Crystal structure of 3,14-diethyl-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/S2056989021001006

research communications

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ISSN: 2056-9890

Volume 77| Part 2| February 2021| Pages 213-216

https://doi.org/10.1107/S2056989021001006

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Crystal structure of 3,14-diethyl-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 ^*

^aBeamline Department, Pohang 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 25 January 2021; accepted 28 January 2021; online 29 January 2021)

The crystal structure of the hydrated title salt, C₂₂H₄₈N₄⁴⁺·4Cl⁻·4H₂O (C₂₂H₄₈N₄ = H₄L = 3,14-diethyl-2,6,13,17-tetraazoniatricyclo[16.4.0.0^7,12]docosane), 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 comprises one half of the macrocyclic cation (completed by crystallographic inversion symmetry), two chloride anions and two water molecules. The macrocyclic ring of the tetracation adopts an exodentate (3,4,3,4)-D conformation. 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 chloride anions as acceptors, giving rise to a three-dimensional network.

Keywords: crystal structure; tetraprotonated macrocycle; exodentate; tetrachloride; hydrogen bonding; synchrotron radiation.

CCDC reference: 2059324

1. Chemical context

In recent years, derivatives of 1,4,8,11-tetraazacyclotetradecane (cyclam) have been found to exhibit anti-HIV effects (Ronconi & Sadler, 2007 ; Ross et al., 2012 ) and to stimulate the activity of stem cells from bone marrow (De Clercq, 2010 ). The conformation of the macrocyclic ligand, the orientations of the N—H bonds and crystal packing forces in respective metal complexes are very important factors for CXCR4 chemokine receptor recognition. Therefore, knowledge of the conformations and crystal-packing features of complexes containing cyclam derivatives has become important in the development of new highly effective anti-HIV drugs that specifically target alternative events in the HIV replicative cycle. The macrocycle 3,14-diethyl-2,6,13,17-tetraazatricyclo(16.4.0.07,12)docosane (C₂₂H₄₄N₄, L) contains a cyclam backbone with two cyclohexane subunits. Ethyl groups are also attached to the 3 and 14 carbon atoms of the propyl chains that bridge opposite pairs of N atoms in the molecule. The macrocycle L is a strongly basic amine capable of forming the dication C₂₂H₄₆N₄²⁺ or even the tetracation C₂₂H₄₈N₄⁴⁺ in which all of the N—H bonds are generally available for hydrogen-bond formation. It is known that the neutral macrocycle and its dication adopt an endodentate conformation along the centre of the macrocyclic cavity. The stabilization of such an endo conformation can be attributed to strong intramolecular N—H⋯N hydrogen bonds. Unlike the free macrocycle and its dication, the tetracation adopts an exodentate conformation. Furthermore, the 14-membered cyclam moiety of the tetracation can adopt four exodentate (3,4,3,4)-(A–D) conformations (Meyer et al., 1998 ; Nowicka et al., 2012 ). Previously, the syntheses and crystal structures of the related compounds (C₂₂H₄₄N₄)·NaClO₄ (Aree et al., 2018 ), [C₂₂H₄₆N₄](ClO₄)₂ (Aree et al., 2018), [C₂₂H₄₆N₄]Cl₂·4H₂O (Moon et al., 2013 ) and [C₂₂H₄₆N₄](NO₃)₂·2H₂O (Moon et al., 2019 ) have been reported. However, there is no report of a compound with the 3,14-diethyl-2,6,13,17-tetraazoniatricyclo(16.4.0.0^7,12)docosane cation and any counter-anions. As another contribution to our research on this macrocyclic compound family, we report here the preparation of a new tetracationic compound [C₂₂H₄₈N₄]Cl₄·4H₂O, (I), as the hydrated tetrachloride salt and its structural characterization by synchrotron single-crystal X-ray diffraction.

2. Structural commentary

The molecular structure of (I) is shown in Fig. 1 along with the atom-numbering scheme. The organic cation lies across a crystallographic inversion centre and hence the asymmetric unit consists of one half of the cationic macrocycle, of two chloride anions and two solvent water molecules. Within the centrosymmetric tetraprotonated amine unit C₂₂H₄₈N₄⁴⁺, the C—C and N—C bond lengths range from 1.5208 (19) to 1.5431 (16) Å and from 1.5076 (15) to 1.5247 (15) Å, respectively; the range of N—C—C and C—N—C angles is 107.08 (9) to 111.72 (10)° and 116.40 (9) to 117.87 (9)°, respectively.

Figure 1
The molecular structure of (I)

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

The four N atoms of the macrocycle are coplanar, and the two ethyl substituents are anti with respect to the macrocyclic plane as a result of the molecular inversion symmetry. The six-membered cyclohexane ring is in its stable chair conformation. The cyclam moiety of the tetracation adopts an exodentate rectangular (3,4,3,4)-D conformation, which differs from the endodentate conformation of the free macrocycle or the dication (Aree et al., 2018; Moon et al., 2013). Only two of the four nitrogen atoms, N2 and N2′ [symmetry code: (') −x + 1, −y + 1, −z + 1] are located at the corners of the macrocyclic square. The other two corner positions are occupied by carbon atoms C2 and C2′. Thus, the remaining two nitrogen atoms, N1 and N1′ are components of the hydrocarbon side chain. Interestingly, the exo-[3,4,3,4]-D conformation of (I) also differs from the exo-[3,4,3,4]-B conformation of [H₄TMC](CrO₃Cl)₂Cl₂ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; Moon & Choi, 2020a ), and the exo-[3,4,3,4]-C conformation of [H₄TMC](ClO₄)₂Cl₂ (Moon & Choi, 2020b ) or (H₄cyclam)[Cr₂O₇]₂·H₂O (Moon & Choi, 2017 ). The detailed understanding and insight into the crystal packing and conformation may be helpful in the development of new anti-HIV drugs.

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 chloride anions and the O atoms of the water molecules serve as hydrogen-bond acceptors. The organic C₂₂H₄₈N₄⁴⁺ cation is linked to four water molecules via N—H⋯O hydrogen bonds whereas the O—H⋯Cl hydrogen bonds link the chloride anions to neighbouring water molecules. In addition, neighbouring organic cations are interconnected to chloride anions via several N—H⋯Cl hydrogen bonds. An extensive array of these contacts generates a three-dimensional network of molecules. The crystal packing of (I) viewed perpendicular to the ab plane is shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯Cl2	0.92 (1)	2.25 (1)	3.1616 (11)	172 (1)
O1—H2O1⋯Cl1	0.92 (1)	2.17 (1)	3.0746 (11)	169 (1)
O2—H1O2⋯Cl2ⁱ	0.92 (1)	2.34 (1)	3.2518 (15)	172 (2)
O2—H2O2⋯Cl2ⁱⁱ	0.91 (1)	2.26 (1)	3.1622 (12)	173 (2)
N1—H1A⋯Cl1ⁱⁱⁱ	0.90	2.22	3.1072 (12)	169
N1—H1B⋯O1	0.90	1.92	2.7740 (15)	157
N2—H2A⋯O2	0.90	1.91	2.7716 (14)	161
N2—H2B⋯Cl2^iv	0.90	2.45	3.3357 (12)	167
Symmetry codes: (i) ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) ; (iv) .

Figure 2
The crystal packing in (I)

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

4. Database survey

A search of the Cambridge Structural Database (CSD; version 5.42, November 2020; Groom et al., 2016 ) revealed five matches for organic compounds containing the macrocycles (C₂₂H₄₄N₄), C₂₂H₄₆N₄²⁺ or C₂₂H₄₈N₄⁴⁺. The crystal structures of (C₂₂H₄₄N₄)·NaClO₄ (Aree et al., 2018), [C₂₂H₄₆N₄](ClO₄)₂ (Aree et al., 2018), [C₂₂H₄₆N₄]Cl₂·4H₂O (Moon et al., 2013) and [C₂₂H₄₆N₄](NO₃)₂·2H₂O (Moon et al., 2019) have been reported previously. All bond lengths and angles within the tetracation C₂₂H₄₈N₄⁴⁺ in (I) are similar to those found in the database structures.

Until now, no crystal structure of a compound with the tetracation C₂₂H₄₈N₄⁴⁺ and any counter-anion has been deposited.

5. Synthesis and crystallization

Ethyl vinyl ketone (97%), trans-1,2-cyclohexanediamine (99%) and copper(II) chloride dihydrate (99%) were purchased from Sigma–Aldrich and were used as received. All other chemicals were of analytical reagent grade. The solvents were of reagent grade and purified by usual methods. As a starting material, the 3,14-diethyl-2,6,13,17-tetraazatricyclo(16.4.0.0^7,12)docosane macrocycle L was prepared according to a published procedure (Lim et al., 2006 ). A solution of L (0.091 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 373 K. After cooling to 298 K, the pH was adjusted to 3.0 by 1.0 M HCl. The solution was filtered and left at room temperature. A mixture of colourless, red and violet crystals formed from the solution over the next few days. The product mixture was added to a 30 ml MeOH–acetone (1:2 v:v) solution under stirring, and the stirring was continued for 30 min at 298 K. The red and violet compounds were manually removed, and block-like colorless single crystals of (I) suitable for X-ray analysis were obtained by filtration.

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, and with an N—H distance of 0.90 Å with U_iso(H) values of 1.2 and 1.5U_eq of the parent atoms, respectively. 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 (0.94 and 1.55 Å, respectively).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₂H₄₈N₄⁴⁺·4Cl⁻·4H₂O
M_r	582.50
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	220
a, b, c (Å)	7.6550 (15), 23.533 (5), 8.3130 (17)
β (°)	102.45 (3)
V (Å³)	1462.3 (5)
Z	2
Radiation type	Synchrotron, λ = 0.610 Å
μ (mm⁻¹)	0.29
Crystal size (mm)	0.08 × 0.07 × 0.04

Data collection
Diffractometer	Rayonix MX225HS CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski et al., 2003 )
T_min, T_max	0.868, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14961, 4016, 3517
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.693

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.105, 1.09
No. of reflections	4016
No. of parameters	167
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)	0.41, −0.22
Computer programs: PAL BL2D-SMDC (Shin et al., 2016 ), HKL3000sm (Otwinowski et al., 2003), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND (Putz & Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2059324

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021001006/wm5597sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021001006/wm5597Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021001006/wm5597Isup3.cml

checkCIF report

Computing details top

Data collection: PAL BL2D-SMDC (Shin et al., 2016); cell refinement: HKL3000sm (Otwinowski et al., 2003); data reduction: HKL3000sm (Otwinowski et al., 2003); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

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

Crystal data top

C₂₂H₄₈N₄⁴⁺·4Cl⁻·4H₂O	F(000) = 632
M_r = 582.50	D_x = 1.323 Mg m⁻³
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.610 Å
a = 7.6550 (15) Å	Cell parameters from 50732 reflections
b = 23.533 (5) Å	θ = 0.4–33.7°
c = 8.3130 (17) Å	µ = 0.28 mm⁻¹
β = 102.45 (3)°	T = 220 K
V = 1462.3 (5) Å³	Block, colorless
Z = 2	0.08 × 0.07 × 0.04 mm

Data collection top

Rayonix MX225HS CCD area detector diffractometer	3517 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.038
ω scan	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: empirical (using intensity measurements) (HKL3000sm Scalepack; Otwinowski et al., 2003)	h = −10→10
T_min = 0.868, T_max = 1.000	k = −32→32
14961 measured reflections	l = −11→11
4016 independent reflections

Refinement top

Refinement on F²	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0597P)² + 0.2081P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
4016 reflections	Δρ_max = 0.41 e Å⁻³
167 parameters	Δρ_min = −0.22 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	0.71371 (4)	0.51779 (2)	1.23367 (4)	0.02947 (10)
Cl2	0.80805 (4)	0.29797 (2)	1.26093 (4)	0.03510 (10)
O1	0.82713 (14)	0.41203 (4)	1.06447 (12)	0.0341 (2)
H1O1	0.822 (2)	0.3768 (4)	1.1119 (19)	0.041*
H2O1	0.792 (2)	0.4405 (5)	1.1271 (18)	0.041*
O2	0.21622 (14)	0.29355 (5)	0.47672 (14)	0.0405 (2)
H1O2	0.1034 (16)	0.2916 (8)	0.4106 (19)	0.049*
H2O2	0.233 (2)	0.2681 (6)	0.5609 (16)	0.049*
N1	0.68792 (13)	0.46398 (4)	0.76471 (12)	0.0234 (2)
H1A	0.576535	0.473733	0.773054	0.028*
H1B	0.728900	0.438497	0.844668	0.028*
N2	0.49393 (13)	0.36101 (4)	0.42080 (12)	0.0239 (2)
H2A	0.409339	0.334408	0.420241	0.029*
H2B	0.588974	0.343395	0.395724	0.029*
C1	0.74209 (15)	0.56567 (5)	0.68089 (15)	0.0247 (2)
H1C	0.713036	0.551403	0.567493	0.030*
H1D	0.840569	0.592881	0.689320	0.030*
C2	0.80442 (16)	0.51617 (5)	0.79715 (16)	0.0255 (2)
H2C	0.926151	0.505782	0.788904	0.031*
H2D	0.809475	0.528837	0.910366	0.031*
C3	0.67631 (15)	0.43519 (5)	0.60043 (14)	0.0232 (2)
H3	0.622610	0.462009	0.511758	0.028*
C4	0.86023 (16)	0.41738 (5)	0.57551 (15)	0.0270 (2)
H4A	0.848164	0.401294	0.464927	0.032*
H4B	0.937435	0.450940	0.583476	0.032*
C5	0.94712 (16)	0.37373 (6)	0.70283 (17)	0.0307 (3)
H5A	0.968765	0.390841	0.812822	0.037*
H5B	1.062841	0.362317	0.680786	0.037*
C6	0.82840 (18)	0.32133 (6)	0.69882 (17)	0.0325 (3)
H6A	0.881223	0.296219	0.790489	0.039*
H6B	0.825026	0.300529	0.596063	0.039*
C7	0.63628 (17)	0.33618 (5)	0.71111 (16)	0.0288 (3)
H7A	0.562168	0.301986	0.687145	0.035*
H7B	0.636910	0.347551	0.824645	0.035*
C8	0.55016 (15)	0.38374 (5)	0.59487 (14)	0.0237 (2)
H8	0.441439	0.396678	0.630583	0.028*
C9	0.42198 (15)	0.40325 (5)	0.28341 (14)	0.0240 (2)
H9	0.516285	0.431990	0.282803	0.029*
C10	0.38798 (17)	0.37228 (5)	0.11758 (15)	0.0285 (2)
H10A	0.361097	0.400848	0.029936	0.034*
H10B	0.499099	0.353289	0.107674	0.034*
C11	0.2386 (2)	0.32840 (6)	0.08671 (18)	0.0371 (3)
H11A	0.259808	0.300603	0.174946	0.056*
H11B	0.235881	0.309471	−0.017459	0.056*
H11C	0.124952	0.347133	0.082958	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02435 (15)	0.02771 (17)	0.04097 (18)	−0.00112 (10)	0.01724 (12)	−0.00061 (11)
Cl2	0.03364 (17)	0.03180 (18)	0.04254 (19)	0.00500 (12)	0.01410 (14)	−0.00293 (12)
O1	0.0398 (5)	0.0299 (5)	0.0361 (5)	0.0030 (4)	0.0156 (4)	0.0005 (4)
O2	0.0314 (5)	0.0430 (6)	0.0482 (6)	−0.0074 (4)	0.0111 (4)	0.0115 (5)
N1	0.0220 (4)	0.0202 (5)	0.0305 (5)	0.0007 (3)	0.0112 (4)	0.0001 (4)
N2	0.0223 (4)	0.0193 (4)	0.0322 (5)	−0.0009 (3)	0.0107 (4)	−0.0002 (4)
C1	0.0242 (5)	0.0191 (5)	0.0339 (6)	−0.0003 (4)	0.0134 (4)	−0.0003 (4)
C2	0.0227 (5)	0.0204 (5)	0.0343 (6)	−0.0008 (4)	0.0083 (4)	−0.0021 (4)
C3	0.0229 (5)	0.0199 (5)	0.0290 (5)	−0.0017 (4)	0.0106 (4)	−0.0011 (4)
C4	0.0250 (5)	0.0241 (5)	0.0361 (6)	−0.0028 (4)	0.0161 (5)	−0.0031 (5)
C5	0.0240 (5)	0.0294 (6)	0.0410 (6)	0.0034 (5)	0.0123 (5)	−0.0023 (5)
C6	0.0343 (6)	0.0239 (6)	0.0400 (7)	0.0035 (5)	0.0097 (5)	0.0025 (5)
C7	0.0299 (6)	0.0224 (6)	0.0352 (6)	−0.0038 (4)	0.0096 (5)	0.0036 (5)
C8	0.0224 (5)	0.0210 (5)	0.0304 (5)	−0.0019 (4)	0.0114 (4)	−0.0011 (4)
C9	0.0229 (5)	0.0203 (5)	0.0312 (5)	−0.0006 (4)	0.0114 (4)	0.0017 (4)
C10	0.0292 (6)	0.0284 (6)	0.0310 (6)	0.0044 (5)	0.0133 (5)	−0.0006 (5)
C11	0.0415 (7)	0.0312 (7)	0.0381 (7)	−0.0035 (6)	0.0077 (6)	−0.0063 (6)

Geometric parameters (Å, º) top

O1—H1O1	0.924 (9)	C4—C5	1.5213 (18)
O1—H2O1	0.922 (9)	C4—H4A	0.9800
O2—H1O2	0.919 (9)	C4—H4B	0.9800
O2—H2O2	0.910 (9)	C5—C6	1.5279 (19)
N1—C2	1.5076 (15)	C5—H5A	0.9800
N1—C3	1.5099 (15)	C5—H5B	0.9800
N1—H1A	0.9000	C6—C7	1.5364 (18)
N1—H1B	0.9000	C6—H6A	0.9800
N2—C8	1.5155 (16)	C6—H6B	0.9800
N2—C9	1.5247 (15)	C7—C8	1.5318 (17)
N2—H2A	0.9000	C7—H7A	0.9800
N2—H2B	0.9000	C7—H7B	0.9800
C1—C2	1.5231 (17)	C8—H8	0.9900
C1—C9ⁱ	1.5366 (16)	C9—C10	1.5312 (17)
C1—H1C	0.9800	C9—H9	0.9900
C1—H1D	0.9800	C10—C11	1.5208 (19)
C2—H2C	0.9800	C10—H10A	0.9800
C2—H2D	0.9800	C10—H10B	0.9800
C3—C4	1.5253 (16)	C11—H11A	0.9700
C3—C8	1.5431 (16)	C11—H11B	0.9700
C3—H3	0.9900	C11—H11C	0.9700

H1O1—O1—H2O1	111.5 (13)	C6—C5—H5A	109.4
H1O2—O2—H2O2	112.6 (15)	C4—C5—H5B	109.4
C2—N1—C3	116.40 (9)	C6—C5—H5B	109.4
C2—N1—H1A	108.2	H5A—C5—H5B	108.0
C3—N1—H1A	108.2	C5—C6—C7	112.85 (11)
C2—N1—H1B	108.2	C5—C6—H6A	109.0
C3—N1—H1B	108.2	C7—C6—H6A	109.0
H1A—N1—H1B	107.3	C5—C6—H6B	109.0
C8—N2—C9	117.87 (9)	C7—C6—H6B	109.0
C8—N2—H2A	107.8	H6A—C6—H6B	107.8
C9—N2—H2A	107.8	C8—C7—C6	114.35 (10)
C8—N2—H2B	107.8	C8—C7—H7A	108.7
C9—N2—H2B	107.8	C6—C7—H7A	108.7
H2A—N2—H2B	107.2	C8—C7—H7B	108.7
C2—C1—C9ⁱ	113.50 (10)	C6—C7—H7B	108.7
C2—C1—H1C	108.9	H7A—C7—H7B	107.6
C9ⁱ—C1—H1C	108.9	N2—C8—C7	109.85 (10)
C2—C1—H1D	108.9	N2—C8—C3	110.65 (9)
C9ⁱ—C1—H1D	108.9	C7—C8—C3	111.90 (10)
H1C—C1—H1D	107.7	N2—C8—H8	108.1
N1—C2—C1	114.66 (10)	C7—C8—H8	108.1
N1—C2—H2C	108.6	C3—C8—H8	108.1
C1—C2—H2C	108.6	N2—C9—C10	109.14 (9)
N1—C2—H2D	108.6	N2—C9—C1ⁱ	110.12 (9)
C1—C2—H2D	108.6	C10—C9—C1ⁱ	114.39 (10)
H2C—C2—H2D	107.6	N2—C9—H9	107.6
N1—C3—C4	111.72 (10)	C10—C9—H9	107.6
N1—C3—C8	107.08 (9)	C1ⁱ—C9—H9	107.6
C4—C3—C8	111.74 (10)	C11—C10—C9	116.80 (10)
N1—C3—H3	108.7	C11—C10—H10A	108.1
C4—C3—H3	108.7	C9—C10—H10A	108.1
C8—C3—H3	108.7	C11—C10—H10B	108.1
C5—C4—C3	111.65 (10)	C9—C10—H10B	108.1
C5—C4—H4A	109.3	H10A—C10—H10B	107.3
C3—C4—H4A	109.3	C10—C11—H11A	109.5
C5—C4—H4B	109.3	C10—C11—H11B	109.5
C3—C4—H4B	109.3	H11A—C11—H11B	109.5
H4A—C4—H4B	108.0	C10—C11—H11C	109.5
C4—C5—C6	111.17 (11)	H11A—C11—H11C	109.5
C4—C5—H5A	109.4	H11B—C11—H11C	109.5

C3—N1—C2—C1	63.32 (13)	C6—C7—C8—N2	76.17 (13)
C9ⁱ—C1—C2—N1	74.65 (13)	C6—C7—C8—C3	−47.14 (14)
C2—N1—C3—C4	57.74 (13)	N1—C3—C8—N2	165.93 (9)
C2—N1—C3—C8	−179.62 (9)	C4—C3—C8—N2	−71.44 (12)
N1—C3—C4—C5	62.83 (13)	N1—C3—C8—C7	−71.22 (12)
C8—C3—C4—C5	−57.11 (13)	C4—C3—C8—C7	51.41 (13)
C3—C4—C5—C6	57.11 (13)	C8—N2—C9—C10	175.45 (9)
C4—C5—C6—C7	−52.02 (14)	C8—N2—C9—C1ⁱ	−58.20 (12)
C5—C6—C7—C8	47.89 (15)	N2—C9—C10—C11	67.17 (13)
C9—N2—C8—C7	−174.08 (9)	C1ⁱ—C9—C10—C11	−56.69 (15)
C9—N2—C8—C3	−50.04 (12)

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···Cl2	0.92 (1)	2.25 (1)	3.1616 (11)	172 (1)
O1—H2O1···Cl1	0.92 (1)	2.17 (1)	3.0746 (11)	169 (1)
O2—H1O2···Cl2ⁱⁱ	0.92 (1)	2.34 (1)	3.2518 (15)	172 (2)
O2—H2O2···Cl2ⁱⁱⁱ	0.91 (1)	2.26 (1)	3.1622 (12)	173 (2)
N1—H1A···Cl1^iv	0.90	2.22	3.1072 (12)	169
N1—H1B···O1	0.90	1.92	2.7740 (15)	157
N2—H2A···O2	0.90	1.91	2.7716 (14)	161
N2—H2B···Cl2^v	0.90	2.45	3.3357 (12)	167

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

Acknowledgements

The X-ray crystallography experiment at the PLS-II BL2D-SMC beamline was supported in part by MSIT and POSTECH.

Funding information

This work was supported by a Research Grant of Andong National University.

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