Crystal structure of 3,14-dimethyl-2,6,13,17-tetra­azoniatri­cyclo­[16.4.0.07,12]docosane tetra­chloride tetra­hydrate from synchrotron X-ray data

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

doi:10.1107/S2056989018009337

research communications

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ISSN: 2056-9890

Volume 74| Part 8| August 2018| Pages 1039-1041

https://doi.org/10.1107/S2056989018009337

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Crystal structure of 3,14-dimethyl-2,6,13,17-tetraazoniatricyclo[16.4.0.0^7,12]docosane tetrachloride tetrahydrate from synchrotron X-ray 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 J. Simpson, University of Otago, New Zealand (Received 27 June 2018; accepted 28 June 2018; online 6 July 2018)

The crystal structure of the title salt, C₂₀H₄₄N₄⁴⁺·4Cl⁻·4H₂O, has been determined using synchrotron radiation at 220 K. The structure determination reveals that protonation has occurred at all four amine N atoms. The asymmetric unit contains one half-cation (completed by crystallographic inversion symmetry), two chloride anions and two water molecules. There are two molecules in the unit cell. The Cl⁻ anions and hydrate molecules are involved in hydrogen bonding. The crystal structure is stabilized by intermolecular hydrogen bonds involving the macrocycle N—H groups and water O—H groups as donors and the O atoms of the water molecules and the Cl⁻ anions as acceptors, giving rise to a three-dimensional network.

Keywords: crystal structure; protonated macrocycle; tetrachloride; tetrahydrate; hydrogen bonding; synchrotron radiation.

CCDC reference: 1852146

1. Chemical context

The macrocycle 3,14-dimethyl-2,6,13,17-tetraazatricyclo(16.4.0.0^7,12)docosane (C₂₀H₄₀N₄, L) is a strongly basic amine capable of forming the [C₂₀H₄₂N₄]²⁺ dication or the [C₂₀H₄₄N₄]⁴⁺ tetracation in which all of the N—H bonds are generally available for hydrogen-bond formation. These di- or tetraammonium cations may be suitable for the removal of toxic heavy metal ions from water. The macrocycle L contains a cyclam backbone with two cyclohexane subunits. Methyl groups are attached to the 3 and 14 carbon atoms of the propyl chains that bridge opposite pairs of N atoms in the structure. Previously, we have reported the crystal structures of [Cu(L)](NO₃)₂·3H₂O, [Cu(L)](NO₃)₂, [Cu(L)](ClO₄)₂ and [Cu(L)(H₂O)₂](BF₄)₂·2H₂O together with [Zn(L)(OCOCH₃)₂]. In these structures, the copper(II) or zinc(II) cations have tetragonally distorted octahedral environments with the four N atoms of the macrocyclic ligand in equatorial positions and O atoms of counter-anions, water molecules or acetato ligands in axial positions (Choi et al., 2006 , 2007 , 2012a ,b ; Ross et al., 2012 ). In these Cu^II and Zn^II complexes, the macrocyclic ligands adopt their most stable trans-III configurations. The crystal structures of the di-cations C₂₀H₄₀N₄·2C₁₁H₁₀O (Choi et al., 2012c ) and [C₂₀H₄₂N₄](SO₄)·2MeOH (White et al., 2015 ) have also been reported. As part of our research program in this area, we report here the preparation of the new tetra-cationic compound, [C₂₀H₄₄N₄]Cl₄·4H₂O, (I), as the hydrated chloride salt and its structural characterization by synchrotron single-crystal X-ray diffraction.

2. Structural commentary

The title compound contains a positively charged macrocyclic cation, 4Cl⁻ anions and four solvent water molecules and was characterized during studies of the macrocyclic ligand and its copper(II) complexes. An ellipsoid plot of the molecular components in (I) with the atom-numbering scheme is shown in Fig. 1. The asymmetric unit consists of one half of the macrocycle, which lies about a center of inversion, two chloride anions and two solvent water molecules. The four N atoms are coplanar, and the two methyl substituents are anti with respect to the macrocyclic plane as a result of the molecular inversion symmetry. The six-membered cyclohexane ring is in a stable chair conformation. Within the centrosymmetric tetra-protonated amine unit [C₂₀H₄₄N₄]⁴⁺, the C—C and N—C bond lengths vary from 1.522 (2) to 1.542 (2) Å and from 1.506 (2) to 1.522 (2) Å, respectively. The ranges of N—C—C and C—N—C angles are 106.85 (10) to 114.32 (11)° and 116.70 (10) to 118.89 (10)°, respectively. The bond lengths and angles within the [C₂₀H₄₄N₄]⁴⁺ tetra-cation are comparable to those found in the free ligand or the di-cation in C₂₀H₄₀N₄·2C₁₁H₁₀O (Choi et al., 2012c), [C₂₀H₄₂N₄](SO₄)·2MeOH (White et al., 2015) and [C₂₀H₄₂N₄][Fe{HB(pz)₃}(CN)₃]₂·2H₂O·2MeOH (Kim et al., 2004 ).

Figure 1
The molecular structure of compound (I)

, drawn with displacement ellipsoids at the 50% probability level. Dashed lines represent hydrogen-bonding interactions and primed atoms are related by the symmetry code (1 − x, 1 − y, 1 − z).

3. Supramolecular features

Extensive O—H⋯Cl, N—H⋯Cl and N—H⋯O hydrogen-bonding interactions occur in the crystal structure (Table 1). All of the Cl⁻ anions and the O atoms of the water molecules serve as hydrogen-bond acceptors. O—H⋯Cl hydrogen bonds link the water molecules to the neighboring Cl⁻ anions, while N—H⋯Cl and N—H⋯O hydrogen bonds interconnect the [C₂₀H₄₄N₄]⁴⁺ cations with both anions and water molecules (Figs. 1 and 2). The hydrogen atoms on N1 and N2 both form bifurcated hydrogen bonds with O and Cl atoms. The extensive array of these contacts generates a three-dimensional network structure (Fig. 2), and these hydrogen-bonding interactions help to stabilize the crystal structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯Cl1	0.84 (1)	2.26 (1)	3.0837 (13)	167 (2)
O1—H2O1⋯Cl2	0.84 (1)	2.30 (1)	3.1329 (13)	173 (2)
O2—H1O2⋯Cl2ⁱ	0.83 (1)	2.32 (1)	3.1403 (14)	172 (2)
O2—H2O2⋯Cl2ⁱⁱ	0.83 (1)	2.35 (1)	3.1839 (16)	174 (2)
N1—H1AN⋯Cl1ⁱⁱⁱ	0.90	2.20	3.0939 (12)	171
N1—H1B⋯O1	0.90	1.90	2.7484 (17)	156
N2—H2AN⋯Cl2^iv	0.90	2.41	3.2819 (13)	164
N2—H2B⋯O2	0.90	1.85	2.7245 (16)	163
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x+1, y, z+1; (iii) -x+1, -y+1, -z; (iv) x, y, z+1.

Figure 2
The crystal packing in compound (I)

, viewed perpendicular to the bc plane. Dashed lines represent N—H⋯O (blue), N—H⋯Cl (pink) and O—H⋯Cl (cyan) hydrogen-bonding interactions, respectively. C-bound H atoms have been omitted.

4. Database survey

A search of the Cambridge Structural Database (Version 5.38, May 2017 with three updates; Groom et al., 2016 ) gave just three hits for compounds containing the macrocycles [C₂₀H₄₄N₄]⁴⁺, [C₂₀H₄₂N₄]²⁺ or (C₂₀H₄₀N₄). The crystal structures of C₂₀H₄₀N₄·2C₁₁H₁₀O (Choi et al., 2012c), [C₂₀H₄₂N₄](SO₄)·2MeOH (White et al., 2015) and [C₂₀H₄₂N₄][Fe{HB(pz)₃}(CN)₃]₂·2H₂O·2MeOH (Kim et al., 2004) were reported previously. However, to our knowledge no crystal structure of any compound with [C₂₀H₄₄N₄]⁴⁺ has been reported.

5. Synthesis and crystallization

Commercially available trans-1,2-cyclohexanediamine and methyl vinyl ketone (Sigma–Aldrich) were used as provided. All chemicals were reagent grade and used without further purification. As a starting material, the macrocycle 3,14-dimethyl-2,6,13,17-tetraazatricyclo(16.4.0.0^7,12)docosane was prepared according to a published procedure (Kang et al., 1991 ). A solution of the macrocyclic ligand (0.084 g, 0.25 mmol) in water (10 mL) was added dropwise to a stirred solution of CuCl₂·2H₂O (0.085 g, 0.5 mmol) in water (15 mL). The solution was heated for 1 h at 338 K. After cooling to 298 K, the pH was adjusted to 3.0 with 1.0 M HCl. The solution was filtered and left at room temperature. Colourless crystals suitable for X-ray analysis were obtained unexpectedly from the solution over a period of a few days.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All C and N-bound H atoms in the complex were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.97–0.99 Å, an N—H distance of 0.9 Å and with U_iso(H) values of 1.2U_eq(C, N) and 1.5U_eq(C-methyl). O-bound H atoms of the water molecules were located in a difference-Fourier map, and the O—H distances and the H—O—H angles were restrained using DFIX and DANG constraints (0.84 and 1.36 Å).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₄₄N₄⁴⁺·4Cl⁻·4H₂O
M_r	554.45
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	220
a, b, c (Å)	7.5450 (15), 23.190 (5), 8.3370 (17)
β (°)	103.32 (3)
V (Å³)	1419.5 (5)
Z	2
Radiation type	Synchrotron, λ = 0.630 Å
μ (mm⁻¹)	0.32
Crystal size (mm)	0.08 × 0.06 × 0.06

Data collection
Diffractometer	Rayonix MX225HS CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.919, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13816, 3797, 3504
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.683

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.141, 1.14
No. of reflections	3797
No. of parameters	158
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.33
Computer programs: PAL BL2D-SMDC (Shin et al., 2016 ), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2015 (Sheldrick, 2015a ), SHELXL2015 (Sheldrick, 2015b ), DIAMOND (Putz & Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1852146

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018009337/sj5559sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018009337/sj5559Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018009337/sj5559Isup3.cml

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: SHELXT2015 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2015 (Sheldrick, 2015b); molecular graphics: DIAMOND (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

3,14-Dimethyl-2,6,13,17-tetraazoniatricyclo[16.4.0.0^7,12]docosane tetrachloride tetrahydrate top

Crystal data top

C₂₀H₄₄N₄⁴⁺·4Cl⁻·4H₂O	F(000) = 600
M_r = 554.45	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.630 Å
a = 7.5450 (15) Å	Cell parameters from 44298 reflections
b = 23.190 (5) Å	θ = 0.4–33.6°
c = 8.3370 (17) Å	µ = 0.32 mm⁻¹
β = 103.32 (3)°	T = 220 K
V = 1419.5 (5) Å³	Block, colourless
Z = 2	0.08 × 0.06 × 0.06 mm

Data collection top

Rayonix MX225HS CCD area detector diffractometer	3504 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.061
ω scans	θ_max = 25.5°, θ_min = 1.6°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −10→10
T_min = 0.919, T_max = 1.000	k = −31→31
13816 measured reflections	l = −11→11
3797 independent reflections

Refinement top

Refinement on F²	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.141	w = 1/[σ²(F_o²) + (0.0863P)² + 0.2986P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max = 0.001
3797 reflections	Δρ_max = 0.80 e Å⁻³
158 parameters	Δρ_min = −0.33 e Å⁻³

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
Cl1	0.28649 (4)	0.48361 (2)	−0.23231 (4)	0.02152 (13)
Cl2	0.23041 (5)	0.70611 (2)	−0.24081 (5)	0.02724 (13)
O1	0.17644 (18)	0.59115 (5)	−0.06048 (14)	0.0292 (3)
H1O1	0.211 (3)	0.5659 (7)	−0.118 (2)	0.044*
H2O1	0.190 (3)	0.6234 (5)	−0.101 (3)	0.044*
O2	0.81871 (15)	0.70598 (5)	0.55335 (16)	0.0285 (3)
H1O2	0.807 (3)	0.7293 (8)	0.476 (2)	0.043*
H2O2	0.9243 (18)	0.7082 (9)	0.612 (2)	0.043*
N1	0.31217 (15)	0.54018 (5)	0.24038 (13)	0.0135 (2)
H1AN	0.424887	0.529030	0.234909	0.016*
H1B	0.273908	0.566098	0.159468	0.016*
N2	0.52610 (14)	0.64198 (5)	0.58563 (14)	0.0145 (2)
H2AN	0.431936	0.660340	0.612559	0.017*
H2B	0.612982	0.668566	0.585565	0.017*
C1	0.24830 (16)	0.43768 (5)	0.32273 (16)	0.0151 (2)
H1A	0.142456	0.413129	0.322216	0.018*
H1AB	0.292168	0.452568	0.434890	0.018*
C2	0.18858 (17)	0.48834 (5)	0.20562 (17)	0.0151 (3)
H2A	0.182324	0.475365	0.092579	0.018*
H2AB	0.065641	0.500024	0.212226	0.018*
C3	0.32531 (16)	0.57005 (5)	0.40305 (15)	0.0139 (2)
H3	0.374735	0.542524	0.493008	0.017*
C4	0.13998 (17)	0.59125 (6)	0.42271 (17)	0.0190 (3)
H4A	0.055377	0.558611	0.409763	0.023*
H4AB	0.152601	0.606815	0.534063	0.023*
C5	0.06125 (19)	0.63767 (7)	0.29694 (19)	0.0240 (3)
H5A	−0.055674	0.650884	0.315737	0.029*
H5AB	0.039283	0.621385	0.185629	0.029*
C6	0.1913 (2)	0.68874 (7)	0.31020 (19)	0.0257 (3)
H6A	0.199462	0.708191	0.416010	0.031*
H6AB	0.142341	0.716389	0.222244	0.031*
C7	0.38260 (19)	0.67021 (6)	0.29703 (18)	0.0205 (3)
H7A	0.378106	0.658961	0.182857	0.025*
H7AB	0.464730	0.703370	0.323138	0.025*
C8	0.46174 (16)	0.62004 (5)	0.41108 (15)	0.0141 (2)
H8	0.569077	0.605031	0.374969	0.017*
C9	0.60141 (16)	0.59907 (5)	0.72246 (16)	0.0144 (2)
H9	0.501674	0.573469	0.737922	0.017*
C10	0.6708 (2)	0.63373 (6)	0.87937 (17)	0.0233 (3)
H10A	0.706638	0.607639	0.972125	0.035*
H10B	0.574944	0.659033	0.897628	0.035*
H10C	0.774932	0.656615	0.868372	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01190 (19)	0.0294 (2)	0.0260 (2)	−0.00148 (11)	0.01001 (14)	−0.00336 (13)
Cl2	0.0223 (2)	0.0314 (2)	0.0275 (2)	0.00606 (13)	0.00466 (16)	−0.00617 (14)
O1	0.0377 (6)	0.0317 (6)	0.0187 (5)	0.0038 (5)	0.0078 (5)	−0.0001 (4)
O2	0.0175 (5)	0.0358 (6)	0.0316 (6)	−0.0066 (4)	0.0043 (5)	0.0089 (5)
N1	0.0089 (4)	0.0188 (5)	0.0133 (5)	0.0003 (4)	0.0036 (4)	−0.0002 (4)
N2	0.0105 (5)	0.0176 (5)	0.0151 (5)	−0.0007 (4)	0.0024 (4)	−0.0005 (4)
C1	0.0102 (5)	0.0195 (5)	0.0163 (6)	0.0012 (4)	0.0045 (4)	0.0007 (5)
C2	0.0093 (5)	0.0183 (5)	0.0162 (6)	−0.0006 (4)	−0.0001 (4)	−0.0021 (5)
C3	0.0106 (5)	0.0192 (5)	0.0124 (5)	−0.0028 (4)	0.0036 (4)	−0.0016 (4)
C4	0.0121 (6)	0.0275 (6)	0.0198 (6)	−0.0038 (5)	0.0083 (5)	−0.0062 (5)
C5	0.0130 (6)	0.0349 (7)	0.0236 (7)	0.0061 (5)	0.0035 (5)	−0.0039 (6)
C6	0.0254 (7)	0.0249 (6)	0.0250 (7)	0.0071 (6)	0.0024 (6)	0.0034 (6)
C7	0.0188 (6)	0.0223 (6)	0.0189 (6)	−0.0018 (5)	0.0012 (5)	0.0054 (5)
C8	0.0104 (5)	0.0192 (5)	0.0127 (5)	−0.0026 (4)	0.0024 (4)	−0.0004 (5)
C9	0.0106 (5)	0.0190 (5)	0.0137 (6)	0.0008 (4)	0.0028 (4)	0.0009 (4)
C10	0.0242 (7)	0.0278 (7)	0.0159 (6)	0.0051 (6)	0.0004 (5)	−0.0054 (5)

Geometric parameters (Å, º) top

O1—H1O1	0.837 (9)	C3—H3	0.9900
O1—H2O1	0.837 (9)	C4—C5	1.524 (2)
O2—H1O2	0.833 (9)	C4—H4A	0.9800
O2—H2O2	0.834 (9)	C4—H4AB	0.9800
N1—C3	1.5056 (16)	C5—C6	1.526 (2)
N1—C2	1.5080 (16)	C5—H5A	0.9800
N1—H1AN	0.9000	C5—H5AB	0.9800
N1—H1B	0.9000	C6—C7	1.534 (2)
N2—C8	1.5122 (17)	C6—H6A	0.9800
N2—C9	1.5217 (16)	C6—H6AB	0.9800
N2—H2AN	0.9000	C7—C8	1.5338 (18)
N2—H2B	0.9000	C7—H7A	0.9800
C1—C2	1.5277 (18)	C7—H7AB	0.9800
C1—C9ⁱ	1.5333 (17)	C8—H8	0.9900
C1—H1A	0.9800	C9—C10	1.5217 (19)
C1—H1AB	0.9800	C9—H9	0.9900
C2—H2A	0.9800	C10—H10A	0.9700
C2—H2AB	0.9800	C10—H10B	0.9700
C3—C4	1.5263 (17)	C10—H10C	0.9700
C3—C8	1.5416 (17)

H1O1—O1—H2O1	108.0 (17)	H4A—C4—H4AB	107.9
H1O2—O2—H2O2	108.9 (18)	C4—C5—C6	110.86 (12)
C3—N1—C2	116.70 (10)	C4—C5—H5A	109.5
C3—N1—H1AN	108.1	C6—C5—H5A	109.5
C2—N1—H1AN	108.1	C4—C5—H5AB	109.5
C3—N1—H1B	108.1	C6—C5—H5AB	109.5
C2—N1—H1B	108.1	H5A—C5—H5AB	108.1
H1AN—N1—H1B	107.3	C5—C6—C7	112.18 (12)
C8—N2—C9	118.89 (10)	C5—C6—H6A	109.2
C8—N2—H2AN	107.6	C7—C6—H6A	109.2
C9—N2—H2AN	107.6	C5—C6—H6AB	109.2
C8—N2—H2B	107.6	C7—C6—H6AB	109.2
C9—N2—H2B	107.6	H6A—C6—H6AB	107.9
H2AN—N2—H2B	107.0	C8—C7—C6	113.98 (11)
C2—C1—C9ⁱ	113.35 (10)	C8—C7—H7A	108.8
C2—C1—H1A	108.9	C6—C7—H7A	108.8
C9ⁱ—C1—H1A	108.9	C8—C7—H7AB	108.8
C2—C1—H1AB	108.9	C6—C7—H7AB	108.8
C9ⁱ—C1—H1AB	108.9	H7A—C7—H7AB	107.7
H1A—C1—H1AB	107.7	N2—C8—C7	109.53 (10)
N1—C2—C1	114.32 (11)	N2—C8—C3	110.97 (10)
N1—C2—H2A	108.7	C7—C8—C3	112.51 (11)
C1—C2—H2A	108.7	N2—C8—H8	107.9
N1—C2—H2AB	108.7	C7—C8—H8	107.9
C1—C2—H2AB	108.7	C3—C8—H8	107.9
H2A—C2—H2AB	107.6	C10—C9—N2	107.10 (11)
N1—C3—C4	111.91 (10)	C10—C9—C1ⁱ	112.18 (11)
N1—C3—C8	106.85 (10)	N2—C9—C1ⁱ	110.41 (10)
C4—C3—C8	111.85 (11)	C10—C9—H9	109.0
N1—C3—H3	108.7	N2—C9—H9	109.0
C4—C3—H3	108.7	C1ⁱ—C9—H9	109.0
C8—C3—H3	108.7	C9—C10—H10A	109.5
C5—C4—C3	112.03 (11)	C9—C10—H10B	109.5
C5—C4—H4A	109.2	H10A—C10—H10B	109.5
C3—C4—H4A	109.2	C9—C10—H10C	109.5
C5—C4—H4AB	109.2	H10A—C10—H10C	109.5
C3—C4—H4AB	109.2	H10B—C10—H10C	109.5

C3—N1—C2—C1	−64.11 (14)	C9—N2—C8—C3	52.13 (14)
C9ⁱ—C1—C2—N1	−80.89 (14)	C6—C7—C8—N2	−76.56 (14)
C2—N1—C3—C4	−58.63 (14)	C6—C7—C8—C3	47.36 (16)
C2—N1—C3—C8	178.63 (10)	N1—C3—C8—N2	−163.70 (10)
N1—C3—C4—C5	−64.60 (14)	C4—C3—C8—N2	73.52 (13)
C8—C3—C4—C5	55.26 (15)	N1—C3—C8—C7	73.18 (13)
C3—C4—C5—C6	−57.49 (15)	C4—C3—C8—C7	−49.60 (15)
C4—C5—C6—C7	54.14 (16)	C8—N2—C9—C10	174.85 (11)
C5—C6—C7—C8	−49.87 (17)	C8—N2—C9—C1ⁱ	52.43 (14)
C9—N2—C8—C7	176.95 (10)

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
O1—H1O1···Cl1	0.84 (1)	2.26 (1)	3.0837 (13)	167 (2)
O1—H2O1···Cl2	0.84 (1)	2.30 (1)	3.1329 (13)	173 (2)
O2—H1O2···Cl2ⁱⁱ	0.83 (1)	2.32 (1)	3.1403 (14)	172 (2)
O2—H2O2···Cl2ⁱⁱⁱ	0.83 (1)	2.35 (1)	3.1839 (16)	174 (2)
N1—H1AN···Cl1^iv	0.90	2.20	3.0939 (12)	171
N1—H1B···O1	0.90	1.90	2.7484 (17)	156
N2—H2AN···Cl2^v	0.90	2.41	3.2819 (13)	164
N2—H2B···O2	0.90	1.85	2.7245 (16)	163

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

Funding information

This work was supported by a Research Grant from Andong National University. The X-ray crystallography experiment at the PLS-II BL2D-SMC beamline was supported in part by MSICT and POSTECH.

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