Crystal structure of 3-bromo-4-di-methyl-amino-1-methyl-1,2,4-triazol-5(4H)-one.

The title compound, C5H9BrN4O, was obtained as a minor by-product in the synthesis of 4-di-methyl-amino-1-methyl-1,2,4-triazolin-5-one. Except for the methyl groups of the 4-dimethylamino moiety, all the non-H atoms lie on a crystallographic mirror plane." In the crystal, the mol-ecules are linked by C-Br⋯O=C inter-actions [Br⋯O = 2.877 (2) Å, C-Br⋯O = 174.6 (1)°] into infinite chains in the c-axis direction.

Related literature

For synthesis of related 4-amino-1-methyl-1,2,4-triazolin-5-ones, see: Kröger et al. (1965 ▸). For related structures with Br⋯O=C inter­actions, see: 5-bromo­pyrimidin-2-one (Yathirajan et al., 2007 ▸); 3,5-di­bromo­pyran-2-one (Reus et al., 2012 ▸); N-bromo­saccharin (Dolenc & Modec, 2009 ▸); N-bromo­succinimide (Jabay et al., 1977 ▸); dibromantin (Kruszynski, 2007 ▸). For the theory of halogen inter­actions, see: Awwadi et al. (2006 ▸). For details of the synthesis, see: Schwärzler et al. (2009 ▸).

Experimental

Crystal data

C5H9BrN4O

M = 221.07

Monoclinic,

a = 15.1993 (6) Å

b = 6.9377 (4) Å

c = 7.8771 (7) Å

β = 93.869 (3)°

V = 828.73 (9) Å3

Z = 4

Mo Kα radiation

μ = 4.91 mm−1

T = 233 K

0.09 × 0.08 × 0.07 mm

Data collection

Nonius KappaCCD diffractometer

2310 measured reflections

806 independent reflections

734 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.065

S = 1.07

806 reflections

75 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.44 e Å−3

Data collection: DENZO (Otwinowski & Minor, 1997 ▸) and COLLECT (Hooft, 1998 ▸); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▸); molecular graphics: Mercury (Macrae et al., 2006 ▸) and ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S205698901402636X/fj2686sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901402636X/fj2686Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901402636X/fj2686Isup3.mol

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901402636X/fj2686Isup4.cml

Click here for additional data file.

x y z . DOI: 10.1107/S205698901402636X/fj2686fig1.tif

The mol­ecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms. One component of the disordered C3 methyl group has been omitted for clarity. Symmetry code (i): x, −y, z.

Click here for additional data file.

ac . DOI: 10.1107/S205698901402636X/fj2686fig2.tif

Arrangement of the triazole rings parallel to the ac plane. One component of the disordered C3 methyl group has been omitted for clarity.

Click here for additional data file.

x y z x y z . DOI: 10.1107/S205698901402636X/fj2686fig3.tif

Infinite chains of mol­ecules linked by Br⋯O inter­actions. One component of the disordered C3 methyl group has been omitted for clarity. Symmetry code (ii): x, y, 1 + z; (iii): x, y, −1 + z.

CCDC reference: 1036852

Additional supporting information: crystallographic information; 3D view; checkCIF report

C5H9BrN4O	F(000) = 440
Mr = 221.07	Dx = 1.772 Mg m−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 15.1993 (6) Å	Cell parameters from 3066 reflections
b = 6.9377 (4) Å	θ = 1.0–25.0°
c = 7.8771 (7) Å	µ = 4.91 mm−1
β = 93.869 (3)°	T = 233 K
V = 828.73 (9) Å3	Prism, colorless
Z = 4	0.09 × 0.08 × 0.07 mm

Nonius KappaCCD diffractometer	734 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 25.1°, θmin = 2.6°
phi and ω scans	h = −13→18
2310 measured reflections	k = −8→8
806 independent reflections	l = −9→8

Refinement on F2	6 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.065	w = 1/[σ2(Fo2) + (0.033P)2 + 0.5344P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
806 reflections	Δρmax = 0.50 e Å−3
75 parameters	Δρmin = −0.44 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.22218 (3)	0.0000	0.18788 (4)	0.03459 (19)
O1	0.17449 (19)	0.0000	−0.4649 (3)	0.0426 (8)
N1	0.3186 (2)	0.0000	−0.1029 (4)	0.0319 (8)
N2	0.2997 (2)	0.0000	−0.2784 (4)	0.0302 (8)
N3	0.1742 (2)	0.0000	−0.1669 (4)	0.0282 (7)
N4	0.0841 (2)	0.0000	−0.1382 (4)	0.0329 (8)
C1	0.2418 (3)	0.0000	−0.0415 (4)	0.0269 (9)
C2	0.2125 (3)	0.0000	−0.3221 (4)	0.0322 (10)
C3	0.3694 (3)	0.0000	−0.3938 (6)	0.0445 (11)
H3A	0.352 (3)	−0.069 (5)	−0.497 (4)	0.067*	0.5
H3B	0.4248 (19)	−0.047 (6)	−0.343 (6)	0.067*	0.5
H3C	0.375 (3)	0.136 (2)	−0.420 (6)	0.067*	0.5
C4	0.04175 (19)	0.1766 (5)	−0.2044 (4)	0.0478 (8)
H4A	0.0726	0.2877	−0.1550	0.072*
H4B	−0.0192	0.1791	−0.1750	0.072*
H4C	0.0438	0.1801	−0.3272	0.072*

	U11	U22	U33	U12	U13	U23
Br1	0.0454 (3)	0.0368 (3)	0.0211 (3)	0.000	−0.00047 (17)	0.000
O1	0.0429 (17)	0.067 (2)	0.0181 (14)	0.000	0.0024 (12)	0.000
N1	0.037 (2)	0.0330 (19)	0.0255 (17)	0.000	−0.0004 (14)	0.000
N2	0.0279 (19)	0.0367 (19)	0.0261 (17)	0.000	0.0020 (13)	0.000
N3	0.0257 (17)	0.0392 (19)	0.0197 (16)	0.000	0.0019 (12)	0.000
N4	0.0290 (18)	0.044 (2)	0.0252 (17)	0.000	0.0013 (13)	0.000
C1	0.035 (2)	0.027 (2)	0.019 (2)	0.000	−0.0026 (16)	0.000
C2	0.040 (3)	0.032 (2)	0.025 (2)	0.000	0.0051 (18)	0.000
C3	0.036 (3)	0.063 (3)	0.036 (2)	0.000	0.0124 (19)	0.000
C4	0.0402 (19)	0.059 (2)	0.0445 (18)	0.0125 (15)	0.0051 (14)	0.0066 (17)

Br1—C1	1.851 (4)	N4—C4	1.464 (4)
O1—C2	1.230 (4)	N4—C4i	1.464 (4)
N1—C1	1.292 (5)	C3—H3A	0.967 (10)
N1—N2	1.392 (5)	C3—H3B	0.965 (10)
N2—C2	1.346 (5)	C3—H3C	0.969 (10)
N2—C3	1.442 (5)	C4—H4A	0.9700
N3—C1	1.377 (4)	C4—H4B	0.9700
N3—C2	1.389 (5)	C4—H4C	0.9700
N3—N4	1.403 (4)
Br1···O1ii	2.876 (3)
C1—N1—N2	103.9 (3)	O1—C2—N3	127.3 (4)
C2—N2—N1	112.8 (3)	N2—C2—N3	103.8 (3)
C2—N2—C3	126.2 (3)	N2—C3—H3A	111 (4)
N1—N2—C3	121.0 (3)	N2—C3—H3B	113 (3)
C1—N3—C2	107.1 (3)	H3A—C3—H3B	111 (2)
C1—N3—N4	125.0 (3)	N2—C3—H3C	102 (4)
C2—N3—N4	127.9 (3)	H3A—C3—H3C	109 (2)
N3—N4—C4	110.6 (2)	H3B—C3—H3C	110 (2)
N3—N4—C4i	110.6 (2)	N4—C4—H4A	109.5
C4—N4—C4i	113.7 (3)	N4—C4—H4B	109.5
N1—C1—N3	112.4 (3)	H4A—C4—H4B	109.5
N1—C1—Br1	125.0 (3)	N4—C4—H4C	109.5
N3—C1—Br1	122.6 (3)	H4A—C4—H4C	109.5
O1—C2—N2	128.9 (4)	H4B—C4—H4C	109.5