A third polymorph of 1,4-bis­(1H-benzimid­azol-2-yl)benzene

Fu, W.-W.; Liang, Y.-F.; Liu, Y.; Zhu, X.-M.

doi:10.1107/S1600536814011179

organic compounds

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ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o699

doi:10.1107/S1600536814011179

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A third polymorph of 1,4-bis(1H-benzimidazol-2-yl)benzene

Wei-Wei Fu,^a ^* Yan-Fei Liang,^a Yang Liu ^a and Xiao-Ming Zhu ^a

^aKey Laboratory of Functional Organometallic Materials of General Colleges and Universities in Hunan Province, Department of Chemistry and Materials Science, Hengyang Normal University, Hengyang 421008, People's Republic of China
^*Correspondence e-mail: w.w.fu@hotmail.com

(Received 30 April 2014; accepted 15 May 2014; online 24 May 2014)

The title compound, C₂₀H₁₄N₄, is a new polymorph of the previously reported structures, which were orthorhombic, space group Pbca [Bei et al. (2000). Acta Cryst. C56, 718–719] and monoclinic, space group P2₁/c [Dudd et al. (2003). Green Chem. 5, 187–192]. The asymmetric unit consists of two independent molecules in which the dihedral angels between the central benzene ring and the outer benzimidazole ring systems are 16.81 (10) and 14.23 (10)° in one molecule and 26.09 (10) and 37.29 (10)° in the other. In the crystal, molecules are linked by N—H⋯N and C—H⋯N hydrogen bonds into a tape running along the c-axis direction.

Related literature

For the synthesis of the title compound, see: Alcalde et al. (1992 ); Zhao et al. (2012 ); Zhuang et al. (2011 ). For the previously reported structures of the title compound, see: Bei et al. (2000 ); Dudd et al. (2003 ). For the structures of the title compound with solvent molecules, see: Wu & Hu (2009 ); Su et al. (2011 ).

Experimental

Crystal data

C₂₀H₁₄N₄
M_r = 310.35
Monoclinic, P 2₁ /c
a = 16.196 (3) Å
b = 20.174 (3) Å
c = 9.9010 (16) Å
β = 106.733 (3)°
V = 3098.1 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.26 × 0.22 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.979, T_max = 0.986
15697 measured reflections
5451 independent reflections
3197 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.126
S = 1.02
5451 reflections
450 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N5	0.91 (2)	2.06 (2)	2.947 (3)	164 (2)
N4—H4⋯N3ⁱ	0.93 (2)	1.91 (2)	2.837 (3)	172 (2)
N6—H6⋯N1ⁱⁱ	0.92 (2)	2.00 (2)	2.910 (3)	171 (2)
N8—H8⋯N7ⁱ	0.90 (2)	2.15 (2)	3.041 (3)	174 (2)
C12—H12⋯N3ⁱ	0.93	2.57	3.396 (3)	148
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y, z-1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2008 ); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814011179/is5361sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814011179/is5361Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814011179/is5361Isup3.cml

checkCIF report

Comment top

Benzimidazole and their derivatives have been widely researched for their potential applications in medicinal chemistry, biochemistry and material chemistry. 1,4-bis(benzimidazol-2-yl)benzene has been synthesized with many methods in different groups. Zhuang have synthesized 1,4-bis(benzimidazol-2-yl)benzene with microwave method (Zhuang et al., 2011). Zhao have synthesized it using phosphoric acid as a catalyst (Zhao et al., 2012) instead of polyphosphoric acid which are commonly used in synthesis of benzimidazole (Alcalde et al., 1992). Its crystal structure has been determined by Bei et al. (2000) and Dudd et al. (2003). Recently, its crystal structures with solvent molecules DMF or methanol have also been reported (Wu & Hu, 2009; Su et al., 2011). Here, we report a new crystal structure of 1,4-bis(benzimidazol-2-yl)benzene.

In the crystal, the asymmetric unit contains two independent 1,4-bis(benzimidazol-2-yl)benzene molecules. The bond lengths are similar with those in literature (Bei et al., 2000; Dudd et al., 2003; Wu & Hu, 2009; Su et al., 2011). The angles between benzimidazole rings (r.m.s. deviations of 0.0028 Å for molecule contain N1 and 0.0140 Å for molecule contain N3) and benzene rings (r.m.s. deviations of 0.0140 Å for C8–C13) are 16.8 and 14.2°. In the other molecule, the angles between benzimidazole rings (r.m.s. deviations of 0.0065 Å for molecule contain N5 and 0.0127 Å for molecule contain N7) and benzene rings (r.m.s. deviations of 0.0045 Å for C28–C33) are 26.1 and 37.3°. These angles are different with those reported by other researchers (31.0°, Bei et al., 2000; Dudd et al., 2003; 9.1°, Wu & Hu, 2009; 24.0° and 11. 6°, Su et al., 2011). There are five kinds of hydrogen bonds which result in one dimensional network as that shown in Fig. 2 and Table 1.

Related literature top

For the synthesis of the title compound, see: Alcalde et al. (1992); Zhao et al. (2012); Zhuang et al. (2011). For the previously reported structures of the title compound, see: Bei et al. (2000); Dudd et al. (2003). For the structures of the title compound with solvent molecules, see: Wu & Hu (2009); Su et al. (2011).

Experimental top

1,4-Bis(benzimidazol-2-yl)benzene was synthesized according to literature method (Alcalde et al., 1992; Zhao et al., 2012) and single crystals suitable for X-ray diffraction were obtained by slow evaporation of DMF solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. An ORTEP drawing for the asymmetric unit of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound viewed along c direction. The hydrogen bonds are highlighted by dashed lines.

1,4-Bis(1H-benzimidazol-2-yl)benzene top

Crystal data top

C₂₀H₁₄N₄	F(000) = 1296
M_r = 310.35	D_x = 1.331 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1697 reflections
a = 16.196 (3) Å	θ = 2.4–22.0°
b = 20.174 (3) Å	µ = 0.08 mm⁻¹
c = 9.9010 (16) Å	T = 296 K
β = 106.733 (3)°	Block, yellow
V = 3098.1 (8) Å³	0.26 × 0.22 × 0.17 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	5451 independent reflections
Radiation source: fine-focus sealed tube	3197 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→19
T_min = 0.979, T_max = 0.986	k = −23→23
15697 measured reflections	l = −11→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.042P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
5451 reflections	Δρ_max = 0.21 e Å⁻³
450 parameters	Δρ_min = −0.21 e Å⁻³
5 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (3)

Crystal data top

C₂₀H₁₄N₄	V = 3098.1 (8) Å³
M_r = 310.35	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.196 (3) Å	µ = 0.08 mm⁻¹
b = 20.174 (3) Å	T = 296 K
c = 9.9010 (16) Å	0.26 × 0.22 × 0.17 mm
β = 106.733 (3)°

Data collection top

Bruker APEXII CCD diffractometer	5451 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3197 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.986	R_int = 0.062
15697 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	5 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.21 e Å⁻³
5451 reflections	Δρ_min = −0.21 e Å⁻³
450 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
N1	0.29247 (12)	−0.04939 (9)	0.8970 (2)	0.0422 (5)
N2	0.27746 (13)	−0.04637 (9)	0.6655 (2)	0.0449 (5)
N3	0.07524 (11)	0.26679 (8)	0.8390 (2)	0.0400 (5)
N4	0.06709 (12)	0.27094 (9)	0.6109 (2)	0.0409 (5)
N5	0.21368 (12)	−0.03614 (9)	0.3559 (2)	0.0457 (5)
N6	0.25379 (13)	−0.06306 (9)	0.1650 (2)	0.0447 (5)
N7	0.38516 (11)	0.29079 (8)	0.3466 (2)	0.0429 (5)
N8	0.39950 (13)	0.27194 (9)	0.1317 (2)	0.0430 (5)
C1	0.32991 (14)	−0.10557 (10)	0.8589 (3)	0.0419 (6)
C2	0.37149 (15)	−0.15816 (11)	0.9408 (3)	0.0523 (7)
H2A	0.3776	−0.1599	1.0371	0.063*
C3	0.40316 (16)	−0.20745 (12)	0.8745 (3)	0.0572 (7)
H3	0.4315	−0.2432	0.9273	0.069*
C4	0.39416 (16)	−0.20559 (12)	0.7306 (3)	0.0585 (7)
H4A	0.4166	−0.2401	0.6897	0.070*
C5	0.35302 (15)	−0.15420 (12)	0.6475 (3)	0.0551 (7)
H5	0.3469	−0.1529	0.5512	0.066*
C6	0.32114 (14)	−0.10441 (10)	0.7147 (3)	0.0416 (6)
C7	0.26227 (14)	−0.01539 (10)	0.7780 (3)	0.0404 (6)
C8	0.22036 (14)	0.04919 (10)	0.7669 (2)	0.0380 (6)
C9	0.18877 (15)	0.07285 (10)	0.8733 (3)	0.0463 (6)
H9	0.1941	0.0470	0.9531	0.056*
C10	0.14979 (15)	0.13358 (11)	0.8634 (3)	0.0483 (6)
H10	0.1300	0.1486	0.9372	0.058*
C11	0.13940 (13)	0.17303 (10)	0.7452 (2)	0.0366 (5)
C12	0.17413 (15)	0.15063 (11)	0.6412 (3)	0.0504 (7)
H12	0.1704	0.1770	0.5627	0.061*
C13	0.21410 (16)	0.08991 (12)	0.6522 (3)	0.0549 (7)
H13	0.2373	0.0760	0.5813	0.066*
C14	0.09418 (14)	0.23666 (10)	0.7334 (2)	0.0379 (6)
C15	0.03436 (14)	0.32525 (11)	0.7812 (3)	0.0425 (6)
C16	0.00158 (16)	0.37657 (12)	0.8445 (3)	0.0597 (7)
H16	0.0040	0.3748	0.9395	0.072*
C17	−0.03427 (19)	0.42969 (13)	0.7627 (4)	0.0739 (9)
H17	−0.0555	0.4650	0.8032	0.089*
C18	−0.03965 (18)	0.43187 (13)	0.6192 (4)	0.0740 (9)
H18	−0.0648	0.4686	0.5665	0.089*
C19	−0.00906 (15)	0.38159 (12)	0.5539 (3)	0.0579 (7)
H19	−0.0133	0.3830	0.4582	0.069*
C20	0.02871 (14)	0.32833 (11)	0.6384 (3)	0.0428 (6)
C21	0.19204 (14)	−0.10180 (11)	0.3204 (3)	0.0441 (6)
C22	0.15135 (16)	−0.14810 (12)	0.3834 (3)	0.0582 (7)
H22	0.1335	−0.1371	0.4619	0.070*
C23	0.13831 (17)	−0.21025 (13)	0.3267 (3)	0.0627 (8)
H23	0.1110	−0.2419	0.3670	0.075*
C24	0.16497 (17)	−0.22720 (12)	0.2103 (3)	0.0637 (8)
H24	0.1561	−0.2703	0.1756	0.076*
C25	0.20405 (16)	−0.18225 (11)	0.1449 (3)	0.0587 (7)
H25	0.2210	−0.1936	0.0658	0.070*
C26	0.21713 (14)	−0.11937 (11)	0.2019 (3)	0.0440 (6)
C27	0.24929 (14)	−0.01533 (10)	0.2595 (2)	0.0396 (6)
C28	0.28177 (14)	0.05166 (10)	0.2531 (2)	0.0371 (6)
C29	0.34685 (14)	0.06484 (10)	0.1920 (3)	0.0447 (6)
H29	0.3704	0.0302	0.1531	0.054*
C30	0.37728 (15)	0.12830 (11)	0.1877 (3)	0.0458 (6)
H30	0.4212	0.1362	0.1466	0.055*
C31	0.34253 (14)	0.18036 (10)	0.2446 (2)	0.0372 (5)
C32	0.27666 (14)	0.16773 (10)	0.3045 (2)	0.0428 (6)
H32	0.2529	0.2024	0.3427	0.051*
C33	0.24615 (14)	0.10442 (10)	0.3080 (2)	0.0427 (6)
H33	0.2013	0.0967	0.3473	0.051*
C34	0.37521 (14)	0.24779 (10)	0.2431 (3)	0.0391 (6)
C35	0.41685 (14)	0.34739 (10)	0.2989 (3)	0.0400 (6)
C36	0.43613 (14)	0.40958 (11)	0.3605 (3)	0.0493 (6)
H36	0.4292	0.4183	0.4488	0.059*
C37	0.46551 (16)	0.45757 (11)	0.2884 (3)	0.0559 (7)
H37	0.4784	0.4995	0.3281	0.067*
C38	0.47638 (18)	0.44489 (13)	0.1577 (3)	0.0677 (8)
H38	0.4973	0.4783	0.1118	0.081*
C39	0.45718 (16)	0.38443 (12)	0.0935 (3)	0.0606 (7)
H39	0.4645	0.3762	0.0052	0.073*
C40	0.42666 (14)	0.33628 (10)	0.1652 (3)	0.0412 (6)
H2	0.2599 (15)	−0.0344 (12)	0.5728 (19)	0.069 (9)*
H4	0.0751 (15)	0.2586 (10)	0.5247 (19)	0.059 (8)*
H6	0.2687 (15)	−0.0543 (12)	0.084 (2)	0.070 (8)*
H8	0.3954 (16)	0.2505 (11)	0.051 (2)	0.069 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0531 (12)	0.0402 (11)	0.0389 (13)	0.0030 (9)	0.0219 (11)	0.0027 (9)
N2	0.0578 (13)	0.0460 (12)	0.0346 (14)	0.0063 (10)	0.0192 (12)	−0.0028 (11)
N3	0.0488 (11)	0.0394 (11)	0.0365 (12)	0.0025 (9)	0.0195 (10)	−0.0018 (9)
N4	0.0485 (12)	0.0412 (11)	0.0381 (14)	0.0025 (9)	0.0204 (11)	−0.0002 (10)
N5	0.0574 (12)	0.0460 (12)	0.0421 (13)	−0.0083 (10)	0.0277 (11)	−0.0020 (10)
N6	0.0608 (13)	0.0405 (11)	0.0409 (14)	−0.0066 (10)	0.0277 (12)	−0.0020 (10)
N7	0.0562 (12)	0.0356 (10)	0.0433 (13)	−0.0040 (9)	0.0249 (11)	−0.0006 (9)
N8	0.0548 (12)	0.0417 (12)	0.0379 (14)	−0.0039 (9)	0.0217 (11)	−0.0011 (10)
C1	0.0443 (13)	0.0400 (13)	0.0443 (17)	0.0018 (11)	0.0175 (13)	−0.0019 (12)
C2	0.0614 (15)	0.0470 (15)	0.0520 (18)	0.0081 (13)	0.0218 (15)	0.0081 (13)
C3	0.0599 (16)	0.0444 (15)	0.069 (2)	0.0109 (13)	0.0207 (17)	0.0033 (14)
C4	0.0586 (16)	0.0531 (16)	0.066 (2)	0.0107 (13)	0.0209 (17)	−0.0101 (15)
C5	0.0618 (16)	0.0547 (16)	0.0511 (19)	0.0094 (13)	0.0197 (15)	−0.0104 (14)
C6	0.0454 (13)	0.0388 (13)	0.0437 (16)	0.0015 (11)	0.0178 (13)	−0.0022 (12)
C7	0.0473 (14)	0.0398 (13)	0.0382 (16)	−0.0010 (11)	0.0190 (13)	−0.0013 (12)
C8	0.0439 (13)	0.0386 (13)	0.0350 (15)	0.0021 (10)	0.0167 (12)	0.0023 (11)
C9	0.0632 (15)	0.0428 (14)	0.0396 (16)	0.0090 (12)	0.0257 (14)	0.0068 (11)
C10	0.0663 (16)	0.0468 (14)	0.0414 (16)	0.0093 (12)	0.0304 (14)	0.0006 (12)
C11	0.0411 (12)	0.0356 (12)	0.0361 (15)	0.0007 (10)	0.0161 (12)	0.0001 (11)
C12	0.0674 (16)	0.0507 (15)	0.0415 (17)	0.0156 (13)	0.0288 (15)	0.0092 (12)
C13	0.0757 (18)	0.0563 (16)	0.0413 (17)	0.0196 (14)	0.0305 (15)	0.0058 (13)
C14	0.0443 (13)	0.0396 (13)	0.0340 (15)	−0.0063 (11)	0.0177 (12)	0.0005 (11)
C15	0.0432 (13)	0.0404 (13)	0.0476 (17)	0.0009 (11)	0.0191 (13)	−0.0013 (12)
C16	0.0655 (17)	0.0596 (17)	0.062 (2)	0.0130 (14)	0.0310 (16)	−0.0032 (15)
C17	0.084 (2)	0.0598 (18)	0.083 (3)	0.0289 (16)	0.033 (2)	−0.0013 (18)
C18	0.081 (2)	0.0575 (18)	0.084 (3)	0.0277 (15)	0.026 (2)	0.0120 (17)
C19	0.0630 (16)	0.0552 (16)	0.059 (2)	0.0122 (13)	0.0232 (15)	0.0148 (14)
C20	0.0419 (13)	0.0395 (13)	0.0504 (18)	0.0022 (11)	0.0185 (13)	0.0022 (12)
C21	0.0498 (14)	0.0458 (14)	0.0390 (16)	−0.0079 (11)	0.0162 (13)	0.0009 (12)
C22	0.0701 (17)	0.0579 (16)	0.0534 (19)	−0.0156 (14)	0.0287 (15)	0.0026 (14)
C23	0.0642 (17)	0.0567 (17)	0.069 (2)	−0.0192 (14)	0.0215 (17)	0.0094 (15)
C24	0.0701 (18)	0.0433 (15)	0.081 (2)	−0.0116 (13)	0.0264 (18)	−0.0039 (15)
C25	0.0723 (17)	0.0469 (15)	0.064 (2)	−0.0089 (13)	0.0310 (16)	−0.0103 (14)
C26	0.0479 (14)	0.0420 (14)	0.0440 (17)	−0.0039 (11)	0.0164 (13)	0.0019 (12)
C27	0.0466 (14)	0.0399 (13)	0.0353 (15)	−0.0014 (11)	0.0166 (12)	−0.0011 (11)
C28	0.0436 (13)	0.0394 (13)	0.0331 (14)	0.0002 (10)	0.0189 (12)	0.0015 (11)
C29	0.0536 (14)	0.0385 (13)	0.0516 (17)	−0.0020 (11)	0.0304 (14)	−0.0060 (12)
C30	0.0518 (14)	0.0473 (14)	0.0487 (17)	−0.0041 (11)	0.0309 (13)	−0.0061 (12)
C31	0.0420 (13)	0.0383 (13)	0.0346 (15)	0.0028 (10)	0.0163 (12)	0.0023 (11)
C32	0.0497 (14)	0.0408 (13)	0.0448 (16)	0.0074 (11)	0.0245 (13)	0.0008 (11)
C33	0.0453 (13)	0.0430 (14)	0.0465 (16)	0.0001 (11)	0.0240 (13)	0.0009 (12)
C34	0.0441 (13)	0.0407 (13)	0.0363 (15)	0.0014 (11)	0.0174 (12)	0.0005 (12)
C35	0.0455 (13)	0.0384 (13)	0.0398 (16)	0.0005 (11)	0.0180 (12)	0.0021 (11)
C36	0.0610 (16)	0.0428 (14)	0.0475 (17)	−0.0050 (12)	0.0210 (14)	−0.0061 (12)
C37	0.0678 (17)	0.0432 (14)	0.059 (2)	−0.0135 (13)	0.0220 (16)	−0.0018 (14)
C38	0.094 (2)	0.0559 (17)	0.059 (2)	−0.0259 (15)	0.0307 (19)	0.0058 (15)
C39	0.0809 (19)	0.0634 (17)	0.0452 (18)	−0.0196 (15)	0.0305 (16)	−0.0002 (14)
C40	0.0458 (13)	0.0400 (13)	0.0415 (16)	−0.0051 (11)	0.0183 (13)	0.0008 (11)

Geometric parameters (Å, º) top

N1—C7	1.329 (3)	C15—C16	1.392 (3)
N1—C1	1.388 (3)	C16—C17	1.368 (3)
N2—H2	0.912 (17)	C16—H16	0.9300
N3—C14	1.319 (3)	C17—H17	0.9300
N3—C15	1.392 (3)	C18—C17	1.400 (4)
N4—C14	1.355 (3)	C18—H18	0.9300
N4—C20	1.378 (3)	C19—C18	1.370 (3)
N4—H4	0.933 (16)	C19—H19	0.9300
N5—C27	1.318 (3)	C20—C19	1.391 (3)
N5—C21	1.389 (3)	C20—C15	1.392 (3)
N6—C27	1.359 (3)	C21—C22	1.391 (3)
N6—C26	1.379 (3)	C21—C26	1.393 (3)
N6—H6	0.916 (16)	C22—C23	1.365 (3)
N7—C34	1.316 (3)	C22—H22	0.9300
N7—C35	1.389 (3)	C23—H23	0.9300
N8—C34	1.363 (3)	C24—C23	1.385 (4)
N8—C40	1.380 (3)	C24—H24	0.9300
N8—H8	0.898 (16)	C25—C24	1.370 (3)
C1—C2	1.386 (3)	C25—H25	0.9300
C2—C3	1.370 (3)	C26—C25	1.380 (3)
C2—H2A	0.9300	C28—C29	1.384 (3)
C3—C4	1.391 (4)	C28—C33	1.393 (3)
C3—H3	0.9300	C28—C27	1.458 (3)
C4—H4A	0.9300	C29—H29	0.9300
C5—C4	1.371 (3)	C30—C29	1.377 (3)
C5—H5	0.9300	C30—H30	0.9300
C6—N2	1.382 (3)	C31—C30	1.385 (3)
C6—C5	1.384 (3)	C31—C32	1.386 (3)
C6—C1	1.393 (3)	C32—H32	0.9300
C7—N2	1.360 (3)	C33—C32	1.373 (3)
C7—C8	1.459 (3)	C33—H33	0.9300
C8—C13	1.381 (3)	C34—C31	1.461 (3)
C9—C10	1.369 (3)	C35—C36	1.391 (3)
C9—C8	1.381 (3)	C35—C40	1.396 (3)
C9—H9	0.9300	C36—C37	1.367 (3)
C10—H10	0.9300	C36—H36	0.9300
C11—C12	1.384 (3)	C37—C38	1.379 (4)
C11—C10	1.385 (3)	C37—H37	0.9300
C11—C14	1.466 (3)	C38—H38	0.9300
C12—C13	1.375 (3)	C39—C38	1.369 (3)
C12—H12	0.9300	C39—H39	0.9300
C13—H13	0.9300	C40—C39	1.376 (3)

C7—N1—C1	104.99 (19)	C29—C30—H30	120.0
C7—N2—C6	107.2 (2)	C31—C30—H30	120.0
C7—N2—H2	128.7 (16)	N6—C26—C25	132.6 (2)
C6—N2—H2	123.9 (16)	N6—C26—C21	105.4 (2)
C14—N3—C15	104.86 (19)	C25—C26—C21	122.0 (2)
C14—N4—C20	107.5 (2)	N5—C27—N6	113.21 (19)
C14—N4—H4	126.0 (14)	N5—C27—C28	124.4 (2)
C20—N4—H4	126.5 (14)	N6—C27—C28	122.4 (2)
C27—N6—C26	106.80 (19)	C20—C15—N3	109.85 (19)
C27—N6—H6	122.9 (15)	C20—C15—C16	120.2 (2)
C26—N6—H6	129.2 (16)	N3—C15—C16	130.0 (2)
C34—N7—C35	104.58 (19)	C12—C13—C8	121.1 (2)
C34—N8—C40	106.7 (2)	C12—C13—H13	119.4
C34—N8—H8	126.0 (16)	C8—C13—H13	119.4
C40—N8—H8	127.2 (16)	C3—C2—C1	117.5 (2)
N1—C7—N2	112.4 (2)	C3—C2—H2A	121.3
N1—C7—C8	124.9 (2)	C1—C2—H2A	121.3
N2—C7—C8	122.6 (2)	C33—C32—C31	120.6 (2)
N7—C34—N8	113.25 (19)	C33—C32—H32	119.7
N7—C34—C31	124.7 (2)	C31—C32—H32	119.7
N8—C34—C31	122.0 (2)	C30—C29—C28	121.1 (2)
C12—C11—C10	117.7 (2)	C30—C29—H29	119.5
C12—C11—C14	121.8 (2)	C28—C29—H29	119.5
C10—C11—C14	120.5 (2)	C38—C39—C40	117.2 (2)
C27—N5—C21	104.58 (18)	C38—C39—H39	121.4
C10—C9—C8	121.3 (2)	C40—C39—H39	121.4
C10—C9—H9	119.4	C4—C5—C6	116.4 (2)
C8—C9—H9	119.4	C4—C5—H5	121.8
N4—C20—C19	132.5 (2)	C6—C5—H5	121.8
N4—C20—C15	105.2 (2)	C37—C36—C35	118.5 (2)
C19—C20—C15	122.3 (2)	C37—C36—H36	120.7
N2—C6—C5	132.0 (2)	C35—C36—H36	120.7
N2—C6—C1	105.44 (19)	C36—C37—C38	121.1 (2)
C5—C6—C1	122.6 (2)	C36—C37—H37	119.5
C9—C10—C11	121.1 (2)	C38—C37—H37	119.5
C9—C10—H10	119.5	C2—C3—C4	121.9 (2)
C11—C10—H10	119.5	C2—C3—H3	119.1
C29—C28—C33	118.47 (19)	C4—C3—H3	119.1
C29—C28—C27	121.76 (19)	C18—C19—C20	116.4 (3)
C33—C28—C27	119.76 (19)	C18—C19—H19	121.8
C2—C1—N1	130.0 (2)	C20—C19—H19	121.8
C2—C1—C6	120.1 (2)	C5—C4—C3	121.6 (2)
N1—C1—C6	109.9 (2)	C5—C4—H4A	119.2
C13—C8—C9	117.7 (2)	C3—C4—H4A	119.2
C13—C8—C7	121.0 (2)	C17—C16—C15	117.9 (3)
C9—C8—C7	121.2 (2)	C17—C16—H16	121.0
N7—C35—C36	130.6 (2)	C15—C16—H16	121.0
N7—C35—C40	110.15 (19)	C23—C22—C21	118.0 (2)
C36—C35—C40	119.2 (2)	C23—C22—H22	121.0
N3—C14—N4	112.65 (19)	C21—C22—H22	121.0
N3—C14—C11	124.4 (2)	C24—C25—C26	116.9 (2)
N4—C14—C11	122.9 (2)	C24—C25—H25	121.5
C13—C12—C11	121.0 (2)	C26—C25—H25	121.5
C13—C12—H12	119.5	C25—C24—C23	121.8 (2)
C11—C12—H12	119.5	C25—C24—H24	119.1
C32—C33—C28	120.6 (2)	C23—C24—H24	119.1
C32—C33—H33	119.7	C19—C18—C17	122.1 (3)
C28—C33—H33	119.7	C19—C18—H18	119.0
C30—C31—C32	119.19 (19)	C17—C18—H18	119.0
C30—C31—C34	120.74 (19)	C22—C23—C24	121.4 (2)
C32—C31—C34	120.06 (19)	C22—C23—H23	119.3
N5—C21—C22	130.1 (2)	C24—C23—H23	119.3
N5—C21—C26	110.01 (19)	C39—C38—C37	121.8 (2)
C22—C21—C26	119.9 (2)	C39—C38—H38	119.1
C39—C40—N8	132.6 (2)	C37—C38—H38	119.1
C39—C40—C35	122.1 (2)	C16—C17—C18	121.2 (3)
N8—C40—C35	105.26 (19)	C16—C17—H17	119.4
C29—C30—C31	120.1 (2)	C18—C17—H17	119.4

C1—N1—C7—N2	0.4 (3)	C27—N6—C26—C21	−0.1 (3)
C1—N1—C7—C8	−177.3 (2)	N5—C21—C26—N6	−0.5 (3)
C35—N7—C34—N8	1.0 (3)	C22—C21—C26—N6	179.2 (2)
C35—N7—C34—C31	−179.7 (2)	N5—C21—C26—C25	179.3 (2)
C40—N8—C34—N7	−0.7 (3)	C22—C21—C26—C25	−0.9 (4)
C40—N8—C34—C31	179.96 (19)	C21—N5—C27—N6	−1.1 (3)
C14—N4—C20—C19	179.1 (2)	C21—N5—C27—C28	179.4 (2)
C14—N4—C20—C15	−0.4 (2)	C26—N6—C27—N5	0.8 (3)
C8—C9—C10—C11	1.1 (4)	C26—N6—C27—C28	−179.7 (2)
C12—C11—C10—C9	−3.6 (4)	C29—C28—C27—N5	153.5 (2)
C14—C11—C10—C9	177.3 (2)	C33—C28—C27—N5	−27.4 (3)
C7—N1—C1—C2	179.8 (2)	C29—C28—C27—N6	−26.0 (3)
C7—N1—C1—C6	−0.2 (2)	C33—C28—C27—N6	153.2 (2)
N2—C6—C1—C2	179.97 (19)	N4—C20—C15—N3	−0.2 (2)
C5—C6—C1—C2	−0.4 (4)	C19—C20—C15—N3	−179.8 (2)
N2—C6—C1—N1	−0.1 (2)	N4—C20—C15—C16	179.6 (2)
C5—C6—C1—N1	179.6 (2)	C19—C20—C15—C16	0.0 (4)
C10—C9—C8—C13	2.3 (4)	C14—N3—C15—C20	0.8 (2)
C10—C9—C8—C7	179.7 (2)	C14—N3—C15—C16	−179.0 (2)
N1—C7—C8—C13	160.4 (2)	C11—C12—C13—C8	0.4 (4)
N2—C7—C8—C13	−17.1 (3)	C9—C8—C13—C12	−3.0 (4)
N1—C7—C8—C9	−16.9 (3)	C7—C8—C13—C12	179.6 (2)
N2—C7—C8—C9	165.6 (2)	N1—C1—C2—C3	−179.6 (2)
C34—N7—C35—C36	177.0 (2)	C6—C1—C2—C3	0.4 (3)
C34—N7—C35—C40	−0.9 (3)	C28—C33—C32—C31	1.0 (3)
N1—C7—N2—C6	−0.4 (3)	C30—C31—C32—C33	0.1 (3)
C8—C7—N2—C6	177.33 (19)	C34—C31—C32—C33	−179.2 (2)
C5—C6—N2—C7	−179.4 (2)	C31—C30—C29—C28	−0.3 (4)
C1—C6—N2—C7	0.3 (2)	C33—C28—C29—C30	1.3 (3)
C15—N3—C14—N4	−1.1 (2)	C27—C28—C29—C30	−179.5 (2)
C15—N3—C14—C11	179.01 (19)	N8—C40—C39—C38	178.1 (2)
C20—N4—C14—N3	1.0 (3)	C35—C40—C39—C38	−1.2 (4)
C20—N4—C14—C11	−179.10 (19)	N2—C6—C5—C4	179.7 (2)
C12—C11—C14—N3	−165.6 (2)	C1—C6—C5—C4	0.1 (4)
C10—C11—C14—N3	13.4 (3)	N7—C35—C36—C37	−178.8 (2)
C12—C11—C14—N4	14.5 (3)	C40—C35—C36—C37	−1.0 (3)
C10—C11—C14—N4	−166.5 (2)	C35—C36—C37—C38	−0.3 (4)
C10—C11—C12—C13	2.9 (4)	C1—C2—C3—C4	−0.2 (4)
C14—C11—C12—C13	−178.1 (2)	N4—C20—C19—C18	−178.6 (2)
C29—C28—C33—C32	−1.7 (3)	C15—C20—C19—C18	0.9 (4)
C27—C28—C33—C32	179.2 (2)	C6—C5—C4—C3	0.1 (4)
N7—C34—C31—C30	−141.3 (2)	C2—C3—C4—C5	0.0 (4)
N8—C34—C31—C30	38.0 (3)	C20—C15—C16—C17	−1.2 (4)
N7—C34—C31—C32	38.0 (3)	N3—C15—C16—C17	178.6 (2)
N8—C34—C31—C32	−142.7 (2)	N5—C21—C22—C23	−179.6 (2)
C27—N5—C21—C22	−178.7 (3)	C26—C21—C22—C23	0.8 (4)
C27—N5—C21—C26	1.0 (3)	N6—C26—C25—C24	179.8 (2)
C34—N8—C40—C39	−179.4 (3)	C21—C26—C25—C24	0.0 (4)
C34—N8—C40—C35	0.0 (3)	C26—C25—C24—C23	1.1 (4)
N7—C35—C40—C39	−180.0 (2)	C20—C19—C18—C17	−0.7 (4)
C36—C35—C40—C39	1.8 (4)	C21—C22—C23—C24	0.3 (4)
N7—C35—C40—N8	0.6 (3)	C25—C24—C23—C22	−1.3 (5)
C36—C35—C40—N8	−177.6 (2)	C40—C39—C38—C37	−0.2 (4)
C32—C31—C30—C29	−0.5 (3)	C36—C37—C38—C39	1.0 (5)
C34—C31—C30—C29	178.9 (2)	C15—C16—C17—C18	1.4 (4)
C27—N6—C26—C25	−180.0 (3)	C19—C18—C17—C16	−0.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N5	0.91 (2)	2.06 (2)	2.947 (3)	164 (2)
N4—H4···N3ⁱ	0.93 (2)	1.91 (2)	2.837 (3)	172 (2)
N6—H6···N1ⁱⁱ	0.92 (2)	2.00 (2)	2.910 (3)	171 (2)
N8—H8···N7ⁱ	0.90 (2)	2.15 (2)	3.041 (3)	174 (2)
C12—H12···N3ⁱ	0.93	2.57	3.396 (3)	148

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N5	0.912 (17)	2.061 (18)	2.947 (3)	164 (2)
N4—H4···N3ⁱ	0.933 (16)	1.909 (17)	2.837 (3)	172 (2)
N6—H6···N1ⁱⁱ	0.916 (16)	2.002 (17)	2.910 (3)	171 (2)
N8—H8···N7ⁱ	0.898 (16)	2.146 (17)	3.041 (3)	174 (2)
C12—H12···N3ⁱ	0.93	2.57	3.396 (3)	148

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

Acknowledgements

Financial support by the key discipline project of Hunan Province is gratefully acknowledged.

References

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