2-(3-Chloro-5,6-diphenyl-2,5-dihydro-1,2,4-triazin-5-yl)-2-methyl-propane-nitrile.

The title compound, C(19)H(17)ClN(4), was obtained from the reaction of 3-chloro-5,6-diphenyl-1,2,4-triazine with isobutyronitrile in the presence of lithium diisopropyl-amide as an unexpected product of covalent addition of isobutyronitrile carbanion to the C-5 atom of the 1,2,4-triazine ring. The 2,5-dihydro-1,2,4-triazine ring is essentially planar (r.m.s. deviation = 0.0059 Å) and the 5- and 6-phenyl substituents are inclined to its mean plane with dihedral angles of 89.97 (4) and 55.52 (5)°, respectively. Intra-molecular C-H⋯N inter-actions occur. In the crystal, mol-ecules related by a c-glide plane are linked into zigzag chains along [001] by N-H⋯N hydrogen bonds.

Related literature

For background information, see: Hargaden & Guiry (2009 ▶); Konno et al. (1987 ▶); Rykowski et al. (2000 ▶). For the synthesis, see: Coeffard et al. (2009 ▶); Fujisawa et al. (1995 ▶). For a related structure, see: Ayato et al. (1981 ▶).

Experimental

Crystal data

C19H17ClN4

M = 336.82

Monoclinic,

a = 8.2422 (1) Å

b = 13.9124 (2) Å

c = 15.4685 (3) Å

β = 93.855 (1)°

V = 1769.74 (5) Å3

Z = 4

Cu Kα radiation

μ = 1.96 mm−1

T = 293 K

0.44 × 0.23 × 0.11 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.817, T max = 1.000

20671 measured reflections

3198 independent reflections

2957 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.110

S = 1.03

3198 reflections

221 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAIn class="Chemical">NT; 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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023252/bt5925sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023252/bt5925Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812023252/bt5925Isup3.cml

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

C19H17ClN4	F(000) = 704
Mr = 336.82	Dx = 1.264 Mg m−3
Monoclinic, P21/c	Melting point: 456 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 8.2422 (1) Å	Cell parameters from 9905 reflections
b = 13.9124 (2) Å	θ = 5.4–67.7°
c = 15.4685 (3) Å	µ = 1.96 mm−1
β = 93.855 (1)°	T = 293 K
V = 1769.74 (5) Å3	Prism, colourless
Z = 4	0.44 × 0.23 × 0.11 mm

Bruker SMART APEXII CCD diffractometer	3198 independent reflections
Radiation source: fine-focus sealed tube	2957 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
φ and ω scans	θmax = 68.1°, θmin = 4.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
Tmin = 0.817, Tmax = 1.000	k = −12→16
20671 measured reflections	l = −18→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.0608P)2 + 0.3505P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
3198 reflections	Δρmax = 0.21 e Å−3
221 parameters	Δρmin = −0.28 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: 0.0014 (3)

Experimental. 1H NMR (400 MHz, CDCl3) δ: 1.50 (s, 3H, CH3), 1.53 (s, 3H), 6.95–6.97 (m, 2H), 7.21–7.25 (m, 2H), 7.34–7.47 (m,4H), 7.70–7.72 (m, 2H), 8.25 (s, 1H); 13C NMR (50 MHz, CDCl3) δ: 22.6, 25.5, 39.0, 70.4, 124.0, 127.9, 128.5, 128.6, 128.7, 129.7, 130.0, 135.4, 140.7, 140.8, 147.5; HR MS ESI calculated for C19H17N4NaCl: 359.10340, found: 359.10469.

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.

	x	y	z	Uiso*/Ueq
Cl3	0.34703 (6)	0.12753 (4)	0.01120 (3)	0.07817 (19)
N1	0.63312 (16)	0.25063 (9)	0.18802 (7)	0.0529 (3)
N2	0.54094 (19)	0.22497 (10)	0.11422 (8)	0.0651 (4)
H2	0.538 (3)	0.2666 (17)	0.0696 (16)	0.098*
N4	0.44978 (15)	0.07957 (9)	0.16785 (7)	0.0505 (3)
N9	0.5113 (2)	0.12362 (10)	0.48082 (9)	0.0693 (4)
C3	0.45641 (18)	0.14300 (11)	0.11027 (9)	0.0510 (3)
C5	0.54108 (15)	0.09677 (9)	0.25203 (7)	0.0391 (3)
C6	0.63422 (15)	0.19302 (9)	0.25246 (8)	0.0425 (3)
C7	0.40539 (16)	0.10027 (10)	0.31926 (9)	0.0446 (3)
C8	0.47297 (19)	0.11233 (10)	0.40948 (9)	0.0498 (3)
C51	0.66526 (15)	0.01512 (9)	0.26417 (8)	0.0432 (3)
C52	0.77159 (19)	0.00305 (13)	0.19886 (11)	0.0624 (4)
H52	0.7590	0.0404	0.1490	0.094*
C53	0.8958 (2)	−0.06387 (16)	0.20727 (16)	0.0840 (6)
H53	0.9659	−0.0708	0.1630	0.126*
C54	0.9167 (2)	−0.11954 (14)	0.27919 (19)	0.0848 (7)
H54	1.0026	−0.1629	0.2853	0.127*
C55	0.8094 (2)	−0.11095 (13)	0.34268 (15)	0.0773 (6)
H55	0.8205	−0.1506	0.3911	0.116*
C56	0.6847 (2)	−0.04408 (11)	0.33588 (10)	0.0562 (4)
H56	0.6136	−0.0390	0.3798	0.084*
C61	0.72769 (17)	0.22915 (10)	0.33162 (8)	0.0489 (3)
C62	0.6891 (2)	0.31924 (12)	0.36333 (10)	0.0610 (4)
H62	0.6081	0.3557	0.3342	0.091*
C63	0.7696 (3)	0.35509 (16)	0.43739 (13)	0.0800 (6)
H63	0.7418	0.4152	0.4582	0.120*
C64	0.8905 (3)	0.3025 (2)	0.48049 (13)	0.0919 (7)
H64	0.9435	0.3263	0.5310	0.138*
C65	0.9325 (2)	0.21470 (19)	0.44865 (13)	0.0859 (6)
H65	1.0160	0.1797	0.4772	0.129*
C66	0.85223 (19)	0.17737 (14)	0.37446 (11)	0.0648 (4)
H66	0.8819	0.1177	0.3535	0.097*
C71	0.2966 (2)	0.18857 (13)	0.29982 (13)	0.0668 (4)
H711	0.2400	0.1813	0.2439	0.100*
H712	0.3627	0.2454	0.3002	0.100*
H713	0.2192	0.1941	0.3433	0.100*
C72	0.29850 (19)	0.00935 (12)	0.31542 (11)	0.0597 (4)
H721	0.2496	0.0014	0.2578	0.090*
H722	0.2148	0.0157	0.3553	0.090*
H723	0.3644	−0.0457	0.3308	0.090*

	U11	U22	U33	U12	U13	U23
Cl3	0.0896 (3)	0.0984 (4)	0.0432 (2)	−0.0087 (2)	−0.0200 (2)	0.01157 (19)
N1	0.0687 (7)	0.0523 (7)	0.0379 (6)	−0.0075 (6)	0.0044 (5)	0.0062 (5)
N2	0.0957 (10)	0.0610 (8)	0.0373 (6)	−0.0108 (7)	−0.0056 (6)	0.0144 (6)
N4	0.0542 (6)	0.0599 (7)	0.0363 (6)	−0.0071 (5)	−0.0053 (5)	0.0048 (5)
N9	0.1083 (11)	0.0611 (8)	0.0406 (8)	−0.0151 (7)	0.0214 (7)	−0.0087 (6)
C3	0.0568 (8)	0.0615 (8)	0.0342 (7)	0.0031 (6)	−0.0006 (6)	0.0045 (6)
C5	0.0436 (6)	0.0443 (7)	0.0294 (6)	−0.0012 (5)	0.0020 (5)	0.0027 (5)
C6	0.0458 (7)	0.0463 (7)	0.0359 (6)	−0.0019 (5)	0.0062 (5)	0.0035 (5)
C7	0.0468 (7)	0.0452 (7)	0.0427 (7)	0.0002 (5)	0.0105 (5)	0.0017 (5)
C8	0.0669 (9)	0.0416 (7)	0.0431 (8)	−0.0056 (6)	0.0199 (6)	−0.0025 (5)
C51	0.0455 (7)	0.0453 (7)	0.0384 (6)	0.0009 (5)	0.0006 (5)	−0.0068 (5)
C52	0.0567 (8)	0.0755 (10)	0.0561 (9)	0.0013 (7)	0.0128 (7)	−0.0147 (8)
C53	0.0544 (9)	0.0908 (14)	0.1085 (17)	0.0050 (9)	0.0188 (10)	−0.0426 (13)
C54	0.0555 (10)	0.0640 (11)	0.132 (2)	0.0144 (8)	−0.0152 (11)	−0.0275 (12)
C55	0.0779 (12)	0.0562 (9)	0.0933 (14)	0.0143 (8)	−0.0274 (11)	−0.0015 (9)
C56	0.0652 (9)	0.0516 (8)	0.0507 (8)	0.0089 (7)	−0.0041 (6)	0.0021 (6)
C61	0.0508 (7)	0.0578 (8)	0.0384 (7)	−0.0150 (6)	0.0063 (5)	0.0044 (6)
C62	0.0713 (10)	0.0604 (9)	0.0523 (8)	−0.0177 (7)	0.0117 (7)	−0.0040 (7)
C63	0.0877 (13)	0.0883 (13)	0.0657 (11)	−0.0331 (11)	0.0168 (10)	−0.0239 (10)
C64	0.0823 (13)	0.137 (2)	0.0561 (10)	−0.0389 (14)	0.0017 (9)	−0.0277 (12)
C65	0.0641 (10)	0.1296 (18)	0.0616 (11)	−0.0149 (11)	−0.0145 (8)	−0.0034 (12)
C66	0.0542 (8)	0.0840 (11)	0.0551 (9)	−0.0092 (8)	−0.0050 (7)	−0.0005 (8)
C71	0.0556 (9)	0.0645 (10)	0.0818 (11)	0.0150 (7)	0.0167 (8)	0.0069 (8)
C72	0.0584 (8)	0.0620 (9)	0.0602 (9)	−0.0148 (7)	0.0150 (7)	−0.0023 (7)

Cl3—C3	1.7383 (14)	C54—H54	0.9300
N1—C6	1.2787 (17)	C55—C56	1.385 (2)
N1—N2	1.3752 (18)	C55—H55	0.9300
N2—C3	1.336 (2)	C56—H56	0.9300
N2—H2	0.90 (2)	C61—C66	1.386 (2)
N4—C3	1.2577 (18)	C61—C62	1.390 (2)
N4—C5	1.4790 (16)	C62—C63	1.378 (2)
N9—C8	1.138 (2)	C62—H62	0.9300
C5—C51	1.5321 (18)	C63—C64	1.372 (3)
C5—C6	1.5433 (18)	C63—H63	0.9300
C5—C7	1.5782 (17)	C64—C65	1.371 (4)
C6—C61	1.4895 (18)	C64—H64	0.9300
C7—C8	1.477 (2)	C65—C66	1.387 (2)
C7—C71	1.539 (2)	C65—H65	0.9300
C7—C72	1.5403 (19)	C66—H66	0.9300
C51—C56	1.382 (2)	C71—H711	0.9600
C51—C52	1.3914 (19)	C71—H712	0.9600
C52—C53	1.383 (3)	C71—H713	0.9600
C52—H52	0.9300	C72—H721	0.9600
C53—C54	1.357 (3)	C72—H722	0.9600
C53—H53	0.9300	C72—H723	0.9600
C54—C55	1.370 (3)
C6—N1—N2	117.32 (12)	C54—C55—C56	121.02 (19)
C3—N2—N1	121.13 (12)	C54—C55—H55	119.5
C3—N2—H2	121.8 (15)	C56—C55—H55	119.5
N1—N2—H2	117.0 (15)	C51—C56—C55	120.44 (16)
C3—N4—C5	117.79 (12)	C51—C56—H56	119.8
N4—C3—N2	127.89 (14)	C55—C56—H56	119.8
N4—C3—Cl3	119.52 (12)	C66—C61—C62	118.65 (15)
N2—C3—Cl3	112.59 (10)	C66—C61—C6	122.90 (14)
N4—C5—C51	106.50 (10)	C62—C61—C6	118.45 (14)
N4—C5—C6	111.57 (10)	C63—C62—C61	120.73 (18)
C51—C5—C6	108.35 (10)	C63—C62—H62	119.6
N4—C5—C7	104.12 (10)	C61—C62—H62	119.6
C51—C5—C7	116.06 (10)	C64—C63—C62	120.3 (2)
C6—C5—C7	110.17 (10)	C64—C63—H63	119.9
N1—C6—C61	113.92 (12)	C62—C63—H63	119.9
N1—C6—C5	124.27 (12)	C65—C64—C63	119.56 (18)
C61—C6—C5	121.74 (10)	C65—C64—H64	120.2
C8—C7—C71	105.76 (12)	C63—C64—H64	120.2
C8—C7—C72	107.95 (11)	C64—C65—C66	120.9 (2)
C71—C7—C72	108.90 (12)	C64—C65—H65	119.6
C8—C7—C5	112.78 (11)	C66—C65—H65	119.6
C71—C7—C5	108.99 (11)	C61—C66—C65	119.87 (19)
C72—C7—C5	112.22 (11)	C61—C66—H66	120.1
N9—C8—C7	173.86 (17)	C65—C66—H66	120.1
C56—C51—C52	117.77 (14)	C7—C71—H711	109.5
C56—C51—C5	125.50 (12)	C7—C71—H712	109.5
C52—C51—C5	116.66 (13)	H711—C71—H712	109.5
C53—C52—C51	120.74 (18)	C7—C71—H713	109.5
C53—C52—H52	119.6	H711—C71—H713	109.5
C51—C52—H52	119.6	H712—C71—H713	109.5
C54—C53—C52	120.91 (18)	C7—C72—H721	109.5
C54—C53—H53	119.5	C7—C72—H722	109.5
C52—C53—H53	119.5	H721—C72—H722	109.5
C53—C54—C55	119.04 (16)	C7—C72—H723	109.5
C53—C54—H54	120.5	H721—C72—H723	109.5
C55—C54—H54	120.5	H722—C72—H723	109.5
C6—N1—N2—C3	−0.1 (2)	C6—C5—C51—C56	112.84 (14)
C5—N4—C3—N2	2.1 (2)	C7—C5—C51—C56	−11.66 (19)
C5—N4—C3—Cl3	−178.37 (10)	N4—C5—C51—C52	56.07 (15)
N1—N2—C3—N4	−1.5 (3)	C6—C5—C51—C52	−64.08 (15)
N1—N2—C3—Cl3	178.95 (12)	C7—C5—C51—C52	171.42 (12)
C3—N4—C5—C51	−119.22 (14)	C56—C51—C52—C53	−2.2 (2)
C3—N4—C5—C6	−1.18 (17)	C5—C51—C52—C53	175.00 (15)
C3—N4—C5—C7	117.62 (13)	C51—C52—C53—C54	0.2 (3)
N2—N1—C6—C61	−176.07 (12)	C52—C53—C54—C55	2.2 (3)
N2—N1—C6—C5	0.8 (2)	C53—C54—C55—C56	−2.5 (3)
N4—C5—C6—N1	−0.21 (18)	C52—C51—C56—C55	1.8 (2)
C51—C5—C6—N1	116.72 (14)	C5—C51—C56—C55	−175.06 (14)
C7—C5—C6—N1	−115.34 (14)	C54—C55—C56—C51	0.5 (3)
N4—C5—C6—C61	176.45 (12)	N1—C6—C61—C66	−125.41 (15)
C51—C5—C6—C61	−66.62 (14)	C5—C6—C61—C66	57.61 (18)
C7—C5—C6—C61	61.32 (15)	N1—C6—C61—C62	53.96 (17)
N4—C5—C7—C8	177.18 (11)	C5—C6—C61—C62	−123.02 (14)
C51—C5—C7—C8	60.49 (15)	C66—C61—C62—C63	−2.0 (2)
C6—C5—C7—C8	−63.07 (14)	C6—C61—C62—C63	178.61 (14)
N4—C5—C7—C71	−65.69 (14)	C61—C62—C63—C64	0.7 (3)
C51—C5—C7—C71	177.63 (12)	C62—C63—C64—C65	1.0 (3)
C6—C5—C7—C71	54.07 (14)	C63—C64—C65—C66	−1.3 (3)
N4—C5—C7—C72	55.01 (14)	C62—C61—C66—C65	1.7 (2)
C51—C5—C7—C72	−61.68 (15)	C6—C61—C66—C65	−178.98 (15)
C6—C5—C7—C72	174.76 (11)	C64—C65—C66—C61	0.0 (3)
N4—C5—C51—C56	−127.01 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C71—H711···N4	0.96	2.58	2.900 (2)	100
C72—H721···N4	0.96	2.48	2.847 (2)	103
N2—H2···N9i	0.90 (2)	2.06 (2)	2.9474 (19)	171 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C71—H711⋯N4	0.96	2.58	2.900 (2)	100
C72—H721⋯N4	0.96	2.48	2.847 (2)	103
N2—H2⋯N9i	0.90 (2)	2.06 (2)	2.9474 (19)	171 (2)

Symmetry code: (i) .