4,4′-(1,2,4,5-Tetra­zine-3,6-di­yl)dibenzo­nitrile

Dutkiewicz, G.; Borowiak, T.; Spychała, J.

doi:10.1107/S1600536809008599

organic compounds

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Volume 65| Part 4| April 2009| Page o824

doi:10.1107/S1600536809008599

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4,4′-(1,2,4,5-Tetrazine-3,6-diyl)dibenzonitrile

Grzegorz Dutkiewicz,^a Teresa Borowiak ^a ^* and Jarosław Spychała ^a

^aDepartment of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland
^*Correspondence e-mail: borowiak@amu.edu.pl

(Received 16 February 2009; accepted 9 March 2009; online 25 March 2009)

Molecules of the title compound, C₁₆H₈N₆, lie on crystallographic inversion centres. A dihedral angle of 16.1 (1)° is formed between the central tetrazine ring and the plane of each cyanophenyl group. The molecules form stacks along [100] with a perpendicular interplanar separation of 3.25 (1) Å. C—H⋯N interactions are formed between molecules in neighbouring stacks.

Related literature

For synthesis details, see: Spychała et al. (1994 , 2000 ). For related structures and discussion, see: Higashi & Osaki (1981 ); Infantes et al. (2003 ).

Experimental

Crystal data

C₁₆H₈N₆
M_r = 284.28
Monoclinic, P 2₁ /c
a = 4.8447 (5) Å
b = 12.1054 (12) Å
c = 11.6927 (11) Å
β = 94.363 (8)°
V = 683.75 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 K
0.45 × 0.2 × 0.1 mm

Data collection

Kuma KM-4-CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Poland, Wrocław, Poland.]$ ) T_min = 0.925, T_max = 0.991
5912 measured reflections
1768 independent reflections
1094 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.135
S = 1.06
1768 reflections
116 parameters
All H-atom parameters refined
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯N10ⁱ	0.989 (17)	2.539 (17)	3.370 (2)	141.6 (13)
C8—H8⋯N2ⁱⁱ	0.956 (17)	2.850 (17)	3.6106 (19)	137.2 (12)
C9—H9⋯N10ⁱⁱⁱ	0.993 (17)	2.754 (17)	3.431 (2)	125.8 (12)
Symmetry codes: (i) -x+2, -y+1, -z; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Poland, Wrocław, Poland.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Poland, Wrocław, Poland.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008599/bi2354sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008599/bi2354Isup2.hkl

checkCIF report

Comment top

Infantes et al. (2003) have found that the supramolecular structures of some substituted phenyl derivatives of 1,2,4,5-tetrazine are comparable to those of their carboxylic acid analogues. Being inspired by that, we have compared the supramolecular structures of the title compound 3,6-bis(4-cyanophenyl)-1,2,4,5-tetrazine (hereafter I) and p-cyanobenzoic acid (Higashi & Osaki, 1981) (hereafter II).

In (I), the tetrazine molecule is located on a crystallographic inversion centre (Fig. 1). The phenyl rings are twisted with respect to the tetrazine ring by 16.1 (1)° in opposite directions. The cyano-groups are coplanar with their phenyl rings. Two C6—H6···N10(cyano) interactions related by a centre of inversion can be considered to link the molecules into 1-D chains (Fig. 2). The chains are "stepped" rather than flat (Fig. 3). Each molecule interacts with the neighbouring chain through C8—H8···N2(tetrazine) and C9—H9···N10(cyano) interactions (Fig. 2), and the molecules are stacked along [100] with a perpendicular interplanar spacing of 3.25 (1) Å. This structure contrasts with the layered structures of other phenyl-derivatives of 1,2,4,5 tetrazines described in the paper by Infantes et al. (2003).

In the crystal structure of (II), similar 1-D chains are formed through the well-known centrosymmetric carboxylic acid dimer on one side of the molecule and centrosymmetric C—H···N(cyano) interactions on the other side of the molecule. The latter interactions are closely comparable to those in (I), except that the chains in (II) lie in approximately flat layers parallel to the (201) planes. The distinction between the two structures arises because of differences between the lateral C—H···O interactions between chains in (II) and the C—H···N(tetrazine) and C—H···N(cyano) interactions in (I).

Related literature top

For synthesis details, see: Spychała et al. (1994, 2000). For related structures and discussion, see: Higashi & Osaki (1981); Infantes et al. (2003).

Experimental top

The title compound was obtained from a multi-step procedure starting from 4-amidinobenzamide hydrochloride and anhydrous hydrazine. Dehydration of the biscarbamoyl intermediate compound to the appropriate biscyano red product was effected by means of phosphorus oxychloride in the same way as described for 2,4-bis(4- carbamoylphenyl)-1,3,5-triazine (Spychała et al., 1994; Spychała (2000). M.p. 568–570 K (acetone); δ_H (CDCl₃, TMS) 7.94 (d, 4H, J = 8.8 Hz, CH), 8.82 (d, 4H, J = 8.8 Hz, CH); δ_C (DMSO-d₆) 114.7, 117.8, 128.2, 133.0, 135.6, 162.4; MS (EI) 284 (M⁺, C₁₆H₈N₆; 13), 128 (100), 102 (9), 101 (33), 100 (7), 77 (9), 76 (12), 75 (16), 74 (4), 64 (11).

Single crystals were grown from hot acetone by slow cooling.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure showing displacement ellipsoids at the 50% probability level for non-H atoms. Symmetry code: (i) -x, -y, -z.
	Fig. 2. Chains of molecules (horizontal) linked by centrosymmetric pairs of C—H···N(cyano) interactions.
	Fig. 3. Stacks of molecules (vertical) showing the "stepped" arrangement within the 1-D chains.

4,4'-(1,2,4,5-Tetrazine-3,6-diyl)dibenzonitrile top

Crystal data top

C₁₆H₈N₆	F(000) = 292
M_r = 284.28	D_x = 1.381 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2059 reflections
a = 4.8447 (5) Å	θ = 2.4–29.6°
b = 12.1054 (12) Å	µ = 0.09 mm⁻¹
c = 11.6927 (11) Å	T = 291 K
β = 94.363 (8)°	Block, orange
V = 683.75 (12) Å³	0.45 × 0.2 × 0.1 mm
Z = 2

Data collection top

Kuma KM-4-CCD diffractometer	1768 independent reflections
Radiation source: fine-focus sealed tube	1094 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 8.1929 pixels mm^-1	θ_max = 29.7°, θ_min = 3.4°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −16→15
T_min = 0.925, T_max = 0.991	l = −15→14
5912 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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F²) = 0.135	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.0683P)² + 0.0311P] where P = (F_o² + 2F_c²)/3
1768 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₆H₈N₆	V = 683.75 (12) Å³
M_r = 284.28	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.8447 (5) Å	µ = 0.09 mm⁻¹
b = 12.1054 (12) Å	T = 291 K
c = 11.6927 (11) Å	0.45 × 0.2 × 0.1 mm
β = 94.363 (8)°

Data collection top

Kuma KM-4-CCD diffractometer	1768 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1094 reflections with I > 2σ(I)
T_min = 0.925, T_max = 0.991	R_int = 0.017
5912 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.135	All H-atom parameters refined
S = 1.06	Δρ_max = 0.16 e Å⁻³
1768 reflections	Δρ_min = −0.13 e Å⁻³
116 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
N1	−0.2003 (2)	0.01444 (9)	−0.08623 (10)	0.0532 (4)
N2	−0.0256 (2)	0.09630 (9)	−0.05942 (10)	0.0528 (4)
C3	0.1693 (2)	0.07922 (10)	0.02639 (10)	0.0418 (3)
C4	0.3614 (2)	0.17078 (10)	0.05676 (11)	0.0434 (3)
C5	0.3849 (3)	0.25828 (12)	−0.01845 (13)	0.0546 (4)
C6	0.5664 (3)	0.34327 (13)	0.00878 (14)	0.0596 (4)
C7	0.7235 (3)	0.34205 (12)	0.11308 (13)	0.0542 (4)
C8	0.7010 (3)	0.25569 (14)	0.18883 (14)	0.0626 (5)
C9	0.5218 (3)	0.16937 (13)	0.16039 (13)	0.0564 (4)
C10	0.9104 (3)	0.43269 (15)	0.14189 (14)	0.0682 (5)
N10	1.0547 (4)	0.50498 (14)	0.16340 (14)	0.0986 (6)
H6	0.588 (3)	0.4047 (13)	−0.0455 (16)	0.080 (5)*
H5	0.271 (3)	0.2606 (13)	−0.0895 (14)	0.065 (4)*
H8	0.811 (3)	0.2535 (13)	0.2601 (15)	0.078 (5)*
H9	0.509 (3)	0.1054 (14)	0.2128 (14)	0.076 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0548 (7)	0.0474 (7)	0.0549 (7)	−0.0081 (5)	−0.0131 (5)	0.0051 (5)
N2	0.0546 (7)	0.0469 (7)	0.0542 (7)	−0.0070 (5)	−0.0128 (5)	0.0056 (5)
C3	0.0429 (7)	0.0433 (7)	0.0388 (7)	−0.0019 (6)	0.0003 (5)	−0.0008 (5)
C4	0.0423 (7)	0.0441 (7)	0.0433 (7)	−0.0026 (6)	−0.0005 (5)	−0.0012 (6)
C5	0.0578 (8)	0.0545 (9)	0.0496 (8)	−0.0100 (7)	−0.0075 (6)	0.0061 (7)
C6	0.0670 (10)	0.0537 (9)	0.0572 (9)	−0.0152 (8)	−0.0005 (7)	0.0056 (7)
C7	0.0534 (8)	0.0538 (9)	0.0553 (9)	−0.0146 (7)	0.0033 (6)	−0.0068 (7)
C8	0.0640 (9)	0.0719 (10)	0.0494 (8)	−0.0190 (8)	−0.0114 (7)	0.0007 (8)
C9	0.0620 (9)	0.0566 (9)	0.0487 (8)	−0.0149 (7)	−0.0086 (7)	0.0060 (7)
C10	0.0749 (10)	0.0741 (11)	0.0554 (9)	−0.0259 (9)	0.0034 (8)	−0.0063 (8)
N10	0.1182 (13)	0.1029 (13)	0.0742 (11)	−0.0672 (11)	0.0037 (9)	−0.0105 (9)

Geometric parameters (Å, º) top

N1—N2	1.3254 (14)	C6—C7	1.388 (2)
N1—C3ⁱ	1.3347 (17)	C6—H6	0.989 (17)
N2—C3	1.3403 (17)	C7—C8	1.380 (2)
C3—N1ⁱ	1.3347 (17)	C7—C10	1.446 (2)
C3—C4	1.4735 (17)	C8—C9	1.383 (2)
C4—C5	1.3869 (19)	C8—H8	0.955 (17)
C4—C9	1.3888 (18)	C9—H9	0.993 (17)
C5—C6	1.375 (2)	C10—N10	1.1360 (18)
C5—H5	0.962 (16)

N2—N1—C3ⁱ	117.81 (11)	C5—C6—H6	120.8 (10)
N1—N2—C3	117.55 (11)	C7—C6—H6	119.6 (10)
N1ⁱ—C3—N2	124.64 (11)	C8—C7—C6	120.49 (13)
N1ⁱ—C3—C4	117.94 (11)	C8—C7—C10	120.27 (13)
N2—C3—C4	117.42 (11)	C6—C7—C10	119.25 (14)
C5—C4—C9	119.68 (12)	C7—C8—C9	119.80 (14)
C5—C4—C3	120.17 (12)	C7—C8—H8	121.0 (10)
C9—C4—C3	120.15 (12)	C9—C8—H8	119.1 (10)
C6—C5—C4	120.43 (13)	C8—C9—C4	119.99 (14)
C6—C5—H5	119.6 (9)	C8—C9—H9	120.7 (10)
C4—C5—H5	120.0 (9)	C4—C9—H9	119.4 (10)
C5—C6—C7	119.60 (14)	N10—C10—C7	178.9 (2)

C3ⁱ—N1—N2—C3	−0.3 (2)	C4—C5—C6—C7	−1.0 (2)
N1—N2—C3—N1ⁱ	0.3 (2)	C5—C6—C7—C8	0.7 (2)
N1—N2—C3—C4	−179.39 (11)	C5—C6—C7—C10	−178.94 (15)
N1ⁱ—C3—C4—C5	164.01 (13)	C6—C7—C8—C9	0.4 (3)
N2—C3—C4—C5	−16.25 (19)	C10—C7—C8—C9	−179.95 (15)
N1ⁱ—C3—C4—C9	−15.40 (19)	C7—C8—C9—C4	−1.2 (3)
N2—C3—C4—C9	164.34 (13)	C5—C4—C9—C8	0.9 (2)
C9—C4—C5—C6	0.2 (2)	C3—C4—C9—C8	−179.71 (14)
C3—C4—C5—C6	−179.18 (13)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N10ⁱⁱ	0.989 (17)	2.539 (17)	3.370 (2)	141.6 (13)
C8—H8···N2ⁱⁱⁱ	0.956 (17)	2.850 (17)	3.6106 (19)	137.2 (12)
C9—H9···N10^iv	0.993 (17)	2.754 (17)	3.431 (2)	125.8 (12)

Symmetry codes: (ii) −x+2, −y+1, −z; (iii) x+1, −y+1/2, z+1/2; (iv) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₈N₆
M_r	284.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	4.8447 (5), 12.1054 (12), 11.6927 (11)
β (°)	94.363 (8)
V (Å³)	683.75 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.45 × 0.2 × 0.1

Data collection
Diffractometer	Kuma KM-4-CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.925, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5912, 1768, 1094
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.135, 1.06
No. of reflections	1768
No. of parameters	116
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.13

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Stereochemical Workstation Operation Manual (Siemens, 1989) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N10ⁱ	0.989 (17)	2.539 (17)	3.370 (2)	141.6 (13)
C8—H8···N2ⁱⁱ	0.956 (17)	2.850 (17)	3.6106 (19)	137.2 (12)
C9—H9···N10ⁱⁱⁱ	0.993 (17)	2.754 (17)	3.431 (2)	125.8 (12)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1, −y+1/2, z+1/2; (iii) −x+2, y−1/2, −z+1/2.

Acknowledgements

This work was supported by funds from Adam Mickiewicz University, Faculty of Chemistry.

References

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