Amino­guanidinium hydrogen succinate

Murugavel, S.; Kannan, P.S.; Subbiah Pandi, A.; Govindarajan, S.; Selvakumar, R.

doi:10.1107/S1600536809003626

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o454

doi:10.1107/S1600536809003626

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Aminoguanidinium hydrogen succinate

S. Murugavel,^a P. S. Kannan,^b A. Subbiah Pandi,^c ^* S. Govindarajan ^d and R. Selvakumar ^d

^aDepartment of Physics, Thanthai Periyar Government Institute of Technology, Vellore 632 002, India, ^bDepartment of Physics, S. M. K. 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 13 January 2009; accepted 29 January 2009; online 4 February 2009)

The title compound, CH₇N₄⁺·C₄H₅O₄⁻, is a molecular salt containing discrete aminoguanidinium and succinate ions. The aminoguanidinium cation is nearly planar, with a maximum deviation of 0.035 (1) Å. The dihedral angle between the aminoguanidinium cation and the succinate anion is 3.35 (6)°. The crystal packing exhibits intermolecular N—H⋯O and O—H⋯·O hydrogen bonds.

Related literature

For related structures, see: Adams (1977 ); Mullen & Hellner (1978 ); Akella & Keszler (1994 ). For biological applications of aminoguanadine, see: Makita et al. (1995 ); Brownlee et al. (1986 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

CH₇N₄⁺·C₄H₅O₄⁻
M_r = 192.19
Monoclinic, C 2/c
a = 15.071 (5) Å
b = 6.565 (2) Å
c = 18.152 (5) Å
β = 109.733 (5)°
V = 1690.5 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 (2) K
0.25 × 0.16 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.968, T_max = 0.980
11302 measured reflections
2773 independent reflections
2107 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.135
S = 1.05
2773 reflections
146 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10B⋯O9	0.87 (2)	1.99 (2)	2.851 (1)	171 (2)
N11—H11⋯O8	0.88 (2)	2.07 (2)	2.939 (1)	166 (1)
N12—H12B⋯O6ⁱ	0.85 (2)	2.07 (2)	2.921 (1)	178 (2)
N10—H10A⋯O7ⁱ	0.84 (2)	2.05 (2)	2.886 (1)	178 (2)
O6—H6⋯O8ⁱⁱ	0.82	1.65	2.456 (1)	167
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y-1, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809003626/lx2087sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003626/lx2087Isup2.hkl

checkCIF report

Comment top

Aminoguanadine is an early inhibitor of Advanced Glycosylation End products (AGEs) (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 nucleophilic 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 hydrogensuccinate (I) (Fig. 1).

The aminoguanidinium is nearly planar, with atom N11 shows the maximum deviation from planarity 0.035 (1) Å. The bond lengths in (I) are normal and comparable with the corresponding values observed in the related structure (Akella & Keszler, 1994). The dihedral angle between the aminoguanidinium cation and succinate anion is 3.35 (6)°. Two main motifs dominate the hydrogen bond in (I). Firstly, a nearly symmetrical simple R₂²(8) ring (Bernstein et al., 1995) forms from hydrogen bond between the two molecules involving the two guanidinium amino groups and the two succinate O atoms, viz. N10—H10B···O9 and N11—H11···O8 (Table 1 and Fig. 2). Secondly, atom N12 and N10 in the molecule at (x, y, z) donate one proton each to atom O6 and O7 in the molecule at (-1/2 + x, 1/2 - y, -1/2 + z), generating R₂²(8) ring motif (Table 1 and Fig. 2). Also, the 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); Mullen & Hellner (1978); Akella & Keszler (1994). For biological applications of aminoguanadine, see: Makita et al. (1995); Brownlee et al. (1986). For graph-set notation, see: Bernstein et al. (1995). [Please check rephrasing]

Experimental top

Aminoguanidine bicarbonate (0.136 g; 0.001 mol) was added in small portions with stirring to an aqueous solution (30 ml) of succinic acid (0.118 g; 0.001 mol). The resulting clear solution of pH<2 was concentrated over water-bath to half of its volume. The transparent single crystals suitable for X-ray diffraction obtained by slow evaporation at room temperature were separated, 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, 2003).

Figures top

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

Aminoguanidinium hydrogen succinate top

Crystal data top

CH₇N₄⁺·C₄H₅O₄⁻	F(000) = 816
M_r = 192.19	D_x = 1.510 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 2773 reflections
a = 15.071 (5) Å	θ = 2.4–31.4°
b = 6.565 (2) Å	µ = 0.13 mm⁻¹
c = 18.152 (5) Å	T = 293 K
β = 109.733 (5)°	Block, colourless
V = 1690.5 (9) Å³	0.25 × 0.16 × 0.16 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	2773 independent reflections
Radiation source: fine-focus sealed tube	2107 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 10.0 pixels mm^-1	θ_max = 31.4°, θ_min = 2.4°
ω scans	h = −22→21
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→9
T_min = 0.968, T_max = 0.980	l = −25→26
11302 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0746P)² + 0.4733P] where P = (F_o² + 2F_c²)/3
2773 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

CH₇N₄⁺·C₄H₅O₄⁻	V = 1690.5 (9) Å³
M_r = 192.19	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.071 (5) Å	µ = 0.13 mm⁻¹
b = 6.565 (2) Å	T = 293 K
c = 18.152 (5) Å	0.25 × 0.16 × 0.16 mm
β = 109.733 (5)°

Data collection top

Bruker APEXII CCD diffractometer	2773 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2107 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.980	R_int = 0.021
11302 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.37 e Å⁻³
2773 reflections	Δρ_min = −0.27 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
H12A	0.1707 (12)	1.015 (3)	0.2850 (10)	0.053 (5)*
H12B	0.1337 (11)	0.802 (3)	0.2512 (9)	0.043 (4)*
H13A	0.3357 (16)	1.149 (3)	0.4112 (13)	0.090 (7)*
H13B	0.2620 (13)	1.136 (3)	0.4466 (12)	0.073 (6)*
H10A	0.1961 (13)	0.509 (3)	0.3165 (11)	0.055 (5)*
H10B	0.2701 (11)	0.531 (2)	0.3943 (10)	0.050 (4)*
H11	0.3229 (11)	0.826 (2)	0.4490 (9)	0.047 (4)*
C1	0.54873 (7)	0.08831 (15)	0.67511 (6)	0.0289 (2)
C2	0.47896 (7)	0.20438 (15)	0.61002 (6)	0.0306 (2)
H2A	0.4158	0.1689	0.6083	0.037*
H2B	0.4853	0.1628	0.5607	0.037*
C3	0.49064 (7)	0.43218 (15)	0.61797 (6)	0.0281 (2)
H3A	0.5542	0.4676	0.6209	0.034*
H3B	0.4826	0.4744	0.6666	0.034*
C4	0.42163 (7)	0.54741 (15)	0.55112 (6)	0.0291 (2)
C5	0.22849 (7)	0.78408 (16)	0.34760 (6)	0.0282 (2)
N10	0.23172 (8)	0.58414 (15)	0.35140 (6)	0.0381 (3)
N11	0.28683 (7)	0.88965 (14)	0.40661 (6)	0.0368 (2)
N12	0.16935 (7)	0.87957 (16)	0.28669 (6)	0.0379 (3)
N13	0.27963 (9)	1.10237 (16)	0.40542 (7)	0.0446 (3)
O6	0.54679 (6)	−0.10939 (12)	0.66765 (5)	0.0436 (2)
H6	0.5057	−0.1414	0.6265	0.065*
O7	0.60494 (6)	0.17027 (12)	0.73220 (5)	0.0386 (2)
O8	0.42768 (6)	0.74200 (11)	0.55212 (5)	0.0395 (2)
O9	0.36190 (7)	0.45581 (13)	0.49819 (5)	0.0489 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0314 (5)	0.0199 (4)	0.0270 (5)	−0.0002 (4)	−0.0011 (4)	0.0023 (3)
C2	0.0343 (5)	0.0190 (4)	0.0269 (5)	0.0002 (4)	−0.0052 (4)	0.0028 (3)
C3	0.0326 (5)	0.0185 (4)	0.0239 (4)	0.0009 (3)	−0.0028 (4)	0.0012 (3)
C4	0.0355 (5)	0.0195 (4)	0.0239 (4)	0.0026 (4)	−0.0012 (4)	0.0013 (3)
C5	0.0296 (5)	0.0241 (4)	0.0242 (4)	0.0005 (4)	0.0005 (4)	−0.0018 (3)
N10	0.0454 (6)	0.0221 (4)	0.0325 (5)	0.0001 (4)	−0.0058 (4)	−0.0020 (4)
N11	0.0443 (5)	0.0223 (4)	0.0285 (4)	0.0002 (4)	−0.0076 (4)	−0.0024 (3)
N12	0.0426 (5)	0.0261 (5)	0.0294 (5)	0.0009 (4)	−0.0082 (4)	0.0004 (4)
N13	0.0525 (7)	0.0224 (4)	0.0443 (6)	−0.0012 (4)	−0.0030 (5)	−0.0061 (4)
O6	0.0503 (5)	0.0181 (3)	0.0396 (5)	0.0004 (3)	−0.0147 (4)	0.0026 (3)
O7	0.0420 (5)	0.0250 (4)	0.0317 (4)	−0.0003 (3)	−0.0097 (3)	0.0007 (3)
O8	0.0485 (5)	0.0181 (3)	0.0347 (4)	0.0009 (3)	−0.0085 (3)	0.0027 (3)
O9	0.0592 (6)	0.0258 (4)	0.0348 (4)	0.0000 (4)	−0.0195 (4)	−0.0018 (3)

Geometric parameters (Å, º) top

C1—O7	1.2200 (13)	C5—N12	1.3207 (13)
C1—O6	1.3043 (13)	C5—N11	1.3285 (13)
C1—C2	1.4978 (13)	N10—H10A	0.840 (19)
C2—C3	1.5071 (15)	N10—H10B	0.871 (17)
C2—H2A	0.9700	N11—N13	1.4003 (15)
C2—H2B	0.9700	N11—H11	0.884 (17)
C3—C4	1.5080 (13)	N12—H12A	0.891 (19)
C3—H3A	0.9700	N12—H12B	0.852 (16)
C3—H3B	0.9700	N13—H13A	0.87 (2)
C4—O9	1.2293 (13)	N13—H13B	0.90 (2)
C4—O8	1.2804 (12)	O6—H6	0.8200
C5—N10	1.3144 (15)

O7—C1—O6	120.79 (9)	O8—C4—C3	117.56 (9)
O7—C1—C2	123.16 (9)	N10—C5—N12	121.37 (10)
O6—C1—C2	116.06 (8)	N10—C5—N11	118.42 (10)
C1—C2—C3	113.65 (8)	N12—C5—N11	120.21 (10)
C1—C2—H2A	108.8	C5—N10—H10A	123.2 (12)
C3—C2—H2A	108.8	C5—N10—H10B	116.7 (11)
C1—C2—H2B	108.8	H10A—N10—H10B	119.9 (16)
C3—C2—H2B	108.8	C5—N11—N13	118.76 (9)
H2A—C2—H2B	107.7	C5—N11—H11	120.0 (10)
C2—C3—C4	113.22 (8)	N13—N11—H11	120.6 (10)
C2—C3—H3A	108.9	C5—N12—H12A	119.1 (11)
C4—C3—H3A	108.9	C5—N12—H12B	115.2 (11)
C2—C3—H3B	108.9	H12A—N12—H12B	125.7 (16)
C4—C3—H3B	108.9	N11—N13—H13A	106.3 (15)
H3A—C3—H3B	107.7	N11—N13—H13B	106.1 (13)
O9—C4—O8	121.94 (9)	H13A—N13—H13B	111 (2)
O9—C4—C3	120.50 (9)	C1—O6—H6	109.5

O7—C1—C2—C3	5.34 (16)	C2—C3—C4—O8	−178.55 (10)
O6—C1—C2—C3	−174.44 (10)	N10—C5—N11—N13	−175.87 (12)
C1—C2—C3—C4	178.57 (9)	N12—C5—N11—N13	4.49 (17)
C2—C3—C4—O9	1.74 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10B···O9	0.87 (2)	1.99 (2)	2.851 (1)	171 (2)
N11—H11···O8	0.88 (2)	2.07 (2)	2.939 (1)	166 (1)
N12—H12B···O6ⁱ	0.85 (2)	2.07 (2)	2.921 (1)	178 (2)
N10—H10A···O7ⁱ	0.84 (2)	2.05 (2)	2.886 (1)	178 (2)
O6—H6···O8ⁱⁱ	0.82	1.65	2.456 (1)	167

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

Experimental details

Crystal data
Chemical formula	CH₇N₄⁺·C₄H₅O₄⁻
M_r	192.19
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	15.071 (5), 6.565 (2), 18.152 (5)
β (°)	109.733 (5)
V (Å³)	1690.5 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.25 × 0.16 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.968, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	11302, 2773, 2107
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.732

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.135, 1.05
No. of reflections	2773
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)	0.37, −0.27

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10B···O9	0.87 (2)	1.99 (2)	2.851 (1)	171 (2)
N11—H11···O8	0.88 (2)	2.07 (2)	2.939 (1)	166 (1)
N12—H12B···O6ⁱ	0.85 (2)	2.07 (2)	2.921 (1)	178 (2)
N10—H10A···O7ⁱ	0.84 (2)	2.05 (2)	2.886 (1)	178 (2)
O6—H6···O8ⁱⁱ	0.82	1.65	2.456 (1)	167.1

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

Acknowledgements

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

References

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