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Volume 68 
Part 1 
Pages o18-o19  
January 2012  

Received 18 November 2011
Accepted 28 November 2011
Online 3 December 2011

Key indicators
Single-crystal X-ray study
T = 150 K
Mean [sigma](N-C) = 0.002 Å
R = 0.041
wR = 0.113
Data-to-parameter ratio = 12.5
Details
Open access

1,1-Dimethylbiguanidium(2+) dinitrate

aDepartment of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12843 Prague 2, Czech Republic
Correspondence e-mail: fantom.ag@seznam.cz

In the crystal structure of the title compound, C4H13N52+·2NO3-, the main intermolecular interactions are the N-H...O hydrogen bonds between the cationic amino groups and the O atoms of the nitrate ions. All amino H atoms and nitrate O atoms are involved in the three-dimensional hydrogen-bond network. There are two graph-set motifs R22(8), which include the amino groups connected to the N atoms in the biguanide 3-, 4- and 5-positions, and the O atoms of a nitrate ion. They are extended along the a axis. An O atom of the second nitrate ion is involved in a graph-set motif C(4) that is a part of a helix-like N-H...O...H-N-H...O... chain oriented along the b axis. There are also two weak C-H...O interactions in the crystal structure.

Related literature

For uses of biguanide derivatives in medicine, see: Watkins et al. (1987[Watkins, W. M., Chulay, J. D., Sixsmith, D. G., Spencer, H. C. & Howells, R. E. (1987). J. Pharm. Pharmacol. 39, 261-265.]). For applications of 1,1-dimethylbiguanide, see: Bell & Hadden (1997[Bell, P. M. & Hadden, D. R. (1997). Metformin. Endocrinol. Metab. Clin. North Am. 26, 523-537.]); Hopker (1961[Hopker, W. (1961). Klin. Wochenschr. 39, 588-590.]); Wiernsperger (2000[Wiernsperger, N. F. (2000). Diabetes Technol. Ther. 2, 259-272.]). For 1,1-dimethylbiguanide in metal complexes, see: Gheorghiu (1969[Gheorghiu, C. (1969). Z. Anorg. Allg. Chem. 365, 91-99.]); Marchi et al. (1999[Marchi, A., Marvelli, L., Cattabriga, M., Rossi, R., Neves, M., Bertolasi, V. & Ferretti, V. (1999). J. Chem. Soc. Dalton Trans. pp. 1937-1944.]); Spacu & Gheorghiu (1968[Spacu, P. & Gheorghiu, C. (1968). J. Less Common Met. 15, 331-339.], 1969[Spacu, P. & Gheorghiu, C. (1969). J. Less Common Met. 18, 117-122.]); Viossat et al. (1995[Viossat, B., Tomas, A. & Dung, N.-H. (1995). Acta Cryst. C51, 213-215.]); Zhu et al. (2002[Zhu, M., Lu, L., Yang, P. & Jin, X. (2002). Acta Cryst. E58, m217-m219.]). For related structures of monocation salts, see: Hariharan et al. (1989[Hariharan, M., Rajan, S. S. & Srinivasan, R. (1989). Acta Cryst. C45, 911-913.]); He et al. (2002[He, Z., Zhu, M. & Ma, G. (2002). Acta Cryst. E58, m647-m649.]); Huang et al. (2008[Huang, L., Xi, P., Xu, M., Liu, T. & Zeng, Z. (2008). Anal. Sci. X-Ray Struct. Anal. Online, 24, x289-x290.]); Lu et al. (2004a[Lu, L., Zhang, H., Feng, S. & Zhu, M. (2004a). Acta Cryst. E60, o640-o641.]); Zhu et al. (2003[Zhu, M., Lu, L. & Yang, P. (2003). Acta Cryst. E59, o586-o588.]). For related structures of dication salts, see: Lemoine et al. (1994[Lemoine, P., Tomas, A., Viossat, B. & Dung, N.-H. (1994). Acta Cryst. C50, 1437-1439.]); Lu et al. (2004b[Lu, L.-P., Zhang, H.-M., Feng, S.-S. & Zhu, M.-L. (2004b). Acta Cryst. C60, o740-o743.]). For related salt materials, see: Fridrichová et al. (2010[Fridrichová, M., Nemec, I., Císarová, I. & Nemec, P. (2010). CrystEngComm, 12, 2054-2056.]); Matulková et al. (2011[Matulková, I., Císarová, I. & Nemec, I. (2011). Acta Cryst. E67, o118-o119.]). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]). For details of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • C4H13N52+·2NO3-

  • Mr = 255.21

  • Monoclinic, P 21 /c

  • a = 7.7850 (2) Å

  • b = 5.7313 (2) Å

  • c = 26.5321 (7) Å

  • [beta] = 101.6020 (15)°

  • V = 1159.63 (6) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.13 mm-1

  • T = 150 K

  • 0.4 × 0.3 × 0.18 mm

Data collection
  • Nonius KappaCCD area-detector diffractometer

  • 13222 measured reflections

  • 2228 independent reflections

  • 1913 reflections with I > 2[sigma](I)

  • Rint = 0.050

Refinement
  • R[F2 > 2[sigma](F2)] = 0.041

  • wR(F2) = 0.113

  • S = 1.08

  • 2228 reflections

  • 178 parameters

  • 7 restraints

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

  • [Delta][rho]max = 0.19 e Å-3

  • [Delta][rho]min = -0.24 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N1-H12...O2 0.89 (1) 2.06 (2) 2.9158 (17) 160 (2)
N1-H12...O1 0.89 (1) 2.57 (2) 3.3151 (17) 142 (1)
N1-H11...O5 0.88 (1) 2.09 (2) 2.9463 (16) 164 (2)
N1-H11...O4 0.88 (1) 2.57 (2) 3.2920 (17) 140 (1)
N2-H21...O4 0.84 (1) 2.15 (2) 2.9571 (18) 161 (2)
N2-H21...O4i 0.84 (1) 2.56 (2) 3.0833 (17) 122 (2)
N2-H22...O6ii 0.87 (1) 2.15 (2) 2.9674 (18) 157 (2)
N2-H22...O6i 0.87 (1) 2.64 (2) 3.2503 (18) 128 (2)
N3-H3...O5ii 0.85 (1) 2.05 (2) 2.8479 (16) 157 (2)
N3-H3...O6ii 0.85 (1) 2.59 (2) 3.2947 (17) 142 (2)
N4-H42...O3iii 0.85 (1) 2.17 (2) 2.9300 (18) 149 (2)
N4-H42...O1iii 0.85 (1) 2.34 (2) 3.1164 (18) 153 (2)
N4-H41...O3iv 0.89 (1) 1.97 (2) 2.8487 (17) 170 (2)
C3-H3B...O2ii 0.98 2.42 3.255 (2) 143
C4-H4A...O6v 0.98 2.55 3.519 (2) 170
Symmetry codes: (i) -x+1, -y, -z; (ii) x-1, y, z; (iii) x, y-1, z; (iv) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (v) -x+1, -y+1, -z.

Data collection: COLLECT (Hooft, 1998[Hooft, R. (1998). COLLECT. Nonius BV, Delft, the Netherlands.]) and DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZQ2139 ).


Acknowledgements

This work was supported by the Grant Agency of Charles University in Prague (grant No. 58608), the Czech Science Foundation (grant No. 203/09/0878) and it is a part of the long term Research Plan of the Ministry of Education of the Czech Republic (No. MSM0021620857). We would like to thank Dr Jan Fábry for his careful supervision and inspiring critique.

References

Allen, F. H. (2002). Acta Cryst. B58, 380-388.  [ISI] [CrossRef] [details]
Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.  [CrossRef] [ISI] [details]
Bell, P. M. & Hadden, D. R. (1997). Metformin. Endocrinol. Metab. Clin. North Am. 26, 523-537.  [CrossRef] [ChemPort]
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.  [CrossRef] [ISI] [details]
Fridrichová, M., Nemec, I., Císarová, I. & Nemec, P. (2010). CrystEngComm, 12, 2054-2056.
Gheorghiu, C. (1969). Z. Anorg. Allg. Chem. 365, 91-99.  [CrossRef] [ChemPort]
Hariharan, M., Rajan, S. S. & Srinivasan, R. (1989). Acta Cryst. C45, 911-913.  [CrossRef] [details]
He, Z., Zhu, M. & Ma, G. (2002). Acta Cryst. E58, m647-m649.  [CSD] [CrossRef] [details]
Hooft, R. (1998). COLLECT. Nonius BV, Delft, the Netherlands.
Hopker, W. (1961). Klin. Wochenschr. 39, 588-590.  [PubMed] [ChemPort] [ISI]
Huang, L., Xi, P., Xu, M., Liu, T. & Zeng, Z. (2008). Anal. Sci. X-Ray Struct. Anal. Online, 24, x289-x290.
Lemoine, P., Tomas, A., Viossat, B. & Dung, N.-H. (1994). Acta Cryst. C50, 1437-1439.  [CrossRef] [details]
Lu, L., Zhang, H., Feng, S. & Zhu, M. (2004a). Acta Cryst. E60, o640-o641.  [CSD] [CrossRef] [details]
Lu, L.-P., Zhang, H.-M., Feng, S.-S. & Zhu, M.-L. (2004b). Acta Cryst. C60, o740-o743.  [CSD] [CrossRef] [details]
Marchi, A., Marvelli, L., Cattabriga, M., Rossi, R., Neves, M., Bertolasi, V. & Ferretti, V. (1999). J. Chem. Soc. Dalton Trans. pp. 1937-1944.  [CSD] [CrossRef]
Matulková, I., Císarová, I. & Nemec, I. (2011). Acta Cryst. E67, o118-o119.  [CrossRef] [details]
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Spacu, P. & Gheorghiu, C. (1968). J. Less Common Met. 15, 331-339.  [ChemPort]
Spacu, P. & Gheorghiu, C. (1969). J. Less Common Met. 18, 117-122.  [ChemPort]
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [ISI] [CrossRef] [details]
Viossat, B., Tomas, A. & Dung, N.-H. (1995). Acta Cryst. C51, 213-215.  [CrossRef] [details]
Watkins, W. M., Chulay, J. D., Sixsmith, D. G., Spencer, H. C. & Howells, R. E. (1987). J. Pharm. Pharmacol. 39, 261-265.  [CrossRef] [ChemPort] [PubMed]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [ISI] [CrossRef] [ChemPort] [details]
Wiernsperger, N. F. (2000). Diabetes Technol. Ther. 2, 259-272.  [CrossRef] [PubMed] [ChemPort]
Zhu, M., Lu, L. & Yang, P. (2003). Acta Cryst. E59, o586-o588.  [CSD] [CrossRef] [details]
Zhu, M., Lu, L., Yang, P. & Jin, X. (2002). Acta Cryst. E58, m217-m219.  [CSD] [CrossRef] [details]


Acta Cryst (2012). E68, o18-o19   [ doi:10.1107/S1600536811051105 ]

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