Crystal structure of cis-di­chlorido­(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4N)chromium(III) (oxalato-κ2O1,O2)(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4N)chromium(III) bis(perchlorate) from synchrotron data

Moon, D.; Choi, J.-H.

doi:10.1107/S2056989016014134

research communications

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ISSN: 2056-9890

Volume 72| Part 10| October 2016| Pages 1417-1420

https://doi.org/10.1107/S2056989016014134

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Crystal structure of cis-dichlorido(1,4,8,11-tetraazacyclotetradecane-κ⁴N)chromium(III) (oxalato-κ²O¹,O²)(1,4,8,11-tetraazacyclotetradecane-κ⁴N)chromium(III) bis(perchlorate) from synchrotron data

Dohyun Moon ^a and Jong-Ha Choi ^b ^*

^aPohang Accelerator Laboratory, POSTECH, Pohang 37673, Republic of Korea, and ^bDepartment of Chemistry, Andong National University, Andong 36729, Republic of Korea
^*Correspondence e-mail: jhchoi@anu.ac.kr

Edited by M. Weil, Vienna University of Technology, Austria (Received 31 August 2016; accepted 5 September 2016; online 9 September 2016)

In the asymmetric unit of the title compound, [CrCl₂(C₁₀H₂₄N₄)][Cr(C₂O₄)(C₁₀H₂₄N₄)](ClO₄)₂ (C₁₀H₂₄N₄ = 1,4,8,11-tetraazacyclotetradecane, cyclam; C₂O₄ = oxalate, ox), there are two independent halves of the [CrCl₂(cyclam)]⁺ and [Cr(ox)(cyclam)]⁺ cations, and one perchlorate anion. In the complex cations, which are completed by application of twofold rotation symmetry, the Cr^III ions are coordinated by the four N atoms of a cyclam ligand, and by two chloride ions or one oxalate bidentate ligand in a cis arrangement, displaying an overall distorted octahedral coordination environment. The Cr—N(cyclam) bond lengths are in the range of 2.075 (5) to 2.096 (4) Å while the Cr—Cl and Cr—O(ox) bond lengths are 2.3358 (14) and 1.956 (4) Å, respectively. Both cyclam moieties adopt the cis-V conformation. The slightly distorted tetrahedral ClO₄⁻ anion remains outside the coordination sphere. The supramolecular architecture includes N—H⋯O and N—H⋯Cl hydrogen bonding between cyclam NH donor groups, O atoms of the oxalate ligand or ClO₄⁻ anions and one Cl ligand as acceptors, leading to a three-dimensional network structure.

Keywords: crystal structure; cyclam; synchrotron radiation; chromium(III) complex; chloride ligand; oxalato ligand; cis-V conformation; hydrogen bonding.

CCDC reference: 1502530

1. Chemical context

Transition metal complexes with cyclam (1,4,8,11-tetraazacyclotetradecane, C₁₀H₂₄N₄) ligands can adopt both planar (trans) and folded (cis) configurations (Poon & Pun, 1980 ). The possible conformers of the trans isomer are trans-I (+ + + +), trans-II (+ – + +), trans-III (+ – – +) and trans-V (+ + – –), which differ in the chirality of the sec-NH groups (Choi, 2009 ) and where + indicates if the H atom of the NH group is above the plane of the macrocycle and – indicates if it is below. The trans-I, trans-II and trans-V conformations can fold to form cis-I, cis-II and cis-V conformers, as shown in Fig. 1. The trans-III conformation gives the most thermodynamically stable complex with two six-membered rings in chair and two five-membered rings in gauche conformations (Choi, 2009). However, the most stable conformation cannot fold to give the cis-III complex as this requires the diagonal NH groups to both lie above or below the plane of the macrocycle.

Figure 1
Possible conformers of cis-[CrL₂(cyclam)]ⁿ⁺ complexes.

Recently, it has been shown that cyclam derivatives and their metal complexes exhibit anti-HIV activity (Ronconi & Sadler, 2007 ; De Clercq, 2010 ; Ross et al., 2012 ). The conformation of the macrocyclic ligand and the orientations of the N—H bonds are very important factors for co-receptor recognition. Therefore, knowledge of the conformation and crystal packing of transition metal complexes containing the cyclam ligand has become important in the development of new highly effective anti-HIV drugs that specially target alternative events in the HIV replicative cycle (De Clercq, 2010).

In this communication, we report on the synthesis and structural characterization of a new double complex, [CrCl₂(cyclam)][Cr(ox)(cyclam)](ClO₄)₂, (I).

2. Structural commentary

The asymmetric unit contains two halves of the [CrCl₂(cyclam)]⁺ and [Cr(ox)(cyclam)]⁺ cations, and one perchlorate anion. Each cyclam moiety exhibits point group symmetry ..2 and can be described as being in the cis-V (anti–anti) conformation (Fig. 1). In each complex cation, the Cr^III ions are coordinated by the N atoms of the cyclam ligands; two oxygen atoms of the oxalato ligand for one and two chlorido ligands for the other cation complete distorted octahedral coordination spheres binding their N atoms in a cis configuration (Fig. 1). The Cr—N bond lengths from the donor atoms of the cyclam ligands are in the range of 2.075 (5) to 2.096 (4) Å, in good agreement with those determined in cis-[Cr(N₃)₂(cyclam)]ClO₄ [2.069 (3)–2.103 (3) Å] (Meyer et al., 1998 ), cis-[Cr(ONO)₂(cyclam)]NO₂ [2.0874 (16)–2.0916 (15) Å] (Choi et al., 2004a ), [Cr(acac)(cyclam)](ClO₄)₂·0.5H₂O [2.070 (5)–2.089 (5) Å] (acac = acetylacetonate; Subhan et al., 2011 ) and cis-[Cr(NCS)₂(cyclam)]NCS [2.0851 (14)–2.0897 (14) Å] (Moon et al., 2013 ). However, the Cr—N bond lengths of the cyclam ligand in the cis conformation are slightly longer than those found in trans-[Cr(NCS)₂(cyclam)]ClO₄ [2.046 (2)–2.060 (2) Å] (Friesen et al., 1997 ), trans-[Cr(ONO)₂(cyclam)]BF₄ [2.064 (4)–2.073 (4) Å] (De Leo et al., 2000 ), trans-[Cr(NH₃)₂(cyclam)][ZnCl₄]Cl·H₂O [2.0501 (15)–2.0615 (15) Å] (Moon & Choi, 2016 ) and trans-[Cr(nic-O)₂(cyclam)]ClO₄ [2.058 (4)–2.064 (4) Å] (nic-O = O-coordinated nicotinate; Choi, 2009). The Cr—N bond lengths of the secondary amine are also comparable to those involving the primary amine found in trans-[CrCl₂(Me₂tn)₂]₂ZnCl₄ (Me₂tn = 2,2-dimethylpropane-1,3-diamine; Choi et al., 2011 ), trans-[Cr(N₃)₂(Me₂tn)₂]ClO₄·2H₂O (Moon & Choi, 2015 ), trans-[Cr(NCS)₂(Me₂tn)₂]SCN·0.5H₂O (Choi & Lee, 2009 ) and trans-[Cr(2,2,3-tet)F₂]ClO₄ (2,2,3-tet = 1,4,7,11-tetraazaundecane; Choi & Moon, 2014 ). The Cr1A—O1A bond length of 1.956 (4) Å for the oxalate ligand is close to the mean of 1.959 (4) Å found in [Cr(ox)(cyclam)]ClO₄ (Choi et al., 2004b ). The Cr1B—Cl1B bond length of 2.3358 (14) Å is comparable to those found in cis-[CrCl₂(cyclam)]ClO₄ [2.331 (2) Å] (House & McKee, 1984 ), cis-[CrCl₂(2,2,3-tet)]ClO₄ [2.3157 (7) Å] (Choi et al., 2008 ), trans-[CrCl₂(Me₂tn)₂]₂ZnCl₄ [2.3112 (6) Å] (Choi et al., 2011) and trans-[CrCl₂(Me₂tn)₂]Cl [2.3253 (7) Å] (Choi et al., 2007 ), respectively. The five-membered and six-membered chelate rings of the cyclam ligands adopt gauche and stable chair conformations, respectively. The O1A—Cr1A—O1Aⁱ angle is 83.3 (3)°, while the Cl1B—Cr1B—ClBⁱ angle is 89.11 (9)° [symmetry code: (i) –x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z]. The folded angles of the cyclam in [CrCl₂(cyclam)]⁺ and [Cr(ox)(cyclam)]⁺ cations are 93.7 (2) and 97.5 (2)°, respectively. The significant distortion of the octahedral coordination sphere and the larger folded angle in the [Cr(ox)(cyclam)] ⁺ cation seem to arise from the small bite angle of the oxalato ligand. The tetrahedral ClO₄⁻ anion remains outside the coordination sphere of two Cr^III ions. It is distorted due to its involvement in hydrogen-bonding interactions. Cl—O bond lengths range from 1.426 (5) to 1.443 (5) Å and the O—Cl—O angles from 107.8 (4)–111.0 (3)°.

3. Supramolecular features

In the asymmetric unit, two N—H⋯O hydrogen bonds link the perchlorate anion to the neighboring [Cr(ox)(cyclam)]⁺ cation while N—H⋯O and N—H⋯Cl contacts interconnect two [Cr(ox)(cyclam)]⁺ and one cis-[CrCl₂(cyclam)]⁺ cation (Table 1, Figs. 2 and 3). An extensive array of these contacts generate a three-dimensional network of molecules stacked along the a-axis direction.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯O1Cⁱ	0.99	2.20	3.090 (8)	148
N1A—H1A⋯O2Cⁱ	0.99	2.42	3.266 (8)	143
N2A—H2A⋯Cl1Bⁱⁱ	0.99	2.42	3.314 (5)	150
N1B—H1B⋯O2A	0.99	1.87	2.762 (7)	149
N2B—H2B⋯O4Cⁱⁱⁱ	0.99	2.39	3.160 (7)	135
Symmetry codes: (i) $[-x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y, z+1; (iii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-1]$ .

Figure 2
A perspective view of the two chromium(III) complex cations and two perchlorate anions in compound (I)

, drawn at the 30% probability level. The primed atoms are related by symmetry code (−x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z).

Figure 3
The crystal packing in compound (I)

, viewed perpendicular to the bc plane. Dashed lines represent N—H⋯O (pink) and N—H⋯Cl (cyan) hydrogen-bonding interactions, respectively.

4. Database survey

A search of the Cambridge Structural Database (Version 5.37, Feb 2016 with two updates; Groom et al., 2016 ) gave 16 hits for a cis-[CrL₂(C₁₀H₂₄N₄)]⁺ unit. The crystal structure of cis-[CrCl₂(cyclam)]ClO₄ (House & McKee, 1984), cis-[Cr(N₃)₂(cyclam)]ClO₄ (Meyer et al., 1998), cis-[Cr(NH₃)₂(cyclam)](ClO₄)Cl₂ (Derwahl et al., 1999 ), cis-[Cr(ONO)₂)(cyclam)]NO₂ (Choi et al., 2004a), [Cr(ox)(cyclam)]ClO₄ (ox = oxalate; Choi et al., 2004b), [Cr(acac)(cyclam)](ClO₄)₂·0.5H₂O (acac = acetylacetonate; Subhan et al., 2011) and cis-[Cr(NCS)₂(cyclam)]NCS (Moon et al., 2013) have been reported previously. All of these complexes show the same folded cis-V conformation for cyclam with different hydrogen-bonding and crystal-packing networks. Until now, no structure of the double complex ion [CrCl₂(cyclam)][Cr(ox)(cyclam)]²⁺ with any anion has been deposited.

5. Synthesis and crystallization

The free ligand cyclam was purchased from Fluka and used as provided. All chemicals were reagent grade materials and were used without further purification. The starting materials, cis-[CrCl₂(cyclam)]ClO₄ and [Cr(ox)(cyclam)]ClO₄, were prepared according to literature methods (House & McKee, 1984). The double complex, cis-[CrCl₂(cyclam)][Cr(ox)(cyclam)](ClO₄)₂, was prepared by mixing concentrated equimolar aqueous solutions of the two starting compounds. A saturated solution of NaClO₄ was added to the resulting solution for crystallization, and allowed to stand at room temperature for two days to give needle-like orange crystals of (I) suitable for X-ray structural analysis.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Non-hydrogen atoms were refined anisotropically. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.98 Å and N—H = 0.99 Å, and with U_iso(H) values of 1.2U_eq of the parent atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[CrCl₂(C₁₀H₂₄N₄)][Cr(C₂O₄)(C₁₀H₂₄N₄)](ClO₄)₂
M_r	862.48
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	243
a, b, c (Å)	18.599 (4), 26.986 (5), 14.042 (3)
V (Å³)	7048 (2)
Z	8
Radiation type	Synchrotron, λ = 0.670 Å
μ (mm⁻¹)	0.84
Crystal size (mm)	0.08 × 0.01 × 0.01

Data collection
Diffractometer	ADSC Q210 CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.939, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	14619, 4764, 4011
R_int	0.118
(sin θ/λ)_max (Å⁻¹)	0.689

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.150, 1.04
No. of reflections	4764
No. of parameters	218
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.54, −0.51
Absolute structure	Flack x determined using 1586 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).
Absolute structure parameter	0.10 (2)
Computer programs: PAL BL2D-SMDC (Shin et al., 2016 ), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Putz & Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1502530

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016014134/wm5323sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016014134/wm5323Isup2.hkl

checkCIF report

Computing details top

Data collection: PAL BL2D-SMDC (Shin et al., 2016); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

cis-Dichlorido(1,4,8,11-tetraazacyclotetradecane-κ⁴N)chromium(III) (oxalato-κ²O¹,O²)(1,4,8,11-tetraazacyclotetradecane-κ⁴N)chromium(III) bis(perchlorate) top

Crystal data top

[CrCl₂(C₁₀H₂₄N₄)][Cr(C₂O₄)(C₁₀H₂₄N₄)](ClO₄)₂	D_x = 1.626 Mg m⁻³
M_r = 862.48	Synchrotron radiation, λ = 0.670 Å
Orthorhombic, Fdd2	Cell parameters from 25281 reflections
a = 18.599 (4) Å	θ = 0.4–33.3°
b = 26.986 (5) Å	µ = 0.84 mm⁻¹
c = 14.042 (3) Å	T = 243 K
V = 7048 (2) Å³	Needle, orange
Z = 8	0.08 × 0.01 × 0.01 mm
F(000) = 3584

Data collection top

ADSC Q210 CCD area detector diffractometer	4011 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.118
ω scan	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: empirical (using intensity measurements) (HKL3000sm Scalepack; Otwinowski & Minor, 1997)	h = −25→25
T_min = 0.939, T_max = 0.996	k = −37→37
14619 measured reflections	l = −19→19
4764 independent 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)] = 0.057	w = 1/[σ²(F_o²) + (0.0928P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.150	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 1.54 e Å⁻³
4764 reflections	Δρ_min = −0.51 e Å⁻³
218 parameters	Absolute structure: Flack x determined using 1586 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
1 restraint	Absolute structure parameter: 0.10 (2)

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
Cr1A	0.2500	0.7500	0.83915 (6)	0.0342 (3)
O1A	0.2305 (3)	0.70375 (18)	0.7351 (3)	0.0554 (10)
O2A	0.2332 (4)	0.6997 (3)	0.5761 (4)	0.092 (2)
N1A	0.3572 (3)	0.72957 (18)	0.8508 (3)	0.0457 (10)
H1A	0.3813	0.7427	0.7932	0.055*
N2A	0.2211 (3)	0.69512 (15)	0.9376 (3)	0.0426 (10)
H2A	0.2340	0.7073	1.0018	0.051*
C1A	0.3891 (4)	0.7568 (2)	0.9331 (5)	0.0557 (14)
H1A1	0.4415	0.7581	0.9271	0.067*
H1A2	0.3771	0.7400	0.9929	0.067*
C2A	0.3745 (4)	0.6746 (2)	0.8539 (4)	0.0624 (17)
H2A1	0.4263	0.6704	0.8636	0.075*
H2A2	0.3622	0.6597	0.7923	0.075*
C3A	0.3344 (4)	0.6470 (2)	0.9325 (5)	0.0603 (15)
H3A1	0.3520	0.6128	0.9338	0.072*
H3A2	0.3471	0.6622	0.9936	0.072*
C4A	0.2546 (4)	0.6455 (2)	0.9255 (5)	0.0603 (17)
H4A1	0.2410	0.6321	0.8631	0.072*
H4A2	0.2357	0.6231	0.9744	0.072*
C5A	0.1417 (4)	0.6917 (2)	0.9327 (5)	0.0587 (15)
H5A1	0.1234	0.6730	0.9874	0.070*
H5A2	0.1273	0.6744	0.8744	0.070*
C6A	0.2399 (3)	0.7232 (3)	0.6505 (4)	0.0637 (18)
Cr1B	0.2500	0.7500	0.28338 (5)	0.0319 (3)
Cl1B	0.26881 (11)	0.69068 (6)	0.16485 (9)	0.0602 (4)
N1B	0.2679 (3)	0.69487 (15)	0.3851 (3)	0.0430 (10)
H1B	0.2563	0.7094	0.4480	0.052*
N2B	0.1403 (3)	0.73775 (18)	0.2995 (3)	0.0446 (9)
H2B	0.1173	0.7524	0.2425	0.054*
C1B	0.3458 (4)	0.6843 (2)	0.3845 (5)	0.0554 (14)
H1B1	0.3582	0.6643	0.3287	0.066*
H1B2	0.3591	0.6657	0.4418	0.066*
C2B	0.2277 (4)	0.64797 (19)	0.3775 (4)	0.0558 (15)
H2B1	0.2429	0.6256	0.4287	0.067*
H2B2	0.2392	0.6321	0.3166	0.067*
C3B	0.1470 (4)	0.6558 (2)	0.3838 (5)	0.0629 (17)
H3B1	0.1235	0.6233	0.3855	0.076*
H3B2	0.1362	0.6726	0.4439	0.076*
C4B	0.1151 (4)	0.6856 (3)	0.3030 (4)	0.0633 (17)
H4B1	0.1271	0.6694	0.2426	0.076*
H4B2	0.0626	0.6854	0.3093	0.076*
C5B	0.1140 (4)	0.7675 (2)	0.3819 (5)	0.0567 (13)
H5B1	0.1218	0.7493	0.4413	0.068*
H5B2	0.0623	0.7738	0.3752	0.068*
Cl1C	0.52532 (8)	0.74678 (4)	1.13543 (9)	0.0464 (3)
O1C	0.5216 (4)	0.7246 (2)	1.2288 (3)	0.0738 (15)
O2C	0.5875 (3)	0.7782 (2)	1.1306 (5)	0.0812 (15)
O3C	0.5278 (3)	0.70980 (16)	1.0630 (3)	0.0666 (13)
O4C	0.4626 (3)	0.7775 (2)	1.1228 (4)	0.0696 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr1A	0.0410 (6)	0.0458 (5)	0.0159 (4)	−0.0046 (4)	0.000	0.000
O1A	0.064 (3)	0.072 (3)	0.0296 (17)	−0.009 (2)	−0.0016 (18)	−0.0161 (18)
O2A	0.091 (4)	0.153 (5)	0.031 (2)	−0.018 (4)	0.004 (2)	−0.032 (3)
N1A	0.043 (2)	0.067 (3)	0.0267 (16)	0.000 (2)	0.0034 (16)	−0.0047 (17)
N2A	0.057 (3)	0.0408 (18)	0.0300 (18)	−0.0026 (18)	0.0062 (18)	0.0020 (14)
C1A	0.052 (4)	0.076 (4)	0.039 (3)	−0.002 (3)	−0.007 (2)	−0.004 (2)
C2A	0.071 (5)	0.075 (4)	0.042 (3)	0.023 (3)	0.004 (3)	−0.007 (3)
C3A	0.077 (4)	0.050 (2)	0.054 (3)	0.014 (3)	−0.001 (3)	−0.004 (2)
C4A	0.087 (5)	0.039 (2)	0.055 (3)	0.005 (2)	0.005 (3)	0.001 (2)
C5A	0.065 (4)	0.064 (3)	0.047 (3)	−0.020 (3)	0.010 (3)	0.004 (2)
C6A	0.047 (3)	0.119 (6)	0.025 (2)	−0.006 (3)	0.0010 (19)	−0.004 (3)
Cr1B	0.0459 (6)	0.0333 (4)	0.0164 (4)	0.0007 (4)	0.000	0.000
Cl1B	0.0926 (11)	0.0583 (7)	0.0297 (6)	0.0046 (7)	0.0025 (6)	−0.0161 (5)
N1B	0.069 (3)	0.0350 (17)	0.0251 (17)	0.0053 (19)	0.0005 (19)	0.0000 (14)
N2B	0.047 (2)	0.062 (2)	0.0255 (18)	0.000 (2)	−0.0011 (15)	0.0011 (17)
C1B	0.064 (4)	0.053 (3)	0.049 (3)	0.014 (3)	−0.003 (3)	0.003 (2)
C2B	0.098 (5)	0.0337 (19)	0.036 (2)	−0.006 (3)	−0.002 (3)	0.0030 (17)
C3B	0.090 (5)	0.055 (3)	0.044 (3)	−0.020 (3)	−0.002 (3)	0.004 (2)
C4B	0.077 (5)	0.072 (3)	0.041 (3)	−0.026 (3)	−0.009 (3)	0.000 (3)
C5B	0.052 (3)	0.076 (3)	0.041 (3)	0.001 (3)	0.011 (3)	−0.006 (3)
Cl1C	0.0524 (8)	0.0494 (6)	0.0372 (6)	0.0003 (5)	−0.0027 (5)	−0.0003 (5)
O1C	0.109 (5)	0.073 (3)	0.040 (2)	0.002 (3)	−0.001 (3)	0.004 (2)
O2C	0.081 (4)	0.084 (3)	0.079 (3)	−0.023 (3)	0.003 (3)	−0.003 (3)
O3C	0.100 (4)	0.053 (2)	0.046 (2)	0.005 (2)	0.009 (2)	−0.0049 (18)
O4C	0.070 (3)	0.077 (3)	0.062 (3)	0.020 (3)	−0.011 (2)	−0.012 (2)

Geometric parameters (Å, º) top

Cr1A—O1Aⁱ	1.956 (4)	Cr1B—N2B	2.080 (5)
Cr1A—O1A	1.956 (4)	Cr1B—N1Bⁱ	2.089 (4)
Cr1A—N1Aⁱ	2.075 (5)	Cr1B—N1B	2.089 (4)
Cr1A—N1A	2.075 (5)	Cr1B—Cl1B	2.3358 (14)
Cr1A—N2A	2.096 (4)	Cr1B—Cl1Bⁱ	2.3358 (14)
Cr1A—N2Aⁱ	2.096 (4)	N1B—C2B	1.474 (7)
O1A—C6A	1.310 (8)	N1B—C1B	1.478 (9)
O2A—C6A	1.228 (8)	N1B—H1B	0.9900
N1A—C1A	1.493 (8)	N2B—C4B	1.484 (8)
N1A—C2A	1.519 (8)	N2B—C5B	1.490 (7)
N1A—H1A	0.9900	N2B—H2B	0.9900
N2A—C5A	1.482 (9)	C1B—C5Bⁱ	1.500 (9)
N2A—C4A	1.485 (7)	C1B—H1B1	0.9800
N2A—H2A	0.9900	C1B—H1B2	0.9800
C1A—C5Aⁱ	1.502 (10)	C2B—C3B	1.518 (11)
C1A—H1A1	0.9800	C2B—H2B1	0.9800
C1A—H1A2	0.9800	C2B—H2B2	0.9800
C2A—C3A	1.526 (10)	C3B—C4B	1.512 (9)
C2A—H2A1	0.9800	C3B—H3B1	0.9800
C2A—H2A2	0.9800	C3B—H3B2	0.9800
C3A—C4A	1.488 (11)	C4B—H4B1	0.9800
C3A—H3A1	0.9800	C4B—H4B2	0.9800
C3A—H3A2	0.9800	C5B—C1Bⁱ	1.500 (9)
C4A—H4A1	0.9800	C5B—H5B1	0.9800
C4A—H4A2	0.9800	C5B—H5B2	0.9800
C5A—C1Aⁱ	1.503 (10)	Cl1C—O3C	1.426 (5)
C5A—H5A1	0.9800	Cl1C—O2C	1.435 (6)
C5A—H5A2	0.9800	Cl1C—O4C	1.442 (5)
C6A—C6Aⁱ	1.496 (18)	Cl1C—O1C	1.443 (5)
Cr1B—N2Bⁱ	2.080 (5)

O1Aⁱ—Cr1A—O1A	83.3 (3)	N2Bⁱ—Cr1B—N1Bⁱ	88.2 (2)
O1Aⁱ—Cr1A—N1Aⁱ	93.85 (19)	N2B—Cr1B—N1Bⁱ	83.26 (19)
O1A—Cr1A—N1Aⁱ	92.9 (2)	N2Bⁱ—Cr1B—N1B	83.26 (19)
O1Aⁱ—Cr1A—N1A	92.9 (2)	N2B—Cr1B—N1B	88.2 (2)
O1A—Cr1A—N1A	93.85 (19)	N1Bⁱ—Cr1B—N1B	93.7 (2)
N1Aⁱ—Cr1A—N1A	171.0 (2)	N2Bⁱ—Cr1B—Cl1B	92.27 (13)
O1Aⁱ—Cr1A—N2A	172.4 (2)	N2B—Cr1B—Cl1B	96.65 (14)
O1A—Cr1A—N2A	89.67 (18)	N1Bⁱ—Cr1B—Cl1B	177.69 (13)
N1Aⁱ—Cr1A—N2A	83.68 (19)	N1B—Cr1B—Cl1B	88.58 (12)
N1A—Cr1A—N2A	90.38 (19)	N2Bⁱ—Cr1B—Cl1Bⁱ	96.65 (14)
O1Aⁱ—Cr1A—N2Aⁱ	89.67 (18)	N2B—Cr1B—Cl1Bⁱ	92.27 (13)
O1A—Cr1A—N2Aⁱ	172.4 (2)	N1Bⁱ—Cr1B—Cl1Bⁱ	88.58 (12)
N1Aⁱ—Cr1A—N2Aⁱ	90.37 (19)	N1B—Cr1B—Cl1Bⁱ	177.69 (13)
N1A—Cr1A—N2Aⁱ	83.68 (19)	Cl1B—Cr1B—Cl1Bⁱ	89.11 (9)
N2A—Cr1A—N2Aⁱ	97.5 (2)	C2B—N1B—C1B	109.4 (5)
C6A—O1A—Cr1A	113.4 (5)	C2B—N1B—Cr1B	118.8 (4)
C1A—N1A—C2A	112.0 (5)	C1B—N1B—Cr1B	106.8 (3)
C1A—N1A—Cr1A	108.2 (4)	C2B—N1B—H1B	107.1
C2A—N1A—Cr1A	117.7 (4)	C1B—N1B—H1B	107.1
C1A—N1A—H1A	106.1	Cr1B—N1B—H1B	107.1
C2A—N1A—H1A	106.1	C4B—N2B—C5B	112.5 (5)
Cr1A—N1A—H1A	106.1	C4B—N2B—Cr1B	117.6 (4)
C5A—N2A—C4A	110.9 (5)	C5B—N2B—Cr1B	108.7 (4)
C5A—N2A—Cr1A	105.6 (4)	C4B—N2B—H2B	105.7
C4A—N2A—Cr1A	117.0 (4)	C5B—N2B—H2B	105.7
C5A—N2A—H2A	107.7	Cr1B—N2B—H2B	105.7
C4A—N2A—H2A	107.7	N1B—C1B—C5Bⁱ	108.8 (5)
Cr1A—N2A—H2A	107.7	N1B—C1B—H1B1	109.9
N1A—C1A—C5Aⁱ	107.5 (5)	C5Bⁱ—C1B—H1B1	109.9
N1A—C1A—H1A1	110.2	N1B—C1B—H1B2	109.9
C5Aⁱ—C1A—H1A1	110.2	C5Bⁱ—C1B—H1B2	109.9
N1A—C1A—H1A2	110.2	H1B1—C1B—H1B2	108.3
C5Aⁱ—C1A—H1A2	110.2	N1B—C2B—C3B	112.2 (5)
H1A1—C1A—H1A2	108.5	N1B—C2B—H2B1	109.2
N1A—C2A—C3A	113.2 (5)	C3B—C2B—H2B1	109.2
N1A—C2A—H2A1	108.9	N1B—C2B—H2B2	109.2
C3A—C2A—H2A1	108.9	C3B—C2B—H2B2	109.2
N1A—C2A—H2A2	108.9	H2B1—C2B—H2B2	107.9
C3A—C2A—H2A2	108.9	C4B—C3B—C2B	114.8 (6)
H2A1—C2A—H2A2	107.7	C4B—C3B—H3B1	108.6
C4A—C3A—C2A	116.9 (6)	C2B—C3B—H3B1	108.6
C4A—C3A—H3A1	108.1	C4B—C3B—H3B2	108.6
C2A—C3A—H3A1	108.1	C2B—C3B—H3B2	108.6
C4A—C3A—H3A2	108.1	H3B1—C3B—H3B2	107.6
C2A—C3A—H3A2	108.1	N2B—C4B—C3B	113.9 (5)
H3A1—C3A—H3A2	107.3	N2B—C4B—H4B1	108.8
N2A—C4A—C3A	112.7 (5)	C3B—C4B—H4B1	108.8
N2A—C4A—H4A1	109.0	N2B—C4B—H4B2	108.8
C3A—C4A—H4A1	109.0	C3B—C4B—H4B2	108.8
N2A—C4A—H4A2	109.0	H4B1—C4B—H4B2	107.7
C3A—C4A—H4A2	109.0	N2B—C5B—C1Bⁱ	108.8 (5)
H4A1—C4A—H4A2	107.8	N2B—C5B—H5B1	109.9
N2A—C5A—C1Aⁱ	108.8 (5)	C1Bⁱ—C5B—H5B1	109.9
N2A—C5A—H5A1	109.9	N2B—C5B—H5B2	109.9
C1Aⁱ—C5A—H5A1	109.9	C1Bⁱ—C5B—H5B2	109.9
N2A—C5A—H5A2	109.9	H5B1—C5B—H5B2	108.3
C1Aⁱ—C5A—H5A2	109.9	O3C—Cl1C—O2C	110.7 (4)
H5A1—C5A—H5A2	108.3	O3C—Cl1C—O4C	110.0 (3)
O2A—C6A—O1A	123.4 (8)	O2C—Cl1C—O4C	107.8 (4)
O2A—C6A—C6Aⁱ	121.7 (5)	O3C—Cl1C—O1C	111.0 (3)
O1A—C6A—C6Aⁱ	114.9 (4)	O2C—Cl1C—O1C	109.1 (4)
N2Bⁱ—Cr1B—N2B	167.5 (2)	O4C—Cl1C—O1C	108.1 (3)

C2A—N1A—C1A—C5Aⁱ	−170.2 (5)	Cr1A—O1A—C6A—C6Aⁱ	−2.7 (9)
Cr1A—N1A—C1A—C5Aⁱ	−38.9 (6)	C2B—N1B—C1B—C5Bⁱ	174.1 (5)
C1A—N1A—C2A—C3A	71.3 (7)	Cr1B—N1B—C1B—C5Bⁱ	44.3 (5)
Cr1A—N1A—C2A—C3A	−55.0 (6)	C1B—N1B—C2B—C3B	176.5 (5)
N1A—C2A—C3A—C4A	63.5 (7)	Cr1B—N1B—C2B—C3B	−60.6 (6)
C5A—N2A—C4A—C3A	−178.5 (5)	N1B—C2B—C3B—C4B	64.6 (6)
Cr1A—N2A—C4A—C3A	60.4 (7)	C5B—N2B—C4B—C3B	−67.7 (8)
C2A—C3A—C4A—N2A	−66.6 (7)	Cr1B—N2B—C4B—C3B	59.8 (7)
C4A—N2A—C5A—C1Aⁱ	−173.1 (5)	C2B—C3B—C4B—N2B	−64.9 (8)
Cr1A—N2A—C5A—C1Aⁱ	−45.5 (5)	C4B—N2B—C5B—C1Bⁱ	167.8 (6)
Cr1A—O1A—C6A—O2A	177.1 (6)	Cr1B—N2B—C5B—C1Bⁱ	35.7 (6)

Symmetry code: (i) −x+1/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1Cⁱⁱ	0.99	2.20	3.090 (8)	148
N1A—H1A···O2Cⁱⁱ	0.99	2.42	3.266 (8)	143
N2A—H2A···Cl1Bⁱⁱⁱ	0.99	2.42	3.314 (5)	150
N1B—H1B···O2A	0.99	1.87	2.762 (7)	149
N2B—H2B···O4C^iv	0.99	2.39	3.160 (7)	135

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

Acknowledgements

This work was supported by a grant from 2016 Research Funds of Andong National University. The X-ray crystallography experiment at PLS-II BL2D-SMC beamline was supported in part by MSIP and POSTECH.

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