Acridine 0.75-hydrate

Einat Schur; Joel Bernstein; Andreas Lemmerer; Radion Vainer

doi:10.1107/S1600536811038220

. 2011 Sep 30;67(Pt 10):o2761. doi: 10.1107/S1600536811038220

Acridine 0.75-hydrate

Einat Schur ^a,^*, Joel Bernstein ^a, Andreas Lemmerer ^a, Radion Vainer ^a

PMCID: PMC3201491 PMID: 22064774

Abstract

The title compound, C₁₃H₉N·0.75H₂O was obtained during a study of the polymorphic system of acridine, by slow evaporation from an ethanol–water solution. There are two acridine molecules (indicated by I and II, respectively) and one and a half water molecules in the asymmetric unit. The half-molecule of water is located on a crystallographic twofold axis. The crystal structure is built up from two threads of molecule II sewn together with water molecules through O—H⋯O and O—H⋯N hydrogen bonds from one side and with π–π interactions [centroid–centroid distance = 3.640 (3) and 3.7431 (3) Å] between overlapping molecules II on the other side. Molecule I is attached to this thread from both sides by C—H⋯O hydrogen bonds. The threads are connected to each other by π–π interactions [centroid–centroid distances = 3.582 (3) and 3.582 (3) Å] between the inner side of molecule I and stabilized by a C—H⋯π interaction on the other side of molecule I. This thread with rows of molecule I hanging on its sides is generated by translation perpendicular to the a axis.

Related literature

For the five anhydrous polymorphs of acridine, see: Phillips (1954 ▶, 1956 ▶), Phillips et al. (1960 ▶) and Mei & Wolf (2004 ▶) for monoclinic forms VI and VII, and Braga et al. (2010 ▶) for orthorhombic form IV and monoclinic forms II and III. For further crystallographic studies of acridine hydrate, see: Groth (1919 ▶); Lowde et al. (1953 ▶).

Experimental

Crystal data

C₁₃H₉N·0.75H₂O
M _r = 192.71
Orthorhombic,
a = 26.400 (5) Å
b = 8.893 (5) Å
c = 17.492 (5) Å
V = 4107 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 197 K
0.3 × 0.3 × 0.3 mm

Data collection

Bruker SMART 6000 diffractometer
14504 measured reflections
3606 independent reflections
1733 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.197
S = 1.00
3606 reflections
272 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811038220/ez2255sup1.cif

e-67-o2761-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038220/ez2255Isup2.hkl

e-67-o2761-Isup2.hkl^{(176.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038220/ez2255Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C1/C6–C8/C13/N1 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯N2	0.933 (3)	1.942 (2)	2.873 (4)	175.2 (2)
C7—H7⋯O1	0.93	2.35	3.271 (4)	171
O1—H1⋯O2ⁱ	0.95 (1)	1.98 (5)	2.777 (4)	139 (6)
C16—H16⋯Cg1ⁱⁱ	0.93	2.93	3.773 (5)	152
C18—H18⋯Cg2ⁱⁱⁱ	0.93	2.93	3.848 (5)	168

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

supplementary crystallographic information

Comment

Acridine hydrate is the hydrated form of the very rich polymorphic system of acridine. There are five anhydrous polymorphs of acridine with fully analyzed structures: an orthorhombic form and four monoclinic forms. For the orthorhombic form (form IV) cell parameters were first published by Phillips (1954), and the full solution was recently published by Braga et al. (2010). The monoclinic forms are designated II, III, VI and VII. The crystal structure of forms III and II respectively were determined by Phillips (1956) and Phillips et al. (1960) and redetermined by Mei and Wolf (2004) and by Braga et al. (2010). Forms VI and VII were reported by Mei and Wolf (2004). The form described in this paper was initially thought to be one of the first polymorphs of acridine and known historically as the orthorhombic form of Groth (1919) and subsequently labeled as acridine I. Lowde et al. (1953) established the unit cell parameters, the space group and the density. From analysis using the Karl Fischer reagent, it was concluded that acridine I is in fact the monohydrate and not a polymorph of acridine.

There are two acridine molecules and one and a half water molecules in the asymmetric unit (see Fig. 1). In the packing diagram (see Fig. 2), molecule I is colored in green, molecule II is colored in blue, the water molecule that is sitting on a two fold axis is red and the other one is in yellow. The molecules are linked by O—H···O and C—H···O hydrogen bonds (see Table 1).

Experimental

The title compound was obtained by slow evaporation from an ethanol-water solution in 3:1 and 2:1 ratio at 4°C. The crystals are unstable at room temperature and transform to the anhydrous form III. The common habit of acridine hydrate is thick yellow needles but other habits may be obtained as well.