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

Abstract

The title compound, C₅H₉BrN₄O, was obtained as a minor by-product in the synthesis of 4-di­methyl­amino-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 mol­ecules are linked by C—Br⋯O=C inter­actions [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 _r = 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) ų

• 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

• Δρ_max = 0.50 e Å⁻³

• Δρ_min = −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 ▸).

Supplementary Material

CCDC reference: 1036852

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

supplementary crystallographic information

S1. Comment

Triazolinones are of relevance due to their wide range of pesticidal activities. The molecular structure of 3-bromo-4-(dimethylamino)-1-methyl-1,2,4-triazolin-5-one is shown in Figure 1. The triazole rings are located in the crystallographic mirror plane (Figure 2), whereas the C4 methyl groups are situated out of this plane. The molecules are linked by short intermolecular C—Br···O=C contacts into infinite chains in the direction of the c axis (Figure 3). The Br···O distance of 2.877 (2) Å is significantly shorter than the sum of van der Waals radii. Theoretical calculations predicted negative ring and positive end cap domains of halogen atoms due to their polarizability (Awwadi et al., 2006). The almost linear C—Br···O angle of 174.6 (1)° indicates an interaction involving the positive end cap of the Br atom. Thus, the Br atom acts as an electron-acceptor (X-bond donor) in this case.

S2. Experimental

The title compound was obtained as a minor by-product in the synthesis of 4-(dimethylamino)-1-methyl-1,2,4-triazolin-5-one by hydrolysis of 5-bromo-4-(dimethylamino)-1-methyl-1,2,4-triazolium hexafluorophosphate (Schwärzler et al., 2009) in MeOH/H₂O. It is assumed that the 5-bromo compound was contaminated with a trace of the corresponding 3,5-dibromo compound which resulted in the formation of the present 3-bromo-1,2,4-triazolin-5-one.

S3. Refinement

The H atoms were identified in a difference map and those of the C4 methyl group were idealized and included as rigid groups, allowed to rotate but not tip (C—H = 0.97 Å). The C3 methyl group was found to be disordered over two orientations related by mirror symmetry. Its H positions were refined with restrained C—H and H···H distances of 0.97 (1) Å and 1.58 (2) Å, respectively. The U_iso parameters of all H atoms were set to 1.5 U_eq(C) of the parent carbon atom.

Figures

Fig. 1.

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.

Fig. 2.

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

Fig. 3.

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.

Crystal data

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

Data collection

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

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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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

Symmetry codes: (i) x, −y, z; (ii) x, y, z+1.