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Acta Crystallogr Sect E Struct Rep Online. 2008 March 1; 64(Pt 3): o551.
Published online 2008 February 6. doi:  10.1107/S1600536808003115
PMCID: PMC2960815

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

Abstract

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

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-0o551-scheme1.jpg

Experimental

Crystal data

  • C18H16N4O2
  • M r = 320.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o551-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.107
  • S = 1.02
  • 2985 reflections
  • 219 parameters
  • H-atom parameters constrained
  • Δρmax = 0.12 e Å−3
  • Δρmin = −0.14 e Å−3

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

Supplementary Material

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

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

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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)°.

Experimental

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).

Refinement

The H atoms were geometrically placed (C—H = 0.93–0.97 Å) and refined as riding with with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

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

Crystal data

C18H16N4O2F000 = 672
Mr = 320.35Dx = 1.291 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4916 reflections
a = 11.7853 (6) Åθ = 2.2–23.9º
b = 14.7217 (7) ŵ = 0.09 mm1
c = 9.5113 (4) ÅT = 298 (2) K
β = 92.350 (1)ºBlock, red
V = 1648.82 (13) Å30.28 × 0.23 × 0.12 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer2985 independent reflections
Radiation source: normal-focus sealed tube2090 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.038
Detector resolution: 8.3 pixels mm-1θmax = 25.3º
T = 298(2) Kθmin = 1.7º
ω scansh = −14→14
Absorption correction: multi-scan(SADABS; Bruker, 2004)k = −17→17
Tmin = 0.973, Tmax = 0.989l = −11→11
24032 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.0508P)2 + 0.1852P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2985 reflectionsΔρmax = 0.12 e Å3
219 parametersΔρmin = −0.14 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
C30.19860 (13)0.04264 (11)0.24262 (17)0.0476 (4)
C60.06963 (13)0.17718 (11)0.30979 (16)0.0443 (4)
C70.01584 (14)0.23941 (12)0.41383 (18)0.0485 (4)
C80.03913 (16)0.33770 (12)0.3984 (2)0.0615 (5)
H8A0.00630.37040.47400.092*
H8B0.00650.35880.31020.092*
H8C0.11970.34760.40090.092*
C90.29164 (15)−0.02517 (13)0.27788 (19)0.0566 (5)
C100.25803 (17)−0.12250 (14)0.2816 (3)0.0861 (7)
H10A0.3228−0.15880.30930.129*
H10B0.2298−0.14090.18990.129*
H10C0.1997−0.13060.34810.129*
C110.31755 (13)0.15724 (12)0.12166 (17)0.0479 (4)
C120.36333 (14)0.24291 (13)0.14032 (19)0.0567 (5)
H120.33380.28250.20570.068*
C130.45313 (16)0.26945 (15)0.0613 (2)0.0681 (5)
H130.48330.32750.07260.082*
C140.49833 (16)0.21120 (16)−0.0338 (2)0.0707 (6)
H140.56000.2291−0.08520.085*
C150.45218 (16)0.12619 (15)−0.0529 (2)0.0666 (5)
H150.48310.0865−0.11710.080*
C160.36055 (15)0.09929 (13)0.02212 (19)0.0582 (5)
H160.32770.04260.00610.070*
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)
H18−0.0705−0.04370.39960.064*
C19−0.23938 (16)−0.02164 (14)0.3785 (2)0.0660 (5)
H19−0.2611−0.07300.42770.079*
C20−0.32094 (16)0.03634 (17)0.3228 (2)0.0744 (6)
H20−0.39740.02460.33510.089*
C21−0.28909 (16)0.11175 (16)0.2489 (2)0.0730 (6)
H21−0.34430.15090.21120.088*
C22−0.17587 (15)0.12967 (13)0.2303 (2)0.0603 (5)
H22−0.15450.18010.17870.072*
N10.16981 (11)0.19907 (9)0.27549 (14)0.0495 (4)
N20.22031 (11)0.13056 (9)0.19490 (14)0.0496 (4)
N40.09917 (11)0.02070 (9)0.28117 (14)0.0489 (4)
N50.02219 (10)0.09373 (9)0.26874 (14)0.0460 (4)
O7−0.04003 (12)0.20784 (9)0.50509 (14)0.0728 (4)
O90.38657 (10)0.00113 (9)0.30439 (15)0.0717 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C30.0384 (9)0.0512 (11)0.0535 (10)0.0003 (8)0.0079 (7)−0.0038 (8)
C60.0394 (9)0.0460 (10)0.0481 (10)0.0020 (7)0.0072 (7)0.0017 (7)
C70.0423 (9)0.0533 (11)0.0504 (10)0.0028 (8)0.0069 (8)−0.0011 (8)
C80.0665 (12)0.0545 (12)0.0640 (12)0.0037 (9)0.0095 (9)−0.0061 (9)
C90.0407 (10)0.0647 (12)0.0653 (12)0.0063 (9)0.0125 (8)0.0026 (9)
C100.0592 (13)0.0587 (13)0.141 (2)0.0137 (10)0.0099 (13)0.0077 (13)
C110.0369 (9)0.0583 (11)0.0488 (10)0.0014 (8)0.0060 (7)0.0026 (8)
C120.0455 (10)0.0626 (12)0.0625 (12)−0.0040 (9)0.0093 (8)−0.0045 (9)
C130.0515 (12)0.0737 (14)0.0797 (14)−0.0133 (10)0.0126 (10)0.0048 (11)
C140.0479 (11)0.0961 (17)0.0691 (14)−0.0026 (11)0.0165 (10)0.0149 (12)
C150.0573 (12)0.0870 (16)0.0567 (12)0.0107 (11)0.0176 (9)0.0008 (10)
C160.0536 (11)0.0616 (12)0.0604 (12)0.0014 (9)0.0136 (9)−0.0035 (9)
C170.0373 (9)0.0525 (10)0.0505 (10)0.0004 (7)0.0088 (7)−0.0066 (8)
C180.0476 (10)0.0567 (11)0.0563 (11)−0.0033 (8)0.0101 (8)−0.0060 (9)
C190.0550 (12)0.0711 (14)0.0732 (13)−0.0173 (10)0.0170 (10)−0.0112 (10)
C200.0398 (11)0.0975 (17)0.0867 (15)−0.0139 (11)0.0098 (10)−0.0248 (13)
C210.0415 (11)0.0894 (16)0.0875 (15)0.0130 (10)−0.0023 (10)−0.0096 (12)
C220.0443 (11)0.0639 (12)0.0728 (13)0.0083 (9)0.0045 (9)0.0018 (10)
N10.0442 (8)0.0493 (8)0.0560 (9)0.0011 (6)0.0128 (6)−0.0039 (7)
N20.0406 (8)0.0492 (8)0.0601 (9)0.0001 (6)0.0163 (6)−0.0047 (7)
N40.0373 (8)0.0484 (8)0.0615 (9)0.0036 (6)0.0076 (6)−0.0027 (7)
N50.0344 (7)0.0457 (8)0.0585 (9)0.0038 (6)0.0088 (6)−0.0009 (7)
O70.0844 (10)0.0649 (9)0.0717 (9)−0.0061 (7)0.0377 (8)−0.0061 (7)
O90.0402 (8)0.0865 (10)0.0887 (10)0.0030 (7)0.0061 (7)0.0111 (8)

Geometric parameters (Å, °)

C3—N41.2834 (19)C13—C141.370 (3)
C3—N21.399 (2)C13—H130.9300
C3—C91.510 (2)C14—C151.374 (3)
C6—N11.2790 (19)C14—H140.9300
C6—N51.399 (2)C15—C161.377 (2)
C6—C71.507 (2)C15—H150.9300
C7—O71.2041 (19)C16—H160.9300
C7—C81.481 (2)C17—C181.378 (2)
C8—H8A0.9600C17—C221.382 (2)
C8—H8B0.9600C17—N51.431 (2)
C8—H8C0.9600C18—C191.382 (2)
C9—O91.201 (2)C18—H180.9300
C9—C101.487 (3)C19—C201.375 (3)
C10—H10A0.9600C19—H190.9300
C10—H10B0.9600C20—C211.375 (3)
C10—H10C0.9600C20—H200.9300
C11—C121.380 (2)C21—C221.379 (3)
C11—C161.386 (2)C21—H210.9300
C11—N21.4207 (19)C22—H220.9300
C12—C131.380 (2)N1—N21.4130 (18)
C12—H120.9300N4—N51.4086 (17)
N4—C3—N2120.46 (15)C13—C14—H14120.2
N4—C3—C9115.67 (15)C15—C14—H14120.2
N2—C3—C9122.88 (14)C14—C15—C16120.54 (19)
N1—C6—N5120.85 (14)C14—C15—H15119.7
N1—C6—C7115.58 (15)C16—C15—H15119.7
N5—C6—C7122.89 (14)C15—C16—C11119.58 (18)
O7—C7—C8123.90 (16)C15—C16—H16120.2
O7—C7—C6119.72 (16)C11—C16—H16120.2
C8—C7—C6116.35 (15)C18—C17—C22120.59 (16)
C7—C8—H8A109.5C18—C17—N5121.77 (15)
C7—C8—H8B109.5C22—C17—N5117.63 (15)
H8A—C8—H8B109.5C17—C18—C19119.19 (18)
C7—C8—H8C109.5C17—C18—H18120.4
H8A—C8—H8C109.5C19—C18—H18120.4
H8B—C8—H8C109.5C20—C19—C18120.6 (2)
O9—C9—C10123.52 (17)C20—C19—H19119.7
O9—C9—C3119.68 (17)C18—C19—H19119.7
C10—C9—C3116.77 (16)C21—C20—C19119.81 (18)
C9—C10—H10A109.5C21—C20—H20120.1
C9—C10—H10B109.5C19—C20—H20120.1
H10A—C10—H10B109.5C20—C21—C22120.40 (19)
C9—C10—H10C109.5C20—C21—H21119.8
H10A—C10—H10C109.5C22—C21—H21119.8
H10B—C10—H10C109.5C21—C22—C17119.41 (19)
C12—C11—C16119.90 (16)C21—C22—H22120.3
C12—C11—N2120.56 (15)C17—C22—H22120.3
C16—C11—N2119.32 (15)C6—N1—N2111.85 (13)
C13—C12—C11119.55 (17)C3—N2—N1113.44 (12)
C13—C12—H12120.2C3—N2—C11125.24 (13)
C11—C12—H12120.2N1—N2—C11115.77 (13)
C14—C13—C12120.68 (19)C3—N4—N5112.11 (13)
C14—C13—H13119.7C6—N5—N4113.47 (12)
C12—C13—H13119.7C6—N5—C17122.19 (13)
C13—C14—C15119.68 (18)N4—N5—C17115.92 (13)
N1—C6—C7—O7−140.54 (17)N5—C6—N1—N20.3 (2)
N5—C6—C7—O730.1 (2)C7—C6—N1—N2171.13 (13)
N1—C6—C7—C837.6 (2)N4—C3—N2—N142.1 (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—O921.2 (3)C9—C3—N2—C1126.4 (2)
N4—C3—C9—C1030.7 (2)C6—N1—N2—C3−40.54 (19)
N2—C3—C9—C10−160.58 (17)C6—N1—N2—C11164.27 (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—C339.0 (2)
C11—C12—C13—C14−1.0 (3)C12—C11—N2—N15.4 (2)
C12—C13—C14—C151.5 (3)C16—C11—N2—N1−169.15 (15)
C13—C14—C15—C160.4 (3)N2—C3—N4—N5−0.1 (2)
C14—C15—C16—C11−2.6 (3)C9—C3—N4—N5168.86 (14)
C12—C11—C16—C153.0 (3)N1—C6—N5—N441.6 (2)
N2—C11—C16—C15177.59 (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—C19179.92 (15)C7—C6—N5—C1718.3 (2)
C17—C18—C19—C200.1 (3)C3—N4—N5—C6−40.05 (18)
C18—C19—C20—C210.6 (3)C3—N4—N5—C17170.98 (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—C656.9 (2)
C18—C17—C22—C212.1 (3)C18—C17—N5—N421.6 (2)
N5—C17—C22—C21−179.28 (16)C22—C17—N5—N4−157.09 (15)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2696).

References

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

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