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ISSN: 2056-9890

A new polymorph of N-phenyl­phthalimide

aInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, H. Abdullaev Str. 83, Tashkent 100125, Uzbekistan, and bInstitut für Organische Chemie, TU, Bergakademie Freiberg, Leipziger Strasse 29, D09596 Freiberg/Sachsen, Germany
*Correspondence e-mail: l_izotova@yahoo.com

(Received 5 February 2009; accepted 24 February 2009; online 28 February 2009)

During an attempt to prepare a cocrystal of N-phenyl­phthalimide, C14H9NO2, with N-(2,3,4,5,6-penta­fluoro­phen­yl)phthalimide, a new ortho­rhom­bic polymorph of the first component was obtained. This new form has Z′ = 0.5 and the mol­ecule is located around a twofold axis, whereas in the previously reported polymorph (space group Pbca), the mol­ecule has no crystallographically imposed symmetry. Pairs of C—H⋯O inter­actions between inversion-related phthalimide units arrange mol­ecules into tapes that are further assembled into (010) layers via stacking inter­actions between phthalimide fragments [inter­planar distance = 3.37 (5) Å].

Related literature

For the crystal structure of another polymorph of N-phenyl­phthalimide, see: Magomedova et al. (1981[Magomedova, M. S., Neigauz, M. G., Zavodnik, V. E. & Bel'skii, V. K. (1981). Kristallografiya, 26, 841-844.]); Schwarzer & Weber (2008[Schwarzer, A. & Weber, E. (2008). Cryst. Growth Des. 8, 2862-2874.]).

[Scheme 1]

Experimental

Crystal data
  • C14H9NO2

  • Mr = 223.22

  • Orthorhombic, P b c n

  • a = 5.5480 (11) Å

  • b = 23.801 (5) Å

  • c = 8.0250 (16) Å

  • V = 1059.7 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 293 K

  • 0.2 × 0.05 × 0.05 mm

Data collection
  • Stoe Stadi-4 diffractometer

  • Absorption correction: none

  • 1039 measured reflections

  • 1039 independent reflections

  • 662 reflections with I > 2σ(I)

  • 3 standard reflections every 60 reflections intensity decay: 3.9%

Refinement
  • R[F2 > 2σ(F2)] = 0.067

  • wR(F2) = 0.137

  • S = 1.17

  • 1039 reflections

  • 80 parameters

  • H-atom parameters constrained

  • Δρmax = 0.17 e Å−3

  • Δρmin = −0.15 e Å−3

Data collection: STADI4 (Stoe & Cie, 1997[Stoe & Cie (1997). STADI4. Stoe & Cie, Darmstadt, Germany.]); cell refinement: STADI4; data reduction: X-RED (Stoe &Cie, 1997[Stoe & Cie (1997). STADI4. Stoe & Cie, Darmstadt, Germany.]); 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: XP (Siemens, 1994[Siemens (1994). XP. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The crystal structure of the polymorph I of the title compound has previously been reported [Magomedova et al., 1981; Schwarzer & Weber, 2008]. In the course of our studies on the crystal-engineering behaviour of N-aryl substituted phthalimides (Schwarzer & Weber, 2008) and on polymorphism in general a new polymorph of N-phenylphthalimide (designated as II), was obtained. The molecular structure of N-phenylphthalimide (Fig. 1) is similar to that in the polymorph I, exept the twist angle between the phenyl and phthalimide units which is larger in polymorph II [64.09 (10)°] than in polymorph I [56.73 (4)°] owing to differences in the crystal packing and intermolecular interactions. The most prominent interactions in the polymorph I are carbonyl-carbonyl interaction leading to a short C1=O1···C2=O2 contact (3.08 Å) and a weak C3—H1···O1 interaction (2.65 Å, 137°). In the form II molecules of N-phenylphthalimide related by inversion interact via C2—H2···O1i hydrogen bonds (2.66 Å, 145°; symmetry code: (i) 1 - x, 1 - y, -z) forming zigzag tapes parallel to the crystallographic (102) plane (Fig. 2). These tapes are arranged into (010) layers via stacking interactions between phthalimide units. Within the stacks, the distance between planes of phthalimide units of consecutive molecules is 3.37 (5) Å.

Related literature top

For the crystal structure of another polymorph of N-phenylphthalimide, see: Magomedova et al. (1981); Schwarzer & Weber (2008).

Experimental top

N-Phenylphthalimide was synthesized from aniline and phthalic anhydride according to the procedure described by Schwarzer & Weber (2008). After evaporation of solvent from an acetone solution containing equimolar mixture of N-phenylphthalimide and N-(2,3,4,5,6,-pentafluorophenyl)phthalimide two types of crystals have deposited. The crystals of the plate form (m.p. 456.5 K) appeared to be the polymorph I of N-phenylphthalimide whereas bulky needles the polymorph II (m.p. 485 K). Both types of crystals were stable in the air.

Refinement top

All H-atoms were positioned geometrically (C—H 0.93 Å) and refined as riding on their carrier atoms with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: STADI4 (Stoe & Cie, 1997); cell refinement: STADI4 (Stoe & Cie, 1997); data reduction: X-RED (Stoe &Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Perspective view of the molecule showing 40% probability displacement ellipsoids for the non-hydrogen atoms.
[Figure 2] Fig. 2. Packing diagram for polymorph II; viewed down the c axis. Hydrogen bonds are shown as dashed lines.
N-phenylphthalimide top
Crystal data top
C14H9NO2F(000) = 464
Mr = 223.22Dx = 1.399 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 25 reflections
a = 5.5480 (11) Åθ = 10–25°
b = 23.801 (5) ŵ = 0.10 mm1
c = 8.0250 (16) ÅT = 293 K
V = 1059.7 (4) Å3Needle, colourless
Z = 40.2 × 0.05 × 0.05 mm
Data collection top
Stoe Stadi-4
diffractometer
Rint = 0.000
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 1.7°
Graphite monochromatorh = 06
ω–2τ scansk = 290
1039 measured reflectionsl = 09
1039 independent reflections3 standard reflections every 60 reflections
662 reflections with I > 2σ(I) intensity decay: 3.9%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.067H-atom parameters constrained
wR(F2) = 0.137 w = 1/[σ2(Fo2) + (0.0266P)2 + 0.8879P]
where P = (Fo2 + 2Fc2)/3
S = 1.17(Δ/σ)max < 0.001
1039 reflectionsΔρmax = 0.17 e Å3
80 parametersΔρmin = 0.15 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0123 (18)
Crystal data top
C14H9NO2V = 1059.7 (4) Å3
Mr = 223.22Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 5.5480 (11) ŵ = 0.10 mm1
b = 23.801 (5) ÅT = 293 K
c = 8.0250 (16) Å0.2 × 0.05 × 0.05 mm
Data collection top
Stoe Stadi-4
diffractometer
Rint = 0.000
1039 measured reflections3 standard reflections every 60 reflections
1039 independent reflections intensity decay: 3.9%
662 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0670 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.17Δρmax = 0.17 e Å3
1039 reflectionsΔρmin = 0.15 e Å3
80 parameters
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
N10.00000.39051 (14)0.25000.0475 (9)
O10.3444 (4)0.40588 (9)0.0909 (3)0.0624 (7)
C10.1048 (7)0.58237 (14)0.2026 (4)0.0740 (12)
H10.17310.61640.17090.089*
C20.2140 (6)0.53244 (14)0.1544 (4)0.0626 (10)
H20.35480.53240.09160.075*
C30.1056 (5)0.48304 (12)0.2034 (3)0.0491 (8)
C40.1752 (6)0.42378 (12)0.1702 (4)0.0479 (8)
C50.00000.33042 (18)0.25000.0498 (11)
C60.1868 (6)0.30175 (13)0.3253 (4)0.0601 (9)
H60.31250.32130.37540.072*
C70.1855 (6)0.24375 (14)0.3257 (5)0.0765 (12)
H70.30990.22410.37710.092*
C80.00000.2150 (2)0.25000.0820 (19)
H80.00000.17590.25000.098*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.044 (2)0.049 (2)0.049 (2)0.0000.0052 (18)0.000
O10.0502 (13)0.0738 (15)0.0631 (15)0.0017 (12)0.0078 (12)0.0049 (12)
C10.088 (3)0.0545 (19)0.079 (3)0.0123 (18)0.033 (2)0.0080 (18)
C20.063 (2)0.066 (2)0.059 (2)0.0128 (18)0.0198 (18)0.0059 (18)
C30.0502 (17)0.0543 (18)0.0427 (18)0.0033 (14)0.0134 (15)0.0018 (14)
C40.0409 (16)0.0589 (19)0.0438 (17)0.0017 (16)0.0061 (15)0.0036 (15)
C50.048 (2)0.050 (3)0.052 (3)0.0000.003 (2)0.000
C60.0476 (18)0.062 (2)0.070 (2)0.0027 (17)0.0001 (18)0.0049 (18)
C70.057 (2)0.067 (2)0.106 (3)0.013 (2)0.011 (2)0.018 (2)
C80.058 (3)0.057 (3)0.130 (5)0.0000.033 (4)0.000
Geometric parameters (Å, º) top
N1—C4i1.408 (3)C3—C41.487 (4)
N1—C41.408 (3)C5—C61.380 (4)
N1—C51.430 (5)C5—C6i1.380 (4)
O1—C41.211 (3)C6—C71.380 (4)
C1—C21.389 (4)C6—H60.9300
C1—C1i1.389 (8)C7—C81.378 (4)
C1—H10.9300C7—H70.9300
C2—C31.378 (4)C8—C7i1.378 (4)
C2—H20.9300C8—H80.9300
C3—C3i1.389 (6)
C4i—N1—C4111.6 (4)N1—C4—C3105.8 (3)
C4i—N1—C5124.22 (18)C6—C5—C6i120.7 (4)
C4—N1—C5124.22 (18)C6—C5—N1119.6 (2)
C2—C1—C1i121.2 (2)C6i—C5—N1119.6 (2)
C2—C1—H1119.4C7—C6—C5119.5 (4)
C1i—C1—H1119.4C7—C6—H6120.3
C3—C2—C1117.4 (3)C5—C6—H6120.3
C3—C2—H2121.3C8—C7—C6120.0 (4)
C1—C2—H2121.3C8—C7—H7120.0
C2—C3—C3i121.4 (2)C6—C7—H7120.0
C2—C3—C4130.2 (3)C7—C8—C7i120.3 (5)
C3i—C3—C4108.40 (16)C7—C8—H8119.8
O1—C4—N1125.2 (3)C7i—C8—H8119.8
O1—C4—C3129.0 (3)
Symmetry code: (i) x, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H9NO2
Mr223.22
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)293
a, b, c (Å)5.5480 (11), 23.801 (5), 8.0250 (16)
V3)1059.7 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.2 × 0.05 × 0.05
Data collection
DiffractometerStoe Stadi-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1039, 1039, 662
Rint0.000
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.137, 1.17
No. of reflections1039
No. of parameters80
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.15

Computer programs: STADI4 (Stoe & Cie, 1997), X-RED (Stoe &Cie, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1994).

 

Acknowledgements

Support of this research by the Uzbek Academy of Sciences (grant No. FA—F3—T141) is gratefully acknowledged.

References

First citationMagomedova, M. S., Neigauz, M. G., Zavodnik, V. E. & Bel'skii, V. K. (1981). Kristallografiya, 26, 841–844.  CAS Google Scholar
First citationSchwarzer, A. & Weber, E. (2008). Cryst. Growth Des. 8, 2862–2874.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSiemens (1994). XP. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.  Google Scholar
First citationStoe & Cie (1997). STADI4. Stoe & Cie, Darmstadt, Germany.  Google Scholar

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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
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