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Volume 68 
Part 12 
Pages o3321-o3322  
December 2012  

Received 22 October 2012
Accepted 2 November 2012
Online 10 November 2012

Key indicators
Single-crystal X-ray study
T = 100 K
Mean [sigma](C-C) = 0.002 Å
R = 0.042
wR = 0.127
Data-to-parameter ratio = 21.6
Details
Open access

Bis(2,6-diamino-4-chloropyrimidin-1-ium) fumarate

In the title salt, 2C4H6ClN4+·C4H2O42-, the complete fumarate dianion is generated by crystallographic inversion symmetry. The cation is essentially planar, with a maximum deviation of 0.018 (1) Å. In the anion, the carboxylate group is twisted slightly away from the attached plane, the dihedral angle between the carboxylate and (E)-but-2-ene planes being 12.78 (13)°. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxylate O atoms of the anion via a pair of N-H...O hydrogen bonds, forming an R22(8) ring motif. In addition, another type of R22(8) motif is formed by centrosymmetrically related pyrimidinium cations via N-H...N hydrogen bonds. These two combined motifs form a heterotetramer. The crystal structure is further stabilized by stong N-H...O, N-H...Cl and weak C-H...O hydrogen bonds, resulting a three-dimensional network.

Related literature

For applications of pyrimidine derivatives, see: Condon et al. (1993[Condon, M. E., Brady, T. E., Feist, D., Malefyt, T., Marc, P., Quakenbush, L. S., Rodaway, S. J., Shaner, D. L. & Tecle, B. (1993). Brighton Crop Protection Conference on Weeds, pp. 41-46. Alton, Hampshire, England: BCPC Publications.]); Maeno et al. (1990[Maeno, S., Miura, I., Masuda, K. & Nagata, T. (1990). Brighton Crop Protection Conference on Pests and Diseases, pp. 415-422. Alton, Hampshire, England: BCPC Publications.]); Gilchrist (1997[Gilchrist, T. L. (1997). Heterocyclic Chemistry, 3rd ed., pp. 261-276. Singapore: Addison Wesley Longman.]). For details of fumaric acid, see: Batchelor et al. (2000[Batchelor, E., Klinowski, J. & Jones, W. (2000). J. Mater. Chem. 10, 839-848.]). For hydrogen-bonded synthons, see: Thakur & Desiraju (2008[Thakur, T. S. & Desiraju, G. R. (2008). Cryst. Growth Des. 8, 4031-4044.]). For hydrogen-bond motifs, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). For stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986[Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105-107.]).

[Scheme 1]

Experimental

Crystal data
  • C4H6ClN4+·0.5C4H2O42-

  • Mr = 202.61

  • Monoclinic, P 21 /c

  • a = 5.4478 (7) Å

  • b = 10.5187 (14) Å

  • c = 14.8171 (18) Å

  • [beta] = 100.990 (4)°

  • V = 833.50 (18) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.43 mm-1

  • T = 100 K

  • 0.71 × 0.31 × 0.17 mm

Data collection
  • Bruker SMART APEXII DUO CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2009[Bruker (2009). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.749, Tmax = 0.931

  • 9206 measured reflections

  • 2984 independent reflections

  • 2708 reflections with I > 2[sigma](I)

  • Rint = 0.033

Refinement
  • R[F2 > 2[sigma](F2)] = 0.042

  • wR(F2) = 0.127

  • S = 1.08

  • 2984 reflections

  • 138 parameters

  • 1 restraint

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

  • [Delta][rho]max = 0.78 e Å-3

  • [Delta][rho]min = -0.78 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
N2-H1...O2i 0.86 (1) 1.69 (1) 2.5281 (14) 165 (3)
N3-H2...O1i 0.81 (2) 2.12 (2) 2.9233 (15) 168 (2)
N3-H3...N1ii 0.85 (2) 2.15 (2) 3.0014 (16) 176 (2)
N4-H4...O1iii 0.78 (2) 2.08 (2) 2.8307 (16) 161 (2)
N4-H5...Cl1iv 0.77 (2) 2.78 (2) 3.3671 (13) 135.0 (19)
N4-H5...O2i 0.77 (2) 2.56 (2) 3.1458 (15) 134.2 (19)
C3-H3A...O2v 0.95 2.39 3.3085 (16) 162
Symmetry codes: (i) [x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (ii) -x+1, -y+1, -z+2; (iii) x+1, y, z; (iv) [-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (v) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2009[Bruker (2009). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ5019 ).


Acknowledgements

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the research facilities and Fundamental Research Grant Scheme (FRGS) No. 203/PFIZIK/6711171 to conduct this work. KT thanks The Academy of Sciences for the Developing World and USM for a TWAS-USM fellowship.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.
Batchelor, E., Klinowski, J. & Jones, W. (2000). J. Mater. Chem. 10, 839-848.  [ISI] [CSD] [CrossRef] [ChemPort]
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.  [CrossRef] [ChemPort] [ISI]
Bruker (2009). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Condon, M. E., Brady, T. E., Feist, D., Malefyt, T., Marc, P., Quakenbush, L. S., Rodaway, S. J., Shaner, D. L. & Tecle, B. (1993). Brighton Crop Protection Conference on Weeds, pp. 41-46. Alton, Hampshire, England: BCPC Publications.
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105-107.  [CrossRef] [ChemPort] [ISI] [details]
Gilchrist, T. L. (1997). Heterocyclic Chemistry, 3rd ed., pp. 261-276. Singapore: Addison Wesley Longman.
Maeno, S., Miura, I., Masuda, K. & Nagata, T. (1990). Brighton Crop Protection Conference on Pests and Diseases, pp. 415-422. Alton, Hampshire, England: BCPC Publications.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [ISI] [CrossRef] [details]
Thakur, T. S. & Desiraju, G. R. (2008). Cryst. Growth Des. 8, 4031-4044.  [CSD] [CrossRef] [ChemPort]


Acta Cryst (2012). E68, o3321-o3322   [ doi:10.1107/S1600536812045308 ]

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