Theoretical insight into the disordered structure of (Z)-2-[(E)-(4-meth­oxy­benzyl­idene)hydrazinyl­idene]-1,2-di­phenyl­ethanone: the role of noncovalent inter­actions

Tan, X.-J.; Wang, D.; Lei, X.-G.; Chen, J.-P.

doi:10.1107/S2053229618009762

Theoretical insight into the disordered structure of (Z)-2-[(E)-(4-methoxybenzylidene)hydrazinylidene]-1,2-diphenylethanone: the role of noncovalent interactions

X.-J. Tan, D. Wang, X.-G. Lei and J.-P. Chen

A global glide disorder has been discovered during an X-ray investigation of the crystal structure of (Z)-2-[(E)-(4-methoxybenzylidene)hydrazinylidene]-1,2-diphenylethanone (MHDE, C₂₂H₁₈N₂O₂) at room temperature. In another crystal, however, such disorder disappears (still at room temperature). Even though the disorder may be partly due to the poor quality of the harvested crystal, the structure can shed light on the nature of disorder. With the help of quantum chemical calculations, it is found that the global disorder seems to be connected with the need for stabilization of the somewhat rigid but mobile and unstable molecular structure. The most relevant feature driving the packing of the disordered structure concerns the slight perturbations (such as glide) of two or more disorder components (fractional occupancies) distributed throughout the crystal.

Keywords: global disorder; noncovalent interactions; crystal structure; quantum calculation.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618009762/jx3017sup1.cif Contains datablocks o-MHDE, d-MHDE, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618009762/jx3017o-MHDEsup2.hkl Contains datablock shelx
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618009762/jx3017d-MHDEsup3.hkl Contains datablock shelx
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618009762/jx3017MHDEsup4.cml Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618009762/jx3017sup5.pdf Comparison geometry tables and additional figures

CCDC references: 1854547; 1854546

Computing details top

For both structures, data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXT2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2000), PLATON (Spek, 2009), DIAMOND (Brandenburg & Putz, 2005) and ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).

(Z)-2-[(E)-(4-Methoxybenzylidene)hydrazinylidene]-1,2-diphenylethanone (o-MHDE) top

Crystal data top

C₂₂H₁₈N₂O₂	D_x = 1.215 Mg m⁻³
M_r = 342.38	Melting point: 419.4(2) K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.2650 (6) Å	Cell parameters from 380 reflections
b = 8.0342 (5) Å	θ = 2.5–26.0°
c = 23.4156 (13) Å	µ = 0.08 mm⁻¹
β = 102.512 (6)°	T = 298 K
V = 1885.2 (2) Å³	Block, yellow
Z = 4	0.35 × 0.25 × 0.25 mm
F(000) = 720

Data collection top

Bruker SMART CCD area-detector diffractometer	4429 independent reflections
Radiation source: fine-focus sealed tube	3156 reflections with I > 2σ(I)
Detector resolution: 10.13 pixels mm^-1	R_int = 0.020
phi and ω scans	θ_max = 29.0°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
T_min = 0.903, T_max = 0.939	k = −9→10
11966 measured reflections	l = −19→29

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.048	w = 1/[σ²(F_o²) + (0.0578P)² + 0.2286P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.136	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.14 e Å⁻³
4429 reflections	Δρ_min = −0.14 e Å⁻³
308 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0045 (8)

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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.29248 (15)	0.6837 (2)	0.43897 (7)	0.0687 (4)
C2	0.40120 (17)	0.6784 (3)	0.48403 (8)	0.0794 (5)
C3	0.51822 (15)	0.7607 (2)	0.48022 (7)	0.0706 (4)
C4	0.52559 (16)	0.8467 (2)	0.43041 (7)	0.0751 (5)
C5	0.41464 (15)	0.8525 (2)	0.38465 (7)	0.0732 (4)
C6	0.29655 (14)	0.77307 (18)	0.38818 (6)	0.0590 (3)
C7	0.17926 (15)	0.7869 (2)	0.34088 (6)	0.0627 (4)
C8	−0.14713 (13)	0.70224 (17)	0.30534 (5)	0.0543 (3)
C9	−0.27222 (14)	0.72320 (17)	0.26105 (6)	0.0587 (3)
C10	−0.27329 (18)	0.8065 (2)	0.20879 (7)	0.0754 (4)
C11	−0.3914 (2)	0.8235 (3)	0.16739 (8)	0.0901 (6)
C12	−0.5081 (2)	0.7576 (3)	0.17737 (9)	0.0887 (6)
C13	−0.50850 (19)	0.6764 (3)	0.22852 (9)	0.0892 (5)
C14	−0.39152 (16)	0.6597 (2)	0.27028 (8)	0.0754 (4)
C15	−0.15335 (13)	0.62706 (18)	0.36447 (5)	0.0547 (3)
C16	−0.12561 (11)	0.44760 (16)	0.37484 (5)	0.0513 (3)
C17	−0.09552 (15)	0.34514 (19)	0.33190 (7)	0.0639 (4)
C18	−0.07578 (19)	0.1767 (2)	0.34192 (9)	0.0813 (5)
C19	−0.0837 (2)	0.1104 (2)	0.39488 (10)	0.0890 (5)
C20	−0.1102 (2)	0.2108 (3)	0.43833 (10)	0.0897 (6)
C21	−0.13144 (16)	0.3790 (2)	0.42878 (7)	0.0707 (4)
C22	0.7400 (2)	0.8338 (4)	0.52974 (11)	0.1036 (8)
N1	0.06922 (12)	0.72182 (16)	0.34438 (5)	0.0628 (3)
N2	−0.03509 (12)	0.75292 (15)	0.29555 (5)	0.0624 (3)
O1	0.61916 (12)	0.74650 (19)	0.52825 (5)	0.0973 (4)
O2	−0.18530 (13)	0.71734 (14)	0.40079 (5)	0.0808 (4)
H1	0.2098 (16)	0.624 (2)	0.4419 (7)	0.080 (5)*
H2	0.4010 (18)	0.613 (3)	0.5184 (8)	0.101 (6)*
H4	0.6030 (17)	0.906 (2)	0.4256 (7)	0.086 (5)*
H5	0.4160 (16)	0.914 (2)	0.3492 (7)	0.086 (5)*
H7	0.1869 (15)	0.857 (2)	0.3076 (7)	0.083 (5)*
H10	−0.1906 (17)	0.851 (2)	0.2028 (7)	0.087 (5)*
H11	−0.389 (2)	0.881 (3)	0.1313 (9)	0.119 (7)*
H12	−0.593 (2)	0.762 (2)	0.1488 (9)	0.108 (6)*
H13	−0.590 (2)	0.630 (3)	0.2360 (8)	0.108 (6)*
H14	−0.3914 (17)	0.602 (2)	0.3054 (8)	0.088 (5)*
H17	−0.0885 (15)	0.394 (2)	0.2933 (7)	0.076 (4)*
H18	−0.060 (2)	0.105 (3)	0.3109 (9)	0.117 (7)*
H19	−0.071 (2)	−0.004 (3)	0.4040 (9)	0.122 (7)*
H20	−0.110 (2)	0.169 (3)	0.4744 (9)	0.113 (7)*
H21	−0.1472 (16)	0.453 (2)	0.4576 (7)	0.082 (5)*
H22A	0.790 (3)	0.805 (3)	0.5676 (12)	0.134 (9)*
H22B	0.726 (3)	0.965 (5)	0.5259 (14)	0.196 (15)*
H22C	0.787 (2)	0.794 (3)	0.5006 (10)	0.121 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0637 (8)	0.0801 (11)	0.0644 (9)	−0.0097 (7)	0.0186 (7)	0.0098 (8)
C2	0.0738 (10)	0.0981 (13)	0.0655 (9)	−0.0077 (9)	0.0137 (8)	0.0169 (9)
C3	0.0627 (8)	0.0847 (11)	0.0630 (9)	0.0002 (7)	0.0106 (7)	−0.0063 (8)
C4	0.0621 (8)	0.0922 (12)	0.0752 (10)	−0.0151 (8)	0.0240 (7)	−0.0046 (9)
C5	0.0701 (9)	0.0912 (12)	0.0627 (9)	−0.0095 (8)	0.0242 (7)	0.0077 (8)
C6	0.0613 (8)	0.0641 (8)	0.0552 (7)	−0.0022 (6)	0.0206 (6)	−0.0001 (6)
C7	0.0661 (8)	0.0712 (9)	0.0547 (8)	−0.0022 (7)	0.0215 (6)	0.0069 (7)
C8	0.0622 (7)	0.0518 (7)	0.0509 (7)	0.0012 (6)	0.0167 (6)	−0.0004 (6)
C9	0.0645 (8)	0.0544 (8)	0.0572 (8)	0.0061 (6)	0.0134 (6)	−0.0012 (6)
C10	0.0772 (10)	0.0876 (12)	0.0613 (9)	0.0069 (9)	0.0150 (8)	0.0078 (8)
C11	0.0994 (14)	0.1025 (15)	0.0632 (10)	0.0230 (11)	0.0066 (9)	0.0096 (10)
C12	0.0768 (12)	0.0915 (14)	0.0875 (13)	0.0196 (10)	−0.0051 (10)	−0.0092 (11)
C13	0.0658 (10)	0.0922 (14)	0.1046 (15)	0.0019 (9)	0.0078 (10)	−0.0003 (11)
C14	0.0673 (9)	0.0778 (11)	0.0802 (11)	−0.0005 (8)	0.0142 (8)	0.0096 (9)
C15	0.0592 (7)	0.0573 (8)	0.0505 (7)	−0.0039 (6)	0.0179 (6)	−0.0043 (6)
C16	0.0495 (6)	0.0563 (8)	0.0486 (6)	−0.0070 (5)	0.0113 (5)	−0.0008 (6)
C17	0.0763 (9)	0.0592 (9)	0.0556 (8)	0.0000 (7)	0.0131 (7)	−0.0052 (7)
C18	0.0979 (12)	0.0590 (10)	0.0852 (12)	0.0013 (8)	0.0163 (9)	−0.0109 (9)
C19	0.0976 (12)	0.0562 (10)	0.1142 (15)	−0.0046 (9)	0.0247 (11)	0.0098 (11)
C20	0.1058 (14)	0.0816 (13)	0.0883 (13)	−0.0025 (10)	0.0354 (11)	0.0284 (11)
C21	0.0839 (10)	0.0703 (11)	0.0644 (9)	−0.0030 (8)	0.0304 (8)	0.0065 (8)
C22	0.0668 (11)	0.161 (3)	0.0821 (14)	−0.0163 (13)	0.0129 (10)	−0.0327 (15)
N1	0.0626 (7)	0.0693 (8)	0.0565 (7)	−0.0049 (5)	0.0132 (5)	0.0087 (6)
N2	0.0650 (7)	0.0700 (8)	0.0530 (6)	0.0000 (6)	0.0141 (5)	0.0085 (6)
O1	0.0747 (8)	0.1313 (12)	0.0787 (8)	−0.0115 (7)	0.0012 (6)	0.0027 (7)
O2	0.1151 (9)	0.0683 (7)	0.0697 (7)	0.0051 (6)	0.0435 (6)	−0.0085 (5)

Geometric parameters (Å, º) top

C1—C2	1.360 (2)	C12—C13	1.365 (3)
C1—C6	1.398 (2)	C12—H12	0.98 (2)
C1—H1	0.991 (17)	C13—C14	1.381 (2)
C2—C3	1.391 (2)	C13—H13	0.96 (2)
C2—H2	0.96 (2)	C14—H14	0.944 (18)
C3—O1	1.3589 (18)	C15—O2	1.2156 (15)
C3—C4	1.372 (2)	C15—C16	1.4794 (19)
C4—C5	1.385 (2)	C16—C17	1.3850 (18)
C4—H4	0.953 (18)	C16—C21	1.3911 (19)
C5—C6	1.388 (2)	C17—C18	1.381 (2)
C5—H5	0.971 (18)	C17—H17	1.004 (16)
C6—C7	1.453 (2)	C18—C19	1.368 (3)
C7—N1	1.2635 (19)	C18—H18	0.97 (2)
C7—H7	0.978 (18)	C19—C20	1.371 (3)
C8—N2	1.2865 (17)	C19—H19	0.95 (3)
C8—C9	1.4751 (19)	C20—C21	1.380 (3)
C8—C15	1.5245 (18)	C20—H20	0.91 (2)
C9—C14	1.386 (2)	C21—H21	0.942 (17)
C9—C10	1.393 (2)	C22—O1	1.419 (3)
C10—C11	1.385 (2)	C22—H22A	0.95 (3)
C10—H10	0.959 (18)	C22—H22B	1.07 (4)
C11—C12	1.375 (3)	C22—H22C	0.97 (3)
C11—H11	0.97 (2)	N1—N2	1.4092 (16)

C2—C1—C6	120.35 (15)	C12—C13—C14	120.02 (19)
C2—C1—H1	120.1 (9)	C12—C13—H13	120.8 (12)
C6—C1—H1	119.5 (9)	C14—C13—H13	119.2 (12)
C1—C2—C3	120.69 (16)	C13—C14—C9	121.07 (18)
C1—C2—H2	121.0 (11)	C13—C14—H14	120.1 (11)
C3—C2—H2	118.2 (11)	C9—C14—H14	118.8 (11)
O1—C3—C4	124.98 (15)	O2—C15—C16	122.56 (12)
O1—C3—C2	114.92 (15)	O2—C15—C8	118.01 (12)
C4—C3—C2	120.10 (15)	C16—C15—C8	119.39 (11)
C3—C4—C5	119.14 (15)	C17—C16—C21	118.94 (14)
C3—C4—H4	123.6 (10)	C17—C16—C15	121.70 (12)
C5—C4—H4	117.3 (10)	C21—C16—C15	119.36 (13)
C4—C5—C6	121.40 (15)	C18—C17—C16	120.45 (15)
C4—C5—H5	121.1 (10)	C18—C17—H17	120.2 (9)
C6—C5—H5	117.5 (10)	C16—C17—H17	119.4 (9)
C5—C6—C1	118.31 (14)	C19—C18—C17	120.02 (18)
C5—C6—C7	120.64 (13)	C19—C18—H18	120.1 (13)
C1—C6—C7	121.03 (13)	C17—C18—H18	119.9 (13)
N1—C7—C6	121.58 (13)	C18—C19—C20	120.24 (18)
N1—C7—H7	121.2 (9)	C18—C19—H19	123.4 (13)
C6—C7—H7	117.1 (9)	C20—C19—H19	116.4 (13)
N2—C8—C9	120.94 (12)	C19—C20—C21	120.40 (18)
N2—C8—C15	120.14 (12)	C19—C20—H20	120.8 (14)
C9—C8—C15	118.84 (11)	C21—C20—H20	118.7 (14)
C14—C9—C10	118.35 (15)	C20—C21—C16	119.91 (16)
C14—C9—C8	120.82 (13)	C20—C21—H21	123.4 (10)
C10—C9—C8	120.84 (14)	C16—C21—H21	116.6 (11)
C11—C10—C9	120.08 (18)	O1—C22—H22A	101.5 (15)
C11—C10—H10	121.9 (10)	O1—C22—H22B	112.9 (18)
C9—C10—H10	118.0 (10)	H22A—C22—H22B	111 (2)
C12—C11—C10	120.37 (19)	O1—C22—H22C	112.7 (14)
C12—C11—H11	121.2 (12)	H22A—C22—H22C	109 (2)
C10—C11—H11	118.4 (13)	H22B—C22—H22C	110 (2)
C13—C12—C11	120.11 (18)	C7—N1—N2	114.00 (12)
C13—C12—H12	116.6 (13)	C8—N2—N1	110.54 (11)
C11—C12—H12	123.2 (12)	C3—O1—C22	118.98 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O2ⁱ	0.95 (3)	2.52 (2)	3.338 (2)	144.8 (17)
C22—H22C···O2ⁱⁱ	0.97 (3)	2.49 (3)	3.404 (3)	156.3 (18)
C10—H10···N2	0.959 (18)	2.527 (16)	2.853 (2)	99.9 (12)
C21—H21···O2	0.942 (17)	2.489 (17)	2.822 (2)	100.8 (12)

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

(Z)-2-[(E)-(4-Methoxybenzylidene)hydrazinylidene]-1,2-diphenylethanone (d-MHDE) top

Crystal data top

C₂₂H₁₈N₂O₂	D_x = 1.215 Mg m⁻³
M_r = 342.38	Melting point: 419.4(2) K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.2458 (4) Å	Cell parameters from 380 reflections
b = 8.0070 (2) Å	θ = 2.5–26.0°
c = 23.3695 (8) Å	µ = 0.08 mm⁻¹
β = 102.461 (3)°	T = 298 K
V = 1872.03 (11) Å³	Block, yellow
Z = 4	0.30 × 0.26 × 0.20 mm
F(000) = 720

Data collection top

Bruker SMART CCD area-detector diffractometer	4659 independent reflections
Radiation source: fine-focus sealed tube	3122 reflections with I > 2σ(I)
Detector resolution: 10.13 pixels mm^-1	R_int = 0.023
phi and ω scans	θ_max = 29.2°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→13
T_min = 0.903, T_max = 0.939	k = −10→10
23780 measured reflections	l = −32→31

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.070	w = 1/[σ²(F_o²) + (0.1488P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.210	(Δ/σ)_max < 0.001
S = 0.99	Δρ_max = 0.19 e Å⁻³
4659 reflections	Δρ_min = −0.15 e Å⁻³
473 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
120 restraints	Extinction coefficient: 0.28 (2)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1A	0.2667 (3)	0.8242 (4)	0.08193 (14)	0.0909 (8)	0.5059 (8)
H1A	0.345996	0.873547	0.077333	0.098*	0.5059 (8)
C2A	0.1484 (10)	0.8363 (12)	0.0418 (5)	0.0622 (18)	0.5059 (8)
H2A	0.140898	0.912459	0.011173	0.084*	0.5059 (8)
C3A	0.0368 (3)	0.7355 (3)	0.04563 (14)	0.0810 (8)	0.5059 (8)
C4A	0.0274 (6)	0.6454 (10)	0.0938 (3)	0.087 (3)	0.5059 (8)
H4A	−0.049503	0.588086	0.097177	0.102*	0.5059 (8)
C5A	0.1428 (3)	0.6466 (5)	0.13735 (17)	0.1045 (10)	0.5059 (8)
H5A	0.144716	0.589781	0.172219	0.127*	0.5059 (8)
C6A	0.2550 (7)	0.7312 (11)	0.1297 (3)	0.0466 (11)	0.5059 (8)
C7A	0.3788 (3)	0.7068 (4)	0.18251 (14)	0.0852 (8)	0.5059 (8)
H7A	0.371520	0.643838	0.215115	0.089*	0.5059 (8)
C8A	0.7014 (5)	0.8008 (5)	0.2169 (2)	0.0338 (7)	0.5059 (8)
C9A	0.8268 (3)	0.7773 (3)	0.25842 (14)	0.0823 (8)	0.5059 (8)
C10A	0.8336 (13)	0.7099 (10)	0.3131 (5)	0.070 (2)	0.5059 (8)
H10A	0.752570	0.687545	0.323311	0.103*	0.5059 (8)
C11A	0.9482 (4)	0.6717 (5)	0.35458 (17)	0.1088 (10)	0.5059 (8)
H11A	0.948844	0.601277	0.386267	0.117*	0.5059 (8)
C12A	1.0625 (3)	0.7496 (4)	0.34404 (15)	0.0902 (9)	0.5059 (8)
H12A	1.138739	0.753257	0.373986	0.105*	0.5059 (8)
C13A	1.0665 (4)	0.8206 (5)	0.29137 (16)	0.1101 (11)	0.5059 (8)
H13A	1.146739	0.856723	0.283148	0.108*	0.5059 (8)
C14A	0.9476 (4)	0.8371 (7)	0.25066 (18)	0.0606 (16)	0.5059 (8)
H14A	0.949281	0.892123	0.215781	0.084*	0.5059 (8)
C15A	0.70901 (19)	0.8714 (3)	0.15667 (8)	0.0557 (5)	0.5059 (8)
C16A	0.68233 (17)	1.0520 (2)	0.14622 (8)	0.0503 (5)	0.5059 (8)
C17A	0.6870 (3)	1.1219 (3)	0.09227 (11)	0.0745 (7)	0.5059 (8)
H17A	0.704771	1.053523	0.062690	0.103*	0.5059 (8)
C18A	0.6660 (3)	1.2898 (3)	0.08155 (15)	0.0879 (8)	0.5059 (8)
H18A	0.668654	1.336485	0.045377	0.107*	0.5059 (8)
C19A	0.6410 (3)	1.3848 (4)	0.12667 (13)	0.0829 (8)	0.5059 (8)
H19A	0.630402	1.499207	0.120572	0.105*	0.5059 (8)
C20A	0.6309 (3)	1.3246 (3)	0.17900 (13)	0.0835 (7)	0.5059 (8)
H20A	0.610870	1.395612	0.207418	0.098*	0.5059 (8)
C21A	0.6507 (2)	1.1530 (3)	0.19055 (10)	0.0625 (5)	0.5059 (8)
H21A	0.643197	1.107804	0.226354	0.078*	0.5059 (8)
C22A	−0.1863 (3)	0.6681 (5)	−0.00851 (16)	0.0980 (10)	0.5059 (8)
H22A	−0.247145	0.742035	0.004931	0.124*	0.5059 (8)
H22B	−0.171947	0.570646	0.015963	0.133*	0.5059 (8)
H22C	−0.223517	0.635604	−0.048222	0.136*	0.5059 (8)
N1A	0.4888 (9)	0.7757 (10)	0.1792 (3)	0.110 (2)	0.5059 (8)
N2A	0.5886 (2)	0.7454 (3)	0.22696 (9)	0.0736 (6)	0.5059 (8)
O1A	−0.0590 (6)	0.7535 (8)	−0.0058 (2)	0.0992 (17)	0.5059 (8)
O2A	0.7413 (2)	0.7809 (2)	0.12045 (8)	0.0811 (5)	0.5059 (8)
C1B	0.1564 (9)	0.7994 (11)	0.0357 (5)	0.0544 (14)	0.4941 (8)
H1B	0.239638	0.833193	0.030198	0.104*	0.4941 (8)
C2B	0.0459 (3)	0.8233 (5)	−0.00874 (14)	0.0945 (9)	0.4941 (8)
H2B	0.049991	0.890242	−0.040832	0.088*	0.4941 (8)
C3B	−0.0739 (6)	0.7428 (9)	−0.00401 (19)	0.0628 (13)	0.4941 (8)
C4B	−0.0819 (4)	0.6603 (5)	0.04770 (15)	0.1017 (10)	0.4941 (8)
H4B	−0.161280	0.610521	0.051896	0.109*	0.4941 (8)
C5B	0.0304 (4)	0.6539 (7)	0.0925 (2)	0.0521 (15)	0.4941 (8)
H5B	0.026336	0.597973	0.126907	0.117*	0.4941 (8)
C6B	0.1478 (3)	0.7282 (4)	0.08732 (16)	0.0927 (9)	0.4941 (8)
C7B	0.2712 (7)	0.7129 (12)	0.1416 (3)	0.0450 (11)	0.4941 (8)
H7B	0.267350	0.656965	0.176116	0.125*	0.4941 (8)
C8B	0.5900 (3)	0.8039 (3)	0.17264 (12)	0.0700 (7)	0.4941 (8)
C9B	0.7230 (6)	0.7626 (5)	0.2174 (3)	0.0500 (11)	0.4941 (8)
C10B	0.7148 (4)	0.6834 (4)	0.26985 (15)	0.0942 (9)	0.4941 (8)
H10B	0.633909	0.643966	0.276459	0.096*	0.4941 (8)
C11B	0.8334 (13)	0.6663 (10)	0.3117 (5)	0.0652 (16)	0.4941 (8)
H11B	0.833056	0.610855	0.346671	0.089*	0.4941 (8)
C12B	0.9514 (3)	0.7309 (4)	0.30194 (16)	0.0860 (9)	0.4941 (8)
H12B	1.031314	0.710620	0.328596	0.099*	0.4941 (8)
C13B	0.9508 (5)	0.8257 (10)	0.2524 (3)	0.104 (3)	0.4941 (8)
H13B	1.027789	0.883007	0.249144	0.109*	0.4941 (8)
C14B	0.8387 (3)	0.8370 (5)	0.20792 (19)	0.1141 (13)	0.4941 (8)
H14B	0.840427	0.892087	0.173060	0.126*	0.4941 (8)
C15B	0.5988 (2)	0.8735 (2)	0.11400 (9)	0.0549 (5)	0.4941 (8)
C16B	0.56805 (18)	1.0528 (2)	0.10388 (8)	0.0531 (5)	0.4941 (8)
C17B	0.5756 (2)	1.1229 (3)	0.04989 (10)	0.0680 (6)	0.4941 (8)
H17B	0.598065	1.055702	0.021009	0.113*	0.4941 (8)
C18B	0.5513 (4)	1.2824 (4)	0.03942 (16)	0.1022 (10)	0.4941 (8)
H18B	0.552992	1.324153	0.002456	0.116*	0.4941 (8)
C19B	0.5229 (3)	1.3924 (4)	0.08224 (14)	0.0922 (9)	0.4941 (8)
H19B	0.510226	1.505878	0.074499	0.103*	0.4941 (8)
C20B	0.5142 (3)	1.3256 (3)	0.13708 (13)	0.0777 (7)	0.4941 (8)
H20B	0.493299	1.392766	0.166310	0.114*	0.4941 (8)
C21B	0.5383 (2)	1.1536 (3)	0.14599 (10)	0.0643 (6)	0.4941 (8)
H21B	0.533620	1.107279	0.181995	0.073*	0.4941 (8)
C22B	−0.2943 (3)	0.6661 (4)	−0.05293 (14)	0.0948 (9)	0.4941 (8)
H22D	−0.369032	0.741265	−0.059852	0.174*	0.4941 (8)
H22E	−0.289133	0.609713	−0.016259	0.187*	0.4941 (8)
H22F	−0.305455	0.585470	−0.084001	0.165*	0.4941 (8)
N1B	0.3714 (2)	0.7823 (2)	0.13333 (10)	0.0671 (6)	0.4941 (8)
N2B	0.4822 (4)	0.7548 (6)	0.17997 (14)	0.0455 (7)	0.4941 (8)
O1B	−0.1764 (3)	0.7564 (3)	−0.05098 (13)	0.1049 (7)	0.4941 (8)
O2B	0.6309 (2)	0.7825 (2)	0.07815 (9)	0.0791 (5)	0.4941 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.0744 (16)	0.106 (2)	0.096 (2)	−0.0030 (14)	0.0259 (15)	0.0042 (16)
C2A	0.072 (2)	0.056 (3)	0.058 (3)	0.0044 (19)	0.0136 (16)	0.000 (2)
C3A	0.0844 (19)	0.0590 (14)	0.098 (2)	0.0078 (12)	0.0157 (17)	0.0005 (13)
C4A	0.084 (4)	0.114 (4)	0.073 (3)	−0.041 (3)	0.041 (3)	−0.016 (3)
C5A	0.090 (2)	0.121 (3)	0.105 (2)	−0.0071 (17)	0.0273 (18)	0.008 (2)
C6A	0.060 (2)	0.053 (2)	0.027 (3)	0.0085 (16)	0.0119 (18)	0.0149 (16)
C7A	0.0821 (14)	0.0863 (14)	0.0909 (15)	−0.0029 (12)	0.0267 (12)	0.0014 (12)
C8A	0.0446 (17)	0.0219 (14)	0.0383 (11)	0.0090 (11)	0.0164 (12)	−0.0007 (11)
C9A	0.097 (2)	0.0618 (14)	0.0881 (19)	0.0314 (13)	0.0191 (17)	−0.0038 (13)
C10A	0.083 (3)	0.068 (5)	0.060 (2)	0.022 (4)	0.0134 (19)	0.008 (3)
C11A	0.118 (3)	0.107 (3)	0.102 (2)	0.015 (2)	0.023 (2)	0.0075 (19)
C12A	0.0845 (19)	0.0771 (18)	0.098 (2)	0.0152 (13)	−0.0044 (17)	−0.0248 (15)
C13A	0.1087 (17)	0.1084 (17)	0.1116 (18)	0.0072 (14)	0.0204 (15)	0.0028 (15)
C14A	0.065 (4)	0.056 (2)	0.063 (3)	−0.0093 (19)	0.019 (2)	0.007 (2)
C15A	0.0551 (11)	0.0624 (12)	0.0516 (10)	0.0062 (8)	0.0159 (9)	−0.0112 (9)
C16A	0.0487 (9)	0.0536 (10)	0.0484 (9)	−0.0069 (7)	0.0103 (8)	0.0015 (7)
C17A	0.0810 (15)	0.0771 (16)	0.0700 (14)	0.0012 (12)	0.0263 (12)	0.0154 (11)
C18A	0.107 (2)	0.0687 (15)	0.094 (2)	−0.0105 (14)	0.0347 (17)	0.0258 (14)
C19A	0.0816 (13)	0.0770 (13)	0.0898 (15)	−0.0040 (10)	0.0181 (12)	0.0031 (11)
C20A	0.0854 (14)	0.0769 (13)	0.0860 (14)	−0.0014 (11)	0.0138 (12)	−0.0049 (11)
C21A	0.0681 (12)	0.0615 (12)	0.0592 (12)	0.0033 (9)	0.0165 (10)	0.0033 (9)
C22A	0.0752 (17)	0.117 (2)	0.098 (2)	−0.0275 (16)	0.0109 (15)	−0.051 (2)
N1A	0.111 (3)	0.112 (3)	0.108 (3)	0.0017 (18)	0.0238 (19)	−0.0022 (17)
N2A	0.0901 (15)	0.0762 (13)	0.0573 (11)	0.0014 (10)	0.0223 (11)	0.0087 (9)
O1A	0.099 (2)	0.100 (2)	0.096 (2)	−0.0029 (16)	0.0170 (15)	−0.0013 (15)
O2A	0.0970 (13)	0.0806 (11)	0.0729 (11)	−0.0022 (9)	0.0343 (10)	−0.0084 (8)
C1B	0.056 (2)	0.059 (4)	0.051 (2)	−0.008 (2)	0.0182 (14)	0.002 (2)
C2B	0.089 (2)	0.118 (2)	0.0787 (19)	−0.0160 (18)	0.0225 (15)	0.0178 (16)
C3B	0.0463 (15)	0.100 (3)	0.0378 (14)	−0.0079 (16)	−0.0007 (11)	−0.0036 (14)
C4B	0.0993 (16)	0.1068 (17)	0.1029 (17)	−0.0007 (13)	0.0303 (14)	0.0023 (14)
C5B	0.0447 (19)	0.0613 (19)	0.051 (2)	0.0011 (14)	0.0118 (14)	0.0042 (15)
C6B	0.0900 (16)	0.0990 (16)	0.0911 (16)	−0.0026 (12)	0.0239 (14)	−0.0053 (13)
C7B	0.0549 (19)	0.054 (2)	0.026 (3)	0.0067 (15)	0.0075 (16)	0.0215 (15)
C8B	0.0789 (17)	0.0545 (12)	0.0798 (17)	0.0105 (11)	0.0243 (14)	0.0131 (11)
C9B	0.0546 (19)	0.036 (2)	0.0592 (16)	0.0172 (14)	0.0117 (13)	−0.0001 (17)
C10B	0.103 (2)	0.0832 (19)	0.102 (2)	0.0255 (16)	0.0349 (19)	0.0133 (16)
C11B	0.097 (3)	0.046 (3)	0.0505 (18)	0.004 (3)	0.0116 (18)	0.003 (2)
C12B	0.092 (2)	0.0730 (18)	0.084 (2)	0.0324 (15)	−0.0005 (16)	0.0079 (15)
C13B	0.046 (3)	0.128 (6)	0.133 (6)	0.002 (3)	0.006 (3)	−0.035 (4)
C14B	0.085 (2)	0.113 (3)	0.135 (3)	0.0153 (18)	0.002 (2)	0.053 (2)
C15B	0.0617 (11)	0.0470 (10)	0.0600 (11)	−0.0031 (8)	0.0221 (9)	0.0006 (8)
C16B	0.0525 (10)	0.0563 (11)	0.0528 (10)	−0.0109 (8)	0.0166 (8)	0.0029 (8)
C17B	0.0838 (15)	0.0703 (15)	0.0585 (12)	−0.0116 (11)	0.0345 (12)	0.0074 (10)
C18B	0.124 (3)	0.100 (2)	0.087 (2)	−0.0013 (18)	0.033 (2)	0.0348 (17)
C19B	0.0972 (15)	0.0831 (15)	0.0961 (15)	0.0010 (12)	0.0205 (13)	0.0000 (13)
C20B	0.0828 (16)	0.0653 (14)	0.0857 (17)	0.0057 (12)	0.0196 (14)	−0.0136 (13)
C21B	0.0810 (14)	0.0578 (12)	0.0553 (12)	−0.0100 (10)	0.0172 (11)	−0.0079 (9)
C22B	0.0937 (19)	0.104 (2)	0.0900 (19)	0.0014 (15)	0.0268 (15)	−0.0059 (15)
N1B	0.0768 (13)	0.0557 (10)	0.0711 (13)	−0.0106 (9)	0.0208 (11)	0.0118 (9)
N2B	0.0396 (11)	0.0633 (14)	0.0322 (10)	0.0048 (9)	0.0048 (7)	0.0022 (8)
O1B	0.1008 (13)	0.1114 (14)	0.0994 (14)	−0.0044 (11)	0.0147 (12)	0.0048 (11)
O2B	0.0915 (12)	0.0772 (11)	0.0752 (11)	0.0066 (8)	0.0324 (10)	−0.0113 (8)

Geometric parameters (Å, º) top

C1A—C2A	1.367 (12)	C1B—C6B	1.354 (11)
C1A—C6A	1.368 (6)	C1B—C2B	1.375 (11)
C1A—H1A	0.9300	C1B—H1B	0.9300
C2A—C3A	1.418 (10)	C2B—C3B	1.412 (7)
C2A—H2A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.357 (5)	C3B—O1B	1.349 (6)
C3A—O1A	1.385 (6)	C3B—C4B	1.395 (5)
C4A—C5A	1.384 (5)	C4B—C5B	1.378 (5)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C6A	1.379 (7)	C5B—C6B	1.370 (5)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—C7A	1.580 (7)	C6B—C7B	1.592 (7)
C7A—N1A	1.272 (9)	C7B—N1B	1.219 (7)
C7A—H7A	0.9300	C7B—H7B	0.9300
C8A—N2A	1.306 (5)	C8B—N2B	1.219 (6)
C8A—C9A	1.445 (6)	C8B—C15B	1.500 (3)
C8A—C15A	1.534 (5)	C8B—C9B	1.563 (7)
C9A—C10A	1.374 (12)	C9B—C14B	1.387 (6)
C9A—C14A	1.375 (4)	C9B—C10B	1.399 (7)
C10A—C11A	1.386 (12)	C10B—C11B	1.394 (13)
C10A—H10A	0.9300	C10B—H10B	0.9300
C11A—C12A	1.394 (5)	C11B—C12B	1.378 (13)
C11A—H11A	0.9300	C11B—H11B	0.9300
C12A—C13A	1.364 (4)	C12B—C13B	1.383 (5)
C12A—H12A	0.9300	C12B—H12B	0.9300
C13A—C14A	1.381 (5)	C13B—C14B	1.376 (5)
C13A—H13A	0.9300	C13B—H13B	0.9300
C14A—H14A	0.9300	C14B—H14B	0.9300
C15A—O2A	1.213 (2)	C15B—O2B	1.208 (3)
C15A—C16A	1.482 (3)	C15B—C16B	1.478 (3)
C16A—C17A	1.390 (3)	C16B—C21B	1.357 (3)
C16A—C21A	1.406 (3)	C16B—C17B	1.398 (3)
C17A—C18A	1.376 (4)	C17B—C18B	1.314 (4)
C17A—H17A	0.9300	C17B—H17B	0.9300
C18A—C19A	1.368 (4)	C18B—C19B	1.410 (5)
C18A—H18A	0.9300	C18B—H18B	0.9300
C19A—C20A	1.339 (4)	C19B—C20B	1.409 (4)
C19A—H19A	0.9300	C19B—H19B	0.9300
C20A—C21A	1.407 (4)	C20B—C21B	1.407 (3)
C20A—H20A	0.9300	C20B—H20B	0.9300
C21A—H21A	0.9300	C21B—H21B	0.9300
C22A—O1A	1.462 (7)	C22B—O1B	1.400 (4)
C22A—H22A	0.9600	C22B—H22D	0.9600
C22A—H22B	0.9600	C22B—H22E	0.9600
C22A—H22C	0.9600	C22B—H22F	0.9600
N1A—N2A	1.363 (8)	N1B—N2B	1.411 (4)

C2A—C1A—C6A	112.2 (6)	C6B—C1B—C2B	122.0 (6)
C2A—C1A—H1A	123.9	C6B—C1B—H1B	119.0
C6A—C1A—H1A	123.9	C2B—C1B—H1B	119.0
C1A—C2A—C3A	121.6 (9)	C1B—C2B—C3B	117.7 (5)
C1A—C2A—H2A	119.2	C1B—C2B—H2B	121.1
C3A—C2A—H2A	119.2	C3B—C2B—H2B	121.1
C4A—C3A—O1A	127.6 (4)	O1B—C3B—C4B	124.2 (5)
C4A—C3A—C2A	123.9 (6)	O1B—C3B—C2B	115.9 (4)
O1A—C3A—C2A	108.4 (6)	C4B—C3B—C2B	119.9 (4)
C3A—C4A—C5A	113.8 (5)	C5B—C4B—C3B	118.7 (4)
C3A—C4A—H4A	123.1	C5B—C4B—H4B	120.7
C5A—C4A—H4A	123.1	C3B—C4B—H4B	120.7
C6A—C5A—C4A	120.8 (4)	C6B—C5B—C4B	121.5 (4)
C6A—C5A—H5A	119.6	C6B—C5B—H5B	119.3
C4A—C5A—H5A	119.6	C4B—C5B—H5B	119.3
C1A—C6A—C5A	126.6 (5)	C1B—C6B—C5B	119.2 (5)
C1A—C6A—C7A	120.5 (5)	C1B—C6B—C7B	123.3 (5)
C5A—C6A—C7A	112.9 (4)	C5B—C6B—C7B	117.3 (4)
N1A—C7A—C6A	118.1 (5)	N1B—C7B—C6B	112.9 (4)
N1A—C7A—H7A	121.0	N1B—C7B—H7B	123.5
C6A—C7A—H7A	121.0	C6B—C7B—H7B	123.5
N2A—C8A—C9A	121.9 (4)	N2B—C8B—C15B	118.9 (3)
N2A—C8A—C15A	120.8 (4)	N2B—C8B—C9B	121.5 (3)
C9A—C8A—C15A	116.8 (3)	C15B—C8B—C9B	118.3 (3)
C10A—C9A—C14A	113.1 (6)	C14B—C9B—C10B	123.4 (6)
C10A—C9A—C8A	122.3 (6)	C14B—C9B—C8B	117.0 (4)
C14A—C9A—C8A	124.1 (3)	C10B—C9B—C8B	118.3 (4)
C9A—C10A—C11A	127.1 (10)	C11B—C10B—C9B	116.9 (6)
C9A—C10A—H10A	116.5	C11B—C10B—H10B	121.6
C11A—C10A—H10A	116.5	C9B—C10B—H10B	121.6
C10A—C11A—C12A	113.2 (6)	C12B—C11B—C10B	120.7 (9)
C10A—C11A—H11A	123.4	C12B—C11B—H11B	119.7
C12A—C11A—H11A	123.4	C10B—C11B—H11B	119.7
C13A—C12A—C11A	122.4 (3)	C11B—C12B—C13B	120.0 (6)
C13A—C12A—H12A	118.8	C11B—C12B—H12B	120.0
C11A—C12A—H12A	118.8	C13B—C12B—H12B	120.0
C12A—C13A—C14A	117.9 (3)	C14B—C13B—C12B	121.4 (5)
C12A—C13A—H13A	121.1	C14B—C13B—H13B	119.3
C14A—C13A—H13A	121.1	C12B—C13B—H13B	119.3
C9A—C14A—C13A	124.1 (3)	C13B—C14B—C9B	117.0 (5)
C9A—C14A—H14A	117.9	C13B—C14B—H14B	121.5
C13A—C14A—H14A	117.9	C9B—C14B—H14B	121.5
O2A—C15A—C16A	122.41 (19)	O2B—C15B—C16B	123.76 (19)
O2A—C15A—C8A	119.7 (2)	O2B—C15B—C8B	119.22 (19)
C16A—C15A—C8A	117.79 (19)	C16B—C15B—C8B	117.02 (17)
C17A—C16A—C21A	119.68 (19)	C21B—C16B—C17B	118.71 (19)
C17A—C16A—C15A	120.08 (17)	C21B—C16B—C15B	122.35 (18)
C21A—C16A—C15A	120.24 (16)	C17B—C16B—C15B	118.88 (18)
C18A—C17A—C16A	121.6 (2)	C18B—C17B—C16B	120.9 (2)
C18A—C17A—H17A	119.2	C18B—C17B—H17B	119.6
C16A—C17A—H17A	119.2	C16B—C17B—H17B	119.6
C19A—C18A—C17A	116.8 (3)	C17B—C18B—C19B	122.3 (3)
C19A—C18A—H18A	121.6	C17B—C18B—H18B	118.8
C17A—C18A—H18A	121.6	C19B—C18B—H18B	118.8
C20A—C19A—C18A	124.6 (3)	C20B—C19B—C18B	118.1 (3)
C20A—C19A—H19A	117.7	C20B—C19B—H19B	120.9
C18A—C19A—H19A	117.7	C18B—C19B—H19B	120.9
C19A—C20A—C21A	119.3 (3)	C21B—C20B—C19B	117.6 (2)
C19A—C20A—H20A	120.3	C21B—C20B—H20B	121.2
C21A—C20A—H20A	120.3	C19B—C20B—H20B	121.2
C16A—C21A—C20A	117.9 (2)	C16B—C21B—C20B	122.3 (2)
C16A—C21A—H21A	121.1	C16B—C21B—H21B	118.8
C20A—C21A—H21A	121.1	C20B—C21B—H21B	118.8
O1A—C22A—H22A	109.5	O1B—C22B—H22D	109.5
O1A—C22A—H22B	109.5	O1B—C22B—H22E	109.5
H22A—C22A—H22B	109.5	H22D—C22B—H22E	109.5
O1A—C22A—H22C	109.5	O1B—C22B—H22F	109.5
H22A—C22A—H22C	109.5	H22D—C22B—H22F	109.5
H22B—C22A—H22C	109.5	H22E—C22B—H22F	109.5
C7A—N1A—N2A	113.0 (6)	C7B—N1B—N2B	111.8 (4)
C8A—N2A—N1A	109.2 (5)	C8B—N2B—N1B	116.3 (3)
C3A—O1A—C22A	116.6 (4)	C3B—O1B—C22B	119.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10A—H10A···N2A	0.93	2.54	2.872 (12)	101
C19A—H19A···O2Aⁱ	0.93	2.53	3.347 (3)	147

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

Hydrogen-bond geometry in o-MHDE (Å, °) top

Notation	D—H···A'	D—H	H···A	D···A	D—H···A
a	C19—H19···O2ⁱ	0.95 (3)	2.52 (2)	3.338 (2)	144.8 (17)
b	C22—H22···O2ⁱⁱ	0.97 (3)	2.49 (3)	3.404 (3)	156.3 (18)
–	C10—H10···N2	0.959 (18)	2.527 (16)	2.853 (2)	99.9 (12)
–	C21—H21···O2	0.942 (17)	2.489 (17)	2.822 (2)	100.8 (12)

Symmetry codes: (i) x, y-1, z; (ii) x+1, y, z.

Selected π–π interaction geometry in o-MHDE [the centroid–centroid distance (d), the dihedral angles (α), the slippage angles between the centroid–centroid distance and the normal to plane I (β), the slippage angle between the centroid–centroid distance and the normal to plane J (γ), the perpendicular distance of centroid I to plane J (e) and the perpendicular distance of centroid J to plane I (f)] (Å, °) top

Notation	π–π interactions (I→J)	d	α	β	γ	e	f
c	Cg1→Cg1 No. 1	5.3601	0.02	57.94	57.94	2.846	2.846
d	Cg1→Cg2 No. 2	4.9638	0.02	40.57	40.57	3.770	3.770
e	Cg1→Cg2 No. 3	5.8545	7.82	54.64	57.65	3.133	3.388
f	Cg1→Cg2 No. 4	5.5148	64.56	22.65	68.81	1.994	5.090
g	Cg1→Cg3 No. 5	5.7854	83.65	58.97	65.31	2.416	2.982
e	Cg2→Cg1 No. 6	5.8545	7.82	57.65	54.64	3.388	3.133
h	Cg2→Cg1 No. 4	5.2178	64.56	18.97	72.99	1.526	4.934
i	Cg2→Cg2 No. 7	4.9693	60.85	15.67	64.45	2.143	4.785
j	Cg3→Cg2 No. 8	5.2407	74.57	9.52	83.66	0.578	5.169

Cg1 is the centroid of the C1–C6 ring, Cg2 that of the C9–C14 ring and Cg3 that of the C16–C21 ring.

Symmetry codes: (No. 1) -x+1, -y, -z; (No. 2) -x+1, -y+1, -z; (No. 3) x-1, y, z; (No. 4) -x+2, y-1/2, -z+1/2; (No. 5) -x+2, -y, -z; (No. 6) x+1, y, z; (No. 7) -x+3, y+1/2, -z+1/2; (No. 8) -x+3, y-1/2, -z+1/2.

Selected C—H···π interaction geometry in o-MHDE [the H–centroid distance (H···Cg), the perpendicular distance of H to plane I (H-Perp), slipping angles between H···Cg and the normal to the plane I (γ), the C—H···Cg angles (C—H···Cg), the C–centroid distance (C···Cg), the angles between C—H bond line and plane I (C—H···π)] (Å, °) top

Notation	C—H···π(plane I)	H···Cg	H-Perp	γ	C—H···Cg	C···Cg	C—H···π
k	C5—H5···Cg2 No. 1	3.0534	2.942	15.52	150.69	3.9286	58.12
l	C12—H12···Cg3 No. 2	3.0454	3.009	8.91	152.76	3.9396	66.84
m	C13—H13···Cg2 No. 3	3.3172	3.248	11.71	122.56	3.9193	41.71
n	C22—H22A···Cg3 No. 4	3.2375	3.009	21.63	131.85	3.9373	35.52
o	C22—H22BB···Cg1 No. 5	2.8267	2.784	10.02	142.55	3.7300	56.07

Cg1 is the centroid of the C1–C6 ring, Cg2 that of the C9–C14 ring and Cg3 that of the C16–C21 ring.

Symmetry codes: (No. 1) -x+2, y+1/2, -z+1/2; (No. 2) -x+3, y+1/2, -z+1/2; (No. 3) -x+3, y-1/2, -z+1/2; (No. 4) -x+1, -y, -z; (No. 5) -x+1, -y+1, -z.

Hydrogen-bond geometry in the major part of d-MHDE (Å, °) top

Notation	D—H···A	D—H	H···A	D···A	D—H···A
a	C19A—H19A···O2Aⁱ	0.93	2.53	3.347 (3)	147
a*	C19B—H19B···O2Bⁱ	0.93	2.53	3.322 (4)	143.4
–	C10A—H10A···N2A	0.93	2.54	2.872 (12)	101

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

Selected C—H···π interaction geometry in d-MHDE (Å, °). The meanings of H···Cg, H-Perp, γ, C—H···Cg, C···Cg, C—H···π are the same as in Tables 4 top

Notation	C—H···π (plane I)	H···Cg	H-Perp	γ	C—H···Cg	C···Cg	C—H···π
h	C11A—H11A···Cg1 No. 2	3.1745	3.042	16.63	139.23	3.9261	62.82
i	C12A—H12A···Cg3 No. 3	2.1440	1.927	26.01	125.90	2.7929	60.42
j	C22A—H22C···Cg1 No. 1	3.2722	3.190	12.90	116.99	3.8053	33.04
k*	C13B—H13B···Cg5 No. 4	3.2906	3.055	21.81	145.96	4.0945	46.64

Cg1 is the centroid of the C1A–C6A ring, Cg3 that of the C16A–C21A ring and Cg5 that of the C9B–C14B ring.

Symmetry codes: (No. 1) -x+1, y-1/2, -z+1/2; (No. 2) -x, y-1/2, -z+1/2; (No. 3) -x+2, -y, -z+1; (No. 4) -x+2, y+1/2, -z+1/2.

Selected π–π interaction geometry in d-MHDE (Å, °). The meanings of d, α, β, γ, e and f are the same as in Table 4 top

Notation	π–π interactions (I→J)	d	α	β	γ	e	f
b	Cg1→Cg1 No. 1	5.9193	0.00	49.11	49.11	3.875	3.875
c	Cg1→Cg2 No. 2	5.7931	3.32	57.37	57.12	3.132	3.131
c	Cg2→Cg1 No. 3	5.7931	3.32	57.12	57.37	3.131	3.132
d	Cg2→Cg1 No. 4	4.9720	61.72	30.23	72.42	1.679	5.136
e	Cg2→Cg2 No. 5	4.8946	61.28	25.70	61.52	2.124	4.652
f	Cg3→Cg1 No. 6	5.9791	83.56	51.61	61.38	2.426	3.426
b*	Cg4→Cg4 No. 1	4.2273	0.00	25.77	25.77	3.807	3.807
c*	Cg4→Cg5 No. 2	5.9106	3.31	57.97	57.20	3.202	3.135
c*	Cg5→Cg4 No. 3	5.9106	3.31	57.20	57.97	3.135	3.202
d*	Cg5→Cg4 No. 4	5.9593	62.92	31.23	73.42	1.700	5.096
e*	Cg5→Cg5 No. 5	5.3232	63.28	28.00	66.57	2.117	4.700
f*	Cg6→Cg4 No. 6	5.8451	87.56	52.01	63.18	2.637	3.598
g*	Cg6→Cg5 No. 4	5.7241	72.12	57.18	62.25	2.665	3.102

Cg1 is the centroid of the C1A–C6A ring, Cg2 that of the C9A–C14A ring, Cg3 that of the C16A–C21A ring, Cg4 that of the C1B–C6B ring, Cg5 that of the C9B–C14B ring and Cg6 that of the C16B–C21B ring.

Symmetry codes: (No. 1) -x+2, -y, -z+1; (No. 2) x-1, y, z; (No. 3) x+1, y, z; (No. 4) -x+1, y+1/2, -z+1/2; (No. 5) -x+2, y-1/2, -z+1/2; (No. 6) -x+1, -y+2, -z.

The intermolecular interaction energies (ΔE) in various pairs of molecules defined in Figs. 2(a)–2(g)^a (kJ mol^-1) top

Intermolecular interactions^b	ΔE[MP2/6-31g(d,p)]	ΔE(MP2/6-31g)
1a	-14.61	-10.18
1b, 1e	-17.30	-15.12
1c, 2n	-13.11	-4.32
1d, 2o	-22.54	-16.06
1f, 1h, 1k	-26.40	-19.71
2g	-17.73	-12.83
1i, 1j, 1m, 1l	-15.93	-11.56

Notes: (a) the interaction energy ΔE is defined as the difference between the energy of the dimer AB and the energy of the isolated molecules [i.e. ΔE = E(AB) - E(A) - E(B)]. The positive ΔE indicates that the intermolecular interactions in this system are repulsive, while the negative value corresponds to a favourable binding energy. The definition of molecular pairings can be found in corresponding packing figures, i.e. Figs. 2(a)–2(g). (b) The interaction parameters can be found in Tables 2–4.

The intermolecular interactions and interaction energies (ΔE) in various pairs of molecule defined in Figs. 3 and S1 (see supporting information) (kJ mol^-1) top

	Intermolecular interactions in the major part^a	Intermolecular interactions in the minor part^b	ΔE[MP2/6-31g(d,p)] in the major part	ΔE[MP2/6-31g(d,p)] in the minor part	ΔE(MP2/6-31g) in the major part	ΔE(MP2/6-31g) in the minor part
I–II	1e, 1i	1e, 1k	44.38	-8.44	62.81	-6.10
I–III	2f	2f*	-12.21	-13.01	-8.57	-2.35
I–IV	1c	1c*	-17.65	-17.05	-15.57	-15.37
I–V	no	no	-2.57	-2.46	-1.48	-1.47
II–III	no	no	-6.01	-5.32	-4.61	-3.76
II–IV	1d, 1h	1d, 1g	5.34	-20.07	17.41	-15.35
II–V	1d, 1h	1d, 1g	5.34	-20.07	17.41	-15.35
III–IV	no	no	-8.24	257.36	-4.34	312.48
III–V	1b, 2j	1b*	-19.47	-23.68	-15.90	-17.09
IV–V	1a	1a*	-14.39	-14.09	-9.91	-9.63
All-five ⁱ	1a, 1b, 1c, 2d, 1e, 2f, 2h, 1i, 2j	1a, 1b, 1c, 2d, 1e, 2f, 1g, 1k	-29.32	126.21	35.83	222.23

Notes: (a) the interaction energy ΔE of all five molecules is defined as the difference between the energy of the five molecules I to V and the energy of the isolated molecules [i.e. ΔE = E(I–V) - E(I) - E(II) - E(III) - E(IV) - E(V)]. (b) The interaction parameters can be found in Tables 5–7.

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Theoretical insight into the disordered structure of (Z)-2-[(E)-(4-meth­oxy­benzyl­idene)hydrazinyl­idene]-1,2-di­phenyl­ethanone: the role of noncovalent inter­actions

Supporting information

Theoretical insight into the disordered structure of (Z)-2-[(E)-(4-methoxybenzylidene)hydrazinylidene]-1,2-diphenylethanone: the role of noncovalent interactions