Crystal structure of pyridinium tetra­iso­thio­cyanato­dipyridine­chromium(III) pyridine monosolvate

Neumann, T.; Jess, I.; Näther, C.

doi:10.1107/S2056989019014488

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ISSN: 2056-9890

Volume 75| Part 12| December 2019| Pages 1875-1879

https://doi.org/10.1107/S2056989019014488

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Crystal structure of pyridinium tetraisothiocyanatodipyridinechromium(III) pyridine monosolvate

Tristan Neumann,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany
^*Correspondence e-mail: t.neumann@ac.uni-kiel.de

Edited by A. J. Lough, University of Toronto, Canada (Received 14 October 2019; accepted 24 October 2019; online 15 November 2019)

In the crystal structure of the title compound, (C₅H₆N)[Cr(NCS)₄(C₅H₅N)₂]·C₅H₅N, the Cr^III ions are octahedrally coordinated by four N-bonding thiocyanate anions and two pyridine ligands into discrete negatively charged complexes, with the Cr^III ion, as well as the two pyridine ligands, located on crystallographic mirror planes. The mean planes of the two pyridine ligands are rotated with respect to each other by 90°. Charge balance is achieved by one protonated pyridine molecule that is hydrogen bonded to one additional pyridine solvent molecule, with both located on crystallographic mirror planes and again rotated by exactly 90°. The pyridinium H atom was refined as disordered between both pyridine N atoms in a 70:30 ratio, leading to a linear N—H⋯N hydrogen bond. In the crystal, discrete complexes are linked by weak C—H⋯S hydrogen bonds into chains that are connected by additional C—H⋯S hydrogen bonding via the pyridinium cations and solvent molecules into layers and finally into a three-dimensional network.

Keywords: crystal structure,discrete complex; chromium(III); pyridinium; hydrogen bonding.

CCDC references: 1962530; 1962530

1. Chemical context

Coordination compounds with paramagnetic transition metals are of great interest because of their diverse magnetic properties (Cirera et al., 2009 ; Giannopoulos et al., 2014 ; Glaser, 2011 ; Yuan et al., 2007 ). Those in which the metal cations are linked by small-sized ligands that can mediate magnetic exchange are of special importance because co-operative magnetic phenomena can be expected. Prominent examples for this class of ligands are azides, oxalates and cyanides (Wang et al., 2005 , 2008 ; Zhang et al., 2012 ; Manson et al., 2005 ; Ding et al., 2012 ). In this context also, thiocyanate ligands are useful because they show a large variety of coordination modes, with the μ-1,3-bridging mode as the most important (Jochim et al., 2018 ; Mautner et al., 2016 , 2017 ; Shurdha et al., 2013 ; Mekuimemba et al., 2018 ; Wöhlert et al., 2014a ; Werner et al., 2015 ). It is noted that these compounds are frequently difficult to prepare because terminal N-coordination is usually preferred for 3d metal cations. Nevertheless, in recent years, an increasing number of bridging compounds have been reported, which might be traced back to the fact that several of them were prepared by thermal decomposition of precursors that contain terminal anionic ligands (Näther et al., 2013 ). In this context, we and others have reported on several new thiocyanate coordination polymers based on transition-metal thiocyanates, in which the metal cations are linked by bridging anionic ligands into chains (Rams et al., 2017 ; Baran et al., 2019 ; Wöhlert et al., 2013 , 2014b ; Mautner et al., 2018 ). Most of these compounds contain Mn^II, Fe^II, Co^II, Ni^II or Cu^II cations, whereas no bridging compounds are reported with chromium. There is only one compound in which alternating Cr^III and K⁺ cations are bridged by μ-1,3-coordinating thiocyanate anions into chains in which each cation is octahedrally sourrounded by two bridging thiocyanate anions and four pyridine ligands (Kitanovski et al., 2007 ). Therefore, we decided to investigated if similar compounds are available with chromium. Hence, CrCl₂ was reacted with NH₄NCS to prepare Cr(NCS)₂ in situ, which is similar to the procedure we frequently use for the synthesis of thiocyanate coordination polymers with other metal cations. Initially, pyridine was selected as the N-donor ligand, because most of our compounds are based on pyridine derivatives as co-ligands. In this reaction, crystals were obtained that were identified by single-crystal X-ray diffraction. This proved that a discrete cationic complex had formed.

2. Structural commentary

The asymmetric unit of the title compound consists of one half of the cation, namely a Cr^III ion, two pyridine ligands which lie on a crystallographic mirror plane and two isothiocyanate anions that occupy general positions, as well as one pyridinium cation and a pyridine molecule that are also located on a crystallographic mirror plane (Fig. 1). The Cr^III ion is sixfold coordinated by four N-bonding isothiocyanate anions and two pyridine ligands, within a slightly distorted octahedral geometry (Figs. 1 and 2). The Cr—N bond lengths (Table 1) to the pyridine ligands (N11 and N21) are slightly longer than that to the isothiocyanate anions (N1 and N2). The distortion of the octahedron is also obvious from the mean quadratic elongation of 1.0015 and the octahedral angle variance of 0.9447° calculated according to Robinson et al. (1971 ). The four isothiocyanate anions are located in the basal plane of the octahedron, whereas the pyridine ligands are in apical positions with the pyridine ring planes rotated by 90° (Fig. 2). Charge balance is achieved by a pyridinium cation that is hydrogen bonded to a pyridine solvent molecule via N—H⋯N hydrogen bonding, forming pyridinium–pyridine dimers (Fig. 3). Several models were tested, but in the final refinement, a split model was used, in which the pyridinium H atom is disordered over two sites in a ratio of 70:30. Presumably, because of sterical reasons, the pyridine-ring planes are perpendicular to each other (Fig. 3).

Table 1
Selected geometric parameters (Å, °)

Cr1—N2ⁱ	1.980 (5)	Cr1—N1ⁱ	1.991 (5)
Cr1—N2	1.980 (5)	Cr1—N21	2.080 (6)
Cr1—N1	1.991 (5)	Cr1—N11	2.102 (6)

N2ⁱ—Cr1—N2	88.4 (3)	N1—Cr1—N21	90.39 (18)
N2ⁱ—Cr1—N1	91.33 (18)	N1ⁱ—Cr1—N21	90.40 (18)
N2—Cr1—N1	178.9 (2)	N2ⁱ—Cr1—N11	88.98 (18)
N2ⁱ—Cr1—N1ⁱ	178.9 (2)	N2—Cr1—N11	88.98 (18)
N2—Cr1—N1ⁱ	91.33 (18)	N1—Cr1—N11	90.00 (18)
N1—Cr1—N1ⁱ	88.9 (3)	N1ⁱ—Cr1—N11	90.00 (18)
N2ⁱ—Cr1—N21	90.62 (18)	N21—Cr1—N11	179.4 (3)
N2—Cr1—N21	90.62 (18)
Symmetry code: (i) -x+1, y, z.

Figure 1
The molecular structure of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level. The pyridinium N-bound H atom is disordered over two sets of sites.

Figure 2
View of the coordination sphere of the Cr^III ion.

Figure 3
View of the pyridinium–pyridine dimer, with N–H⋯N hydrogen bonding shown as dashed lines. The pyridinium N-bound H atom is disordered over two sets of sites.

3. Supramolecular features

In the crystal, discrete complexes and pyridinium cations are arranged in alternating layers parallel to the bc plane (Fig. 4, bottom). The discrete complexes are linked by pairs of C—H⋯S hydrogen bonds between the thiocyanate S atoms of one complex and two H atoms of one of the pyridine ligands of a neighbouring complex into chains, that elongate along the crystallographic b axis (Fig. 4, top). The bond lengths and angles of these hydrogen bonds show that this is only a very weak interaction (Table 2). These chains are further linked by additional very weak C—H⋯S interactions between the thiocyanate S atoms that are not involved in chain formation and one H atom of the pyridinium–pyridine dimers (Fig. 4, bottom, and Table 2). Finally, further C—H⋯S interactions link all building blocks into a three-dimensional network. It is noted that both the discrete complexes, as well as the pyridinium–pyridine dimers, point in the same direction along the crystallographic c axis, clearly showing the presence of a polar structure (Fig. 4, bottom).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯S1ⁱⁱ	0.93	2.93	3.647 (6)	135
C32—H32⋯S2ⁱⁱⁱ	0.93	3.01	3.719 (8)	134
C32—H32⋯S2^iv	0.93	3.01	3.719 (8)	134
C35—H35⋯S2^v	0.93	2.90	3.494 (7)	123
C35—H35⋯S2^vi	0.93	2.90	3.494 (7)	123
N31—H31A⋯N41	0.86	1.82	2.684 (11)	179
N41—H41A⋯N31	0.86	1.82	2.684 (11)	180
Symmetry codes: (ii) x, y+1, z; (iii) $[-x, -y+2, z-{\script{1\over 2}}]$ ; (iv) $[x, -y+2, z-{\script{1\over 2}}]$ ; (v) x, y, z-1; (vi) -x, y, z-1.

Figure 4
View of a chain (top) and the crystal structure of the title compound viewed along the crystallographic b-axis and with the intermolecular hydrogen bonding shown as dashed lines.

4. Database survey

There are four structures published in the CSD (Version 5.4, Update 1, February 2019; Groom et al., 2016 ) that consist of chromium(II) and thiocyanate anions. In all of them, the Cr^II cations are square-planar coordinated by two isothiocyanate anions and two co-ligands (Jubb et al., 1989 , 1991 ; Shurdha et al., 2012 , 2013). With chromium(III) there are two structures in which the cations are octahedrally coordinated by only two terminal isothiocyanate anions and by two 4,4′-dimethyl-2,2′-pyridine ligands and the positive charge is neutralized by iodide or triiodide anions (Walter & Elliott, 2001 ). In most of the reported structures with Cr^III, the cations are surrounded by four or six isothiocyanate anions and the positive charges are neutralized by protonated solvent or ligand molecules. There is also one discrete complex with pyridine as co-ligand, in which the Cr^III cations are coordinated by three isothiocyanate anions and three pyridine ligands (Malecki, 2016 ). A similar structure is also known with 4-methylpyridine (Kitanovski et al., 2007). Finally, there is one structure reported that is comparable to that of the title compound with 4-methylpyridine, in which the Cr^III cations are coordinated by two 4-methylpyridine ligands and four N-terminal thiocyanate anions. Charge balance is achieved by one 4-methylpyridinium cation that is hydrogen bonded to one 4-methylpyridine solvent molecule (Young et al., 2011 ). In contrast to the title compound, the N—H distances are not symmetrical (N—H = 1.16 Å and N⋯H = 1.5 Å), but the N—H⋯N hydrogen-bond distance is comparable (2.686 Å) to that in the title compound (2.684 Å).

5. Synthesis and crystallization

CrCl₂ (0.5 mmol, 66.5 mg) was reacted with NH₄NCS (1.0 mmol, 76.1 mg) in 2.0 ml pyridine. The precipitate was filtered off and the filtrate was stored at room temperature. After a few days, crystals of the title compound suitable for single-crystal x-ray diffraction were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atoms were positioned with idealized geometry and refined with U_iso(H) = 1.2U_eq(C) using a riding model. The pyridinium H atom was located in a difference map and was initially freely refined. In this case, it is located nearly in the middle between both pyridine N atoms, leading to very long N—H bonds of 1.32 (16) and 1.35 (16) Å, an N—H⋯N angle close to linearity and a relatively large isotropic displacement parameter. For such N—H⋯N hydrogen bonds, both symmetric and asymmetric hydrogen bonds were determined by neutron diffraction, but the symmetric bonds are usually observed at shorter N⋯N distances (Rozière et al., 1980 , 1982 ). Therefore, the pyridinium H atom was placed at an ideal distance and the displacement parameter was refined. In this case, there is a strong indication that the H atom is disordered and therefore a split model was used with the site-occupation factor for each H atom in a ratio of 70:30, which leads to similar isotropic displacement parameters that are lower than that obtained by the refinement of a symmetrical hydrogen bond. In the final refinement, both H atoms were placed in ideal positions and were refined with U_iso(H) = 1.2U_eq(N) using a riding model.

Table 3
Experimental details

Crystal data
Chemical formula	(C₅H₆N)[Cr(NCS)₄(C₅H₅N)₂]·C₅H₅N
M_r	601.73
Crystal system, space group	Orthorhombic, Pmc2₁
Temperature (K)	293
a, b, c (Å)	10.1068 (5), 8.8168 (6), 16.2628 (9)
V (Å³)	1449.17 (15)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.71
Crystal size (mm)	0.12 × 0.07 × 0.02

Data collection
Diffractometer	Stoe IPDS1
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 )
T_min, T_max	0.786, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	12253, 3153, 2452
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.106, 1.02
No. of reflections	3153
No. of parameters	193
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.42
Absolute structure	Flack x determined using 925 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.027 (19)
Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1962530; 1962530

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989019014488/lh5933sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019014488/lh5933Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Pyridinium tetraisothiocyanatobis(pyridine)chromium(III) pyridine monosolvate top

Crystal data top

(C₅H₆N)[Cr(NCS)₄(C₅H₅N)₂]·C₅H₅N	D_x = 1.379 Mg m⁻³
M_r = 601.73	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pmc2₁	Cell parameters from 12253 reflections
a = 10.1068 (5) Å	θ = 2.6–28.1°
b = 8.8168 (6) Å	µ = 0.71 mm⁻¹
c = 16.2628 (9) Å	T = 293 K
V = 1449.17 (15) Å³	Plate, green
Z = 2	0.12 × 0.07 × 0.02 mm
F(000) = 618

Data collection top

Stoe IPDS1 diffractometer	2452 reflections with I > 2σ(I)
Phi scans	R_int = 0.062
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	θ_max = 27.0°, θ_min = 2.6°
T_min = 0.786, T_max = 0.966	h = −11→12
12253 measured reflections	k = −11→11
3153 independent reflections	l = −20→20

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0503P)² + 0.4808P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.106	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.30 e Å⁻³
3153 reflections	Δρ_min = −0.42 e Å⁻³
193 parameters	Absolute structure: Flack x determined using 925 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.027 (19)

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)
Cr1	0.500000	0.64497 (13)	0.99944 (7)	0.0350 (3)
N1	0.6380 (5)	0.5526 (5)	0.9278 (3)	0.0456 (11)
C1	0.7030 (6)	0.4870 (6)	0.8803 (3)	0.0409 (12)
S1	0.7901 (2)	0.39515 (18)	0.81396 (11)	0.0671 (5)
N2	0.3635 (5)	0.7405 (5)	1.0697 (3)	0.0453 (11)
C2	0.2924 (6)	0.8219 (6)	1.1063 (3)	0.0410 (12)
S2	0.1955 (2)	0.9312 (2)	1.15735 (11)	0.0689 (5)
N11	0.500000	0.8403 (7)	0.9254 (4)	0.0378 (13)
C11	0.6137 (6)	0.9059 (6)	0.9028 (3)	0.0446 (13)
H11	0.693081	0.859637	0.917262	0.053*
C12	0.6175 (7)	1.0412 (6)	0.8584 (4)	0.0522 (14)
H12	0.697858	1.084674	0.843515	0.063*
C13	0.500000	1.1087 (10)	0.8372 (5)	0.054 (2)
H13	0.499999	1.200033	0.808600	0.065*
N21	0.500000	0.4529 (7)	1.0738 (4)	0.0380 (14)
C21	0.500000	0.4633 (10)	1.1565 (5)	0.051 (2)
H21	0.500000	0.558953	1.180637	0.061*
C22	0.500000	0.3371 (11)	1.2067 (6)	0.065 (3)
H22	0.500000	0.348073	1.263584	0.078*
C23	0.500000	0.1953 (12)	1.1719 (6)	0.068 (3)
H23	0.500000	0.109435	1.205088	0.082*
C24	0.500000	0.1805 (10)	1.0868 (6)	0.059 (2)
H24	0.500000	0.085445	1.061946	0.070*
C25	0.500000	0.3110 (9)	1.0405 (5)	0.0441 (18)
H25	0.500000	0.301981	0.983543	0.053*
N31	0.000000	1.0017 (9)	0.4322 (5)	0.061 (2)
H31A	0.000000	0.920955	0.461881	0.073*	0.3
C31	0.000000	0.9933 (10)	0.3502 (6)	0.057 (2)
H31	0.000000	0.898380	0.325264	0.068*
C32	0.000000	1.1428 (12)	0.4678 (6)	0.062 (2)
H32	0.000000	1.150849	0.524812	0.075*
C33	0.000000	1.2701 (11)	0.4217 (6)	0.060 (2)
H33	0.000000	1.364655	0.447130	0.072*
C34	0.000000	1.2604 (10)	0.3374 (5)	0.051 (2)
H34	0.000000	1.347438	0.305068	0.061*
C35	0.000000	1.1195 (10)	0.3021 (5)	0.051 (2)
H35	0.000000	1.109984	0.245176	0.062*
N41	0.000000	0.7526 (8)	0.5271 (5)	0.0557 (19)
H41A	0.000000	0.832178	0.496530	0.067*	0.7
C41	0.1138 (8)	0.6919 (8)	0.5505 (5)	0.0686 (19)
H41	0.192859	0.735531	0.533295	0.082*
C42	0.1165 (8)	0.5636 (8)	0.6004 (5)	0.071 (2)
H42	0.196943	0.522486	0.617040	0.085*
C43	0.000000	0.4985 (10)	0.6248 (5)	0.057 (2)
H43	0.000001	0.411685	0.657268	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr1	0.0346 (6)	0.0369 (5)	0.0333 (5)	0.000	0.000	−0.0032 (5)
N1	0.048 (3)	0.049 (3)	0.039 (2)	0.001 (2)	0.000 (2)	0.001 (2)
C1	0.040 (3)	0.037 (3)	0.045 (3)	−0.001 (2)	0.006 (3)	−0.001 (2)
S1	0.0761 (13)	0.0503 (8)	0.0749 (11)	−0.0015 (8)	0.0372 (9)	−0.0093 (8)
N2	0.045 (3)	0.047 (3)	0.044 (3)	0.002 (2)	0.006 (2)	−0.003 (2)
C2	0.040 (3)	0.045 (3)	0.038 (3)	0.001 (2)	−0.003 (2)	0.001 (2)
S2	0.0684 (12)	0.0846 (12)	0.0537 (9)	0.0326 (9)	0.0046 (9)	−0.0143 (8)
N11	0.036 (4)	0.040 (3)	0.037 (3)	0.000	0.000	−0.001 (3)
C11	0.041 (3)	0.046 (3)	0.047 (3)	−0.003 (2)	0.001 (2)	0.004 (2)
C12	0.059 (4)	0.045 (3)	0.052 (3)	−0.007 (3)	0.010 (3)	0.005 (3)
C13	0.071 (6)	0.045 (4)	0.046 (5)	0.000	0.000	0.006 (4)
N21	0.040 (4)	0.035 (3)	0.039 (3)	0.000	0.000	−0.004 (2)
C21	0.064 (6)	0.054 (5)	0.035 (4)	0.000	0.000	−0.001 (3)
C22	0.090 (8)	0.064 (6)	0.042 (4)	0.000	0.000	0.007 (4)
C23	0.096 (8)	0.059 (6)	0.050 (5)	0.000	0.000	0.022 (5)
C24	0.074 (7)	0.047 (5)	0.055 (5)	0.000	0.000	0.007 (4)
C25	0.051 (5)	0.042 (4)	0.039 (4)	0.000	0.000	0.001 (3)
N31	0.051 (5)	0.055 (4)	0.075 (5)	0.000	0.000	0.020 (4)
C31	0.059 (6)	0.045 (4)	0.066 (6)	0.000	0.000	−0.005 (4)
C32	0.066 (6)	0.076 (6)	0.045 (4)	0.000	0.000	0.003 (5)
C33	0.073 (7)	0.051 (5)	0.055 (5)	0.000	0.000	−0.010 (4)
C34	0.054 (5)	0.053 (5)	0.045 (4)	0.000	0.000	−0.001 (4)
C35	0.052 (5)	0.059 (5)	0.043 (4)	0.000	0.000	−0.009 (4)
N41	0.054 (5)	0.050 (4)	0.063 (5)	0.000	0.000	0.014 (3)
C41	0.051 (4)	0.064 (4)	0.091 (5)	0.000 (3)	0.004 (4)	0.017 (4)
C42	0.056 (5)	0.071 (4)	0.086 (5)	0.016 (3)	−0.002 (4)	0.018 (4)
C43	0.079 (7)	0.045 (4)	0.047 (5)	0.000	0.000	0.009 (4)

Geometric parameters (Å, º) top

Cr1—N2ⁱ	1.980 (5)	C23—H23	0.9300
Cr1—N2	1.980 (5)	C24—C25	1.375 (11)
Cr1—N1	1.991 (5)	C24—H24	0.9300
Cr1—N1ⁱ	1.991 (5)	C25—H25	0.9300
Cr1—N21	2.080 (6)	N31—C31	1.336 (13)
Cr1—N11	2.102 (6)	N31—C32	1.372 (13)
N1—C1	1.168 (7)	N31—H31A	0.8600
C1—S1	1.610 (6)	C31—C35	1.360 (13)
N2—C2	1.177 (7)	C31—H31	0.9300
C2—S2	1.605 (6)	C32—C33	1.350 (13)
N11—C11	1.338 (7)	C32—H32	0.9300
N11—C11ⁱ	1.338 (7)	C33—C34	1.375 (12)
C11—C12	1.395 (7)	C33—H33	0.9300
C11—H11	0.9300	C34—C35	1.368 (11)
C12—C13	1.373 (8)	C34—H34	0.9300
C12—H12	0.9300	C35—H35	0.9300
C13—H13	0.9300	N41—C41	1.324 (8)
N21—C21	1.349 (10)	N41—C41ⁱⁱ	1.324 (8)
N21—C25	1.363 (10)	N41—H41A	0.8600
C21—C22	1.379 (12)	C41—C42	1.393 (9)
C21—H21	0.9300	C41—H41	0.9300
C22—C23	1.373 (15)	C42—C43	1.369 (9)
C22—H22	0.9300	C42—H42	0.9300
C23—C24	1.390 (13)	C43—H43	0.9300

N2ⁱ—Cr1—N2	88.4 (3)	C22—C23—C24	119.8 (9)
N2ⁱ—Cr1—N1	91.33 (18)	C22—C23—H23	120.1
N2—Cr1—N1	178.9 (2)	C24—C23—H23	120.1
N2ⁱ—Cr1—N1ⁱ	178.9 (2)	C25—C24—C23	117.8 (9)
N2—Cr1—N1ⁱ	91.33 (18)	C25—C24—H24	121.1
N1—Cr1—N1ⁱ	88.9 (3)	C23—C24—H24	121.1
N2ⁱ—Cr1—N21	90.62 (18)	N21—C25—C24	123.5 (7)
N2—Cr1—N21	90.62 (18)	N21—C25—H25	118.3
N1—Cr1—N21	90.39 (18)	C24—C25—H25	118.3
N1ⁱ—Cr1—N21	90.40 (18)	C31—N31—C32	118.1 (8)
N2ⁱ—Cr1—N11	88.98 (18)	C31—N31—H31A	120.9
N2—Cr1—N11	88.98 (18)	C32—N31—H31A	120.9
N1—Cr1—N11	90.00 (18)	N31—C31—C35	121.9 (8)
N1ⁱ—Cr1—N11	90.00 (18)	N31—C31—H31	119.0
N21—Cr1—N11	179.4 (3)	C35—C31—H31	119.0
C1—N1—Cr1	169.7 (5)	C33—C32—N31	121.4 (9)
N1—C1—S1	178.9 (6)	C33—C32—H32	119.3
C2—N2—Cr1	167.6 (5)	N31—C32—H32	119.3
N2—C2—S2	179.1 (5)	C32—C33—C34	120.1 (9)
C11—N11—C11ⁱ	118.4 (7)	C32—C33—H33	119.9
C11—N11—Cr1	120.8 (3)	C34—C33—H33	119.9
C11ⁱ—N11—Cr1	120.7 (3)	C35—C34—C33	118.3 (8)
N11—C11—C12	122.4 (6)	C35—C34—H34	120.8
N11—C11—H11	118.8	C33—C34—H34	120.8
C12—C11—H11	118.8	C31—C35—C34	120.1 (8)
C13—C12—C11	118.5 (6)	C31—C35—H35	119.9
C13—C12—H12	120.8	C34—C35—H35	119.9
C11—C12—H12	120.8	C41—N41—C41ⁱⁱ	120.6 (8)
C12ⁱ—C13—C12	119.8 (8)	C41—N41—H41A	119.7
C12ⁱ—C13—H13	120.1	C41ⁱⁱ—N41—H41A	119.7
C12—C13—H13	120.1	N41—C41—C42	120.9 (7)
C21—N21—C25	117.3 (7)	N41—C41—H41	119.6
C21—N21—Cr1	121.6 (5)	C42—C41—H41	119.6
C25—N21—Cr1	121.1 (5)	C43—C42—C41	119.5 (7)
N21—C21—C22	122.4 (8)	C43—C42—H42	120.3
N21—C21—H21	118.8	C41—C42—H42	120.3
C22—C21—H21	118.8	C42—C43—C42ⁱⁱ	118.7 (8)
C23—C22—C21	119.4 (8)	C42—C43—H43	120.6
C23—C22—H22	120.3	C42ⁱⁱ—C43—H43	120.6
C21—C22—H22	120.3

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···S1ⁱⁱⁱ	0.93	2.93	3.647 (6)	135
C32—H32···S2^iv	0.93	3.01	3.719 (8)	134
C32—H32···S2^v	0.93	3.01	3.719 (8)	134
C35—H35···S2^vi	0.93	2.90	3.494 (7)	123
C35—H35···S2^vii	0.93	2.90	3.494 (7)	123
N31—H31A···N41	0.86	1.82	2.684 (11)	179
N41—H41A···N31	0.86	1.82	2.684 (11)	180

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

Acknowledgements

We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

Funding information

Funding for this research was provided by: Deutsche Forschungsgemeinschaft (grant No. NA 720/5-2).

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