5,5′,6,6′-Tetra­methyl-3,3′-bi-1,2,4-tri­azine

Wolińska, E.; Karczmarzyk, Z.; Rykowski, A.; Wysocki, W.

doi:10.1107/S1600536811020691

organic compounds

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doi:10.1107/S1600536811020691

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5,5′,6,6′-Tetramethyl-3,3′-bi-1,2,4-triazine

Ewa Wolińska,^a Zbigniew Karczmarzyk,^a ^* Andrzej Rykowski ^a and Waldemar Wysocki ^a

^aDepartment of Chemistry, University of Podlasie, ul. 3 Maja 54, 08-110 Siedlce, Poland
^*Correspondence e-mail: kar@uph.edu.pl

(Received 18 May 2011; accepted 30 May 2011; online 11 June 2011)

In the title compound, C₁₀H₁₂N₆, the two 5,6-dimethyl-1,2,4-triazine halves of the molecule are related by a centre of symmetry. The two triazine rings are coplanar to within a maximum deviation of 0.013 (2) Å from the mean plane of the ring atoms. In the crystal, molecules form layers parallel to the (100) crystallographic plane. Adjacent layers are held together via a C—H⋯π interaction involving molecules related by an a-glide plane.

Related literature

For background information, see: Branowska & Rykowski (2002 ); Branowska (2003 ); Boger & Weinrab (1987 ); Pabst et al. (1998 ). For the synthesis, see: Dedichen (1936 , 1937 ). For a related structure, see: Breu & Range (1993 ).

Experimental

Crystal data

C₁₀H₁₂N₆
M_r = 216.26
Orthorhombic, P b c a
a = 8.1167 (7) Å
b = 10.6662 (12) Å
c = 12.7127 (11) Å
V = 1100.59 (18) Å³
Z = 4
Cu Kα radiation
μ = 0.71 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.10 mm

Data collection

Kuma KM4 four-circle diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.830, T_max = 0.929
1637 measured reflections
1205 independent reflections
910 reflections with I > 2σ(I)
R_int = 0.100
2 standard reflections every 100 reflections intensity decay: 1.3%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.272
S = 1.16
1205 reflections
92 parameters
All H-atom parameters refined
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

CgA is the centroid of the triazine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C51—H511⋯CgAⁱ	1.09 (5)	2.96 (4)	3.616 (3)	119 (3)
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

Data collection: KM4B8 (Gałdecki et al., 1996 $[Gałdecki, Z., Kowalski, A., Kucharczyk, D. & Uszyński, L. (1996). KM4B8. Kuma Diffraction, Wrocław, Poland.]$ ); cell refinement: KM4B8; data reduction: DATAPROC (Gałdecki et al., 1995 $[Gałdecki, Z., Kowalski, A. & Uszyński, L. (1995). DATAPROC. Kuma Diffraction, Wrocław, Poland.]$ ); 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: SHELXL97 and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020691/fy2014sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020691/fy2014Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811020691/fy2014Isup3.cml

checkCIF report

Comment top

In the course of our research we widely explored the synthesis of cycloalkeno[c]fused 2,2'-bipyridines using Diels–Alder reactions of 5,5'-bi-1,2,4-triazine derivatives as dienes (Branowska & Rykowski, 2002; Branowska, 2003). However, when we turned our attention to the synthesis of 5,5',6,6'-tetrasubstituted-2,2'-bipyridines, these dienes did not appear useful. Considering the mechanism of the Diels–Alder reaction of 5,5'-bi-1,2,4-triazine, it is clear that to obtain 5,5',6,6'-tetrasubstituted-2,2'-bipyridines, the substituents in positions 5 and 5' of the product have to originate from an unsymmetrical dienofile. Unfortunately, application of such a dienofile can lead to a mixture of 5,5',6,6'- and 3,3',6,6'-tetrasubstituted-2,2'-bipyridines (Boger & Weinrab, 1987). To solve the problem with selectivity, we envisaged that 3,3'-bi-1,2,4-triazines with substituents in 5 and 5' positions can be structurally ideal diene partners in the Diels–Alder synthesis of 5,5',6,6'-tetrasubstituted-2,2'-bipyridines (Pabst et al., 1998). The title compound 5,5',6,6'-tetramethyl-3,3'-bi-1,2,4-triazine was synthesized and its X-ray structure was determined as a part of this research.

The two 5,6-dimethyl-1,2,4-triazine parts of the molecule (I) are related by a crystallographic center of symmetry and possess the trans conformation, with the triazine rings being coplanar to within a 0.013 (2) Å maximum deviation from the mean plane. The geometry and conformation of (I) are very similar to those observed in the related structure of 5,5',6,6'-tetraphenyl-3,3'-bi-1,2,4-triazine (Breu & Range, 1993).

In the crystal structure, the molecules of (I) form molecular layers parallel to the (100) crystallographic plane (Fig. 2), with the molecular mean planes being inclined to this plane at an angle of 34.8 (5)°. The layers are held together via C—H···π interaction involving the C51—H151 atoms of the methyl group and the triazine ring from the molecule related by an a-glide plane.

Related literature top

For background information, see: Branowska & Rykowski (2002); Branowska (2003); Boger & Weinrab (1987); Pabst et al. (1998). For the synthesis, see: Dedichen (1936, 1937). For a related structure, see: Breu & Range (1993).

Experimental top

The title compound, (I), was prepared by the condensation of oxalhydrazidine with 2,3-butanedione according to the procedure of Dedichen (1936, 1937). Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a benzene solution.

Computing details top

Data collection: KM4B8 (Gałdecki et al., 1996); cell refinement: KM4B8 (Gałdecki et al., 1996); data reduction: DATAPROC (Gałdecki et al., 1995); 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: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. A view of the molecular packing in (I). H atoms are omitted for clarity.

3-(5,6-dimethyl-1,2,4-triazin-3-yl)-5,6-dimethyl-1,2,4-triazine top

Crystal data top

C₁₀H₁₂N₆	D_x = 1.305 Mg m⁻³
M_r = 216.26	Melting point = 441–442 K
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 8.1167 (7) Å	θ = 11.5–22.4°
b = 10.6662 (12) Å	µ = 0.71 mm⁻¹
c = 12.7127 (11) Å	T = 293 K
V = 1100.59 (18) Å³	Prism, yellow
Z = 4	0.20 × 0.20 × 0.10 mm
F(000) = 456

Data collection top

Kuma KM4 four-circle diffractometer	910 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.100
Graphite monochromator	θ_max = 80.2°, θ_min = 7.0°
ω/2θ scans	h = −1→10
Absorption correction: ψ scan (North et al., 1968)	k = −1→13
T_min = 0.830, T_max = 0.929	l = −1→16
1637 measured reflections	2 standard reflections every 100 reflections
1205 independent reflections	intensity decay: 1.3%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.064	All H-atom parameters refined
wR(F²) = 0.272	w = 1/[σ²(F_o²) + (0.2P)²] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max < 0.001
1205 reflections	Δρ_max = 0.29 e Å⁻³
92 parameters	Δρ_min = −0.24 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: 0.032 (7)

Crystal data top

C₁₀H₁₂N₆	V = 1100.59 (18) Å³
M_r = 216.26	Z = 4
Orthorhombic, Pbca	Cu Kα radiation
a = 8.1167 (7) Å	µ = 0.71 mm⁻¹
b = 10.6662 (12) Å	T = 293 K
c = 12.7127 (11) Å	0.20 × 0.20 × 0.10 mm

Data collection top

Kuma KM4 four-circle diffractometer	910 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.100
T_min = 0.830, T_max = 0.929	2 standard reflections every 100 reflections
1637 measured reflections	intensity decay: 1.3%
1205 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.272	All H-atom parameters refined
S = 1.16	Δρ_max = 0.29 e Å⁻³
1205 reflections	Δρ_min = −0.24 e Å⁻³
92 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
N1	0.4275 (4)	0.2701 (2)	0.50737 (19)	0.0750 (8)
N2	0.4248 (3)	0.1532 (2)	0.4693 (2)	0.0733 (8)
N4	0.58882 (19)	0.08158 (18)	0.61103 (13)	0.0491 (6)
C3	0.5036 (2)	0.0648 (2)	0.52195 (15)	0.0488 (7)
C5	0.5959 (2)	0.1973 (2)	0.64669 (16)	0.0501 (7)
C6	0.5112 (3)	0.2946 (2)	0.59397 (18)	0.0541 (7)
C51	0.6953 (4)	0.2213 (3)	0.7429 (2)	0.0750 (9)
H511	0.771 (6)	0.142 (5)	0.767 (3)	0.113*
H512	0.762 (7)	0.297 (4)	0.732 (3)	0.113*
H513	0.621 (6)	0.241 (6)	0.803 (3)	0.113*
C61	0.5097 (4)	0.4263 (3)	0.6326 (3)	0.0733 (9)
H611	0.482 (6)	0.431 (4)	0.709 (4)	0.110*
H612	0.427 (5)	0.476 (6)	0.599 (4)	0.110*
H613	0.617 (5)	0.462 (5)	0.618 (3)	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.1042 (18)	0.0492 (13)	0.0717 (14)	0.0018 (11)	−0.0267 (12)	0.0010 (10)
N2	0.1037 (18)	0.0482 (12)	0.0680 (13)	0.0020 (10)	−0.0359 (11)	−0.0007 (9)
N4	0.0483 (9)	0.0560 (12)	0.0431 (9)	−0.0048 (6)	−0.0053 (6)	−0.0018 (6)
C3	0.0512 (10)	0.0529 (13)	0.0424 (10)	−0.0044 (8)	−0.0061 (7)	0.0006 (8)
C5	0.0484 (10)	0.0574 (13)	0.0445 (10)	−0.0097 (7)	0.0017 (7)	−0.0064 (8)
C6	0.0610 (12)	0.0471 (12)	0.0543 (11)	−0.0093 (8)	0.0071 (8)	−0.0029 (8)
C51	0.0804 (16)	0.0834 (19)	0.0613 (14)	−0.0116 (15)	−0.0183 (12)	−0.0177 (13)
C61	0.092 (2)	0.0515 (15)	0.0760 (18)	−0.0118 (12)	0.0119 (14)	−0.0092 (12)

Geometric parameters (Å, º) top

N1—C6	1.320 (3)	C6—C61	1.488 (3)
N1—N2	1.337 (3)	C51—H511	1.09 (5)
N2—C3	1.322 (3)	C51—H512	0.98 (5)
N4—C5	1.316 (3)	C51—H513	1.00 (5)
N4—C3	1.339 (2)	C61—H611	1.00 (5)
C3—C3ⁱ	1.492 (4)	C61—H612	0.96 (5)
C5—C6	1.414 (4)	C61—H613	0.97 (5)
C5—C51	1.488 (3)

C6—N1—N2	119.7 (2)	C5—C51—H511	114 (2)
C3—N2—N1	118.3 (2)	C5—C51—H512	109 (3)
C5—N4—C3	116.05 (19)	H511—C51—H512	112 (4)
N2—C3—N4	125.6 (2)	C5—C51—H513	110 (3)
N2—C3—C3ⁱ	116.9 (2)	H511—C51—H513	107 (4)
N4—C3—C3ⁱ	117.4 (2)	H512—C51—H513	106 (4)
N4—C5—C6	120.27 (19)	C6—C61—H611	112 (3)
N4—C5—C51	118.0 (2)	C6—C61—H612	113 (3)
C6—C5—C51	121.8 (2)	H611—C61—H612	105 (4)
N1—C6—C5	120.0 (2)	C6—C61—H613	108 (3)
N1—C6—C61	117.3 (2)	H611—C61—H613	111 (4)
C5—C6—C61	122.7 (2)	H612—C61—H613	109 (4)

C6—N1—N2—C3	1.8 (4)	N2—N1—C6—C5	−0.8 (4)
N1—N2—C3—N4	−0.7 (4)	N2—N1—C6—C61	180.0 (2)
N1—N2—C3—C3ⁱ	179.2 (2)	N4—C5—C6—N1	−1.4 (3)
C5—N4—C3—N2	−1.4 (3)	C51—C5—C6—N1	178.4 (3)
C5—N4—C3—C3ⁱ	178.6 (2)	N4—C5—C6—C61	177.8 (2)
C3—N4—C5—C6	2.4 (3)	C51—C5—C6—C61	−2.4 (3)
C3—N4—C5—C51	−177.4 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

CgA is the centroid of the triazine ring.

D—H···A	D—H	H···A	D···A	D—H···A
C51—H511···CgAⁱⁱ	1.09 (5)	2.96 (4)	3.616 (3)	119 (3)

Symmetry code: (ii) x−1/2, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₆
M_r	216.26
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	8.1167 (7), 10.6662 (12), 12.7127 (11)
V (Å³)	1100.59 (18)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Kuma KM4 four-circle diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.830, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	1637, 1205, 910
R_int	0.100
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.272, 1.16
No. of reflections	1205
No. of parameters	92
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24

Computer programs: KM4B8 (Gałdecki et al., 1996), DATAPROC (Gałdecki et al., 1995), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

CgA is the centroid of the triazine ring.

D—H···A	D—H	H···A	D···A	D—H···A
C51—H511···CgAⁱ	1.09 (5)	2.96 (4)	3.616 (3)	119 (3)

Symmetry code: (i) x−1/2, y, −z+3/2.

References

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1613

doi:10.1107/S1600536811020691

Open

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