Crystal structure of 1,4,8,11-tetra­methyl-1,4,8,11-tetra­azonia­cyclo­tetra­decane bis­(perchlorate) dichloride from synchrotron X-ray data

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

doi:10.1107/S2056989020001322

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ISSN: 2056-9890

Volume 76| Part 3| March 2020| Pages 324-327

https://doi.org/10.1107/S2056989020001322

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Crystal structure of 1,4,8,11-tetramethyl-1,4,8,11-tetraazoniacyclotetradecane bis(perchlorate) dichloride 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 L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 27 January 2020; accepted 30 January 2020; online 11 February 2020)

The crystal structure of title salt, C₁₄H₃₆N₄⁴⁺·2ClO₄⁻·2Cl⁻, 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), one perchlorate anion and one chloride anion. A distortion of the perchlorate anion is due to its involvement in hydrogen-bonding interactions with the cations. The crystal structure is consolidated by intermolecular hydrogen bonds involving the 1,4,8,11-tetramethyl-1,4,8,11-tetraazoniacyclotetradecane N—H and C—H groups as donor groups, and the O atoms of the perchlorate and chloride anion as acceptor groups, giving rise to a three-dimensional network.

Keywords: crystal structure; 1,4,8,11-tetramethyl-1,4,8,11-tetraazoniacyclotetradecane; bis(perchlorate) dichloride; hydrogen bonding; synchrotron radiation.

CCDC reference: 1980910

1. Chemical context

Tetraazamacrocycle 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (TMC, C₁₄H₃₂N₄) is one of the most useful azamacrocycles because of its ability to act as an effective metal-ion binding site and its basic properties. N-Substituted TMC is a basic amine that may form a dication, C₁₄H₃₄N₄²⁺, or a tetracation, C₁₄H₃₆N₄⁴⁺, in which the N—H bonds are generally active in hydrogen-bond formation. These di- or tetraammonium cations may be suitable for the removal of toxic heavy-metal ions. Because of a difference in the chirality of the secondary NH centers, the macrocyclic compounds can exhibit five conformations, viz. trans-I (RSRS), trans-II (RSRR), trans-III (RRSS), trans-IV (SRRS) and trans-V (RRRR) (Choi, 2009 ). Previously, the crystal structures for trans-[Ni(TMC)(H₂O)₂]Cl₂·2H₂O, [Ni(TMC)](O₃SCF₃) (Barefield et al., 1986 ), [Cu(TMC)(H₂O)](ClO₄)₂·H₂O (Lee et al., 1986 ), [Cu(TMC)](ClO₄)₂ (Maimon et al., 2001 ), [Ag(TMC)](ClO₄)₂ (Po et al., 1991 ), [Cu(NCS)(TMC)]ClO₄ (Lu et al., 1998 ) and [Cu(TMC)](BF₄)₂ (Bucher et al., 2001b ) have been characterized crystallographically. In addition, first-row transition-metal complexes of the form [M^IICl(TMC)]⁺ [M = Zn (Alcock et al., 1978 ), Mn (Bucher et al., 2001a ), Ni (Nishigaki et al., 2010 ), Fe (Bedford et al., 2016 ) and Co (Van Heuvelen et al., 2017 )] have been determined. Two independent ring conformations, trans-III and trans-IV, in the crystal structure of free TMC were also found (Willey et al., 1994 ), but there is no report of a structure with any combination of the 1,4,8,11-tetramethyl-1,4,8,11-tetraazoniacyclotetradecane cation and ClO₄⁻ and Cl⁻ anions. We report here the preparation of a new compound [H₄TMC](ClO₄)₂Cl₂, (I), and its structural characterization by synchrotron single-crystal X-ray diffraction.

2. Structural commentary

An ellipsoid plot of the molecular components in (I) is shown in Fig. 1 along with the atom-numbering scheme. The asymmetric unit consists of one half of the macrocycle, which lies about a center of inversion, one perchlorate anion and one chloride anion. The tetra-protonated amine of the title compound has a distorted trans-IV conformation, which is comparable to the trans-I or trans-III conformations of the dications in [H₂TMC][As₄O₂Cl₁₀] and [H₂TMC][Sb₂OCl₆], respectively (Willey et al., 1993 ). Within the centrosymmetric tetra-protonated C₁₄H₃₆N₄⁴⁺ amine unit, the C—C and N—C bond lengths vary from 1.522 (2) to 1.527 (2) Å and from 1.5033 (19) to 1.5181 (18) Å, respectively. The N—C—C and C—N—C angles range from 113.55 (12) to 116.19 (12)° and 108.49 (12) to 112.37 (11)°, respectively. The bond lengths and angles within the tetraammonium cations are comparable to the corresponding values determined for the TMC moiety in [H₄TMC]₂[Sb₄F₁₅][HF₂]F₄ (Becker & Mattes, 1996 ), [H₂TMC][As₄O₂Cl₁₀], [H₂TMC][Sb₂OCl₆] (Willey et al., 1993), [H₄TMC][H₂TMC][W(CN)₈]₂·4H₂O (Nowicka et al., 2012 ), [Ga₂(C₃H₇)₄(OH)₂](TMC) (Boag et al., 2000 ), TMC (Willey et al., 1994), trans-[Ni(TMC)(H₂O)₂]Cl₂·2H₂O (Barefield et al., 1986), trans-[Os(TMC)(O)₂](PF₆)₂ (Kelly et al., 1996 ), [Cu(TMC)(H₂O)](ClO₄)₂·H₂O (Lee et al., 1986), [Cu(NCS)(TMC)]ClO₄ (Lu et al., 1998) and [Cu(TMC)](BF₄)₂ (Bucher et al., 2001b). The Cl—O bond distances in the tetrahedral ClO₄⁻ anion range from 1.4180 (17) to 1.4380 (16) Å and the O—Cl—O angles from 106.85 (14)–110.94 (12)°. A distortion of the ClO₄⁻ anion undoubtedly results from its involvement in hydrogen-bonding interactions with the cations.

Figure 1
The structures of the molecular components in (I)

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

3. Supramolecular features

Extensive N—H⋯Cl, C—H⋯Cl and C—H⋯O hydrogen-bonding interactions occur in the crystal structure (Table 1). A crystal packing diagram 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
N1—H1⋯Cl2	0.99	2.13	3.0701 (14)	159
N2—H2⋯Cl2	0.99	2.17	3.1038 (15)	156
C1—H1A⋯Cl2	0.98	2.77	3.6868 (17)	157
C5—H5AB⋯O3	0.98	2.39	3.351 (3)	167
C3—H3A⋯Cl2ⁱ	0.98	2.67	3.6274 (17)	164
C3—H3AB⋯O2ⁱⁱ	0.98	2.52	3.288 (3)	135
C4—H4A⋯O4ⁱⁱⁱ	0.97	2.49	3.429 (3)	164
C4—H4C⋯O2ⁱⁱ	0.97	2.39	3.171 (3)	137
C5—H5A⋯O3ⁱⁱⁱ	0.98	2.34	3.317 (3)	173
C6—H6AB⋯O4^iv	0.98	2.31	3.231 (3)	156
C6—H6A⋯Cl2ⁱ	0.98	2.80	3.7414 (17)	161
C7—H7B⋯O3ⁱⁱⁱ	0.97	2.40	3.333 (3)	161
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x, -y+1, -z+1.

Figure 2
The crystal packing of compound (I)

, viewed perpendicular to the ab plane. Dashed lines represent N—H⋯Cl (purple), C—H⋯Cl (blue) and C—H⋯O (green) hydrogen-bonding interactions, respectively.

The N—H⋯Cl and C—H⋯Cl hydrogen bonds link the two Cl⁻ anions to the C₁₄H₃₆N₄⁴⁺ cation while C—H⋯O hydrogen bonds interconnect neighboring cations with the ClO₄⁻ anions. An extensive array of these contacts generates a three-dimensional network of molecules, and these hydrogen-bonding interactions help to consolidate the crystal structure.

4. Database survey

A search of the Cambridge Structural Database (Version 5.41, November 2019; Groom et al., 2016 ) gave just seven hits for organic compounds containing C₁₄H₃₆N₄⁴⁺, C₁₄H₃₄N₄²⁺ or C₁₄H₃₂N₄ macrocycles: [C₁₄H₃₆N₄]₂[Sb₄F₁₅][HF₂]F₄ (Becker et al., 1996), [C₁₄H₃₄N₄][As₄O₂Cl₁₀] and [C₁₄H₃₄N₄][Sb₂OCl₆] (Willey et al., 1993), [C₁₄H₃₆N₄][C₁₄H₃₄N₄][W(CN)₈]₂·4H₂O (Nowicka et al., 2012), [Ga₂(C₃H₇)₄(OH)₂](C₁₄H₃₂N₄) (Boag et al., 2000) and (C₁₄H₃₂N₄) (Willey et al., 1994). However, the crystal structure of the title compound had not been deposited until now. The tetra-protonated amine of the title compound has a trans-IV conformation, which is comparable to the trans-I or trans-III conformation of the dications in [H₂TMC][As₄O₂Cl₁₀] and [H₂TMC][Sb₂OCl₆], respectively (Willey et al., 1993).

5. Synthesis and crystallization

The free ligand TMC (98%) was purchased from Sigma–Aldrich and used without further purification. All chemicals were reagent grade materials, and were used as received. TMC (0.128 g, 0.5 mmol) was dissolved in 15 mL of 6 M HCl, and 5 mL of a saturated solution of sodium perchlorate including chromium trioxide (0.1 g, 1 mmol) was added to the resulting solution at 298 K. The mixture was stirred for 2 h and the solution was filtered. Block-like pale yellow crystals of (I) suitable for X-ray structural analysis were unexpectedly obtained from the solution at 298 K over a period of a few days.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.97–0.98 Å and N—H = 0.99 Å, and with U_iso(H) values of 1.5 and 1.2 times the U_eq of the parent atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₃₆N₄⁴⁺·2ClO₄⁻·2Cl⁻
M_r	530.27
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	220
a, b, c (Å)	7.4990 (15), 8.0790 (16), 9.980 (2)
α, β, γ (°)	81.31 (3), 77.32 (3), 78.39 (3)
V (Å³)	574.2 (2)
Z	1
Radiation type	Synchrotron, λ = 0.610 Å
μ (mm⁻¹)	0.36
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	Rayonix MX225HS CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.710, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6573, 3361, 3208
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.147, 1.05
No. of reflections	3361
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.97, −0.56
Computer programs: PAL BL2D-SMDC Program (Shin et al., 2016 ), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND4 (Putz & Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1980910

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020001322/vm2227sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020001322/vm2227Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020001322/vm2227Isup3.cml

checkCIF report

Computing details top

Data collection: PAL BL2D-SMDC Program (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: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND4 (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

1,4,8,11-Tetramethyl-1,4,8,11-tetraazoniacyclotetradecane bis(perchlorate) dichloride top

Crystal data top

C₁₄H₃₆N₄⁴⁺·2ClO₄⁻·2Cl⁻	Z = 1
M_r = 530.27	F(000) = 280
Triclinic, P1	D_x = 1.533 Mg m⁻³
a = 7.4990 (15) Å	Synchrotron radiation, λ = 0.610 Å
b = 8.0790 (16) Å	Cell parameters from 91694 reflections
c = 9.980 (2) Å	θ = 0.4–33.7°
α = 81.31 (3)°	µ = 0.36 mm⁻¹
β = 77.32 (3)°	T = 220 K
γ = 78.39 (3)°	Block, pale yellow
V = 574.2 (2) Å³	0.10 × 0.10 × 0.08 mm

Data collection top

Rayonix MX225HS CCD area detector diffractometer	3208 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.038
ω scan	θ_max = 25.5°, θ_min = 1.8°
Absorption correction: empirical (using intensity measurements) (HKL3000sm Scalepack; Otwinowski & Minor, 1997)	h = −10→10
T_min = 0.710, T_max = 1.000	k = −11→11
6573 measured reflections	l = −14→14
3361 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.1013P)² + 0.2815P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3361 reflections	Δρ_max = 0.97 e Å⁻³
138 parameters	Δρ_min = −0.56 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
N1	0.67545 (16)	0.40154 (15)	0.21687 (13)	0.0182 (2)
H1	0.702337	0.480395	0.131812	0.022*
N2	0.32976 (16)	0.70943 (15)	0.15397 (13)	0.0187 (2)
H2	0.447969	0.698634	0.085623	0.022*
C1	0.82761 (19)	0.26947 (19)	−0.07624 (16)	0.0213 (3)
H1A	0.844476	0.382168	−0.061678	0.026*
H1AB	0.942570	0.216566	−0.133336	0.026*
C2	0.7951 (2)	0.16181 (18)	0.06343 (16)	0.0222 (3)
H2A	0.911494	0.135809	0.097951	0.027*
H2AB	0.766041	0.053719	0.048851	0.027*
C3	0.6416 (2)	0.24003 (18)	0.17554 (15)	0.0202 (3)
H3A	0.524235	0.264324	0.142544	0.024*
H3AB	0.628253	0.156392	0.257539	0.024*
C4	0.8394 (2)	0.3698 (2)	0.2869 (2)	0.0289 (3)
H4A	0.852000	0.474931	0.316837	0.043*
H4B	0.951096	0.328712	0.222555	0.043*
H4C	0.820747	0.285389	0.366416	0.043*
C5	0.5084 (2)	0.48877 (19)	0.31152 (15)	0.0219 (3)
H5A	0.541977	0.588041	0.339066	0.026*
H5AB	0.480340	0.410569	0.395386	0.026*
C6	0.3326 (2)	0.54741 (19)	0.25240 (16)	0.0220 (3)
H6A	0.315943	0.456530	0.203864	0.026*
H6AB	0.226499	0.564160	0.329274	0.026*
C7	0.3152 (2)	0.8628 (2)	0.22684 (18)	0.0267 (3)
H7A	0.305431	0.964466	0.161379	0.040*
H7B	0.424822	0.852681	0.266082	0.040*
H7C	0.205791	0.870354	0.300087	0.040*
Cl1	0.21029 (5)	0.17202 (5)	0.52791 (4)	0.02439 (13)
O1	0.2471 (3)	0.1745 (2)	0.38061 (17)	0.0494 (4)
O2	0.1539 (3)	0.0175 (3)	0.5935 (3)	0.0669 (6)
O3	0.3753 (3)	0.1946 (3)	0.5690 (2)	0.0560 (5)
O4	0.0647 (3)	0.3129 (3)	0.5618 (3)	0.0662 (6)
Cl2	0.73888 (5)	0.71235 (4)	0.00536 (4)	0.02198 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0174 (5)	0.0170 (5)	0.0224 (5)	−0.0036 (4)	−0.0087 (4)	−0.0011 (4)
N2	0.0150 (5)	0.0180 (5)	0.0242 (5)	−0.0023 (4)	−0.0058 (4)	−0.0042 (4)
C1	0.0144 (6)	0.0238 (6)	0.0281 (7)	−0.0034 (5)	−0.0074 (5)	−0.0056 (5)
C2	0.0200 (6)	0.0181 (6)	0.0301 (7)	0.0004 (5)	−0.0105 (5)	−0.0041 (5)
C3	0.0201 (6)	0.0175 (6)	0.0263 (6)	−0.0051 (5)	−0.0095 (5)	−0.0026 (5)
C4	0.0247 (7)	0.0285 (8)	0.0402 (8)	−0.0049 (6)	−0.0196 (6)	−0.0047 (6)
C5	0.0237 (6)	0.0216 (6)	0.0213 (6)	−0.0028 (5)	−0.0066 (5)	−0.0032 (5)
C6	0.0183 (6)	0.0193 (6)	0.0278 (7)	−0.0035 (5)	−0.0043 (5)	−0.0012 (5)
C7	0.0304 (8)	0.0198 (7)	0.0346 (8)	−0.0038 (5)	−0.0133 (6)	−0.0085 (6)
Cl1	0.0237 (2)	0.0222 (2)	0.0294 (2)	−0.00633 (14)	−0.00871 (15)	−0.00105 (14)
O1	0.0545 (10)	0.0648 (11)	0.0346 (7)	−0.0209 (8)	−0.0060 (7)	−0.0131 (7)
O2	0.0720 (13)	0.0481 (10)	0.0887 (15)	−0.0350 (9)	−0.0404 (12)	0.0356 (10)
O3	0.0533 (10)	0.0629 (11)	0.0691 (12)	−0.0267 (9)	−0.0400 (9)	0.0023 (9)
O4	0.0504 (10)	0.0561 (11)	0.0837 (15)	0.0128 (9)	−0.0007 (10)	−0.0290 (10)
Cl2	0.01828 (19)	0.0202 (2)	0.0293 (2)	−0.00692 (13)	−0.00735 (14)	0.00056 (13)

Geometric parameters (Å, º) top

N1—C4	1.5037 (19)	C4—H4A	0.9700
N1—C3	1.5095 (18)	C4—H4B	0.9700
N1—C5	1.5116 (19)	C4—H4C	0.9700
N1—H1	0.9900	C5—C6	1.522 (2)
N2—C7	1.5033 (19)	C5—H5A	0.9800
N2—C6	1.513 (2)	C5—H5AB	0.9800
N2—C1ⁱ	1.5181 (18)	C6—H6A	0.9800
N2—H2	0.9900	C6—H6AB	0.9800
C1—C2	1.526 (2)	C7—H7A	0.9700
C1—H1A	0.9800	C7—H7B	0.9700
C1—H1AB	0.9800	C7—H7C	0.9700
C2—C3	1.527 (2)	Cl1—O2	1.4180 (17)
C2—H2A	0.9800	Cl1—O1	1.4328 (16)
C2—H2AB	0.9800	Cl1—O4	1.4342 (19)
C3—H3A	0.9800	Cl1—O3	1.4380 (16)
C3—H3AB	0.9800

C4—N1—C3	111.91 (12)	N1—C4—H4A	109.5
C4—N1—C5	108.49 (12)	N1—C4—H4B	109.5
C3—N1—C5	112.37 (11)	H4A—C4—H4B	109.5
C4—N1—H1	108.0	N1—C4—H4C	109.5
C3—N1—H1	108.0	H4A—C4—H4C	109.5
C5—N1—H1	108.0	H4B—C4—H4C	109.5
C7—N2—C6	112.12 (12)	N1—C5—C6	116.19 (12)
C7—N2—C1ⁱ	111.00 (11)	N1—C5—H5A	108.2
C6—N2—C1ⁱ	109.81 (11)	C6—C5—H5A	108.2
C7—N2—H2	107.9	N1—C5—H5AB	108.2
C6—N2—H2	107.9	C6—C5—H5AB	108.2
C1ⁱ—N2—H2	107.9	H5A—C5—H5AB	107.4
N2ⁱ—C1—C2	113.55 (12)	N2—C6—C5	115.16 (12)
N2ⁱ—C1—H1A	108.9	N2—C6—H6A	108.5
C2—C1—H1A	108.9	C5—C6—H6A	108.5
N2ⁱ—C1—H1AB	108.9	N2—C6—H6AB	108.5
C2—C1—H1AB	108.9	C5—C6—H6AB	108.5
H1A—C1—H1AB	107.7	H6A—C6—H6AB	107.5
C1—C2—C3	116.36 (12)	N2—C7—H7A	109.5
C1—C2—H2A	108.2	N2—C7—H7B	109.5
C3—C2—H2A	108.2	H7A—C7—H7B	109.5
C1—C2—H2AB	108.2	N2—C7—H7C	109.5
C3—C2—H2AB	108.2	H7A—C7—H7C	109.5
H2A—C2—H2AB	107.4	H7B—C7—H7C	109.5
N1—C3—C2	114.13 (12)	O2—Cl1—O1	110.75 (13)
N1—C3—H3A	108.7	O2—Cl1—O4	110.14 (15)
C2—C3—H3A	108.7	O1—Cl1—O4	106.85 (14)
N1—C3—H3AB	108.7	O2—Cl1—O3	110.94 (12)
C2—C3—H3AB	108.7	O1—Cl1—O3	108.56 (12)
H3A—C3—H3AB	107.6	O4—Cl1—O3	109.50 (14)

N2ⁱ—C1—C2—C3	−69.05 (16)	C3—N1—C5—C6	−61.62 (16)
C4—N1—C3—C2	−66.31 (16)	C7—N2—C6—C5	−69.95 (16)
C5—N1—C3—C2	171.33 (11)	C1ⁱ—N2—C6—C5	166.15 (12)
C1—C2—C3—N1	−62.42 (16)	N1—C5—C6—N2	−77.80 (16)
C4—N1—C5—C6	174.11 (13)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.99	2.13	3.0701 (14)	159
N2—H2···Cl2	0.99	2.17	3.1038 (15)	156
C1—H1A···Cl2	0.98	2.77	3.6868 (17)	157
C5—H5AB···O3	0.98	2.39	3.351 (3)	167
C3—H3A···Cl2ⁱ	0.98	2.67	3.6274 (17)	164
C3—H3AB···O2ⁱⁱ	0.98	2.52	3.288 (3)	135
C4—H4A···O4ⁱⁱⁱ	0.97	2.49	3.429 (3)	164
C4—H4C···O2ⁱⁱ	0.97	2.39	3.171 (3)	137
C5—H5A···O3ⁱⁱⁱ	0.98	2.34	3.317 (3)	173
C6—H6AB···O4^iv	0.98	2.31	3.231 (3)	156
C6—H6A···Cl2ⁱ	0.98	2.80	3.7414 (17)	161
C7—H7B···O3ⁱⁱⁱ	0.97	2.40	3.333 (3)	161

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

Acknowledgements

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

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