Methyl 4-{N′-[(1E)-1-(pyrazin-2-yl)ethyl­idene]hydrazinecarbon­yl}benzoate

Wang, Z.; Ni, H.

doi:10.1107/S2414314618012300

organic compounds

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ISSN: 2414-3146

Volume 3| Part 9| September 2018| x181230

https://doi.org/10.1107/S2414314618012300

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Methyl 4-{N′-[(1E)-1-(pyrazin-2-yl)ethylidene]hydrazinecarbonyl}benzoate

Zhaodong Wang ^a ^* and Haitao Ni ^b

^aChongqing Key Laboratory of Environmental Materials and Remediation Technologies, Chongqing University of Arts and Sciences, Yongchuan, Chongqing 402160, People's Republic of China, and ^bCollege of Materials and Chemical Engineering, Chongqing University of Arts and Sciences, Yongchuan, Chongqing 402160, People's Republic of China
^*Correspondence e-mail: ouwzdong@qq.com

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 21 August 2018; accepted 30 August 2018; online 7 September 2018)

The title Schiff base, C₁₅H₁₄N₄O₃, was synthesized by the condensation reaction between caprylic hydrazide and 2-acetylpyrazine. There are two independent pseudo-enantiomeric molecules, A and B, in the asymmetric unit that differ mainly in the orientation of the hydrazone units. For example, the dihedral angles between the benzene and pyrazine rings are 20.836 (13) (A) and 15.701 (14)° (B). The molecular packing features N—H⋯O hydrogen bonds that lead to a twisted supramolecular chain along the b-axis direction. The presence of C—H⋯O interactions consolidates the chains into a three-dimensional architecture. The studied sample was a two-component twin.

Keywords: crystal structure; Schiff base; acylhydrazone ligand; hydrogen bonding.

CCDC reference: 1859548

Structure description

Hydrazone-based Schiff bases are important members of the Schiff base family. Their method of synthesis is simple and products can be tailored by changing the aldehyde or ketone and caprylic hydrazide precursors. Their applications are focused upon molecular switches (Coskun et al., 2012 ), sensors (Albelda et al., 2012 ) and single molecule magnets (SMMs; Tian et al., 2013 ) as a result of their ability to adopt variable coordination modes towards metals. 2-Acetylpyrazine-based hydrazone ligands and their transition metal chemistry have also been reported (Hou et al., 2018 ; Li et al., 2015 ). Herein, we aimed to synthesize a new hydrazone ligand substituted with 2-acetylpyrazine to enrich its potential coordination chemistry with transition metals; the successful synthesis of the hydrazone ligand was confirmed by its X-ray crystal structure determination.

The asymmetric unit of the title molecule, Fig. 1, comprises two independent molecules (A and B) that differ primarily in the relative orientation about the hydrazone bond. In molecule A, the benzene and pyrazine rings make a dihedral angle of 20.836 (13)°, the corresponding angle in molecule B being 15.701 (14)°. In the crystal, N—H⋯O hydrogen bonds lead to twisted supramolecular chains along the b-axis direction, which are consolidated by C—H⋯O interactions, Table 1 and Fig. 2, leading to a three-dimensional architecture. Molecules A and B are also linked through π–π interactions between benzene rings with an offset centroid–centroid distance of 3.739 (3) Å, and pyrazine rings with an offset centroid–centroid distance of 4.0519 (3) Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6ⁱ	0.86	2.31	3.063 (5)	147
N5—H5⋯O3ⁱⁱ	0.86	2.39	3.172 (5)	151
C10—H10⋯O4ⁱⁱⁱ	0.93	2.51	3.440 (7)	175
C12—H12A⋯O3^iv	0.96	2.38	3.327 (6)	171
C12—H12C⋯O6ⁱ	0.96	2.58	3.360 (6)	139
C28—H28A⋯O3ⁱⁱ	0.96	2.59	3.422 (6)	145
Symmetry codes: (i) x-1, y, z; (ii) x+1, y-1, z; (iii) x-1, y+1, z-1; (iv) x+1, y, z.

Figure 1
The molecular structure of the title compound showing the atom numbering and displacement ellipsoids drawn at the 50% probability level.

Figure 2
Molecular packing for the title compound viewed along the b-axis direction. Dashed lines indicate hydrogen bonding.

Synthesis and crystallization

All reagents and solvents were purchased from commercial sources and used as received without further purification. The title molecule was synthesized via two steps; firstly, the intermediate caprylic hydrazide was prepared by refluxing dimethyl terephthalate (3.08 g,19.4 mmol) and an excess of hydrazine hydrate (2.94 g, 58.8 mmol) in methanol (40 ml). After 50 min., a white precipitate was evident, and after refluxing for an additional 15 h the suspension was cooled to room temperature. A white solid was filtered off and used in the next step. The title molecule was prepared by the condensation reaction of pyrazine-2-carbohydrazide (1.38 g, 10 mmol) with 2-acetylpyrazine (1.22 g,10 mmol) under reflux in ethanol (50 ml) for 16 h. A transparent, light-yellow solution resulted. Colourless crystals suitable for X-ray analysis precipitated overnight.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The sample was refined as an inversion twin.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₄O₃
M_r	298.30
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.859 (5), 7.479 (6), 16.329 (14)
α, β, γ (°)	93.818 (12), 91.29 (3), 94.252 (10)
V (Å³)	711.7 (10)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.2 × 0.14 × 0.12

Data collection
Diffractometer	Bruker P4
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.654, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	5678, 4773, 3720
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.106, 1.12
No. of reflections	4773
No. of parameters	402
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.29
Absolute structure	Refined as an inversion twin.
Absolute structure parameter	−2 (2)
Computer programs: APEX2 and SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1859548

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012300/tk4050sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012300/tk4050Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618012300/tk4050Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Methyl 4-{N'-[(1E)-1-(pyrazin-2-yl)ethylidene]hydrazinecarbonyl}benzoate top

Crystal data top

C₁₅H₁₄N₄O₃	Z = 2
M_r = 298.30	F(000) = 312
Triclinic, P1	D_x = 1.392 Mg m⁻³
a = 5.859 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.479 (6) Å	Cell parameters from 1904 reflections
c = 16.329 (14) Å	θ = 2.5–27.2°
α = 93.818 (12)°	µ = 0.10 mm⁻¹
β = 91.29 (3)°	T = 296 K
γ = 94.252 (10)°	Block, colourless
V = 711.7 (10) Å³	0.2 × 0.14 × 0.12 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.026
ω scan	θ_max = 27.6°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −7→7
T_min = 0.654, T_max = 0.746	k = −9→9
5678 measured reflections	l = −21→21
4773 independent reflections	1 standard reflections every 60 reflections
3720 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.050	w = 1/[σ²(F_o²) + (0.0382P)² + 0.0177P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.106	(Δ/σ)_max < 0.001
S = 1.12	Δρ_max = 0.19 e Å⁻³
4773 reflections	Δρ_min = −0.29 e Å⁻³
402 parameters	Absolute structure: Refined as an inversion twin.
3 restraints	Absolute structure parameter: −2 (2)
Primary atom site location: dual

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. Refined as a 2-component inversion twin. The carbon-bound H-atoms were placed in calculated positions (C—H = 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_equiv(C). The N-bound H atoms were fixed with a distance restraint of 0.86 Å, and with U_iso(H) = 1.2U_eq(N).

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

	x	y	z	U_iso*/U_eq
O1	0.3039 (5)	0.6312 (5)	0.84591 (19)	0.0456 (9)
O2	−0.0696 (6)	0.5807 (5)	0.8700 (2)	0.0603 (11)
O3	−0.2556 (5)	0.9093 (4)	0.48052 (17)	0.0385 (8)
N1	0.0715 (6)	0.7886 (5)	0.4389 (2)	0.0363 (9)
H1	0.184869	0.728662	0.452142	0.044*
N2	0.0480 (6)	0.8439 (5)	0.3598 (2)	0.0347 (9)
N3	0.3753 (6)	0.8849 (5)	0.1848 (2)	0.0426 (10)
N4	−0.0495 (6)	0.9510 (6)	0.1154 (2)	0.0473 (11)
C1	0.0809 (8)	0.6288 (6)	0.8255 (3)	0.0385 (12)
C2	0.0443 (7)	0.6855 (6)	0.7409 (3)	0.0289 (10)
C3	−0.1726 (7)	0.6523 (6)	0.7041 (3)	0.0345 (11)
H3	−0.291685	0.600059	0.733219	0.041*
C4	−0.2120 (7)	0.6966 (6)	0.6244 (3)	0.0317 (10)
H4	−0.357790	0.674991	0.600369	0.038*
C5	−0.0347 (7)	0.7733 (5)	0.5799 (3)	0.0280 (10)
C6	−0.0871 (7)	0.8304 (6)	0.4950 (3)	0.0289 (10)
C7	0.2074 (7)	0.8007 (6)	0.3105 (3)	0.0309 (10)
C8	0.1809 (7)	0.8627 (5)	0.2262 (2)	0.0304 (10)
C9	0.3527 (8)	0.9423 (7)	0.1097 (3)	0.0505 (14)
H9	0.483598	0.960426	0.079224	0.061*
C10	0.1469 (8)	0.9758 (7)	0.0753 (3)	0.0498 (14)
H10	0.142571	1.016919	0.022801	0.060*
C11	−0.0282 (7)	0.8952 (6)	0.1906 (3)	0.0394 (12)
H11	−0.159514	0.877206	0.220823	0.047*
C12	0.4108 (7)	0.7020 (6)	0.3303 (3)	0.0383 (11)
H12A	0.507850	0.773304	0.370007	0.057*
H12B	0.494175	0.678822	0.281220	0.057*
H12C	0.361537	0.590111	0.352291	0.057*
C13	0.1824 (7)	0.8081 (6)	0.6165 (3)	0.0326 (10)
H13	0.301552	0.859409	0.587081	0.039*
C14	0.2203 (7)	0.7662 (6)	0.6966 (3)	0.0322 (10)
H14	0.364645	0.792025	0.721296	0.039*
C15	0.3571 (8)	0.5638 (7)	0.9260 (3)	0.0579 (15)
H15A	0.295206	0.441498	0.927091	0.087*
H15B	0.290641	0.636338	0.968545	0.087*
H15C	0.520079	0.569500	0.934761	0.087*
O4	1.0985 (5)	0.1083 (5)	0.8783 (2)	0.0585 (11)
O5	0.7286 (5)	0.0840 (5)	0.83908 (19)	0.0499 (9)
O6	1.3020 (4)	0.4597 (4)	0.49293 (17)	0.0372 (7)
N5	0.9896 (6)	0.2855 (5)	0.4416 (2)	0.0319 (9)
H5	0.880665	0.207106	0.451585	0.038*
N6	1.0116 (6)	0.3429 (5)	0.3625 (2)	0.0326 (9)
N7	0.6591 (6)	0.3785 (6)	0.1892 (2)	0.0441 (10)
N8	1.0817 (6)	0.4420 (6)	0.1156 (2)	0.0468 (11)
C16	0.9514 (7)	0.1210 (6)	0.8273 (3)	0.0339 (11)
C17	0.6688 (9)	0.0272 (8)	0.9194 (3)	0.0625 (16)
H17A	0.505206	0.015827	0.923408	0.094*
H17B	0.732812	0.114865	0.960868	0.094*
H17C	0.728723	−0.086637	0.927206	0.094*
C18	0.9934 (7)	0.1775 (5)	0.7422 (3)	0.0296 (10)
C19	1.2130 (7)	0.2443 (6)	0.7237 (3)	0.0321 (11)
H19	1.330460	0.250763	0.763264	0.039*
C20	1.2559 (6)	0.3010 (5)	0.6461 (3)	0.0293 (10)
H20	1.401801	0.348178	0.634193	0.035*
C21	1.0823 (7)	0.2879 (5)	0.5858 (3)	0.0262 (9)
C22	1.1377 (7)	0.3515 (5)	0.5028 (3)	0.0285 (10)
C23	0.8349 (7)	0.3018 (5)	0.3149 (3)	0.0287 (10)
C24	0.8557 (7)	0.3584 (5)	0.2296 (3)	0.0297 (10)
C25	0.6773 (8)	0.4326 (7)	0.1131 (3)	0.0520 (15)
H25	0.544231	0.449099	0.083317	0.062*
C26	0.8838 (8)	0.4646 (7)	0.0771 (3)	0.0491 (14)
H26	0.886154	0.503283	0.024169	0.059*
C27	1.0638 (7)	0.3898 (6)	0.1920 (3)	0.0369 (11)
H27	1.197488	0.373669	0.221456	0.044*
C28	0.6158 (7)	0.2061 (7)	0.3387 (3)	0.0447 (12)
H28A	0.645604	0.089600	0.355952	0.067*
H28B	0.510368	0.192739	0.292468	0.067*
H28C	0.550842	0.274419	0.383007	0.067*
C29	0.8626 (7)	0.2227 (5)	0.6058 (3)	0.0301 (10)
H29	0.744564	0.215790	0.566363	0.036*
C30	0.8188 (7)	0.1685 (6)	0.6832 (3)	0.0316 (10)
H30	0.671581	0.125808	0.695868	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0410 (19)	0.068 (2)	0.029 (2)	0.0028 (16)	−0.0042 (14)	0.0172 (17)
O2	0.046 (2)	0.107 (3)	0.033 (2)	0.0108 (19)	0.0100 (16)	0.031 (2)
O3	0.0421 (17)	0.0496 (19)	0.0261 (18)	0.0162 (14)	−0.0021 (13)	0.0071 (15)
N1	0.042 (2)	0.050 (2)	0.020 (2)	0.0162 (18)	0.0068 (16)	0.0125 (18)
N2	0.042 (2)	0.043 (2)	0.020 (2)	0.0056 (17)	0.0027 (17)	0.0098 (18)
N3	0.035 (2)	0.065 (3)	0.029 (2)	0.0008 (18)	0.0042 (16)	0.013 (2)
N4	0.043 (2)	0.071 (3)	0.029 (2)	0.010 (2)	0.0032 (18)	0.012 (2)
C1	0.043 (3)	0.045 (3)	0.029 (3)	0.010 (2)	0.003 (2)	0.007 (2)
C2	0.035 (2)	0.034 (2)	0.019 (2)	0.0088 (19)	0.0041 (18)	0.0047 (19)
C3	0.032 (2)	0.045 (3)	0.029 (3)	0.009 (2)	0.009 (2)	0.012 (2)
C4	0.028 (2)	0.040 (3)	0.028 (3)	0.0039 (19)	0.0027 (19)	0.006 (2)
C5	0.035 (2)	0.027 (2)	0.024 (3)	0.0105 (18)	0.0020 (19)	0.0052 (19)
C6	0.037 (2)	0.031 (2)	0.020 (3)	0.0042 (19)	0.0016 (18)	0.0074 (19)
C7	0.033 (2)	0.035 (3)	0.024 (2)	−0.0014 (18)	−0.0006 (18)	0.0042 (19)
C8	0.037 (2)	0.032 (2)	0.022 (3)	−0.0007 (19)	0.0042 (19)	0.007 (2)
C9	0.039 (3)	0.086 (4)	0.028 (3)	−0.001 (3)	0.007 (2)	0.020 (3)
C10	0.053 (3)	0.073 (4)	0.025 (3)	0.009 (3)	0.005 (2)	0.019 (3)
C11	0.036 (2)	0.057 (3)	0.027 (3)	0.009 (2)	0.008 (2)	0.013 (2)
C12	0.036 (2)	0.049 (3)	0.031 (3)	0.003 (2)	0.0014 (19)	0.011 (2)
C13	0.035 (2)	0.039 (3)	0.025 (3)	0.0038 (19)	0.0061 (18)	0.008 (2)
C14	0.031 (2)	0.037 (3)	0.028 (3)	0.0043 (18)	−0.0003 (19)	0.003 (2)
C15	0.060 (3)	0.086 (4)	0.030 (3)	0.003 (3)	−0.010 (2)	0.025 (3)
O4	0.0445 (19)	0.102 (3)	0.031 (2)	0.0038 (19)	−0.0030 (16)	0.027 (2)
O5	0.0430 (19)	0.082 (3)	0.026 (2)	−0.0021 (17)	0.0066 (15)	0.0185 (18)
O6	0.0362 (16)	0.0478 (19)	0.0270 (19)	−0.0075 (14)	−0.0005 (13)	0.0101 (15)
N5	0.0328 (19)	0.042 (2)	0.021 (2)	−0.0054 (16)	0.0013 (16)	0.0086 (17)
N6	0.038 (2)	0.041 (2)	0.019 (2)	−0.0029 (16)	−0.0004 (16)	0.0102 (18)
N7	0.033 (2)	0.068 (3)	0.033 (2)	0.0083 (19)	0.0006 (17)	0.015 (2)
N8	0.041 (2)	0.071 (3)	0.028 (2)	−0.003 (2)	0.0023 (18)	0.009 (2)
C16	0.039 (3)	0.041 (3)	0.024 (3)	0.006 (2)	0.007 (2)	0.009 (2)
C17	0.056 (3)	0.099 (5)	0.035 (3)	0.001 (3)	0.011 (2)	0.028 (3)
C18	0.034 (2)	0.034 (3)	0.022 (3)	0.0071 (19)	0.0039 (18)	0.006 (2)
C19	0.030 (2)	0.045 (3)	0.023 (3)	0.007 (2)	−0.0037 (18)	0.009 (2)
C20	0.027 (2)	0.035 (2)	0.026 (3)	0.0004 (18)	0.0025 (18)	0.007 (2)
C21	0.030 (2)	0.028 (2)	0.021 (2)	0.0056 (17)	0.0024 (17)	0.0057 (18)
C22	0.029 (2)	0.030 (2)	0.027 (3)	0.0055 (19)	−0.0018 (18)	0.0025 (19)
C23	0.031 (2)	0.030 (2)	0.026 (3)	0.0031 (18)	0.0007 (18)	0.004 (2)
C24	0.032 (2)	0.033 (3)	0.025 (2)	0.0012 (18)	−0.0008 (18)	0.003 (2)
C25	0.041 (3)	0.087 (4)	0.030 (3)	0.007 (3)	−0.007 (2)	0.021 (3)
C26	0.047 (3)	0.074 (4)	0.027 (3)	−0.001 (3)	−0.002 (2)	0.015 (3)
C27	0.033 (2)	0.051 (3)	0.027 (3)	0.002 (2)	−0.0041 (19)	0.007 (2)
C28	0.040 (3)	0.058 (3)	0.037 (3)	−0.004 (2)	−0.002 (2)	0.023 (2)
C29	0.028 (2)	0.040 (3)	0.023 (3)	0.0053 (18)	−0.0037 (18)	0.004 (2)
C30	0.029 (2)	0.042 (3)	0.024 (3)	0.0025 (19)	0.0037 (18)	0.008 (2)

Geometric parameters (Å, º) top

O1—C1	1.339 (5)	O4—C16	1.198 (5)
O1—C15	1.468 (5)	O5—C16	1.335 (5)
O2—C1	1.204 (5)	O5—C17	1.448 (5)
O3—C6	1.214 (4)	O6—C22	1.231 (5)
N1—H1	0.8600	N5—H5	0.8600
N1—N2	1.388 (4)	N5—N6	1.393 (5)
N1—C6	1.358 (5)	N5—C22	1.351 (5)
N2—C7	1.292 (5)	N6—C23	1.287 (5)
N3—C8	1.343 (5)	N7—C24	1.338 (5)
N3—C9	1.332 (5)	N7—C25	1.336 (5)
N4—C10	1.343 (6)	N8—C26	1.334 (6)
N4—C11	1.329 (5)	N8—C27	1.334 (5)
C1—C2	1.488 (6)	C16—C18	1.499 (6)
C2—C3	1.392 (6)	C17—H17A	0.9600
C2—C14	1.396 (6)	C17—H17B	0.9600
C3—H3	0.9300	C17—H17C	0.9600
C3—C4	1.383 (6)	C18—C19	1.392 (6)
C4—H4	0.9300	C18—C30	1.384 (6)
C4—C5	1.392 (5)	C19—H19	0.9300
C5—C6	1.509 (6)	C19—C20	1.384 (5)
C5—C13	1.392 (6)	C20—H20	0.9300
C7—C8	1.490 (5)	C20—C21	1.394 (5)
C7—C12	1.488 (5)	C21—C22	1.501 (6)
C8—C11	1.389 (6)	C21—C29	1.395 (6)
C9—H9	0.9300	C23—C24	1.487 (6)
C9—C10	1.366 (6)	C23—C28	1.495 (6)
C10—H10	0.9300	C24—C27	1.389 (6)
C11—H11	0.9300	C25—H25	0.9300
C12—H12A	0.9600	C25—C26	1.369 (6)
C12—H12B	0.9600	C26—H26	0.9300
C12—H12C	0.9600	C27—H27	0.9300
C13—H13	0.9300	C28—H28A	0.9600
C13—C14	1.383 (6)	C28—H28B	0.9600
C14—H14	0.9300	C28—H28C	0.9600
C15—H15A	0.9600	C29—H29	0.9300
C15—H15B	0.9600	C29—C30	1.377 (6)
C15—H15C	0.9600	C30—H30	0.9300

C1—O1—C15	115.6 (4)	C16—O5—C17	116.0 (3)
N2—N1—H1	120.5	N6—N5—H5	119.6
C6—N1—H1	120.5	C22—N5—H5	119.6
C6—N1—N2	119.1 (3)	C22—N5—N6	120.7 (4)
C7—N2—N1	115.2 (3)	C23—N6—N5	114.5 (3)
C9—N3—C8	115.7 (4)	C25—N7—C24	116.3 (4)
C11—N4—C10	115.4 (4)	C26—N8—C27	115.3 (4)
O1—C1—C2	111.8 (4)	O4—C16—O5	123.9 (4)
O2—C1—O1	123.5 (4)	O4—C16—C18	124.6 (4)
O2—C1—C2	124.7 (4)	O5—C16—C18	111.5 (4)
C3—C2—C1	118.4 (4)	O5—C17—H17A	109.5
C3—C2—C14	119.0 (4)	O5—C17—H17B	109.5
C14—C2—C1	122.5 (4)	O5—C17—H17C	109.5
C2—C3—H3	119.8	H17A—C17—H17B	109.5
C4—C3—C2	120.3 (4)	H17A—C17—H17C	109.5
C4—C3—H3	119.8	H17B—C17—H17C	109.5
C3—C4—H4	119.8	C19—C18—C16	118.4 (4)
C3—C4—C5	120.4 (4)	C30—C18—C16	121.6 (4)
C5—C4—H4	119.8	C30—C18—C19	120.0 (4)
C4—C5—C6	118.9 (4)	C18—C19—H19	120.1
C4—C5—C13	119.6 (4)	C20—C19—C18	119.8 (4)
C13—C5—C6	121.3 (4)	C20—C19—H19	120.1
O3—C6—N1	124.5 (4)	C19—C20—H20	119.7
O3—C6—C5	121.5 (4)	C19—C20—C21	120.5 (4)
N1—C6—C5	114.0 (3)	C21—C20—H20	119.7
N2—C7—C8	114.6 (3)	C20—C21—C22	118.4 (4)
N2—C7—C12	126.9 (4)	C20—C21—C29	118.9 (4)
C12—C7—C8	118.6 (4)	C29—C21—C22	122.7 (4)
N3—C8—C7	115.5 (3)	O6—C22—N5	123.6 (4)
N3—C8—C11	120.7 (4)	O6—C22—C21	121.7 (4)
C11—C8—C7	123.7 (4)	N5—C22—C21	114.7 (4)
N3—C9—H9	118.4	N6—C23—C24	115.6 (4)
N3—C9—C10	123.3 (4)	N6—C23—C28	125.5 (4)
C10—C9—H9	118.4	C24—C23—C28	118.9 (4)
N4—C10—C9	121.7 (4)	N7—C24—C23	116.1 (3)
N4—C10—H10	119.2	N7—C24—C27	120.3 (4)
C9—C10—H10	119.2	C27—C24—C23	123.6 (4)
N4—C11—C8	123.1 (4)	N7—C25—H25	118.6
N4—C11—H11	118.4	N7—C25—C26	122.7 (4)
C8—C11—H11	118.4	C26—C25—H25	118.6
C7—C12—H12A	109.5	N8—C26—C25	122.1 (4)
C7—C12—H12B	109.5	N8—C26—H26	119.0
C7—C12—H12C	109.5	C25—C26—H26	119.0
H12A—C12—H12B	109.5	N8—C27—C24	123.4 (4)
H12A—C12—H12C	109.5	N8—C27—H27	118.3
H12B—C12—H12C	109.5	C24—C27—H27	118.3
C5—C13—H13	120.1	C23—C28—H28A	109.5
C14—C13—C5	119.8 (4)	C23—C28—H28B	109.5
C14—C13—H13	120.1	C23—C28—H28C	109.5
C2—C14—H14	119.6	H28A—C28—H28B	109.5
C13—C14—C2	120.7 (4)	H28A—C28—H28C	109.5
C13—C14—H14	119.6	H28B—C28—H28C	109.5
O1—C15—H15A	109.5	C21—C29—H29	119.7
O1—C15—H15B	109.5	C30—C29—C21	120.7 (4)
O1—C15—H15C	109.5	C30—C29—H29	119.7
H15A—C15—H15B	109.5	C18—C30—H30	119.9
H15A—C15—H15C	109.5	C29—C30—C18	120.1 (4)
H15B—C15—H15C	109.5	C29—C30—H30	119.9

O1—C1—C2—C3	165.9 (4)	O4—C16—C18—C19	−9.4 (7)
O1—C1—C2—C14	−12.4 (6)	O4—C16—C18—C30	172.1 (5)
O2—C1—C2—C3	−11.9 (7)	O5—C16—C18—C19	171.3 (4)
O2—C1—C2—C14	169.9 (5)	O5—C16—C18—C30	−7.2 (6)
N1—N2—C7—C8	−179.4 (4)	N5—N6—C23—C24	−178.8 (3)
N1—N2—C7—C12	−1.0 (6)	N5—N6—C23—C28	1.9 (6)
N2—N1—C6—O3	2.5 (7)	N6—N5—C22—O6	−2.3 (6)
N2—N1—C6—C5	−176.3 (4)	N6—N5—C22—C21	175.6 (3)
N2—C7—C8—N3	154.8 (4)	N6—C23—C24—N7	−156.3 (4)
N2—C7—C8—C11	−25.7 (6)	N6—C23—C24—C27	23.7 (6)
N3—C8—C11—N4	−0.7 (7)	N7—C24—C27—N8	0.6 (7)
N3—C9—C10—N4	−0.7 (9)	N7—C25—C26—N8	0.7 (9)
C1—C2—C3—C4	−177.5 (4)	C16—C18—C19—C20	−178.7 (4)
C1—C2—C14—C13	176.4 (4)	C16—C18—C30—C29	179.5 (4)
C2—C3—C4—C5	0.6 (6)	C17—O5—C16—O4	0.5 (7)
C3—C2—C14—C13	−1.8 (6)	C17—O5—C16—C18	179.8 (4)
C3—C4—C5—C6	−176.2 (4)	C18—C19—C20—C21	−1.5 (6)
C3—C4—C5—C13	−1.0 (6)	C19—C18—C30—C29	1.1 (6)
C4—C5—C6—O3	43.3 (6)	C19—C20—C21—C22	179.9 (4)
C4—C5—C6—N1	−137.9 (4)	C19—C20—C21—C29	2.3 (6)
C4—C5—C13—C14	0.0 (6)	C20—C21—C22—O6	−21.9 (6)
C5—C13—C14—C2	1.4 (7)	C20—C21—C22—N5	160.2 (4)
C6—N1—N2—C7	179.2 (4)	C20—C21—C29—C30	−1.4 (6)
C6—C5—C13—C14	175.1 (4)	C21—C29—C30—C18	−0.3 (6)
C7—C8—C11—N4	179.8 (4)	C22—N5—N6—C23	−165.4 (4)
C8—N3—C9—C10	−0.6 (7)	C22—C21—C29—C30	−178.9 (4)
C9—N3—C8—C7	−179.3 (4)	C23—C24—C27—N8	−179.4 (4)
C9—N3—C8—C11	1.2 (6)	C24—N7—C25—C26	0.6 (8)
C10—N4—C11—C8	−0.5 (7)	C25—N7—C24—C23	178.8 (4)
C11—N4—C10—C9	1.2 (8)	C25—N7—C24—C27	−1.2 (7)
C12—C7—C8—N3	−23.8 (6)	C26—N8—C27—C24	0.7 (7)
C12—C7—C8—C11	155.8 (4)	C27—N8—C26—C25	−1.3 (8)
C13—C5—C6—O3	−131.8 (4)	C28—C23—C24—N7	23.0 (6)
C13—C5—C6—N1	47.0 (6)	C28—C23—C24—C27	−157.0 (4)
C14—C2—C3—C4	0.8 (6)	C29—C21—C22—O6	155.6 (4)
C15—O1—C1—O2	2.3 (7)	C29—C21—C22—N5	−22.3 (6)
C15—O1—C1—C2	−175.5 (4)	C30—C18—C19—C20	−0.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱ	0.86	2.31	3.063 (5)	147
N5—H5···O3ⁱⁱ	0.86	2.39	3.172 (5)	151
C10—H10···O4ⁱⁱⁱ	0.93	2.51	3.440 (7)	175
C12—H12A···O3^iv	0.96	2.38	3.327 (6)	171
C12—H12C···O6ⁱ	0.96	2.58	3.360 (6)	139
C28—H28A···O3ⁱⁱ	0.96	2.59	3.422 (6)	145

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

Funding information

The authors would like to thank the major cultivation project of Chongqing University of Arts and Sciences (No. P2017CH10) for financial support.

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