6-Methyl-1,3,5-triazine-2,4-diamine butane-1,4-diol monosolvate

Abstract

The title co-crystal, C₄H₇N₅·C₄H₁₀O₂, crystallizes with one mol­ecule of 6-methyl-1,3,5-triazine-2,4-diamine (DMT) and one mol­ecule of butane-1,4-diol in the asymmetric unit. The DMT mol­ecules form ribbons involving centrosymmetric R ₂ ²(8) dimer motifs between DMT mol­ecules along the c-axis direction. These ribbons are further hydrogen bonded to each other through butane-1,4-diol, forming sheets parallel to (121).

Related literature  

For background to DMT and related structural studies, see: Šebenik et al. (1989 ▶); Kaczmarek et al. (2008 ▶); Portalone (2008 ▶); Xiao (2008 ▶); Fan et al. (2009 ▶); Qian & Huang (2010 ▶); Thanigaimani et al. (2010 ▶); Perpétuo & Janczak (2007 ▶); Portalone & Colapietro (2007 ▶); Delori et al. (2008 ▶). For details of experimental methods used, see: Florence et al. (2003 ▶). For ring-motif nomenclature, see: Etter (1990 ▶).

Experimental  

Crystal data  

• C₄H₇N₅·C₄H₁₀O₂

• M _r = 215.27

• Triclinic,

• a = 5.8755 (3) Å

• b = 9.0515 (5) Å

• c = 10.7607 (5) Å

• α = 87.911 (3)°

• β = 74.346 (3)°

• γ = 83.550 (3)°

• V = 547.55 (5) ų

• Z = 2

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 123 K

• 0.50 × 0.05 × 0.04 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.637, T _max = 0.745

• 7713 measured reflections

• 1911 independent reflections

• 1288 reflections with I > 2σ(I)

• R _int = 0.045

Refinement  

• R[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 0.093

• S = 1.00

• 1911 reflections

• 155 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶) and WinGX (Farrugia, 1999) ▶.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2i	0.84	1.92	2.764 (2)	176
O2—H2⋯N1ii	0.84	1.94	2.777 (2)	178
N4—H7N⋯O1iii	0.92 (3)	2.52 (2)	3.173 (2)	128.5 (7)
N4—H8N⋯N2iv	0.85 (2)	2.19 (2)	3.037 (2)	178 (2)
N5—H9N⋯O1v	0.88 (2)	2.069 (19)	2.909 (2)	160.1 (18)
N5—H10N⋯N3v	0.87 (2)	2.14 (2)	3.008 (3)	179 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

2,4-diamino-6-methyl-1,3,5-triazine (DMT, acetoguanamine, Fig. 1) is used as an intermediate for pharmaceutical and resin synthesis (Šebenik et al., 1989). The crystal structures of the methanol, ethanol, DMF solvates and trifluoroacetate, phthalate, nitrate and chloride salts as well as of various complexes with aliphatic dicarboxylic acids have been reported in the literature (Kaczmarek et al., 2008; Portalone, 2008; Xiao, 2008; Fan et al., 2009; Qian & Huang, 2010; Thanigaimani et al., 2010; Portalone & Colapietro, 2007; Perpétuo & Janczak, 2007; Delori et al., 2008). The sample of DMT butane-1,4-diol solvate was isolated during an experimental physical form screen. The sample was identified as a novel form using multi-sample foil transmission X-ray powder diffraction analysis (Florence et al., 2003). A suitable sample for single-crystal X-ray diffraction analysis was obtained from slow evaporation of saturated butane-1,4-diol solution at room temperature. The title compound crystallizes in space group P1, with one molecule of DMT and one molecule of butane-1,4-diol in the asymmetric unit. Each DMT molecule forms two hydrogen-bonded dimers via an R₂²(8) motif (Etter, 1990) that extends to form a ribbon structure along the c-direction (Fig. 2). The hydrogen bonded DMT ribbons connect to adjacent ribbons through the solvent molecule, butane-1,4-diol, thus forming a second R₃²(8) ring motif (Fig. 2).These solvent separated ribbon structures extended to form sheets parallel to (121) plane, and are connected through hydrogen bond interactions via the hydroxyl groups. Solvent hydroxyl group also donates a hydrogen bond to the solvent in adjacent sheet, creating a three-dimensional layered structure (Fig. 3).

Experimental

A single needle shape crystal was grown from the saturated solution of DMT in butane-1,4-diol by isothermal solvent evaporation at 298 K.

Refinement

The positions of the N-bound H atoms were refined freely. All other H atoms were placed in calculated positions and refined in riding modes with X—H = 0.98 or 0.99 or 0.84 Å for the CH₃, CH₂ and OH groups, respectively. The U_iso(H) values were set to 1.5 or 1.2 times U_eq of their parent C atoms for the CH₃ and CH₂ groups, respectively. The U_iso(H) values were set to 1.5 times U_eq of their parent O atoms for the OH groups.

Figures

Fig. 1.

The asymmetric unit of 2,4-diamino-6-methyl-1,3,5-triazine (DMT), butane-1,4-diol solvate. Displacement ellipsoids are drawn at 50% probability level.

Fig. 2.

DMT molecules form ribbons through R22(8) dimer, ribbons are connected via H-bonding (shown in cyan dotted line) interactions mediated by butane-1,4-diol, thus give rise to sheet structure. C, N and H atoms are shown in black, blue and tan colour respectively. Other H atoms are omitted for clarity.

Fig. 3.

3-D Layered structure formed by sheets connected through H-bonding (cyan dotted line) mediated by butane-1,4-diol. C, N and H atoms are shown in grey, blue and white colour respectively. Other H atoms are omitted for clarity.

Crystal data

C4H7N5·C4H10O2	Z = 2
Mr = 215.27	F(000) = 232
Triclinic, P1	Dx = 1.306 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8755 (3) Å	Cell parameters from 1602 reflections
b = 9.0515 (5) Å	θ = 2.3–24.6°
c = 10.7607 (5) Å	µ = 0.10 mm−1
α = 87.911 (3)°	T = 123 K
β = 74.346 (3)°	Needle, colourless
γ = 83.550 (3)°	0.50 × 0.05 × 0.04 mm
V = 547.55 (5) Å3

Data collection

Bruker APEXII CCD diffractometer	1911 independent reflections
Radiation source: fine-focus sealed tube	1288 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −6→6
Tmin = 0.637, Tmax = 0.745	k = −10→10
7713 measured reflections	l = −12→12

Refinement

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0401P)2 + 0.1476P] where P = (Fo2 + 2Fc2)/3
1911 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.22 e Å−3
0 constraints

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

	x	y	z	Uiso*/Ueq
C1	0.5923 (3)	0.3881 (2)	0.16893 (18)	0.0160 (5)
C2	0.2419 (3)	0.4825 (2)	0.30267 (18)	0.0163 (5)
C3	0.5020 (3)	0.3277 (2)	0.38201 (19)	0.0174 (5)
C4	0.5670 (4)	0.2448 (2)	0.49230 (19)	0.0243 (5)
H4A	0.4317	0.2559	0.5692	0.036*
H4B	0.7035	0.2850	0.5095	0.036*
H4C	0.6083	0.1393	0.4705	0.036*
C5	0.3181 (3)	0.1867 (2)	0.9133 (2)	0.0207 (5)
H5A	0.2639	0.1078	0.9771	0.025*
H5B	0.3114	0.2788	0.9615	0.025*
C6	0.5730 (3)	0.1418 (2)	0.83897 (19)	0.0182 (5)
H6A	0.6744	0.1373	0.8993	0.022*
H6B	0.6254	0.2195	0.7737	0.022*
C7	0.6115 (3)	−0.0072 (2)	0.77120 (19)	0.0191 (5)
H7A	0.5611	−0.0855	0.8363	0.023*
H7B	0.5099	−0.0033	0.7110	0.023*
C8	0.8673 (3)	−0.0489 (2)	0.69683 (19)	0.0220 (5)
H8A	0.8820	−0.1465	0.6551	0.026*
H8B	0.9165	0.0260	0.6282	0.026*
N1	0.6600 (3)	0.31119 (18)	0.26599 (15)	0.0175 (4)
N2	0.3851 (3)	0.47401 (18)	0.18167 (15)	0.0162 (4)
N3	0.2928 (3)	0.41094 (18)	0.40710 (15)	0.0174 (4)
N4	0.7434 (3)	0.3769 (2)	0.05127 (17)	0.0221 (4)
N5	0.0347 (3)	0.5670 (2)	0.32441 (19)	0.0201 (4)
O1	0.1589 (2)	0.21134 (16)	0.83288 (14)	0.0238 (4)
H1	0.1221	0.1293	0.8146	0.036*
O2	1.0196 (2)	−0.05639 (16)	0.78135 (13)	0.0229 (4)
H2	1.1154	−0.1339	0.7660	0.034*
H7N	0.883 (4)	0.316 (3)	0.040 (2)	0.037 (7)*
H8N	0.704 (4)	0.418 (2)	−0.013 (2)	0.028 (7)*
H9N	−0.008 (3)	0.618 (2)	0.262 (2)	0.019 (6)*
H10N	−0.059 (4)	0.572 (2)	0.402 (2)	0.026 (6)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0178 (11)	0.0139 (11)	0.0162 (11)	−0.0025 (9)	−0.0042 (9)	0.0004 (9)
C2	0.0158 (11)	0.0155 (11)	0.0169 (11)	−0.0015 (9)	−0.0036 (9)	0.0005 (9)
C3	0.0192 (12)	0.0152 (11)	0.0180 (11)	0.0017 (9)	−0.0069 (9)	−0.0010 (9)
C4	0.0269 (12)	0.0266 (13)	0.0167 (11)	0.0075 (10)	−0.0055 (10)	0.0007 (9)
C5	0.0165 (11)	0.0232 (13)	0.0221 (11)	0.0028 (9)	−0.0062 (9)	−0.0016 (9)
C6	0.0144 (11)	0.0194 (12)	0.0210 (11)	−0.0004 (9)	−0.0055 (9)	−0.0001 (9)
C7	0.0166 (11)	0.0200 (12)	0.0212 (11)	−0.0005 (9)	−0.0067 (9)	0.0007 (9)
C8	0.0202 (12)	0.0240 (13)	0.0230 (11)	0.0021 (9)	−0.0088 (10)	−0.0032 (9)
N1	0.0176 (9)	0.0180 (10)	0.0151 (9)	0.0024 (7)	−0.0031 (8)	−0.0012 (7)
N2	0.0151 (9)	0.0164 (9)	0.0148 (9)	0.0024 (7)	−0.0016 (7)	0.0008 (7)
N3	0.0184 (9)	0.0175 (10)	0.0145 (9)	0.0025 (7)	−0.0033 (7)	0.0023 (7)
N4	0.0184 (11)	0.0272 (11)	0.0152 (10)	0.0082 (9)	0.0004 (9)	0.0015 (8)
N5	0.0172 (10)	0.0258 (11)	0.0120 (10)	0.0071 (8)	0.0005 (9)	0.0047 (8)
O1	0.0201 (8)	0.0202 (8)	0.0340 (9)	0.0013 (7)	−0.0139 (7)	0.0009 (7)
O2	0.0171 (8)	0.0223 (9)	0.0299 (9)	0.0073 (6)	−0.0102 (7)	−0.0055 (7)

Geometric parameters (Å, º)

C1—N4	1.336 (2)	C6—C7	1.522 (3)
C1—N2	1.345 (2)	C6—H6A	0.9900
C1—N1	1.357 (2)	C6—H6B	0.9900
C2—N5	1.331 (3)	C7—C8	1.512 (3)
C2—N2	1.346 (2)	C7—H7A	0.9900
C2—N3	1.362 (2)	C7—H7B	0.9900
C3—N3	1.334 (2)	C8—O2	1.434 (2)
C3—N1	1.342 (2)	C8—H8A	0.9900
C3—C4	1.494 (3)	C8—H8B	0.9900
C4—H4A	0.9800	N4—H7N	0.92 (2)
C4—H4B	0.9800	N4—H8N	0.85 (2)
C4—H4C	0.9800	N5—H9N	0.87 (2)
C5—O1	1.431 (2)	N5—H10N	0.87 (2)
C5—C6	1.512 (3)	O1—H1	0.8400
C5—H5A	0.9900	O2—H2	0.8400
C5—H5B	0.9900
N4—C1—N2	117.48 (18)	C7—C6—H6B	108.7
N4—C1—N1	117.24 (18)	H6A—C6—H6B	107.6
N2—C1—N1	125.28 (18)	C8—C7—C6	113.03 (17)
N5—C2—N2	118.72 (19)	C8—C7—H7A	109.0
N5—C2—N3	116.41 (18)	C6—C7—H7A	109.0
N2—C2—N3	124.86 (18)	C8—C7—H7B	109.0
N3—C3—N1	125.76 (18)	C6—C7—H7B	109.0
N3—C3—C4	117.45 (18)	H7A—C7—H7B	107.8
N1—C3—C4	116.79 (17)	O2—C8—C7	110.49 (16)
C3—C4—H4A	109.5	O2—C8—H8A	109.6
C3—C4—H4B	109.5	C7—C8—H8A	109.6
H4A—C4—H4B	109.5	O2—C8—H8B	109.6
C3—C4—H4C	109.5	C7—C8—H8B	109.6
H4A—C4—H4C	109.5	H8A—C8—H8B	108.1
H4B—C4—H4C	109.5	C3—N1—C1	114.53 (16)
O1—C5—C6	113.42 (16)	C1—N2—C2	114.71 (17)
O1—C5—H5A	108.9	C3—N3—C2	114.85 (17)
C6—C5—H5A	108.9	C1—N4—H7N	118.7 (14)
O1—C5—H5B	108.9	C1—N4—H8N	120.1 (15)
C6—C5—H5B	108.9	H7N—N4—H8N	121 (2)
H5A—C5—H5B	107.7	C2—N5—H9N	121.4 (13)
C5—C6—C7	114.11 (17)	C2—N5—H10N	119.2 (14)
C5—C6—H6A	108.7	H9N—N5—H10N	119.4 (19)
C7—C6—H6A	108.7	C5—O1—H1	109.5
C5—C6—H6B	108.7	C8—O2—H2	109.5
O1—C5—C6—C7	−64.5 (2)	N1—C1—N2—C2	1.1 (3)
C5—C6—C7—C8	179.55 (17)	N5—C2—N2—C1	178.99 (18)
C6—C7—C8—O2	59.0 (2)	N3—C2—N2—C1	−0.6 (3)
N3—C3—N1—C1	−0.1 (3)	N1—C3—N3—C2	0.5 (3)
C4—C3—N1—C1	179.68 (18)	C4—C3—N3—C2	−179.23 (18)
N4—C1—N1—C3	179.49 (18)	N5—C2—N3—C3	−179.76 (18)
N2—C1—N1—C3	−0.8 (3)	N2—C2—N3—C3	−0.1 (3)
N4—C1—N2—C2	−179.17 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.84	1.92	2.764 (2)	176
O2—H2···N1ii	0.84	1.94	2.777 (2)	178
N4—H7N···O1iii	0.92 (3)	2.52 (2)	3.173 (2)	128.5 (7)
N4—H8N···N2iv	0.85 (2)	2.19 (2)	3.037 (2)	178 (2)
N5—H9N···O1v	0.88 (2)	2.069 (19)	2.909 (2)	160.1 (18)
N5—H10N···N3v	0.87 (2)	2.14 (2)	3.008 (3)	179 (2)

Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y, −z+1; (iii) x+1, y, z−1; (iv) −x+1, −y+1, −z; (v) −x, −y+1, −z+1.