organic compounds
Aminoguanidinium hydrogen succinate
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
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
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell 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
10.1107/S1600536809003626/lx2087sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809003626/lx2087Isup2.hkl
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.
All N bound H atoms were located in a difference map and refined freely. All other H atoms were fixed geometrically and allowed to ride on their parent atoms, with O—H = 0.82 Å and C—H = 0.97 Å with Uiso(H)=
1.2Ueq.
Data collection: APEX2 (Bruker, 2004); cell
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).CH7N4+·C4H5O4− | F(000) = 816 |
Mr = 192.19 | Dx = 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 |
Bruker APEXII CCD diffractometer | 2773 independent reflections |
Radiation source: fine-focus sealed tube | 2107 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 10.0 pixels mm-1 | θmax = 31.4°, θmin = 2.4° |
ω scans | h = −22→21 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→9 |
Tmin = 0.968, Tmax = 0.980 | l = −25→26 |
11302 measured reflections |
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(Fo2) + (0.0746P)2 + 0.4733P] where P = (Fo2 + 2Fc2)/3 |
2773 reflections | (Δ/σ)max < 0.001 |
146 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
CH7N4+·C4H5O4− | V = 1690.5 (9) Å3 |
Mr = 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)° |
Bruker APEXII CCD diffractometer | 2773 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2107 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.980 | Rint = 0.021 |
11302 measured reflections |
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 | Δρmax = 0.37 e Å−3 |
2773 reflections | Δρmin = −0.27 e Å−3 |
146 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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− |
Mr | 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) |
Tmin, Tmax | 0.968, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11302, 2773, 2107 |
Rint | 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 |
Δρmax, Δρmin (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).
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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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.