Crystal structure of pymetrozine

Jeon, Y.; Kim, J.; Kang, G.; Kim, T.H.

doi:10.1107/S2056989015010804

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 7| July 2015| Pages o461-o462

doi:10.1107/S2056989015010804

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Crystal structure of pymetrozine

Youngeun Jeon,^a Jineun Kim,^a ^* Gihaeng Kang ^a and Tae Ho Kim ^a ^*

^aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea
^*Correspondence e-mail: thkim@gnu.ac.kr, jekim@gnu.ac.kr

Edited by J. Simpson, University of Otago, New Zealand (Received 28 May 2015; accepted 4 June 2015; online 10 June 2015)

The title compound, C₁₀H₁₁N₅O {systematic name: 6-methyl-4-[(E)-(pyridin-3-ylmethylidene)amino]-4,5-dihydro-1,2,4-triazin-3(2H)-one}, C₁₀H₁₁N₅O, is used as an antifeedant in pest control. The asymmetric unit comprises two independent molecules, A and B, in which the dihedral angles between the pyridinyl and triazinyl ring planes [r.m.s. deviations = 0.0132 and 0.0255 ] are 11.60 (6) and 18.06 (4)°, respectively. In the crystal, N—H⋯O, N—H⋯N, C—H⋯N and C—H⋯O hydrogen bonds, together with weak π–π interactions [ring-centroid separations = 3.5456 (9) and 3.9142 (9) Å], link the pyridinyl and triazinyl rings of A molecules, generating a three-dimensional network.

Keywords: crystal structure; pymetrozine; triazinone; insecticide; antifeedant; hydrogen bonding; π–π interactions.

CCDC reference: 1404941

1. Related literature

For information on the toxicity and insecticidal properties of the title compound, see: He et al. (2011 ); Torres et al. (2003 ); Ausborn et al. (2005 ); Barati et al. (2013 ). For a related crystal structure, see: Wang et al. (2012 ).

2. Experimental

2.1. Crystal data

C₁₀H₁₁N₅O
M_r = 217.24
Monoclinic, P 2₁ /n
a = 8.0803 (2) Å
b = 23.7497 (6) Å
c = 10.7846 (3) Å
β = 98.962 (1)°
V = 2044.35 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 K
0.37 × 0.16 × 0.09 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.964, T_max = 0.991
19037 measured reflections
3987 independent reflections
3103 reflections with I > 2σ(I)
R_int = 0.042

2.3. Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.107
S = 1.04
3987 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O2ⁱ	0.88	2.32	2.9545 (17)	129
N4—H4⋯N7ⁱ	0.88	2.43	3.2346 (17)	152
N9—H9⋯N6ⁱⁱ	0.88	2.04	2.882 (2)	159
C19—H19A⋯N1ⁱⁱⁱ	0.99	2.57	3.0852 (19)	112
C19—H19A⋯O1^iv	0.99	2.60	3.5596 (19)	164
C20—H20C⋯O1^v	0.98	2.53	3.3906 (19)	147
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) x-1, y, z-1; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1404941

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015010804/sj5463sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015010804/sj5463Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015010804/sj5463Isup3.cml

checkCIF report

Comment top

Pymetrozine: 4,5-dihydro-6-methyl-4-[(E)-(3-pyridinylmethylene)amino]-1,2,4-triazin-3(2H)-one, is an insecticide for the control of sucking insects, including the brown planthopper, Nilaparvata lugens, one of the most serious pests to affect rice crops (He et al., 2011). Its crystal structure is reported herein. In the title compound (Fig. 1), the asymmetric unit comprises two independent molecules (A and B) and the dihedral angles between the pyridinyl and triazinyl ring planes are 11.60 (6) and 18.06 (4)° for A and B, respectively. All bond lengths and bond angles are normal and comparable to those observed in a similar crystal structure (Wang et al., 2012).

The crystal structure, Fig. 2, is stabilized by intermolecular N—H···O, N—H···N, C—H···N and C—H···O hydrogen bonds (Table 1). In addition, weak intermolecular π···π interactions between the pyridinyl and triazinyl rings link adjacent A molecules [Cg1···Cg2ⁱ, 3.5456 (9) Å and Cg1···Cg2ⁱⁱ, 3.9142 (9) Å] symmetry codes: (i) = x + 1/2, -y + 1/2, z + 1/2, (ii) = x + 1, y, z; Cg1 and Cg2 are the centroids of the N1···C5 and N3···C9 rings, respectively]. The π···π interactions together with C1–H1···N5 hydrogen bonds generate sheets of A molecules in the ac plane. All of these contacts combine to generate a three dimensional network, Fig. 2.

Related literature top

For information on the toxicity and insecticidal properties of the title compound, see: He et al. (2011); Torres et al. (2003); Ausborn et al. (2005); Barati et al. (2013). For a related crystal structure, see: Wang et al. (2012).

Experimental top

The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation of a solution in CH₂Cl₂ gave single crystals suitable for X-ray analysis.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. Crystal packing viewed along the a axis. The hydrogen bonds are shown as dashed lines.

6-Methyl-4-[(E)-(pyridin-3-ylmethylidene)amino]-4,5-dihydro-1,2,4-triazin-3(2H)-one top

Crystal data top

C₁₀H₁₁N₅O	F(000) = 912
M_r = 217.24	D_x = 1.412 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.0803 (2) Å	Cell parameters from 3981 reflections
b = 23.7497 (6) Å	θ = 2.7–27.3°
c = 10.7846 (3) Å	µ = 0.10 mm⁻¹
β = 98.962 (1)°	T = 173 K
V = 2044.35 (9) Å³	Block, colourless
Z = 8	0.37 × 0.16 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	3987 independent reflections
Radiation source: fine-focus sealed tube	3103 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→9
T_min = 0.964, T_max = 0.991	k = −28→29
19037 measured reflections	l = −13→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0528P)² + 0.3325P] where P = (F_o² + 2F_c²)/3
3987 reflections	(Δ/σ)_max = 0.001
291 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₀H₁₁N₅O	V = 2044.35 (9) Å³
M_r = 217.24	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.0803 (2) Å	µ = 0.10 mm⁻¹
b = 23.7497 (6) Å	T = 173 K
c = 10.7846 (3) Å	0.37 × 0.16 × 0.09 mm
β = 98.962 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3987 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3103 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.991	R_int = 0.042
19037 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.04	Δρ_max = 0.19 e Å⁻³
3987 reflections	Δρ_min = −0.31 e Å⁻³
291 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
O1	0.54588 (13)	0.37396 (4)	0.67454 (12)	0.0371 (3)
O2	0.65704 (12)	0.09515 (4)	−0.11461 (10)	0.0298 (3)
N1	1.18740 (16)	0.17122 (6)	0.90565 (15)	0.0353 (4)
N2	0.70889 (14)	0.27719 (5)	0.72493 (13)	0.0269 (3)
N3	0.54303 (15)	0.27730 (5)	0.67218 (13)	0.0272 (3)
N4	0.31072 (15)	0.32889 (5)	0.58809 (14)	0.0333 (3)
H4	0.2610	0.3618	0.5750	0.040*
N5	0.21533 (15)	0.28219 (5)	0.54719 (14)	0.0314 (3)
N6	0.56087 (18)	0.08007 (6)	0.54024 (13)	0.0362 (3)
N7	0.53681 (14)	0.07233 (5)	0.09543 (12)	0.0226 (3)
N8	0.43763 (14)	0.06556 (5)	−0.01909 (12)	0.0212 (3)
N9	0.41093 (15)	0.07374 (5)	−0.23457 (12)	0.0273 (3)
H9	0.4531	0.0850	−0.3008	0.033*
N10	0.24931 (16)	0.05238 (5)	−0.25699 (13)	0.0266 (3)
C1	1.28109 (19)	0.21759 (7)	0.91859 (17)	0.0325 (4)
H1	1.3940	0.2145	0.9587	0.039*
C2	1.22268 (19)	0.26979 (7)	0.87674 (17)	0.0346 (4)
H2	1.2949	0.3016	0.8865	0.041*
C3	1.05822 (19)	0.27537 (6)	0.82046 (17)	0.0319 (4)
H3	1.0158	0.3109	0.7900	0.038*
C4	0.95585 (18)	0.22816 (6)	0.80914 (15)	0.0253 (3)
C5	1.02808 (19)	0.17746 (6)	0.85192 (16)	0.0305 (4)
H5	0.9594	0.1448	0.8423	0.037*
C6	0.77874 (18)	0.22966 (6)	0.75433 (16)	0.0269 (4)
H6	0.7162	0.1958	0.7407	0.032*
C7	0.47257 (18)	0.32978 (6)	0.64618 (16)	0.0275 (4)
C8	0.28134 (18)	0.23414 (7)	0.57182 (16)	0.0281 (4)
C9	0.45481 (18)	0.22477 (6)	0.63922 (16)	0.0274 (4)
H9A	0.4495	0.2029	0.7167	0.033*
H9B	0.5183	0.2022	0.5853	0.033*
C10	0.1823 (2)	0.18265 (7)	0.53033 (19)	0.0397 (5)
H10A	0.0639	0.1927	0.5073	0.060*
H10B	0.1946	0.1552	0.5989	0.060*
H10C	0.2234	0.1663	0.4575	0.060*
C11	0.7273 (2)	0.08409 (7)	0.55839 (17)	0.0368 (4)
H11	0.7839	0.0886	0.6418	0.044*
C12	0.8219 (2)	0.08200 (7)	0.46212 (17)	0.0340 (4)
H12	0.9406	0.0842	0.4797	0.041*
C13	0.74117 (19)	0.07667 (6)	0.34017 (16)	0.0283 (4)
H13	0.8032	0.0761	0.2722	0.034*
C14	0.56786 (18)	0.07210 (6)	0.31837 (15)	0.0247 (3)
C15	0.4844 (2)	0.07337 (7)	0.42216 (16)	0.0315 (4)
H15	0.3661	0.0692	0.4080	0.038*
C16	0.46794 (19)	0.06629 (6)	0.19390 (15)	0.0250 (3)
H16	0.3517	0.0580	0.1860	0.030*
C17	0.51141 (17)	0.07926 (6)	−0.12215 (14)	0.0219 (3)
C18	0.18317 (18)	0.03964 (6)	−0.16097 (15)	0.0241 (3)
C19	0.26507 (17)	0.04665 (6)	−0.02804 (15)	0.0233 (3)
H19A	0.2010	0.0744	0.0140	0.028*
H19B	0.2626	0.0103	0.0164	0.028*
C20	0.01097 (18)	0.01533 (7)	−0.17992 (17)	0.0324 (4)
H20A	−0.0309	0.0125	−0.2700	0.049*
H20B	−0.0633	0.0397	−0.1402	0.049*
H20C	0.0140	−0.0222	−0.1420	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0312 (6)	0.0260 (6)	0.0533 (9)	0.0021 (5)	0.0041 (5)	−0.0001 (6)
O2	0.0280 (6)	0.0374 (6)	0.0254 (7)	−0.0084 (4)	0.0079 (5)	−0.0027 (5)
N1	0.0292 (7)	0.0321 (7)	0.0420 (10)	0.0044 (6)	−0.0023 (6)	0.0034 (7)
N2	0.0211 (7)	0.0294 (7)	0.0295 (8)	0.0016 (5)	0.0015 (5)	0.0001 (6)
N3	0.0219 (6)	0.0254 (7)	0.0327 (8)	0.0026 (5)	−0.0004 (6)	0.0018 (6)
N4	0.0254 (7)	0.0264 (7)	0.0465 (10)	0.0062 (5)	0.0010 (6)	0.0034 (7)
N5	0.0243 (7)	0.0336 (7)	0.0354 (9)	0.0011 (5)	0.0024 (6)	0.0027 (6)
N6	0.0471 (9)	0.0417 (8)	0.0204 (8)	−0.0003 (6)	0.0073 (6)	−0.0018 (7)
N7	0.0266 (7)	0.0222 (6)	0.0185 (7)	−0.0007 (5)	0.0024 (5)	−0.0007 (6)
N8	0.0214 (6)	0.0250 (6)	0.0170 (7)	−0.0028 (5)	0.0029 (5)	0.0000 (5)
N9	0.0299 (7)	0.0342 (7)	0.0182 (7)	−0.0078 (5)	0.0045 (5)	0.0019 (6)
N10	0.0275 (7)	0.0257 (7)	0.0256 (8)	−0.0025 (5)	0.0004 (6)	−0.0010 (6)
C1	0.0243 (8)	0.0389 (9)	0.0330 (10)	0.0029 (7)	0.0007 (7)	−0.0018 (8)
C2	0.0274 (8)	0.0322 (9)	0.0431 (12)	−0.0046 (6)	0.0024 (7)	−0.0014 (8)
C3	0.0310 (9)	0.0248 (8)	0.0392 (11)	0.0023 (6)	0.0031 (7)	0.0020 (8)
C4	0.0252 (8)	0.0270 (8)	0.0236 (9)	0.0028 (6)	0.0037 (6)	−0.0019 (7)
C5	0.0291 (8)	0.0256 (8)	0.0352 (10)	−0.0008 (6)	0.0002 (7)	−0.0008 (7)
C6	0.0260 (8)	0.0264 (8)	0.0278 (9)	0.0006 (6)	0.0031 (7)	−0.0001 (7)
C7	0.0257 (8)	0.0265 (8)	0.0313 (10)	0.0039 (6)	0.0080 (7)	0.0031 (7)
C8	0.0246 (8)	0.0332 (8)	0.0267 (9)	0.0011 (6)	0.0049 (7)	0.0029 (7)
C9	0.0271 (8)	0.0246 (8)	0.0299 (10)	0.0011 (6)	0.0022 (7)	0.0017 (7)
C10	0.0313 (9)	0.0361 (9)	0.0482 (12)	−0.0030 (7)	−0.0046 (8)	0.0022 (9)
C11	0.0496 (11)	0.0346 (9)	0.0233 (10)	0.0021 (8)	−0.0032 (8)	−0.0025 (8)
C12	0.0341 (9)	0.0313 (9)	0.0344 (11)	−0.0002 (7)	−0.0015 (7)	−0.0027 (8)
C13	0.0357 (9)	0.0231 (8)	0.0270 (9)	−0.0011 (6)	0.0078 (7)	−0.0009 (7)
C14	0.0320 (8)	0.0206 (7)	0.0219 (9)	−0.0001 (6)	0.0052 (6)	−0.0004 (7)
C15	0.0358 (9)	0.0349 (9)	0.0249 (9)	−0.0010 (7)	0.0079 (7)	−0.0005 (8)
C16	0.0270 (8)	0.0268 (8)	0.0221 (9)	−0.0006 (6)	0.0064 (6)	−0.0003 (7)
C17	0.0268 (8)	0.0190 (7)	0.0207 (8)	−0.0017 (6)	0.0067 (6)	−0.0010 (6)
C18	0.0257 (8)	0.0194 (7)	0.0267 (9)	0.0016 (6)	0.0023 (7)	−0.0004 (7)
C19	0.0223 (7)	0.0240 (7)	0.0243 (9)	−0.0006 (5)	0.0059 (6)	0.0024 (7)
C20	0.0268 (8)	0.0328 (8)	0.0367 (10)	−0.0015 (6)	0.0021 (7)	0.0004 (8)

Geometric parameters (Å, º) top

O1—C7	1.2202 (18)	C4—C5	1.385 (2)
O2—C17	1.2263 (16)	C4—C6	1.461 (2)
N1—C1	1.331 (2)	C5—H5	0.9500
N1—C5	1.3352 (19)	C6—H6	0.9500
N2—C6	1.2797 (19)	C8—C10	1.491 (2)
N2—N3	1.3719 (17)	C8—C9	1.492 (2)
N3—C7	1.3807 (18)	C9—H9A	0.9900
N3—C9	1.4534 (18)	C9—H9B	0.9900
N4—C7	1.3594 (19)	C10—H10A	0.9800
N4—N5	1.3832 (17)	C10—H10B	0.9800
N4—H4	0.8800	C10—H10C	0.9800
N5—C8	1.2701 (19)	C11—C12	1.383 (2)
N6—C11	1.332 (2)	C11—H11	0.9500
N6—C15	1.335 (2)	C12—C13	1.380 (2)
N7—C16	1.281 (2)	C12—H12	0.9500
N7—N8	1.3730 (17)	C13—C14	1.388 (2)
N8—C17	1.3795 (19)	C13—H13	0.9500
N8—C19	1.4536 (17)	C14—C15	1.394 (2)
N9—C17	1.3564 (19)	C14—C16	1.461 (2)
N9—N10	1.3867 (17)	C15—H15	0.9500
N9—H9	0.8800	C16—H16	0.9500
N10—C18	1.274 (2)	C18—C20	1.491 (2)
C1—C2	1.377 (2)	C18—C19	1.492 (2)
C1—H1	0.9500	C19—H19A	0.9900
C2—C3	1.379 (2)	C19—H19B	0.9900
C2—H2	0.9500	C20—H20A	0.9800
C3—C4	1.387 (2)	C20—H20B	0.9800
C3—H3	0.9500	C20—H20C	0.9800

C1—N1—C5	116.61 (13)	N3—C9—H9B	109.2
C6—N2—N3	117.97 (12)	C8—C9—H9B	109.2
N2—N3—C7	115.55 (12)	H9A—C9—H9B	107.9
N2—N3—C9	120.66 (11)	C8—C10—H10A	109.5
C7—N3—C9	123.66 (12)	C8—C10—H10B	109.5
C7—N4—N5	127.42 (12)	H10A—C10—H10B	109.5
C7—N4—H4	116.3	C8—C10—H10C	109.5
N5—N4—H4	116.3	H10A—C10—H10C	109.5
C8—N5—N4	117.31 (13)	H10B—C10—H10C	109.5
C11—N6—C15	117.07 (15)	N6—C11—C12	123.42 (16)
C16—N7—N8	117.67 (12)	N6—C11—H11	118.3
N7—N8—C17	115.60 (11)	C12—C11—H11	118.3
N7—N8—C19	121.02 (12)	C13—C12—C11	118.97 (16)
C17—N8—C19	123.36 (12)	C13—C12—H12	120.5
C17—N9—N10	127.41 (13)	C11—C12—H12	120.5
C17—N9—H9	116.3	C12—C13—C14	118.91 (16)
N10—N9—H9	116.3	C12—C13—H13	120.5
C18—N10—N9	116.63 (13)	C14—C13—H13	120.5
N1—C1—C2	123.36 (14)	C13—C14—C15	117.63 (15)
N1—C1—H1	118.3	C13—C14—C16	124.17 (15)
C2—C1—H1	118.3	C15—C14—C16	118.20 (14)
C1—C2—C3	119.24 (15)	N6—C15—C14	123.96 (15)
C1—C2—H2	120.4	N6—C15—H15	118.0
C3—C2—H2	120.4	C14—C15—H15	118.0
C2—C3—C4	118.79 (14)	N7—C16—C14	120.11 (14)
C2—C3—H3	120.6	N7—C16—H16	119.9
C4—C3—H3	120.6	C14—C16—H16	119.9
C5—C4—C3	117.30 (14)	O2—C17—N9	121.57 (14)
C5—C4—C6	119.41 (13)	O2—C17—N8	123.36 (14)
C3—C4—C6	123.28 (13)	N9—C17—N8	115.07 (12)
N1—C5—C4	124.65 (14)	N10—C18—C20	118.78 (14)
N1—C5—H5	117.7	N10—C18—C19	125.12 (13)
C4—C5—H5	117.7	C20—C18—C19	116.10 (14)
N2—C6—C4	119.22 (14)	N8—C19—C18	112.06 (12)
N2—C6—H6	120.4	N8—C19—H19A	109.2
C4—C6—H6	120.4	C18—C19—H19A	109.2
O1—C7—N4	121.57 (14)	N8—C19—H19B	109.2
O1—C7—N3	123.81 (14)	C18—C19—H19B	109.2
N4—C7—N3	114.60 (13)	H19A—C19—H19B	107.9
N5—C8—C10	119.06 (14)	C18—C20—H20A	109.5
N5—C8—C9	124.62 (14)	C18—C20—H20B	109.5
C10—C8—C9	116.31 (13)	H20A—C20—H20B	109.5
N3—C9—C8	112.26 (12)	C18—C20—H20C	109.5
N3—C9—H9A	109.2	H20A—C20—H20C	109.5
C8—C9—H9A	109.2	H20B—C20—H20C	109.5

C6—N2—N3—C7	177.92 (15)	C7—N3—C9—C8	1.3 (2)
C6—N2—N3—C9	−6.1 (2)	N5—C8—C9—N3	−1.1 (2)
C7—N4—N5—C8	4.1 (2)	C10—C8—C9—N3	178.12 (14)
C16—N7—N8—C17	172.24 (12)	C15—N6—C11—C12	0.4 (2)
C16—N7—N8—C19	−6.07 (19)	N6—C11—C12—C13	1.4 (3)
C17—N9—N10—C18	4.7 (2)	C11—C12—C13—C14	−1.7 (2)
C5—N1—C1—C2	−1.8 (3)	C12—C13—C14—C15	0.2 (2)
N1—C1—C2—C3	1.3 (3)	C12—C13—C14—C16	179.96 (14)
C1—C2—C3—C4	0.8 (3)	C11—N6—C15—C14	−2.0 (2)
C2—C3—C4—C5	−2.1 (2)	C13—C14—C15—N6	1.7 (2)
C2—C3—C4—C6	178.24 (16)	C16—C14—C15—N6	−178.07 (14)
C1—N1—C5—C4	0.3 (3)	N8—N7—C16—C14	179.00 (12)
C3—C4—C5—N1	1.7 (3)	C13—C14—C16—N7	−8.9 (2)
C6—C4—C5—N1	−178.69 (16)	C15—C14—C16—N7	170.84 (14)
N3—N2—C6—C4	179.19 (14)	N10—N9—C17—O2	174.79 (13)
C5—C4—C6—N2	174.00 (15)	N10—N9—C17—N8	−5.0 (2)
C3—C4—C6—N2	−6.4 (3)	N7—N8—C17—O2	1.8 (2)
N5—N4—C7—O1	177.59 (16)	C19—N8—C17—O2	−179.92 (13)
N5—N4—C7—N3	−3.9 (2)	N7—N8—C17—N9	−178.42 (11)
N2—N3—C7—O1	−4.7 (2)	C19—N8—C17—N9	−0.15 (19)
C9—N3—C7—O1	179.44 (15)	N9—N10—C18—C20	−178.69 (13)
N2—N3—C7—N4	176.77 (13)	N9—N10—C18—C19	0.8 (2)
C9—N3—C7—N4	1.0 (2)	N7—N8—C19—C18	−177.33 (11)
N4—N5—C8—C10	179.51 (15)	C17—N8—C19—C18	4.49 (19)
N4—N5—C8—C9	−1.3 (2)	N10—C18—C19—N8	−5.0 (2)
N2—N3—C9—C8	−174.34 (14)	C20—C18—C19—N8	174.58 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O2ⁱ	0.88	2.32	2.9545 (17)	129
N4—H4···N7ⁱ	0.88	2.43	3.2346 (17)	152
N9—H9···N6ⁱⁱ	0.88	2.04	2.882 (2)	159
C19—H19A···N1ⁱⁱⁱ	0.99	2.57	3.0852 (19)	112
C19—H19A···O1^iv	0.99	2.60	3.5596 (19)	164
C20—H20C···O1^v	0.98	2.53	3.3906 (19)	147

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O2ⁱ	0.88	2.32	2.9545 (17)	128.7
N4—H4···N7ⁱ	0.88	2.43	3.2346 (17)	152.4
N9—H9···N6ⁱⁱ	0.88	2.04	2.882 (2)	159.0
C19—H19A···N1ⁱⁱⁱ	0.99	2.57	3.0852 (19)	112.0
C19—H19A···O1^iv	0.99	2.60	3.5596 (19)	163.8
C20—H20C···O1^v	0.98	2.53	3.3906 (19)	147.0

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

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2014R1A1A4A01009105).

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