Order and disorder in (E)-[1-(biphenyl-4-yl)ethyl­idene]hydrazine: a structural, spectroscopic and theoretical study

An unexpected global disorder (co-existing rotational disorder and glide disorder) has been observed during an X-ray investigation of the crystal structure of (E)-[1-(biphenyl-4-yl)ethyl­idene]hydrazine, C₁₄H₁₄N₂, at room temperature. When the temperature decreases to 273 K, the disorder disappears, but the quality of the data set is low. The diffraction data were collected again at 110 K. Differential scanning calorimetry (DSC) analysis and polarizing-microscopy experiments, as well as a fourth set of single-crystal data collected at 283 K, proved that the order–disorder transformation occurs continuously. The analyses of these crystal structures and full-range relaxed potential energy surface scans showed that this kind of global disorder is not very difficult to achieve inside the crystal. Experimental and theoretical studies via UV–Vis and fluorescence spectra impart an understanding on the prediction methods of optical properties, which are essential for the rational design of biphenyl-based materials with pre-defined properties.

Computing details

For both structures, data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b). Molecular graphics: SHELXTL (Bruker, 2000), PLATON (Spek, 2009) WinGX2014 (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 1999) for o-BEH-110; SHELXTL (Bruker, 2000) and PLATON (Spek, 2009) for dBEH. For both structures, software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).

(E)-[1-(Biphenyl-4-yl)ethylidene]hydrazine (o-BEH-110)

Crystal data

C14H14N2	Dx = 1.264 Mg m^−3
Mr = 210.27	Melting point: 422.7(4) K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.740 (2) Å	Cell parameters from 380 reflections
b = 5.5154 (6) Å	θ = 2.5–26.0°
c = 8.1367 (8) Å	µ = 0.08 mm^−1
β = 95.727 (9)°	T = 110 K
V = 1104.71 (19) Å^3	Plate, colorless
Z = 4	0.6 × 0.4 × 0.05 mm
F(000) = 448

Data collection

Bruker SMART CCD area detector diffractometer	2249 independent reflections
Radiation source: fine-focus sealed tube	1283 reflections with I > 2σ(I)
Detector resolution: 10.10 pixels mm^-1	Rint = 0.036
phi and ω scans	θmax = 26.4°, θmin = 3.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −30→30
Tmin = 0.976, Tmax = 0.991	k = −6→6
6798 measured reflections	l = −10→10

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	All H-atom parameters refined
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0556P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
2249 reflections	Δρmax = 0.13 e Å^−3
201 parameters	Δρmin = −0.15 e Å^−3

Special details

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

The structures were solved by SHELXL-97 [Sheldrick, 2015]. Diagrams and publication material were prepared using PLATON [Spek, 2009]. WinGX-2014 [Farrugia, 2012] and DIAMOND (crystal packing diagram) [Brandenburg & Putz, 1999] were also used.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.87333 (7)	0.6786 (3)	0.4854 (2)	0.0502 (5)
C2	0.92711 (7)	0.6754 (4)	0.5540 (2)	0.0569 (5)
C3	0.94541 (7)	0.4964 (3)	0.6609 (2)	0.0513 (5)
C4	0.91024 (7)	0.3212 (4)	0.7026 (2)	0.0581 (5)
C5	0.85648 (7)	0.3229 (3)	0.6346 (2)	0.0486 (5)
C6	0.83701 (6)	0.5017 (3)	0.52435 (17)	0.0356 (4)
C7	0.77929 (6)	0.5012 (2)	0.44764 (17)	0.0332 (4)
C8	0.74336 (7)	0.3197 (3)	0.4809 (2)	0.0499 (5)
C9	0.69049 (7)	0.3165 (3)	0.4096 (2)	0.0499 (5)
C10	0.67029 (6)	0.4953 (2)	0.30037 (17)	0.0344 (4)
C11	0.70597 (7)	0.6775 (3)	0.2679 (2)	0.0504 (5)
C12	0.75911 (7)	0.6797 (3)	0.3400 (2)	0.0483 (4)
C13	0.61364 (6)	0.4869 (3)	0.21933 (18)	0.0378 (4)
C14	0.59471 (9)	0.6695 (4)	0.0922 (3)	0.0564 (5)
N1	0.58372 (5)	0.3143 (2)	0.26501 (17)	0.0471 (4)
N2	0.53027 (6)	0.3034 (3)	0.1868 (2)	0.0564 (4)
H1	0.8610 (7)	0.808 (3)	0.407 (2)	0.069 (6)*
H2	0.9521 (8)	0.801 (3)	0.525 (2)	0.072 (6)*
H3	0.9819 (8)	0.493 (3)	0.706 (2)	0.069 (5)*
H4	0.9212 (8)	0.199 (3)	0.780 (2)	0.076 (6)*
H5	0.8320 (7)	0.195 (3)	0.662 (2)	0.061 (5)*
H8	0.7540 (8)	0.192 (3)	0.558 (2)	0.077 (6)*
H9	0.6656 (8)	0.184 (3)	0.437 (2)	0.077 (6)*
H11	0.6939 (8)	0.802 (3)	0.192 (2)	0.072 (6)*
H12	0.7813 (7)	0.808 (3)	0.311 (2)	0.068 (6)*
H14A	0.6175 (10)	0.796 (4)	0.084 (3)	0.102 (8)*
H14B	0.5573 (9)	0.726 (3)	0.106 (2)	0.084 (6)*
H14C	0.5906 (9)	0.600 (4)	−0.015 (3)	0.105 (8)*
H15A	0.5151 (7)	0.144 (4)	0.209 (2)	0.069 (6)*
H15B	0.5285 (8)	0.323 (4)	0.079 (3)	0.076 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0435 (10)	0.0475 (11)	0.0577 (10)	−0.0082 (8)	−0.0044 (8)	0.0084 (9)
C2	0.0461 (11)	0.0601 (12)	0.0632 (11)	−0.0162 (9)	−0.0015 (8)	0.0036 (10)
C3	0.0358 (9)	0.0609 (12)	0.0561 (11)	−0.0012 (9)	−0.0013 (8)	−0.0037 (10)
C4	0.0459 (11)	0.0603 (12)	0.0666 (11)	0.0061 (9)	−0.0019 (9)	0.0138 (10)
C5	0.0393 (9)	0.0469 (10)	0.0595 (10)	0.0007 (8)	0.0045 (8)	0.0138 (9)
C6	0.0366 (8)	0.0352 (9)	0.0358 (8)	−0.0003 (7)	0.0080 (6)	−0.0038 (7)
C7	0.0346 (8)	0.0316 (8)	0.0338 (8)	0.0007 (6)	0.0062 (6)	−0.0023 (7)
C8	0.0441 (10)	0.0455 (10)	0.0575 (10)	−0.0072 (8)	−0.0082 (8)	0.0223 (9)
C9	0.0415 (10)	0.0470 (10)	0.0594 (10)	−0.0106 (8)	−0.0035 (8)	0.0171 (9)
C10	0.0349 (8)	0.0344 (8)	0.0346 (8)	0.0017 (7)	0.0072 (6)	−0.0012 (7)
C11	0.0416 (10)	0.0457 (10)	0.0628 (11)	−0.0009 (8)	−0.0011 (8)	0.0190 (9)
C12	0.0383 (9)	0.0439 (10)	0.0620 (10)	−0.0085 (7)	0.0012 (8)	0.0190 (9)
C13	0.0355 (8)	0.0406 (9)	0.0376 (8)	0.0028 (7)	0.0061 (6)	−0.0041 (8)
C14	0.0407 (10)	0.0642 (14)	0.0635 (12)	0.0055 (10)	0.0009 (9)	0.0135 (11)
N1	0.0365 (7)	0.0477 (8)	0.0562 (8)	−0.0025 (6)	−0.0004 (6)	0.0000 (7)
N2	0.0370 (8)	0.0564 (11)	0.0732 (11)	−0.0045 (7)	−0.0074 (7)	−0.0013 (9)

Geometric parameters (Å, º)

C1—C6	1.384 (2)	C9—C10	1.387 (2)
C1—C2	1.391 (2)	C9—H9	0.994 (19)
C1—H1	0.983 (18)	C10—C11	1.380 (2)
C2—C3	1.363 (2)	C10—C13	1.489 (2)
C2—H2	0.973 (19)	C11—C12	1.385 (2)
C3—C4	1.366 (2)	C11—H11	0.950 (19)
C3—H3	0.939 (18)	C12—H12	0.942 (18)
C4—C5	1.389 (2)	C13—N1	1.2835 (18)
C4—H4	0.94 (2)	C13—C14	1.486 (2)
C5—C6	1.387 (2)	C14—H14A	0.91 (2)
C5—H5	0.970 (17)	C14—H14B	0.99 (2)
C6—C7	1.5003 (19)	C14—H14C	0.95 (2)
C7—C12	1.378 (2)	N1—N2	1.4104 (18)
C7—C8	1.383 (2)	N2—H15A	0.98 (2)
C8—C9	1.377 (2)	N2—H15B	0.88 (2)
C8—H8	0.960 (19)
C6—C1—C2	121.06 (17)	C8—C9—H9	119.9 (11)
C6—C1—H1	119.5 (10)	C10—C9—H9	118.3 (11)
C2—C1—H1	119.5 (10)	C11—C10—C9	116.35 (15)
C3—C2—C1	120.60 (17)	C11—C10—C13	121.98 (14)
C3—C2—H2	119.5 (11)	C9—C10—C13	121.64 (13)
C1—C2—H2	119.9 (11)	C10—C11—C12	121.57 (16)
C2—C3—C4	119.46 (17)	C10—C11—H11	119.0 (11)
C2—C3—H3	120.6 (11)	C12—C11—H11	119.4 (11)
C4—C3—H3	120.0 (11)	C7—C12—C11	122.08 (15)
C3—C4—C5	120.32 (18)	C7—C12—H12	120.9 (11)
C3—C4—H4	121.6 (12)	C11—C12—H12	117.0 (11)
C5—C4—H4	118.0 (12)	N1—C13—C14	123.62 (15)
C6—C5—C4	121.31 (16)	N1—C13—C10	116.07 (13)
C6—C5—H5	118.8 (10)	C14—C13—C10	120.30 (14)
C4—C5—H5	119.9 (10)	C13—C14—H14A	114.9 (15)
C1—C6—C5	117.24 (15)	C13—C14—H14B	111.4 (10)
C1—C6—C7	121.23 (14)	H14A—C14—H14B	111.2 (18)
C5—C6—C7	121.52 (13)	C13—C14—H14C	111.4 (14)
C12—C7—C8	116.26 (15)	H14A—C14—H14C	104 (2)
C12—C7—C6	122.19 (13)	H14B—C14—H14C	102.6 (17)
C8—C7—C6	121.56 (13)	C13—N1—N2	116.27 (14)
C9—C8—C7	121.93 (15)	N1—N2—H15A	108.2 (11)
C9—C8—H8	116.8 (12)	N1—N2—H15B	113.3 (13)
C7—C8—H8	121.2 (12)	H15A—N2—H15B	108.3 (17)
C8—C9—C10	121.81 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H15A···N2^i	0.98 (2)	2.39 (2)	3.349 (2)	167.0 (14)

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

(E)-[1-(Biphenyl-4-yl)ethylidene]hydrazine (dBEH)

Crystal data

C14H14N2	Dx = 1.258 Mg m^−3
Mr = 210.27	Melting point: 422.7(4) K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.8153 (19) Å	Cell parameters from 380 reflections
b = 5.5146 (4) Å	θ = 2.5–26.0°
c = 8.1513 (9) Å	µ = 0.08 mm^−1
β = 95.719 (9)°	T = 298 K
V = 1109.92 (17) Å^3	Plate, colorless
Z = 4	0.30 × 0.25 × 0.06 mm
F(000) = 448

Data collection

Bruker SMART CCD area detector diffractometer	2643 independent reflections
Radiation source: fine-focus sealed tube	1328 reflections with I > 2σ(I)
Detector resolution: 10.13 pixels mm^-1	Rint = 0.040
phi and ω scans	θmax = 29.0°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −33→33
Tmin = 0.976, Tmax = 0.991	k = −7→6
7644 measured reflections	l = −7→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.073	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.243	w = 1/[σ^2(Fo^2) + (0.1217P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
2643 reflections	Δρmax = 0.19 e Å^−3
339 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.058 (11)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1A	0.3306 (2)	0.3201 (9)	0.5939 (6)	0.0939 (15)	0.587 (2)
H1A	0.3071	0.1973	0.6191	0.109 (16)*	0.587 (2)
C2A	0.3836 (2)	0.3115 (19)	0.6653 (11)	0.053 (2)	0.587 (2)
H2A	0.3957	0.1847	0.7347	0.16 (2)*	0.587 (2)
C3A	0.41696 (19)	0.4930 (9)	0.6308 (6)	0.0814 (13)	0.587 (2)
H3A	0.4524	0.4955	0.6805	0.12 (3)*	0.587 (2)
C4A	0.3989 (3)	0.6794 (11)	0.5201 (10)	0.0403 (14)	0.587 (2)
H4A	0.4231	0.7971	0.4915	0.34 (8)*	0.587 (2)
C5A	0.3474 (3)	0.6881 (11)	0.4563 (8)	0.1256 (2)	0.587 (2)
H5A	0.3348	0.8171	0.3898	0.13 (2)*	0.587 (2)
C6A	0.3116 (5)	0.493 (3)	0.492 (2)	0.042 (3)	0.587 (2)
C7A	0.2523 (2)	0.4981 (9)	0.4070 (6)	0.0891 (14)	0.587 (2)
C8A	0.2332 (4)	0.6777 (12)	0.3093 (15)	0.045 (2)	0.587 (2)
H8A	0.2553	0.8075	0.2870	0.14 (2)*	0.587 (2)
C9A	0.1797 (2)	0.6680 (10)	0.2410 (6)	0.0942 (15)	0.587 (2)
H9A	0.1668	0.7978	0.1755	0.14 (2)*	0.587 (2)
C10A	0.1435 (4)	0.4789 (19)	0.2625 (8)	0.0257 (11)	0.587 (2)
C11A	0.1625 (3)	0.3111 (11)	0.3787 (8)	0.1095 (18)	0.587 (2)
H11A	0.1393	0.1925	0.4118	0.14 (2)*	0.587 (2)
C12A	0.21717 (15)	0.3166 (7)	0.4487 (6)	0.0325 (9)	0.587 (2)
H12A	0.2297	0.1971	0.5234	0.069 (13)*	0.587 (2)
C13A	0.08530 (18)	0.4874 (8)	0.1799 (5)	0.0786 (12)	0.587 (2)
C14A	0.0682 (7)	0.659 (2)	0.0592 (16)	0.081 (3)	0.587 (2)
H14A	0.0345	0.7287	0.0841	0.095*	0.587 (2)
H14B	0.0632	0.5807	−0.0466	0.16 (2)*	0.587 (2)
H14C	0.0950	0.7836	0.0573	0.098*	0.587 (2)
N1A	0.05682 (7)	0.3088 (3)	0.2274 (3)	0.0319 (6)	0.587 (2)
N2A	0.00263 (15)	0.3039 (9)	0.1401 (6)	0.0851 (12)	0.587 (2)
C1B	0.3822 (6)	0.340 (3)	0.6724 (16)	0.069 (5)	0.413 (2)
H1B	0.3578	0.2284	0.7085	0.14 (3)*	0.413 (2)
C2B	0.4359 (3)	0.3351 (12)	0.7403 (10)	0.088 (2)	0.413 (2)
H2B	0.4473	0.2184	0.8186	0.18 (4)*	0.413 (2)
C3B	0.4719 (2)	0.5008 (7)	0.6927 (5)	0.0451 (12)	0.413 (2)
H3B	0.5085	0.4907	0.7301	0.13 (2)*	0.413 (2)
C4B	0.4527 (3)	0.6842 (11)	0.5873 (8)	0.0784 (17)	0.413 (2)
H4B	0.4751	0.8130	0.5650	0.083 (18)*	0.413 (2)
C5B	0.4051 (8)	0.675 (3)	0.522 (2)	0.103 (5)	0.413 (2)
H5B	0.3947	0.7939	0.4444	0.109*	0.413 (2)
C6B	0.3648 (2)	0.5017 (10)	0.5554 (7)	0.0673 (16)	0.413 (2)
C7B	0.3051 (6)	0.517 (4)	0.483 (3)	0.026 (3)	0.413 (2)
C8B	0.2840 (2)	0.6726 (8)	0.3711 (7)	0.0624 (14)	0.413 (2)
H8B	0.3077	0.7928	0.3425	0.12 (2)*	0.413 (2)
C9B	0.2321 (6)	0.686 (3)	0.289 (3)	0.072 (5)	0.413 (2)
H9B	0.2215	0.8025	0.2106	0.18 (4)*	0.413 (2)
C10B	0.1975 (2)	0.5039 (9)	0.3383 (6)	0.0540 (13)	0.413 (2)
C11B	0.2168 (9)	0.320 (3)	0.436 (2)	0.1518 (7)	0.413 (2)
H11B	0.1948	0.1850	0.4465	0.252*	0.413 (2)
C12B	0.2696 (2)	0.3231 (9)	0.5225 (7)	0.0678 (15)	0.413 (2)
H12B	0.2806	0.2062	0.6010	0.22 (5)*	0.413 (2)
C13B	0.1403 (8)	0.528 (3)	0.2582 (19)	0.060 (5)	0.413 (2)
C14B	0.11061 (16)	0.3231 (7)	0.3007 (6)	0.0457 (11)	0.413 (2)
H14D	0.1102	0.3164	0.4182	0.205*	0.413 (2)
H14E	0.1273	0.1788	0.2632	0.12 (2)*	0.413 (2)
H14F	0.0741	0.3346	0.2495	0.123*	0.413 (2)
N1B	0.12152 (18)	0.6649 (7)	0.1208 (5)	0.0656 (13)	0.413 (2)
N2B	0.0690 (8)	0.727 (3)	0.101 (2)	0.098 (4)	0.413 (2)
H2M	−0.006 (2)	0.417 (11)	0.068 (6)	0.12 (2)*	0.587 (2)
H2N	−0.016 (2)	0.199 (8)	0.171 (6)	0.097 (18)*	0.587 (2)
H2O	0.047 (3)	0.673 (14)	0.174 (11)	0.11 (3)*	0.413 (2)
H2P	0.057 (3)	0.802 (14)	0.013 (10)	0.10 (3)*	0.413 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.085 (3)	0.107 (4)	0.088 (3)	−0.022 (3)	0.000 (3)	0.029 (3)
C2A	0.021 (2)	0.060 (4)	0.075 (5)	0.002 (2)	−0.007 (2)	0.001 (3)
C3A	0.064 (3)	0.094 (3)	0.087 (3)	0.007 (2)	0.011 (2)	−0.012 (3)
C4A	0.032 (2)	0.037 (3)	0.050 (3)	−0.0163 (19)	−0.005 (2)	0.007 (2)
C5A	0.107	0.130	0.139	0.008 (3)	0.012 (4)	0.061 (4)
C6A	0.055 (7)	0.024 (2)	0.051 (5)	0.015 (3)	0.017 (4)	−0.003 (3)
C7A	0.083 (3)	0.084 (3)	0.103 (4)	0.000 (3)	0.023 (3)	−0.019 (3)
C8A	0.056 (5)	0.028 (2)	0.052 (3)	0.004 (3)	0.003 (3)	0.023 (2)
C9A	0.090 (3)	0.100 (4)	0.091 (3)	−0.002 (3)	−0.004 (3)	0.009 (3)
C10A	0.029 (2)	0.019 (3)	0.029 (2)	0.0075 (19)	0.0030 (14)	0.0027 (14)
C11A	0.107 (5)	0.111 (4)	0.110 (4)	−0.011 (4)	0.009 (4)	−0.005 (3)
C12A	0.0202 (12)	0.0282 (14)	0.0471 (18)	−0.0088 (14)	−0.0057 (15)	0.0236 (18)
C13A	0.092 (3)	0.082 (3)	0.063 (3)	−0.001 (2)	0.008 (2)	−0.010 (2)
C14A	0.087 (4)	0.086 (6)	0.069 (6)	−0.007 (4)	0.001 (4)	−0.022 (4)
N1A	0.0156 (9)	0.0306 (11)	0.0472 (13)	−0.0020 (7)	−0.0078 (8)	0.0054 (9)
N2A	0.060 (2)	0.084 (3)	0.107 (3)	−0.0024 (19)	−0.009 (2)	−0.001 (3)
C1B	0.096 (9)	0.045 (5)	0.074 (7)	0.016 (4)	0.054 (6)	0.022 (4)
C2B	0.063 (4)	0.076 (4)	0.117 (5)	0.001 (3)	−0.029 (3)	0.003 (4)
C3B	0.028 (2)	0.054 (3)	0.051 (3)	−0.0027 (16)	−0.0084 (17)	−0.0028 (19)
C4B	0.068 (4)	0.084 (4)	0.082 (4)	−0.019 (3)	−0.003 (3)	0.009 (3)
C5B	0.098 (11)	0.131 (11)	0.083 (10)	0.033 (8)	0.026 (8)	0.016 (8)
C6B	0.065 (4)	0.078 (4)	0.060 (3)	−0.015 (3)	0.013 (3)	−0.015 (3)
C7B	0.011 (2)	0.036 (7)	0.032 (4)	0.000 (4)	0.0003 (19)	0.000 (4)
C8B	0.048 (3)	0.041 (3)	0.099 (4)	−0.001 (2)	0.011 (3)	0.018 (2)
C9B	0.049 (6)	0.098 (8)	0.066 (7)	−0.040 (5)	−0.004 (4)	0.018 (6)
C10B	0.075 (4)	0.045 (3)	0.045 (3)	−0.005 (2)	0.019 (2)	0.010 (2)
C11B	0.159	0.152	0.153	−0.037 (12)	0.059 (10)	−0.032 (12)
C12B	0.063 (3)	0.059 (3)	0.079 (4)	−0.009 (2)	−0.006 (3)	0.029 (3)
C13B	0.051 (5)	0.039 (8)	0.094 (8)	0.019 (4)	0.024 (4)	0.004 (4)
C14B	0.033 (2)	0.038 (2)	0.067 (3)	−0.0043 (17)	0.0081 (19)	−0.0040 (19)
N1B	0.061 (3)	0.066 (3)	0.069 (3)	0.011 (2)	0.006 (2)	0.018 (2)
N2B	0.092 (6)	0.107 (10)	0.095 (10)	0.005 (7)	0.006 (7)	−0.003 (6)

Geometric parameters (Å, º)

C1A—C6A	1.316 (17)	C1B—C2B	1.393 (15)
C1A—C2A	1.386 (9)	C1B—C6B	1.346 (15)
C1A—H1A	0.9300	C1B—H1B	0.9300
C2A—C3A	1.347 (10)	C2B—C3B	1.361 (8)
C2A—H2A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.412 (10)	C3B—C4B	1.381 (8)
C3A—H3A	0.9300	C3B—H3B	0.9300
C4A—C5A	1.330 (10)	C4B—C5B	1.247 (19)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C6A	1.446 (15)	C5B—C6B	1.429 (19)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—C7A	1.565 (14)	C6B—C7B	1.542 (17)
C7A—C8A	1.328 (11)	C7B—C8B	1.32 (2)
C7A—C12A	1.392 (7)	C7B—C12B	1.444 (17)
C8A—C9A	1.390 (11)	C8B—C9B	1.392 (18)
C8A—H8A	0.9300	C8B—H8B	0.9300
C9A—C10A	1.398 (12)	C9B—C10B	1.403 (15)
C9A—H9A	0.9300	C9B—H9B	0.9300
C10A—C11A	1.373 (12)	C10B—C11B	1.35 (2)
C10A—C13A	1.532 (10)	C10B—C13B	1.509 (18)
C11A—C12A	1.419 (8)	C11B—C12B	1.43 (2)
C11A—H11A	0.9300	C11B—H11B	0.9300
C12A—H12A	0.9300	C12B—H12B	0.9300
C13A—N1A	1.294 (4)	C13B—N1B	1.393 (17)
C13A—C14A	1.399 (17)	C13B—C14B	1.409 (18)
C14A—H14A	0.9600	C14B—H14D	0.9600
C14A—H14B	0.9600	C14B—H14E	0.9600
C14A—H14C	0.9600	C14B—H14F	0.9600
N1A—N2A	1.458 (4)	N1B—N2B	1.34 (2)
N2A—H2M	0.87 (5)	N2B—H2O	0.89 (9)
N2A—H2N	0.79 (5)	N2B—H2P	0.86 (8)
C6A—C1A—C2A	123.6 (8)	C2B—C1B—C6B	121.3 (10)
C6A—C1A—H1A	118.2	C2B—C1B—H1B	119.3
C2A—C1A—H1A	118.2	C6B—C1B—H1B	119.3
C3A—C2A—C1A	117.7 (7)	C3B—C2B—C1B	120.3 (8)
C3A—C2A—H2A	121.2	C3B—C2B—H2B	119.9
C1A—C2A—H2A	121.2	C1B—C2B—H2B	119.9
C2A—C3A—C4A	120.8 (5)	C2B—C3B—C4B	118.3 (6)
C2A—C3A—H3A	119.6	C2B—C3B—H3B	120.9
C4A—C3A—H3A	119.6	C4B—C3B—H3B	120.9
C5A—C4A—C3A	120.5 (5)	C3B—C4B—C5B	119.3 (11)
C5A—C4A—H4A	119.7	C3B—C4B—H4B	120.4
C3A—C4A—H4A	119.7	C5B—C4B—H4B	120.4
C4A—C5A—C6A	118.6 (8)	C6B—C5B—C4B	126.7 (17)
C4A—C5A—H5A	120.7	C6B—C5B—H5B	116.7
C6A—C5A—H5A	120.7	C4B—C5B—H5B	116.7
C1A—C6A—C5A	118.6 (10)	C5B—C6B—C1B	113.5 (12)
C1A—C6A—C7A	123.7 (10)	C5B—C6B—C7B	123.6 (12)
C5A—C6A—C7A	117.7 (12)	C1B—C6B—C7B	122.4 (10)
C8A—C7A—C12A	119.2 (6)	C8B—C7B—C12B	115.3 (12)
C8A—C7A—C6A	123.0 (8)	C8B—C7B—C6B	126.9 (11)
C12A—C7A—C6A	117.5 (7)	C12B—C7B—C6B	117.2 (15)
C7A—C8A—C9A	118.8 (7)	C7B—C8B—C9B	130.4 (10)
C7A—C8A—H8A	120.6	C7B—C8B—H8B	114.8
C9A—C8A—H8A	120.6	C9B—C8B—H8B	114.8
C8A—C9A—C10A	125.3 (6)	C8B—C9B—C10B	113.0 (13)
C8A—C9A—H9A	117.3	C8B—C9B—H9B	123.5
C10A—C9A—H9A	117.3	C10B—C9B—H9B	123.5
C11A—C10A—C9A	114.1 (7)	C11B—C10B—C9B	121.0 (12)
C11A—C10A—C13A	124.6 (7)	C11B—C10B—C13B	125.7 (12)
C9A—C10A—C13A	120.7 (7)	C9B—C10B—C13B	113.1 (11)
C10A—C11A—C12A	120.8 (6)	C10B—C11B—C12B	122.5 (15)
C10A—C11A—H11A	119.6	C10B—C11B—H11B	118.8
C12A—C11A—H11A	119.6	C12B—C11B—H11B	118.8
C7A—C12A—C11A	121.0 (4)	C11B—C12B—C7B	116.7 (13)
C7A—C12A—H12A	119.5	C11B—C12B—H12B	121.6
C11A—C12A—H12A	119.5	C7B—C12B—H12B	121.6
N1A—C13A—C14A	126.0 (7)	N1B—C13B—C14B	119.4 (13)
N1A—C13A—C10A	111.3 (5)	N1B—C13B—C10B	128.3 (13)
C14A—C13A—C10A	122.5 (8)	C14B—C13B—C10B	108.5 (11)
C13A—C14A—H14A	109.5	C13B—C14B—H14D	109.5
C13A—C14A—H14B	109.5	C13B—C14B—H14E	109.5
H14A—C14A—H14B	109.5	H14D—C14B—H14E	109.5
C13A—C14A—H14C	109.5	C13B—C14B—H14F	109.5
H14A—C14A—H14C	109.5	H14D—C14B—H14F	109.5
H14B—C14A—H14C	109.5	H14E—C14B—H14F	109.5
C13A—N1A—N2A	111.9 (3)	N2B—N1B—C13B	118.4 (12)
N1A—N2A—H2M	118 (4)	N1B—N2B—H2O	119 (5)
N1A—N2A—H2N	113 (4)	N1B—N2B—H2P	119 (6)
H2M—N2A—H2N	129 (6)	H2O—N2B—H2P	122 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2M···N2A^i	0.87 (5)	2.30 (5)	3.139 (12)	163 (5)
N2A—H2N···N1A^ii	0.79 (5)	2.56 (5)	3.334 (6)	168 (5)
C14A—H14A···N2A^iii	0.96	2.55	3.255 (14)	131
C14A—H14B···N2A^i	0.96	1.85	2.280 (16)	104
C14B—H14F···N2B	0.96	2.47	2.89 (2)	106

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