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Volume 69 
Part 10 
Pages o1506-o1507  
October 2013  

Received 10 August 2013
Accepted 21 August 2013
Online 4 September 2013

Key indicators
Single-crystal X-ray study
T = 98 K
Mean [sigma](C-C) = 0.005 Å
Disorder in main residue
R = 0.065
wR = 0.166
Data-to-parameter ratio = 14.1
Details
Open access

The co-crystal N,N'-bis[(pyridin-1-ium-2-yl)methyl]ethanedithioamide bis(2,6-dinitrobenzoate)-2,6-dinitrobenzoic acid (1/4)

aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA,bChemical Abstracts Service, 2540 Olentangy River Rd, Columbus, Ohio 43202, USA, and cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
Correspondence e-mail: edward.tiekink@gmail.com

The asymmetric unit of title co-crystal, C14H16N4S22+·2C7H3N2O6-·4C7H4N2O6, comprises a centrosymmetric dipyridinium dication, a 2,6-dinitrobenzoate anion and two independent 2,6-dinitrobenzoic acid molecules. The pyridinium rings are each approximately perpendicular to the central dithioamide unit [dihedral angle = 80.67 (12)°]. The carboxylate/carboxylic acid groups are approximately perpendicular to the benzene ring to which they are attached [dihedral angles = 78.85 (16), 81.46 (19) and 71.28 (15)°]. By contrast, the major twist exhibited by a nitro group is manifested in a dihedral angle of 32.66 (17)°. The most prominent feature of the crystal packing is linear supramolecular chains along [1-10], featuring O-H...O(carboxylate) and pyridinium-N-H...O hydrogen bonds. These are consolidated into a three-dimensional architecture by thioamide-nitro N-H...O, C-H...O and [pi]-[pi] [inter-centroid distance = 3.524 (2) Å] interactions. One of the nitro O atoms was refined over two sites; the major site was 0.65 (7) occupied.

Related literature

For the 2:1 salts of 2,6-dinitrobenzoate with isomeric n-({[(pyridin-1-ium-n-ylmethyl)carbamoyl]formamido}methyl)pyridin-1-ium, n = 2, 3 and 4, see: Arman et al. (2013[Arman, H. D., Miller, T. & Tiekink, E. R. T. (2013). Z. Kristallogr. Cryst. Mat. 228, 295-303.]). For co-crystals of 4-nitrophenylacetic acid with N,N'-bis(pyridin-3-ylmethyl)oxalamide and the thioxalamide analogue, see: Arman et al. (2012[Arman, H. D., Miller, T., Kaulgud, T., Poplaukhin, P. & Tiekink, E. R. T. (2012). J. Chem. Crystallogr. 42, 673-679.]).

[Scheme 1]

Experimental

Crystal data
  • C14H16N4S22+·2C7H3N2O6-·4C7H4N2O6

  • Mr = 1575.14

  • Triclinic, [P \overline 1]

  • a = 11.157 (2) Å

  • b = 11.524 (3) Å

  • c = 14.967 (4) Å

  • [alpha] = 79.601 (18)°

  • [beta] = 72.859 (17)°

  • [gamma] = 61.237 (12)°

  • V = 1610.3 (7) Å3

  • Z = 1

  • Mo K[alpha] radiation

  • [mu] = 0.20 mm-1

  • T = 98 K

  • 0.35 × 0.10 × 0.09 mm

Data collection
  • Rigaku AFC12/SATURN724 diffractometer

  • 10659 measured reflections

  • 7317 independent reflections

  • 5680 reflections with I > 2[sigma](I)

  • Rint = 0.040

  • Standard reflections: 0

Refinement
  • R[F2 > 2[sigma](F2)] = 0.065

  • wR(F2) = 0.166

  • S = 1.06

  • 7317 reflections

  • 518 parameters

  • 4 restraints

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

  • [Delta][rho]max = 1.01 e Å-3

  • [Delta][rho]min = -0.50 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
O2-H1o...O13i 0.84 (3) 1.70 (3) 2.536 (3) 169 (5)
O8-H2o...O14 0.85 (3) 1.70 (3) 2.546 (3) 178 (4)
N1-H1n...O14 0.88 (3) 1.86 (3) 2.733 (3) 171 (3)
N2-H2n...O15ii 0.88 (3) 2.53 (3) 3.202 (3) 134 (2)
C3-H3...O18iii 0.95 2.39 3.141 (5) 136
C12-H12...O16iv 0.95 2.41 3.301 (4) 157
C25-H25...O10iv 0.95 2.38 3.078 (5) 130
Symmetry codes: (i) x-1, y+1, z; (ii) -x+1, -y, -z+1; (iii) -x+2, -y, -z+1; (iv) -x+1, -y, -z.

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005[Molecular Structure Corporation & Rigaku (2005). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]) 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: XU5732 ).


Acknowledgements

We gratefully thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/03).

References

Arman, H. D., Miller, T., Kaulgud, T., Poplaukhin, P. & Tiekink, E. R. T. (2012). J. Chem. Crystallogr. 42, 673-679.  [Web of Science] [CSD] [CrossRef]
Arman, H. D., Miller, T. & Tiekink, E. R. T. (2013). Z. Kristallogr. Cryst. Mat. 228, 295-303.  [CrossRef] [ChemPort]
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Molecular Structure Corporation & Rigaku (2005). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]


Acta Cryst (2013). E69, o1506-o1507   [ doi:10.1107/S1600536813023490 ]

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