—Mo3—Mo1	60.287 (13)	C12—C10—C11	116.9 (14)
Mo2—Mo3—Mo1ⁱ	59.830 (12)	C10—C11—H11A	109.5
Mo2—Mo3—Mo2ⁱ	90.00 (2)	C10—C11—H11B	109.5
Cl2ⁱ—Mo3—Mo1	118.50 (2)	C10—C11—H11C	109.5
Cl2ⁱ—Mo3—Mo1ⁱ	58.24 (2)	H11A—C11—H11B	109.5
Cl2ⁱ—Mo3—Mo2	58.23 (2)	H11A—C11—H11C	109.5
Cl2ⁱ—Mo3—Mo2ⁱ	118.42 (2)	H11B—C11—H11C	109.5
Cl2ⁱ—Mo3—Cl3ⁱ	89.77 (3)	C10—C12—H12A	109.5
Cl2ⁱ—Mo3—Cl5	175.88 (3)	C10—C12—H12B	109.5
Cl2ⁱ—Mo3—Cl6	89.79 (3)	C10—C12—H12C	109.5
Cl3ⁱ—Mo3—Mo1ⁱ	58.03 (2)	H12A—C12—H12B	109.5
Cl3ⁱ—Mo3—Mo1	117.94 (2)	H12A—C12—H12C	109.5
Cl3ⁱ—Mo3—Mo2ⁱ	58.24 (2)	H12B—C12—H12C	109.5
Cl3ⁱ—Mo3—Mo2	117.85 (2)

N1—C5—C6—C4ⁱⁱ	176.9 (3)	C5—N1—C2—C1	174.4 (3)
C2—N1—C5—C4	−46.6 (5)	C5—N1—C2—C3	−4.4 (5)
C2—N1—C5—C6	136.5 (3)	C6ⁱⁱ—C4—C5—N1	−176.7 (3)
C4—C5—C6—C4ⁱⁱ	−0.1 (5)	C6ⁱⁱ—C4—C5—C6	0.1 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱⁱ	0.87 (2)	1.93 (2)	2.791 (4)	172 (3)

Symmetry code: (iii) x, y−1, z.

1,1'-Dimethyl-4,4'-bipyridinium octa-µ₃-chlorido-hexachlorido-octahedro-hexamolybdate N,N-dimethylformamide tetrasolvate (4) top

Crystal data top

(C₁₂H₁₄N₂)[Mo₆Cl₈Cl₆]·4C₃H₇NO	Z = 1
M_r = 1550.57	F(000) = 750
Triclinic, P1	D_x = 2.161 Mg m⁻³
a = 9.8252 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0933 (11) Å	Cell parameters from 6604 reflections
c = 12.6319 (15) Å	θ = 2.6–25.0°
α = 107.395 (3)°	µ = 2.35 mm⁻¹
β = 91.881 (3)°	T = 200 K
γ = 93.309 (3)°	Block, orange
V = 1191.8 (2) Å³	0.32 × 0.30 × 0.28 mm

Data collection top

Bruker SMART X2S benchtop diffractometer	4187 independent reflections
Radiation source: sealed microfocus source, XOS X-beam microfocus source	3743 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 8.3330 pixels mm^-1	θ_max = 25.1°, θ_min = 2.3°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −11→11
T_min = 0.815, T_max = 1.000	l = −15→15
11498 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.020	w = 1/[σ²(F_o²) + (0.0184P)² + 0.8263P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.049	(Δ/σ)_max = 0.002
S = 1.02	Δρ_max = 0.42 e Å⁻³
4187 reflections	Δρ_min = −0.44 e Å⁻³
250 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0075 (3)
Primary atom site location: heavy-atom method

Special details top

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

	x	y	z	U_iso*/U_eq
Mo1	0.34350 (2)	0.52105 (2)	0.42443 (2)	0.01878 (7)
Mo2	0.43880 (2)	0.61443 (2)	0.62913 (2)	0.01930 (7)
Mo3	0.41622 (2)	0.34763 (2)	0.52876 (2)	0.01916 (7)
Cl4	0.21336 (6)	0.48336 (6)	0.57792 (5)	0.02520 (14)
Cl2	0.51113 (6)	0.44527 (7)	0.72253 (5)	0.02551 (14)
Cl7	0.30745 (7)	0.14843 (7)	0.56719 (6)	0.03486 (17)
Cl6	0.35663 (7)	0.76331 (7)	0.79813 (6)	0.03874 (18)
Cl3	0.32970 (6)	0.26780 (6)	0.33243 (5)	0.02516 (14)
Cl1	0.37330 (6)	0.77313 (6)	0.52328 (5)	0.02510 (14)
Cl5	0.13401 (6)	0.54800 (7)	0.32618 (5)	0.03256 (16)
N1	0.0168 (2)	0.9093 (3)	0.7467 (2)	0.0392 (6)
C3	0.0031 (2)	0.9806 (3)	0.5519 (2)	0.0299 (6)
C6	0.0223 (4)	0.8700 (4)	0.8508 (3)	0.0560 (9)
H6A	0.092144	0.930439	0.903109	0.084*
H6B	0.045141	0.772867	0.834244	0.084*
H6C	−0.066769	0.880619	0.883944	0.084*
O1	0.0987 (4)	0.2529 (3)	0.9699 (2)	0.0947 (11)
N2	0.1930 (3)	0.4599 (3)	0.9693 (2)	0.0462 (7)
C7	0.1610 (5)	0.3616 (4)	1.0150 (3)	0.0661 (11)
H7	0.190127	0.378592	1.090665	0.079*
C9	0.1539 (4)	0.4414 (4)	0.8553 (3)	0.0642 (10)
H9A	0.191569	0.357250	0.808268	0.096*
H9B	0.189323	0.522299	0.834281	0.096*
H9C	0.054111	0.432088	0.845257	0.096*
C8	0.2613 (6)	0.5918 (5)	1.0316 (4)	0.0954 (17)
H8A	0.274154	0.595293	1.109641	0.143*
H8B	0.205703	0.667344	1.026178	0.143*
H8C	0.350353	0.602489	1.001246	0.143*
O2	0.2430 (3)	0.9764 (3)	0.1097 (2)	0.0629 (7)
N3	0.4369 (3)	0.9015 (3)	0.1660 (2)	0.0425 (6)
C10	0.3573 (4)	0.9392 (3)	0.0942 (3)	0.0479 (8)
H10	0.393572	0.936671	0.024855	0.058*
C12	0.3883 (4)	0.9057 (4)	0.2736 (3)	0.0567 (9)
H12A	0.311583	0.965299	0.289780	0.085*
H12B	0.462220	0.943321	0.330545	0.085*
H12C	0.358102	0.811373	0.273342	0.085*
C11	0.5716 (4)	0.8576 (4)	0.1409 (4)	0.0698 (11)
H11A	0.576876	0.762359	0.144373	0.105*
H11B	0.638360	0.920002	0.195053	0.105*
H11C	0.591481	0.860583	0.066069	0.105*
C2	0.0219 (3)	0.8454 (3)	0.5522 (2)	0.0407 (7)
H2	0.030656	0.774946	0.483942	0.049*
C1	0.0281 (3)	0.8128 (4)	0.6492 (3)	0.0450 (8)
H1	0.040636	0.719562	0.647548	0.054*
C4	−0.0086 (4)	1.0768 (3)	0.6542 (3)	0.0499 (9)
H4	−0.021238	1.170823	0.658585	0.060*
C5	−0.0023 (4)	1.0392 (3)	0.7493 (3)	0.0539 (9)
H5	−0.011812	1.107404	0.818648	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01652 (11)	0.02000 (13)	0.02050 (12)	0.00181 (8)	0.00057 (8)	0.00707 (9)
Mo2	0.01846 (11)	0.01990 (13)	0.01947 (12)	0.00228 (9)	0.00309 (8)	0.00547 (9)
Mo3	0.01755 (11)	0.01909 (13)	0.02210 (12)	0.00020 (8)	0.00183 (8)	0.00827 (9)
Cl4	0.0185 (3)	0.0295 (3)	0.0290 (3)	0.0021 (2)	0.0059 (2)	0.0103 (3)
Cl2	0.0272 (3)	0.0301 (4)	0.0223 (3)	0.0025 (3)	0.0018 (2)	0.0124 (3)
Cl7	0.0300 (3)	0.0327 (4)	0.0474 (4)	−0.0075 (3)	−0.0014 (3)	0.0226 (3)
Cl6	0.0430 (4)	0.0374 (4)	0.0305 (4)	0.0072 (3)	0.0131 (3)	0.0001 (3)
Cl3	0.0239 (3)	0.0227 (3)	0.0259 (3)	−0.0016 (2)	−0.0023 (2)	0.0038 (3)
Cl1	0.0240 (3)	0.0207 (3)	0.0318 (3)	0.0047 (2)	0.0021 (2)	0.0090 (3)
Cl5	0.0254 (3)	0.0383 (4)	0.0335 (4)	0.0070 (3)	−0.0058 (3)	0.0100 (3)
N1	0.0294 (12)	0.0537 (17)	0.0346 (13)	0.0046 (11)	0.0096 (10)	0.0125 (12)
C3	0.0193 (12)	0.0339 (16)	0.0316 (14)	−0.0056 (11)	0.0078 (11)	0.0031 (12)
C6	0.054 (2)	0.082 (3)	0.0421 (19)	0.0242 (19)	0.0164 (16)	0.0289 (19)
O1	0.166 (3)	0.0601 (18)	0.0529 (17)	−0.046 (2)	0.0022 (19)	0.0192 (15)
N2	0.0566 (17)	0.0467 (16)	0.0351 (14)	−0.0092 (13)	−0.0047 (12)	0.0153 (13)
C7	0.105 (3)	0.061 (3)	0.0329 (18)	−0.010 (2)	0.0046 (19)	0.0184 (19)
C9	0.078 (3)	0.070 (3)	0.047 (2)	−0.013 (2)	−0.0116 (19)	0.028 (2)
C8	0.132 (4)	0.080 (3)	0.067 (3)	−0.046 (3)	−0.033 (3)	0.026 (3)
O2	0.0563 (16)	0.0770 (18)	0.0618 (16)	0.0167 (14)	−0.0073 (13)	0.0295 (14)
N3	0.0483 (15)	0.0320 (14)	0.0497 (16)	0.0033 (12)	−0.0034 (13)	0.0165 (12)
C10	0.060 (2)	0.0404 (19)	0.0432 (18)	−0.0019 (16)	−0.0034 (16)	0.0146 (16)
C12	0.078 (3)	0.048 (2)	0.047 (2)	0.0120 (18)	−0.0094 (18)	0.0183 (17)
C11	0.056 (2)	0.064 (3)	0.100 (3)	0.0104 (19)	0.009 (2)	0.038 (2)
C2	0.0383 (16)	0.0433 (19)	0.0360 (16)	0.0171 (14)	0.0025 (13)	0.0024 (14)
C1	0.0423 (17)	0.049 (2)	0.0455 (19)	0.0226 (15)	0.0062 (14)	0.0125 (16)
C4	0.079 (2)	0.0295 (17)	0.0366 (17)	−0.0111 (16)	0.0227 (16)	0.0043 (14)
C5	0.080 (3)	0.039 (2)	0.0360 (18)	−0.0106 (17)	0.0218 (17)	0.0016 (15)

Geometric parameters (Å, º) top

Mo1—Mo2ⁱ	2.6043 (4)	C6—H6C	0.9800
Mo1—Mo2	2.5948 (4)	O1—C7	1.195 (4)
Mo1—Mo3	2.6026 (3)	N2—C7	1.318 (4)
Mo1—Mo3ⁱ	2.5996 (4)	N2—C9	1.432 (4)
Mo1—Cl4	2.4671 (6)	N2—C8	1.442 (5)
Mo1—Cl2ⁱ	2.4692 (6)	C7—H7	0.9500
Mo1—Cl3	2.4650 (7)	C9—H9A	0.9800
Mo1—Cl1	2.4716 (7)	C9—H9B	0.9800
Mo1—Cl5	2.4392 (7)	C9—H9C	0.9800
Mo2—Mo3ⁱ	2.5949 (3)	C8—H8A	0.9800
Mo2—Mo3	2.6037 (4)	C8—H8B	0.9800
Mo2—Cl4	2.4760 (6)	C8—H8C	0.9800
Mo2—Cl2	2.4701 (6)	O2—C10	1.208 (4)
Mo2—Cl6	2.4088 (7)	N3—C10	1.331 (4)
Mo2—Cl3ⁱ	2.4683 (6)	N3—C12	1.445 (4)
Mo2—Cl1	2.4720 (6)	N3—C11	1.435 (4)
Mo3—Cl4	2.4745 (6)	C10—H10	0.9500
Mo3—Cl2	2.4766 (7)	C12—H12A	0.9800
Mo3—Cl7	2.4061 (7)	C12—H12B	0.9800
Mo3—Cl3	2.4719 (7)	C12—H12C	0.9800
Mo3—Cl1ⁱ	2.4689 (6)	C11—H11A	0.9800
N1—C6	1.484 (4)	C11—H11B	0.9800
N1—C1	1.334 (4)	C11—H11C	0.9800
N1—C5	1.327 (4)	C2—H2	0.9500
C3—C3ⁱⁱ	1.477 (5)	C2—C1	1.361 (4)
C3—C2	1.388 (4)	C1—H1	0.9500
C3—C4	1.377 (4)	C4—H4	0.9500
C6—H6A	0.9800	C4—C5	1.363 (4)
C6—H6B	0.9800	C5—H5	0.9500

Mo2—Mo1—Mo2ⁱ	89.921 (11)	Cl7—Mo3—Mo2ⁱ	135.04 (2)
Mo2—Mo1—Mo3ⁱ	59.942 (8)	Cl7—Mo3—Cl4	92.33 (2)
Mo2—Mo1—Mo3	60.128 (10)	Cl7—Mo3—Cl2	92.13 (2)
Mo3—Mo1—Mo2ⁱ	59.784 (9)	Cl7—Mo3—Cl3	92.61 (2)
Mo3ⁱ—Mo1—Mo2ⁱ	60.045 (11)	Cl7—Mo3—Cl1ⁱ	91.81 (2)
Mo3ⁱ—Mo1—Mo3	89.992 (11)	Cl3—Mo3—Mo1	58.057 (16)
Cl4—Mo1—Mo2ⁱ	118.129 (17)	Cl3—Mo3—Mo1ⁱ	118.159 (16)
Cl4—Mo1—Mo2	58.503 (17)	Cl3—Mo3—Mo2	117.829 (17)
Cl4—Mo1—Mo3ⁱ	118.428 (17)	Cl3—Mo3—Mo2ⁱ	58.247 (16)
Cl4—Mo1—Mo3	58.357 (16)	Cl3—Mo3—Cl4	89.57 (2)
Cl4—Mo1—Cl2ⁱ	175.80 (2)	Cl3—Mo3—Cl2	175.25 (2)
Cl4—Mo1—Cl1	90.24 (2)	Cl1ⁱ—Mo3—Mo1	118.500 (16)
Cl2ⁱ—Mo1—Mo2	118.347 (18)	Cl1ⁱ—Mo3—Mo1ⁱ	58.302 (17)
Cl2ⁱ—Mo1—Mo2ⁱ	58.200 (16)	Cl1ⁱ—Mo3—Mo2ⁱ	58.376 (16)
Cl2ⁱ—Mo1—Mo3ⁱ	58.426 (16)	Cl1ⁱ—Mo3—Mo2	118.352 (17)
Cl2ⁱ—Mo1—Mo3	117.975 (17)	Cl1ⁱ—Mo3—Cl4	175.86 (2)
Cl2ⁱ—Mo1—Cl1	90.06 (2)	Cl1ⁱ—Mo3—Cl2	89.95 (2)
Cl3—Mo1—Mo2ⁱ	58.199 (15)	Cl1ⁱ—Mo3—Cl3	90.20 (2)
Cl3—Mo1—Mo2	118.426 (17)	Mo1—Cl4—Mo2	63.328 (16)
Cl3—Mo1—Mo3	58.314 (17)	Mo1—Cl4—Mo3	63.562 (15)
Cl3—Mo1—Mo3ⁱ	118.235 (16)	Mo3—Cl4—Mo2	63.465 (17)
Cl3—Mo1—Cl4	89.90 (2)	Mo1ⁱ—Cl2—Mo2	63.638 (16)
Cl3—Mo1—Cl2ⁱ	89.50 (2)	Mo1ⁱ—Cl2—Mo3	63.422 (17)
Cl3—Mo1—Cl1	175.83 (2)	Mo2—Cl2—Mo3	63.519 (17)
Cl1—Mo1—Mo2ⁱ	118.234 (17)	Mo1—Cl3—Mo2ⁱ	63.726 (16)
Cl1—Mo1—Mo2	58.347 (15)	Mo1—Cl3—Mo3	63.629 (16)
Cl1—Mo1—Mo3ⁱ	58.203 (15)	Mo2ⁱ—Cl3—Mo3	63.372 (16)
Cl1—Mo1—Mo3	118.456 (18)	Mo1—Cl1—Mo2	63.322 (17)
Cl5—Mo1—Mo2	134.428 (19)	Mo3ⁱ—Cl1—Mo1	63.496 (16)
Cl5—Mo1—Mo2ⁱ	135.644 (19)	Mo3ⁱ—Cl1—Mo2	63.363 (16)
Cl5—Mo1—Mo3	134.380 (19)	C1—N1—C6	119.9 (3)
Cl5—Mo1—Mo3ⁱ	135.62 (2)	C5—N1—C6	120.5 (3)
Cl5—Mo1—Cl4	91.17 (2)	C5—N1—C1	119.6 (3)
Cl5—Mo1—Cl2ⁱ	93.01 (2)	C2—C3—C3ⁱⁱ	122.0 (3)
Cl5—Mo1—Cl3	92.03 (2)	C4—C3—C3ⁱⁱ	121.9 (3)
Cl5—Mo1—Cl1	92.13 (2)	C4—C3—C2	116.1 (3)
Mo1—Mo2—Mo1ⁱ	90.078 (10)	N1—C6—H6A	109.5
Mo1—Mo2—Mo3ⁱ	60.121 (11)	N1—C6—H6B	109.5
Mo1—Mo2—Mo3	60.084 (8)	N1—C6—H6C	109.5
Mo3—Mo2—Mo1ⁱ	59.890 (9)	H6A—C6—H6B	109.5
Mo3ⁱ—Mo2—Mo1ⁱ	60.076 (9)	H6A—C6—H6C	109.5
Mo3ⁱ—Mo2—Mo3	90.070 (10)	H6B—C6—H6C	109.5
Cl4—Mo2—Mo1ⁱ	118.113 (18)	C7—N2—C9	120.4 (3)
Cl4—Mo2—Mo1	58.169 (15)	C7—N2—C8	122.3 (3)
Cl4—Mo2—Mo3	58.238 (16)	C9—N2—C8	117.2 (3)
Cl4—Mo2—Mo3ⁱ	118.272 (17)	O1—C7—N2	125.8 (3)
Cl2—Mo2—Mo1	118.429 (18)	O1—C7—H7	117.1
Cl2—Mo2—Mo1ⁱ	58.164 (15)	N2—C7—H7	117.1
Cl2—Mo2—Mo3	58.360 (17)	N2—C9—H9A	109.5
Cl2—Mo2—Mo3ⁱ	118.230 (17)	N2—C9—H9B	109.5
Cl2—Mo2—Cl4	90.05 (2)	N2—C9—H9C	109.5
Cl2—Mo2—Cl1	175.86 (2)	H9A—C9—H9B	109.5
Cl6—Mo2—Mo1	134.52 (2)	H9A—C9—H9C	109.5
Cl6—Mo2—Mo1ⁱ	135.40 (2)	H9B—C9—H9C	109.5
Cl6—Mo2—Mo3	134.68 (2)	N2—C8—H8A	109.5
Cl6—Mo2—Mo3ⁱ	135.25 (2)	N2—C8—H8B	109.5
Cl6—Mo2—Cl4	91.70 (2)	N2—C8—H8C	109.5
Cl6—Mo2—Cl2	92.13 (2)	H8A—C8—H8B	109.5
Cl6—Mo2—Cl3ⁱ	92.69 (2)	H8A—C8—H8C	109.5
Cl6—Mo2—Cl1	92.01 (3)	H8B—C8—H8C	109.5
Cl3ⁱ—Mo2—Mo1ⁱ	58.075 (17)	C10—N3—C12	119.7 (3)
Cl3ⁱ—Mo2—Mo1	118.479 (16)	C10—N3—C11	122.2 (3)
Cl3ⁱ—Mo2—Mo3ⁱ	58.382 (16)	C11—N3—C12	118.1 (3)
Cl3ⁱ—Mo2—Mo3	117.956 (16)	O2—C10—N3	125.6 (3)
Cl3ⁱ—Mo2—Cl4	175.60 (2)	O2—C10—H10	117.2
Cl3ⁱ—Mo2—Cl2	89.40 (2)	N3—C10—H10	117.2
Cl3ⁱ—Mo2—Cl1	90.21 (2)	N3—C12—H12A	109.5
Cl1—Mo2—Mo1ⁱ	118.322 (16)	N3—C12—H12B	109.5
Cl1—Mo2—Mo1	58.332 (17)	N3—C12—H12C	109.5
Cl1—Mo2—Mo3ⁱ	58.262 (16)	H12A—C12—H12B	109.5
Cl1—Mo2—Mo3	118.397 (19)	H12A—C12—H12C	109.5
Cl1—Mo2—Cl4	90.03 (2)	H12B—C12—H12C	109.5
Mo1ⁱ—Mo3—Mo1	90.008 (11)	N3—C11—H11A	109.5
Mo1ⁱ—Mo3—Mo2	60.064 (8)	N3—C11—H11B	109.5
Mo1—Mo3—Mo2	59.788 (11)	N3—C11—H11C	109.5
Mo2ⁱ—Mo3—Mo1	60.140 (9)	H11A—C11—H11B	109.5
Mo2ⁱ—Mo3—Mo1ⁱ	59.936 (10)	H11A—C11—H11C	109.5
Mo2ⁱ—Mo3—Mo2	89.930 (10)	H11B—C11—H11C	109.5
Cl4—Mo3—Mo1ⁱ	118.345 (18)	C3—C2—H2	119.6
Cl4—Mo3—Mo1	58.082 (15)	C1—C2—C3	120.8 (3)
Cl4—Mo3—Mo2	58.296 (16)	C1—C2—H2	119.6
Cl4—Mo3—Mo2ⁱ	118.209 (17)	N1—C1—C2	121.2 (3)
Cl4—Mo3—Cl2	89.94 (2)	N1—C1—H1	119.4
Cl2—Mo3—Mo1	117.894 (18)	C2—C1—H1	119.4
Cl2—Mo3—Mo1ⁱ	58.152 (15)	C3—C4—H4	119.4
Cl2—Mo3—Mo2ⁱ	118.066 (17)	C5—C4—C3	121.1 (3)
Cl2—Mo3—Mo2	58.121 (16)	C5—C4—H4	119.4
Cl7—Mo3—Mo1	135.303 (19)	N1—C5—C4	121.2 (3)
Cl7—Mo3—Mo1ⁱ	134.689 (19)	N1—C5—H5	119.4
Cl7—Mo3—Mo2	135.02 (2)	C4—C5—H5	119.4

C3ⁱⁱ—C3—C2—C1	179.5 (3)	C8—N2—C7—O1	176.1 (5)
C3ⁱⁱ—C3—C4—C5	−179.8 (3)	C12—N3—C10—O2	−1.1 (5)
C3—C2—C1—N1	−0.3 (5)	C11—N3—C10—O2	179.6 (3)
C3—C4—C5—N1	0.8 (5)	C2—C3—C4—C5	−0.3 (5)
C6—N1—C1—C2	179.3 (3)	C1—N1—C5—C4	−1.0 (5)
C6—N1—C5—C4	−179.5 (3)	C4—C3—C2—C1	0.0 (4)
C9—N2—C7—O1	−0.6 (7)	C5—N1—C1—C2	0.8 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱⁱⁱ	0.95	2.23	3.063 (4)	145
C6—H6C···O2ⁱⁱ	0.98	2.31	3.088 (4)	136

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

Acknowledgements

This work was supported in part by the National Science Foundation. The authors thank H. Kaur and A. Maldonado for initial work on this project.

Funding information

Funding for this research was provided by: National Science Foundation, Division Of Undergraduate Education (grant No. 0942850 to DHJ).

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1705-1711

https://doi.org/10.1107/S205698901901380X

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures and hydrogen-bonding analysis of a series of solvated ammonium salts of molybdenum(II) chloride clusters

1. Chemical context

2. Structural commentary

3. Hydrogen-bonding analysis

4. Database survey

5. Synthesis and crystallization

5.1. Cluster synthesis, metathesis, and crystallization of (I), (II), and (IV)

5.2. Synthesis and crystallization of Schiff base salt (III)

6. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications