Propane-1,3-diaminium–2-carboxy­pyridine-6-carboxyl­ate–pyridine-2,6-dicarboxylic acid–water (1/2/2/8)

Janet Soleimannejad; Hossein Aghabozorg; Elham Motyeian; Mohammad Ghadermazi; Jafar Attar Gharamaleki; Harry Adams

doi:10.1107/S1600536807065270

. 2007 Dec 12;64(Pt 1):o231–o232. doi: 10.1107/S1600536807065270

Propane-1,3-diaminium–2-carboxypyridine-6-carboxylate–pyridine-2,6-dicarboxylic acid–water (1/2/2/8)

Janet Soleimannejad ^a, Hossein Aghabozorg ^b,^*, Elham Motyeian ^b, Mohammad Ghadermazi ^c, Jafar Attar Gharamaleki ^b, Harry Adams ^d

PMCID: PMC2915292 PMID: 21200799

Abstract

The title proton-transfer compound, C₃H₁₂N₂ ²⁺·2C₇H₄NO₄ ⁻·2C₇H₅NO₄·8H₂O or (pnH₂)(pydcH)₂.2(pydcH₂)·8H₂O, was obtained by the reaction of pyridine-2,6-dicarboxylic acid (pydcH₂) and propane-1,3-diamine (pn) in aqueous solution. Both neutral and monoanionic forms of the diacid are observed in the crystal structure. The negative charge of two monoanions is balanced by the dicationic propane-1,3-diaminium species. In addition, considerable π–π stacking interactions between the aromatic rings of the (pydcH)⁻ and (pydcH₂) fragments [with centroid–centroid distances of 3.5108 (11)–3.5949 (11) Å] are observed. The most important feature of this crystal structure is the presence of a large number of O—H⋯O, O—H⋯N, N—H⋯O, N—H⋯N, C—H⋯O and C—H⋯N hydrogen bonds, with D⋯A ranging from 2.445 (2) to 3.485 (3) Å. These interactions as well as ion pairing and π–π stacking connect the various fragments into a supramolecular structure.

Related literature

For related literature, see: Aghabozorg, Attar Gharamaleki, Ghadermazi, Ghasemikhah & Soleimannejad (2007 ▶); Aghabozorg, Attar Gharamaleki, Ghasemikhah, Ghadermazi & Soleimannejad, 2007 ▶; Aghabozorg, Daneshvar et al. (2007 ▶).

Experimental

Crystal data

C₃H₁₂N₂ ²⁺·2C₇H₄NO₄ ⁻·2C₇H₅NO₄·8H₂O
M _r = 886.73
Monoclinic,
a = 13.5425 (2) Å
b = 13.5237 (2) Å
c = 21.7538 (3) Å
β = 99.914 (1)°
V = 3924.60 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 150 (2) K
0.26 × 0.12 × 0.12 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.967, T _max = 0.985
56174 measured reflections
9031 independent reflections
6702 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.139
S = 1.02
9031 reflections
550 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 2005 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807065270/bq2048sup1.cif

e-64-0o231-sup1.cif^{(31.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065270/bq2048Isup2.hkl

e-64-0o231-Isup2.hkl^{(337.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O19	0.95	1.94	2.830 (2)	154
O5—H5AA⋯O20	0.95	1.67	2.592 (2)	164
O7—H7A⋯O3	0.95	1.51	2.455 (2)	177
O7—H7A⋯O4	0.95	2.57	3.119 (2)	117
O9—H9A⋯O22	0.95	1.64	2.588 (2)	172
O11—H11A⋯O13ⁱ	0.95	1.50	2.445 (2)	177
O11—H11A⋯O14ⁱ	0.95	2.61	3.181 (2)	119
O16—H16A⋯O24	0.95	1.60	2.551 (2)	174
O17—H17A⋯O15	0.95	1.90	2.838 (2)	167
O17—H17A⋯N4	0.95	2.43	2.956 (2)	115
O17—H17B⋯O14	0.95	1.87	2.821 (2)	175
O18—H18B⋯O1	0.95	1.89	2.815 (2)	164
O18—H18A⋯O17ⁱⁱ	0.95	1.88	2.809 (2)	166
O19—H19B⋯N1	0.95	2.22	3.092 (2)	152
O19—H19A⋯O13ⁱ	0.95	2.34	3.174 (2)	146
O20—H20B⋯O12ⁱⁱⁱ	0.95	1.87	2.793 (2)	164
O20—H20A⋯O22	0.95	1.95	2.875 (3)	165
O21—H21B⋯O10	0.95	1.89	2.834 (2)	170
O21—H21A⋯O19ⁱⁱⁱ	0.95	1.85	2.784 (2)	166
O22—H22A⋯O21	0.95	1.88	2.818 (2)	168
O22—H22B⋯O17^iv	0.95	1.81	2.742 (2)	167
O23—H23B⋯O6	0.95	1.85	2.749 (2)	157
O23—H23A⋯O12ⁱⁱⁱ	0.95	1.96	2.899 (2)	170
O24—H24B⋯O18^v	0.95	1.79	2.706 (2)	161
O24—H24A⋯O12^vi	0.95	1.86	2.761 (2)	157
N5—H5A⋯N2	0.95	2.40	3.342 (3)	171
N5—H5A⋯O6	0.95	2.61	3.227 (2)	123
N5—H5B⋯O4	0.95	1.95	2.879 (2)	166
N5—H5C⋯O23^vii	0.95	2.06	2.991 (3)	166
N6—H6A⋯O14ⁱ	0.95	2.01	2.938 (2)	164
N6—H6B⋯O21^viii	0.95	1.90	2.849 (2)	174
N6—H6C⋯N3	0.95	2.17	3.070 (2)	158
C5—H5⋯O18ⁱⁱⁱ	0.95	2.56	3.429 (3)	153
C10—H10⋯O1^ix	0.95	2.50	3.335 (3)	147
C11—H11⋯O18^ix	0.95	2.52	3.427 (3)	159
C19—H19⋯O15^x	0.95	2.46	3.266 (3)	143
C25—H25⋯O24^xi	0.95	2.56	3.485 (3)	165
C26—H26⋯O16^xi	0.95	2.56	3.287 (3)	134
C31—H31A⋯N2	0.99	2.52	3.391 (3)	146
C31—H31B⋯O10	0.99	2.54	3.175 (3)	122

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) .

Acknowledgments

Financial support from Ilam University and the Teacher Training University is gratefully acknowledged.

supplementary crystallographic information

Comment

Intermolecular interactions, such as hydrogen bonding, π-π stacking, ion pairing and donor-acceptor interactions, are famous for making aggregates of molecules. Hydrogen bonding has been described as the most important interaction in supramolecular chemistry. Dicarboxylic acids possess a good potential to be used as proton donors in the synthesis of proton transfer compounds. Among these diacids, pyridine-2,6-dicarboxylic acid has been used by our research group for preparing of such compounds. For example, (pydaH)(pydcH) in which pyridine-2,6-diamine (pyda) was used as a proton acceptor. The resulting compounds with some remaining sites as electron donors can coordinate to metallic ions (Aghabozorg, Attar Gharamaleki, Ghadermazi, Ghasemikhah & Soleimannejad, 2007; Aghabozorg, Attar Gharamaleki, Ghasemikhah, Ghadermazi & Soleimannejad, 2007; Aghabozorg, Daneshvar et al., 2007).

Here we report a new proton transfer compound obtained from (pydcH₂) as a proton donor and propane-1,3-diamine (pn) as an acceptor. The molecular structure of the title compound is shown in Fig. 1. The intermolecular hydrogen bond distances are listed in Table 1.

The structure of this compound contains two neutral pydcH₂ molecules, two monoanionic (pydcH)^-, one (pnH₂)²⁺ species and eight uncoordinated water molecules. The negative charge of two monoanions is neutralized by dicationic propane-1,3-diaminium fragments.

A considerable π-π stacking interactions between aromatic rings of (pydcH₂) and (pydcH)^- fragments with centroid-centroid distances of 3.5108 (11)–3.5949 (11) Å are observed in the prepared compound (Fig. 2). A remarkable feature in the crystal structure of compound (I) is the presence of a large number of O—H···O, O—H···N, N—H···O, N—H···N, C—H···O and C—H···N hydrogen bonds interactions ranging from 2.450 (2) to 3.488 (3) Å. The shortest hydrogen bond is O11—H11A···O13 (-x + 1, y + 1/2, -z + 1/2) with D···A = 2.450 (2) Å, a very strong interaction (Table 1). These extensive hydrogen bond interactions as well as ion pairing and π-π stacking connect the different components to form a three-dimensional supramolecular structure (Fig. 3).

Experimental

The reaction of pyridine-2,6-dicarboxylic acid (pydcH₂) (330 mg, 2 mmol) with propane-1,3-diamine (pn) (76 mg, 1 mmol) in a 2:1 molar ratio in tetrahydrofuran (THF) led to the formation of a white precipitate which was filtered off and dried. The resulting powder was dissolved in water to give colorless crystals of the title compound after four weeks.