(C7H6NS)2[Nb6Cl18]·2C4H8O: first niobium cluster with an N,S-heterocyclic cation

Sperlich, E.; Köckerling, M.

doi:10.1107/S2414314618017601

metal-organic compounds

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ISSN: 2414-3146

Volume 3| Part 12| December 2018| x181760

https://doi.org/10.1107/S2414314618017601

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(C₇H₆NS)₂[Nb₆Cl₁₈]·2C₄H₈O: first niobium cluster with an N,S-heterocyclic cation

Eric Sperlich ^a and Martin Köckerling ^a ^*

^aUniversität Rostock, Institut für Chemie, Anorganische Festkörperchemie, Albert-Einstein-Strasse 3a, D-18059 Rostock, Germany
^*Correspondence e-mail: Martin.Koeckerling@uni-rostock.de

Edited by O. Blacque, University of Zürich, Switzerland (Received 13 November 2018; accepted 12 December 2018; online 18 December 2018)

The title compound bis(benzothiazolium) dodeca-μ-chlorido-hexachlorido-octahedro-hexaniobium(12 Nb—Nb) tetrahydrofuran disolvate, (C₇H₆NS)₂[Nb₆Cl₁₈]·2C₄H₈O or (HBTh)₂[Nb₆Cl₁₈]·2THF, is the first known niobium cluster compound to contain an N,S-heterocyclic cation. The synthesis takes place within a few hours as an one-pot reaction at room temperature of the cluster precursor compound [Nb₆Cl₁₄(H₂O)₄]·4H₂O with SOCl₂ in the presence of BTh (benzothiazole) in very high yield. The stabilization of the acidic proton of the cation is achieved by the use of tetrahydrofuran as a co-solvent and by the formation of hydrogen bonds.

Keywords: crystal structure; niobium; cluster; dehydration; halides.

CCDC reference: 1884787

Structure description

In 2016, we reported a new synthetic route that allows the generation of niobium cluster compounds of the composition A₂[Nb₆Cl₁₈], where A is an organic cation) by the reaction of [Nb₆Cl₁₄(H₂O)₄]·4H₂O with thionyl chloride (König et al., 2016 ). The addition of ACl results in the formation of the new compounds. Here, we present a further way to synthesize such compounds. In this case, a neutral heterocyclic compound L is used instead of ACl. L is protonated and the resulting acidic cation acts as the counter-ion in cluster compounds of the formula (HL)₂[Nb₆Cl₁₈].

The title compound consists of the well known [Nb₆Cl₁₈]²⁻ anion, two benzothiazolium cations (HBTh)⁺, and two co-crystallized tetrahydrofuran molecules (THF) that bond to the acidic proton of the cation through hydrogen bonds. The disordered THF molecule is present in two different orientations with an occupancy ratio of 0.560 (9):0.440 (9). Only one orientation is shown in Fig. 1 for the sake of clarity. The average Nb—Nb distance of the metal cluster unit (Cotton, 1964 ; Simon, 1988 ) is 3.0257 Å, which is in the expected range for the doubly negatively charged [Nb₆Cl₁₈]²⁻ anion, and the Nb—Clⁱ and Nb—Cl^a distances with averages of 2.4261 and 2.4863 Å, respectively, are also typical for this anion (Koknat & McCarley, 1972 ; Field et al., 1973 ; Lin & Williams, 1996 ; Ströbele & Meyer, 2001 ; Flemming et al., 2008 ).

Figure 1
View of the structure of the niobium cluster anion, the benzothiazolium cation and the co-crystallized tetrahydrofuran molecule in crystals of (HBTh)₂[Nb₆Cl₁₈]·2THF with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed red line represents a hydrogen bond. The dashed red line represents a hydrogen bond. Symmetry code: (i) −x, 1 − y, 1 − z.

The position of the acidic proton of the cation was freely refined, resulting in bond lengths [N1—H1A 0.83 (4), O1A⋯H1A = 1.86 (4), N1—H1B = 0.83 (4), O1B⋯H1A = 1.75 (4), N1⋯O1A = 2.691 (5) and N1⋯O1B = 2.573 (6) Å; Table 1] that agree well with those found in similar bonding situations (Steiner, 2002 ). The packing is shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1A	0.83 (4)	1.86 (4)	2.691 (5)	175 (4)
N1—H1A⋯O1B	0.83 (4)	1.75 (4)	2.573 (6)	172 (4)

Figure 2
Packing of the cluster anions, cations and THF molecules in the unit cell of (HBTh)₂[Nb₆Cl₁₈]·2THF in a view along the a axis. The niobium cluster core is shown in a polyhedral representation. Hydrogen bonds are shown as red dashed lines.

Synthesis and crystallization

The preparation of the title compound was carried out via an one-pot reaction. 20 mg (16.70 µmol) of the niobium cluster starting compound [Nb₆Cl₁₄(H₂O)₄]·4H₂O and 0.05 ml (0.46 µmol) of benzothiazole (BTh) were dissolved in a mixture of 1 ml (13.79 mmol) thionyl chloride (SOCl₂) and 1 ml (12.50 mmol) tetrahydrofuran (THF). The niobium cluster precursor [Nb₆Cl₁₄(H₂O)₄]·4H₂O was dehydrated with thionyl chloride, under evolution of SO₂ and HCl. The remaining chloride ions occupied the vacant ligand positions on the niobium cluster and the neutral ligand was protonated to the benzothiazonium cation. In addition, the niobium cluster core was oxidized from [Nb₆Cl₁₂]²⁺ to [Nb₆Cl₁₂]⁴⁺. SOCl₂ functionalized as oxidation agent, forming SCl₂ (König et al., 2016). Crystallization was favored by the formation of hydrogen bonds between the proton of the cation and the THF molecules. After one day at room temperature, brown crystals of the title compound (HBTh)₂[Nb₆Cl₁₈]·2THF formed. The supernatant solution was removed and the crystals were washed three times with diethyl ether. The product was obtained in a yield of 96% (26.60 mg).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The disordered THF molecule was refined with split atom positions over two orientations [occupancy ratio of 0.560 (9):0.440 (9)] with the sum of the occupational factors of each atom being fixed to unity.

Table 2
Experimental details

Crystal data
Chemical formula	(C₇H₆NS)₂[Nb₆Cl₁₈]·2C₄H₈O
M_r	1612.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	8.7110 (3), 24.171 (1), 11.0653 (4)
β (°)	102.598 (1)
V (Å³)	2273.8 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.61
Crystal size (mm)	0.20 × 0.15 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2017 )
No. of measured, independent and observed [I > 2σ(I)] reflections	102833, 5454, 4867
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.047, 1.05
No. of reflections	5454
No. of parameters	286
No. of restraints	86
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.25, −1.00
Computer programs: APEX3 and SAINT (Bruker, 2017), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), SHELXTL (Sheldrick, 2008 ) and DIAMOND (Brandenburg & Putz, 2014 ).

Structural data

CCDC reference: 1884787

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618017601/zq4033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618017601/zq4033Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2014); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Bis(benzothiazolium) dodeca-µ-chlorido-hexachlorido-octahedro-hexaniobium(12 Nb—Nb) tetrahydrofuran disolvate top

Crystal data top

(C₇H₆NS)₂[Nb₆Cl₁₈]·2C₄H₈O	F(000) = 1548
M_r = 1612.14	D_x = 2.355 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.7110 (3) Å	Cell parameters from 9607 reflections
b = 24.171 (1) Å	θ = 2.4–27.9°
c = 11.0653 (4) Å	µ = 2.61 mm⁻¹
β = 102.598 (1)°	T = 123 K
V = 2273.8 (2) Å³	Block, brown
Z = 2	0.20 × 0.15 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	4867 reflections with I > 2σ(I)
Radiation source: microfocus sealed tube	R_int = 0.045
φ and ω scans	θ_max = 27.9°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −11→11
	k = −31→31
102833 measured reflections	l = −14→14
5454 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.047	w = 1/[σ²(F_o²) + (0.0133P)² + 5.1918P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.003
5454 reflections	Δρ_max = 1.25 e Å⁻³
286 parameters	Δρ_min = −1.00 e Å⁻³
86 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00216 (7)

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	Occ. (<1)
Nb1	0.16489 (2)	0.43379 (2)	0.54806 (2)	0.01537 (6)
Nb2	−0.17270 (2)	0.44311 (2)	0.40346 (2)	0.01362 (6)
Nb3	0.08185 (2)	0.51378 (2)	0.33389 (2)	0.01343 (6)
Cl1	−0.00984 (7)	0.36126 (3)	0.44714 (6)	0.0230 (1)
Cl2	0.27598 (7)	0.44047 (3)	0.36589 (6)	0.0229 (1)
Cl3	0.35309 (8)	0.35643 (3)	0.60609 (8)	0.0366 (2)
Cl4	0.09382 (7)	0.40977 (3)	0.74224 (6)	0.0223 (1)
Cl5	−0.10366 (8)	0.45219 (3)	0.20332 (5)	0.0257 (2)
Cl6	−0.38072 (7)	0.51032 (3)	0.34026 (6)	0.0235 (1)
Cl7	−0.36886 (8)	0.37615 (3)	0.29128 (6)	0.0278 (2)
Cl8	0.17478 (8)	0.53147 (3)	0.13888 (6)	0.0303 (2)
Cl9	0.28546 (6)	0.57995 (2)	0.42073 (5)	0.0157 (1)
S1	0.4979 (1)	0.43271 (4)	−0.04878 (8)	0.0383 (2)
N1	0.3389 (3)	0.3668 (1)	0.0501 (2)	0.0333 (6)
H1A	0.273 (5)	0.356 (2)	0.089 (4)	0.05 (1)*
C1	0.3572 (4)	0.4193 (1)	0.0308 (3)	0.0310 (7)
H1B	0.2971	0.4474	0.0589	0.037*
C2	0.5361 (4)	0.3627 (2)	−0.0584 (3)	0.0369 (8)
C3	0.6409 (5)	0.3356 (2)	−0.1173 (3)	0.050 (1)
H3	0.7055	0.3557	−0.1609	0.060*
C4	0.6474 (5)	0.2793 (2)	−0.1103 (4)	0.059 (1)
H4	0.7164	0.2600	−0.1512	0.071*
C5	0.5551 (6)	0.2490 (2)	−0.0442 (4)	0.063 (1)
H5	0.5659	0.2099	−0.0384	0.076*
C6	0.4500 (5)	0.2751 (2)	0.0121 (4)	0.057 (1)
H6	0.3864	0.2547	0.0559	0.068*
C7	0.4395 (4)	0.3324 (1)	0.0030 (3)	0.0378 (8)
O1A	0.1371 (5)	0.3338 (2)	0.1885 (4)	0.034 (1)	0.560 (9)
C8A	−0.0116 (7)	0.3094 (2)	0.1260 (5)	0.038 (1)	0.560 (9)
H8A	−0.0305	0.3156	0.0355	0.046*	0.560 (9)
H8B	−0.0999	0.3256	0.1572	0.046*	0.560 (9)
C9A	0.0044 (6)	0.2488 (2)	0.1553 (5)	0.040 (1)	0.560 (9)
H9A	−0.0972	0.2332	0.1654	0.048*	0.560 (9)
H9B	0.0393	0.2284	0.0885	0.048*	0.560 (9)
C10A	0.1238 (7)	0.2450 (2)	0.2726 (6)	0.038 (1)	0.560 (9)
H10A	0.1850	0.2103	0.2756	0.046*	0.560 (9)
H10B	0.0732	0.2458	0.3445	0.046*	0.560 (9)
C11A	0.2283 (6)	0.2943 (2)	0.2740 (5)	0.034 (1)	0.560 (9)
H11A	0.2578	0.3103	0.3583	0.041*	0.560 (9)
H11B	0.3254	0.2839	0.2469	0.041*	0.560 (9)
O1B	0.1404 (9)	0.3237 (3)	0.1642 (7)	0.062 (2)	0.440 (9)
C8B	−0.0152 (9)	0.3084 (3)	0.0947 (7)	0.063 (2)	0.440 (9)
H8C	−0.0089	0.2916	0.0142	0.076*	0.440 (9)
H8D	−0.0848	0.3412	0.0790	0.076*	0.440 (9)
C9B	−0.0757 (8)	0.2673 (3)	0.1745 (7)	0.063 (2)	0.440 (9)
H9C	−0.1426	0.2858	0.2241	0.075*	0.440 (9)
H9D	−0.1384	0.2382	0.1231	0.075*	0.440 (9)
C10B	0.066 (1)	0.2432 (3)	0.2560 (8)	0.062 (2)	0.440 (9)
H10C	0.0982	0.2091	0.2188	0.075*	0.440 (9)
H10D	0.0444	0.2340	0.3380	0.075*	0.440 (9)
C11B	0.1908 (8)	0.2866 (4)	0.2683 (8)	0.061 (2)	0.440 (9)
H11C	0.2014	0.3067	0.3476	0.073*	0.440 (9)
H11D	0.2934	0.2696	0.2656	0.073*	0.440 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Nb1	0.0085 (1)	0.0181 (1)	0.0207 (1)	0.00211 (8)	0.00572 (8)	0.00766 (8)
Nb2	0.0103 (1)	0.0202 (1)	0.0109 (1)	−0.00342 (8)	0.00341 (7)	0.00206 (8)
Nb3	0.0105 (1)	0.0203 (1)	0.0106 (1)	−0.00263 (8)	0.00461 (7)	0.00265 (8)
Cl1	0.0214 (3)	0.0175 (3)	0.0344 (3)	−0.0016 (2)	0.0154 (3)	−0.0019 (2)
Cl2	0.0189 (3)	0.0219 (3)	0.0337 (3)	0.0011 (2)	0.0184 (3)	0.0020 (3)
Cl3	0.0192 (3)	0.0299 (4)	0.0647 (5)	0.0131 (3)	0.0181 (3)	0.0254 (4)
Cl4	0.0140 (3)	0.0303 (3)	0.0215 (3)	−0.0005 (2)	0.0017 (2)	0.0159 (3)
Cl5	0.0271 (3)	0.0392 (4)	0.0125 (3)	−0.0172 (3)	0.0082 (2)	−0.0039 (3)
Cl6	0.0082 (3)	0.0335 (4)	0.0265 (3)	−0.0021 (2)	−0.0013 (2)	0.0150 (3)
Cl7	0.0272 (3)	0.0379 (4)	0.0182 (3)	−0.0185 (3)	0.0051 (2)	−0.0044 (3)
Cl8	0.0316 (4)	0.0476 (4)	0.0158 (3)	−0.0161 (3)	0.0139 (3)	−0.0001 (3)
Cl9	0.0112 (2)	0.0224 (3)	0.0147 (3)	−0.0039 (2)	0.0053 (2)	0.0028 (2)
S1	0.0379 (4)	0.0470 (5)	0.0320 (4)	−0.0094 (4)	0.0118 (3)	0.0157 (4)
N1	0.043 (2)	0.042 (2)	0.018 (1)	−0.026 (1)	0.013 (1)	−0.010 (1)
C1	0.032 (2)	0.042 (2)	0.017 (1)	−0.014 (1)	0.003 (1)	0.001 (1)
C2	0.047 (2)	0.046 (2)	0.020 (1)	−0.019 (2)	0.013 (1)	−0.002 (1)
C3	0.060 (2)	0.063 (3)	0.034 (2)	−0.020 (2)	0.029 (2)	−0.003 (2)
C4	0.076 (3)	0.063 (3)	0.049 (2)	−0.022 (2)	0.038 (2)	−0.025 (2)
C5	0.098 (3)	0.042 (2)	0.064 (3)	−0.034 (2)	0.051 (3)	−0.032 (2)
C6	0.089 (3)	0.041 (2)	0.055 (2)	−0.040 (2)	0.047 (2)	−0.031 (2)
C7	0.054 (2)	0.042 (2)	0.022 (1)	−0.028 (2)	0.019 (1)	−0.017 (1)
O1A	0.035 (2)	0.030 (2)	0.043 (2)	−0.010 (1)	0.020 (1)	−0.007 (1)
C8A	0.038 (2)	0.033 (2)	0.047 (2)	−0.011 (1)	0.016 (1)	−0.007 (1)
C9A	0.040 (2)	0.033 (2)	0.049 (2)	−0.010 (1)	0.015 (1)	−0.008 (1)
C10A	0.038 (2)	0.032 (2)	0.048 (2)	−0.010 (1)	0.017 (1)	−0.007 (1)
C11A	0.034 (2)	0.030 (2)	0.044 (2)	−0.010 (1)	0.021 (1)	−0.006 (1)
O1B	0.067 (3)	0.055 (3)	0.078 (4)	−0.021 (2)	0.050 (3)	−0.002 (2)
C8B	0.068 (3)	0.056 (3)	0.080 (4)	−0.022 (2)	0.049 (3)	−0.003 (2)
C9B	0.068 (3)	0.055 (3)	0.080 (4)	−0.022 (2)	0.049 (3)	−0.004 (2)
C10B	0.068 (3)	0.054 (3)	0.079 (4)	−0.021 (2)	0.050 (3)	−0.003 (2)
C11B	0.067 (3)	0.054 (3)	0.078 (4)	−0.021 (2)	0.051 (3)	−0.002 (2)

Geometric parameters (Å, º) top

Nb1—Cl6ⁱ	2.4234 (7)	C3—C4	1.363 (6)
Nb1—Cl2	2.4242 (6)	C3—H3	0.9500
Nb1—Cl1	2.4281 (7)	C4—C5	1.405 (5)
Nb1—Cl4	2.4326 (6)	C4—H4	0.9500
Nb1—Cl3	2.4774 (7)	C5—C6	1.368 (6)
Nb1—Nb2ⁱ	3.0215 (3)	C5—H5	0.9500
Nb1—Nb3	3.0216 (3)	C6—C7	1.392 (5)
Nb1—Nb3ⁱ	3.0261 (3)	C6—H6	0.9500
Nb1—Nb2	3.0342 (3)	O1A—C11A	1.452 (3)
Nb2—Cl6	2.4206 (7)	O1A—C8A	1.454 (3)
Nb2—Cl1	2.4209 (7)	C8A—C9A	1.501 (4)
Nb2—Cl9ⁱ	2.4276 (6)	C8A—H8A	0.9900
Nb2—Cl5	2.4280 (6)	C8A—H8B	0.9900
Nb2—Cl7	2.4809 (7)	C9A—C10A	1.479 (7)
Nb2—Nb1ⁱ	3.0215 (3)	C9A—H9A	0.9900
Nb2—Nb3ⁱ	3.0258 (3)	C9A—H9B	0.9900
Nb2—Nb3	3.0286 (3)	C10A—C11A	1.498 (4)
Nb3—Cl2	2.4215 (7)	C10A—H10A	0.9900
Nb3—Cl9	2.4256 (6)	C10A—H10B	0.9900
Nb3—Cl5	2.4282 (7)	C11A—H11A	0.9900
Nb3—Cl4ⁱ	2.4296 (7)	C11A—H11B	0.9900
Nb3—Cl8	2.5013 (6)	O1B—C11B	1.451 (3)
Nb3—Nb2ⁱ	3.0258 (3)	O1B—C8B	1.453 (3)
Nb3—Nb1ⁱ	3.0260 (3)	C8B—C9B	1.500 (4)
Cl4—Nb3ⁱ	2.4297 (7)	C8B—H8C	0.9900
Cl6—Nb1ⁱ	2.4234 (7)	C8B—H8D	0.9900
Cl9—Nb2ⁱ	2.4276 (6)	C9B—C10B	1.477 (7)
S1—C1	1.689 (3)	C9B—H9C	0.9900
S1—C2	1.733 (4)	C9B—H9D	0.9900
N1—C1	1.304 (4)	C10B—C11B	1.497 (4)
N1—C7	1.388 (4)	C10B—H10C	0.9900
N1—H1A	0.83 (4)	C10B—H10D	0.9900
C1—H1B	0.9500	C11B—H11C	0.9900
C2—C3	1.396 (5)	C11B—H11D	0.9900
C2—C7	1.398 (4)

Cl6ⁱ—Nb1—Cl2	88.91 (2)	Cl5—Nb3—Nb1ⁱ	94.04 (2)
Cl6ⁱ—Nb1—Cl1	167.35 (2)	Cl4ⁱ—Nb3—Nb1ⁱ	51.55 (2)
Cl2—Nb1—Cl1	89.40 (2)	Cl8—Nb3—Nb1ⁱ	134.01 (2)
Cl6ⁱ—Nb1—Cl4	90.07 (2)	Nb1—Nb3—Nb1ⁱ	90.026 (8)
Cl2—Nb1—Cl4	167.17 (2)	Nb2ⁱ—Nb3—Nb1ⁱ	60.181 (7)
Cl1—Nb1—Cl4	88.80 (2)	Cl2—Nb3—Nb2	94.40 (2)
Cl6ⁱ—Nb1—Cl3	83.84 (3)	Cl9—Nb3—Nb2	141.61 (2)
Cl2—Nb1—Cl3	84.50 (2)	Cl5—Nb3—Nb2	51.42 (2)
Cl1—Nb1—Cl3	83.52 (3)	Cl4ⁱ—Nb3—Nb2	94.38 (2)
Cl4—Nb1—Cl3	82.67 (2)	Cl8—Nb3—Nb2	135.10 (2)
Cl6ⁱ—Nb1—Nb2ⁱ	51.37 (2)	Nb1—Nb3—Nb2	60.198 (7)
Cl2—Nb1—Nb2ⁱ	94.84 (2)	Nb2ⁱ—Nb3—Nb2	90.153 (8)
Cl1—Nb1—Nb2ⁱ	141.28 (2)	Nb1ⁱ—Nb3—Nb2	59.874 (7)
Cl4—Nb1—Nb2ⁱ	94.50 (2)	Nb2—Cl1—Nb1	77.47 (2)
Cl3—Nb1—Nb2ⁱ	135.18 (2)	Nb3—Cl2—Nb1	77.15 (2)
Cl6ⁱ—Nb1—Nb3	94.00 (2)	Nb3ⁱ—Cl4—Nb1	76.98 (2)
Cl2—Nb1—Nb3	51.38 (2)	Nb2—Cl5—Nb3	77.17 (2)
Cl1—Nb1—Nb3	94.73 (2)	Nb2—Cl6—Nb1ⁱ	77.18 (2)
Cl4—Nb1—Nb3	141.44 (2)	Nb3—Cl9—Nb2ⁱ	77.14 (2)
Cl3—Nb1—Nb3	135.89 (2)	C1—S1—C2	90.9 (2)
Nb2ⁱ—Nb1—Nb3	60.092 (8)	C1—N1—C7	114.3 (3)
Cl6ⁱ—Nb1—Nb3ⁱ	95.25 (2)	C1—N1—H1A	121 (3)
Cl2—Nb1—Nb3ⁱ	141.35 (2)	C7—N1—H1A	125 (3)
Cl1—Nb1—Nb3ⁱ	93.89 (2)	N1—C1—S1	113.6 (3)
Cl4—Nb1—Nb3ⁱ	51.47 (2)	N1—C1—H1B	123.2
Cl3—Nb1—Nb3ⁱ	134.14 (2)	S1—C1—H1B	123.2
Nb2ⁱ—Nb1—Nb3ⁱ	60.105 (7)	C3—C2—C7	120.4 (3)
Nb3—Nb1—Nb3ⁱ	89.974 (8)	C3—C2—S1	129.9 (3)
Cl6ⁱ—Nb1—Nb2	141.48 (2)	C7—C2—S1	109.7 (3)
Cl2—Nb1—Nb2	94.21 (2)	C4—C3—C2	117.7 (3)
Cl1—Nb1—Nb2	51.16 (2)	C4—C3—H3	121.1
Cl4—Nb1—Nb2	94.55 (2)	C2—C3—H3	121.1
Cl3—Nb1—Nb2	134.68 (2)	C3—C4—C5	121.9 (4)
Nb2ⁱ—Nb1—Nb2	90.127 (8)	C3—C4—H4	119.1
Nb3—Nb1—Nb2	60.015 (7)	C5—C4—H4	119.1
Nb3ⁱ—Nb1—Nb2	59.906 (7)	C6—C5—C4	120.9 (4)
Cl6—Nb2—Cl1	167.24 (2)	C6—C5—H5	119.6
Cl6—Nb2—Cl9ⁱ	88.70 (2)	C4—C5—H5	119.6
Cl1—Nb2—Cl9ⁱ	88.53 (2)	C5—C6—C7	117.7 (3)
Cl6—Nb2—Cl5	89.69 (2)	C5—C6—H6	121.1
Cl1—Nb2—Cl5	90.29 (2)	C7—C6—H6	121.1
Cl9ⁱ—Nb2—Cl5	167.33 (2)	N1—C7—C6	127.3 (3)
Cl6—Nb2—Cl7	84.42 (3)	N1—C7—C2	111.5 (3)
Cl1—Nb2—Cl7	82.90 (3)	C6—C7—C2	121.3 (3)
Cl9ⁱ—Nb2—Cl7	84.05 (2)	C11A—O1A—C8A	110.3 (3)
Cl5—Nb2—Cl7	83.29 (2)	O1A—C8A—C9A	105.2 (3)
Cl6—Nb2—Nb1ⁱ	51.45 (2)	O1A—C8A—H8A	110.7
Cl1—Nb2—Nb1ⁱ	141.24 (2)	C9A—C8A—H8A	110.7
Cl9ⁱ—Nb2—Nb1ⁱ	94.66 (2)	O1A—C8A—H8B	110.7
Cl5—Nb2—Nb1ⁱ	94.15 (2)	C9A—C8A—H8B	110.7
Cl7—Nb2—Nb1ⁱ	135.86 (2)	H8A—C8A—H8B	108.8
Cl6—Nb2—Nb3ⁱ	93.95 (2)	C10A—C9A—C8A	105.3 (2)
Cl1—Nb2—Nb3ⁱ	94.05 (2)	C10A—C9A—H9A	110.7
Cl9ⁱ—Nb2—Nb3ⁱ	51.40 (2)	C8A—C9A—H9A	110.7
Cl5—Nb2—Nb3ⁱ	141.26 (2)	C10A—C9A—H9B	110.7
Cl7—Nb2—Nb3ⁱ	135.44 (2)	C8A—C9A—H9B	110.7
Nb1ⁱ—Nb2—Nb3ⁱ	59.955 (7)	H9A—C9A—H9B	108.8
Cl6—Nb2—Nb3	95.25 (2)	C9A—C10A—C11A	105.6 (2)
Cl1—Nb2—Nb3	94.71 (2)	C9A—C10A—H10A	110.6
Cl9ⁱ—Nb2—Nb3	141.25 (2)	C11A—C10A—H10A	110.6
Cl5—Nb2—Nb3	51.42 (2)	C9A—C10A—H10B	110.6
Cl7—Nb2—Nb3	134.70 (2)	C11A—C10A—H10B	110.6
Nb1ⁱ—Nb2—Nb3	60.022 (7)	H10A—C10A—H10B	108.7
Nb3ⁱ—Nb2—Nb3	89.847 (8)	O1A—C11A—C10A	105.8 (3)
Cl6—Nb2—Nb1	141.31 (2)	O1A—C11A—H11A	110.6
Cl1—Nb2—Nb1	51.37 (2)	C10A—C11A—H11A	110.6
Cl9ⁱ—Nb2—Nb1	94.32 (2)	O1A—C11A—H11B	110.6
Cl5—Nb2—Nb1	94.78 (2)	C10A—C11A—H11B	110.6
Cl7—Nb2—Nb1	134.27 (2)	H11A—C11A—H11B	108.7
Nb1ⁱ—Nb2—Nb1	89.874 (8)	C11B—O1B—C8B	110.4 (3)
Nb3ⁱ—Nb2—Nb1	59.915 (7)	O1B—C8B—C9B	105.3 (3)
Nb3—Nb2—Nb1	59.787 (7)	O1B—C8B—H8C	110.7
Cl2—Nb3—Cl9	89.86 (2)	C9B—C8B—H8C	110.7
Cl2—Nb3—Cl5	89.50 (3)	O1B—C8B—H8D	110.7
Cl9—Nb3—Cl5	166.95 (2)	C9B—C8B—H8D	110.7
Cl2—Nb3—Cl4ⁱ	166.95 (2)	H8C—C8B—H8D	108.8
Cl9—Nb3—Cl4ⁱ	89.24 (2)	C10B—C9B—C8B	105.5 (2)
Cl5—Nb3—Cl4ⁱ	88.45 (3)	C10B—C9B—H9C	110.6
Cl2—Nb3—Cl8	84.50 (2)	C8B—C9B—H9C	110.6
Cl9—Nb3—Cl8	83.27 (2)	C10B—C9B—H9D	110.6
Cl5—Nb3—Cl8	83.69 (2)	C8B—C9B—H9D	110.6
Cl4ⁱ—Nb3—Cl8	82.46 (2)	H9C—C9B—H9D	108.8
Cl2—Nb3—Nb1	51.46 (2)	C9B—C10B—C11B	105.9 (2)
Cl9—Nb3—Nb1	94.70 (2)	C9B—C10B—H10C	110.6
Cl5—Nb3—Nb1	95.09 (2)	C11B—C10B—H10C	110.6
Cl4ⁱ—Nb3—Nb1	141.58 (2)	C9B—C10B—H10D	110.6
Cl8—Nb3—Nb1	135.96 (2)	C11B—C10B—H10D	110.6
Cl2—Nb3—Nb2ⁱ	94.79 (2)	H10C—C10B—H10D	108.7
Cl9—Nb3—Nb2ⁱ	51.46 (1)	O1B—C11B—C10B	105.8 (3)
Cl5—Nb3—Nb2ⁱ	141.56 (2)	O1B—C11B—H11C	110.6
Cl4ⁱ—Nb3—Nb2ⁱ	94.82 (2)	C10B—C11B—H11C	110.6
Cl8—Nb3—Nb2ⁱ	134.73 (2)	O1B—C11B—H11D	110.6
Nb1—Nb3—Nb2ⁱ	59.953 (8)	C10B—C11B—H11D	110.6
Cl2—Nb3—Nb1ⁱ	141.48 (2)	H11C—C11B—H11D	108.7
Cl9—Nb3—Nb1ⁱ	94.57 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1A	0.83 (4)	1.86 (4)	2.691 (5)	175 (4)
N1—H1A···O1B	0.83 (4)	1.75 (4)	2.573 (6)	172 (4)

Acknowledgements

We gratefully acknowledge the maintenance of the XRD equipment through Dr Alexander Villinger (University of Rostock).

Funding information

Funding for this research was provided by: DFG-SPP 1708; Material Synthesis Near Room Temperature .

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