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Acta Cryst. (2011). E67, o2761    [ doi:10.1107/S1600536811038220 ]

Acridine 0.75-hydrate

E. Schur, J. Bernstein, A. Lemmerer and R. Vainer

Abstract top

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 [pi]-[pi] 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 [pi]-[pi] 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...[pi] 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.

Comment top

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).

Related literature top

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 top

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.

Refinement top

The water H atoms were located in a difference map and refined with distance restraints of O—H = 0.94 (2) Å. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.930 (1) Å.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The asymmetric unit with atom labels and 50% probability displacement ellipsoids for non-H atoms. Atom H1i is generated by a two-fold axis (-x, y, -z-1/2).
[Figure 2] Fig. 2. The packing of acridine hydrate viewed down the b axis. Hydrogen bonds are marked in dashed lines.
Acridine 0.75-hydrate top
Crystal data top
C13H9N·0.75H2OF(000) = 1632
Mr = 192.71Dx = 1.247 Mg m−3
Dm = 1.247 Mg m−3
Dm measured by not measured
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 1764 reflections
a = 26.400 (5) Åθ = 2.3–21.8°
b = 8.893 (5) ŵ = 0.08 mm−1
c = 17.492 (5) ÅT = 197 K
V = 4107 (3) Å3Cube, yellow
Z = 160.3 × 0.3 × 0.3 mm
Data collection top
Bruker SMART 6000
diffractometer		1733 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.068
graphiteθmax = 25.0°, θmin = 3.3°
phi and ω scansh = −31→22
14504 measured reflectionsk = −10→9
3606 independent reflectionsl = −20→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.197H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0837P)2 + 1.779P]
where P = (Fo2 + 2Fc2)/3
3606 reflections(Δ/σ)max = 0.035
272 parametersΔρmax = 0.35 e Å−3
2 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C13H9N·0.75H2OV = 4107 (3) Å3
Mr = 192.71Z = 16
Orthorhombic, PbcnMo Kα radiation
a = 26.400 (5) ŵ = 0.08 mm−1
b = 8.893 (5) ÅT = 197 K
c = 17.492 (5) Å0.3 × 0.3 × 0.3 mm
Data collection top
Bruker SMART 6000
diffractometer		1733 reflections with I > 2σ(I)
14504 measured reflectionsRint = 0.068
3606 independent reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.058H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.197Δρmax = 0.35 e Å−3
S = 1.00Δρmin = −0.29 e Å−3
3606 reflectionsAbsolute structure: ?
272 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.08797 (12)0.6902 (4)−0.0316 (2)0.0579 (9)
C20.10417 (14)0.8419 (5)−0.0350 (2)0.0746 (11)
H20.11660.88830.00880.090*
C30.10180 (15)0.9206 (5)−0.1017 (3)0.0846 (13)
H30.11251.0202−0.10310.102*
C40.08311 (15)0.8515 (6)−0.1688 (3)0.0839 (13)
H40.08130.9066−0.21400.101*
C50.06791 (14)0.7066 (5)−0.1681 (2)0.0741 (11)
H50.05630.6625−0.21300.089*
C60.06934 (11)0.6201 (5)−0.0995 (2)0.0581 (9)
C70.05310 (11)0.4738 (4)−0.09624 (19)0.0551 (9)
H70.04090.4271−0.14010.066*
C80.05470 (11)0.3952 (4)−0.0281 (2)0.0571 (9)
C90.03850 (13)0.2431 (5)−0.0214 (2)0.0703 (11)
H90.02680.1922−0.06440.084*
C100.03996 (14)0.1718 (5)0.0472 (3)0.0789 (12)
H100.02930.07240.05070.095*
C110.05760 (14)0.2473 (6)0.1135 (2)0.0798 (12)
H110.05830.19690.16010.096*
C120.07325 (13)0.3910 (5)0.1097 (2)0.0689 (11)
H120.08430.43920.15380.083*
C130.07305 (11)0.4701 (4)0.0390 (2)0.0578 (9)
C140.19756 (12)0.7990 (4)0.28030 (18)0.0503 (8)
C150.16763 (13)0.7107 (4)0.3315 (2)0.0628 (10)
H150.13250.71150.32710.075*
C160.18986 (15)0.6257 (4)0.3863 (2)0.0716 (11)
H160.16970.56860.41890.086*
C170.24310 (16)0.6224 (4)0.3950 (2)0.0708 (11)
H170.25770.56450.43340.085*
C180.27294 (14)0.7039 (4)0.3470 (2)0.0638 (10)
H180.30790.70090.35300.077*
C190.25146 (12)0.7941 (4)0.28769 (18)0.0514 (8)
C200.28036 (11)0.8773 (4)0.23658 (18)0.0524 (8)
H200.31550.87490.23980.063*
C210.25709 (12)0.9640 (4)0.18072 (18)0.0504 (8)
C220.28402 (14)1.0520 (4)0.1261 (2)0.0639 (10)
H220.31921.05240.12710.077*
C230.25950 (17)1.1351 (4)0.0727 (2)0.0737 (11)
H230.27791.19140.03760.088*
C240.20596 (17)1.1363 (4)0.0705 (2)0.0734 (11)
H240.18931.19320.03360.088*
C250.17860 (13)1.0551 (4)0.1217 (2)0.0632 (10)
H250.14341.05840.11990.076*
C260.20288 (12)0.9648 (4)0.17826 (18)0.0514 (8)
N10.08930 (10)0.6160 (4)0.03670 (17)0.0675 (9)
N20.17409 (9)0.8829 (3)0.22676 (15)0.0528 (7)
O10.00000.3361 (6)−0.25000.1183 (16)
O20.07381 (11)0.8227 (5)0.17081 (17)0.1234 (14)
H2A0.04990.90040.20310.137 (18)*
H2B0.10710.83850.18690.137 (18)*
H1−0.0308 (14)0.280 (6)−0.248 (4)0.205*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0437 (18)0.066 (2)0.064 (2)0.0044 (17)0.0016 (16)−0.010 (2)
C20.065 (2)0.075 (3)0.084 (3)−0.003 (2)0.015 (2)−0.021 (3)
C30.074 (3)0.071 (3)0.110 (3)−0.002 (2)0.029 (3)−0.009 (3)
C40.077 (3)0.095 (4)0.080 (3)0.006 (3)0.017 (2)0.008 (3)
C50.066 (2)0.093 (3)0.064 (2)−0.002 (2)0.0025 (18)−0.005 (2)
C60.0389 (17)0.073 (3)0.063 (2)0.0082 (17)0.0009 (15)−0.012 (2)
C70.0434 (18)0.068 (2)0.054 (2)0.0046 (18)−0.0042 (15)−0.0172 (19)
C80.0383 (17)0.062 (2)0.071 (2)0.0124 (17)−0.0010 (16)−0.016 (2)
C90.056 (2)0.069 (3)0.086 (3)0.005 (2)0.0002 (19)−0.016 (2)
C100.058 (2)0.067 (3)0.112 (3)0.011 (2)0.010 (2)0.003 (3)
C110.060 (2)0.097 (4)0.082 (3)0.017 (2)−0.002 (2)0.010 (3)
C120.053 (2)0.086 (3)0.068 (3)0.010 (2)−0.0068 (18)−0.003 (2)
C130.0365 (17)0.071 (3)0.066 (2)0.0093 (17)−0.0025 (15)−0.011 (2)
C140.0470 (18)0.047 (2)0.0574 (19)0.0011 (16)0.0037 (16)−0.0130 (17)
C150.054 (2)0.063 (2)0.072 (2)−0.0028 (19)0.0115 (18)−0.010 (2)
C160.087 (3)0.059 (3)0.069 (2)−0.006 (2)0.013 (2)−0.003 (2)
C170.087 (3)0.063 (3)0.063 (2)0.002 (2)−0.008 (2)−0.003 (2)
C180.063 (2)0.063 (2)0.066 (2)0.008 (2)−0.0122 (19)−0.009 (2)
C190.0486 (18)0.049 (2)0.0570 (19)0.0012 (16)−0.0049 (16)−0.0135 (18)
C200.0380 (17)0.054 (2)0.065 (2)−0.0018 (16)−0.0014 (15)−0.0157 (19)
C210.0512 (18)0.0441 (19)0.0560 (19)−0.0004 (16)0.0004 (16)−0.0157 (17)
C220.064 (2)0.061 (2)0.066 (2)−0.0080 (19)0.0095 (19)−0.014 (2)
C230.099 (3)0.058 (3)0.065 (2)−0.011 (2)0.011 (2)−0.005 (2)
C240.095 (3)0.059 (2)0.066 (2)−0.001 (2)−0.015 (2)−0.005 (2)
C250.060 (2)0.057 (2)0.073 (2)0.0022 (19)−0.0128 (19)−0.011 (2)
C260.0475 (18)0.047 (2)0.060 (2)0.0032 (16)−0.0039 (16)−0.0153 (18)
N10.0478 (16)0.082 (2)0.073 (2)0.0054 (16)−0.0043 (14)−0.0156 (19)
N20.0406 (15)0.0505 (17)0.0672 (17)0.0005 (13)−0.0006 (13)−0.0101 (15)
O10.077 (3)0.118 (4)0.160 (4)0.0000.014 (3)0.000
O20.0619 (18)0.204 (4)0.104 (2)−0.034 (2)−0.0056 (17)−0.013 (3)
Geometric parameters (Å, °) top
C1—C21.416 (5)C14—N21.348 (4)
C1—C61.430 (5)C15—H150.9300
C1—N11.365 (4)C15—C161.354 (5)
C2—H20.9300C16—H160.9300
C2—C31.362 (5)C16—C171.414 (5)
C3—H30.9300C17—H170.9300
C3—C41.414 (6)C17—C181.359 (5)
C4—H40.9300C18—H180.9300
C4—C51.350 (6)C18—C191.429 (4)
C5—H50.9300C19—C201.389 (4)
C5—C61.425 (5)C20—H200.9300
C6—C71.371 (5)C20—C211.388 (4)
C7—H70.9300C21—C221.425 (5)
C7—C81.382 (5)C21—C261.432 (4)
C8—C91.423 (5)C22—H220.9300
C8—C131.434 (5)C22—C231.356 (5)
C9—H90.9300C23—H230.9300
C9—C101.358 (5)C23—C241.414 (5)
C10—H100.9300C24—H240.9300
C10—C111.420 (5)C24—C251.359 (5)
C11—H110.9300C25—H250.9300
C11—C121.345 (6)C25—C261.426 (4)
C12—H120.9300C26—N21.352 (4)
C12—C131.423 (5)O1—H10.954 (11)
C13—N11.367 (5)O2—H2A1.093 (4)
C14—C151.430 (5)O2—H2B0.933 (3)
C14—C191.430 (4)
C2—C1—C6118.9 (4)N2—C14—C19122.5 (3)
N1—C1—C2119.3 (3)C14—C15—H15119.7
N1—C1—C6121.7 (3)C16—C15—C14120.7 (3)
C1—C2—H2119.6C16—C15—H15119.7
C3—C2—C1120.8 (4)C15—C16—H16119.4
C3—C2—H2119.6C15—C16—C17121.2 (4)
C2—C3—H3119.9C17—C16—H16119.4
C2—C3—C4120.3 (4)C16—C17—H17120.0
C4—C3—H3119.9C18—C17—C16119.9 (4)
C3—C4—H4119.6C18—C17—H17120.0
C5—C4—C3120.7 (4)C17—C18—H18119.4
C5—C4—H4119.6C17—C18—C19121.2 (3)
C4—C5—H5119.5C19—C18—H18119.4
C4—C5—C6121.0 (4)C18—C19—C14118.5 (3)
C6—C5—H5119.5C20—C19—C14118.2 (3)
C5—C6—C1118.3 (4)C20—C19—C18123.3 (3)
C7—C6—C1119.1 (3)C19—C20—H20119.8
C7—C6—C5122.6 (3)C21—C20—C19120.4 (3)
C6—C7—H7119.8C21—C20—H20119.8
C6—C7—C8120.4 (3)C20—C21—C22123.8 (3)
C8—C7—H7119.8C20—C21—C26117.8 (3)
C7—C8—C9122.8 (3)C22—C21—C26118.4 (3)
C7—C8—C13118.8 (3)C21—C22—H22119.2
C9—C8—C13118.4 (4)C23—C22—C21121.5 (3)
C8—C9—H9119.7C23—C22—H22119.2
C10—C9—C8120.5 (4)C22—C23—H23120.0
C10—C9—H9119.7C22—C23—C24120.0 (4)
C9—C10—H10119.6C24—C23—H23120.0
C9—C10—C11120.7 (4)C23—C24—H24119.7
C11—C10—H10119.6C25—C24—C23120.6 (4)
C10—C11—H11119.7C25—C24—H24119.7
C12—C11—C10120.6 (4)C24—C25—H25119.4
C12—C11—H11119.7C24—C25—C26121.2 (3)
C11—C12—H12119.6C26—C25—H25119.4
C11—C12—C13120.8 (4)C25—C26—C21118.2 (3)
C13—C12—H12119.6N2—C26—C21122.7 (3)
C12—C13—C8118.9 (4)N2—C26—C25119.1 (3)
N1—C13—C8121.5 (3)C13—N1—C1118.5 (3)
N1—C13—C12119.6 (3)C14—N2—C26118.4 (3)
C19—C14—C15118.5 (3)H2A—O2—H2B107.1 (3)
N2—C14—C15119.0 (3)
Hydrogen-bond geometry (Å, °) top
Cg1 and Cg2 are the centroids of the C1/C6–C8/C13/N1 and C1–C6 rings, respectively.
D—H···AD—HH···AD···AD—H···A
O2—H2B···N20.933 (3)1.942 (2)2.873 (4)175.2 (2)
C7—H7···O10.932.353.271 (4)171.
O1—H1···O2i0.95 (1)1.98 (5)2.777 (4)139 (6)
C16—H16···Cg1ii0.932.933.773 (5)152
C18—H18···Cg2iii0.932.933.848 (5)168
Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+1, z+1/2; (iii) −x+1/2, −y+3/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
Cg1 and Cg2 are the centroids of the C1/C6–C8/C13/N1 and C1–C6 rings, respectively.
D—H···AD—HH···AD···AD—H···A
O2—H2B···N20.933 (3)1.942 (2)2.873 (4)175.2 (2)
C7—H7···O10.932.353.271 (4)171.
O1—H1···O2i0.95 (1)1.98 (5)2.777 (4)139 (6)
C16—H16···Cg1ii0.932.933.773 (5)152
C18—H18···Cg2iii0.932.933.848 (5)168
Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+1, z+1/2; (iii) −x+1/2, −y+3/2, z+1/2.
references
References top

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