Amino­guanidinium hydrogen fumarate

Murugavel, S.; Ganesh, G.; Subbiah Pandi, A.; Govindarajan, S.; Selvakumar, R.

doi:10.1107/S1600536809004553

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o548

doi:10.1107/S1600536809004553

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Aminoguanidinium hydrogen fumarate

Swaminathan Murugavel,^a Gnanavelu Ganesh,^b Arunachalathevar Subbiah Pandi,^c ^* Subbiah Govindarajan ^d and Rajendran Selvakumar ^d

^aDepartment of Physics, Thanthai Periyar Government Institute of Technology, Vellore 632 002, India, ^bDepartment of Physics, SMK Fomra Institute of Technology, Thaiyur, Chennai 603 103, India, ^cDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and ^dDepartment of Chemistry, Bharathiar University, Coimbatore 641 046, India
^*Correspondence e-mail: a_spandian@yahoo.com

(Received 4 February 2009; accepted 8 February 2009; online 18 February 2009)

The title compound, CH₇N₄⁺·C₄H₃O₄⁻, is a molecular salt in which the aminoguanidinium cations and fumarate monoanions are close to planar, with maximum deviations of 0.011 (1) and 0.177 (1) Å, respectively. The crystal packing is stabilized by intermolecular N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For related structures, see: Adams (1977 ); Akella & Keszler (1994 ); Mullen & Hellner (1978 ). For biological applications, see: Makita et al. (1995 ); Brownlee et al. (1986 ).

Experimental

Crystal data

CH₇N₄⁺·C₄H₃O₄⁻
M_r = 190.17
Monoclinic, P 2₁ /c
a = 6.3869 (3) Å
b = 19.8731 (10) Å
c = 7.0482 (4) Å
β = 114.688 (3)°
V = 812.84 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.26 × 0.15 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.966, T_max = 0.976
10713 measured reflections
2340 independent reflections
1824 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.132
S = 1.04
2340 reflections
146 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8⋯O7ⁱ	0.82	1.68	2.489 (1)	168
N10—H10A⋯O7ⁱⁱ	0.91 (2)	2.09 (2)	2.993 (1)	177 (2)
N11—H11A⋯O6ⁱⁱ	0.92 (2)	1.91 (2)	2.827 (2)	173 (2)
Symmetry codes: (i) x-1, y, z; (ii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004553/wm2220sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004553/wm2220Isup2.hkl

checkCIF report

Comment top

Aminoguanadine is an early inhibitor of advanced glycosylation end products (Makita et al., 1995). It helps prevent proteins cross-linking and is being used in diabetes, atherosclerosis, renal and aging disorders (Brownlee et al., 1986). Aminoguanadine is a highly reactive nucleophillic reagent that reacts with many biological molecules (pyridoxal phosphate, pyruvate, glucose, malondialdehyde, and others). The crystal structures of several guanidinium salts have previously been reported over the last three decades (Adams, 1977; Mullen & Hellner, 1978). Here we report the crystal structure of the title compound, aminoguanidinium hydrogenfumarate, (I), (Fig. 1). In the molecular salt (I), the aminoguanidinium cation and fumarate anion each are nearly planar, with maximum deviations of -0.011 (1) Å and -0.177 (1) Å for atom N12 and O7, respectively ( Fig. 1). The bond lengths in (I) are comparable with the corresponding values observed in related structures (Akella & Keszler , 1994). The angle between the best planes of the aminoguanidinium cation and the fumarate anion is 12.78 (6)°. Atom N10 and N11 in the molecule at (x, y, z) donate one proton each to the atoms O7 and O6 in the molecule at (-1+x, 3/2-y, -1/2+z), generating a R₂²(8) ring motif (Table 1 and Fig. 2). Also, an O—H···O interaction is observed (Table 1). Thus, the symmetry-related molecules are cross linked by these hydrogen bonds to generate a three-dimensional network.

Related literature top

For related structures, see: Adams (1977); Akella & Keszler (1994); Mullen & Hellner (1978). For biological applications, see: Makita et al. (1995); Brownlee et al. (1986).

Experimental top

Needle-shaped single crystals of aminoguanidium hydrogenfumarate were prepared by slow evaporation of the aqueous solution obtained by dissolving of aminoguanidinium hydrogencarbonate (0.136g; 0.001mol) in fumaric acid (0.116 g; 1 mmol) solution (30 mL) at ambient condition. Colourless single crystals suitable for X-ray diffraction obtained after four days were collected, washed with ethanol and air dried.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the ions present in compound (I) showing 50% probability displacement ellipsoids.
	Fig. 2. N—H···O and O—H···O hydrogen bonds (dotted lines) in the title compound. [Symmetry codes: (i) x-1, -y+3/2, z-1/2; (ii)x-1, y, z].

Aminoguanidinium hydrogen fumarate top

Crystal data top

CH₇N₄⁺·C₄H₃O₄⁻	F(000) = 400
M_r = 190.17	D_x = 1.554 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1824 reflections
a = 6.3869 (3) Å	θ = 2–29.9°
b = 19.8731 (10) Å	µ = 0.13 mm⁻¹
c = 7.0482 (4) Å	T = 293 K
β = 114.688 (3)°	Block, colourless
V = 812.84 (8) Å³	0.26 × 0.15 × 0.15 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2340 independent reflections
Radiation source: fine-focus sealed tube	1824 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 10.0 pixels mm^-1	θ_max = 29.9°, θ_min = 2.1°
ω scans	h = −8→7
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −24→27
T_min = 0.966, T_max = 0.976	l = −9→9
10713 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0756P)² + 0.1408P] where P = (F_o² + 2F_c²)/3
2340 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

CH₇N₄⁺·C₄H₃O₄⁻	V = 812.84 (8) Å³
M_r = 190.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.3869 (3) Å	µ = 0.13 mm⁻¹
b = 19.8731 (10) Å	T = 293 K
c = 7.0482 (4) Å	0.26 × 0.15 × 0.15 mm
β = 114.688 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2340 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1824 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.976	R_int = 0.028
10713 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.33 e Å⁻³
2340 reflections	Δρ_min = −0.31 e Å⁻³
146 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
H11B	0.243 (3)	0.4484 (12)	0.254 (3)	0.057 (5)*
H12	0.573 (3)	0.3932 (11)	0.302 (3)	0.056 (5)*
H13A	0.861 (4)	0.3941 (12)	0.204 (3)	0.072 (6)*
C1	1.12336 (19)	0.84396 (5)	0.68336 (19)	0.0281 (3)
C2	0.9984 (2)	0.78049 (5)	0.68320 (19)	0.0274 (2)
H2	1.0738	0.7396	0.6953	0.033*
C3	0.7863 (2)	0.78034 (6)	0.6666 (2)	0.0292 (3)
H3	0.7125	0.8212	0.6595	0.035*
C4	0.6603 (2)	0.71704 (5)	0.65888 (19)	0.0279 (3)
O6	1.04931 (17)	0.89803 (5)	0.71551 (19)	0.0466 (3)
O7	1.30209 (15)	0.83829 (4)	0.64654 (17)	0.0362 (2)
O8	0.45191 (15)	0.72255 (4)	0.64769 (17)	0.0374 (2)
H8	0.4189	0.7625	0.6465	0.056*
O9	0.74557 (17)	0.66199 (4)	0.66416 (19)	0.0434 (3)
H10A	0.521 (3)	0.5783 (9)	0.214 (3)	0.046 (5)*
H10B	0.747 (4)	0.5370 (10)	0.245 (3)	0.057 (5)*
H11A	0.221 (3)	0.5225 (10)	0.224 (3)	0.053 (5)*
C5	0.5133 (2)	0.48405 (6)	0.25398 (18)	0.0277 (3)
N10	0.6094 (2)	0.54110 (5)	0.23653 (19)	0.0350 (3)
N11	0.3028 (2)	0.48299 (6)	0.2428 (2)	0.0412 (3)
N12	0.6265 (2)	0.42625 (5)	0.2812 (2)	0.0361 (3)
N13	0.8519 (2)	0.42556 (6)	0.2974 (2)	0.0431 (3)
H13B	0.935 (4)	0.4125 (10)	0.424 (3)	0.061 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0233 (5)	0.0217 (5)	0.0413 (6)	−0.0015 (4)	0.0153 (5)	0.0003 (4)
C2	0.0253 (5)	0.0198 (5)	0.0400 (6)	−0.0004 (4)	0.0166 (5)	0.0010 (4)
C3	0.0270 (6)	0.0179 (5)	0.0477 (7)	−0.0010 (4)	0.0206 (5)	−0.0004 (4)
C4	0.0264 (5)	0.0200 (5)	0.0412 (6)	−0.0018 (4)	0.0180 (5)	0.0000 (4)
O6	0.0395 (5)	0.0226 (4)	0.0891 (8)	−0.0035 (4)	0.0382 (6)	−0.0077 (5)
O7	0.0291 (4)	0.0264 (4)	0.0620 (6)	−0.0027 (3)	0.0279 (4)	0.0003 (4)
O8	0.0280 (4)	0.0228 (4)	0.0683 (7)	−0.0027 (3)	0.0272 (4)	−0.0004 (4)
O9	0.0390 (5)	0.0196 (4)	0.0796 (7)	0.0023 (3)	0.0328 (5)	0.0019 (4)
C5	0.0301 (6)	0.0208 (5)	0.0345 (6)	0.0007 (4)	0.0158 (5)	0.0002 (4)
N10	0.0341 (6)	0.0206 (5)	0.0553 (7)	−0.0007 (4)	0.0238 (5)	0.0025 (4)
N11	0.0350 (6)	0.0254 (5)	0.0713 (9)	0.0000 (5)	0.0304 (6)	0.0024 (5)
N12	0.0353 (6)	0.0193 (5)	0.0599 (7)	0.0021 (4)	0.0260 (5)	0.0052 (4)
N13	0.0345 (6)	0.0348 (6)	0.0638 (9)	0.0076 (5)	0.0244 (6)	0.0025 (6)

Geometric parameters (Å, º) top

C1—O6	1.2325 (14)	C5—N10	1.3190 (15)
C1—O7	1.2770 (14)	C5—N12	1.3278 (15)
C1—C2	1.4922 (15)	N10—H10A	0.905 (18)
C2—C3	1.3105 (16)	N10—H10B	0.86 (2)
C2—H2	0.9300	N11—H11B	0.80 (2)
C3—C4	1.4820 (15)	N11—H11A	0.92 (2)
C3—H3	0.9300	N12—N13	1.3960 (16)
C4—O9	1.2159 (14)	N12—H12	0.78 (2)
C4—O8	1.3044 (14)	N13—H13A	0.93 (2)
O8—H8	0.8200	N13—H13B	0.87 (2)
C5—N11	1.3136 (17)

O6—C1—O7	123.96 (10)	N11—C5—N12	118.46 (11)
O6—C1—C2	119.40 (10)	N10—C5—N12	120.71 (11)
O7—C1—C2	116.64 (10)	C5—N10—H10A	115.9 (12)
C3—C2—C1	122.32 (10)	C5—N10—H10B	114.5 (14)
C3—C2—H2	118.8	H10A—N10—H10B	129.6 (19)
C1—C2—H2	118.8	C5—N11—H11B	121.4 (15)
C2—C3—C4	122.04 (10)	C5—N11—H11A	120.0 (12)
C2—C3—H3	119.0	H11B—N11—H11A	119 (2)
C4—C3—H3	119.0	C5—N12—N13	120.06 (11)
O9—C4—O8	120.67 (10)	C5—N12—H12	120.1 (15)
O9—C4—C3	122.22 (10)	N13—N12—H12	119.5 (15)
O8—C4—C3	117.11 (10)	N12—N13—H13A	108.3 (15)
C4—O8—H8	109.5	N12—N13—H13B	104.9 (14)
N11—C5—N10	120.83 (11)	H13A—N13—H13B	109.7 (19)

O6—C1—C2—C3	16.50 (19)	C2—C3—C4—O8	178.28 (11)
O7—C1—C2—C3	−162.59 (12)	N11—C5—N12—N13	−178.90 (13)
C1—C2—C3—C4	177.74 (11)	N10—C5—N12—N13	1.8 (2)
C2—C3—C4—O9	−1.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O7ⁱ	0.82	1.68	2.489 (1)	168
N10—H10A···O7ⁱⁱ	0.91 (2)	2.09 (2)	2.993 (1)	177 (2)
N11—H11A···O6ⁱⁱ	0.92 (2)	1.91 (2)	2.827 (2)	173 (2)

Symmetry codes: (i) x−1, y, z; (ii) x−1, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	CH₇N₄⁺·C₄H₃O₄⁻
M_r	190.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.3869 (3), 19.8731 (10), 7.0482 (4)
β (°)	114.688 (3)
V (Å³)	812.84 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.26 × 0.15 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.966, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	10713, 2340, 1824
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.702

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.132, 1.04
No. of reflections	2340
No. of parameters	146
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.31

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O7ⁱ	0.82	1.68	2.489 (1)	168.3
N10—H10A···O7ⁱⁱ	0.91 (2)	2.09 (2)	2.993 (1)	177 (2)
N11—H11A···O6ⁱⁱ	0.92 (2)	1.91 (2)	2.827 (2)	173 (2)

Symmetry codes: (i) x−1, y, z; (ii) x−1, −y+3/2, z−1/2.

Acknowledgements

SM and ASP thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.

References

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