Methyl 2-(4,6-dichloro-1,3,5-triazin-2-yl-amino)acetate.

The title compound, C(6)H(6)Cl(2)N(4)O(2), was prepared by the nucleophilic substitution of 2,4,6-trichloro-1,3,5-triazine by glycine methyl ester hydro-chloride, and was isolated from the reaction by using flash chromatography. The crystal structure at 150 K reveals the presence two crystallographically independent mol-ecules in the asymmetric unit which differ in the orientation of the pendant methoxy-carbonyl group. Each mol-ecular unit is engaged in strong and highly directional N-H⋯N hydrogen-bonding inter-actions with a symmetry-related mol-ecule, forming supra-molecular dimers which act as the synthons in the crystal packing.

Related literature

For background to nucleophilic reactions based on 1,3,5-triazine derivatives, see: Blotny (2006 ▶); Giacomelli et al. (2004 ▶). For coordination polymers based 1,3,5-triazine derivatives, see: Wang, Xing et al. (2007 ▶); Wang, Bai, Xing et al. (2007 ▶); Wang, Bai, Li et al. (2007 ▶). For general background studies on crystal-engineering approaches from our research group, see: Vilela et al. (2009 ▶); Shi et al. (2008 ▶); Paz & Klinowski (2003 ▶, 2007 ▶); Paz et al. (2002 ▶, 2005 ▶). For a description of the graph-set notation for hydrogen-bonded aggregates, see: Bernstein et al. (1995 ▶). For a description of the Cambridge Structural Database and the Mercury software package, see: Allen (2002 ▶); Macrae et al. (2008 ▶).

Experimental

Crystal data

C6H6Cl2N4O2

M = 237.05

Triclinic,

a = 7.3543 (4) Å

b = 9.7523 (5) Å

c = 13.4133 (7) Å

α = 97.714 (3)°

β = 92.714 (3)°

γ = 90.225 (3)°

V = 952.19 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.66 mm−1

T = 150 K

0.18 × 0.16 × 0.04 mm

Data collection

Bruker X8 Kappa CCD APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.890, T max = 0.974

23605 measured reflections

5043 independent reflections

3753 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.165

S = 1.04

5043 reflections

261 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.78 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT-Plus (Bruker, 2005 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028670/tk2507sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028670/tk2507Isup2.hkl

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

Enhanced figure: interactive version of Fig. 5

Enhanced figure: interactive version of Fig. 6

C6H6Cl2N4O2	Z = 4
Mr = 237.05	F(000) = 480
Triclinic, P1	Dx = 1.654 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3543 (4) Å	Cell parameters from 6830 reflections
b = 9.7523 (5) Å	θ = 2.8–28.9°
c = 13.4133 (7) Å	µ = 0.66 mm−1
α = 97.714 (3)°	T = 150 K
β = 92.714 (3)°	Plate, colourless
γ = 90.225 (3)°	0.18 × 0.16 × 0.04 mm
V = 952.19 (9) Å3

Bruker X8 Kappa CCD APEXII diffractometer	5043 independent reflections
Radiation source: fine-focus sealed tube	3753 reflections with I > 2σ(I)
graphite	Rint = 0.047
ω and φ scans	θmax = 29.1°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −10→10
Tmin = 0.890, Tmax = 0.974	k = −13→13
23605 measured reflections	l = −18→18

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)] = 0.059	Hydrogen site location: mixed
wR(F2) = 0.165	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0886P)2 + 1.283P] where P = (Fo2 + 2Fc2)/3
5043 reflections	(Δ/σ)max = 0.001
261 parameters	Δρmax = 1.78 e Å−3
2 restraints	Δρmin = −0.42 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.

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
Cl1	0.03910 (11)	0.76811 (9)	0.64289 (6)	0.02802 (19)
Cl2	0.05165 (10)	0.83098 (7)	1.03313 (5)	0.02279 (18)
Cl3	0.55099 (12)	0.59177 (9)	0.63658 (6)	0.0312 (2)
Cl4	0.54953 (10)	0.68082 (7)	1.02721 (6)	0.02374 (18)
N1	0.0584 (3)	0.8055 (2)	0.83787 (18)	0.0195 (5)
N2	0.3083 (3)	0.9206 (2)	0.93391 (18)	0.0172 (5)
N3	0.3084 (3)	0.8875 (2)	0.75349 (18)	0.0177 (5)
N4	0.5544 (3)	0.9858 (2)	0.85124 (18)	0.0182 (5)
H4	0.610 (5)	1.014 (4)	0.9155 (14)	0.027*
N5	0.5630 (3)	0.6316 (2)	0.83184 (19)	0.0214 (5)
N6	0.8095 (3)	0.5542 (2)	0.93194 (17)	0.0160 (5)
N7	0.8146 (3)	0.5166 (2)	0.75176 (18)	0.0178 (5)
N8	1.0585 (3)	0.4599 (2)	0.85293 (18)	0.0174 (5)
H8	1.109 (5)	0.456 (4)	0.9184 (13)	0.026*
C1	0.1492 (4)	0.8273 (3)	0.7573 (2)	0.0179 (5)
C2	0.1510 (4)	0.8563 (3)	0.9232 (2)	0.0173 (5)
C3	0.3874 (4)	0.9307 (3)	0.8456 (2)	0.0163 (5)
C4	0.6573 (4)	0.9941 (3)	0.7636 (2)	0.0194 (6)
H4A	0.6299	0.9116	0.7136	0.023*
H4B	0.7888	0.9934	0.7830	0.023*
C5	0.6151 (4)	1.1235 (3)	0.7156 (2)	0.0175 (5)
C6	0.6440 (5)	1.2261 (4)	0.5677 (3)	0.0321 (8)
H6A	0.5217	1.2643	0.5759	0.048*
H6B	0.6629	1.1990	0.4959	0.048*
H6C	0.7349	1.2963	0.5957	0.048*
C7	0.6559 (4)	0.5773 (3)	0.7536 (2)	0.0194 (6)
C8	0.6527 (4)	0.6144 (3)	0.9185 (2)	0.0172 (5)
C9	0.8913 (4)	0.5102 (3)	0.8450 (2)	0.0156 (5)
C10	1.1643 (4)	0.4189 (3)	0.7663 (2)	0.0181 (5)
H10A	1.2954	0.4260	0.7871	0.022*
H10B	1.1405	0.4833	0.7162	0.022*
C11	1.1208 (4)	0.2724 (3)	0.7175 (2)	0.0175 (5)
C12	1.1656 (5)	0.1125 (3)	0.5745 (2)	0.0296 (7)
H12A	1.2338	0.0502	0.6137	0.044*
H12B	1.2142	0.1072	0.5073	0.044*
H12C	1.0368	0.0849	0.5682	0.044*
O1	0.6625 (3)	1.1059 (2)	0.62027 (16)	0.0241 (5)
O2	0.5510 (3)	1.2274 (2)	0.75767 (17)	0.0289 (5)
O3	1.1833 (3)	0.2526 (2)	0.62497 (15)	0.0222 (4)
O4	1.0454 (3)	0.1858 (2)	0.75626 (17)	0.0298 (5)

	U11	U22	U33	U12	U13	U23
Cl1	0.0294 (4)	0.0362 (4)	0.0181 (4)	−0.0088 (3)	−0.0034 (3)	0.0043 (3)
Cl2	0.0263 (4)	0.0243 (3)	0.0186 (3)	−0.0070 (3)	0.0063 (3)	0.0042 (3)
Cl3	0.0374 (5)	0.0337 (4)	0.0217 (4)	0.0070 (3)	−0.0087 (3)	0.0045 (3)
Cl4	0.0263 (4)	0.0231 (3)	0.0221 (4)	0.0093 (3)	0.0070 (3)	0.0016 (3)
N1	0.0204 (12)	0.0204 (11)	0.0188 (12)	−0.0048 (9)	0.0021 (10)	0.0058 (9)
N2	0.0194 (12)	0.0155 (10)	0.0173 (11)	−0.0006 (9)	0.0032 (9)	0.0041 (9)
N3	0.0194 (12)	0.0180 (11)	0.0165 (11)	0.0009 (9)	0.0011 (9)	0.0045 (9)
N4	0.0176 (12)	0.0208 (11)	0.0163 (11)	−0.0014 (9)	0.0026 (9)	0.0017 (9)
N5	0.0217 (13)	0.0195 (11)	0.0223 (13)	0.0046 (10)	−0.0028 (10)	0.0012 (9)
N6	0.0179 (11)	0.0140 (10)	0.0161 (11)	0.0015 (8)	0.0017 (9)	0.0015 (8)
N7	0.0220 (12)	0.0167 (11)	0.0146 (11)	−0.0015 (9)	0.0013 (9)	0.0017 (8)
N8	0.0190 (12)	0.0186 (11)	0.0144 (11)	0.0020 (9)	0.0017 (9)	0.0010 (9)
C1	0.0212 (14)	0.0182 (12)	0.0143 (13)	0.0001 (10)	−0.0026 (10)	0.0030 (10)
C2	0.0198 (13)	0.0168 (12)	0.0161 (13)	−0.0009 (10)	0.0039 (10)	0.0040 (10)
C3	0.0190 (13)	0.0138 (11)	0.0170 (13)	0.0031 (10)	0.0021 (10)	0.0048 (10)
C4	0.0185 (13)	0.0215 (13)	0.0190 (14)	0.0020 (10)	0.0046 (11)	0.0040 (11)
C5	0.0160 (13)	0.0193 (12)	0.0170 (13)	−0.0012 (10)	0.0035 (10)	0.0007 (10)
C6	0.043 (2)	0.0308 (16)	0.0269 (17)	0.0052 (14)	0.0134 (15)	0.0146 (14)
C7	0.0263 (15)	0.0153 (12)	0.0169 (13)	−0.0008 (11)	−0.0031 (11)	0.0043 (10)
C8	0.0185 (13)	0.0137 (12)	0.0191 (13)	0.0016 (10)	0.0033 (10)	0.0002 (10)
C9	0.0185 (13)	0.0107 (11)	0.0171 (13)	−0.0024 (9)	0.0017 (10)	0.0003 (9)
C10	0.0176 (13)	0.0186 (12)	0.0177 (13)	−0.0016 (10)	0.0043 (10)	−0.0006 (10)
C11	0.0154 (13)	0.0209 (13)	0.0160 (13)	0.0006 (10)	0.0001 (10)	0.0015 (10)
C12	0.0411 (19)	0.0255 (15)	0.0194 (15)	0.0042 (13)	0.0031 (13)	−0.0075 (12)
O1	0.0330 (12)	0.0227 (10)	0.0178 (10)	0.0049 (9)	0.0089 (9)	0.0046 (8)
O2	0.0384 (13)	0.0257 (11)	0.0242 (12)	0.0106 (10)	0.0135 (10)	0.0047 (9)
O3	0.0316 (12)	0.0195 (10)	0.0152 (10)	0.0002 (8)	0.0057 (8)	−0.0006 (8)
O4	0.0389 (13)	0.0254 (11)	0.0252 (12)	−0.0109 (10)	0.0121 (10)	0.0002 (9)

Cl1—C1	1.728 (3)	N8—C10	1.442 (4)
Cl2—C2	1.723 (3)	N8—H8	0.943 (10)
Cl3—C7	1.739 (3)	C4—C5	1.519 (4)
Cl4—C8	1.725 (3)	C4—H4A	0.9900
N1—C1	1.337 (4)	C4—H4B	0.9900
N1—C2	1.337 (4)	C5—O2	1.200 (4)
N2—C2	1.306 (4)	C5—O1	1.331 (3)
N2—C3	1.359 (4)	C6—O1	1.451 (4)
N3—C1	1.314 (4)	C6—H6A	0.9800
N3—C3	1.354 (4)	C6—H6B	0.9800
N4—C3	1.333 (4)	C6—H6C	0.9800
N4—C4	1.439 (4)	C10—C11	1.516 (4)
N4—H4	0.945 (10)	C10—H10A	0.9900
N5—C7	1.330 (4)	C10—H10B	0.9900
N5—C8	1.340 (4)	C11—O4	1.197 (4)
N6—C8	1.312 (4)	C11—O3	1.334 (3)
N6—C9	1.357 (4)	C12—O3	1.444 (4)
N7—C7	1.311 (4)	C12—H12A	0.9800
N7—C9	1.357 (4)	C12—H12B	0.9800
N8—C9	1.330 (4)	C12—H12C	0.9800
C1—N1—C2	111.0 (2)	O1—C6—H6B	109.5
C2—N2—C3	114.0 (2)	H6A—C6—H6B	109.5
C1—N3—C3	113.1 (2)	O1—C6—H6C	109.5
C3—N4—C4	122.6 (2)	H6A—C6—H6C	109.5
C3—N4—H4	119 (2)	H6B—C6—H6C	109.5
C4—N4—H4	119 (2)	N7—C7—N5	129.7 (3)
C7—N5—C8	110.5 (2)	N7—C7—Cl3	115.6 (2)
C8—N6—C9	113.7 (2)	N5—C7—Cl3	114.6 (2)
C7—N7—C9	113.1 (2)	N6—C8—N5	128.6 (3)
C9—N8—C10	122.3 (2)	N6—C8—Cl4	115.4 (2)
C9—N8—H8	117 (2)	N5—C8—Cl4	116.0 (2)
C10—N8—H8	120 (2)	N8—C9—N6	117.2 (2)
N3—C1—N1	129.1 (3)	N8—C9—N7	118.7 (2)
N3—C1—Cl1	116.2 (2)	N6—C9—N7	124.1 (3)
N1—C1—Cl1	114.7 (2)	N8—C10—C11	112.5 (2)
N2—C2—N1	128.4 (3)	N8—C10—H10A	109.1
N2—C2—Cl2	115.8 (2)	C11—C10—H10A	109.1
N1—C2—Cl2	115.8 (2)	N8—C10—H10B	109.1
N4—C3—N3	118.5 (3)	C11—C10—H10B	109.1
N4—C3—N2	117.2 (3)	H10A—C10—H10B	107.8
N3—C3—N2	124.3 (3)	O4—C11—O3	124.6 (3)
N4—C4—C5	112.4 (2)	O4—C11—C10	125.6 (3)
N4—C4—H4A	109.1	O3—C11—C10	109.8 (2)
C5—C4—H4A	109.1	O3—C12—H12A	109.5
N4—C4—H4B	109.1	O3—C12—H12B	109.5
C5—C4—H4B	109.1	H12A—C12—H12B	109.5
H4A—C4—H4B	107.9	O3—C12—H12C	109.5
O2—C5—O1	124.8 (3)	H12A—C12—H12C	109.5
O2—C5—C4	125.2 (3)	H12B—C12—H12C	109.5
O1—C5—C4	109.9 (2)	C5—O1—C6	115.8 (2)
O1—C6—H6A	109.5	C11—O3—C12	114.9 (2)
C3—N3—C1—N1	0.7 (4)	C8—N5—C7—N7	−1.6 (4)
C3—N3—C1—Cl1	−179.70 (19)	C8—N5—C7—Cl3	179.3 (2)
C2—N1—C1—N3	0.7 (4)	C9—N6—C8—N5	3.2 (4)
C2—N1—C1—Cl1	−178.9 (2)	C9—N6—C8—Cl4	−176.48 (19)
C3—N2—C2—N1	−2.7 (4)	C7—N5—C8—N6	−0.1 (4)
C3—N2—C2—Cl2	176.07 (19)	C7—N5—C8—Cl4	179.6 (2)
C1—N1—C2—N2	0.5 (4)	C10—N8—C9—N6	−175.6 (2)
C1—N1—C2—Cl2	−178.3 (2)	C10—N8—C9—N7	3.4 (4)
C4—N4—C3—N3	−3.4 (4)	C8—N6—C9—N8	173.8 (2)
C4—N4—C3—N2	175.9 (2)	C8—N6—C9—N7	−5.1 (4)
C1—N3—C3—N4	175.9 (2)	C7—N7—C9—N8	−175.2 (2)
C1—N3—C3—N2	−3.4 (4)	C7—N7—C9—N6	3.7 (4)
C2—N2—C3—N4	−175.1 (2)	C9—N8—C10—C11	−84.5 (3)
C2—N2—C3—N3	4.3 (4)	N8—C10—C11—O4	−18.0 (4)
C3—N4—C4—C5	86.3 (3)	N8—C10—C11—O3	163.6 (2)
N4—C4—C5—O2	21.8 (4)	O2—C5—O1—C6	4.0 (4)
N4—C4—C5—O1	−159.3 (2)	C4—C5—O1—C6	−174.9 (3)
C9—N7—C7—N5	−0.1 (4)	O4—C11—O3—C12	−4.2 (4)
C9—N7—C7—Cl3	178.98 (19)	C10—C11—O3—C12	174.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N2i	0.95 (1)	2.09 (1)	3.028 (3)	171 (3)
N8—H8···N6ii	0.94 (1)	2.08 (1)	3.022 (3)	173 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯N2i	0.945 (10)	2.092 (12)	3.028 (3)	171 (3)
N8—H8⋯N6ii	0.943 (10)	2.083 (11)	3.022 (3)	173 (3)

Symmetry codes: (i) ; (ii) .