Acetoguanamine N,N-dimethyl­formamide solvate

Portalone, G.

doi:10.1107/S1600536808023842

organic compounds

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Volume 64| Part 9| September 2008| Page o1685

doi:10.1107/S1600536808023842

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Acetoguanamine N,N-dimethylformamide solvate

Gustavo Portalone ^a ^*

^aChemistry Department, "Sapienza" University of Rome, P. le A. Moro, 5, I-00185 Rome, Italy
^*Correspondence e-mail: g.portalone@caspur.it

(Received 18 July 2008; accepted 28 July 2008; online 6 August 2008)

The structure of acetoguanamine (or 2,4-diamino-6-methyl-1,3,5-triazine) has been determined as the N,N-dimethylformamide solvate, C₄H₇N₅·C₃H₇NO. The molecular components are associated in the crystal structure to form ribbons stabilized by three N—H⋯N and one N—H⋯O hydrogen bonds which involve NH groups as donors and the N atoms of the heterocyclic ring and the carbonyl O atom of the solvent as acceptors.

Related literature

For related literature, see: Portalone & Colapietro (2007a ). For a general approach to the use of multiple-hydrogen-bonding DNA/RNA nucleobases as potential supramolecular reagents, see: Portalone et al. (1999 ); Portalone & Colapietro (2007a,b and references therein). For the computation of ring patterns formed by hydrogen bonds in crystal structures, see: Etter et al. (1990 ); Bernstein et al. (1995 ); Motherwell et al. (1999 ).

Experimental

Crystal data

C₄H₇N₅·C₃H₇NO
M_r = 198.24
Orthorhombic, F d d 2
a = 25.548 (2) Å
b = 23.0626 (19) Å
c = 7.2689 (9) Å
V = 4282.8 (7) Å³
Z = 16
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.15 × 0.14 × 0.14 mm

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.985, T_max = 0.990
27177 measured reflections
1127 independent reflections
698 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.127
S = 0.91
1127 reflections
132 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6B⋯O1	0.89	2.05	2.890 (5)	157
N6—H6A⋯N5ⁱ	0.89	2.13	3.022 (4)	174
N7—H7B⋯N1ⁱⁱ	0.82	2.18	2.989 (4)	168
N7—H7A⋯N3ⁱⁱⁱ	0.82	2.17	2.993 (4)	176
Symmetry codes: (i) $[-x+{\script{5\over 4}}, y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (ii) $[-x+{\script{5\over 4}}, y-{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (iii) -x+1, -y, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3? (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023842/tk2285sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808023842/tk2285Isup2.hkl

checkCIF report

Comment top

As a part of a more general study of multiple-hydrogen-bonding DNA/RNA nucleobases as potential supramolecular reagents (Portalone et al., 1999; Portalone & Colapietro, 2007a, b), this work is a continuation of our studies on crystal adducts of DNA/RNA pyrimidine bases coupled with amino-derivatives of aromatic N-heterocycles via multiple hydrogen bonds to mimic the base-pairing of nucleic acids.

The asymmetric unit of (I) comprises a planar independent molecule of acetoguanamine hydrogen-bonded to N,N-dimethylformamide (DMF) (Fig. 1). A comparison of the molecular geometry of acetoguanamine with that reported for the corresponding molecule in the 1:1 monohydrated molecular adduct formed between acetoguanaminium chloride and acetoguanamine (Portalone & Colapietro, 2007a) shows that the corresponding bond lengths and angles are equal within experimental error. An analysis of the crystal packing of (I) shows (Table 1) that adjacent molecules of acetoguanamine are linked into ribbons (Fig. 2) by three independent intermolecular N—H···N hydrogen bonds between NH moieties and N atoms of the heterocyclic ring to form hydrogen-bonded rings (one centrosymmetric) of descriptor R²₂(8) (Etter et al., 1990; Bernstein et al., 1995; Motherwell et al., 1999). These hydrogen bonds that lead to two-dimensional arrays in the ab plane are bridged by DMF molecules via N–H ···O interactions forming C¹₁(3) chains.

Related literature top

For related literature, see: Portalone & Colapietro (2007a). For a general approach to the use of multiple-hydrogen-bonding DNA/RNA nucleobases as potential supramolecular reagents, see: Portalone et al. (1999); Portalone & Colapietro (2007a,b and references therein). For thcomputation of ring patterns formed by hydrogen bonds in crystal structures, see: Etter et al. (1990); Bernstein et al. (1995); Motherwell et al. (1999).

Experimental top

Acetoguanamine (0.1 mmol, Sigma Aldrich at 98% purity) was dissolved in N,N-dimethylformamide (9 ml) and heated under reflux for 3 h. After cooling the solution to an ambient temperature, crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of the solvent after a few days.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacements ellipsoids are at the 50% probability level.
	Fig. 2. Crystal packing diagram for (I) viewed approximately down the c-axis. All atoms are shown as small spheres of arbitrary radii. For the sake of clarity, only H atoms involved in hydrogen bonding are shown. Hydrogen bonding is indicated by dashed lines.

2,4-diamino-6-methyl-1,3,5-triazine N,N-dimethylformamide solvate top

Crystal data top

C₄H₇N₅·C₃H₇NO	F(000) = 1696
M_r = 198.24	D_x = 1.230 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 11018 reflections
a = 25.548 (2) Å	θ = 3.0–25.6°
b = 23.0626 (19) Å	µ = 0.09 mm⁻¹
c = 7.2689 (9) Å	T = 298 K
V = 4282.8 (7) Å³	Tablets, colourless
Z = 16	0.15 × 0.14 × 0.14 mm

Data collection top

Oxford Diffraction Xcalibur S CCD diffractometer	1127 independent reflections
Radiation source: Enhance (Mo) X-ray source	698 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
Detector resolution: 16.0696 pixels mm^-1	θ_max = 25.9°, θ_min = 3.0°
ω and ϕ scans	h = −31→31
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −27→28
T_min = 0.985, T_max = 0.990	l = −8→8
27177 measured reflections

Refinement top

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0841P)²] where P = (F_o² + 2F_c²)/3
1127 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 0.15 e Å⁻³
1 restraint	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₄H₇N₅·C₃H₇NO	V = 4282.8 (7) Å³
M_r = 198.24	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 25.548 (2) Å	µ = 0.09 mm⁻¹
b = 23.0626 (19) Å	T = 298 K
c = 7.2689 (9) Å	0.15 × 0.14 × 0.14 mm

Data collection top

Oxford Diffraction Xcalibur S CCD diffractometer	1127 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	698 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.990	R_int = 0.064
27177 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	1 restraint
wR(F²) = 0.127	H-atom parameters constrained
S = 0.91	Δρ_max = 0.15 e Å⁻³
1127 reflections	Δρ_min = −0.14 e Å⁻³
132 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.63312 (11)	0.10945 (11)	0.5765 (4)	0.0495 (9)
C2	0.58170 (12)	0.10315 (14)	0.6030 (6)	0.0431 (9)
N3	0.55453 (10)	0.05414 (12)	0.5797 (4)	0.0447 (8)
C4	0.58328 (13)	0.00862 (13)	0.5267 (5)	0.0416 (9)
N5	0.63552 (11)	0.01049 (12)	0.4927 (5)	0.0471 (8)
C6	0.65836 (13)	0.06118 (15)	0.5210 (5)	0.0463 (9)
N6	0.55533 (11)	0.15017 (12)	0.6581 (5)	0.0592 (10)
H6A	0.5721	0.1836	0.6753	0.071*
H6B	0.5210	0.14808	0.6776	0.071*
N7	0.55992 (11)	−0.04163 (11)	0.5010 (5)	0.0598 (10)
H7A	0.5282	−0.04463	0.5175	0.072*
H7B	0.5771	−0.0700	0.4684	0.072*
C8	0.71557 (14)	0.06575 (18)	0.4923 (7)	0.0710 (13)
H8A	0.7319	0.0329	0.5395	0.106*
H8B	0.7282	0.0985	0.5522	0.106*
H8C	0.7226	0.0687	0.3671	0.106*
O1	0.44754 (15)	0.1783 (2)	0.7397 (7)	0.1196 (16)
N8	0.36343 (14)	0.20435 (17)	0.7802 (5)	0.0738 (11)
C9	0.4016 (3)	0.1667 (3)	0.7697 (9)	0.113 (2)
H9	0.3931	0.1279	0.7864	0.226*
C10	0.3107 (3)	0.1868 (4)	0.8156 (11)	0.160 (4)
H10A	0.2905	0.1891	0.7028	0.319*
H10B	0.2954	0.2122	0.9074	0.319*
H10C	0.3105	0.1472	0.8606	0.319*
C11	0.3722 (4)	0.2647 (2)	0.7568 (11)	0.140 (3)
H11A	0.3839	0.2813	0.8722	0.279*
H11B	0.3399	0.2833	0.7189	0.279*
H11C	0.3988	0.2706	0.6634	0.279*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0426 (16)	0.0337 (16)	0.072 (2)	−0.0041 (13)	−0.0033 (15)	−0.0092 (16)
C2	0.0385 (18)	0.0307 (18)	0.060 (2)	−0.0004 (15)	−0.0048 (19)	−0.0032 (16)
N3	0.0391 (14)	0.0311 (14)	0.0638 (19)	−0.0001 (13)	−0.0004 (15)	−0.0059 (14)
C4	0.0400 (19)	0.0273 (17)	0.057 (2)	−0.0005 (14)	0.0046 (18)	−0.0045 (15)
N5	0.0406 (16)	0.0310 (15)	0.070 (2)	−0.0008 (12)	−0.0009 (16)	−0.0103 (15)
C6	0.0399 (17)	0.0381 (19)	0.061 (2)	−0.0037 (16)	−0.0027 (18)	−0.0038 (18)
N6	0.0457 (17)	0.0298 (15)	0.102 (3)	0.0009 (13)	−0.0020 (18)	−0.0156 (17)
N7	0.0414 (16)	0.0319 (15)	0.106 (3)	−0.0013 (13)	0.0115 (19)	−0.0126 (18)
C8	0.042 (2)	0.062 (2)	0.108 (4)	−0.0064 (19)	0.006 (3)	−0.019 (3)
O1	0.063 (2)	0.153 (4)	0.143 (4)	0.013 (2)	−0.005 (3)	−0.037 (3)
N8	0.070 (2)	0.072 (3)	0.079 (3)	0.006 (2)	0.0083 (19)	−0.012 (2)
C9	0.133 (6)	0.109 (5)	0.096 (5)	0.018 (5)	−0.008 (4)	−0.017 (4)
C10	0.101 (5)	0.266 (10)	0.112 (5)	−0.053 (6)	0.036 (4)	−0.050 (6)
C11	0.242 (9)	0.073 (4)	0.104 (5)	−0.002 (4)	0.001 (5)	0.008 (4)

Geometric parameters (Å, º) top

N1—C2	1.336 (4)	C8—H8B	0.9300
N1—C6	1.348 (5)	C8—H8C	0.9300
C2—N3	1.337 (4)	O1—C9	1.223 (7)
C2—N6	1.338 (4)	N8—C9	1.307 (7)
N3—C4	1.338 (4)	N8—C11	1.419 (6)
C4—N7	1.317 (4)	N8—C10	1.429 (7)
C4—N5	1.358 (4)	C9—H9	0.9300
N5—C6	1.323 (4)	C10—H10A	0.9700
C6—C8	1.480 (5)	C10—H10B	0.9700
N6—H6A	0.8907	C10—H10C	0.9700
N6—H6B	0.8907	C11—H11A	0.9700
N7—H7A	0.8226	C11—H11B	0.9700
N7—H7B	0.8226	C11—H11C	0.9700
C8—H8A	0.9300

C2—N1—C6	115.1 (3)	C6—C8—H8C	109.5
N1—C2—N3	125.8 (3)	H8A—C8—H8C	109.5
N1—C2—N6	116.8 (3)	H8B—C8—H8C	109.5
N3—C2—N6	117.5 (3)	C9—N8—C11	121.7 (6)
C2—N3—C4	114.5 (3)	C9—N8—C10	121.7 (6)
N7—C4—N3	118.9 (3)	C11—N8—C10	116.6 (6)
N7—C4—N5	116.6 (3)	O1—C9—N8	125.6 (7)
N3—C4—N5	124.5 (3)	O1—C9—H9	117.2
C6—N5—C4	115.7 (3)	N8—C9—H9	117.2
N5—C6—N1	124.4 (3)	N8—C10—H10A	109.5
N5—C6—C8	118.5 (3)	N8—C10—H10B	109.5
N1—C6—C8	117.1 (3)	H10A—C10—H10B	109.5
C2—N6—H6A	120.0	N8—C10—H10C	109.5
C2—N6—H6B	120.0	H10A—C10—H10C	109.5
H6A—N6—H6B	120.0	H10B—C10—H10C	109.5
C4—N7—H7A	120.0	N8—C11—H11A	109.5
C4—N7—H7B	120.0	N8—C11—H11B	109.5
H7A—N7—H7B	120.0	H11A—C11—H11B	109.5
C6—C8—H8A	109.5	N8—C11—H11C	109.5
C6—C8—H8B	109.5	H11A—C11—H11C	109.5
H8A—C8—H8B	109.5	H11B—C11—H11C	109.5

C6—N1—C2—N3	0.2 (6)	N3—C4—N5—C6	2.1 (5)
C6—N1—C2—N6	180.0 (4)	C4—N5—C6—N1	−1.2 (6)
N1—C2—N3—C4	0.6 (6)	C4—N5—C6—C8	178.1 (4)
N6—C2—N3—C4	−179.2 (3)	C2—N1—C6—N5	0.2 (6)
C2—N3—C4—N7	179.7 (4)	C2—N1—C6—C8	−179.2 (4)
C2—N3—C4—N5	−1.8 (5)	C11—N8—C9—O1	0.0 (10)
N7—C4—N5—C6	−179.4 (4)	C10—N8—C9—O1	179.9 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6B···O1	0.89	2.05	2.890 (5)	157
N6—H6A···N5ⁱ	0.89	2.13	3.022 (4)	174
N7—H7B···N1ⁱⁱ	0.82	2.18	2.989 (4)	168
N7—H7A···N3ⁱⁱⁱ	0.82	2.17	2.993 (4)	176

Symmetry codes: (i) −x+5/4, y+1/4, z+1/4; (ii) −x+5/4, y−1/4, z−1/4; (iii) −x+1, −y, z.

Experimental details

Crystal data
Chemical formula	C₄H₇N₅·C₃H₇NO
M_r	198.24
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	298
a, b, c (Å)	25.548 (2), 23.0626 (19), 7.2689 (9)
V (Å³)	4282.8 (7)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.15 × 0.14 × 0.14

Data collection
Diffractometer	Oxford Diffraction Xcalibur S CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.985, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	27177, 1127, 698
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.127, 0.91
No. of reflections	1127
No. of parameters	132
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.14

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6B···O1	0.89	2.05	2.890 (5)	157
N6—H6A···N5ⁱ	0.89	2.13	3.022 (4)	174
N7—H7B···N1ⁱⁱ	0.82	2.18	2.989 (4)	168
N7—H7A···N3ⁱⁱⁱ	0.82	2.17	2.993 (4)	176

Symmetry codes: (i) −x+5/4, y+1/4, z+1/4; (ii) −x+5/4, y−1/4, z−1/4; (iii) −x+1, −y, z.

Acknowledgements

We thank MIUR (Rome) for 2006 financial support of the project `X-ray diffractometry and spectrometry'.

References

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