3-Phenyl-6-(2-pyrid-yl)-1,2,4,5-tetra-zine.

The title compound, C(13)H(9)N(5), is the first asymmetric diaryl-1,2,4,5-tetra-zine to be crystallographically characterized. We have been inter-ested in this motif for incorporation into supra-molecular assemblies based on coordination chemistry. The solid state structure shows a centrosymmetric mol-ecule, forcing a positional disorder of the terminal phenyl and pyridyl rings. The mol-ecule is completely planar, unusual for aromatic rings with N atoms in adjacent ortho positions. The stacking observed is very common in diaryl-tetra-zines and is dominated by π stacking [centroid-to-centroid distance between the tetrazine ring and the aromatic ring of an adjacent molecule is 3.6 Å, perpendicular (centroid-to-plane) distance of about 3.3 Å].

Related literature

For a review of the potential applications of this type of mol­ecule, see: Cooke & Hanan (2007 ▶). Many symmetric tetra­zine mol­ecules have been studied for their reactivity in reverse electron-demand [2 + 2] cyclo­addition reactions, unusually well resolved EPR spectra and X-ray crystallography (Neunhoffer, 1984 ▶). Pertinent articles for this mol­ecule include work by Dinolfo et al. (2004 ▶), Ahmed & Kitaigorodsky (1972 ▶) and Klein et al. (1998 ▶).

Experimental

Crystal data

C13H9N5

M = 235.25

Monoclinic,

a = 5.3129 (3) Å

b = 5.2867 (3) Å

c = 18.9052 (12) Å

β = 91.940 (4)°

V = 530.70 (5) Å3

Z = 2

Cu Kα radiation

μ = 0.77 mm−1

T = 100 (2) K

0.24 × 0.10 × 0.03 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick,1996 ▶) T min = 0.784, T max = 0.98

8349 measured reflections

879 independent reflections

842 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.112

S = 1.17

879 reflections

82 parameters

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.15 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 1997 ▶); software used to prepare material for publication: UdMX (local program).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807064057/hj2003sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064057/hj2003Isup2.hkl

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

C13H9N5	F000 = 244
Mr = 235.25	Dx = 1.472 Mg m−3
Monoclinic, P21/n	Cu Kα radiation λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 5451 reflections
a = 5.3129 (3) Å	θ = 8.4–67.6º
b = 5.2867 (3) Å	µ = 0.77 mm−1
c = 18.9052 (12) Å	T = 100 (2) K
β = 91.940 (4)º	Plate, pink
V = 530.70 (5) Å3	0.24 × 0.10 × 0.03 mm
Z = 2

Bruker Microstar diffractometer	879 independent reflections
Radiation source: Rotating Anode	842 reflections with I > 2σ(I)
Monochromator: Helios optics	Rint = 0.036
Detector resolution: 8.2 pixels mm-1	θmax = 67.9º
T = 100(2) K	θmin = 8.7º
ω scans	h = −6→6
Absorption correction: multi-scan(SADABS; Sheldrick,1996)	k = −6→6
Tmin = 0.784, Tmax = 0.98	l = −20→21
8349 measured reflections

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)] = 0.041	H-atom parameters constrained
wR(F2) = 0.112	w = 1/[σ2(Fo2) + (0.0547P)2 + 0.1464P] where P = (Fo2 + 2Fc2)/3
S = 1.17	(Δ/σ)max < 0.001
879 reflections	Δρmax = 0.15 e Å−3
82 parameters	Δρmin = −0.15 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. X-ray crystallographic data for the title compound were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker microstar diffractometer equiped with a Platinum 135 CCD Detector, a Montel 200 optics and a Kappa goniometer. The crystal-to-detector distance was 4.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 10.0 degree scan in 33 frames over three different parts of the reciprocal space (99 frames total). One complete sphere of data was collected.Due to geometrical constraints of the instrument and the use of copper radiation, we obtain consistently a data completeness lower than 100% in dependence of the crystal system and the orientation of the mounted crystal, even with appropriate data collection routines. Typical values for data completeness range from 83–92% for triclinic, 85–97% for monoclinic and 85–98% for all other crystal systems.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	−0.2061 (2)	−0.1514 (2)	0.99344 (7)	0.0346 (4)
N2	−0.1772 (2)	0.0302 (2)	0.94668 (7)	0.0346 (4)
N3	−0.1139 (2)	0.4124 (2)	0.84843 (8)	0.0355 (4)	0.50
C1	0.0294 (2)	0.1780 (3)	0.95437 (8)	0.0319 (4)
C2	0.0639 (2)	0.3820 (3)	0.90237 (8)	0.0318 (4)
C3	0.2726 (2)	0.5426 (3)	0.90769 (8)	0.0351 (4)
H3	0.3971	0.5185	0.9443	0.042*
C4	0.2969 (3)	0.7360 (3)	0.85966 (9)	0.0368 (4)
H4	0.4373	0.8471	0.8634	0.044*
C5	0.1164 (3)	0.7682 (3)	0.80592 (9)	0.0360 (4)
H5	0.1308	0.9011	0.7725	0.043*
C6	−0.0864 (3)	0.6023 (3)	0.80185 (9)	0.0370 (4)
H6	−0.2101	0.6236	0.7649	0.044*
C7	−0.1139 (2)	0.4124 (2)	0.84843 (8)	0.0355 (4)	0.50
H7	−0.2540	0.3011	0.8441	0.043*	0.50

	U11	U22	U33	U12	U13	U23
N1	0.0242 (6)	0.0391 (7)	0.0406 (8)	−0.0021 (5)	0.0014 (5)	−0.0054 (5)
N2	0.0236 (6)	0.0393 (7)	0.0411 (8)	−0.0036 (5)	0.0029 (5)	−0.0052 (5)
N3	0.0255 (6)	0.0338 (7)	0.0467 (9)	0.0002 (5)	−0.0060 (6)	−0.0032 (6)
C1	0.0204 (6)	0.0357 (8)	0.0397 (9)	0.0008 (5)	0.0025 (6)	−0.0113 (6)
C2	0.0217 (6)	0.0335 (7)	0.0403 (10)	0.0025 (5)	0.0027 (6)	−0.0096 (6)
C3	0.0223 (7)	0.0429 (8)	0.0402 (10)	−0.0016 (6)	−0.0008 (6)	−0.0072 (7)
C4	0.0239 (7)	0.0385 (8)	0.0483 (10)	−0.0029 (6)	0.0044 (7)	−0.0087 (7)
C5	0.0290 (7)	0.0334 (7)	0.0456 (10)	0.0030 (6)	0.0043 (6)	−0.0018 (6)
C6	0.0286 (7)	0.0375 (8)	0.0445 (10)	0.0016 (6)	−0.0067 (6)	0.0013 (6)
C7	0.0255 (6)	0.0338 (7)	0.0467 (9)	0.0002 (5)	−0.0060 (6)	−0.0032 (6)

N1—N2	1.3177 (18)	C3—C4	1.376 (2)
N1—C1i	1.3462 (19)	C3—H3	0.9500
N2—C1	1.3514 (18)	C4—C5	1.384 (2)
N3—C6	1.347 (2)	C4—H4	0.9500
N3—C2	1.3758 (19)	C5—C6	1.389 (2)
C1—N1i	1.3462 (19)	C5—H5	0.9500
C1—C2	1.475 (2)	C6—H6	0.9500
C2—C3	1.398 (2)
N2—N1—C1i	118.26 (12)	C2—C3—H3	120.1
N1—N2—C1	117.52 (12)	C3—C4—C5	119.83 (13)
C6—N3—C2	118.99 (12)	C3—C4—H4	120.1
N1i—C1—N2	124.22 (15)	C5—C4—H4	120.1
N1i—C1—C2	117.74 (12)	C4—C5—C6	118.68 (15)
N2—C1—C2	118.04 (13)	C4—C5—H5	120.7
N3—C2—C3	120.37 (14)	C6—C5—H5	120.7
N3—C2—C1	118.80 (12)	N3—C6—C5	122.39 (13)
C3—C2—C1	120.83 (13)	N3—C6—H6	118.8
C4—C3—C2	119.73 (13)	C5—C6—H6	118.8
C4—C3—H3	120.1
C1i—N1—N2—C1	0.0 (2)	N2—C1—C2—C3	179.51 (12)
N1—N2—C1—N1i	0.0 (2)	N3—C2—C3—C4	1.6 (2)
N1—N2—C1—C2	180.00 (11)	C1—C2—C3—C4	−178.19 (12)
C6—N3—C2—C3	−1.4 (2)	C2—C3—C4—C5	−0.8 (2)
C6—N3—C2—C1	178.37 (12)	C3—C4—C5—C6	−0.1 (2)
N1i—C1—C2—N3	179.81 (12)	C2—N3—C6—C5	0.5 (2)
N2—C1—C2—N3	−0.2 (2)	C4—C5—C6—N3	0.3 (2)
N1i—C1—C2—C3	−0.4 (2)