4-Benzyl-3-[(1-oxidoethylidene)amino]-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-5-iminium.

The title compound, C(17)H(17)N(5)O, exists in the zwitterionic form with the amide group deprotonated. The mean planes of the 1,2,4-triazole and N-phenyl rings form a dihedral angle of 39.14 (8)°. The N atom of the amino group adopts a trigonal configuration. Inter-moleculat C-H⋯O and C-H⋯N hydrogen bonds occur. In the crystal, mol-ecules are linked into a two-dimensional network parallel to (10[Formula: see text]) by N-H⋯O and N-H⋯N hydrogen bonds. C-H⋯N contacts are also observed.

Related literature

For the synthesis of the starting compound, <span class="Chemical">N-(5-amino-1-phenyl-1H-1,2,4-triazol-3-yl)acetamide, see: Chernyshev et al. (2005 ▶). For alkyl­ation and other reactions of related compounds with electrophiles, see: Chernyshev et al. (2008a ▶,b ▶). For crystal structures of 3(5)-acyl­amino-<class="Chemical">span class="Chemical">1,2,4-triazoles, see: Selby & Lepone (1984 ▶); Gyorgydeak et al. (1995 ▶); Chernyshev et al. (2006 ▶); Masiukiewicz et al. (2007 ▶); Miao et al. (2009 ▶). For crystal structures of 5-amino-1,2,4-triazolium salts, see: Darwich et al. (2008a ▶,b ▶); Klapotke & Sabate (2008 ▶); Tao et al. (2009 ▶); Chernyshev et al. (2010 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For the correlation of bond lengths with bond orders in sp 2-hybridized C and N atoms, see: Burke-Laing & Laing (1976 ▶).

Experimental

Crystal data

<span class="Chemical">C17H17N5O

M = 307.36

Monoclinic,

a = 10.262 (2) Å

b = 15.240 (3) Å

c = 10.967 (2) Å

β = 113.86 (2)°

V = 1568.6 (6) Å3

Z = 4

Ag Kα radiation

λ = 0.56085 Å

μ = 0.06 mm−1

T = 295 K

0.20 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

3582 measured reflections

3412 independent reflections

2294 reflections with I > 2σ(I)

R int = 0.068

1 standard reflections every 6 min intensity decay: 0%

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.160

S = 1.03

3412 reflections

218 parameters

<span class="Disease">H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811006751/aa2002sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006751/aa2002Isup2.hkl

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

C17H17N5O	F(000) = 648
Mr = 307.36	Dx = 1.301 Mg m−3
Monoclinic, P21/n	Melting point = 472–473 K
Hall symbol: -P 2yn	Ag Kα radiation, λ = 0.56085 Å
a = 10.262 (2) Å	Cell parameters from 25 reflections
b = 15.240 (3) Å	θ = 13.2–14.4°
c = 10.967 (2) Å	µ = 0.06 mm−1
β = 113.86 (2)°	T = 295 K
V = 1568.6 (6) Å3	Prism, colourless
Z = 4	0.20 × 0.20 × 0.20 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.068
Radiation source: fine-focus sealed tube	θmax = 21.0°, θmin = 1.8°
graphite	h = −13→11
Non–profiled ω scans	k = 0→19
3582 measured reflections	l = 0→13
3412 independent reflections	1 standard reflections every 6 min
2294 reflections with I > 2σ(I)	intensity decay: −1%

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)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.160	w = 1/[σ2(Fo2) + (0.0799P)2 + 0.4611P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
3412 reflections	Δρmax = 0.30 e Å−3
218 parameters	Δρmin = −0.22 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: 0.066 (6)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.86753 (18)	0.33588 (11)	0.43051 (16)	0.0345 (4)
N2	0.96176 (18)	0.26764 (11)	0.49396 (16)	0.0355 (4)
C3	0.9547 (2)	0.21474 (13)	0.39830 (19)	0.0314 (5)
N4	0.85963 (17)	0.24731 (11)	0.27474 (15)	0.0314 (4)
C5	0.8081 (2)	0.32385 (13)	0.29796 (19)	0.0315 (5)
C6	0.8381 (2)	0.21434 (14)	0.14185 (19)	0.0340 (5)
H6A	0.7417	0.2280	0.0797	0.041*
H6B	0.8481	0.1510	0.1459	0.041*
C7	0.9406 (2)	0.25232 (14)	0.0901 (2)	0.0383 (5)
C8	1.0832 (3)	0.2325 (2)	0.1442 (3)	0.0597 (7)
H8	1.1190	0.1948	0.2169	0.072*
C9	1.1747 (3)	0.2673 (2)	0.0931 (3)	0.0688 (8)
H9	1.2711	0.2533	0.1322	0.083*
C10	1.1255 (4)	0.3211 (2)	−0.0126 (4)	0.0812 (10)
H10	1.1868	0.3434	−0.0484	0.097*
C11	0.9848 (5)	0.3428 (3)	−0.0668 (5)	0.128 (2)
H11	0.9499	0.3807	−0.1395	0.153*
C12	0.8939 (3)	0.3090 (3)	−0.0146 (4)	0.0911 (12)
H12	0.7983	0.3252	−0.0518	0.109*
N13	1.04305 (18)	0.14482 (11)	0.41734 (17)	0.0371 (4)
C14	0.9911 (2)	0.06725 (14)	0.3633 (2)	0.0393 (5)
O14	0.86200 (18)	0.04827 (10)	0.30395 (16)	0.0492 (5)
C15	1.1022 (3)	−0.00100 (17)	0.3782 (3)	0.0563 (7)
H15A	1.0685	−0.0575	0.3914	0.084*
H15B	1.1885	0.0131	0.4536	0.084*
H15C	1.1207	−0.0022	0.2991	0.084*
C16	0.8529 (2)	0.40728 (14)	0.5074 (2)	0.0381 (5)
C17	0.7220 (3)	0.44477 (17)	0.4786 (2)	0.0520 (6)
H17	0.6411	0.4231	0.4095	0.062*
C18	0.7124 (4)	0.5152 (2)	0.5538 (3)	0.0678 (8)
H18	0.6249	0.5424	0.5333	0.081*
C19	0.8311 (5)	0.5452 (2)	0.6586 (3)	0.0751 (10)
H19	0.8238	0.5924	0.7092	0.090*
C20	0.9602 (4)	0.50577 (19)	0.6889 (3)	0.0637 (8)
H20	1.0397	0.5256	0.7614	0.076*
C21	0.9741 (3)	0.43706 (16)	0.6133 (2)	0.0474 (6)
H21	1.0624	0.4112	0.6327	0.057*
N51	0.7197 (2)	0.37631 (13)	0.2071 (2)	0.0438 (5)
H51A	0.695 (3)	0.433 (2)	0.223 (2)	0.053 (7)*
H51B	0.689 (3)	0.361 (2)	0.127 (3)	0.070 (9)*

	U11	U22	U33	U12	U13	U23
N1	0.0351 (9)	0.0355 (9)	0.0252 (9)	0.0034 (7)	0.0041 (7)	−0.0009 (7)
N2	0.0372 (10)	0.0353 (10)	0.0254 (8)	0.0043 (7)	0.0036 (7)	0.0026 (7)
C3	0.0282 (10)	0.0337 (10)	0.0258 (10)	−0.0020 (8)	0.0040 (8)	0.0037 (8)
N4	0.0315 (9)	0.0324 (9)	0.0220 (8)	−0.0001 (7)	0.0022 (7)	0.0010 (7)
C5	0.0309 (10)	0.0290 (10)	0.0269 (10)	−0.0015 (8)	0.0036 (8)	−0.0007 (8)
C6	0.0371 (11)	0.0330 (11)	0.0229 (9)	−0.0005 (9)	0.0029 (8)	−0.0017 (8)
C7	0.0432 (12)	0.0380 (11)	0.0307 (11)	−0.0021 (10)	0.0119 (9)	−0.0026 (9)
C8	0.0503 (16)	0.0741 (19)	0.0557 (16)	0.0122 (13)	0.0223 (13)	0.0085 (14)
C9	0.0537 (17)	0.083 (2)	0.079 (2)	−0.0007 (15)	0.0357 (16)	−0.0137 (18)
C10	0.082 (2)	0.092 (2)	0.088 (2)	−0.021 (2)	0.053 (2)	0.001 (2)
C11	0.085 (3)	0.190 (5)	0.111 (3)	0.003 (3)	0.043 (2)	0.089 (4)
C12	0.0585 (19)	0.130 (3)	0.080 (2)	0.0083 (19)	0.0224 (17)	0.063 (2)
N13	0.0355 (9)	0.0360 (10)	0.0298 (9)	0.0032 (8)	0.0029 (7)	0.0018 (8)
C14	0.0459 (13)	0.0349 (11)	0.0293 (11)	0.0040 (10)	0.0071 (9)	0.0053 (9)
O14	0.0477 (10)	0.0357 (8)	0.0474 (10)	−0.0052 (7)	0.0019 (7)	0.0030 (7)
C15	0.0608 (16)	0.0463 (14)	0.0544 (16)	0.0123 (12)	0.0158 (13)	−0.0009 (12)
C16	0.0493 (13)	0.0356 (11)	0.0290 (11)	−0.0031 (10)	0.0154 (9)	0.0011 (9)
C17	0.0600 (16)	0.0531 (15)	0.0425 (13)	0.0068 (12)	0.0202 (12)	−0.0015 (11)
C18	0.096 (2)	0.0560 (17)	0.0662 (19)	0.0191 (16)	0.0479 (18)	0.0045 (15)
C19	0.135 (3)	0.0474 (16)	0.0628 (19)	−0.0084 (19)	0.061 (2)	−0.0137 (14)
C20	0.099 (2)	0.0552 (16)	0.0436 (15)	−0.0323 (17)	0.0357 (15)	−0.0163 (12)
C21	0.0587 (15)	0.0486 (13)	0.0332 (12)	−0.0147 (11)	0.0167 (11)	−0.0057 (10)
N51	0.0510 (12)	0.0332 (10)	0.0284 (10)	0.0102 (9)	−0.0033 (8)	−0.0023 (8)

N4—C5	1.347 (3)	C11—H11	0.9300
N4—C3	1.402 (2)	C12—H12	0.9300
N4—C6	1.471 (3)	N13—C14	1.333 (3)
C5—N51	1.313 (3)	C14—O14	1.251 (3)
C5—N1	1.342 (2)	C14—C15	1.503 (3)
N1—N2	1.399 (2)	C15—H15A	0.9600
N1—C16	1.422 (3)	C15—H15B	0.9600
N2—C3	1.302 (3)	C15—H15C	0.9600
C3—N13	1.359 (3)	C16—C17	1.374 (3)
C6—C7	1.499 (3)	C16—C21	1.390 (3)
C6—H6A	0.9700	C17—C18	1.382 (4)
C6—H6B	0.9700	C17—H17	0.9300
C7—C12	1.360 (4)	C18—C19	1.371 (5)
C7—C8	1.371 (3)	C18—H18	0.9300
C8—C9	1.379 (4)	C19—C20	1.368 (5)
C8—H8	0.9300	C19—H19	0.9300
C9—C10	1.341 (5)	C20—C21	1.378 (4)
C9—H9	0.9300	C20—H20	0.9300
C10—C11	1.361 (5)	C21—H21	0.9300
C10—H10	0.9300	N51—H51A	0.94 (3)
C11—C12	1.378 (5)	N51—H51B	0.84 (3)
C5—N4—C3	107.27 (16)	C7—C12—C11	121.5 (3)
C5—N4—C6	124.75 (16)	C7—C12—H12	119.3
C3—N4—C6	127.11 (17)	C11—C12—H12	119.3
N51—C5—N1	127.6 (2)	C14—N13—C3	120.35 (18)
N51—C5—N4	125.98 (19)	O14—C14—N13	125.8 (2)
N1—C5—N4	106.38 (16)	O14—C14—C15	119.6 (2)
C5—N1—N2	110.92 (16)	N13—C14—C15	114.6 (2)
C5—N1—C16	129.54 (17)	C14—C15—H15A	109.5
N2—N1—C16	119.44 (16)	C14—C15—H15B	109.5
C3—N2—N1	104.94 (15)	H15A—C15—H15B	109.5
N2—C3—N13	123.07 (17)	C14—C15—H15C	109.5
N2—C3—N4	110.47 (17)	H15A—C15—H15C	109.5
N13—C3—N4	125.89 (18)	H15B—C15—H15C	109.5
N4—C6—C7	113.32 (17)	C17—C16—C21	121.2 (2)
N4—C6—H6A	108.9	C17—C16—N1	120.7 (2)
C7—C6—H6A	108.9	C21—C16—N1	118.2 (2)
N4—C6—H6B	108.9	C16—C17—C18	119.0 (3)
C7—C6—H6B	108.9	C16—C17—H17	120.5
H6A—C6—H6B	107.7	C18—C17—H17	120.5
C12—C7—C8	117.1 (2)	C19—C18—C17	120.3 (3)
C12—C7—C6	120.2 (2)	C19—C18—H18	119.8
C8—C7—C6	122.7 (2)	C17—C18—H18	119.8
C7—C8—C9	121.5 (3)	C20—C19—C18	120.2 (3)
C7—C8—H8	119.2	C20—C19—H19	119.9
C9—C8—H8	119.2	C18—C19—H19	119.9
C10—C9—C8	120.4 (3)	C19—C20—C21	120.9 (3)
C10—C9—H9	119.8	C19—C20—H20	119.6
C8—C9—H9	119.8	C21—C20—H20	119.6
C9—C10—C11	119.3 (3)	C20—C21—C16	118.4 (3)
C9—C10—H10	120.4	C20—C21—H21	120.8
C11—C10—H10	120.4	C16—C21—H21	120.8
C10—C11—C12	120.3 (3)	C5—N51—H51A	125.1 (15)
C10—C11—H11	119.9	C5—N51—H51B	118 (2)
C12—C11—H11	119.9	H51A—N51—H51B	116 (3)
C3—N4—C5—N51	177.4 (2)	C7—C8—C9—C10	−0.7 (5)
C6—N4—C5—N51	7.4 (3)	C8—C9—C10—C11	1.6 (6)
C3—N4—C5—N1	−1.2 (2)	C9—C10—C11—C12	−0.8 (7)
C6—N4—C5—N1	−171.22 (18)	C8—C7—C12—C11	2.0 (6)
N51—C5—N1—N2	−177.0 (2)	C6—C7—C12—C11	−178.0 (4)
N4—C5—N1—N2	1.6 (2)	C10—C11—C12—C7	−1.1 (8)
N51—C5—N1—C16	−0.7 (4)	N2—C3—N13—C14	135.3 (2)
N4—C5—N1—C16	177.9 (2)	N4—C3—N13—C14	−54.2 (3)
C5—N1—N2—C3	−1.4 (2)	C3—N13—C14—O14	−7.3 (3)
C16—N1—N2—C3	−178.07 (18)	C3—N13—C14—C15	172.8 (2)
N1—N2—C3—N13	172.37 (18)	C5—N1—C16—C17	42.3 (3)
N1—N2—C3—N4	0.5 (2)	N2—N1—C16—C17	−141.7 (2)
C5—N4—C3—N2	0.4 (2)	C5—N1—C16—C21	−138.6 (2)
C6—N4—C3—N2	170.09 (18)	N2—N1—C16—C21	37.4 (3)
C5—N4—C3—N13	−171.11 (19)	C21—C16—C17—C18	2.2 (4)
C6—N4—C3—N13	−1.4 (3)	N1—C16—C17—C18	−178.7 (2)
C5—N4—C6—C7	82.4 (2)	C16—C17—C18—C19	−2.2 (4)
C3—N4—C6—C7	−85.5 (2)	C17—C18—C19—C20	0.4 (5)
N4—C6—C7—C12	−110.7 (3)	C18—C19—C20—C21	1.5 (4)
N4—C6—C7—C8	69.3 (3)	C19—C20—C21—C16	−1.5 (4)
C12—C7—C8—C9	−1.1 (4)	C17—C16—C21—C20	−0.4 (3)
C6—C7—C8—C9	178.9 (2)	N1—C16—C21—C20	−179.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N51—H51A···O14i	0.94 (3)	1.83 (3)	2.739 (3)	161 (2)
N51—H51B···N13ii	0.84 (3)	2.18 (3)	2.971 (3)	157 (3)
C6—H6B···O14	0.97	2.30	3.045 (3)	133
C8—H8···N13	0.93	2.72	3.454 (4)	136
C17—H17···N51	0.93	2.75	3.146 (4)	107
C12—H12···N13ii	0.93	2.54	3.441 (4)	162

Bond	Uncorrected	Lower bound	Upper bound	Riding motion	Non–correlated motion
C6–C7	1.499 (3)	1.499	1.583	1.504	1.541
C7–C8	1.371 (3)	1.375	1.517	1.394	1.446
C7–C12	1.360 (4)	1.375	1.575	1.418	1.475
C8–C9	1.379 (4)	1.380	1.573	1.388	1.476
C9–C10	1.341 (5)	1.342	1.539	1.356	1.440
C10–C11	1.361 (5)	1.370	1.679	1.413	1.524
C11–C12	1.378 (5)	1.382	1.773	1.417	1.577
N13–C14	1.333 (3)	1.333	1.449	1.335	1.391
C14–O14	1.251 (3)	1.252	1.393	1.264	1.323
C14–C15	1.503 (3)	1.505	1.636	1.519	1.570
C16–C17	1.374 (3)	1.375	1.493	1.388	1.434
C16–C21	1.390 (3)	1.391	1.519	1.401	1.455
C17–C18	1.382 (4)	1.383	1.573	1.397	1.478
C18–C19	1.371 (5)	1.372	1.538	1.378	1.455
C19–C20	1.368 (5)	1.369	1.500	1.379	1.434
C20–C21	1.378 (4)	1.380	1.549	1.394	1.464

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N51—H51A⋯O14i	0.94 (3)	1.83 (3)	2.739 (3)	161 (2)
N51—H51B⋯N13ii	0.84 (3)	2.18 (3)	2.971 (3)	157 (3)
C6—H6B⋯O14	0.97	2.30	3.045 (3)	133
C8—H8⋯N13	0.93	2.72	3.454 (4)	136
C12—H12⋯N13ii	0.93	2.54	3.441 (4)	162

Symmetry codes: (i) ; (ii) .