1,10-Phenanthrolin-1-ium hydrogen d,l-tartrate dihydrate

Sit Foon Cheng; Seik Weng Ng

doi:10.1107/S1600536811015972

. 2011 May 7;67(Pt 6):o1306. doi: 10.1107/S1600536811015972

1,10-Phenanthrolin-1-ium hydrogen d,l-tartrate dihydrate

Sit Foon Cheng ^a, Seik Weng Ng ^a,^*

PMCID: PMC3120439 PMID: 21754708

Abstract

In the title hydrated molecular salt, C₁₂H₉N₂ ⁺·C₄H₅O₆ ⁻·2H₂O, the cation is almost planar (r.m.s. deviation = 0.014 Å); the carbon skeleton of the anion assumes a trans conformation [C—C—C—C torsion angle = −179.86 (14)°]. The carboxyl end of one hydrogen tartrate anion forms a short hydrogen bond to the carboxylate end of another anion [O⋯O = 2.508 (2) Å] in a head-to-tail manner, forming a chain; the chains and water molecules interact, generating an O—H⋯O hydrogen-bonded layer. The cation binds to the layer by an N—H⋯O hydrogen bond.

Related literature

For the trihydrated 1,10-phenanthrolin-1-ium salts of d- and l-tartaric acid, see: Derikvand & Olmstead (2010 ▶); Wang et al. (2006 ▶).

Experimental

Crystal data

C₁₂H₉N₂ ⁺·C₄H₅O₆ ⁻·2H₂O
M _r = 366.32
Triclinic,
a = 7.0933 (7) Å
b = 10.5849 (11) Å
c = 11.4694 (11) Å
α = 98.081 (1)°
β = 100.350 (1)°
γ = 103.903 (1)°
V = 806.95 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.40 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
7610 measured reflections
3635 independent reflections
2880 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.160
S = 1.04
3635 reflections
267 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015972/bt5536sup1.cif

e-67-o1306-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015972/bt5536Isup2.hkl

e-67-o1306-Isup2.hkl^{(178.2KB, 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
O3—H3⋯O1wⁱ	0.89 (3)	1.82 (3)	2.709 (2)	175 (3)
O4—H4⋯O2wⁱⁱ	0.90 (3)	1.84 (3)	2.739 (2)	172 (3)
O5—H5⋯O2ⁱⁱⁱ	0.99 (3)	1.52 (3)	2.508 (2)	169 (3)
O1w—H12⋯O1	0.93 (3)	1.97 (3)	2.846 (2)	157 (3)
O1w—H11⋯O1^iv	0.90 (4)	1.86 (4)	2.753 (2)	173 (4)
O2w—H21⋯O2	0.84 (4)	1.93 (4)	2.764 (2)	168 (3)
O2w—H22⋯O6^v	0.87 (3)	1.97 (3)	2.835 (2)	176 (3)
N1—H1⋯O1w	0.93 (3)	1.89 (3)	2.753 (2)	153 (3)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

We thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

D-tartaric acid transfers one proton to 1,10-phenanthroline to yield 1,10-phenanthroline hydrogen D-tartrate, which separates from solution as a trihydrate. The hydrogen D-tartrate anions are connected in a head-to-tail fashion by an O–H_{carboxylic acid}···O_carboxyl hydrogen bond [O···O 2.455 (1) Å] (Derikvand & Olmstead, 2010). The identical feature should be presented in the L analog (Wang et al., 2006). The anion and water molecules are linked by extensive O–H···O hydrogen bonds into a three-dimensional network, with the cations occupying the cavities. Racemic tartaric furnishes the corresponding dihydrate. In C₁₂H₉N₂⁺ C₄H₅O₄^-.2H₂O (Scheme I, Fig. 1), the carboxylic acid –CO₂H end of one hydrogen (D,L)-tartrate anion forms a short hydrogen bond to the carboxylate –CO₂^- end of another anion [O···O 2.508 (2) Å] in a head-to-tail manner to form a chain; the chains and water molecules interact to generate an O–H···O hydrogen-bonded layer. The cation binds to the layer by an N–H···O hydrogen bond (Table 1).

Experimental

D,L-Tartaric acid (2 mmol, 0.30 g) and 1,10-phenanthroline (0.33 mmol, 0.06 g) were dissolved in water (5 ml). The solution was heated briefly to dissolve the reactants. The solution was set aside for the growth of colorless crystals, which were isolated after 10 days. The bulk crystals were faintly tinted a shade of pink.