2-Amino-5-methyl-3-(2-oxo-2-phenyl-eth-yl)-7-phenyl-4,5,6,7-tetra-hydro-3H-[1,2,4]triazolo[1,5-a]pyrimidin-8-ium bromide ethanol monosolvate.

In the title compound, C20H22N5O(+)·Br(-)·C2H6O, the tetra-hydro-pyrimidine ring of the bicyclic cation adopts a half-chair conformation with an equatorial orientation of the phenyl and methyl substituents. The amino group is nearly coplanar with the 1,2,4-triazole ring [interplanar angle = 4.08 (8)°] and has a slightly pyramidal configuration. The mean planes of the triazole ring and the benzene ring of the phenacyl group form a dihedral angle of 88.58 (7)°. In the crystal, N-H⋯Br, N-H⋯O and O-H⋯Br hydrogen bonds link the cations, anions and ethanol mol-ecules into layers parallel to the bc plane.

Related literature

For the synthesis and reactivity of partially hydrogenated [1,2,4]triazolo[1,5-a]pyrimidines, see: Desenko (1995 ▶); Desenko et al. (1994 ▶); Chebanov et al. (2008 ▶, 2010 ▶); Gorobets et al. (2012 ▶); Lipson et al. (2012 ▶), Chernyshev et al. (2008a ▶,b ▶). For applications of partially hydrogenated triazolo­pyrimidines in the synthesis of polycondensed heterocycles, see: Beck et al. (2011 ▶); Lipson et al. (2006 ▶); Sidorenko & Orlov (2011 ▶); Sokolov et al. (2011 ▶). For structures of protonated C-amino-1,2,4-triazoles and quaternized derivatives of tetra­hydro­triazolo­pyrimidines, see: Chernyshev et al. (2008a ▶, 2010 ▶); Matulkova et al. (2012 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For the correlation of bond lengths with bond orders between the sp 2 hybridized C and N atoms, see: Burke-Laing & Laing (1976 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C20H22N5O+·Br−·C2H6O

M = 474.40

Monoclinic,

a = 10.7471 (13) Å

b = 13.3261 (16) Å

c = 15.5792 (19) Å

β = 95.735 (2)°

V = 2220.0 (5) Å3

Z = 4

Mo Kα radiation

μ = 1.88 mm−1

T = 120 K

0.22 × 0.19 × 0.18 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.520, T max = 0.713

31509 measured reflections

5356 independent reflections

4309 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.082

S = 1.01

5356 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.87 e Å−3

Δρmin = −0.48 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813025853/aa2095sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813025853/aa2095Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813025853/aa2095Isup3.cdx

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813025853/aa2095Isup4.cml

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

C20H22N5O+·Br−·C2H6O	F(000) = 984
Mr = 474.40	Dx = 1.419 Mg m−3
Monoclinic, P21/c	Melting point: 190 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.7471 (13) Å	Cell parameters from 8717 reflections
b = 13.3261 (16) Å	θ = 2.4–28.0°
c = 15.5792 (19) Å	µ = 1.88 mm−1
β = 95.735 (2)°	T = 120 K
V = 2220.0 (5) Å3	Prizm, colourless
Z = 4	0.22 × 0.19 × 0.18 mm

Bruker SMART APEXII CCD area-detector diffractometer	5356 independent reflections
Radiation source: fine-focus sealed tube	4309 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
phi and ω scans	θmax = 28.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.520, Tmax = 0.713	k = −17→17
31509 measured reflections	l = −20→20

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)] = 0.032	Hydrogen site location: mixed
wR(F2) = 0.082	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.037P)2 + 1.2826P] where P = (Fo2 + 2Fc2)/3
5356 reflections	(Δ/σ)max = 0.001
273 parameters	Δρmax = 0.87 e Å−3
0 restraints	Δρmin = −0.48 e Å−3

Geometry. All s.u.'s (except the s.u.'s 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 > 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
Br1	0.543412 (18)	0.702949 (15)	0.181863 (12)	0.02186 (7)
O1	0.83014 (13)	0.48942 (12)	0.72034 (9)	0.0258 (3)
N1	0.62069 (14)	0.47059 (12)	0.61743 (10)	0.0168 (3)
N2	0.67921 (15)	0.46201 (12)	0.48350 (10)	0.0192 (3)
N3	0.68765 (14)	0.36830 (12)	0.52479 (10)	0.0178 (3)
N4	0.64780 (15)	0.29581 (12)	0.65761 (10)	0.0204 (3)
H3N	0.5982	0.2991	0.7008	0.025*
N5	0.62162 (16)	0.62146 (13)	0.53199 (11)	0.0229 (4)
H1N	0.6464	0.6474	0.4831	0.028*
H2N	0.6076	0.6534	0.5810	0.028*
C1	0.65153 (17)	0.37328 (14)	0.60340 (12)	0.0174 (4)
C2	0.64195 (17)	0.52227 (15)	0.54245 (12)	0.0175 (4)
C3	0.72309 (18)	0.27569 (14)	0.48255 (12)	0.0190 (4)
H3A	0.6502	0.2511	0.4432	0.023*
C4	0.75412 (19)	0.19832 (15)	0.55517 (13)	0.0221 (4)
H4A	0.7612	0.1310	0.5292	0.027*
H4B	0.8363	0.2152	0.5864	0.027*
C5	0.65589 (19)	0.19465 (14)	0.61958 (13)	0.0219 (4)
H5A	0.5730	0.1765	0.5885	0.026*
C6	0.6897 (2)	0.11877 (16)	0.69099 (14)	0.0282 (5)
H6A	0.6306	0.1245	0.7348	0.042*
H6B	0.7746	0.1320	0.7175	0.042*
H6C	0.6856	0.0509	0.6667	0.042*
C7	0.83408 (17)	0.28950 (14)	0.43140 (12)	0.0180 (4)
C8	0.92976 (18)	0.35757 (16)	0.45378 (13)	0.0235 (4)
H8A	0.9239	0.4023	0.5007	0.028*
C9	1.0336 (2)	0.36042 (17)	0.40785 (14)	0.0281 (5)
H9A	1.0979	0.4080	0.4229	0.034*
C10	1.0448 (2)	0.29453 (17)	0.34016 (14)	0.0295 (5)
H10A	1.1168	0.2963	0.3095	0.035*
C11	0.9504 (2)	0.22620 (18)	0.31757 (13)	0.0298 (5)
H11A	0.9574	0.1806	0.2715	0.036*
C12	0.8450 (2)	0.22454 (16)	0.36260 (13)	0.0240 (4)
H12A	0.7796	0.1784	0.3462	0.029*
C13	0.60915 (17)	0.51128 (15)	0.70338 (11)	0.0181 (4)
H13A	0.5505	0.4696	0.7332	0.022*
H13B	0.5755	0.5804	0.6985	0.022*
C14	0.73822 (18)	0.51207 (14)	0.75576 (12)	0.0188 (4)
C15	0.74642 (18)	0.54203 (14)	0.84815 (12)	0.0194 (4)
C16	0.8639 (2)	0.56537 (17)	0.88979 (14)	0.0275 (4)
H16A	0.9360	0.5606	0.8594	0.033*
C17	0.8757 (2)	0.59558 (18)	0.97557 (14)	0.0316 (5)
H17A	0.9557	0.6123	1.0034	0.038*
C18	0.7711 (2)	0.60135 (17)	1.02054 (13)	0.0285 (5)
H18A	0.7794	0.6226	1.0790	0.034*
C19	0.6546 (2)	0.57634 (16)	0.98056 (13)	0.0259 (4)
H19A	0.5833	0.5793	1.0119	0.031*
C20	0.64158 (19)	0.54670 (15)	0.89427 (12)	0.0222 (4)
H20A	0.5614	0.5297	0.8669	0.027*
O1S	0.69870 (16)	0.69468 (12)	0.37452 (10)	0.0329 (4)
H1S	0.6682	0.7057	0.3229	0.049*
C1S	0.8245 (2)	0.6690 (2)	0.36528 (16)	0.0407 (6)
H1SA	0.8698	0.6601	0.4233	0.049*
H1SB	0.8644	0.7252	0.3368	0.049*
C2S	0.8375 (2)	0.57495 (19)	0.31379 (17)	0.0395 (6)
H2SA	0.9263	0.5579	0.3141	0.059*
H2SB	0.8013	0.5858	0.2543	0.059*
H2SC	0.7936	0.5198	0.3394	0.059*

	U11	U22	U33	U12	U13	U23
Br1	0.02512 (11)	0.02392 (11)	0.01705 (10)	−0.00020 (8)	0.00457 (7)	0.00345 (8)
O1	0.0210 (7)	0.0330 (8)	0.0241 (7)	0.0005 (6)	0.0060 (6)	−0.0020 (6)
N1	0.0212 (8)	0.0161 (8)	0.0135 (7)	0.0028 (6)	0.0038 (6)	−0.0005 (6)
N2	0.0223 (8)	0.0176 (8)	0.0180 (8)	0.0019 (6)	0.0032 (6)	0.0014 (6)
N3	0.0200 (8)	0.0176 (8)	0.0163 (7)	0.0023 (6)	0.0033 (6)	−0.0010 (6)
N4	0.0258 (8)	0.0176 (8)	0.0190 (8)	0.0014 (6)	0.0078 (6)	0.0015 (6)
N5	0.0322 (9)	0.0194 (9)	0.0185 (8)	0.0042 (7)	0.0095 (7)	0.0023 (6)
C1	0.0155 (9)	0.0189 (9)	0.0178 (9)	−0.0002 (7)	0.0020 (7)	−0.0007 (7)
C2	0.0161 (9)	0.0217 (10)	0.0148 (8)	0.0001 (7)	0.0022 (7)	0.0015 (7)
C3	0.0201 (9)	0.0192 (10)	0.0179 (9)	−0.0008 (7)	0.0034 (7)	−0.0055 (7)
C4	0.0256 (10)	0.0162 (9)	0.0255 (10)	−0.0006 (8)	0.0069 (8)	−0.0025 (8)
C5	0.0241 (10)	0.0177 (10)	0.0246 (10)	−0.0023 (8)	0.0060 (8)	−0.0015 (8)
C6	0.0381 (12)	0.0191 (10)	0.0285 (11)	−0.0004 (9)	0.0098 (9)	0.0021 (8)
C7	0.0186 (9)	0.0184 (9)	0.0170 (8)	0.0026 (7)	0.0023 (7)	−0.0001 (7)
C8	0.0233 (10)	0.0229 (10)	0.0244 (10)	−0.0003 (8)	0.0027 (8)	−0.0037 (8)
C9	0.0235 (10)	0.0262 (11)	0.0348 (12)	−0.0026 (8)	0.0042 (9)	0.0020 (9)
C10	0.0276 (11)	0.0338 (12)	0.0291 (11)	0.0055 (9)	0.0132 (9)	0.0063 (9)
C11	0.0357 (12)	0.0328 (12)	0.0219 (10)	0.0047 (9)	0.0091 (9)	−0.0056 (9)
C12	0.0265 (10)	0.0232 (10)	0.0223 (10)	−0.0001 (8)	0.0032 (8)	−0.0036 (8)
C13	0.0220 (9)	0.0193 (9)	0.0140 (8)	0.0027 (7)	0.0064 (7)	−0.0005 (7)
C14	0.0227 (10)	0.0148 (9)	0.0194 (9)	−0.0014 (7)	0.0044 (7)	0.0015 (7)
C15	0.0249 (10)	0.0157 (9)	0.0171 (9)	0.0010 (7)	−0.0003 (7)	0.0017 (7)
C16	0.0253 (11)	0.0288 (11)	0.0282 (11)	−0.0008 (8)	0.0023 (8)	−0.0024 (9)
C17	0.0310 (12)	0.0350 (13)	0.0269 (11)	−0.0038 (9)	−0.0070 (9)	−0.0023 (9)
C18	0.0414 (13)	0.0245 (11)	0.0185 (10)	0.0009 (9)	−0.0027 (8)	−0.0022 (8)
C19	0.0335 (11)	0.0231 (10)	0.0214 (10)	0.0020 (8)	0.0052 (8)	0.0009 (8)
C20	0.0258 (10)	0.0212 (10)	0.0195 (9)	0.0013 (8)	0.0013 (7)	−0.0006 (8)
O1S	0.0432 (9)	0.0366 (9)	0.0191 (7)	0.0049 (7)	0.0041 (6)	0.0034 (6)
C1S	0.0407 (14)	0.0546 (16)	0.0265 (12)	−0.0076 (12)	0.0015 (10)	−0.0021 (11)
C2S	0.0408 (14)	0.0338 (13)	0.0462 (14)	0.0064 (10)	0.0156 (11)	0.0128 (11)

O1—C14	1.217 (2)	C9—H9A	0.9500
N1—C1	1.361 (2)	C10—C11	1.382 (3)
N1—C2	1.394 (2)	C10—H10A	0.9500
N1—C13	1.461 (2)	C11—C12	1.390 (3)
N2—C2	1.312 (2)	C11—H11A	0.9500
N2—N3	1.403 (2)	C12—H12A	0.9500
N3—C1	1.323 (2)	C13—C14	1.537 (3)
N3—C3	1.467 (2)	C13—H13A	0.9900
N4—C1	1.337 (2)	C13—H13B	0.9900
N4—C5	1.479 (2)	C14—C15	1.488 (3)
N4—H3N	0.9001	C15—C16	1.396 (3)
N5—C2	1.347 (2)	C15—C20	1.397 (3)
N5—H1N	0.9000	C16—C17	1.389 (3)
N5—H2N	0.9001	C16—H16A	0.9500
C3—C7	1.510 (3)	C17—C18	1.385 (3)
C3—C4	1.542 (3)	C17—H17A	0.9500
C3—H3A	1.0000	C18—C19	1.382 (3)
C4—C5	1.528 (3)	C18—H18A	0.9500
C4—H4A	0.9900	C19—C20	1.395 (3)
C4—H4B	0.9900	C19—H19A	0.9500
C5—C6	1.520 (3)	C20—H20A	0.9500
C5—H5A	1.0000	O1S—C1S	1.416 (3)
C6—H6A	0.9800	O1S—H1S	0.8502
C6—H6B	0.9800	C1S—C2S	1.503 (4)
C6—H6C	0.9800	C1S—H1SA	0.9900
C7—C8	1.389 (3)	C1S—H1SB	0.9900
C7—C12	1.392 (3)	C2S—H2SA	0.9800
C8—C9	1.385 (3)	C2S—H2SB	0.9800
C8—H8A	0.9500	C2S—H2SC	0.9800
C9—C10	1.387 (3)
C1—N1—C2	105.84 (14)	C10—C9—H9A	119.6
C1—N1—C13	123.01 (15)	C11—C10—C9	119.59 (19)
C2—N1—C13	128.34 (16)	C11—C10—H10A	120.2
C2—N2—N3	103.54 (14)	C9—C10—H10A	120.2
C1—N3—N2	111.60 (15)	C10—C11—C12	119.7 (2)
C1—N3—C3	124.82 (16)	C10—C11—H11A	120.1
N2—N3—C3	123.43 (15)	C12—C11—H11A	120.1
C1—N4—C5	116.37 (16)	C11—C12—C7	121.0 (2)
C1—N4—H3N	119.5	C11—C12—H12A	119.5
C5—N4—H3N	114.0	C7—C12—H12A	119.5
C2—N5—H1N	114.9	N1—C13—C14	109.53 (14)
C2—N5—H2N	113.6	N1—C13—H13A	109.8
H1N—N5—H2N	128.6	C14—C13—H13A	109.8
N3—C1—N4	125.18 (17)	N1—C13—H13B	109.8
N3—C1—N1	107.16 (16)	C14—C13—H13B	109.8
N4—C1—N1	127.66 (17)	H13A—C13—H13B	108.2
N2—C2—N5	124.96 (17)	O1—C14—C15	122.21 (18)
N2—C2—N1	111.78 (16)	O1—C14—C13	119.20 (17)
N5—C2—N1	123.22 (16)	C15—C14—C13	118.58 (16)
N3—C3—C7	112.85 (16)	C16—C15—C20	119.32 (18)
N3—C3—C4	106.27 (15)	C16—C15—C14	118.22 (17)
C7—C3—C4	110.14 (16)	C20—C15—C14	122.45 (18)
N3—C3—H3A	109.2	C17—C16—C15	120.2 (2)
C7—C3—H3A	109.2	C17—C16—H16A	119.9
C4—C3—H3A	109.2	C15—C16—H16A	119.9
C5—C4—C3	112.97 (16)	C18—C17—C16	120.1 (2)
C5—C4—H4A	109.0	C18—C17—H17A	119.9
C3—C4—H4A	109.0	C16—C17—H17A	119.9
C5—C4—H4B	109.0	C19—C18—C17	120.2 (2)
C3—C4—H4B	109.0	C19—C18—H18A	119.9
H4A—C4—H4B	107.8	C17—C18—H18A	119.9
N4—C5—C6	109.42 (16)	C18—C19—C20	120.15 (19)
N4—C5—C4	107.82 (15)	C18—C19—H19A	119.9
C6—C5—C4	111.81 (17)	C20—C19—H19A	119.9
N4—C5—H5A	109.3	C19—C20—C15	119.98 (19)
C6—C5—H5A	109.2	C19—C20—H20A	120.0
C4—C5—H5A	109.2	C15—C20—H20A	120.0
C5—C6—H6A	109.5	C1S—O1S—H1S	103.1
C5—C6—H6B	109.5	O1S—C1S—C2S	113.4 (2)
H6A—C6—H6B	109.5	O1S—C1S—H1SA	108.9
C5—C6—H6C	109.5	C2S—C1S—H1SA	108.9
H6A—C6—H6C	109.5	O1S—C1S—H1SB	108.9
H6B—C6—H6C	109.5	C2S—C1S—H1SB	108.9
C8—C7—C12	118.81 (18)	H1SA—C1S—H1SB	107.7
C8—C7—C3	123.43 (17)	C1S—C2S—H2SA	109.5
C12—C7—C3	117.55 (17)	C1S—C2S—H2SB	109.5
C9—C8—C7	120.17 (19)	H2SA—C2S—H2SB	109.5
C9—C8—H8A	119.9	C1S—C2S—H2SC	109.5
C7—C8—H8A	119.9	H2SA—C2S—H2SC	109.5
C8—C9—C10	120.7 (2)	H2SB—C2S—H2SC	109.5
C8—C9—H9A	119.6
C2—N2—N3—C1	2.6 (2)	N3—C3—C7—C8	31.3 (3)
C2—N2—N3—C3	178.23 (16)	C4—C3—C7—C8	−87.2 (2)
N2—N3—C1—N4	179.06 (17)	N3—C3—C7—C12	−154.10 (17)
C3—N3—C1—N4	3.5 (3)	C4—C3—C7—C12	87.3 (2)
N2—N3—C1—N1	−1.3 (2)	C12—C7—C8—C9	0.2 (3)
C3—N3—C1—N1	−176.87 (16)	C3—C7—C8—C9	174.75 (19)
C5—N4—C1—N3	−15.1 (3)	C7—C8—C9—C10	−1.2 (3)
C5—N4—C1—N1	165.38 (18)	C8—C9—C10—C11	0.9 (3)
C2—N1—C1—N3	−0.5 (2)	C9—C10—C11—C12	0.3 (3)
C13—N1—C1—N3	−162.89 (16)	C10—C11—C12—C7	−1.2 (3)
C2—N1—C1—N4	179.17 (18)	C8—C7—C12—C11	1.0 (3)
C13—N1—C1—N4	16.7 (3)	C3—C7—C12—C11	−173.87 (19)
N3—N2—C2—N5	179.50 (18)	C1—N1—C13—C14	66.8 (2)
N3—N2—C2—N1	−2.8 (2)	C2—N1—C13—C14	−91.5 (2)
C1—N1—C2—N2	2.2 (2)	N1—C13—C14—O1	6.3 (2)
C13—N1—C2—N2	163.37 (17)	N1—C13—C14—C15	−174.53 (15)
C1—N1—C2—N5	179.90 (18)	O1—C14—C15—C16	13.9 (3)
C13—N1—C2—N5	−18.9 (3)	C13—C14—C15—C16	−165.25 (18)
C1—N3—C3—C7	−140.15 (18)	O1—C14—C15—C20	−165.57 (19)
N2—N3—C3—C7	44.8 (2)	C13—C14—C15—C20	15.3 (3)
C1—N3—C3—C4	−19.3 (2)	C20—C15—C16—C17	−1.8 (3)
N2—N3—C3—C4	165.59 (16)	C14—C15—C16—C17	178.8 (2)
N3—C3—C4—C5	46.9 (2)	C15—C16—C17—C18	0.9 (3)
C7—C3—C4—C5	169.40 (16)	C16—C17—C18—C19	0.5 (3)
C1—N4—C5—C6	163.01 (17)	C17—C18—C19—C20	−1.0 (3)
C1—N4—C5—C4	41.2 (2)	C18—C19—C20—C15	0.2 (3)
C3—C4—C5—N4	−59.0 (2)	C16—C15—C20—C19	1.2 (3)
C3—C4—C5—C6	−179.28 (17)	C14—C15—C20—C19	−179.30 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H3N···Br1i	0.90	2.49	3.392 (2)	176
N5—H1N···O1S	0.90	1.94	2.839 (2)	176
N5—H2N···Br1ii	0.90	2.61	3.468 (2)	159
O1S—H1S···Br1	0.85	2.46	3.287 (2)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H3N⋯Br1i	0.90	2.49	3.392 (2)	176
N5—H1N⋯O1S	0.90	1.94	2.839 (2)	176
N5—H2N⋯Br1ii	0.90	2.61	3.468 (2)	159
O1S—H1S⋯Br1	0.85	2.46	3.287 (2)	165

Symmetry codes: (i) ; (ii) .