1,1′-Methyl­enebis{4-[(E)-2-(pyridin-4-yl)ethen­yl]pyridinium} dibromide dihydrate

Neal, H.C.; Nesterov, V.V.; Smucker, B.W.

doi:10.1107/S2414314622005259

organic compounds

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ISSN: 2414-3146

Volume 7| Part 5| May 2022| x220525

https://doi.org/10.1107/S2414314622005259

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1,1′-Methylenebis{4-[(E)-2-(pyridin-4-yl)ethenyl]pyridinium} dibromide dihydrate

Henry C. Neal,^a Volodymyr V. Nesterov ^b and Bradley W. Smucker ^a ^*

^aAustin College, 900 N Grand, Sherman, TX 75090, USA, and ^bDepartment of Chemistry, University of North Texas, 1508 W. Mulberry, Denton, TX, 76201, USA
^*Correspondence e-mail: bsmucker@austincollege.edu

Edited by I. Brito, University of Antofagasta, Chile (Received 27 January 2022; accepted 17 May 2022; online 20 May 2022)

The chevron-shaped cations of the title hydrated salt, C₂₅H₂₂N₄²⁺·2Br⁻·2H₂O, are arranged in back-to-back alternating directions to form a zigzag ribbon propagating along the [010] direction. Intermolecular interactions comprising these ribbons are π–π interactions between the pyridinium and adjacent pyridyl rings, as well as O—H⋯O hydrogen bonding between water molecules and two adjacent pyridyl N atoms. Half of the cation is generated by the mirror plane. The water O atoms, the central C atom and one Br atom are located on this mirror plane while the other Br atom is on a twofold screw axis.

Keywords: crystal structure; pyridinium; hydrogen bonding; π–π interactions.

CCDC reference: 2173317

Structure description

Half of the cation is generated by the mirror plane (x, $[{1\over 2}]$ − y, z). The O1, O2, Br1, and C1 atoms are located on this mirror plane and the Br2 atom is on a twofold screw axis (−x, $[{1\over 2}]$ + y, −z). The pyridyl–vinyl–pyridinium moiety (Fig. 1) is essentially planar with a 1.7 (3)° dihedral angle between the planes of the pyridinium (N1/C2–C6) and pyridyl (N2/C9–C13) rings. The N1—C1—N1(x, $[{1\over 2}]$ − y, z) angle is 110.9 (10)°, which is similar to the N—C—N angles of 111.1 (4) or 112.3 (4)° found in the bromide (Schuster et al. 2022 ) or PF₆⁻ (Blanco et al., 2007 ) salts, respectively, of the 1,1′-methylenebis-4,4′-bipyridinium cation. When two of the title cations are used in a supramolecular cyclic compound with two Pd(ethylenediamine) moieties, the crystal structure had this same N—C—N angle remaining relatively unchanged at 109.1 (19) and 111.2 (11)° (Blanco et al., 2009 ).

Figure 1
Ellipsoid (50%) representation of the title complex with disorder omitted for clarity.

In the extended structure, the chevron-shaped cations of the title compound arrange in back-to-back alternating directions to form a zigzag ribbon (Fig. 2) propagating along the [010] direction. Water molecules are positioned to interact with the terminal pyridyl nitrogen atom, N2, with an N2—H1D( $[{3\over 2}]$ − x, 1 − y, $[{1\over 2}]$ + z) distance of 2.01 Å (Table 1). The distance between back-to-back pyridinium and pyridyl rings [the closest distance between carbon atoms, C6 of the pyridinium and C13(1 − x, 1 − y, 1 − z) of a pyridyl ring, being 3.46 (1) Å (Fig. 2)] is suitable for π–π interactions (Sinnokrot et al., 2002 ), which further consolidate these zigzag ribbons. Water molecules and bromide ions pack between the ribbons (Fig. 3). Other hydrogen-bonded zigzag ribbon structures are observed in 1,3-bis[(tetrahydrofuran-2-yl)methyl]thiourea (Peña et al., 2009 ) or 1-(4-bromophenyl)-3-(4-ethoxyphenyl)prop-2-en-1-one (Fun et al., 2008 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1C⋯N2ⁱ	0.88	2.26	2.880 (11)	128
O1—H1D⋯N2ⁱⁱ	0.88	2.01	2.880 (11)	171
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Figure 2
Zigzag ribbons composed of back-to-back chevron-shaped cations of the title complex. The distance between N2 and H1D( $[{3\over 2}]$ − x, 1 − y, $[{1\over 2}]$ + z) is shown. Ellipsoids at 50% with disorder, bromide ions and some water molecules omitted for clarity.

Figure 3
Ellipsoid (50%) representation of ribbons of cations with bromide ions (brown) and water molecules positioned between them. Ellipsoids at 50% with disorder omitted for clarity.

Synthesis and crystallization

The title compound was synthesized according to published procedures (Blanco et al., 2009). Colorless plates were grown from liquid diffusion of tetrahydrofuran into a dimethylformamide solution of the pyridinium bromide salt.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Disorder of the 4-[(E)-2-(pyridin-4-yl)ethenyl]pyridinium moiety was refined using `PART 1' and `PART 2' with the ratio of occupancies at 47 and 53%. All our attempts to refine the structure to achieve equal occupancies led to a drastic worsening of R1 and wR2 values.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₅H₂₂N₄²⁺·2Br⁻·2H₂O
M_r	574.32
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	220
a, b, c (Å)	15.4863 (2), 22.2936 (3), 7.2100 (1)
V (Å³)	2489.22 (6)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	4.37
Crystal size (mm)	0.04 × 0.03 × 0.02

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.671, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	25704, 2780, 2439
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.104, 1.09
No. of reflections	2780
No. of parameters	244
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.99, −0.86
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2173317

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622005259/bx4021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622005259/bx4021Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622005259/bx4021Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2414314622005259/bx4021Isup4.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) Mercury (Macrae et al., 2020); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

1,1'-Methylenebis{4-[(E)-2-(pyridin-4-yl)ethenyl]pyridinium} dibromide dihydrate top

Crystal data top

C₂₅H₂₂N₄²⁺·2Br⁻·2H₂O	D_x = 1.532 Mg m⁻³
M_r = 574.32	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pnma	Cell parameters from 14220 reflections
a = 15.4863 (2) Å	θ = 6.1–79.8°
b = 22.2936 (3) Å	µ = 4.37 mm⁻¹
c = 7.2100 (1) Å	T = 220 K
V = 2489.22 (6) Å³	Plate, clear light colourless
Z = 4	0.04 × 0.03 × 0.02 mm
F(000) = 1160

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	2780 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2439 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.030
Detector resolution: 10.0000 pixels mm^-1	θ_max = 80.3°, θ_min = 4.0°
ω scans	h = −17→19
Absorption correction: multi-scan CrysAlisPro (Rigaku OD, 2021)	k = −28→27
T_min = 0.671, T_max = 1.000	l = −9→9
25704 measured reflections

Refinement top

Refinement on F²	8 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0464P)² + 1.8748P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2780 reflections	Δρ_max = 0.99 e Å⁻³
244 parameters	Δρ_min = −0.86 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	Occ. (<1)
Br1	0.83013 (2)	0.250000	0.51496 (5)	0.05780 (16)
Br2	0.500000	0.500000	0.000000	0.06787 (19)
O1	0.59949 (18)	0.250000	−0.0276 (5)	0.0644 (5)
H1C	0.628097	0.228712	0.053830	0.097*	0.5
H1D	0.637353	0.279127	−0.030494	0.097*	0.5
O2	0.61749 (17)	0.250000	0.5693 (5)	0.0644 (5)
H2B	0.666046	0.234075	0.534382	0.097*	0.5
H2C	0.616243	0.229500	0.676421	0.097*	0.5
N1	0.4441 (7)	0.3047 (4)	0.4944 (11)	0.0280 (19)	0.471 (7)
C2	0.4622 (7)	0.3261 (4)	0.6635 (9)	0.0336 (16)	0.471 (7)
H2	0.441055	0.306491	0.769534	0.040*	0.471 (7)
C3	0.5120 (5)	0.3769 (3)	0.6814 (7)	0.0338 (14)	0.471 (7)
H3	0.523534	0.392117	0.800374	0.041*	0.471 (7)
C4	0.5451 (3)	0.4059 (2)	0.5289 (9)	0.0259 (12)	0.471 (7)
C5	0.5254 (4)	0.3821 (3)	0.3578 (7)	0.0355 (15)	0.471 (7)
H5	0.546674	0.400906	0.250362	0.043*	0.471 (7)
C6	0.4753 (6)	0.3316 (4)	0.3410 (8)	0.0375 (17)	0.471 (7)
H6	0.462840	0.315841	0.223042	0.045*	0.471 (7)
N2	0.7822 (9)	0.6508 (4)	0.5018 (14)	0.048 (3)	0.471 (7)
C11	0.7660 (7)	0.6282 (4)	0.3350 (11)	0.0430 (17)	0.471 (7)
H11	0.788849	0.647826	0.230565	0.052*	0.471 (7)
C10	0.7170 (5)	0.5769 (3)	0.3083 (8)	0.0383 (15)	0.471 (7)
H10	0.707421	0.562561	0.187380	0.046*	0.471 (7)
C9	0.6822 (3)	0.54692 (19)	0.4566 (10)	0.0301 (12)	0.471 (7)
C13	0.6980 (5)	0.5710 (3)	0.6290 (8)	0.0394 (16)	0.471 (7)
H13	0.674916	0.552711	0.735506	0.047*	0.471 (7)
C12	0.7480 (8)	0.6224 (4)	0.6452 (10)	0.050 (2)	0.471 (7)
H12	0.758017	0.637927	0.764548	0.060*	0.471 (7)
C1	0.39067 (17)	0.250000	0.4756 (4)	0.0281 (5)
C7	0.5974 (3)	0.4592 (2)	0.5575 (7)	0.0328 (12)	0.471 (7)
H7	0.608461	0.470689	0.680642	0.039*	0.471 (7)
C8	0.6307 (3)	0.4929 (2)	0.4239 (6)	0.0321 (13)	0.471 (7)
H8	0.620576	0.481388	0.300419	0.038*	0.471 (7)
C8A	0.6252 (3)	0.4946 (2)	0.5660 (6)	0.0352 (12)	0.529 (7)
H8A	0.604322	0.485675	0.685211	0.042*	0.529 (7)
C7A	0.6033 (3)	0.4578 (2)	0.4290 (6)	0.0330 (11)	0.529 (7)
H7A	0.624114	0.466670	0.309581	0.040*	0.529 (7)
N1A	0.4453 (6)	0.3041 (3)	0.4673 (9)	0.0244 (15)	0.529 (7)
C2A	0.4791 (5)	0.3212 (3)	0.3033 (8)	0.0290 (12)	0.529 (7)
H2A	0.467537	0.298861	0.195459	0.035*	0.529 (7)
C3A	0.5305 (3)	0.3713 (2)	0.2945 (6)	0.0307 (12)	0.529 (7)
H3A	0.553479	0.383222	0.179661	0.037*	0.529 (7)
C4A	0.5489 (3)	0.40443 (19)	0.4506 (8)	0.0264 (11)	0.529 (7)
C5A	0.5131 (4)	0.3853 (3)	0.6147 (7)	0.0341 (13)	0.529 (7)
H5A	0.523793	0.407169	0.723830	0.041*	0.529 (7)
C6A	0.4621 (6)	0.3349 (3)	0.6226 (7)	0.0323 (13)	0.529 (7)
H6A	0.439049	0.322149	0.736540	0.039*	0.529 (7)
N2A	0.7859 (8)	0.6497 (4)	0.5226 (13)	0.052 (3)	0.529 (7)
C11A	0.7539 (7)	0.6311 (4)	0.6829 (10)	0.0468 (16)	0.529 (7)
H11A	0.767754	0.652790	0.790561	0.056*	0.529 (7)
C10A	0.7011 (4)	0.5811 (3)	0.7003 (7)	0.0401 (14)	0.529 (7)
H10A	0.680077	0.569719	0.817495	0.048*	0.529 (7)
C9A	0.6796 (3)	0.54816 (18)	0.5456 (9)	0.0325 (11)	0.529 (7)
C13A	0.7118 (4)	0.5682 (3)	0.3798 (8)	0.0442 (15)	0.529 (7)
H13A	0.698343	0.547622	0.269787	0.053*	0.529 (7)
C12A	0.7641 (7)	0.6187 (4)	0.3728 (10)	0.054 (2)	0.529 (7)
H12A	0.785018	0.631399	0.256891	0.065*	0.529 (7)
H1A	0.359 (2)	0.250000	0.584 (4)	0.025 (7)*
H1B	0.363 (2)	0.250000	0.372 (5)	0.036 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0341 (2)	0.1080 (4)	0.03128 (19)	0.000	0.00029 (12)	0.000
Br2	0.1255 (5)	0.0507 (2)	0.0274 (2)	0.0236 (2)	0.00356 (18)	0.00004 (13)
O1	0.0401 (9)	0.0554 (10)	0.0978 (16)	0.000	−0.0060 (10)	0.000
O2	0.0401 (9)	0.0554 (10)	0.0978 (16)	0.000	−0.0060 (10)	0.000
N1	0.023 (3)	0.025 (4)	0.036 (3)	0.001 (3)	0.004 (2)	0.007 (3)
C2	0.045 (3)	0.030 (3)	0.025 (3)	−0.006 (3)	0.007 (3)	−0.003 (2)
C3	0.046 (3)	0.033 (3)	0.022 (3)	−0.006 (2)	0.003 (3)	−0.008 (3)
C4	0.029 (2)	0.023 (2)	0.026 (3)	0.0000 (16)	0.002 (2)	−0.004 (3)
C5	0.048 (3)	0.033 (3)	0.025 (4)	−0.002 (2)	0.008 (3)	0.008 (3)
C6	0.051 (4)	0.036 (3)	0.026 (3)	−0.003 (3)	−0.010 (3)	−0.004 (3)
N2	0.039 (6)	0.025 (6)	0.078 (6)	0.000 (5)	0.003 (5)	0.007 (5)
C11	0.042 (3)	0.028 (3)	0.060 (4)	−0.005 (2)	0.005 (3)	0.006 (3)
C10	0.040 (3)	0.035 (3)	0.040 (4)	−0.002 (2)	0.004 (3)	−0.001 (3)
C9	0.028 (2)	0.023 (2)	0.039 (4)	0.0008 (16)	0.001 (3)	0.001 (3)
C13	0.040 (3)	0.036 (4)	0.042 (4)	−0.004 (2)	0.000 (3)	0.001 (3)
C12	0.052 (4)	0.032 (3)	0.065 (5)	−0.001 (3)	−0.014 (4)	−0.011 (3)
C1	0.0243 (12)	0.0240 (11)	0.0360 (14)	0.000	−0.0007 (11)	0.000
C7	0.033 (2)	0.027 (3)	0.038 (3)	−0.0030 (19)	0.0006 (18)	−0.0038 (17)
C8	0.032 (2)	0.028 (3)	0.035 (3)	−0.0021 (19)	−0.0027 (17)	−0.0009 (16)
C8A	0.0346 (19)	0.032 (2)	0.039 (3)	−0.0033 (18)	0.0025 (16)	0.0023 (16)
C7A	0.0326 (19)	0.029 (2)	0.037 (2)	−0.0024 (17)	0.0024 (15)	0.0007 (16)
N1A	0.026 (3)	0.022 (3)	0.026 (2)	0.000 (2)	−0.004 (2)	−0.004 (2)
C2A	0.034 (2)	0.032 (3)	0.022 (2)	−0.008 (2)	0.0000 (18)	0.0004 (19)
C3A	0.032 (2)	0.034 (2)	0.026 (3)	−0.0048 (18)	0.004 (2)	0.003 (2)
C4A	0.0276 (18)	0.027 (2)	0.024 (3)	0.0010 (14)	−0.001 (2)	−0.008 (2)
C5A	0.047 (3)	0.032 (3)	0.024 (3)	−0.002 (2)	0.000 (3)	−0.008 (3)
C6A	0.039 (3)	0.034 (3)	0.023 (3)	0.001 (2)	0.006 (2)	−0.002 (2)
N2A	0.041 (5)	0.033 (6)	0.081 (5)	−0.010 (5)	−0.001 (5)	−0.007 (5)
C11A	0.045 (3)	0.035 (3)	0.061 (4)	−0.006 (2)	−0.007 (3)	−0.007 (3)
C10A	0.042 (2)	0.034 (3)	0.044 (3)	−0.001 (2)	−0.006 (3)	0.000 (3)
C9A	0.0290 (19)	0.028 (2)	0.041 (3)	0.0021 (16)	−0.001 (2)	−0.003 (3)
C13A	0.053 (3)	0.037 (3)	0.042 (4)	−0.007 (2)	0.005 (3)	−0.005 (3)
C12A	0.058 (4)	0.036 (3)	0.068 (5)	−0.005 (3)	0.017 (4)	0.003 (3)

Geometric parameters (Å, º) top

O1—H1C	0.8753	C1—N1Aⁱ	1.474 (4)
O1—H1Cⁱ	0.88 (6)	C1—H1A	0.92 (3)
O1—H1D	0.8752	C1—H1B	0.86 (4)
O1—H1Dⁱ	0.88 (8)	C7—H7	0.9400
O2—H2B	0.8688	C7—C8	1.326 (7)
O2—H2Bⁱ	0.87 (5)	C8—H8	0.9400
O2—H2C	0.8975	C8A—H8A	0.9400
O2—H2Cⁱ	0.90 (6)	C8A—C7A	1.328 (6)
N1—C2	1.3385	C8A—C9A	1.468 (6)
N1—C6	1.3481	C7A—H7A	0.9400
N1—C1	1.480 (5)	C7A—C4A	1.467 (7)
C2—H2	0.9400	N1A—C2A	1.3482
C2—C3	1.3755	N1A—C6A	1.3387
C3—H3	0.9400	C2A—H2A	0.9400
C3—C4	1.3742	C2A—C3A	1.3735
C4—C5	1.3759	C3A—H3A	0.9400
C4—C7	1.453 (7)	C3A—C4A	1.3761
C5—H5	0.9400	C4A—C5A	1.3737
C5—C6	1.3734	C5A—H5A	0.9400
C6—H6	0.9400	C5A—C6A	1.3753
N2—C11	1.3275	C6A—H6A	0.9400
N2—C12	1.3235	N2A—C11A	1.3241
C11—H11	0.9400	N2A—C12A	1.3271
C11—C10	1.3868	C11A—H11A	0.9400
C10—H10	0.9400	C11A—C10A	1.3883
C10—C9	1.3715	C10A—H10A	0.9400
C9—C13	1.3756	C10A—C9A	1.3758
C9—C8	1.464 (7)	C9A—C13A	1.3709
C13—H13	0.9400	C13A—H13A	0.9400
C13—C12	1.3883	C13A—C12A	1.3864
C12—H12	0.9400	C12A—H12A	0.9400
C1—N1A	1.474 (4)

H1C—O1—H1Cⁱ	65.7	N1A—C1—H1A	110.0 (10)
H1Cⁱ—O1—H1Dⁱ	94.5	N1Aⁱ—C1—H1A	110.0 (10)
H1C—O1—H1Dⁱ	43.5	N1Aⁱ—C1—H1B	104.5 (13)
H1C—O1—H1D	94.5	N1A—C1—H1B	104.5 (13)
H1D—O1—H1Cⁱ	43.5	H1A—C1—H1B	118 (3)
H1D—O1—H1Dⁱ	95.8	C4—C7—H7	117.4
H2B—O2—H2Bⁱ	48.2	C8—C7—C4	125.3 (6)
H2Bⁱ—O2—H2Cⁱ	93.4	C8—C7—H7	117.4
H2B—O2—H2Cⁱ	118.4	C9—C8—H8	117.9
H2B—O2—H2C	93.4	C7—C8—C9	124.2 (5)
H2C—O2—H2Bⁱ	118.4	C7—C8—H8	117.9
H2C—O2—H2Cⁱ	61.2	C7A—C8A—H8A	117.5
C2—N1—C6	120.9	C7A—C8A—C9A	125.1 (5)
C2—N1—C1	119.6 (5)	C9A—C8A—H8A	117.5
C6—N1—C1	119.4 (5)	C8A—C7A—H7A	117.7
N1—C2—H2	120.1	C8A—C7A—C4A	124.7 (5)
N1—C2—C3	119.8	C4A—C7A—H7A	117.7
C3—C2—H2	120.1	C2A—N1A—C1	119.3 (4)
C2—C3—H3	119.3	C6A—N1A—C1	119.8 (4)
C4—C3—C2	121.4	C6A—N1A—C2A	120.9
C4—C3—H3	119.3	N1A—C2A—H2A	120.2
C3—C4—C5	117.0	N1A—C2A—C3A	119.7
C3—C4—C7	118.6 (4)	C3A—C2A—H2A	120.2
C5—C4—C7	124.4 (4)	C2A—C3A—H3A	119.4
C4—C5—H5	119.4	C2A—C3A—C4A	121.3
C6—C5—C4	121.3	C4A—C3A—H3A	119.4
C6—C5—H5	119.4	C3A—C4A—C7A	117.9 (4)
N1—C6—C5	119.7	C5A—C4A—C7A	125.1 (4)
N1—C6—H6	120.2	C5A—C4A—C3A	117.0
C5—C6—H6	120.2	C4A—C5A—H5A	119.3
C12—N2—C11	116.8	C4A—C5A—C6A	121.4
N2—C11—H11	118.6	C6A—C5A—H5A	119.3
N2—C11—C10	122.9	N1A—C6A—C5A	119.8
C10—C11—H11	118.6	N1A—C6A—H6A	120.1
C11—C10—H10	119.7	C5A—C6A—H6A	120.1
C9—C10—C11	120.6	C11A—N2A—C12A	116.8
C9—C10—H10	119.7	N2A—C11A—H11A	118.2
C10—C9—C13	116.4	N2A—C11A—C10A	123.5
C10—C9—C8	119.3 (5)	C10A—C11A—H11A	118.2
C13—C9—C8	124.3 (5)	C11A—C10A—H10A	120.1
C9—C13—H13	120.1	C9A—C10A—C11A	119.8
C9—C13—C12	119.8	C9A—C10A—H10A	120.1
C12—C13—H13	120.1	C10A—C9A—C8A	119.4 (4)
N2—C12—C13	123.5	C13A—C9A—C8A	124.2 (4)
N2—C12—H12	118.2	C13A—C9A—C10A	116.4
C13—C12—H12	118.2	C9A—C13A—H13A	119.7
N1ⁱ—C1—N1	110.9 (10)	C9A—C13A—C12A	120.6
N1—C1—H1A	102.9 (11)	C12A—C13A—H13A	119.7
N1ⁱ—C1—H1A	102.9 (11)	N2A—C12A—C13A	122.8
N1—C1—H1B	110.9 (11)	N2A—C12A—H12A	118.6
N1ⁱ—C1—H1B	110.9 (11)	C13A—C12A—H12A	118.6
N1A—C1—N1Aⁱ	109.8 (9)

N1—C2—C3—C4	−1.2	C7—C4—C5—C6	−179.8 (6)
C2—N1—C6—C5	−0.9	C8—C9—C13—C12	179.8 (6)
C2—N1—C1—N1ⁱ	−84.1 (7)	C8A—C7A—C4A—C3A	178.8 (4)
C2—C3—C4—C5	0.7	C8A—C7A—C4A—C5A	0.2 (6)
C2—C3—C4—C7	−179.8 (6)	C8A—C9A—C13A—C12A	−178.8 (6)
C3—C4—C5—C6	−0.3	C7A—C8A—C9A—C10A	−176.9 (4)
C3—C4—C7—C8	−177.3 (5)	C7A—C8A—C9A—C13A	2.7 (7)
C4—C5—C6—N1	0.4	C7A—C4A—C5A—C6A	179.4 (5)
C4—C7—C8—C9	179.1 (4)	N1Aⁱ—C1—N1A—C2A	76.4 (7)
C5—C4—C7—C8	2.2 (7)	N1Aⁱ—C1—N1A—C6A	−102.3 (5)
C6—N1—C2—C3	1.3	N1A—C2A—C3A—C4A	0.5
C6—N1—C1—N1ⁱ	94.7 (7)	C2A—N1A—C6A—C5A	1.2
N2—C11—C10—C9	0.2	C2A—C3A—C4A—C7A	−179.2 (5)
C11—N2—C12—C13	0.7	C2A—C3A—C4A—C5A	−0.5
C11—C10—C9—C13	0.8	C3A—C4A—C5A—C6A	0.8
C11—C10—C9—C8	180.0 (6)	C4A—C5A—C6A—N1A	−1.2
C10—C9—C13—C12	−1.1	C6A—N1A—C2A—C3A	−0.9
C10—C9—C8—C7	177.0 (5)	N2A—C11A—C10A—C9A	0.0
C9—C13—C12—N2	0.3	C11A—N2A—C12A—C13A	−1.1
C13—C9—C8—C7	−3.9 (7)	C11A—C10A—C9A—C8A	178.7 (6)
C12—N2—C11—C10	−1.0	C11A—C10A—C9A—C13A	−1.0
C1—N1—C2—C3	180.0 (10)	C10A—C9A—C13A—C12A	0.8
C1—N1—C6—C5	−179.6 (9)	C9A—C8A—C7A—C4A	−180.0 (4)
C1—N1A—C2A—C3A	−179.6 (8)	C9A—C13A—C12A—N2A	0.2
C1—N1A—C6A—C5A	179.9 (8)	C12A—N2A—C11A—C10A	1.0

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···N2ⁱⁱ	0.88	2.26	2.880 (11)	128
O1—H1D···N2ⁱⁱⁱ	0.88	2.01	2.880 (11)	171

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

Funding information

Funding for this research was provided by: National Science Foundation (grant No. 1726652 to UNT; grant No. 1712066 to Austin College); Welch Foundation (grant No. AD-0007 to Austin College).

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