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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 62| Part 5| May 2006| Pages o240-o242
doi:10.1107/S0108270106008651

An ortho­rhom­bic polymorph of 10,11-di­hydro­carbamazepine

CROSSMARK_Color_square_no_text.svg
William T. A. Harrison,a* H. S. Yathirajanb and H. G. Anilkumarb

aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, and bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India
*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 20 February 2006; accepted 8 March 2006; online 13 April 2006)

The title compound (systematic name: 10,11-dihydro-5H-dibenz[b,f]azepine-5-carboxamide), C15H14N2O, is shown to crystallize as an ortho­rhom­bic polymorph to complement the known monoclinic form. The mol­ecular conformations of both forms are very similar, involving a bent conformation for the seven-membered azepine ring and an overall `butterfly' shape. The mol­ecules assemble into chains by way of N—H⋯O bonds and N—H⋯π inter­actions in both crystal modifications. The two polymorphs appear to form due to different van der Waals inter­actions between the layer-like sheets of mol­ecules.

Comment

Carbamazepine, (I)[link], is an anti­convulsant agent with many pharmaceutical and medicinal applications (Birkhimer et al., 1985[Birkhimer, L. J., Curtis, J. L. & Jann, M. W. (1985). Clin. Pharm. 4, 425-434.]; Nagaraj et al., 2005[Nagaraj, B., Yathirajan, H. S. & Lynch, D. (2005). Acta Cryst. E61, o1757-o1759.]). Compound (I)[link] is of considerable structural inter­est as it serves as a model compound for mol­ecular-crystal polymorphism, with four crystalline forms known (Grzesiak et al., 2003[Grzesiak, A. L., Lang, M., Kim, K. & Matzger, A. J. (2003). J. Pharm. Sci. 92, 2260-2271.]). It has been estimated (Henck et al., 1997[Henck, J. O., Griesser, U. J. & Burger, A. (1997). Pharm. Ind. 59, 165-169.]) that as many as one third of pharmaceutical solids may display crystal polymorphism which can have a dramatic effect on their physiological properties (Knapman, 2000[Knapman, K. (2000). Modern Drug Discov. 3, 53-57.]).

[Scheme 1]

The crystal structures of various derivatives of carbamazepine have been reported (Himes et al., 1981[Himes, V. L., Mighell, A. D. & De Camp, W. H. (1981). Acta Cryst. B37, 2242-2245.]; Lisgarten et al., 1989[Lisgarten, J. N., Palmer, R. A. & Saldhana, J. W. (1989). Acta Cryst. C45, 656-658.]; Hempel et al., 2005[Hempel, A., Camerman, N., Camerman, A. & Mastropaolo, D. (2005). Acta Cryst. E61, o1313-o1315.]; Nagaraj et al., 2005[Nagaraj, B., Yathirajan, H. S. & Lynch, D. (2005). Acta Cryst. E61, o1757-o1759.]; Johnston et al., 2005[Johnston, A., Florence, A. J. & Kennedy, A. R. (2005). Acta Cryst. E61, o1777-o1779.]). Recently, the crystal structure of 5-chloro­carbonyl-10,11-dihydro-5H-dibenz[b,f]azepine, (II)[link], was published (Vijay et al., 2005[Vijay, T., Anilkumar, H. G., Yathirajan, H. S., Narasimhamurthy, T. & Rathore, R. S. (2005). Acta Cryst. E61, o3718-o3720.]). The structure of the title compound, 10,11-dihydro­carbamaza­pine, (III)[link], was reported by Bandoli et al. (1992[Bandoli, G., Nicolini, M., Onagaro, A., Volpe, G. & Rubello, A. (1992). J. Chem. Crystallogr. 22, 177-183.]) to be monoclinic, space group P21/c. We report here a second, ortho­rhom­bic (space group Pbca), modification of (III)[link] (Table 1[link] and Fig. 1[link]).

The geometric parameters for (III)[link] fall within their expected ranges (Allen et al., 1995[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1995). International Tables for Crystallography, Vol. C, edited by A. J. C. Wilson, pp. 685-706. Dordrecht: Kluwer Academic Publishers.]). The dihedral angle between the best planes of the two benzene rings (C1–C6 and C9–C14) is 119.03 (4)°, compared with an equivalent value of 118.20 (12)° [calculated with PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.])] in the monoclinic form of (III)[link] (Bandoli et al., 1992[Bandoli, G., Nicolini, M., Onagaro, A., Volpe, G. & Rubello, A. (1992). J. Chem. Crystallogr. 22, 177-183.]). The Bandoli paper cites this dihedral angle as 128°, perhaps as the result of a misprint. The central seven-membered azepine ring (C1/C6–C9/C14/N1) in (I)[link] adopts the so-called bent transition state conformation (Hendrickson, 1967[Hendrickson, D. J. (1967). J. Am. Chem. Soc. 89, 7047-7061.]; Bocian & Strauss, 1977[Bocian, D. F. & Strauss, H. L. (1977). J. Am. Chem. Soc. 99, 2876-2882.]), inter­mediate between the boat and chair forms of a classical cyclo­heptane ring. In this conformation, five atoms (C1/C6–C8/N1) are almost coplanar [r.m.s. deviation from the best plane = 0.042 Å; maximum deviation = 0.050 (1) Å for atom C7], and atoms C9 and C14 are substantially displaced from the plane by 1.108 (2) and 1.149 (2) Å, respectively. This conformation, commonly seen in 10,11-dihydro­carbamazepines (Vijay et al., 2005[Vijay, T., Anilkumar, H. G., Yathirajan, H. S., Narasimhamurthy, T. & Rathore, R. S. (2005). Acta Cryst. E61, o3718-o3720.]), has approximate Cs (mirror) symmetry, with the mirror plane passing through atom C6 and the mid-point of the C9—C14 bond, if atom N1 takes on the identity of a C atom for this analysis. The bond-angle sum of 359.7° about atom N1 in (III)[link] indicates sp2 hybridization for this atom and the N1/C15/O1/N2 grouping is statistically planar [r.m.s. deviation = 0.0004 Å; maximum deviation = 0.0008 (11) Å for atom C15]. Overall, this azepine conformation results in the mol­ecule of (III)[link] taking on a `butterfly' shape, as previously described for related carbamazepine derivatives (Vijay et al., 2005[Vijay, T., Anilkumar, H. G., Yathirajan, H. S., Narasimhamurthy, T. & Rathore, R. S. (2005). Acta Cryst. E61, o3718-o3720.]).

The –NH2 unit in (III)[link] makes only one N—H⋯O hydrogen bond (Table 2[link]). The H⋯O separation of 2.206 (18) Å suggests that it is a relatively weak inter­action. This bond links the mol­ecules into one-dimensional strings propagating in the a direction. The second H atom points towards the centroid of a nearby C9–C14 benzene ring (Fig. 2[link]) and the resulting almost linear N—H⋯π inter­action (Rodham et al., 1993[Rodham, D. A., Suzuki, S., Suenram, R. D., Lovas, F. J., Dasgupta, S., Goddard, W. A. III & Blake, G. A. (1993). Nature (London), 362, 736-737.]) thus appears to help to stabilize the [100] chains.

Any π–π stacking in (III)[link] must be extremely weak, with the shortest aromatic ring centroid–centroid separation being 4.82 Å (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]). A very similar situation occurs for the monoclinic polymorph (the shortest centroid–centroid sep­aration is 4.78 Å). This contrasts strongly with the situation in (II)[link], where no conventional hydrogen bonds are possible and π–π stacking dominates the crystal packing.

The monoclinic form of (III)[link] shows a very similar mol­ecular conformation to the title compound. It possesses the same extended chain structure (propagating in the [010] direction), consolidated by N—H⋯O and N—H⋯π inter­actions as in the ortho­rhom­bic form of (III)[link]. It differs in the arrangements of adjacent sheets of chains with respect to the monoclinic [001] and ortho­rhom­bic [001] directions. In the monoclinic phase, adjacent pseudo-sheets in the c direction all show the same orientation of the carbamoyl groupings (Fig. 3[link]a). In the ortho­rhom­bic form (Fig. 3[link]b), adjacent sheets of carbamoyl groupings alternate in a zigzag pattern. Inversion symmetry generates the adjacent [001] layer in the monoclinic phase and a glide operation performs the same task in the ortho­rhom­bic modification. No unusually short inter-sheet [001] inter­molecular contacts were identified in either phase.

The fact that the density of 1.352 Mg m−3 of ortho­rhom­bic (III)[link] reported here is significantly greater than that of the monoclinic form (1.301 Mg m−3) suggests that the new form of (III)[link] may be a more thermodynamically stable polymorph. Monoclinic (III)[link] was recrystallized from ethanol, resulting in parallelepiped-shaped crystals. Thus, it seems likely (and typical) that the solvent plays an important role in determining the polymorph that results.

[Figure 1]
Figure 1
A view of (III)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitray radii.
[Figure 2]
Figure 2
Detail of the structure of (III)[link], showing a chain resulting from N—H⋯O and N—H⋯π inter­actions. All C-bound H atoms have been omitted for clarity. [Symmetry codes are as in Table 2[link]; additionally: (iii) x − 1, y, z.]
[Figure 3]
Figure 3
(a) Unit-cell packing in the monoclinic form of (III)[link], viewed approxi­mately down [100]. Displacement ellipsoids are drawn at the 50% probability level and all H atoms have been omitted for clarity. (b) Unit-cell packing in the ortho­rhom­bic form of (III)[link], viewed approximately down [010]. Displacement ellipsoids are drawn at the 30% probability level and all H atoms have been omitted for clarity [redrawn from Bandoli et al. (1992[Bandoli, G., Nicolini, M., Onagaro, A., Volpe, G. & Rubello, A. (1992). J. Chem. Crystallogr. 22, 177-183.])].

Experimental

The sample of (III)[link] was kindly supplied by Jubilant Organosys, Nanjangud, India. The compound was recrystallized from acetonitrile (m.p. 473 K).

Crystal data

  • C15H14N2O

  • Mr = 238.28

  • Orthorhombic, P b c a

  • a = 9.0592 (4) Å

  • b = 10.3156 (5) Å

  • c = 25.0534 (12) Å

  • V = 2341.27 (19) Å3

  • Z = 8

  • Dx = 1.352 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3022 reflections

  • θ = 2.9–27.5°

  • μ = 0.09 mm−1

  • T = 120 (2) K

  • Block, colourless

  • 0.28 × 0.24 × 0.18 mm
Data collection

  • Nonius KappaCCD area-detector diffractometer

  • ω and φ scans

  • Absorption correction: multi-scan(SADABS; Bruker, 2003[Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])Tmin = 0.976, Tmax = 0.987

  • 16158 measured reflections

  • 2680 independent reflections

  • 2289 reflections with I > 2σ(I)

  • Rint = 0.042

  • θmax = 27.6°

  • h = −11 → 8

  • k = −13 → 12

  • l = −32 → 32
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.108

  • S = 1.09

  • 2680 reflections

  • 169 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.0384P)2 + 1.5004P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Selected torsion angles (°)

N1—C1—C6—C7 −4.2 (2)
C1—C6—C7—C8 −4.4 (2)
C6—C7—C8—C9 62.06 (16)
C7—C8—C9—C14 −70.51 (15)
C8—C9—C14—N1 −2.76 (17)
C6—C1—N1—C14 −52.01 (17)
C9—C14—N1—C1 73.18 (16)

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C9–C14 ring at (−0.3474, 0.3861, 0.3981).
D—H⋯A D—H H⋯A D⋯A D—H⋯A
N2—H1⋯Cg1i 0.887 (18) 2.86 3.75 173
N2—H2⋯O1ii 0.915 (18) 2.206 (18) 2.8970 (16) 131.7 (14)
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1].

The N-bound H atoms were located in a difference map and their positions were freely refined. The C-bound H atoms were positioned geometrically, with C—H distances in the range 0.95–0.99 Å, and refined as riding. The constraint Uiso(H) = 1.2Ueq(carrier) was applied in all cases.

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]), SCALEPACK and SORTAV (Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks III, global. DOI: 10.1107/S0108270106008651/fg3005sup1.cif

Structure factors: contains datablock III. DOI: 10.1107/S0108270106008651/fg3005IIIsup2.hkl


Comment top

Carbamazepine, (I), is an anticonvulsant agent with many pharmaceutical and medicinal applications (Birkhimer et al., 1985; Nagaraj et al., 2005). Compound (I) is of considerable structural interest as it serves as a model compound for molecular-crystal polymorphism, with four crystalline forms known (Grzesiak et al., 2003). It has been estimated (Henck et al., 1997) that as many as one third of pharmaceutical solids may display crystal polymorphism which can have a dramatic effect on their physiological properties (Knapman, 2000).

The crystal structures of various derivatives of carbamazepine have been reported (Himes et al., 1981; Lisgarten et al., 1989; Hempel et al., 2005; Nagaraj et al., 2005; Johnston et al., 2005). Recently, the crystal structure of 5-chlorocarbonyl-10,11-dihydro-5H-dibenz[b,f]azepine, (II), was published (Vijay et al., 2005). The structure of the title compound, 10,11-dihydrocarbamazapine, (III), was reported by Bandoli et al. (1992) to be monoclinic, space group P21/c. Here, we report a second, orthorhombic (space group Pbca), modification of (III) (Table 1; Fig. 1).

The geometric parameters for (III) fall within their expected ranges (Allen et al., 1995). The dihedral angle between the best planes of the two benzene rings (C1–C6 and C9–C14) is 119.03 (4)°, compared with an equivalent value of 118.20 (12)° [calculated with PLATON (Spek, 2003)] in the monoclinic form of (III) (Bandoli et al., 1992). The Bandoli paper cites this dihedral angle as 128°, perhaps as the result of a misprint. The central seven-membered azepine ring (C1/C6–C9/C14/N1) in (I) adopts the so-called bent transition state conformation (Hendrickson, 1967; Bocian & Strauss, 1977), intermediate between the boat and chair forms of a classical cycloheptane ring. In this conformation, five atoms (C1/C6–C8/N1) are almost co-planar [r.m.s. deviation from the best plane = 0.042 Å; maximum deviation = 0.050 (1) Å for C7], and atoms C9 and C14 are substantially displaced from the plane by 1.108 (2) and 1.149 (2) Å, respectively. This conformation, commonly seen in 10,11-dihydrocarbamazepines (Vijay et al., 2005), has approximate Cs (mirror) symmetry, with the mirror plane passing through atom C6 and the midpoint of the C9—C14 bond, if atom N1 takes on the identity of a C atom for this analysis. The bond-angle sum of 359.7° about N1 in (III) indicates sp2 hybridization for this atom and the N1/C15/O1/N2 grouping is statistically planar [r.m.s. deviation = 0.0004 Å; maximum deviation = 0.0008 (11) Å for atom C15]. Overall, this azepine conformation results in the molecule of (III) taking on a `butterfly' shape, as previously described for related carbamazepine derivatives (Vijay et al., 2005).

The –NH2 unit in (III) makes only one N—H···O hydrogen bond (Table 2). The H···O separation of 2.206 (18) Å suggests it is a relatively weak interaction. This bond links the molecules into one-dimensional strings propagating in the a direction. The second H atom points towards the centroid of a nearby C9–C14 benzene ring (Fig. 2) and the resulting almost linear N—H···π interaction (Rodham et al., 1993) thus appears to help to stabilize the [100] chains.

Any π–π stacking in (III) must be extremely weak, with the shortest aromatic ring centriod···centroid separation being 4.82 Å (Spek, 2003). A very similar situation occurs for the monoclinic polymorph (shortest centroid···centroid separation = 4.78 Å). This contrasts strongly with the situation in (II), where no conventional hydrogen bonds are possible and π–π stacking dominates the crystal packing.

The monoclinic form of (III) shows a very similar molecular conformation to the title compound. It possesses the same extended chain structure (propagating in the [010] direction), consolidated by N—H···O and N—H···π interactions as in the orthorhombic form of (III). It differs in the arrangements of adjacent sheets of chains with respect to the monoclinic [001] and orthorhombic [001] directions. In the monoclinic phase, adjacent pseudo-sheets in the c direction all show the same orientation of the carbamoyl groupings (Fig. 3a). In the orthorhombic form (Fig. 3b), adjacent sheets of carbamoyl groupings alternate in a zigzag pattern. Inversion symmetry generates the adjacent [001] layer in the monoclinic phase and a glide operation performs the same task in the orthorhombic modification. No unusually short inter-sheet [001] intermolecular contacts were identified in either phase.

The fact that the density of 1.352 Mg m−3 of orthorhombic (III) reported here is significantly greater than that of the monoclinic form (1.301 Mg m−3) suggests that the new form of (III) may be a more stable polymorph. Monoclinic (III) was recrystallized from ethanol, resulting in parallelepiped-shaped crystals. Thus, it seems likely (and typical) that the solvent plays an important role in determining the polymorph that results.

Experimental top

The sample of (III) was kindly supplied by Jubilant Organosys, Nanjangud, India. The compound was recrystallized from acetonitrile (m.p. 473 K).

Refinement top

The N-bound H atoms were located in a difference map and their positions were freely refined. The C-bound H atoms were positioned geometrically, with C—H distances in the range 0.95–0.99 Å, and refined as riding. The constraint Uiso(H) = 1.2Ueq(carrier) was applied in all cases.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997), SCALEPACK and SORTAV (Blessing 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitray radii.
[Figure 2] Fig. 2. Detail of the structure of (III), showing a chain resulting from N—H···O and N—H···π interactions. All C-bound H atoms have been omitted for clarity. [Symmetry codes as in Table 2; additionally: (iii) x − 1, y, z.]
[Figure 3] Fig. 3. (a) Unit-cell packing in the orthorhombic version of (III), viewed approximately down [100]. Displacement ellipsoids are drawn at the 50% probability level and all H atoms have been omitted for clarity. (b) Unit-cell packing in the monoclinic form of (III), viewed approximately down [010]. Displacement ellipsoids are drawn at the 30% probability level and all H atoms have been omitted for clarity [redrawn from Bandoli et al. (1992)].
10,11-dihydro-5H-dibenz[b,f]azepine-5-carboxamide top
Crystal data top
C15H14N2OF(000) = 1008
Mr = 238.28Dx = 1.352 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3022 reflections
a = 9.0592 (4) Åθ = 2.9–27.5°
b = 10.3156 (5) ŵ = 0.09 mm−1
c = 25.0534 (12) ÅT = 120 K
V = 2341.27 (19) Å3Block, colourless
Z = 80.28 × 0.24 × 0.18 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer		2680 independent reflections
Radiation source: fine-focus sealed tube2289 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
ω and ϕ scansθmax = 27.6°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		h = −11→8
Tmin = 0.976, Tmax = 0.987k = −13→12
16158 measured reflectionsl = −32→32
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)] = 0.042Hydrogen site location: difmap (N-H) and geom (C-H)
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0384P)2 + 1.5004P]
where P = (Fo2 + 2Fc2)/3
2680 reflections(Δ/σ)max < 0.001
169 parametersΔρmax = 0.24 e Å−3
0 restraintsΔρmin = −0.20 e Å−3
Crystal data top
C15H14N2OV = 2341.27 (19) Å3
Mr = 238.28Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.0592 (4) ŵ = 0.09 mm−1
b = 10.3156 (5) ÅT = 120 K
c = 25.0534 (12) Å0.28 × 0.24 × 0.18 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer		2680 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		2289 reflections with I > 2σ(I)
Tmin = 0.976, Tmax = 0.987Rint = 0.042
16158 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.24 e Å−3
2680 reflectionsΔρmin = −0.20 e Å−3
169 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
C10.04963 (15)0.45082 (13)0.37391 (5)0.0177 (3)
C20.14657 (15)0.54877 (14)0.38949 (5)0.0200 (3)
H2A0.15360.57140.42620.024*
C30.23264 (16)0.61353 (14)0.35245 (6)0.0228 (3)
H30.30000.67870.36360.027*
C40.21937 (17)0.58193 (15)0.29865 (6)0.0253 (3)
H40.27690.62620.27270.030*
C50.12199 (16)0.48575 (15)0.28318 (6)0.0234 (3)
H50.11290.46610.24630.028*
C60.03620 (15)0.41617 (13)0.31986 (5)0.0188 (3)
C7−0.06149 (16)0.30985 (14)0.29711 (5)0.0208 (3)
H7A0.00130.25240.27510.025*
H7B−0.13390.35100.27290.025*
C8−0.14691 (16)0.22474 (14)0.33658 (5)0.0207 (3)
H8A−0.20160.15700.31670.025*
H8B−0.07660.18110.36090.025*
C9−0.25370 (16)0.30443 (13)0.36874 (5)0.0184 (3)
C10−0.40531 (16)0.30161 (14)0.36045 (5)0.0212 (3)
H10−0.44570.24400.33470.025*
C11−0.49873 (16)0.38233 (14)0.38948 (5)0.0220 (3)
H11−0.60230.37940.38360.026*
C12−0.44072 (16)0.46712 (13)0.42704 (5)0.0212 (3)
H12−0.50470.52240.44660.025*
C13−0.28875 (16)0.47151 (13)0.43614 (5)0.0197 (3)
H13−0.24870.52930.46180.024*
C14−0.19696 (15)0.38982 (13)0.40696 (5)0.0172 (3)
C150.02724 (16)0.32816 (13)0.45697 (5)0.0182 (3)
N1−0.03947 (12)0.39139 (11)0.41466 (4)0.0181 (3)
N2−0.06459 (15)0.27514 (13)0.49331 (5)0.0228 (3)
H1−0.0204 (19)0.2325 (18)0.5196 (7)0.027*
H2−0.165 (2)0.2717 (17)0.4898 (7)0.027*
O10.16274 (11)0.32075 (10)0.46096 (4)0.0238 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0158 (7)0.0189 (6)0.0186 (6)0.0031 (5)0.0004 (5)0.0026 (5)
C20.0180 (7)0.0211 (7)0.0210 (6)0.0029 (5)−0.0015 (5)−0.0005 (5)
C30.0187 (7)0.0214 (7)0.0283 (7)−0.0003 (6)−0.0011 (6)0.0027 (5)
C40.0217 (8)0.0286 (8)0.0255 (7)−0.0020 (6)0.0021 (6)0.0075 (6)
C50.0230 (7)0.0289 (7)0.0181 (6)0.0022 (6)0.0015 (5)0.0029 (5)
C60.0172 (7)0.0204 (6)0.0189 (6)0.0031 (5)0.0004 (5)0.0021 (5)
C70.0208 (7)0.0248 (7)0.0168 (6)0.0008 (6)0.0008 (5)−0.0007 (5)
C80.0227 (7)0.0188 (7)0.0207 (6)−0.0006 (5)−0.0002 (5)−0.0013 (5)
C90.0195 (7)0.0184 (6)0.0174 (6)−0.0008 (5)−0.0001 (5)0.0037 (5)
C100.0216 (7)0.0224 (7)0.0196 (6)−0.0036 (6)−0.0021 (5)0.0028 (5)
C110.0165 (7)0.0244 (7)0.0251 (7)−0.0007 (6)−0.0010 (5)0.0080 (6)
C120.0214 (7)0.0212 (7)0.0209 (6)0.0039 (5)0.0034 (5)0.0042 (5)
C130.0220 (7)0.0196 (6)0.0175 (6)0.0001 (5)0.0000 (5)0.0017 (5)
C140.0166 (7)0.0188 (6)0.0163 (6)0.0003 (5)−0.0003 (5)0.0041 (5)
C150.0208 (7)0.0187 (6)0.0152 (6)0.0014 (5)−0.0010 (5)−0.0016 (5)
N10.0156 (6)0.0234 (6)0.0153 (5)0.0002 (5)−0.0001 (4)0.0023 (4)
N20.0203 (6)0.0288 (7)0.0192 (6)0.0010 (5)−0.0009 (5)0.0065 (5)
O10.0181 (5)0.0315 (6)0.0219 (5)0.0017 (4)−0.0021 (4)0.0045 (4)
Geometric parameters (Å, º) top
C1—C21.3945 (19)C8—H8B0.9900
C1—C61.4057 (18)C9—C101.389 (2)
C1—N11.4387 (17)C9—C141.3989 (18)
C2—C31.3841 (19)C10—C111.392 (2)
C2—H2A0.9500C10—H100.9500
C3—C41.392 (2)C11—C121.388 (2)
C3—H30.9500C11—H110.9500
C4—C51.383 (2)C12—C131.396 (2)
C4—H40.9500C12—H120.9500
C5—C61.4013 (19)C13—C141.3914 (19)
C5—H50.9500C13—H130.9500
C6—C71.5201 (19)C14—N11.4398 (17)
C7—C81.5321 (19)C15—O11.2339 (17)
C7—H7A0.9900C15—N21.3492 (18)
C7—H7B0.9900C15—N11.3836 (16)
C8—C91.5036 (19)N2—H10.887 (18)
C8—H8A0.9900N2—H20.915 (18)
C2—C1—C6120.56 (12)H8A—C8—H8B108.0
C2—C1—N1117.60 (12)C10—C9—C14118.60 (13)
C6—C1—N1121.79 (12)C10—C9—C8122.99 (12)
C3—C2—C1121.11 (13)C14—C9—C8118.34 (12)
C3—C2—H2A119.4C9—C10—C11120.68 (13)
C1—C2—H2A119.4C9—C10—H10119.7
C2—C3—C4119.19 (14)C11—C10—H10119.7
C2—C3—H3120.4C12—C11—C10120.06 (13)
C4—C3—H3120.4C12—C11—H11120.0
C5—C4—C3119.63 (13)C10—C11—H11120.0
C5—C4—H4120.2C11—C12—C13120.29 (13)
C3—C4—H4120.2C11—C12—H12119.9
C4—C5—C6122.51 (13)C13—C12—H12119.9
C4—C5—H5118.7C14—C13—C12118.95 (13)
C6—C5—H5118.7C14—C13—H13120.5
C5—C6—C1116.97 (13)C12—C13—H13120.5
C5—C6—C7116.53 (12)C13—C14—C9121.42 (13)
C1—C6—C7126.50 (12)C13—C14—N1120.99 (12)
C6—C7—C8117.75 (11)C9—C14—N1117.58 (12)
C6—C7—H7A107.9O1—C15—N2122.25 (12)
C8—C7—H7A107.9O1—C15—N1121.72 (12)
C6—C7—H7B107.9N2—C15—N1116.03 (12)
C8—C7—H7B107.9C15—N1—C1119.97 (11)
H7A—C7—H7B107.2C15—N1—C14122.02 (11)
C9—C8—C7110.94 (11)C1—N1—C14117.75 (10)
C9—C8—H8A109.5C15—N2—H1115.0 (11)
C7—C8—H8A109.5C15—N2—H2124.3 (11)
C9—C8—H8B109.5H1—N2—H2120.1 (16)
C7—C8—H8B109.5
C6—C1—C2—C3−0.5 (2)C11—C12—C13—C140.1 (2)
N1—C1—C2—C3−177.94 (12)C12—C13—C14—C90.34 (19)
C1—C2—C3—C41.4 (2)C12—C13—C14—N1179.59 (12)
C2—C3—C4—C5−0.7 (2)C10—C9—C14—C13−0.45 (19)
C3—C4—C5—C6−1.0 (2)C8—C9—C14—C13176.52 (12)
C4—C5—C6—C11.8 (2)C10—C9—C14—N1−179.73 (11)
C4—C5—C6—C7−177.74 (13)C8—C9—C14—N1−2.76 (17)
C2—C1—C6—C5−1.08 (19)O1—C15—N1—C1−0.1 (2)
N1—C1—C6—C5176.22 (12)N2—C15—N1—C1−179.94 (12)
C2—C1—C6—C7178.44 (13)O1—C15—N1—C14173.90 (13)
N1—C1—C6—C7−4.2 (2)N2—C15—N1—C14−5.95 (19)
C5—C6—C7—C8175.09 (12)C2—C1—N1—C15−60.38 (17)
C1—C6—C7—C8−4.4 (2)C6—C1—N1—C15122.24 (14)
C6—C7—C8—C962.06 (16)C2—C1—N1—C14125.37 (13)
C7—C8—C9—C10106.33 (15)C6—C1—N1—C14−52.01 (17)
C7—C8—C9—C14−70.51 (15)C13—C14—N1—C1579.78 (17)
C14—C9—C10—C110.17 (19)C9—C14—N1—C15−100.94 (15)
C8—C9—C10—C11−176.66 (12)C13—C14—N1—C1−106.10 (14)
C9—C10—C11—C120.2 (2)C9—C14—N1—C173.18 (16)
C10—C11—C12—C13−0.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1···Cg1i0.887 (18)2.863.75173
N2—H2···O1ii0.915 (18)2.206 (18)2.8970 (16)131.7 (14)
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formulaC15H14N2O
Mr238.28
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)120
a, b, c (Å)9.0592 (4), 10.3156 (5), 25.0534 (12)
V (Å3)2341.27 (19)
Z8
Radiation typeMo Kα
µ (mm−1)0.09
Crystal size (mm)0.28 × 0.24 × 0.18
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.976, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections		16158, 2680, 2289
Rint0.042
(sin θ/λ)max (Å−1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.108, 1.09
No. of reflections2680
No. of parameters169
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.24, −0.20

Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO (Otwinowski & Minor 1997), SCALEPACK and SORTAV (Blessing 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected torsion angles (º) top
N1—C1—C6—C7−4.2 (2)C8—C9—C14—N1−2.76 (17)
C1—C6—C7—C8−4.4 (2)C6—C1—N1—C14−52.01 (17)
C6—C7—C8—C962.06 (16)C9—C14—N1—C173.18 (16)
C7—C8—C9—C14−70.51 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1···Cg1i0.887 (18)2.863.75173
N2—H2···O1ii0.915 (18)2.206 (18)2.8970 (16)131.7 (14)
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, −z+1.
 

References

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 62| Part 5| May 2006| Pages o240-o242
doi:10.1107/S0108270106008651
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