(3,6-Dimethyl-1,2,4,5-tetra­zine-1,4-di­yl)bis­[(morpholin-4-yl)methanone]

Sun, N.-B.; Guo, Y.-M.; Rao, G.-W.

doi:10.1107/S1600536812004849

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o681

doi:10.1107/S1600536812004849

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(3,6-Dimethyl-1,2,4,5-tetrazine-1,4-diyl)bis[(morpholin-4-yl)methanone]

Na-Bo Sun,^a Yan-Mei Guo ^b and Guo-Wu Rao ^b ^*

^aCollege of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015, People's Republic of China, and ^bCollege of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: rgw@zjut.edu.cn

(Received 28 January 2012; accepted 4 February 2012; online 10 February 2012)

In the title molecule, C₁₄H₂₂N₆O₄, the amide-substituted N atoms of the tetrazine ring deviate from the approximate plane of the four other atoms in the ring by 0.160 (2) and 0.243 (2) Å, forming a slight boat conformation. The morpholine rings are in chair conformations.

Related literature

For chemical reactions of 1,2,4,5-tetrazine derivatives, see: Domingo et al. (2009 ); Lorincz et al. (2010 ). For their biological activities, see: Devaraj et al. (2009 ); Eremeev et al. (1978 , 1980 ); Han et al. (2010 ); Neunhoeffer (1984 ); Sauer (1996 ). For anti-tumor activity of 1,2,4,5-tetrazine derivatives, see: Hu et al. (2002 , 2004 ); Rao & Hu, (2005 , 2006 ). For details of the synthesis, see: Hu et al. (2004); Skorianetz & Kováts (1970 , 1971 ); Sun et al. (2003 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₂₂N₆O₄
M_r = 338.38
Monoclinic, P 2₁ /n
a = 15.285 (3) Å
b = 6.5977 (14) Å
c = 16.729 (4) Å
β = 106.576 (3)°
V = 1617.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.55 × 0.42 × 0.28 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.944, T_max = 0.971
9248 measured reflections
3714 independent reflections
2908 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.142
S = 1.03
3714 reflections
220 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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/S1600536812004849/lh5412sup1.cif

Supporting information file. DOI: 10.1107/S1600536812004849/lh5412Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004849/lh5412Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536812004849/lh5412Isup4.cml

checkCIF report

Comment top

Tetrazine derivatives have high activity in chemical reactions (Domingo et al., 2009; Lorincz et al., 2010), and have been widely used in pesticides and medicines (Devaraj et al., 2009; Eremeev et al., 1978, 1980; Han et al., 2010; Neunhoeffer, 1984; Sauer, 1996). In a continuation of our studies of antitumor activities in 1,2,4,5-tetrazine derivatives (Hu et al., 2002, 2004; Rao & Hu, 2005, 2006), we have obtained a yellow crystalline compound, (I). The structure was confirmed by single-crystal X-ray diffraction.

The molecular structure of (I) is illustrated in Fig. 1. The N2═C3 [1.2730 (17) Å] and N5═C6 [1.2748 (18) Å] bonds lengths are typical for double bonds, as are the C3—N4 [1.3821 (17) Å], N4—N5 [1.4235 (17) Å], C6—N1 [1.3728 (17) Å] and N1—N2 [1.4207 (16) Å] bond lengths (Allen et al., 1987). The tetrazine ring is a 1,4-dihydro structure with the N-substituted groups at the 1,4-positions.

In (I), atoms N2, C3, N5 and C6 are approximately planar, with the largest deviation from this plane being 0.0137 (6) Å. Atoms N1 and N4 deviate from this plane by 0.1604 (21) and 0.2429 (20) Å, respectively. The dihedral angle between the N2/C3/N5/C6 plane and the N1/N2/C6 plane is 13.37 (24)°, and between the N2/C3/N5/C6 plane and the N4/N5/C3 plane is 19.79 (21)°. The tetrazine ring has a slight boat conformation. Atoms C7, C8, C9 and C10 are approximately planar, with the largest deviation from this plane being 0.0114 (9) Å. Atoms O3 and N3 deviate from this plane by 0.6616 (23) and -0.5938 (21) Å, respectively. Atoms C11, C12, C13 and C14 are approximately planar, with the largest deviation from this plane being 0.0137 (9) Å. Atoms O4 and N6 deviate from this plane by 0.6576 (20) and -0.5953 (21) Å, respectively. The two morpholine rings exhibit chair conformations.

Related literature top

For chemical reactions of 1,2,4,5-tetrazine derivatives, see: Domingo et al. (2009); Lorincz et al. (2010). For their biological activities, see: Devaraj et al. (2009); Eremeev et al. (1978, 1980); Han et al. (2010); Neunhoeffer (1984); Sauer (1996). For anti-tumor activity of 1,2,4,5-tetrazine derivatives, see: Hu et al. (2002, 2004); Rao & Hu, (2005, 2006). For details of the synthesis, see: Hu et al. (2004); Skorianetz & Kováts (1970, 1971); Sun et al. (2003). For standard bond lengths, see: Allen et al. (1987).

Experimental top

The title compound was the product of the reaction of bis(trichloromethyl) carbonate, morpholine, and 3,6-dimethyl-1,6-dihydro-1,2,4,5-tetrazine according to the procedure (Hu et al., 2004; Sun et al., 2003; Skorianetz & Kováts, 1970, 1971). A solution of the title compound in acetone was concentrated gradually at room temperature to afford yellow blocks.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. 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-1,2,4,5-tetrazine-1,4-diyl)bis[(morpholin-4-yl)methanone] top

Crystal data top

C₁₄H₂₂N₆O₄	F(000) = 720
M_r = 338.38	D_x = 1.390 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6920 reflections
a = 15.285 (3) Å	θ = 2.9–28.2°
b = 6.5977 (14) Å	µ = 0.10 mm⁻¹
c = 16.729 (4) Å	T = 298 K
β = 106.576 (3)°	Block, yellow
V = 1617.0 (6) Å³	0.55 × 0.42 × 0.28 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	3714 independent reflections
Radiation source: fine-focus sealed tube	2908 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −15→20
T_min = 0.944, T_max = 0.971	k = −8→8
9248 measured reflections	l = −18→21

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)] = 0.049	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0823P)² + 0.2523P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3714 reflections	Δρ_max = 0.27 e Å⁻³
220 parameters	Δρ_min = −0.27 e Å⁻³
0 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: 0.036 (3)

Crystal data top

C₁₄H₂₂N₆O₄	V = 1617.0 (6) Å³
M_r = 338.38	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.285 (3) Å	µ = 0.10 mm⁻¹
b = 6.5977 (14) Å	T = 298 K
c = 16.729 (4) Å	0.55 × 0.42 × 0.28 mm
β = 106.576 (3)°

Data collection top

Bruker SMART CCD diffractometer	3714 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2908 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.971	R_int = 0.020
9248 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.03	Δρ_max = 0.27 e Å⁻³
3714 reflections	Δρ_min = −0.27 e Å⁻³
220 parameters

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
N2	0.68618 (8)	0.70860 (18)	0.11259 (7)	0.0374 (3)
N4	0.59388 (8)	0.60296 (19)	0.19430 (7)	0.0409 (3)
N5	0.55633 (9)	0.43942 (18)	0.13981 (8)	0.0450 (3)
N1	0.66936 (9)	0.51243 (19)	0.07644 (8)	0.0456 (3)
O4	0.49306 (9)	0.2853 (2)	0.41742 (7)	0.0586 (3)
O3	0.74085 (9)	0.7091 (2)	−0.18200 (7)	0.0620 (4)
N6	0.53166 (9)	0.5633 (2)	0.30490 (8)	0.0444 (3)
C6	0.59824 (9)	0.3973 (2)	0.08605 (8)	0.0359 (3)
N3	0.75197 (8)	0.57709 (19)	−0.01932 (7)	0.0416 (3)
O1	0.75909 (9)	0.27148 (18)	0.04345 (9)	0.0643 (4)
C3	0.64652 (9)	0.7449 (2)	0.16842 (8)	0.0333 (3)
O2	0.48046 (10)	0.8161 (2)	0.21322 (9)	0.0764 (5)
C4	0.72971 (10)	0.4435 (2)	0.03193 (8)	0.0397 (3)
C5	0.52962 (10)	0.6716 (2)	0.23773 (9)	0.0415 (3)
C11	0.59485 (10)	0.3983 (2)	0.33971 (10)	0.0461 (4)
H11A	0.6405	0.4442	0.3895	0.055*
H11B	0.6258	0.3549	0.2994	0.055*
C12	0.54193 (11)	0.2249 (3)	0.36082 (10)	0.0492 (4)
H12A	0.4994	0.1738	0.3101	0.059*
H12B	0.5836	0.1161	0.3854	0.059*
C7	0.82145 (11)	0.5206 (3)	−0.06011 (10)	0.0490 (4)
H7A	0.8456	0.3874	−0.0413	0.059*
H7B	0.8714	0.6170	−0.0455	0.059*
C10	0.70416 (11)	0.7647 (2)	−0.05175 (9)	0.0461 (4)
H10A	0.7453	0.8788	−0.0350	0.055*
H10B	0.6533	0.7839	−0.0287	0.055*
C14	0.47410 (12)	0.6227 (3)	0.35760 (11)	0.0531 (4)
H14A	0.4279	0.7179	0.3278	0.064*
H14B	0.5111	0.6889	0.4076	0.064*
C1	0.66582 (12)	0.9416 (3)	0.21394 (11)	0.0535 (4)
H1A	0.6875	0.9164	0.2728	0.080*
H1B	0.6109	1.0208	0.2020	0.080*
H1C	0.7115	1.0143	0.1963	0.080*
C13	0.42906 (12)	0.4385 (3)	0.38095 (11)	0.0548 (4)
H13A	0.3958	0.4774	0.4200	0.066*
H13B	0.3854	0.3847	0.3315	0.066*
C2	0.56523 (12)	0.2236 (3)	0.02845 (12)	0.0594 (5)
H2A	0.5571	0.2667	−0.0280	0.089*
H2B	0.5081	0.1761	0.0345	0.089*
H2C	0.6093	0.1159	0.0418	0.089*
C9	0.66960 (12)	0.7561 (3)	−0.14556 (10)	0.0588 (5)
H9A	0.6222	0.6540	−0.1618	0.071*
H9B	0.6429	0.8858	−0.1666	0.071*
C8	0.77950 (13)	0.5188 (3)	−0.15316 (10)	0.0581 (5)
H8A	0.8259	0.4854	−0.1803	0.070*
H8B	0.7326	0.4153	−0.1678	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0443 (6)	0.0343 (6)	0.0378 (6)	−0.0095 (5)	0.0183 (5)	−0.0074 (5)
N4	0.0480 (7)	0.0397 (7)	0.0428 (6)	−0.0052 (5)	0.0255 (5)	−0.0037 (5)
N5	0.0469 (7)	0.0330 (6)	0.0625 (8)	−0.0085 (5)	0.0278 (6)	−0.0075 (5)
N1	0.0601 (8)	0.0379 (7)	0.0506 (7)	−0.0152 (6)	0.0346 (6)	−0.0145 (5)
O4	0.0659 (7)	0.0694 (8)	0.0489 (6)	0.0032 (6)	0.0302 (6)	0.0145 (6)
O3	0.0741 (8)	0.0787 (9)	0.0390 (6)	0.0023 (7)	0.0255 (6)	0.0062 (6)
N6	0.0515 (7)	0.0449 (7)	0.0471 (7)	0.0098 (6)	0.0306 (6)	0.0054 (5)
C6	0.0375 (7)	0.0288 (7)	0.0417 (7)	−0.0002 (5)	0.0119 (6)	−0.0014 (5)
N3	0.0471 (7)	0.0461 (7)	0.0390 (6)	0.0091 (5)	0.0239 (5)	0.0036 (5)
O1	0.0768 (8)	0.0459 (7)	0.0819 (9)	0.0174 (6)	0.0417 (7)	0.0147 (6)
C3	0.0353 (6)	0.0348 (7)	0.0297 (6)	−0.0013 (5)	0.0089 (5)	−0.0013 (5)
O2	0.0777 (9)	0.0787 (9)	0.0906 (10)	0.0378 (8)	0.0525 (8)	0.0386 (8)
C4	0.0438 (7)	0.0405 (8)	0.0376 (7)	0.0007 (6)	0.0163 (6)	−0.0037 (6)
C5	0.0431 (7)	0.0416 (8)	0.0456 (8)	0.0033 (6)	0.0221 (6)	0.0017 (6)
C11	0.0434 (8)	0.0514 (9)	0.0468 (8)	0.0064 (7)	0.0182 (6)	0.0062 (7)
C12	0.0541 (9)	0.0496 (9)	0.0457 (8)	0.0062 (7)	0.0173 (7)	0.0079 (7)
C7	0.0487 (8)	0.0588 (10)	0.0483 (8)	0.0086 (7)	0.0278 (7)	0.0008 (7)
C10	0.0564 (9)	0.0445 (8)	0.0424 (8)	0.0095 (7)	0.0223 (7)	0.0053 (6)
C14	0.0653 (10)	0.0531 (10)	0.0544 (9)	0.0064 (8)	0.0386 (8)	−0.0022 (7)
C1	0.0623 (10)	0.0481 (9)	0.0552 (9)	−0.0113 (8)	0.0248 (8)	−0.0196 (7)
C13	0.0541 (9)	0.0674 (11)	0.0531 (9)	0.0012 (8)	0.0316 (8)	0.0028 (8)
C2	0.0529 (9)	0.0473 (9)	0.0776 (12)	−0.0106 (7)	0.0179 (9)	−0.0261 (8)
C9	0.0598 (10)	0.0707 (12)	0.0452 (9)	0.0083 (9)	0.0138 (8)	0.0096 (8)
C8	0.0704 (11)	0.0663 (11)	0.0470 (9)	−0.0035 (9)	0.0318 (8)	−0.0119 (8)

Geometric parameters (Å, º) top

N2—C3	1.2730 (17)	C11—H11B	0.9700
N2—N1	1.4207 (16)	C12—H12A	0.9700
N4—C3	1.3821 (17)	C12—H12B	0.9700
N4—N5	1.4235 (17)	C7—C8	1.505 (2)
N4—C5	1.4509 (17)	C7—H7A	0.9700
N5—C6	1.2748 (18)	C7—H7B	0.9700
N1—C6	1.3728 (17)	C10—C9	1.507 (2)
N1—C4	1.4155 (17)	C10—H10A	0.9700
O4—C13	1.418 (2)	C10—H10B	0.9700
O4—C12	1.4201 (19)	C14—C13	1.502 (2)
O3—C8	1.413 (2)	C14—H14A	0.9700
O3—C9	1.426 (2)	C14—H14B	0.9700
N6—C5	1.3245 (19)	C1—H1A	0.9600
N6—C11	1.4620 (19)	C1—H1B	0.9600
N6—C14	1.4653 (17)	C1—H1C	0.9600
C6—C2	1.490 (2)	C13—H13A	0.9700
N3—C4	1.3392 (18)	C13—H13B	0.9700
N3—C10	1.4609 (19)	C2—H2A	0.9600
N3—C7	1.4650 (17)	C2—H2B	0.9600
O1—C4	1.2158 (18)	C2—H2C	0.9600
C3—C1	1.4911 (19)	C9—H9A	0.9700
O2—C5	1.2104 (19)	C9—H9B	0.9700
C11—C12	1.500 (2)	C8—H8A	0.9700
C11—H11A	0.9700	C8—H8B	0.9700

C3—N2—N1	114.67 (11)	C8—C7—H7B	109.8
C3—N4—N5	118.51 (11)	H7A—C7—H7B	108.2
C3—N4—C5	118.88 (12)	N3—C10—C9	110.14 (13)
N5—N4—C5	110.52 (11)	N3—C10—H10A	109.6
C6—N5—N4	115.15 (11)	C9—C10—H10A	109.6
C6—N1—C4	122.73 (12)	N3—C10—H10B	109.6
C6—N1—N2	120.49 (11)	C9—C10—H10B	109.6
C4—N1—N2	116.78 (11)	H10A—C10—H10B	108.1
C13—O4—C12	110.04 (12)	N6—C14—C13	109.79 (13)
C8—O3—C9	110.07 (13)	N6—C14—H14A	109.7
C5—N6—C11	126.36 (12)	C13—C14—H14A	109.7
C5—N6—C14	119.56 (13)	N6—C14—H14B	109.7
C11—N6—C14	113.66 (12)	C13—C14—H14B	109.7
N5—C6—N1	122.43 (12)	H14A—C14—H14B	108.2
N5—C6—C2	118.58 (13)	C3—C1—H1A	109.5
N1—C6—C2	118.90 (13)	C3—C1—H1B	109.5
C4—N3—C10	127.14 (12)	H1A—C1—H1B	109.5
C4—N3—C7	118.76 (13)	C3—C1—H1C	109.5
C10—N3—C7	113.26 (12)	H1A—C1—H1C	109.5
N2—C3—N4	122.96 (12)	H1B—C1—H1C	109.5
N2—C3—C1	118.17 (12)	O4—C13—C14	112.17 (14)
N4—C3—C1	118.54 (12)	O4—C13—H13A	109.2
O1—C4—N3	124.47 (13)	C14—C13—H13A	109.2
O1—C4—N1	118.89 (13)	O4—C13—H13B	109.2
N3—C4—N1	116.62 (13)	C14—C13—H13B	109.2
O2—C5—N6	125.04 (13)	H13A—C13—H13B	107.9
O2—C5—N4	121.32 (13)	C6—C2—H2A	109.5
N6—C5—N4	113.63 (12)	C6—C2—H2B	109.5
N6—C11—C12	108.81 (12)	H2A—C2—H2B	109.5
N6—C11—H11A	109.9	C6—C2—H2C	109.5
C12—C11—H11A	109.9	H2A—C2—H2C	109.5
N6—C11—H11B	109.9	H2B—C2—H2C	109.5
C12—C11—H11B	109.9	O3—C9—C10	111.70 (14)
H11A—C11—H11B	108.3	O3—C9—H9A	109.3
O4—C12—C11	111.39 (14)	C10—C9—H9A	109.3
O4—C12—H12A	109.4	O3—C9—H9B	109.3
C11—C12—H12A	109.4	C10—C9—H9B	109.3
O4—C12—H12B	109.4	H9A—C9—H9B	107.9
C11—C12—H12B	109.4	O3—C8—C7	111.07 (14)
H12A—C12—H12B	108.0	O3—C8—H8A	109.4
N3—C7—C8	109.40 (13)	C7—C8—H8A	109.4
N3—C7—H7A	109.8	O3—C8—H8B	109.4
C8—C7—H7A	109.8	C7—C8—H8B	109.4
N3—C7—H7B	109.8	H8A—C8—H8B	108.0

C3—N4—N5—C6	23.26 (19)	C11—N6—C5—O2	−174.99 (17)
C5—N4—N5—C6	165.46 (12)	C14—N6—C5—O2	−2.9 (3)
C3—N2—N1—C6	16.02 (19)	C11—N6—C5—N4	4.4 (2)
C3—N2—N1—C4	−163.17 (13)	C14—N6—C5—N4	176.51 (13)
N4—N5—C6—N1	−5.6 (2)	C3—N4—C5—O2	44.9 (2)
N4—N5—C6—C2	177.96 (14)	N5—N4—C5—O2	−97.15 (18)
C4—N1—C6—N5	164.79 (14)	C3—N4—C5—N6	−134.55 (14)
N2—N1—C6—N5	−14.4 (2)	N5—N4—C5—N6	83.42 (15)
C4—N1—C6—C2	−18.8 (2)	C5—N6—C11—C12	−134.69 (16)
N2—N1—C6—C2	162.09 (14)	C14—N6—C11—C12	52.82 (18)
N1—N2—C3—N4	2.27 (19)	C13—O4—C12—C11	61.50 (17)
N1—N2—C3—C1	175.66 (13)	N6—C11—C12—O4	−57.44 (17)
N5—N4—C3—N2	−22.2 (2)	C4—N3—C7—C8	117.84 (16)
C5—N4—C3—N2	−161.22 (13)	C10—N3—C7—C8	−52.37 (18)
N5—N4—C3—C1	164.45 (13)	C4—N3—C10—C9	−118.42 (16)
C5—N4—C3—C1	25.42 (19)	C7—N3—C10—C9	50.80 (18)
C10—N3—C4—O1	163.86 (16)	C5—N6—C14—C13	135.96 (16)
C7—N3—C4—O1	−4.8 (2)	C11—N6—C14—C13	−50.99 (19)
C10—N3—C4—N1	−17.6 (2)	C12—O4—C13—C14	−59.39 (18)
C7—N3—C4—N1	173.67 (13)	N6—C14—C13—O4	53.49 (19)
C6—N1—C4—O1	−44.3 (2)	C8—O3—C9—C10	59.94 (19)
N2—N1—C4—O1	134.89 (16)	N3—C10—C9—O3	−53.83 (19)
C6—N1—C4—N3	137.12 (15)	C9—O3—C8—C7	−61.71 (18)
N2—N1—C4—N3	−43.71 (18)	N3—C7—C8—O3	57.37 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···O2	0.97	2.37	2.758 (2)	103
C1—H1B···O2	0.96	2.46	2.949 (2)	111
C2—H2C···O1	0.96	2.50	2.919 (2)	106
C7—H7A···O1	0.97	2.33	2.748 (2)	105
C10—H10B···N1	0.97	2.47	2.881 (2)	105
C10—H10B···N2	0.97	2.33	2.8640 (19)	114
C11—H11B···N4	0.97	2.35	2.7787 (19)	106

Experimental details

Crystal data
Chemical formula	C₁₄H₂₂N₆O₄
M_r	338.38
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	15.285 (3), 6.5977 (14), 16.729 (4)
β (°)	106.576 (3)
V (Å³)	1617.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.55 × 0.42 × 0.28

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.944, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	9248, 3714, 2908
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.142, 1.03
No. of reflections	3714
No. of parameters	220
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.27

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
C14—H14A···O2	0.97	2.37	2.758 (2)	103.2
C1—H1B···O2	0.96	2.46	2.949 (2)	111.4
C2—H2C···O1	0.96	2.50	2.919 (2)	106.2
C7—H7A···O1	0.97	2.33	2.748 (2)	105.4
C10—H10B···N1	0.97	2.47	2.881 (2)	105.1
C10—H10B···N2	0.97	2.33	2.8640 (19)	114.2
C11—H11B···N4	0.97	2.35	2.7787 (19)	106.0

Acknowledgements

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

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