Crystal structure of trans-bis­(ethane-1,2-diamine-κ²N,N′)bis­(thio­cyanato-κN)chromium(III) perchlorate from synchrotron data

The centrosymmetric Cr^III ion in the title compound shows a distorted octa­hedral coordination with four N atoms of two ethane-1,2-di­amine ligands in the equatorial plane and two N-coordinated NCS⁻ groups in trans-axial positions. The ethane-1,2-di­amine ligand in the complex cation and the ClO₄⁻ anion are both disordered.

Key indicators

• Single-crystal synchrotron study
• T = 260 K
• Mean [sigma](N-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.060
• wR factor = 0.178
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT019_ALERT_1_C  _diffrn_measured_fraction_theta_full/_max < 1.0      0.987 Report
PLAT234_ALERT_4_C Large Hirshfeld Difference C2A    --  C3A     ..       0.17 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       >N3A    -  >H3A2   ..     Please Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         50 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....         40 Note
PLAT918_ALERT_3_C Reflection(s) with I(obs) much smaller I(calc) .          2 Check
PLAT939_ALERT_3_C Large Value of Not (SHELXL) Weight Optimized S .      13.32

Alert level G
ABSMU01_ALERT_1_G  Calculation of _exptl_absorpt_correction_mu
                not performed for this radiation type.
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          8 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT Unusually Large.       0.11 Report
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          2 Report
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1     --  C1      ..        5.2 su
PLAT300_ALERT_4_G Atom Site Occupancy of *Cl1B   is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O1B    is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O2B    is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *Cl1C   is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O1C    is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O2C    is Constrained at      0.500 Check
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =         53 Note
PLAT302_ALERT_4_G Anion/Solvent Disorder ............ Percentage =        100 Note
PLAT304_ALERT_4_G Non-Integer Number of Atoms (   1.25) in Resd. #          2 Check
PLAT304_ALERT_4_G Non-Integer Number of Atoms (   1.25) in Resd. #          3 Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         16 Note
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.18 Ratio
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   7 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  20 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
  13 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Chemical context

Considerable attention has been focussed for some time on metal complexes containing thio­cyanate ligands because of their ability to coordinate through either the N or S atoms. Ethane-1,2-di­amine (en) can coordinate to a central metal ion as a bidentate ligand via the two N atoms, forming a five-membered chelate ring. The [Cr(NCS)₂(en)₂]⁺ cation can form either trans or cis geometric isomers. Trans and cis isomers of the complex cation with SCN^- or ClO₄^- counter-anions have been prepared and their IR spectral properties reported (House, 1973; Sandrini et al., 1978; De et al., 1987). IR and electronic spectral properties are useful in determining the geometric isomers of chromium(III) complexes with mixed ligands (Choi, 2000; Choi et al., 2004; Choi & Moon, 2014). However, it should be noted that the geometric assignments based on spectroscopic studies are not always definitive. In a recent publication, we described the synthesis and crystal structure of trans-[Cr(NCS)₂(en)₂]₂[ZnCl₄] (Moon & Choi, 2015). The asymmetric unit of this complex contained four halves of centrosymmetric [Cr(NCS)₂(en)₂]⁺ complex cations and one [ZnCl₄]^2- anion. To compare and contrast this structure with a complex of this cation with a different counter-anion we report here the structure of trans-[Cr(NCS)₂(en)₂]ClO₄, (I).

S2. Structural commentary

Fig. 1 shows an ellipsoid plot of trans-[Cr(NCS)₂(en)₂]ClO₄, (I), with the atom-numbering scheme. In the structure of (I), there is a centrosymmetric Cr^III complex cation with two en ligands bound through their N atoms in equatorial sites and the two axial N-bound thio­cyanate anions in a trans configuration. The asymmetric unit is composed of half of one complex cation and half a ClO₄^- anion. The Cr atom is located on crystallographic centres of symmetry, so this complex cation has molecular C_i symmetry, while the the Cl atom of the perchlorate anion lies on a twofold rotation axis. The bidentate en ligand adopts a stable gauche conformation similar to that observed in related compounds (Brencic & Leban, 1981; Choi et al., 2010). The Cr—N bond distances for the en ligand range from 2.037 (17) to 2.109 (19) Å [2.053 (16) to 2.09 (2) Å ?], and these bond lengths are in good agreement with those observed in trans-[CrF₂(en)₂]ClO₄ (Brencic & Leban, 1981), trans-[CrBr₂(en)₂]ClO₄ (Choi et al., 2010), trans-[CrCl₂(Me₂tn)₂]₂ZnCl₄ (Me₂tn = 2,2-di­methyl­propane-1,3-di­amine; Choi et al., 2011) and trans-[CrF₂(2,2,3-tet)]ClO₄ (2,2,3-tet = 1,4,7,11-tetra­aza­undecane; Choi & Moon, 2014). The Cr—N(thio­cyanate) bond distance is 1.983 (2) Å and is similar to the average values of 1.985 (2), 1.995 (6), 1.983 (2) and 1.996 (15) Å found in trans-[Cr(NCS)₂(en)₂]₂ZnCl₄ (Moon & Choi, 2015), trans-[Cr(NCS)₂(cyclam)]₂ZnCl₄ (cyclam = 1,4,8,11-tetra­aza­cyclo­tetra­decane (Moon et al., 2015), trans-[Cr(NCS)₂(Me₂tn)₂]NCS (Choi & Lee, 2009) and cis-[Cr(NCS)₂(cyclam)]NCS (Moon et al., 2013), respectively. The N-coordinated iso­thio­cyanate group is almost linear, with an N—C—S angle 179.3 (3)°. The ClO₄^- counter-anion lies well outside the coordination sphere of the complex and, because of significant disorder, the tetra­hedral geometry of this anion is severely distorted.

S3. Supra­molecular features

In the crystal, an N—H···S hydrogen bond links neighbouring cations, while a series of N—H···O contacts link the cations to neighbouring anions (Table 1). An extensive array of these contacts generate a three-dimensional network of molecules stacked along the b-axis direction (Fig. 2). These hydrogen-bonded networks help to stabilize the crystal structure.

S4. Database survey

A search of the Cambridge Structural Database (Version 5.36, last update February 2015; Groom & Allen, 2014) indicates a total of 13 hits for Cr^III complexes with a [CrL₂(en)₂]⁺ unit. The crystal structures of trans-[CrCl₂(en)₂]Cl.HCl.2H₂O (Ooi et al., 1960), trans-[CrF₂(en)₂]X (X = ClO₄, Cl, Br) (Brencic & Leban, 1981), cis-[CrF₂(en)₂]ClO₄ (Brencic et al., 1987), trans-[CrBr₂(en)₂]ClO₄ (Choi et al., 2010) have been reported previously. Recently, we have also reported the closely related crystal structure of Cr(NCS)₂(en)₂]₂ZnCl₄, in which there are four crystallographically independent Cr^III complex cations that also adopt a trans configuration. However, crystal structure of [Cr(NCS)₂(en)₂]⁺ with a ClO₄ anion has not been reported previously.

S5. Synthesis and crystallization

All chemicals were reagent grade materials and were used without further purification. The title compound, trans-[Cr(NCS)₂(en)₂]ClO₄ was prepared according to the literature method of Sandrini et al. (1978). The crude perchlorate salt (0.33 g) was dissolved in 20 ml of 0.1 M HCl at 333 K. The filtrate was added to 6 ml of 60% HClO₄. The resulting solution was allowed to stand at room temperature for 2 d to give orange block-like crystals suitable for X-ray structural analysis. IR spectrum (KBr, cm^-1 ): 3247 (vs), 3208 (vs), 3131 (vs) and 3097 (vs) (ν NH), 2966 (s), 2955 (s) and 2893 (s) (ν CH), 2077 (vs) (ν_a CN), 1586 (vs) (δ NH₂), 1459 (s) (δ CH₂), 1365 (m) (ν CN), 1326 (s) (ω NH₂), 1290 (vs) (ω CH₂), 1146 (vs) (γ NH₂), 1117 (vs) (ν CN), 1088 (vs) (ν_a Cl—O), 1047 (vs) (γ CH₂), 1007 (s), 983 (s), 873 (m) (ρ CH₂), 849 (w) (ρ NH₂), 729 (vs), 636 (s) and 626 (vs) (δ OClO), 558 (vs), 559 (s) (δ CCC), 501 (vs), 478 (s) (δ NCS), 444 (m) and 419 (m) (ν Cr—N).

S6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. In the title compound, the ethane-1,2-di­amine group is disordered with atoms N2A/N2B, C2A/C2B, C3A/C3B and N3A/N3B positionally disordered over two sets of sites with a refined occupancy ratio of 0.522 (16):0.478 (16). The half molecules of each distorted perchlorate anion are disordered over two sites of equal occupancy, with atoms Cl1B/Cl1C and O2B/O1C refined using EXYZ/EADP constraints. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.97 Å and N—H = 0.89 Å, and with U_iso(H) values of 1.2 of the parent atoms.

Computing details

Data collection: PAL ADSC Quantum-210 ADX Program (Arvai & Nielsen, 1983); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor,1997); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: DIAMOND (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I), drawn with 20% probability displacement ellipsoids. Atoms of the minor disorder components have been omitted for clarity.
	Fig. 2. The crystal packing of (I), viewed perpendicular to the ac plane. H atoms on C atoms have been omitted. Dashed lines represent N—H···O (red) and N—H···S (blue) hydrogen-bonding interactions, respectively. The minor disorder components have been omitted for clarity.

trans-Bis(ethane-1,2-diamine-κ²N,N')bis(thiocyanato-κN)chromium(III) perchlorate

Crystal data

[Cr(NCS)2(C2H8N2)2]ClO4	F(000) = 796
Mr = 387.82	Dx = 1.672 Mg m^−3
Monoclinic, C2/c	Synchrotron radiation, λ = 0.630 Å
a = 15.599 (3) Å	Cell parameters from 46962 reflections
b = 7.4440 (15) Å	θ = 0.4–33.6°
c = 13.792 (3) Å	µ = 0.86 mm^−1
β = 105.83 (3)°	T = 260 K
V = 1540.8 (6) Å^3	Block, orange
Z = 4	0.14 × 0.13 × 0.13 mm

Data collection

ADSC Q210 CCD area-detector diffractometer	2019 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.015
ω scan	θmax = 26.0°, θmin = 2.7°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEAPCK; Otwinowski & Minor, 1997)	h = −21→21
Tmin = 0.893, Tmax = 0.897	k = −10→10
8172 measured reflections	l = −19→19
2121 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.060	w = 1/[σ^2(Fo^2) + (0.1146P)^2 + 2.4721P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.178	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 0.74 e Å^−3
2121 reflections	Δρmin = −1.12 e Å^−3
140 parameters	Extinction correction: SHELXL2014/7 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.045 (12)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cr1	0.2500	0.2500	0.5000	0.0273 (3)
S1	0.21080 (8)	0.77661 (11)	0.67477 (8)	0.0586 (3)
N1	0.24831 (15)	0.4775 (3)	0.57426 (17)	0.0433 (5)
C1	0.23290 (16)	0.6026 (3)	0.61573 (17)	0.0363 (5)
N2A	0.3423 (12)	0.1308 (19)	0.6213 (13)	0.036 (2)	0.522 (16)
H2A1	0.3272	0.1503	0.6781	0.043*	0.522 (16)
H2A2	0.3442	0.0127	0.6118	0.043*	0.522 (16)
N3A	0.3624 (11)	0.337 (2)	0.4641 (10)	0.043 (3)	0.522 (16)
H3A1	0.3553	0.3266	0.3981	0.052*	0.522 (16)
H3A2	0.3722	0.4525	0.4807	0.052*	0.522 (16)
C2A	0.4311 (5)	0.2126 (10)	0.6277 (8)	0.057 (2)	0.522 (16)
H2A3	0.4784	0.1375	0.6678	0.068*	0.522 (16)
H2A4	0.4355	0.3305	0.6587	0.068*	0.522 (16)
C3A	0.4385 (5)	0.2274 (14)	0.5199 (10)	0.066 (3)	0.522 (16)
H3A3	0.4943	0.2842	0.5191	0.079*	0.522 (16)
H3A4	0.4362	0.1092	0.4897	0.079*	0.522 (16)
N2B	0.3570 (13)	0.164 (2)	0.6143 (14)	0.041 (3)	0.478 (16)
H2B1	0.3654	0.2382	0.6667	0.049*	0.478 (16)
H2B2	0.3464	0.0548	0.6342	0.049*	0.478 (16)
N3B	0.3502 (13)	0.341 (3)	0.4378 (9)	0.040 (2)	0.478 (16)
H3B1	0.3527	0.2732	0.3856	0.048*	0.478 (16)
H3B2	0.3396	0.4543	0.4167	0.048*	0.478 (16)
C2B	0.4369 (4)	0.1614 (15)	0.5773 (8)	0.056 (2)	0.478 (16)
H2B3	0.4355	0.0582	0.5339	0.067*	0.478 (16)
H2B4	0.4902	0.1541	0.6334	0.067*	0.478 (16)
C3B	0.4370 (5)	0.3297 (19)	0.5203 (7)	0.060 (3)	0.478 (16)
H3B3	0.4869	0.3303	0.4911	0.072*	0.478 (16)
H3B4	0.4427	0.4322	0.5651	0.072*	0.478 (16)
Cl1B	0.5000	0.7072 (3)	0.7500	0.0989 (7)	0.5
O1B	0.4393 (4)	0.5672 (9)	0.7711 (5)	0.0762 (16)	0.5
O2B	0.4350 (6)	0.7462 (8)	0.6376 (6)	0.159 (3)	0.5
Cl1C	0.5000	0.7072 (3)	0.7500	0.0989 (7)	0.5
O1C	0.4350 (6)	0.7462 (8)	0.6376 (6)	0.159 (3)	0.5
O2C	0.4488 (11)	0.8416 (15)	0.7860 (8)	0.152 (5)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr1	0.0366 (4)	0.0229 (3)	0.0251 (3)	0.00353 (14)	0.0128 (2)	−0.00135 (14)
S1	0.0988 (7)	0.0298 (4)	0.0630 (6)	0.0072 (3)	0.0492 (5)	−0.0070 (3)
N1	0.0553 (12)	0.0327 (11)	0.0427 (10)	0.0052 (9)	0.0145 (9)	−0.0097 (8)
C1	0.0472 (12)	0.0289 (10)	0.0356 (10)	0.0012 (9)	0.0163 (9)	−0.0012 (8)
N2A	0.050 (5)	0.024 (3)	0.034 (3)	−0.001 (2)	0.011 (3)	0.004 (2)
N3A	0.047 (5)	0.036 (3)	0.056 (7)	0.006 (3)	0.028 (5)	0.017 (5)
C2A	0.048 (3)	0.044 (3)	0.065 (5)	−0.003 (2)	−0.006 (3)	−0.001 (3)
C3A	0.038 (3)	0.044 (4)	0.121 (8)	0.008 (3)	0.031 (4)	0.026 (5)
N2B	0.048 (6)	0.044 (8)	0.031 (3)	0.012 (5)	0.014 (3)	0.005 (4)
N3B	0.050 (5)	0.043 (4)	0.031 (4)	0.005 (3)	0.019 (4)	0.002 (3)
C2B	0.041 (3)	0.073 (5)	0.051 (5)	0.017 (3)	0.007 (3)	0.003 (4)
C3B	0.045 (3)	0.068 (7)	0.070 (4)	−0.014 (4)	0.023 (3)	−0.013 (4)
Cl1B	0.1112 (15)	0.0671 (10)	0.1316 (18)	0.000	0.0553 (13)	0.000
O1B	0.074 (3)	0.073 (4)	0.083 (4)	−0.009 (3)	0.024 (3)	0.029 (3)
O2B	0.152 (6)	0.199 (8)	0.130 (5)	0.028 (4)	0.045 (5)	0.035 (4)
Cl1C	0.1112 (15)	0.0671 (10)	0.1316 (18)	0.000	0.0553 (13)	0.000
O1C	0.152 (6)	0.199 (8)	0.130 (5)	0.028 (4)	0.045 (5)	0.035 (4)
O2C	0.255 (15)	0.095 (7)	0.121 (8)	−0.038 (9)	0.076 (9)	−0.014 (6)

Geometric parameters (Å, º)

Cr1—N1	1.983 (2)	C3A—H3A3	0.9700
Cr1—N1^i	1.983 (2)	C3A—H3A4	0.9700
Cr1—N3A^i	2.053 (16)	N2B—C2B	1.471 (18)
Cr1—N3A	2.053 (16)	N2B—H2B1	0.8900
Cr1—N2B	2.06 (2)	N2B—H2B2	0.8900
Cr1—N2B^i	2.06 (2)	N3B—C3B	1.514 (17)
Cr1—N2A^i	2.085 (19)	N3B—H3B1	0.8900
Cr1—N2A	2.085 (19)	N3B—H3B2	0.8900
Cr1—N3B^i	2.09 (2)	C2B—C3B	1.479 (17)
Cr1—N3B	2.09 (2)	C2B—H2B3	0.9700
S1—C1	1.617 (3)	C2B—H2B4	0.9700
N1—C1	1.152 (3)	C3B—H3B3	0.9700
N2A—C2A	1.493 (15)	C3B—H3B4	0.9700
N2A—H2A1	0.8900	Cl1B—O1B^ii	1.489 (6)
N2A—H2A2	0.8900	Cl1B—O1B	1.489 (6)
N3A—C3A	1.475 (16)	Cl1B—O2B^ii	1.630 (8)
N3A—H3A1	0.8900	Cl1B—O2B	1.630 (8)
N3A—H3A2	0.8900	Cl1C—O2C^ii	1.450 (13)
C2A—C3A	1.527 (17)	Cl1C—O2C	1.450 (13)
C2A—H2A3	0.9700	Cl1C—O1C^ii	1.630 (8)
C2A—H2A4	0.9700	Cl1C—O1C	1.630 (8)
N1—Cr1—N1^i	180.0	N2A—C2A—H2A4	110.4
N1—Cr1—N3A^i	90.8 (5)	C3A—C2A—H2A4	110.4
N1^i—Cr1—N3A^i	89.2 (5)	H2A3—C2A—H2A4	108.6
N1—Cr1—N3A	89.2 (5)	N3A—C3A—C2A	106.5 (10)
N1^i—Cr1—N3A	90.8 (5)	N3A—C3A—H3A3	110.4
N3A^i—Cr1—N3A	180.0	C2A—C3A—H3A3	110.4
N1—Cr1—N2B	89.5 (5)	N3A—C3A—H3A4	110.4
N1^i—Cr1—N2B	90.5 (5)	C2A—C3A—H3A4	110.4
N1—Cr1—N2B^i	90.5 (5)	H3A3—C3A—H3A4	108.6
N1^i—Cr1—N2B^i	89.5 (5)	C2B—N2B—Cr1	109.0 (9)
N2B—Cr1—N2B^i	180.0 (9)	C2B—N2B—H2B1	109.9
N1—Cr1—N2A^i	87.0 (4)	Cr1—N2B—H2B1	109.9
N1^i—Cr1—N2A^i	93.0 (5)	C2B—N2B—H2B2	109.9
N3A^i—Cr1—N2A^i	83.1 (5)	Cr1—N2B—H2B2	109.9
N3A—Cr1—N2A^i	96.9 (5)	H2B1—N2B—H2B2	108.3
N1—Cr1—N2A	93.0 (4)	C3B—N3B—Cr1	106.7 (8)
N1^i—Cr1—N2A	87.0 (4)	C3B—N3B—H3B1	110.4
N3A^i—Cr1—N2A	96.9 (5)	Cr1—N3B—H3B1	110.4
N3A—Cr1—N2A	83.1 (5)	C3B—N3B—H3B2	110.4
N2A^i—Cr1—N2A	180.0	Cr1—N3B—H3B2	110.4
N1—Cr1—N3B^i	87.1 (5)	H3B1—N3B—H3B2	108.6
N1^i—Cr1—N3B^i	92.9 (5)	N2B—C2B—C3B	107.1 (10)
N2B—Cr1—N3B^i	97.2 (5)	N2B—C2B—H2B3	110.3
N2B^i—Cr1—N3B^i	82.8 (5)	C3B—C2B—H2B3	110.3
N1—Cr1—N3B	92.9 (5)	N2B—C2B—H2B4	110.3
N1^i—Cr1—N3B	87.1 (5)	C3B—C2B—H2B4	110.3
N2B—Cr1—N3B	82.8 (5)	H2B3—C2B—H2B4	108.5
N2B^i—Cr1—N3B	97.2 (5)	C2B—C3B—N3B	108.6 (10)
N3B^i—Cr1—N3B	180.0	C2B—C3B—H3B3	110.0
C1—N1—Cr1	168.7 (2)	N3B—C3B—H3B3	110.0
N1—C1—S1	179.3 (3)	C2B—C3B—H3B4	110.0
C2A—N2A—Cr1	107.5 (7)	N3B—C3B—H3B4	110.0
C2A—N2A—H2A1	110.2	H3B3—C3B—H3B4	108.4
Cr1—N2A—H2A1	110.2	O1B^ii—Cl1B—O1B	91.2 (5)
C2A—N2A—H2A2	110.2	O1B^ii—Cl1B—O2B^ii	92.7 (4)
Cr1—N2A—H2A2	110.2	O1B—Cl1B—O2B^ii	101.7 (3)
H2A1—N2A—H2A2	108.5	O1B^ii—Cl1B—O2B	101.7 (3)
C3A—N3A—Cr1	108.5 (8)	O1B—Cl1B—O2B	92.7 (4)
C3A—N3A—H3A1	110.0	O2B^ii—Cl1B—O2B	159.4 (5)
Cr1—N3A—H3A1	110.0	O2C^ii—Cl1C—O2C	92.7 (9)
C3A—N3A—H3A2	110.0	O2C^ii—Cl1C—O1C^ii	86.8 (6)
Cr1—N3A—H3A2	110.0	O2C—Cl1C—O1C^ii	79.0 (6)
H3A1—N3A—H3A2	108.4	O2C^ii—Cl1C—O1C	79.0 (6)
N2A—C2A—C3A	106.7 (9)	O2C—Cl1C—O1C	86.8 (6)
N2A—C2A—H2A3	110.4	O1C^ii—Cl1C—O1C	159.4 (5)
C3A—C2A—H2A3	110.4
Cr1—N2A—C2A—C3A	−42.0 (11)	Cr1—N2B—C2B—C3B	44.2 (13)
Cr1—N3A—C3A—C2A	−44.8 (13)	N2B—C2B—C3B—N3B	−56.3 (15)
N2A—C2A—C3A—N3A	57.9 (14)	Cr1—N3B—C3B—C2B	40.2 (12)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2A1···S1^iii	0.89	2.45	3.324 (17)	167
N2A—H2A2···O2B^iv	0.89	2.41	3.187 (19)	146
N3A—H3A1···O1B^v	0.89	2.58	3.282 (16)	136
N2B—H2B1···S1^iii	0.89	2.77	3.459 (17)	135
N3B—H3B1···O2C^v	0.89	2.45	3.22 (2)	145
N3B—H3B2···S1^vi	0.89	2.38	3.255 (18)	166

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