3,6-Dimethyl-N1,N4-bis­(1-phenyl­eth­yl)-1,4-dihydro-1,2,4,5-tetra­zine-1,4-dicarboxamide

Rao, G.-W.; Li, Q.; Lu, X.-J.

doi:10.1107/S160053681200133X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o428

doi:10.1107/S160053681200133X

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3,6-Dimethyl-N¹,N⁴-bis(1-phenylethyl)-1,4-dihydro-1,2,4,5-tetrazine-1,4-dicarboxamide

Guo-Wu Rao,^a ^* Qi Li ^a and Xiao-Jing Lu ^a

^aCollege of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou, 310014, People's Republic of China
^*Correspondence e-mail: rgw@zjut.edu.cn

(Received 3 January 2012; accepted 11 January 2012; online 18 January 2012)

In the title molecule, C₂₂H₂₆N₆O₂, the central tetrazine ring exhibits a boat conformation, and the two phenyl rings form a dihedral angle of 88.39 (6)°. In the crystal, weak N—H⋯O and C—H⋯O hydrogen bonds link molecules into layers parallel to the ab plane.

Related literature

For structure–activity relationships in 1,2,4,5-tetrazine derivatives, see: Hu et al. (2002 , 2004 ); Rao & Hu (2005 , 2006 ). For standard bond lengths in organic compounds, see: Allen et al. (1987 ). For details of the synthesis, see: Hu et al. (2004); Skorianetz & Kovats (1970 , 1971 ); Sun et al. (2003 ).

Experimental

Crystal data

C₂₂H₂₆N₆O₂
M_r = 406.49
Monoclinic, P 2₁
a = 10.4653 (15) Å
b = 8.0606 (12) Å
c = 13.711 (2) Å
β = 108.702 (1)°
V = 1095.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.37 × 0.31 × 0.26 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.970, T_max = 0.979
8343 measured reflections
4014 independent reflections
3809 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.072
S = 1.06
4014 reflections
276 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.09 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6⋯O1ⁱ	0.86	2.44	3.2497 (15)	158
N3—H3⋯O2ⁱⁱ	0.86	2.54	3.2706 (16)	144
C13—H13⋯O2ⁱⁱ	0.93	2.57	3.4701 (17)	163
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681200133X/cv5230sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200133X/cv5230Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200133X/cv5230Isup3.cdx

Supporting information file. DOI: 10.1107/S160053681200133X/cv5230Isup4.cml

checkCIF report

Comment top

In a continuation of our studies of structure-activity relationships in 1,2,4,5-tetrazine derivatives (Hu et al., 2002, 2004; Rao & Hu, 2005, 2006), we have obtained the title compound (I) as colourless crystalline solid. However, IR, NMR, and MS studies failed to prove whether the substituted groups of the nitrogen are located at the 1,4 or 1,2 positions. The structure was confirmed by single-crystal X-ray diffraction.

In (I) (Fig. 1), the N2═C3 [1.2753 (17) Å] and N5═C6 [1.2752 (18) Å] bonds correspond to typical double bonds, and the C3—N4 [1.4013 (16) Å], N4—N5 [1.4194 (15) Å], C6—N1 [1.3959 (18) Å] and N1—N2 [1.4247 (15) Å] bond lengths are typical for single bonds (Allen et al., 1987). Therefore, the tetrazine ring is the 1,4-dihydro structure with the N-substituted groups at the 1,4-positions and not the 1,2-positions, the compound being 3,6-dimethyl-N¹,N⁴-bis(1-phenylethyl)-1,2,4,5-tetrazine-1,4-dicarboxamide. Atoms N2, C3, N5 and C6 are coplanar, with the largest deviation from the plane being -0.0237 (7) Å for atom N2 and 0.0237 (7) Å for atom C6. Atoms N1 and N4 deviate from this plane by 0.3601 (21) and 0.3674 (20) Å, respectively. The dihedral angle between the N2/C3/N5/C6 plane and the N1/N2/C6 plane is 29.04 (15)°, and between the N2/C3/N5/C6 plane and the N4/N5/C3 plane is 29.72 (12)°. Therefore, the central six-member ring of the compound, the tetrazine ring, has an obvious boat conformation. The dihedral angles between the N2/C3/N5/C6 plane and the two phenyl rings are 33.24 (7) and 58.46 (6)°, respectively. The dihedral angle between the two phenyl rings is 88.39 (6)°.

In the crystal structure, weak intermolecular N—H···O and C—H···O hydrogen bonds (Table 1) link molecules into layers parallel to ab plane (Fig. 2).

Related literature top

For structure–activity relationships in 1,2,4,5-tetrazine derivatives, see: Hu et al. (2002, 2004); Rao & Hu (2005, 2006). For standard bond lengths in organic compounds, see: Allen et al. (1987). For details of the synthesis, see: Hu et al. (2004); Skorianetz & Kovats (1970, 1971); Sun et al. (2003).

Experimental top

The title compound was prepared according to the known procedure (Hu et al., 2004; Sun et al., 2003; Skorianetz et al., 1970, 1971). A solution of the compound in ethanol was concentrated gradually at room temperature to afford colourless blocks (m.p. 414–416 K).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I) shown with 30% probability displacement ellipsoids.
	Fig. 2. A portion of the crystal packing of (I). Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding were omitted for clarity.

3,6-Dimethyl-N¹,N⁴-bis(1-phenylethyl)-1,4-dihydro- 1,2,4,5-tetrazine-1,4-dicarboxamide top

Crystal data top

C₂₂H₂₆N₆O₂	F(000) = 432
M_r = 406.49	D_x = 1.232 Mg m⁻³
Monoclinic, P2₁	Melting point = 414–416 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 10.4653 (15) Å	Cell parameters from 5504 reflections
b = 8.0606 (12) Å	θ = 3.0–28.2°
c = 13.711 (2) Å	µ = 0.08 mm⁻¹
β = 108.702 (1)°	T = 298 K
V = 1095.5 (3) Å³	Block, colourless
Z = 2	0.37 × 0.31 × 0.26 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4014 independent reflections
Radiation source: fine-focus sealed tube	3809 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
phi and ω scans	θ_max = 25.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
T_min = 0.970, T_max = 0.979	k = −9→9
8343 measured reflections	l = −16→16

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)] = 0.028	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0351P)² + 0.1082P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
4014 reflections	Δρ_max = 0.12 e Å⁻³
276 parameters	Δρ_min = −0.09 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.079 (3)

Crystal data top

C₂₂H₂₆N₆O₂	V = 1095.5 (3) Å³
M_r = 406.49	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 10.4653 (15) Å	µ = 0.08 mm⁻¹
b = 8.0606 (12) Å	T = 298 K
c = 13.711 (2) Å	0.37 × 0.31 × 0.26 mm
β = 108.702 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4014 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3809 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.979	R_int = 0.016
8343 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	1 restraint
wR(F²) = 0.072	H-atom parameters constrained
S = 1.06	Δρ_max = 0.12 e Å⁻³
4014 reflections	Δρ_min = −0.09 e Å⁻³
276 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
C6	0.61215 (13)	0.43115 (19)	0.45138 (10)	0.0457 (3)
C2	0.46716 (15)	0.3828 (3)	0.42427 (14)	0.0711 (5)
H2A	0.4590	0.2892	0.4652	0.107*
H2B	0.4330	0.3540	0.3526	0.107*
H2C	0.4163	0.4742	0.4376	0.107*
C3	0.87224 (13)	0.45508 (17)	0.46277 (10)	0.0426 (3)
C4	1.00874 (16)	0.4220 (3)	0.45547 (13)	0.0663 (5)
H4A	1.0746	0.4853	0.5069	0.099*
H4B	1.0107	0.4533	0.3884	0.099*
H4C	1.0290	0.3059	0.4664	0.099*
C5	0.57571 (13)	0.67504 (18)	0.33409 (9)	0.0415 (3)
C1	0.57492 (15)	0.9210 (2)	0.23003 (11)	0.0541 (4)
H1	0.4798	0.9198	0.2263	0.065*
C7	0.6404 (2)	1.0771 (3)	0.28855 (15)	0.0829 (6)
H7A	0.7352	1.0766	0.2974	0.124*
H7B	0.6274	1.0790	0.3548	0.124*
H7C	0.5995	1.1737	0.2501	0.124*
C8	0.58090 (13)	0.92220 (18)	0.12079 (10)	0.0443 (3)
C9	0.46735 (16)	0.9574 (3)	0.03815 (13)	0.0680 (5)
H9	0.3853	0.9760	0.0492	0.082*
C10	0.47455 (17)	0.9652 (3)	−0.06069 (14)	0.0762 (6)
H10	0.3974	0.9893	−0.1155	0.091*
C11	0.59346 (17)	0.9381 (3)	−0.07856 (12)	0.0671 (5)
H11	0.5977	0.9432	−0.1452	0.080*
C12	0.70692 (17)	0.9031 (3)	0.00266 (13)	0.0667 (5)
H12	0.7885	0.8839	−0.0089	0.080*
C13	0.70020 (14)	0.8965 (2)	0.10129 (11)	0.0565 (4)
H13	0.7781	0.8741	0.1558	0.068*
C14	0.91963 (12)	0.34611 (17)	0.64199 (9)	0.0372 (3)
C15	0.92829 (13)	0.22812 (17)	0.80845 (9)	0.0400 (3)
H15	1.0155	0.2853	0.8314	0.048*
C16	0.85082 (18)	0.2769 (2)	0.88085 (12)	0.0582 (4)
H16A	0.7633	0.2259	0.8584	0.087*
H16B	0.8408	0.3953	0.8805	0.087*
H16C	0.8994	0.2403	0.9494	0.087*
C17	0.95569 (12)	0.04323 (17)	0.81019 (9)	0.0381 (3)
C18	1.08568 (15)	−0.0187 (2)	0.84585 (12)	0.0520 (4)
H18	1.1579	0.0542	0.8700	0.062*
C19	1.11002 (18)	−0.1875 (2)	0.84623 (14)	0.0625 (4)
H19	1.1980	−0.2273	0.8705	0.075*
C20	1.00479 (19)	−0.2956 (2)	0.81091 (13)	0.0660 (4)
H20	1.0208	−0.4091	0.8111	0.079*
C21	0.87547 (19)	−0.2360 (2)	0.77518 (16)	0.0734 (5)
H21	0.8038	−0.3095	0.7506	0.088*
C22	0.85099 (15)	−0.0688 (2)	0.77539 (13)	0.0582 (4)
H22	0.7626	−0.0303	0.7518	0.070*
N1	0.65789 (11)	0.55475 (16)	0.39939 (8)	0.0449 (3)
N2	0.78681 (11)	0.52904 (15)	0.38757 (8)	0.0461 (3)
N4	0.83276 (10)	0.39916 (16)	0.54557 (8)	0.0433 (3)
N5	0.69652 (11)	0.34775 (17)	0.52228 (9)	0.0489 (3)
N3	0.64017 (12)	0.77317 (17)	0.28704 (9)	0.0520 (3)
H3	0.7215	0.7495	0.2901	0.062*
N6	0.85493 (10)	0.28577 (15)	0.70385 (8)	0.0426 (3)
H6	0.7683	0.2805	0.6819	0.051*
O1	0.45662 (10)	0.68726 (15)	0.32671 (8)	0.0580 (3)
O2	1.04136 (9)	0.36545 (14)	0.66573 (7)	0.0497 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C6	0.0430 (7)	0.0569 (8)	0.0349 (6)	−0.0023 (6)	0.0093 (5)	0.0085 (6)
C2	0.0442 (8)	0.0935 (14)	0.0659 (10)	−0.0094 (9)	0.0040 (7)	0.0340 (10)
C3	0.0460 (7)	0.0469 (8)	0.0368 (6)	0.0050 (6)	0.0157 (6)	0.0089 (6)
C4	0.0557 (9)	0.0945 (13)	0.0574 (9)	0.0236 (9)	0.0304 (7)	0.0280 (9)
C5	0.0440 (7)	0.0486 (8)	0.0320 (6)	0.0077 (6)	0.0122 (5)	0.0025 (6)
C1	0.0555 (8)	0.0560 (9)	0.0537 (8)	0.0184 (7)	0.0216 (7)	0.0170 (7)
C7	0.1244 (17)	0.0603 (11)	0.0657 (12)	0.0200 (12)	0.0330 (12)	0.0012 (9)
C8	0.0419 (7)	0.0415 (7)	0.0478 (7)	0.0038 (6)	0.0119 (6)	0.0127 (6)
C9	0.0425 (8)	0.0951 (14)	0.0638 (10)	0.0123 (8)	0.0133 (7)	0.0306 (10)
C10	0.0515 (9)	0.1116 (17)	0.0542 (10)	0.0021 (10)	0.0010 (7)	0.0309 (10)
C11	0.0693 (10)	0.0853 (13)	0.0443 (8)	−0.0056 (10)	0.0148 (7)	0.0120 (9)
C12	0.0543 (9)	0.0927 (13)	0.0554 (9)	0.0067 (9)	0.0209 (7)	0.0111 (9)
C13	0.0400 (7)	0.0769 (11)	0.0476 (8)	0.0076 (7)	0.0071 (6)	0.0097 (8)
C14	0.0391 (7)	0.0386 (6)	0.0332 (6)	0.0035 (5)	0.0104 (5)	0.0027 (5)
C15	0.0402 (7)	0.0460 (8)	0.0304 (6)	−0.0022 (5)	0.0068 (5)	0.0044 (5)
C16	0.0776 (11)	0.0564 (9)	0.0449 (8)	0.0074 (8)	0.0254 (7)	−0.0005 (7)
C17	0.0414 (7)	0.0457 (7)	0.0261 (6)	−0.0016 (6)	0.0093 (5)	0.0034 (5)
C18	0.0437 (8)	0.0514 (8)	0.0556 (9)	−0.0002 (6)	0.0087 (6)	0.0029 (7)
C19	0.0574 (9)	0.0585 (10)	0.0672 (10)	0.0145 (8)	0.0139 (8)	0.0049 (8)
C20	0.0843 (12)	0.0439 (9)	0.0656 (11)	0.0055 (8)	0.0182 (9)	−0.0025 (8)
C21	0.0668 (11)	0.0516 (10)	0.0899 (14)	−0.0146 (9)	0.0084 (9)	−0.0079 (9)
C22	0.0436 (8)	0.0546 (10)	0.0683 (9)	−0.0037 (7)	0.0064 (7)	−0.0005 (8)
N1	0.0406 (6)	0.0557 (7)	0.0404 (6)	0.0081 (5)	0.0156 (5)	0.0130 (5)
N2	0.0447 (6)	0.0567 (7)	0.0412 (6)	0.0093 (5)	0.0198 (5)	0.0124 (5)
N4	0.0366 (5)	0.0573 (7)	0.0352 (5)	−0.0019 (5)	0.0103 (4)	0.0103 (5)
N5	0.0384 (6)	0.0635 (7)	0.0407 (6)	−0.0066 (5)	0.0069 (5)	0.0153 (6)
N3	0.0487 (7)	0.0588 (8)	0.0535 (7)	0.0166 (6)	0.0232 (6)	0.0212 (6)
N6	0.0352 (6)	0.0533 (7)	0.0366 (6)	0.0004 (5)	0.0078 (4)	0.0116 (5)
O1	0.0446 (6)	0.0702 (7)	0.0606 (7)	0.0120 (5)	0.0189 (5)	0.0167 (6)
O2	0.0371 (5)	0.0695 (7)	0.0409 (5)	0.0005 (5)	0.0104 (4)	0.0072 (5)

Geometric parameters (Å, º) top

C6—N5	1.2752 (18)	C11—H11	0.9300
C6—N1	1.3959 (18)	C12—C13	1.377 (2)
C6—C2	1.4935 (19)	C12—H12	0.9300
C2—H2A	0.9600	C13—H13	0.9300
C2—H2B	0.9600	C14—O2	1.2195 (15)
C2—H2C	0.9600	C14—N6	1.3351 (17)
C3—N2	1.2753 (17)	C14—N4	1.4094 (16)
C3—N4	1.4013 (16)	C15—N6	1.4684 (16)
C3—C4	1.4879 (19)	C15—C17	1.516 (2)
C4—H4A	0.9600	C15—C16	1.5210 (19)
C4—H4B	0.9600	C15—H15	0.9800
C4—H4C	0.9600	C16—H16A	0.9600
C5—O1	1.2217 (16)	C16—H16B	0.9600
C5—N3	1.3326 (18)	C16—H16C	0.9600
C5—N1	1.4098 (17)	C17—C22	1.382 (2)
C1—N3	1.4678 (19)	C17—C18	1.383 (2)
C1—C8	1.519 (2)	C18—C19	1.384 (2)
C1—C7	1.531 (3)	C18—H18	0.9300
C1—H1	0.9800	C19—C20	1.366 (3)
C7—H7A	0.9600	C19—H19	0.9300
C7—H7B	0.9600	C20—C21	1.370 (3)
C7—H7C	0.9600	C20—H20	0.9300
C8—C13	1.3738 (19)	C21—C22	1.372 (3)
C8—C9	1.383 (2)	C21—H21	0.9300
C9—C10	1.383 (2)	C22—H22	0.9300
C9—H9	0.9300	N1—N2	1.4247 (15)
C10—C11	1.361 (2)	N4—N5	1.4194 (15)
C10—H10	0.9300	N3—H3	0.8600
C11—C12	1.372 (2)	N6—H6	0.8600

N5—C6—N1	119.91 (12)	C8—C13—H13	119.3
N5—C6—C2	116.88 (13)	C12—C13—H13	119.3
N1—C6—C2	123.12 (12)	O2—C14—N6	125.18 (11)
C6—C2—H2A	109.5	O2—C14—N4	121.06 (11)
C6—C2—H2B	109.5	N6—C14—N4	113.60 (11)
H2A—C2—H2B	109.5	N6—C15—C17	111.31 (11)
C6—C2—H2C	109.5	N6—C15—C16	109.54 (12)
H2A—C2—H2C	109.5	C17—C15—C16	112.43 (12)
H2B—C2—H2C	109.5	N6—C15—H15	107.8
N2—C3—N4	119.54 (12)	C17—C15—H15	107.8
N2—C3—C4	117.96 (12)	C16—C15—H15	107.8
N4—C3—C4	122.39 (12)	C15—C16—H16A	109.5
C3—C4—H4A	109.5	C15—C16—H16B	109.5
C3—C4—H4B	109.5	H16A—C16—H16B	109.5
H4A—C4—H4B	109.5	C15—C16—H16C	109.5
C3—C4—H4C	109.5	H16A—C16—H16C	109.5
H4A—C4—H4C	109.5	H16B—C16—H16C	109.5
H4B—C4—H4C	109.5	C22—C17—C18	117.87 (14)
O1—C5—N3	124.99 (12)	C22—C17—C15	120.80 (12)
O1—C5—N1	120.43 (12)	C18—C17—C15	121.32 (12)
N3—C5—N1	114.53 (11)	C17—C18—C19	121.00 (15)
N3—C1—C8	111.78 (12)	C17—C18—H18	119.5
N3—C1—C7	109.55 (13)	C19—C18—H18	119.5
C8—C1—C7	111.00 (14)	C20—C19—C18	119.98 (16)
N3—C1—H1	108.1	C20—C19—H19	120.0
C8—C1—H1	108.1	C18—C19—H19	120.0
C7—C1—H1	108.1	C19—C20—C21	119.65 (16)
C1—C7—H7A	109.5	C19—C20—H20	120.2
C1—C7—H7B	109.5	C21—C20—H20	120.2
H7A—C7—H7B	109.5	C20—C21—C22	120.49 (16)
C1—C7—H7C	109.5	C20—C21—H21	119.8
H7A—C7—H7C	109.5	C22—C21—H21	119.8
H7B—C7—H7C	109.5	C21—C22—C17	121.00 (15)
C13—C8—C9	117.85 (14)	C21—C22—H22	119.5
C13—C8—C1	121.22 (12)	C17—C22—H22	119.5
C9—C8—C1	120.85 (13)	C6—N1—C5	125.16 (11)
C10—C9—C8	120.65 (15)	C6—N1—N2	116.52 (11)
C10—C9—H9	119.7	C5—N1—N2	115.78 (10)
C8—C9—H9	119.7	C3—N2—N1	114.83 (10)
C11—C10—C9	120.62 (15)	C3—N4—C14	126.05 (11)
C11—C10—H10	119.7	C3—N4—N5	116.58 (10)
C9—C10—H10	119.7	C14—N4—N5	114.94 (10)
C10—C11—C12	119.37 (16)	C6—N5—N4	114.68 (11)
C10—C11—H11	120.3	C5—N3—C1	121.22 (12)
C12—C11—H11	120.3	C5—N3—H3	119.4
C11—C12—C13	120.10 (15)	C1—N3—H3	119.4
C11—C12—H12	119.9	C14—N6—C15	121.52 (11)
C13—C12—H12	119.9	C14—N6—H6	119.2
C8—C13—C12	121.39 (14)	C15—N6—H6	119.2

N3—C1—C8—C13	−50.2 (2)	O1—C5—N1—C6	7.0 (2)
C7—C1—C8—C13	72.40 (19)	N3—C5—N1—C6	−175.44 (14)
N3—C1—C8—C9	132.96 (16)	O1—C5—N1—N2	168.28 (13)
C7—C1—C8—C9	−104.41 (19)	N3—C5—N1—N2	−14.20 (18)
C13—C8—C9—C10	0.4 (3)	N4—C3—N2—N1	3.17 (19)
C1—C8—C9—C10	177.27 (18)	C4—C3—N2—N1	179.28 (15)
C8—C9—C10—C11	0.2 (3)	C6—N1—N2—C3	−34.68 (18)
C9—C10—C11—C12	−0.2 (3)	C5—N1—N2—C3	162.40 (13)
C10—C11—C12—C13	−0.3 (3)	N2—C3—N4—C14	−166.55 (13)
C9—C8—C13—C12	−0.8 (3)	C4—C3—N4—C14	17.5 (2)
C1—C8—C13—C12	−177.74 (17)	N2—C3—N4—N5	32.1 (2)
C11—C12—C13—C8	0.8 (3)	C4—C3—N4—N5	−143.84 (16)
N6—C15—C17—C22	−57.93 (17)	O2—C14—N4—C3	9.7 (2)
C16—C15—C17—C22	65.39 (16)	N6—C14—N4—C3	−174.56 (14)
N6—C15—C17—C18	121.65 (14)	O2—C14—N4—N5	171.31 (13)
C16—C15—C17—C18	−115.02 (15)	N6—C14—N4—N5	−12.93 (17)
C22—C17—C18—C19	0.3 (2)	N1—C6—N5—N4	3.8 (2)
C15—C17—C18—C19	−179.33 (15)	C2—C6—N5—N4	−179.63 (15)
C17—C18—C19—C20	0.1 (3)	C3—N4—N5—C6	−35.42 (19)
C18—C19—C20—C21	0.0 (3)	C14—N4—N5—C6	161.14 (13)
C19—C20—C21—C22	−0.5 (3)	O1—C5—N3—C1	7.4 (2)
C20—C21—C22—C17	0.9 (3)	N1—C5—N3—C1	−169.98 (13)
C18—C17—C22—C21	−0.7 (2)	C8—C1—N3—C5	−126.84 (15)
C15—C17—C22—C21	178.87 (16)	C7—C1—N3—C5	109.70 (17)
N5—C6—N1—C5	−167.49 (14)	O2—C14—N6—C15	−2.9 (2)
C2—C6—N1—C5	16.2 (2)	N4—C14—N6—C15	−178.49 (12)
N5—C6—N1—N2	31.4 (2)	C17—C15—N6—C14	−93.33 (15)
C2—C6—N1—N2	−144.94 (16)	C16—C15—N6—C14	141.71 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···O1ⁱ	0.86	2.44	3.2497 (15)	158
N3—H3···O2ⁱⁱ	0.86	2.54	3.2706 (16)	144
C13—H13···O2ⁱⁱ	0.93	2.57	3.4701 (17)	163

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

Experimental details

Crystal data
Chemical formula	C₂₂H₂₆N₆O₂
M_r	406.49
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	10.4653 (15), 8.0606 (12), 13.711 (2)
β (°)	108.702 (1)
V (Å³)	1095.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.37 × 0.31 × 0.26

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.970, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	8343, 4014, 3809
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.072, 1.06
No. of reflections	4014
No. of parameters	276
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.09

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···O1ⁱ	0.86	2.44	3.2497 (15)	158
N3—H3···O2ⁱⁱ	0.86	2.54	3.2706 (16)	144
C13—H13···O2ⁱⁱ	0.93	2.57	3.4701 (17)	163

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

Acknowledgements

The authors are very grateful to the Natural Science Foundation of Zhejiang Province (grant No. Y2090985) and the National Natural Science Foundation of China (grant No. 20802069) for financial support.

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