3,6-Bis(4-chloro­phen­yl)-N 1,N 4-bis­(1-phenyl­eth­yl)-1,2,4,5-tetra­zine-1,4-di­carboxamide

Na-Bo Sun; Jia-Bin Ni; Guo-Wu Rao

doi:10.1107/S1600536812003765

. 2012 Feb 4;68(Pt 3):o598–o599. doi: 10.1107/S1600536812003765

3,6-Bis(4-chlorophenyl)-N ¹,N ⁴-bis(1-phenylethyl)-1,2,4,5-tetrazine-1,4-dicarboxamide

Na-Bo Sun ^a, Jia-Bin Ni ^b, Guo-Wu Rao ^b,^*

PMCID: PMC3297322 PMID: 22412512

Abstract

In the title molecule, C₃₂H₂₈Cl₂N₆O₂, the amide-substituted N atoms of the tetrazine ring deviate from the approximate plane of the four other atoms in the ring by 0.468 (3) and 0.484 (3) Å, forming a boat conformation. The dihedral angle between the two phenyl rings is 67.0 (1)° and that between the two chloro-substituted benzene rings is 73.8 (1)°. Two intramolecular N—H⋯N hydrogen bonds are observed.

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 standard bond lengths, see: Allen et al. (1987 ▶). For the synthesis of the title compound, see: Abdel-rahman et al. (1968 ▶); Hu et al. (2004 ▶); Rao & Hu (2006 ▶).

Experimental

Crystal data

C₃₂H₂₈Cl₂N₆O₂
M _r = 599.50
Orthorhombic,
a = 9.715 (2) Å
b = 14.725 (3) Å
c = 21.159 (5) Å
V = 3027.0 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 298 K
0.23 × 0.19 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.944, T _max = 0.970
19445 measured reflections
7314 independent reflections
4680 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.099
S = 1.01
7314 reflections
380 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ▶), with 3185 Friedel pairs
Flack parameter: 0.03 (5)

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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812003765/lh5409sup1.cif

e-68-0o598-sup1.cif^{(26.3KB, cif)}

Supplementary material file. DOI: 10.1107/S1600536812003765/lh5409Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003765/lh5409Isup3.hkl

e-68-0o598-Isup3.hkl^{(350.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812003765/lh5409Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N2	0.86	2.21	2.613 (2)	109
N6—H6⋯N5	0.86	2.13	2.573 (2)	112

Open in a new tab

Acknowledgments

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.

supplementary crystallographic information

Comment

Tetrazine derivatives have high activity in chemical reactions (Domingo et al., 2009; Lorincz et al., 2010), and have been widely used in medicines and pesticides (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). 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 position. The structure was confirmed by single-crystal X-ray diffraction. The molecular structure of (I) is illustrated in Fig. 1.

The N2═C3 [1.282 (2) Å] and N5═C6 [1.285 (2) Å] bonds are typical as are the C3—N4 [1.407 (3) Å], N4—N5 [1.429 (2) Å], C6—N1 [1.396 (2) Å] and N1—N2 [1.417 (2) Å] bonds (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 0.0236 (9) Å. Atoms N1 and N4 deviate from this plane by 0.468 (3) and 0.484 (3) Å, respectively. The dihedral angle between the N2/C3/N5/C6 plane and the N1/N2/C6 plane is 38.00 (17)°, and between the N2/C3/N5/C6 plane and the N4/N5/C3 plane is 38.81 (14)°. The tetrazine ring has a boat conformation. The dihedral angles between the N2/C3/N5/C6 plane and the two benzene rings at the 3,6-positions are 35.91 (10) and 42.87 (8)°, respectively. And the two benzene rings form a dihedral angle of 73.8 (1)°. Two intramolecular N—H···N hydrogen bonds are observed.

Experimental

The title compound was prepared according to the procedure of Abdel-rahman et al. (1968); Hu et al. (2004); Rao & Hu, (2006). A solution of the compound in ethanol was concentrated gradually at room temperature to afford yellow blocks.