3,6-Diacetyl-1,4-diphenyl-1,4-dihydro-1,2,4,5-tetra­zine

Al-Noaimi, M.; Haddad, S.F.

doi:10.1107/S1600536808003115

organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page o551

doi:10.1107/S1600536808003115

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3,6-Diacetyl-1,4-diphenyl-1,4-dihydro-1,2,4,5-tetrazine

Mousa Al-Noaimi ^a ^* and Salim F. Haddad ^b

^aChemistry Department, The Hashemite University, Zarka, Jordan, and ^bDepartment of Chemistry, Faculty of Science, The University of Jordan, Amman 11942, Jordan
^*Correspondence e-mail: manoaimi@hu.edu.jo

(Received 3 September 2007; accepted 28 January 2008; online 6 February 2008)

In the title compound, C₁₈H₁₆N₄O₂, the central six-membered ring has a boat conformation.

Related literature

For background, see: Sauer (1996 ). For further synthetic details, see: Al-Noaimi et al. (2007 ).

Experimental

Crystal data

C₁₈H₁₆N₄O₂
M_r = 320.35
Monoclinic, P 2₁ /c
a = 11.7853 (6) Å
b = 14.7217 (7) Å
c = 9.5113 (4) Å
β = 92.350 (1)°
V = 1648.82 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.28 × 0.23 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.973, T_max = 0.989
24032 measured reflections
2985 independent reflections
2090 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.107
S = 1.02
2985 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: SMART (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: XS in SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808003115/hb2696sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808003115/hb2696Isup2.hkl

checkCIF report

Comment top

1,2,4,5-Tetrazine derivatives have high potential for biological activity, possessing a wide spectrum of antiviral and antitumor properties. They have been widely used in pesticides and herbicides (Sauer, 1996).

As part of our studies in this area, the title compound, (I), was prepared and its structure determined by X-ray diffraction (Fig. 1).

In (I), atoms N1, C3, N4 and C6 are coplanar [r.m.s. deviation = 0.010 Å] and atoms N2 and N5 deviate from the plane by 0.457 and 0.451 Å, respectively. Thus, the central tetrazine ring in (I) has a boat conformation.

The dihedral angle between the plane defined by atoms N1 C3 N4 C6 and the C11—C16 benzene ring plane is 28.27 (9)°. The dihedral angle between the same atoms and the C17—C22 benzene ring is 40.11 (5)°. The dihedral angle between the C11—C16 and C17—C22 benzene rings is 66.19 (9)°.

Related literature top

For background, see: Sauer (1996). For further synthetic details, see: Al-Noaimi et al. (2007).

Experimental top

A solution of 1-phenylhydrazono-1-chloropropanone (10 g, 55 mmol) (Al-Noaimi et al., 2007) and triethylamine (7.2 g, 71 mmol) in ethanol (80 ml) was refluxed for 2 h, and then the solvent was partially removed under reduced pressure. A solution of the compound in ethanol was concentrated gradually at room temperature to afford red blocks of (I) (m.p. 439–441 K).

Computing details top

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: XS in SHELXTL (Sheldrick, 2008); program(s) used to refine structure: XL in SHELXTL (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms).

3,6-Diacetyl-1,4-diphenyl-1,4-dihydro-1,2,4,5-tetrazine top

Crystal data top

C₁₈H₁₆N₄O₂	F(000) = 672
M_r = 320.35	D_x = 1.291 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4916 reflections
a = 11.7853 (6) Å	θ = 2.2–23.9°
b = 14.7217 (7) Å	µ = 0.09 mm⁻¹
c = 9.5113 (4) Å	T = 298 K
β = 92.350 (1)°	Block, red
V = 1648.82 (13) Å³	0.28 × 0.23 × 0.12 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2985 independent reflections
Radiation source: normal-focus sealed tube	2090 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 8.3 pixels mm^-1	θ_max = 25.3°, θ_min = 1.7°
ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −17→17
T_min = 0.973, T_max = 0.989	l = −11→11
24032 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0508P)² + 0.1852P] where P = (F_o² + 2F_c²)/3
2985 reflections	(Δ/σ)_max < 0.001
219 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₈H₁₆N₄O₂	V = 1648.82 (13) Å³
M_r = 320.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.7853 (6) Å	µ = 0.09 mm⁻¹
b = 14.7217 (7) Å	T = 298 K
c = 9.5113 (4) Å	0.28 × 0.23 × 0.12 mm
β = 92.350 (1)°

Data collection top

Bruker SMART APEX diffractometer	2985 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2090 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.989	R_int = 0.038
24032 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.02	Δρ_max = 0.12 e Å⁻³
2985 reflections	Δρ_min = −0.14 e Å⁻³
219 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
C3	0.19860 (13)	0.04264 (11)	0.24262 (17)	0.0476 (4)
C6	0.06963 (13)	0.17718 (11)	0.30979 (16)	0.0443 (4)
C7	0.01584 (14)	0.23941 (12)	0.41383 (18)	0.0485 (4)
C8	0.03913 (16)	0.33770 (12)	0.3984 (2)	0.0615 (5)
H8A	0.0063	0.3704	0.4740	0.092*
H8B	0.0065	0.3588	0.3102	0.092*
H8C	0.1197	0.3476	0.4009	0.092*
C9	0.29164 (15)	−0.02517 (13)	0.27788 (19)	0.0566 (5)
C10	0.25803 (17)	−0.12250 (14)	0.2816 (3)	0.0861 (7)
H10A	0.3228	−0.1588	0.3093	0.129*
H10B	0.2298	−0.1409	0.1899	0.129*
H10C	0.1997	−0.1306	0.3481	0.129*
C11	0.31755 (13)	0.15724 (12)	0.12166 (17)	0.0479 (4)
C12	0.36333 (14)	0.24291 (13)	0.14032 (19)	0.0567 (5)
H12	0.3338	0.2825	0.2057	0.068*
C13	0.45313 (16)	0.26945 (15)	0.0613 (2)	0.0681 (5)
H13	0.4833	0.3275	0.0726	0.082*
C14	0.49833 (16)	0.21120 (16)	−0.0338 (2)	0.0707 (6)
H14	0.5600	0.2291	−0.0852	0.085*
C15	0.45218 (16)	0.12619 (15)	−0.0529 (2)	0.0666 (5)
H15	0.4831	0.0865	−0.1171	0.080*
C16	0.36055 (15)	0.09929 (13)	0.02212 (19)	0.0582 (5)
H16	0.3277	0.0426	0.0061	0.070*
C17	−0.09434 (13)	0.07208 (11)	0.28912 (17)	0.0466 (4)
C18	−0.12547 (14)	−0.00429 (12)	0.36200 (18)	0.0533 (5)
H18	−0.0705	−0.0437	0.3996	0.064*
C19	−0.23938 (16)	−0.02164 (14)	0.3785 (2)	0.0660 (5)
H19	−0.2611	−0.0730	0.4277	0.079*
C20	−0.32094 (16)	0.03634 (17)	0.3228 (2)	0.0744 (6)
H20	−0.3974	0.0246	0.3351	0.089*
C21	−0.28909 (16)	0.11175 (16)	0.2489 (2)	0.0730 (6)
H21	−0.3443	0.1509	0.2112	0.088*
C22	−0.17587 (15)	0.12967 (13)	0.2303 (2)	0.0603 (5)
H22	−0.1545	0.1801	0.1787	0.072*
N1	0.16981 (11)	0.19907 (9)	0.27549 (14)	0.0495 (4)
N2	0.22031 (11)	0.13056 (9)	0.19490 (14)	0.0496 (4)
N4	0.09917 (11)	0.02070 (9)	0.28117 (14)	0.0489 (4)
N5	0.02219 (10)	0.09373 (9)	0.26874 (14)	0.0460 (4)
O7	−0.04003 (12)	0.20784 (9)	0.50509 (14)	0.0728 (4)
O9	0.38657 (10)	0.00113 (9)	0.30439 (15)	0.0717 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.0384 (9)	0.0512 (11)	0.0535 (10)	0.0003 (8)	0.0079 (7)	−0.0038 (8)
C6	0.0394 (9)	0.0460 (10)	0.0481 (10)	0.0020 (7)	0.0072 (7)	0.0017 (7)
C7	0.0423 (9)	0.0533 (11)	0.0504 (10)	0.0028 (8)	0.0069 (8)	−0.0011 (8)
C8	0.0665 (12)	0.0545 (12)	0.0640 (12)	0.0037 (9)	0.0095 (9)	−0.0061 (9)
C9	0.0407 (10)	0.0647 (12)	0.0653 (12)	0.0063 (9)	0.0125 (8)	0.0026 (9)
C10	0.0592 (13)	0.0587 (13)	0.141 (2)	0.0137 (10)	0.0099 (13)	0.0077 (13)
C11	0.0369 (9)	0.0583 (11)	0.0488 (10)	0.0014 (8)	0.0060 (7)	0.0026 (8)
C12	0.0455 (10)	0.0626 (12)	0.0625 (12)	−0.0040 (9)	0.0093 (8)	−0.0045 (9)
C13	0.0515 (12)	0.0737 (14)	0.0797 (14)	−0.0133 (10)	0.0126 (10)	0.0048 (11)
C14	0.0479 (11)	0.0961 (17)	0.0691 (14)	−0.0026 (11)	0.0165 (10)	0.0149 (12)
C15	0.0573 (12)	0.0870 (16)	0.0567 (12)	0.0107 (11)	0.0176 (9)	0.0008 (10)
C16	0.0536 (11)	0.0616 (12)	0.0604 (12)	0.0014 (9)	0.0136 (9)	−0.0035 (9)
C17	0.0373 (9)	0.0525 (10)	0.0505 (10)	0.0004 (7)	0.0088 (7)	−0.0066 (8)
C18	0.0476 (10)	0.0567 (11)	0.0563 (11)	−0.0033 (8)	0.0101 (8)	−0.0060 (9)
C19	0.0550 (12)	0.0711 (14)	0.0732 (13)	−0.0173 (10)	0.0170 (10)	−0.0112 (10)
C20	0.0398 (11)	0.0975 (17)	0.0867 (15)	−0.0139 (11)	0.0098 (10)	−0.0248 (13)
C21	0.0415 (11)	0.0894 (16)	0.0875 (15)	0.0130 (10)	−0.0023 (10)	−0.0096 (12)
C22	0.0443 (11)	0.0639 (12)	0.0728 (13)	0.0083 (9)	0.0045 (9)	0.0018 (10)
N1	0.0442 (8)	0.0493 (8)	0.0560 (9)	0.0011 (6)	0.0128 (6)	−0.0039 (7)
N2	0.0406 (8)	0.0492 (8)	0.0601 (9)	0.0001 (6)	0.0163 (6)	−0.0047 (7)
N4	0.0373 (8)	0.0484 (8)	0.0615 (9)	0.0036 (6)	0.0076 (6)	−0.0027 (7)
N5	0.0344 (7)	0.0457 (8)	0.0585 (9)	0.0038 (6)	0.0088 (6)	−0.0009 (7)
O7	0.0844 (10)	0.0649 (9)	0.0717 (9)	−0.0061 (7)	0.0377 (8)	−0.0061 (7)
O9	0.0402 (8)	0.0865 (10)	0.0887 (10)	0.0030 (7)	0.0061 (7)	0.0111 (8)

Geometric parameters (Å, º) top

C3—N4	1.2834 (19)	C13—C14	1.370 (3)
C3—N2	1.399 (2)	C13—H13	0.9300
C3—C9	1.510 (2)	C14—C15	1.374 (3)
C6—N1	1.2790 (19)	C14—H14	0.9300
C6—N5	1.399 (2)	C15—C16	1.377 (2)
C6—C7	1.507 (2)	C15—H15	0.9300
C7—O7	1.2041 (19)	C16—H16	0.9300
C7—C8	1.481 (2)	C17—C18	1.378 (2)
C8—H8A	0.9600	C17—C22	1.382 (2)
C8—H8B	0.9600	C17—N5	1.431 (2)
C8—H8C	0.9600	C18—C19	1.382 (2)
C9—O9	1.201 (2)	C18—H18	0.9300
C9—C10	1.487 (3)	C19—C20	1.375 (3)
C10—H10A	0.9600	C19—H19	0.9300
C10—H10B	0.9600	C20—C21	1.375 (3)
C10—H10C	0.9600	C20—H20	0.9300
C11—C12	1.380 (2)	C21—C22	1.379 (3)
C11—C16	1.386 (2)	C21—H21	0.9300
C11—N2	1.4207 (19)	C22—H22	0.9300
C12—C13	1.380 (2)	N1—N2	1.4130 (18)
C12—H12	0.9300	N4—N5	1.4086 (17)

N4—C3—N2	120.46 (15)	C13—C14—H14	120.2
N4—C3—C9	115.67 (15)	C15—C14—H14	120.2
N2—C3—C9	122.88 (14)	C14—C15—C16	120.54 (19)
N1—C6—N5	120.85 (14)	C14—C15—H15	119.7
N1—C6—C7	115.58 (15)	C16—C15—H15	119.7
N5—C6—C7	122.89 (14)	C15—C16—C11	119.58 (18)
O7—C7—C8	123.90 (16)	C15—C16—H16	120.2
O7—C7—C6	119.72 (16)	C11—C16—H16	120.2
C8—C7—C6	116.35 (15)	C18—C17—C22	120.59 (16)
C7—C8—H8A	109.5	C18—C17—N5	121.77 (15)
C7—C8—H8B	109.5	C22—C17—N5	117.63 (15)
H8A—C8—H8B	109.5	C17—C18—C19	119.19 (18)
C7—C8—H8C	109.5	C17—C18—H18	120.4
H8A—C8—H8C	109.5	C19—C18—H18	120.4
H8B—C8—H8C	109.5	C20—C19—C18	120.6 (2)
O9—C9—C10	123.52 (17)	C20—C19—H19	119.7
O9—C9—C3	119.68 (17)	C18—C19—H19	119.7
C10—C9—C3	116.77 (16)	C21—C20—C19	119.81 (18)
C9—C10—H10A	109.5	C21—C20—H20	120.1
C9—C10—H10B	109.5	C19—C20—H20	120.1
H10A—C10—H10B	109.5	C20—C21—C22	120.40 (19)
C9—C10—H10C	109.5	C20—C21—H21	119.8
H10A—C10—H10C	109.5	C22—C21—H21	119.8
H10B—C10—H10C	109.5	C21—C22—C17	119.41 (19)
C12—C11—C16	119.90 (16)	C21—C22—H22	120.3
C12—C11—N2	120.56 (15)	C17—C22—H22	120.3
C16—C11—N2	119.32 (15)	C6—N1—N2	111.85 (13)
C13—C12—C11	119.55 (17)	C3—N2—N1	113.44 (12)
C13—C12—H12	120.2	C3—N2—C11	125.24 (13)
C11—C12—H12	120.2	N1—N2—C11	115.77 (13)
C14—C13—C12	120.68 (19)	C3—N4—N5	112.11 (13)
C14—C13—H13	119.7	C6—N5—N4	113.47 (12)
C12—C13—H13	119.7	C6—N5—C17	122.19 (13)
C13—C14—C15	119.68 (18)	N4—N5—C17	115.92 (13)

N1—C6—C7—O7	−140.54 (17)	N5—C6—N1—N2	0.3 (2)
N5—C6—C7—O7	30.1 (2)	C7—C6—N1—N2	171.13 (13)
N1—C6—C7—C8	37.6 (2)	N4—C3—N2—N1	42.1 (2)
N5—C6—C7—C8	−151.76 (15)	C9—C3—N2—N1	−126.06 (16)
N4—C3—C9—O9	−147.50 (17)	N4—C3—N2—C11	−165.46 (15)
N2—C3—C9—O9	21.2 (3)	C9—C3—N2—C11	26.4 (2)
N4—C3—C9—C10	30.7 (2)	C6—N1—N2—C3	−40.54 (19)
N2—C3—C9—C10	−160.58 (17)	C6—N1—N2—C11	164.27 (14)
C16—C11—C12—C13	−1.2 (3)	C12—C11—N2—C3	−146.46 (17)
N2—C11—C12—C13	−175.75 (17)	C16—C11—N2—C3	39.0 (2)
C11—C12—C13—C14	−1.0 (3)	C12—C11—N2—N1	5.4 (2)
C12—C13—C14—C15	1.5 (3)	C16—C11—N2—N1	−169.15 (15)
C13—C14—C15—C16	0.4 (3)	N2—C3—N4—N5	−0.1 (2)
C14—C15—C16—C11	−2.6 (3)	C9—C3—N4—N5	168.86 (14)
C12—C11—C16—C15	3.0 (3)	N1—C6—N5—N4	41.6 (2)
N2—C11—C16—C15	177.59 (17)	C7—C6—N5—N4	−128.49 (15)
C22—C17—C18—C19	−1.5 (3)	N1—C6—N5—C17	−171.60 (15)
N5—C17—C18—C19	179.92 (15)	C7—C6—N5—C17	18.3 (2)
C17—C18—C19—C20	0.1 (3)	C3—N4—N5—C6	−40.05 (18)
C18—C19—C20—C21	0.6 (3)	C3—N4—N5—C17	170.98 (14)
C19—C20—C21—C22	−0.1 (3)	C18—C17—N5—C6	−124.46 (17)
C20—C21—C22—C17	−1.3 (3)	C22—C17—N5—C6	56.9 (2)
C18—C17—C22—C21	2.1 (3)	C18—C17—N5—N4	21.6 (2)
N5—C17—C22—C21	−179.28 (16)	C22—C17—N5—N4	−157.09 (15)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₄O₂
M_r	320.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.7853 (6), 14.7217 (7), 9.5113 (4)
β (°)	92.350 (1)
V (Å³)	1648.82 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.28 × 0.23 × 0.12

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.973, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	24032, 2985, 2090
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.02
No. of reflections	2985
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.14

Computer programs: SMART (Bruker, 2006), SAINT (Bruker, 2006), XS in SHELXTL (Sheldrick, 2008), XL in SHELXTL (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), XCIF in SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported in part by the Deanship of Academic Research, The Hashemite University, Jordan. The authors also thank Brendan Twamley, University Research Office, U. of Idaho, Moscow, Idaho, USA.

References

Al-Noaimi, M. Z., Saadeh, H., Haddad, S. F., El-Barghouthi, M., El-khateeb, M. & Crutchley, R. J. (2007). Polyhedron, 26, 3675–3685. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2004). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2006). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sauer, J. (1996). Comprehensive Heterocyclic Chemistry, 2nd ed., edited by A. J. Boulton, Vol. 24, pp. 901–955. Oxford: Elsevier. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar