Synthesis and crystal structure of N-(4-chloro­phen­yl)-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidin-2-amine

The title compound, N-(4-chloro­phen­yl)-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidin-2-amine, was synthesized by cyclization of 1-(4,6-di­methyl­pyrimidin-2-yl)-4-phenyl­thio­semicarbazide in the presence of Ni(NO₃)₂. In the crystal, mol­ecules form inversion dimers via pairs of N—H...N hydrogen bonds, which are packed into layers by π-stacking inter­actions between the aromatic systems of neighbouring mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.039
• wR factor = 0.100
• Data-to-parameter ratio = 21.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2 Report

Alert level G
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         11 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         10 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

N-(4-Chlorophenyl)-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidin-2-amine

Crystal data

C13H12ClN5	F(000) = 568
Mr = 273.73	Dx = 1.451 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.0640 (1) Å	Cell parameters from 5527 reflections
b = 25.2362 (4) Å	θ = 3.0–30.5°
c = 7.6494 (1) Å	µ = 0.30 mm^−1
β = 113.243 (1)°	T = 100 K
V = 1252.97 (3) Å^3	Plate, colorless
Z = 4	0.40 × 0.30 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer	3347 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.018
φ and ω scans	θmax = 30.6°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→8
Tmin = 0.874, Tmax = 0.985	k = −36→33
11572 measured reflections	l = −6→10
3837 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: mixed
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.047P)^2 + 0.6408P] where P = (Fo^2 + 2Fc^2)/3
3837 reflections	(Δ/σ)max = 0.001
178 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.39001 (18)	−0.06515 (5)	0.47760 (19)	0.0212 (2)
H1A	−0.4039	−0.0542	0.5949	0.032*
H1B	−0.4903	−0.0931	0.4153	0.032*
H1C	−0.4154	−0.0347	0.3919	0.032*
C2	−0.17835 (18)	−0.08555 (5)	0.52419 (16)	0.0163 (2)
C3	−0.12544 (19)	−0.13199 (5)	0.46223 (17)	0.0176 (2)
H3	−0.2303	−0.1544	0.3786	0.021*
C4	0.08323 (19)	−0.14699 (5)	0.52120 (17)	0.0171 (2)
C5	0.1395 (2)	−0.19827 (5)	0.45558 (19)	0.0212 (2)
H5C	0.2813	−0.1962	0.4637	0.032*
H5B	0.0457	−0.2050	0.3235	0.032*
H5A	0.1285	−0.2272	0.5366	0.032*
C6	0.18434 (17)	−0.07241 (4)	0.69865 (16)	0.0154 (2)
C7	0.17125 (17)	0.00081 (4)	0.82697 (16)	0.0152 (2)
C8	0.13730 (18)	0.08741 (4)	0.96620 (16)	0.0156 (2)
C9	−0.07753 (18)	0.08999 (5)	0.89705 (17)	0.0179 (2)
H9	−0.1590	0.0613	0.8262	0.022*
C10	−0.17128 (19)	0.13482 (5)	0.93266 (18)	0.0203 (2)
H10	−0.3172	0.1366	0.8871	0.024*
C11	−0.0532 (2)	0.17674 (5)	1.03401 (17)	0.0199 (2)
C12	0.1601 (2)	0.17448 (5)	1.10631 (18)	0.0202 (2)
H12	0.2404	0.2031	1.1785	0.024*
C13	0.25465 (19)	0.12990 (5)	1.07201 (17)	0.0184 (2)
H13	0.4008	0.1281	1.1208	0.022*
Cl1	−0.17415 (6)	0.23384 (2)	1.06639 (5)	0.02889 (10)
H1	0.378 (3)	0.0447 (7)	1.006 (2)	0.023 (4)*
N1	−0.01741 (15)	−0.05610 (4)	0.64112 (14)	0.01484 (19)
N3	0.30697 (15)	−0.03648 (4)	0.81768 (15)	0.01627 (19)
N5	0.24606 (16)	0.04442 (4)	0.93749 (15)	0.0171 (2)
N4	−0.02837 (15)	−0.00828 (4)	0.72245 (14)	0.01575 (19)
N2	0.23744 (16)	−0.11766 (4)	0.63896 (15)	0.0173 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0139 (5)	0.0218 (6)	0.0243 (6)	−0.0013 (4)	0.0036 (5)	0.0008 (5)
C2	0.0154 (5)	0.0171 (5)	0.0145 (5)	−0.0025 (4)	0.0038 (4)	0.0020 (4)
C3	0.0183 (5)	0.0169 (5)	0.0161 (5)	−0.0041 (4)	0.0050 (4)	−0.0006 (4)
C4	0.0210 (5)	0.0155 (5)	0.0163 (5)	−0.0013 (4)	0.0090 (4)	0.0000 (4)
C5	0.0253 (6)	0.0178 (5)	0.0220 (6)	−0.0013 (4)	0.0109 (5)	−0.0046 (4)
C6	0.0144 (5)	0.0160 (5)	0.0161 (5)	−0.0008 (4)	0.0064 (4)	0.0012 (4)
C7	0.0153 (5)	0.0147 (5)	0.0156 (5)	−0.0002 (4)	0.0060 (4)	0.0006 (4)
C8	0.0176 (5)	0.0146 (5)	0.0144 (5)	0.0018 (4)	0.0063 (4)	0.0017 (4)
C9	0.0168 (5)	0.0180 (5)	0.0178 (5)	0.0006 (4)	0.0056 (4)	−0.0002 (4)
C10	0.0186 (5)	0.0223 (6)	0.0192 (6)	0.0053 (4)	0.0068 (5)	0.0024 (4)
C11	0.0271 (6)	0.0167 (5)	0.0166 (5)	0.0073 (4)	0.0092 (5)	0.0026 (4)
C12	0.0264 (6)	0.0156 (5)	0.0174 (5)	0.0003 (4)	0.0074 (5)	0.0006 (4)
C13	0.0189 (5)	0.0162 (5)	0.0184 (5)	0.0002 (4)	0.0056 (4)	0.0006 (4)
Cl1	0.03686 (19)	0.02176 (16)	0.02714 (18)	0.01310 (12)	0.01167 (14)	0.00019 (12)
N1	0.0142 (4)	0.0138 (4)	0.0160 (5)	−0.0005 (3)	0.0053 (4)	−0.0002 (3)
N3	0.0140 (4)	0.0153 (4)	0.0190 (5)	−0.0003 (3)	0.0061 (4)	−0.0019 (4)
N5	0.0128 (4)	0.0158 (4)	0.0203 (5)	0.0002 (3)	0.0040 (4)	−0.0031 (4)
N4	0.0149 (4)	0.0134 (4)	0.0175 (5)	−0.0003 (3)	0.0050 (4)	−0.0013 (3)
N2	0.0177 (5)	0.0161 (4)	0.0192 (5)	−0.0011 (4)	0.0084 (4)	−0.0015 (4)

Geometric parameters (Å, º)

C1—C2	1.4857 (16)	C7—N5	1.3612 (15)
C1—H1A	0.9800	C7—N3	1.3651 (14)
C1—H1B	0.9800	C8—N5	1.3960 (14)
C1—H1C	0.9800	C8—C9	1.3977 (16)
C2—N1	1.3574 (15)	C8—C13	1.4008 (16)
C2—C3	1.3702 (16)	C9—C10	1.3911 (16)
C3—C4	1.4124 (17)	C9—H9	0.9500
C3—H3	0.9500	C10—C11	1.3805 (18)
C4—N2	1.3309 (15)	C10—H10	0.9500
C4—C5	1.4976 (16)	C11—C12	1.3859 (18)
C5—H5C	0.9800	C11—Cl1	1.7423 (12)
C5—H5B	0.9800	C12—C13	1.3855 (16)
C5—H5A	0.9800	C12—H12	0.9500
C6—N3	1.3338 (15)	C13—H13	0.9500
C6—N2	1.3374 (15)	N1—N4	1.3737 (13)
C6—N1	1.3781 (15)	N5—H1	0.870 (18)
C7—N4	1.3381 (15)
C2—C1—H1A	109.5	N5—C8—C9	124.01 (11)
C2—C1—H1B	109.5	N5—C8—C13	116.67 (11)
H1A—C1—H1B	109.5	C9—C8—C13	119.32 (11)
C2—C1—H1C	109.5	C10—C9—C8	119.56 (11)
H1A—C1—H1C	109.5	C10—C9—H9	120.2
H1B—C1—H1C	109.5	C8—C9—H9	120.2
N1—C2—C3	115.11 (10)	C11—C10—C9	120.28 (11)
N1—C2—C1	118.05 (11)	C11—C10—H10	119.9
C3—C2—C1	126.84 (11)	C9—C10—H10	119.9
C2—C3—C4	120.77 (11)	C10—C11—C12	120.89 (11)
C2—C3—H3	119.6	C10—C11—Cl1	119.47 (10)
C4—C3—H3	119.6	C12—C11—Cl1	119.62 (10)
N2—C4—C3	122.65 (11)	C11—C12—C13	119.16 (11)
N2—C4—C5	116.91 (11)	C11—C12—H12	120.4
C3—C4—C5	120.42 (11)	C13—C12—H12	120.4
C4—C5—H5C	109.5	C12—C13—C8	120.76 (11)
C4—C5—H5B	109.5	C12—C13—H13	119.6
H5C—C5—H5B	109.5	C8—C13—H13	119.6
C4—C5—H5A	109.5	C2—N1—N4	126.67 (10)
H5C—C5—H5A	109.5	C2—N1—C6	122.58 (10)
H5B—C5—H5A	109.5	N4—N1—C6	110.72 (9)
N3—C6—N2	128.28 (11)	C6—N3—C7	102.94 (9)
N3—C6—N1	109.03 (10)	C7—N5—C8	128.56 (10)
N2—C6—N1	122.69 (10)	C7—N5—H1	116.2 (11)
N4—C7—N5	124.68 (10)	C8—N5—H1	115.1 (11)
N4—C7—N3	116.54 (10)	C7—N4—N1	100.77 (9)
N5—C7—N3	118.77 (10)	C4—N2—C6	116.17 (10)
N1—C2—C3—C4	0.80 (16)	N2—C6—N1—C2	2.19 (17)
C1—C2—C3—C4	−178.75 (11)	N3—C6—N1—N4	0.47 (13)
C2—C3—C4—N2	0.44 (18)	N2—C6—N1—N4	−179.62 (10)
C2—C3—C4—C5	178.90 (11)	N2—C6—N3—C7	−179.97 (12)
N5—C8—C9—C10	−179.67 (11)	N1—C6—N3—C7	−0.07 (12)
C13—C8—C9—C10	0.64 (17)	N4—C7—N3—C6	−0.38 (14)
C8—C9—C10—C11	0.64 (18)	N5—C7—N3—C6	−179.42 (10)
C9—C10—C11—C12	−1.73 (19)	N4—C7—N5—C8	0.2 (2)
C9—C10—C11—Cl1	176.72 (9)	N3—C7—N5—C8	179.17 (11)
C10—C11—C12—C13	1.50 (18)	C9—C8—N5—C7	6.89 (19)
Cl1—C11—C12—C13	−176.95 (9)	C13—C8—N5—C7	−173.41 (11)
C11—C12—C13—C8	−0.19 (18)	N5—C7—N4—N1	179.62 (11)
N5—C8—C13—C12	179.42 (11)	N3—C7—N4—N1	0.64 (13)
C9—C8—C13—C12	−0.87 (18)	C2—N1—N4—C7	177.46 (11)
C3—C2—N1—N4	−179.95 (10)	C6—N1—N4—C7	−0.64 (12)
C1—C2—N1—N4	−0.35 (17)	C3—C4—N2—C6	−0.44 (17)
C3—C2—N1—C6	−2.06 (16)	C5—C4—N2—C6	−178.96 (10)
C1—C2—N1—C6	177.54 (10)	N3—C6—N2—C4	179.07 (11)
N3—C6—N1—C2	−177.72 (10)	N1—C6—N2—C4	−0.82 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H1···N3^i	0.870 (18)	2.109 (18)	2.9748 (14)	173.5 (16)

Symmetry code: (i) −x+1, −y, −z+2.