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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 10| October 2006| Pages o608-o611
doi:10.1107/S0108270106033968

3-[5-(4-Bromo­phenyl)-1H-pyrazol-3-ylamino]-5,5-di­methyl­cyclo­hex-2-en-1-one–(Z)-3-(4-bromo­phenyl)-3-chloro­acrylo­nitrile (2/1): a stoichiometric cocrystal of a reaction product with one of its early precursors

CROSSMARK_Color_square_no_text.svg
Silvia Cruz,a Jairo Quiroga,b José M. de la Torre,c Justo Cobo,c John N. Lowd and Christopher Glidewelle*

aDepartamento de Química, Universidad de Nariño, Ciudad universitaria, Torobajo, AA 1175 Pasto, Colombia, bGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, cDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, dDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and eSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 8 August 2006; accepted 23 August 2006; online 12 September 2006)

The title compound, 2C17H18BrN3O·C9H5BrClN, was crystallized from the reaction between 5,5-dimethyl­cyclo­hexane-1,3-dione, triethyl orthoformate and 5-amino-3-(4-bromo­phenyl)pyrazole, which had itself been prepared from the reaction between (Z)-3-(4-bromo­phenyl)-3-chloro­acrylo­nitrile and hydrazine. The compound is a stoichiometric 2:1 cocrystal of the reaction product 3-[5-(4-bromo­phenyl)-1H-pyrazol-3-ylamino]-5,5-dimethyl­cyclo­hex-2-en-1-one and the early reactant (Z)-3-(4-bromo­phenyl)-3-chloro­acrylonitrile. The two independent mol­ecules of cyclo­hex-2-en-1-one are linked by N—H⋯N and N—H⋯O hydrogen bonds into complex bilayers and the mol­ecules of acrylonitrile are trapped within large cavities in the substructure formed by the cyclo­hex-2-en-1-one mol­ecules.

Comment

We report here the mol­ecular and supra­molecular structure of the title compound, (I)[link], which is a stoichiometric cocrystal of two mol­ecules of 3-[3-(4-bromo­phenyl)-1H-pyrazol-5-ylamino]-5,5-dimethyl-2-cyclo­hexen-1-one, hereinafter designated P (for product) and one mol­ecule of one of its upstream precursors, viz. (Z)-3-(4-bromo­phenyl)-3-chloro­acrylonitrile, which had evidently been carried through the entire synthetic sequence and which is hereinafter designated R (for reactant).

The compound was obtained from the reaction between 5-amino-3-(4-bromo­phenyl)pyrazole, 5,5-dimethyl­cyclo­hexane-1,3-dione (dimedone) and triethyl orthoformate, which, it had been hoped, would yield a pyrazolo[3,4-b]quinoline derivative. The pyrazole component of this reaction had itself been prepared using the reaction of (Z)-3-(4-bromo­phenyl)-3-chloro­acrylonitrile (component R) and hydrazine (see scheme[link]), and evidently the excess of component R had been carried right through the synthesis, leading to the isolation of the cocrystal, compound (I)[link].

[Scheme 1]

For the sake of convenience, we shall refer to the mol­ecules containing N11, N21 and N31 (Fig. 1[link]) as types 1–3, respectively. The cocrystal thus contains two mol­ecules, those of types 1 and 2, of the expected product P, along with one mol­ecule, that of type 3, of the precursor compound R. Although the atomic displacement parameters of mol­ecule 3 are generally higher than those of mol­ecules 1 and 2, refinement of the site occupancy for component R confirmed that the occupancy is unity and that the composition of the cocrystal is stoichiometrically 2:1. While the two independent mol­ecules of component P are linked into bilayers by a combination of N—H⋯N and N—H⋯O hydrogen bonds, there are no direction-specific inter­molecular inter­actions involving the mol­ecules of component R. Hence, this component is, in effect, captive within the supra­molecular structure generated by component P, in the manner of a clathrate, and the mol­ecule of R thus has somewhat greater freedom of movement than the mol­ecules of P.

The non-aromatic carbocyclic rings in the type 1 and 2 mol­ecules both adopt envelope conformations, folded across the vectors C134⋯C136 and C234⋯C236. The ring-puckering parameters (Cremer & Pople, 1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]) for the atom sequences C131–C136 and C231–C236 are θ = 52.2 (4)° and φ = 234.7 (5)° for the type 1 mol­ecule, and θ = 128.5 (4)° and φ = 48.3 (5)° for the type 2 mol­ecule, so that the two mol­ecules of P in the selected asymmetric unit are nearly enantiomeric. However, this choice has no significance, as the space group accommodates equal numbers of both enantiomers of the type 1 and 2 mol­ecules. For an idealized envelope conformation, the ring-puckering parameters are 54.7° (or 125.3° for the enantiomorphic ring) and φ = (60k)° (where k = zero or integer). The dihedral angle between the planes of the aryl and pyrazole rings is 19.0 (2)° in the type 1 mol­ecule and 18.4 (2)° in the type 2 mol­ecule, and the corresponding torsion angles (Table 1[link]) indicate the near-enantiomeric relationship of the two reference mol­ecules. The type 3 mol­ecule is nearly planar, as shown by the leading torsion angles. The bond distances and inter­bond angles present no unusual features.

The mol­ecules of component P are linked into bilayers by three N—H⋯O hydrogen bonds and one N—H⋯N hydrogen bond (Table 2[link]), and the formation of the bilayer is readily analysed, firstly in terms of the formation of single sheets by the three N—H⋯O hydrogen bonds only, and then of the pairwise linking of these sheets by the N—H⋯N hydrogen bond. Within the selected asymmetric unit, the two independent mol­ecules of component P are linked by an N—H⋯O hydrogen bond. In addition, atom N11 in the type 1 mol­ecule at (x, y, z) acts as hydrogen-bond donor to atom O13 in the type 1 mol­ecule at ([{1\over 2}] + x, [{1\over 2}] + y, z), so generating by translation a C(9) (Bernstein et al., 1995[Bernstein, J., Davis, R., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) chain of type 1 mol­ecules running parallel to the [110] direction. Similarly, atom N21 in the type 2 mol­ecule at (x, y, z) acts as hydrogen-bond donor to atom O23 in the type 2 mol­ecule at (−[{1\over 2}] + x, [{1\over 2}] + y, z), so generating by translation a second C(9) chain, this time built from type 2 mol­ecules and running parallel to the [[\overline{1}]10] direction. The combination of the [110] and [[\overline{1}]10] chains, linked by the N—H⋯O hydrogen bond within the asymmetric unit, generates a sheet of R88(44) rings parallel to (001) (Fig. 2[link]).

Four such sheets pass through each unit cell, lying in the domains −0.05 < z < 0.29, 0.21 < z < 0.55, 0.45 < z < 0.79 and 0.71 < z < 1.05. Pairs of these sheets, related by twofold rotation axes, are linked by paired N—H⋯N hydrogen bonds involving type 2 mol­ecules only. Atom N23 in the type 2 mol­ecule at (x, y, z), which lies in the domain 0.45 < z < 0.79, acts as hydrogen-bond donor to atom N22 in the type 2 mol­ecule at (1 − x, y, [{3\over 2}] − z), which lies in the domain 0.71 < z < 1.05. The resulting R22(8) motif (Fig. 3[link]), generated by the twofold rotation axis along ([{1\over 2}], y, [{3\over 4}]), thus links pairs of (001) sheets to form bilayers. Two bilayers pass through each unit cell, in the domains 0.45 < z < 1.05 and −0.05 < z < 0.55, generated by the twofold rotation axes at z = [{3\over 4}] and z = [{1\over 4}], respectively, but there are no direction-specific inter­actions between the bilayers.

The bilayers built from the mol­ecules of types 1 and 2 occupy ca 71% of the total unit-cell volume, as indicated by the VOID calculation in PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]), equivalent to ca 377 Å3 per mol­ecule of component P, leaving ca 319 Å3 per mol­ecule of component R. Thus, for the mol­ecules of component P, the mean volume per non-H atom is ca 17.1 Å3, satisfactorily close to the average value of 18 Å3 proposed by Kempster & Lipson (1972[Kempster, C. J. E. & Lipson, H. (1972). Acta Cryst. B28, 3674.]) for light-atom structures, while the mean volume available per non-H atom for component R is ca 26.6 Å3, some 50% higher. The use of element-specific atomic volumes (Hofmann, 2002[Hofmann, D. W. M. (2002). Acta Cryst. B58, 489-493.]) leads to estimated volumes for the mol­ecules of components P and R of 406.7 and 210.5 Å3, respectively, which differ from the available volumes estimated by PLATON by ca 8 and −34%, respectively. The substantial mol­ecular volume available to the mol­ecules for component R, coupled with the absence of any direction-specific inter­molecular forces involving the mol­ecules of R, may account for the apparently large atomic displacement parameter values for component R.

The 29% of the cell volume not occupied by the bilayers forms four large centrosymmetric cavities per unit cell, centred at (±[{1\over 4}], ±[{1\over 4}], 0) and (±[{1\over 4}], ∓[{1\over 4}], [{1\over 2}]) (Fig. 4[link]), each of which accommodates two mol­ecules of component R related to one another by inversion (Fig. 5[link]).

[Figure 1]
Figure 1
The three independent mol­ecules in compound (I)[link], showing the atom-labelling scheme, viz. (a) the type 1 mol­ecule of component P, (b) the type 2 mol­ecule of component P and (c) the mol­ecule of component R. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2]
Figure 2
A stereoview of part of the crystal structure of compound (I)[link], showing the formation of a hydrogen-bonded sheet parallel to (001) built from the type 1 and 2 mol­ecules only. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 3]
Figure 3
Part of the crystal structure of compound (I)[link], showing the R22(8) motif, built from type 2 mol­ecules only, which links the (001) sheets into bilayers. For the sake of clarity, the unit-cell outline and H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, y, [{3\over 2}] − z).
[Figure 4]
Figure 4
A space-filling stereoview of part of the crystal structure of compound (I)[link], showing only the type 1 and 2 mol­ecules in the domain [{1\over 4}] < z < [{3\over 4}] and the resulting cavities.
[Figure 5]
Figure 5
A space-filling stereoview of part of the crystal structure of compound (I)[link], showing the pairwise arrangement of the type 3 mol­ecules in the domain [{1\over 4}] < z < [{3\over 4}].

Experimental

A solution of 5-amino-3-(4-bromo­phenyl)pyrazole [1.0 mmol, itself prepared from the reaction of (Z)-3-(4-bromo­phenyl)-3-chloro­acrylonitrile with excess hydrazine; see scheme[link] in Comment], 5,5-dimethyl­cyclo­hexane-1,3-dione (dimedone; 1.0 mmol) and triethyl orthoformate (1.0 mmol) in ethanol (20 ml) was heated under reflux for 10 h. The reaction mixture was cooled to ambient temperature and crystals of the title compound, (I)[link], were collected by filtration.

Crystal data

  • 2C17H18BrN3O·C9H5BrClN

  • Mr = 963.01

  • Monoclinic, C 2/c

  • a = 13.4390 (4) Å

  • b = 13.8680 (4) Å

  • c = 46.1620 (15) Å

  • β = 93.050 (2)°

  • V = 8591.1 (5) Å3

  • Z = 8

  • Dx = 1.489 Mg m−3

  • Mo Kα radiation

  • μ = 2.92 mm−1

  • T = 293 (2) K

  • Block, colourless

  • 0.44 × 0.26 × 0.20 mm
Data collection

  • Bruker–Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.338, Tmax = 0.557

  • 49869 measured reflections

  • 9729 independent reflections

  • 5997 reflections with I > 2σ(I)

  • Rint = 0.037

  • θmax = 27.5°
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.051

  • wR(F2) = 0.136

  • S = 1.03

  • 9729 reflections

  • 505 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0539P)2 + 16.273P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.002

  • Δρmax = 0.62 e Å−3

  • Δρmin = −0.73 e Å−3

Table 1
Selected torsion angles (°)

N11—C15—C151—C152 17.8 (5)
N21—C25—C251—C252 −16.9 (5)
C32—C31—C37—C38 −6.1 (6)
C31—C37—C38—C39 177.1 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N11—H11⋯O13i 0.86 1.96 2.801 (3) 166
N13—H13⋯O23 0.86 2.02 2.880 (3) 177
N21—H21⋯O23ii 0.86 1.96 2.798 (3) 164
N23—H23⋯N22iii 0.86 2.16 3.009 (3) 169
Symmetry codes: (i) [x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (ii) [x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (iii) [-x+1, y, -z+{\script{3\over 2}}].

The systematic absences permitted C2/c and Cc as possible space groups; C2/c was selected and confirmed by the successful structure analysis. All H atoms were located in difference maps and then treated as riding atoms, with distances C—H = 0.93 (aromatic and alkenic), 0.96 (CH3) or 0.97 Å (CH2) and N—H = 0.86 Å, and with Uiso(H) = kUeq(C,N), where k = 1.5 for the methyl groups and 1.2 for all other H atoms.

Data collection: COLLECT (Nonius, 1999[Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: 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.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR2004 (Burla et al., 2005[Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.]); program(s) used to refine structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270106033968/fa3037sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106033968/fa3037Isup2.hkl


Comment top

We report here the molecular and supramolecular structure of the title compound, (I), which is a stoichiometric co-crystal of two molecules of 3-{[3-(4-bromophenyl)-1H-pyrazol-5-yl]amino}-5,5-dimethyl-2-cyclohexen-1-one], hereinafter designated P (for product) and one molecule of one of its upstream precursors, (Z)-3-(4-bromophenyl)-3-chloroacrylonitrile, which had evidently been carried through the entire synthetic sequence and which is hereinafter designated R (for reactant).

The compound was obtained from the reaction between 5-amino-3-(4-bromophenyl)pyrazole, 5,5-dimethylcyclohexane-1,3-dione (dimedone) and triethyl orthoformate, which, it had been hoped, would yield a pyrazolo[3,4-b]quinoline derivative. The pyrazole component of this reaction had itself been prepared using the reaction of (Z)-3-(4-bromophenyl)-3-chloroacrylonitrile (component R) and hydrazine (see scheme), and evidently the excess of component R had been carried right through the synthesis, leading to the isolation of the co-crystal, compound (I).

For the sake of convenience, we shall refer to the molecules containing N11, N21 and N31 (Fig. 1) as types 1–3, respectively. The co-crystal thus contains two molecules, those of types 1 and 2, of the expected product, P, along with one molecule, that of type 3, of the precursor compound, R. Although the atomic displacement parameters of molecule 3 are generally higher than those of molecules 1 and 2, refinement of the site occupancy for component R confirmed that the occupancy is unity and that the composition of the co-crystal is stoichiometrically 2:1. While the two independent molecules of component P are linked into bilayers by a combination of N—H···N and N—H···O hydrogen bonds, there are no direction-specific intermolecular interactions involving the molecules of component R. Hence this component is, in effect, captive within the supramolecular structure generated by component P, in the manner of a clathrate, and the molecule of R thus has somewhat greater freedom of movement than the molecules of P.

The non-aromatic carbocyclic rings in the type 1 and 2 molecules both adopt envelope conformations, folded across the vectors C134···C136 and C234···C236. The ring-puckering parameters (Cremer & Pople, 1975) for the atom sequences C131–C136 and C231–C236 are θ = 52.2 (4)° and ϕ = 234.7 (5)° for the type 1 molecule and θ = 128.5 (4)° and ϕ = 48.3 (5)° for the type 2 molecule, so that the two molecules of P in the selected asymmetric unit are nearly enantiomeric. However, this choice has no significance, as the space group accommodates equal numbers of both enantiomers of the type 1 and 2 molecules. For an idealized envelope conformation, the ring-puckering parameters are 54.7° (or 125.3° for the enantiomorphic ring) and ϕ = (60k)° [k = what?]. The dihedral angles between the planes of the aryl and pyrazole rings are 19.0 (2)° in the type 1 molecule and 18.4 (2)° in the type 2 molecule, and the corresponding torsion angles (Table 1) indicate the near-enantiomeric relationship of the two reference molecules. The type 3 molecule is nearly planar, as shown by the leading torsion angles. The bond distances and interbond angles present no unusual features.

The molecules of component P are linked into bilayers by three N—H···O hydrogen bonds and one N—H···N hydrogen bond (Table 2), and the formation of the bilayer is readily analysed, firstly in terms of the formation of single sheets by the three N—H···O hydrogen bonds only, and then of the pairwise linking of these sheets by the N—H···N hydrogen bond. Within the selected asymmetric unit, the two independent molecules of component P are linked by an N—H···O hydrogen bond. In addition, atom N11 in the type 1 molecule at (x, y, z) acts as hydrogen-bond donor to atom O13 in the type 1 molecule at (1/2 + x, 1/2 + y, z), so generating by translation a C(9) (Bernstein et al., 1995) chain of type 1 molecules running parallel to the [110] direction. Similarly, atom N21 in the type 2 molecule at (x, y, z) acts as hydrogen-bond donor to atom O23 in the type 2 molecule at (−1/2 + x, 1/2 + y, z), so generating by translation a second C(9) chain, this time built from type 2 molecules and running parallel to the [110] direction. The combination of the [110] and [110] chains, linked by the N—H···O hydrogen bond within the asymmetric unit, generates a sheet of R88(44) rings parallel to (001) (Fig. 2).

Four such sheets pass through each unit cell, lying in the domains −0.05 < z < 0.29, 0.21 < z < 0.55, 0.45 < z < 0.79 and 0.71 < z < 1.05. Pairs of these sheets, related by twofold rotation axes, are linked by paired N—H···N hydrogen bonds involving type 2 molecules only. Atom N23 in the type 2 molecule at (x, y, z), which lies in the domain 0.45 < z < 0.79, acts as hydrogen-bond donor to atom N22 in the type 2 molecule at (1 − x, y, 3/2 − z), which lies in the domain 0.71 < z < 1.05. The resulting R22(8) motif (Fig. 3), generated by the twofold rotation axis along (1/2, y, 3/4), thus links pairs of (001) sheets to form bilayers. Two bilayers pass through each unit cell, in the domains 0.45 < z < 1.05 and −0.05 < z < 0.55, generated by the twofold rotation axes at z = 3/4 and z = 1/4, respectively, but there are no direction-specific interactions between the bilayers.

The bilayers built from the molecules of types 1 and 2 occupy ca 71% of the total unit-cell volume, as indicated by the VOID calculation in PLATON (Spek, 2003), equivalent to ca 377 Å3 per molecule of component P, leaving ca 319 Å3 per molecule of component R. Thus, for the molecules of component P, the mean volume per non-H atom is ca 17.1 Å3, satisfactorily close to the average value of 18 Å3 proposed by Kempster & Lipson (1972) for light-atom structures, while the mean volume available per non-H atom for component R is ca 26.6 Å3, some 50% higher. The use of element-specific atomic volumes (Hofmann, 2002) leads to estimated volumes for the molecules of components P and R of 406.7 Å3 and 210.5 Å3, respectively, which differ from the available volumes estimated by PLATON by ca 8 and −34%, respectively. The substantial molecular volume available to the molecules for component R, coupled with the absence of any direction-specific intermolecular forces involving the molecules of R, may account for the apparently large atomic displacement parameter values for component R.

The 29% of the cell volume not occupied by the bilayers forms four large centrosymmetric cavities per unit cell, centred at (±1/4, ±1/4, 0) and (±1/4, ∓1/4, 1/2) (Fig. 4), each of which accommodates two molecules of component R, related to one another by inversion (Fig. 5).

Experimental top

A solution of 5-amino-3-(4-bromophenyl)pyrazole [1.0 mmol, itself prepared from the reaction of (Z)-3-(4-bromophenyl)-3-chloroacrylonitrile with excess hydrazine; see scheme], 5,5-dimethylcyclohexane-1,3-dione (dimedone; 1.0 mmol) and triethyl orthoformate (1.0 mmol) in ethanol (20 ml) was heated under reflux for 10 h. The reaction mixture was cooled to ambient temperature and crystals of the title compound, (I), were collected by filtration [Yield?].

Refinement top

The systematic absences permitted C2/c and Cc as possible space groups. C2/c was selected, and confirmed by the successful structure analysis. All H atoms were located in difference maps and then treated as riding atoms, with distances C—H = 0.93 (aromatic and alkenic), 0.96 (CH3) or 0.97 Å (CH2), and N—H = 0.86 Å, and with Uiso(H) = kUeq(C,N), where k = 1.5 for the methyl groups and 1.2 for all other H atoms.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The three independent molecules in compound (I), showing the atom-labelling scheme. (a) The type 1 molecule of component P. (b) The type 2 molecule of component P. (c) The molecule of component R. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded sheet parallel to (001) built from the type 1 and 2 molecules only. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 3] Fig. 3. Part of the crystal structure of compound (I), showing the R22(8) motif, built from type 2 molecules only, which links the (001) sheets into bilayers. For the sake of clarity, the unit-cell outline and H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, y, 3/2 − z).
[Figure 4] Fig. 4. A space-filling stereoview of part of the crystal structure of compound (I), showing only the type 1 and 2 molecules in the domain 1/4 < z < 3/4 and the resulting cavities.
[Figure 5] Fig. 5. A space-filling stereoview of part of the crystal structure of compound (I), showing the pairwise arrangement of the type 3 molecules in the domain 1/4 < z < 3/4.
3-[5-(4-Bromophenyl)-1H-pyrazol-3-ylamino]-5,5-dimethylcyclohex- 2-en-1-one–(Z)-3-(4-bromophenyl)-3-chloroacrylonitrile (2:1) top
Crystal data top
2C17H18BrN3O·C9H5BrClNF(000) = 3888
Mr = 963.01Dx = 1.489 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9729 reflections
a = 13.4390 (4) Åθ = 2.7–27.5°
b = 13.8680 (4) ŵ = 2.92 mm−1
c = 46.1620 (15) ÅT = 293 K
β = 93.050 (2)°Block, colourless
V = 8591.1 (5) Å30.44 × 0.26 × 0.20 mm
Z = 8
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer		9729 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode5997 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.7°
ϕ and ω scansh = −17→17
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −17→17
Tmin = 0.338, Tmax = 0.557l = −59→59
49869 measured reflections
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0539P)2 + 16.273P]
where P = (Fo2 + 2Fc2)/3
9729 reflections(Δ/σ)max = 0.002
505 parametersΔρmax = 0.62 e Å−3
0 restraintsΔρmin = −0.73 e Å−3
Crystal data top
2C17H18BrN3O·C9H5BrClNV = 8591.1 (5) Å3
Mr = 963.01Z = 8
Monoclinic, C2/cMo Kα radiation
a = 13.4390 (4) ŵ = 2.92 mm−1
b = 13.8680 (4) ÅT = 293 K
c = 46.1620 (15) Å0.44 × 0.26 × 0.20 mm
β = 93.050 (2)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer		9729 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		5997 reflections with I > 2σ(I)
Tmin = 0.338, Tmax = 0.557Rint = 0.037
49869 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0539P)2 + 16.273P]
where P = (Fo2 + 2Fc2)/3
9729 reflectionsΔρmax = 0.62 e Å−3
505 parametersΔρmin = −0.73 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.72058 (18)0.53668 (18)0.59783 (5)0.0402 (6)
N120.70276 (18)0.49426 (18)0.62347 (5)0.0399 (6)
C130.6575 (2)0.4121 (2)0.61591 (6)0.0347 (6)
N130.63325 (18)0.35040 (18)0.63842 (5)0.0394 (6)
C1310.5517 (2)0.2931 (2)0.63988 (6)0.0366 (7)
C1320.4808 (2)0.2803 (2)0.61823 (7)0.0432 (7)
C1330.3947 (2)0.2219 (2)0.62222 (7)0.0439 (7)
O130.32996 (17)0.20842 (18)0.60233 (5)0.0572 (6)
C1340.3813 (3)0.1789 (3)0.65180 (7)0.0520 (9)
C1350.4790 (2)0.1561 (2)0.66871 (7)0.0443 (8)
C1370.4584 (3)0.1280 (3)0.69996 (8)0.0599 (10)
C1380.5322 (3)0.0741 (3)0.65425 (9)0.0646 (10)
C1360.5430 (2)0.2473 (2)0.66919 (6)0.0443 (7)
C140.6459 (2)0.4020 (2)0.58578 (6)0.0389 (7)
C150.6880 (2)0.4832 (2)0.57472 (6)0.0374 (7)
C1510.6956 (2)0.5150 (2)0.54449 (6)0.0410 (7)
C1520.7595 (3)0.5882 (3)0.53719 (8)0.0586 (10)
C1530.7594 (3)0.6211 (3)0.50869 (8)0.0647 (11)
C1540.6951 (3)0.5813 (3)0.48807 (7)0.0559 (9)
Br140.68478 (4)0.63626 (4)0.450228 (8)0.08209 (17)
C1550.6340 (3)0.5069 (3)0.49457 (8)0.0625 (10)
C1560.6346 (3)0.4740 (3)0.52291 (7)0.0562 (9)
N210.44637 (17)0.73043 (17)0.68758 (5)0.0349 (5)
N220.46885 (18)0.68138 (17)0.71252 (5)0.0353 (5)
C230.5588 (2)0.6451 (2)0.70864 (6)0.0326 (6)
N230.60783 (18)0.59969 (17)0.73254 (5)0.0375 (6)
C2310.6742 (2)0.5272 (2)0.73191 (6)0.0344 (6)
C2320.6928 (2)0.4753 (2)0.70766 (6)0.0374 (7)
C2330.7644 (2)0.4010 (2)0.70837 (6)0.0348 (6)
O230.77738 (15)0.34844 (16)0.68687 (4)0.0429 (5)
C2340.8283 (3)0.3860 (2)0.73582 (7)0.0462 (8)
C2350.7736 (3)0.4074 (2)0.76312 (6)0.0441 (8)
C2370.8476 (4)0.4040 (3)0.78961 (8)0.0751 (13)
C2380.6926 (3)0.3335 (3)0.76674 (9)0.0700 (11)
C2360.7288 (3)0.5079 (2)0.76053 (6)0.0431 (7)
C240.5928 (2)0.6678 (2)0.68149 (6)0.0355 (7)
C250.5192 (2)0.7248 (2)0.66861 (6)0.0323 (6)
C2510.5172 (2)0.7812 (2)0.64170 (6)0.0354 (6)
C2520.4317 (2)0.8246 (2)0.62995 (7)0.0449 (8)
C2530.4336 (3)0.8819 (3)0.60555 (7)0.0532 (9)
C2540.5217 (3)0.8975 (3)0.59299 (7)0.0527 (9)
Br240.52528 (4)0.97913 (4)0.560088 (10)0.0937 (2)
C2550.6072 (3)0.8546 (3)0.60370 (8)0.0715 (12)
C2560.6046 (3)0.7971 (3)0.62803 (8)0.0595 (10)
C310.3846 (3)0.6492 (3)0.57618 (8)0.0546 (9)
C320.4804 (3)0.6534 (3)0.56680 (9)0.0639 (10)
C330.5015 (3)0.7011 (3)0.54151 (10)0.0712 (11)
C340.4260 (3)0.7464 (3)0.52568 (9)0.0708 (11)
Br30.45317 (5)0.80922 (5)0.490599 (13)0.1110 (2)
C350.3310 (4)0.7464 (4)0.53497 (11)0.0900 (15)
C360.3106 (3)0.6965 (4)0.56010 (10)0.0831 (14)
C370.3646 (3)0.5981 (3)0.60357 (9)0.0644 (10)
Cl310.24768 (11)0.61343 (18)0.61582 (4)0.1504 (8)
C380.4278 (4)0.5474 (3)0.61964 (10)0.0797 (13)
C390.4065 (5)0.5024 (4)0.64675 (12)0.0927 (15)
N310.3898 (5)0.4670 (3)0.66755 (11)0.128 (2)
H110.74950.59170.59640.048*
H130.67510.34850.65320.047*
H1320.48820.31000.60040.052*
H13A0.34280.12010.64950.062*
H13B0.34340.22360.66300.062*
H17A0.52020.11350.71040.072*
H17B0.41600.07240.69980.072*
H17C0.42630.18070.70920.072*
H18A0.59370.06040.66500.078*
H18C0.54590.09220.63480.078*
H18B0.49080.01770.65380.078*
H16A0.51460.29400.68210.053*
H16B0.60920.23140.67710.053*
H140.61610.35120.57550.047*
H1520.80260.61550.55130.070*
H1530.80280.66990.50370.078*
H1550.59250.47870.48020.075*
H1560.59290.42330.52750.067*
H210.39170.76170.68420.042*
H230.59390.62050.74940.045*
H2320.65730.48910.69030.045*
H23A0.88640.42730.73540.055*
H23B0.85130.31970.73650.055*
H27A0.87630.34070.79130.090*
H27B0.81330.41850.80680.090*
H27C0.89940.45050.78730.090*
H28A0.72170.27030.76820.084*
H28B0.64600.33570.75030.084*
H28C0.65860.34730.78400.084*
H36A0.68310.51670.77590.052*
H36B0.78180.55500.76340.052*
H240.65220.64870.67380.043*
H2520.37160.81500.63870.054*
H2530.37510.90960.59770.064*
H2550.66670.86400.59470.086*
H2560.66320.76830.63540.071*
H320.53180.62350.57770.077*
H330.56620.70230.53530.085*
H350.28060.77940.52460.108*
H360.24570.69500.56610.100*
H380.49160.53970.61310.096*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0413 (14)0.0384 (15)0.0405 (14)−0.0103 (11)−0.0031 (11)0.0077 (11)
N120.0394 (14)0.0419 (15)0.0380 (13)−0.0098 (12)−0.0018 (11)0.0043 (11)
C130.0284 (14)0.0365 (17)0.0391 (15)−0.0037 (13)0.0002 (12)0.0042 (13)
N130.0391 (14)0.0433 (15)0.0353 (12)−0.0108 (12)−0.0036 (11)0.0083 (11)
C1310.0396 (16)0.0329 (16)0.0374 (15)−0.0046 (13)0.0024 (13)0.0044 (13)
C1320.0437 (18)0.0459 (19)0.0395 (16)−0.0116 (15)−0.0018 (14)0.0099 (14)
C1330.0412 (18)0.0419 (18)0.0482 (18)−0.0062 (15)−0.0003 (15)0.0076 (15)
O130.0499 (14)0.0638 (16)0.0561 (14)−0.0247 (12)−0.0136 (12)0.0122 (12)
C1340.0449 (19)0.059 (2)0.0517 (19)−0.0160 (17)0.0029 (15)0.0100 (17)
C1350.0492 (19)0.0429 (19)0.0414 (16)−0.0080 (15)0.0070 (14)0.0102 (14)
C1370.068 (2)0.063 (2)0.050 (2)−0.0061 (19)0.0124 (18)0.0141 (18)
C1380.085 (3)0.046 (2)0.064 (2)0.004 (2)0.016 (2)0.0055 (18)
C1360.0486 (18)0.0490 (19)0.0350 (15)−0.0077 (15)−0.0010 (13)0.0072 (14)
C140.0415 (17)0.0389 (17)0.0358 (15)−0.0077 (14)−0.0037 (13)0.0017 (13)
C150.0326 (15)0.0413 (18)0.0379 (15)−0.0033 (13)−0.0032 (12)0.0040 (13)
C1510.0373 (16)0.0464 (19)0.0390 (16)−0.0012 (14)0.0001 (13)0.0065 (14)
C1520.046 (2)0.076 (3)0.053 (2)−0.0199 (18)−0.0078 (16)0.0192 (19)
C1530.051 (2)0.087 (3)0.055 (2)−0.022 (2)−0.0017 (17)0.028 (2)
C1540.056 (2)0.074 (3)0.0382 (17)−0.0015 (19)0.0093 (16)0.0118 (17)
Br140.0903 (3)0.1159 (4)0.0405 (2)−0.0089 (3)0.00762 (19)0.0224 (2)
C1550.073 (3)0.073 (3)0.0408 (19)−0.012 (2)−0.0032 (18)−0.0001 (18)
C1560.066 (2)0.058 (2)0.0447 (19)−0.0176 (19)0.0021 (17)0.0015 (16)
N210.0323 (12)0.0397 (14)0.0326 (12)0.0116 (11)0.0022 (10)0.0039 (10)
N220.0376 (13)0.0381 (14)0.0304 (12)0.0092 (11)0.0035 (10)0.0024 (10)
C230.0343 (15)0.0321 (15)0.0316 (14)0.0064 (12)0.0025 (11)−0.0017 (12)
N230.0474 (14)0.0388 (14)0.0266 (11)0.0168 (12)0.0028 (10)−0.0001 (10)
C2310.0384 (16)0.0326 (16)0.0321 (14)0.0071 (13)0.0015 (12)0.0035 (12)
C2320.0417 (16)0.0411 (17)0.0290 (14)0.0156 (14)−0.0026 (12)0.0005 (13)
C2330.0359 (15)0.0379 (17)0.0307 (14)0.0054 (13)0.0012 (12)0.0018 (12)
O230.0440 (12)0.0488 (13)0.0355 (11)0.0186 (10)−0.0019 (9)−0.0057 (10)
C2340.0518 (19)0.0456 (19)0.0404 (17)0.0149 (15)−0.0055 (14)−0.0007 (14)
C2350.063 (2)0.0371 (17)0.0313 (15)0.0105 (16)−0.0036 (14)0.0019 (13)
C2370.117 (4)0.058 (2)0.047 (2)0.030 (2)−0.030 (2)−0.0062 (18)
C2380.095 (3)0.057 (2)0.059 (2)−0.001 (2)0.018 (2)0.0082 (19)
C2360.056 (2)0.0420 (18)0.0309 (15)0.0118 (15)−0.0036 (14)−0.0013 (13)
C240.0336 (15)0.0394 (17)0.0338 (14)0.0118 (13)0.0033 (12)0.0023 (12)
C250.0326 (15)0.0349 (16)0.0296 (13)0.0031 (12)0.0030 (11)−0.0033 (12)
C2510.0370 (16)0.0389 (17)0.0303 (14)0.0039 (13)0.0017 (12)−0.0016 (12)
C2520.0416 (18)0.055 (2)0.0388 (16)0.0089 (15)0.0049 (14)0.0057 (15)
C2530.055 (2)0.059 (2)0.0450 (18)0.0188 (17)−0.0031 (16)0.0097 (16)
C2540.068 (2)0.049 (2)0.0402 (17)0.0071 (18)−0.0007 (16)0.0140 (15)
Br240.1160 (4)0.0969 (4)0.0683 (3)0.0041 (3)0.0050 (3)0.0482 (3)
C2550.056 (2)0.104 (3)0.057 (2)0.006 (2)0.0186 (18)0.033 (2)
C2560.0400 (19)0.087 (3)0.052 (2)0.0164 (18)0.0080 (16)0.0255 (19)
C310.049 (2)0.056 (2)0.059 (2)0.0044 (17)0.0043 (17)−0.0114 (18)
C320.053 (2)0.063 (2)0.076 (3)0.0088 (19)0.005 (2)0.002 (2)
C330.058 (2)0.076 (3)0.080 (3)−0.004 (2)0.007 (2)0.003 (2)
C340.069 (3)0.075 (3)0.067 (3)−0.003 (2)−0.005 (2)0.005 (2)
Br30.1159 (5)0.1258 (5)0.0898 (4)−0.0234 (4)−0.0085 (3)0.0353 (3)
C350.078 (3)0.112 (4)0.078 (3)0.023 (3)−0.010 (3)0.009 (3)
C360.054 (2)0.116 (4)0.080 (3)0.015 (3)0.006 (2)−0.002 (3)
C370.062 (2)0.063 (3)0.070 (3)−0.002 (2)0.016 (2)−0.014 (2)
Cl310.0730 (9)0.246 (2)0.1367 (14)0.0168 (11)0.0436 (9)0.0561 (15)
C380.100 (3)0.069 (3)0.073 (3)0.019 (3)0.029 (3)0.007 (2)
C390.135 (5)0.062 (3)0.083 (3)0.015 (3)0.026 (3)−0.002 (3)
N310.206 (6)0.085 (3)0.100 (4)0.005 (3)0.068 (4)0.012 (3)
Geometric parameters (Å, º) top
N11—C151.353 (4)C231—C2361.500 (4)
N11—N121.355 (3)C232—C2331.409 (4)
N11—H110.86C232—H2320.93
N12—C131.329 (4)C233—O231.251 (3)
C13—N131.398 (4)C233—C2341.507 (4)
C13—C141.399 (4)C234—C2351.521 (4)
N13—C1311.358 (4)C234—H23A0.97
N13—H130.86C234—H23B0.97
C131—C1321.356 (4)C235—C2381.511 (5)
C131—C1361.505 (4)C235—C2361.520 (4)
C132—C1331.432 (4)C235—C2371.535 (4)
C132—H1320.93C237—H27A0.96
C133—O131.244 (4)C237—H27B0.96
C133—C1341.509 (4)C237—H27C0.96
C134—C1351.524 (5)C238—H28A0.96
C134—H13A0.97C238—H28B0.96
C134—H13B0.97C238—H28C0.96
C135—C1381.518 (5)C236—H36A0.97
C135—C1361.529 (4)C236—H36B0.97
C135—C1371.533 (4)C24—C251.376 (4)
C137—H17A0.96C24—H240.93
C137—H17B0.96C25—C2511.467 (4)
C137—H17C0.96C251—C2561.380 (4)
C138—H18A0.96C251—C2521.383 (4)
C138—H18C0.96C252—C2531.380 (4)
C138—H18B0.96C252—H2520.93
C136—H16A0.97C253—C2541.363 (5)
C136—H16B0.97C253—H2530.93
C14—C151.370 (4)C254—C2551.363 (5)
C14—H140.93C254—Br241.897 (3)
C15—C1511.472 (4)C255—C2561.379 (5)
C151—C1561.379 (5)C255—H2550.93
C151—C1521.383 (5)C256—H2560.93
C152—C1531.392 (5)C31—C361.374 (6)
C152—H1520.93C31—C321.381 (5)
C153—C1541.367 (5)C31—C371.487 (6)
C153—H1530.93C32—C331.384 (6)
C154—C1551.362 (5)C32—H320.93
C154—Br141.904 (3)C33—C341.371 (6)
C155—C1561.385 (5)C33—H330.93
C155—H1550.93C34—C351.368 (6)
C156—H1560.93C34—Br31.891 (4)
N21—C251.350 (3)C35—C361.391 (7)
N21—N221.357 (3)C35—H350.93
N21—H210.86C36—H360.93
N22—C231.330 (4)C37—C381.303 (6)
C23—C241.393 (4)C37—Cl311.711 (4)
C23—N231.404 (3)C38—C391.441 (7)
N23—C2311.345 (4)C38—H380.93
N23—H230.86C39—N311.111 (6)
C231—C2321.366 (4)
C15—N11—N12112.7 (2)C231—C232—C233121.4 (3)
C15—N11—H11123.7C231—C232—H232119.3
N12—N11—H11123.7C233—C232—H232119.3
C13—N12—N11104.0 (2)O23—C233—C232122.1 (3)
N12—C13—N13116.8 (3)O23—C233—C234119.3 (3)
N12—C13—C14111.9 (3)C232—C233—C234118.6 (3)
N13—C13—C14131.3 (3)C233—C234—C235113.0 (3)
C131—N13—C13128.0 (2)C233—C234—H23A109.0
C131—N13—H13116.0C235—C234—H23A109.0
C13—N13—H13116.0C233—C234—H23B109.0
C132—C131—N13125.3 (3)C235—C234—H23B109.0
C132—C131—C136121.4 (3)H23A—C234—H23B107.8
N13—C131—C136113.2 (3)C238—C235—C236110.3 (3)
C131—C132—C133121.4 (3)C238—C235—C234110.0 (3)
C131—C132—H132119.3C236—C235—C234108.7 (3)
C133—C132—H132119.3C238—C235—C237109.3 (3)
O13—C133—C132121.9 (3)C236—C235—C237109.2 (3)
O13—C133—C134119.7 (3)C234—C235—C237109.4 (3)
C132—C133—C134118.4 (3)C235—C237—H27A109.5
C133—C134—C135113.9 (3)C235—C237—H27B109.5
C133—C134—H13A108.8H27A—C237—H27B109.5
C135—C134—H13A108.8C235—C237—H27C109.5
C133—C134—H13B108.8H27A—C237—H27C109.5
C135—C134—H13B108.8H27B—C237—H27C109.5
H13A—C134—H13B107.7C235—C238—H28A109.5
C138—C135—C134110.1 (3)C235—C238—H28B109.5
C138—C135—C136110.4 (3)H28A—C238—H28B109.5
C134—C135—C136107.7 (3)C235—C238—H28C109.5
C138—C135—C137109.6 (3)H28A—C238—H28C109.5
C134—C135—C137110.0 (3)H28B—C238—H28C109.5
C136—C135—C137109.0 (3)C231—C236—C235114.0 (2)
C135—C137—H17A109.5C231—C236—H36A108.8
C135—C137—H17B109.5C235—C236—H36A108.8
H17A—C137—H17B109.5C231—C236—H36B108.8
C135—C137—H17C109.5C235—C236—H36B108.8
H17A—C137—H17C109.5H36A—C236—H36B107.7
H17B—C137—H17C109.5C25—C24—C23104.8 (2)
C135—C138—H18A109.5C25—C24—H24127.6
C135—C138—H18C109.5C23—C24—H24127.6
H18A—C138—H18C109.5N21—C25—C24106.4 (2)
C135—C138—H18B109.5N21—C25—C251122.5 (2)
H18A—C138—H18B109.5C24—C25—C251130.7 (3)
H18C—C138—H18B109.5C256—C251—C252117.5 (3)
C131—C136—C135114.0 (3)C256—C251—C25119.6 (3)
C131—C136—H16A108.7C252—C251—C25122.8 (3)
C135—C136—H16A108.7C253—C252—C251121.3 (3)
C131—C136—H16B108.7C253—C252—H252119.3
C135—C136—H16B108.7C251—C252—H252119.3
H16A—C136—H16B107.6C254—C253—C252119.5 (3)
C15—C14—C13105.2 (3)C254—C253—H253120.2
C15—C14—H14127.4C252—C253—H253120.2
C13—C14—H14127.4C255—C254—C253120.7 (3)
N11—C15—C14106.2 (3)C255—C254—Br24119.6 (3)
N11—C15—C151123.2 (3)C253—C254—Br24119.7 (3)
C14—C15—C151130.6 (3)C254—C255—C256119.4 (3)
C156—C151—C152118.7 (3)C254—C255—H255120.3
C156—C151—C15119.5 (3)C256—C255—H255120.3
C152—C151—C15121.8 (3)C255—C256—C251121.5 (3)
C151—C152—C153120.1 (3)C255—C256—H256119.2
C151—C152—H152120.0C251—C256—H256119.2
C153—C152—H152120.0C36—C31—C32118.1 (4)
C154—C153—C152119.6 (3)C36—C31—C37121.9 (4)
C154—C153—H153120.2C32—C31—C37120.0 (4)
C152—C153—H153120.2C31—C32—C33121.4 (4)
C155—C154—C153121.2 (3)C31—C32—H32119.3
C155—C154—Br14119.3 (3)C33—C32—H32119.3
C153—C154—Br14119.3 (3)C34—C33—C32119.3 (4)
C154—C155—C156119.0 (3)C34—C33—H33120.3
C154—C155—H155120.5C32—C33—H33120.3
C156—C155—H155120.5C35—C34—C33120.6 (4)
C151—C156—C155121.3 (3)C35—C34—Br3119.6 (3)
C151—C156—H156119.4C33—C34—Br3119.8 (3)
C155—C156—H156119.4C34—C35—C36119.4 (4)
C25—N21—N22112.6 (2)C34—C35—H35120.3
C25—N21—H21123.7C36—C35—H35120.3
N22—N21—H21123.7C31—C36—C35121.2 (4)
C23—N22—N21103.8 (2)C31—C36—H36119.4
N22—C23—C24112.3 (2)C35—C36—H36119.4
N22—C23—N23117.1 (2)C38—C37—C31126.9 (4)
C24—C23—N23130.2 (3)C38—C37—Cl31117.4 (4)
C231—N23—C23127.0 (2)C31—C37—Cl31115.6 (3)
C231—N23—H23116.5C37—C38—C39125.1 (5)
C23—N23—H23116.5C37—C38—H38117.5
N23—C231—C232124.2 (3)C39—C38—H38117.5
N23—C231—C236114.1 (2)N31—C39—C38179.4 (7)
C232—C231—C236121.7 (3)
C15—N11—N12—C13−0.1 (3)C236—C231—C232—C233−0.2 (5)
N11—N12—C13—N13177.6 (2)C231—C232—C233—O23175.0 (3)
N11—N12—C13—C14−0.3 (3)C231—C232—C233—C234−6.0 (5)
N12—C13—N13—C131144.1 (3)O23—C233—C234—C235−147.0 (3)
C14—C13—N13—C131−38.5 (5)C232—C233—C234—C23533.9 (4)
C13—N13—C131—C1325.1 (5)C233—C234—C235—C23867.7 (4)
C13—N13—C131—C136−171.7 (3)C233—C234—C235—C236−53.1 (4)
N13—C131—C132—C133−177.0 (3)C233—C234—C235—C237−172.2 (3)
C136—C131—C132—C133−0.4 (5)N23—C231—C236—C235158.8 (3)
C131—C132—C133—O13−178.8 (3)C232—C231—C236—C235−21.9 (4)
C131—C132—C133—C1343.3 (5)C238—C235—C236—C231−73.5 (4)
O13—C133—C134—C135151.0 (3)C234—C235—C236—C23147.1 (4)
C132—C133—C134—C135−31.1 (5)C237—C235—C236—C231166.4 (3)
C133—C134—C135—C138−67.9 (4)N22—C23—C24—C252.2 (3)
C133—C134—C135—C13652.5 (4)N23—C23—C24—C25−170.7 (3)
C133—C134—C135—C137171.2 (3)N22—N21—C25—C241.0 (3)
C132—C131—C136—C13525.3 (4)N22—N21—C25—C251−172.6 (3)
N13—C131—C136—C135−157.8 (3)C23—C24—C25—N21−1.9 (3)
C138—C135—C136—C13170.8 (4)C23—C24—C25—C251171.0 (3)
C134—C135—C136—C131−49.5 (4)N21—C25—C251—C256159.3 (3)
C137—C135—C136—C131−168.8 (3)C24—C25—C251—C256−12.6 (5)
N12—C13—C14—C150.6 (3)N21—C25—C251—C252−16.9 (5)
N13—C13—C14—C15−176.9 (3)C24—C25—C251—C252171.2 (3)
N12—N11—C15—C140.5 (3)C256—C251—C252—C253−0.2 (5)
N12—N11—C15—C151178.0 (3)C25—C251—C252—C253176.1 (3)
C13—C14—C15—N11−0.7 (3)C251—C252—C253—C254−1.1 (5)
C13—C14—C15—C151−177.8 (3)C252—C253—C254—C2552.2 (6)
N11—C15—C151—C156−159.3 (3)C252—C253—C254—Br24−178.2 (3)
C14—C15—C151—C15617.5 (5)C253—C254—C255—C256−1.9 (7)
N11—C15—C151—C15217.8 (5)Br24—C254—C255—C256178.5 (3)
C14—C15—C151—C152−165.5 (3)C254—C255—C256—C2510.5 (7)
C156—C151—C152—C1531.8 (6)C252—C251—C256—C2550.5 (6)
C15—C151—C152—C153−175.3 (3)C25—C251—C256—C255−175.9 (4)
C151—C152—C153—C1540.7 (6)C36—C31—C32—C33−1.9 (6)
C152—C153—C154—C155−2.9 (6)C37—C31—C32—C33−179.5 (4)
C152—C153—C154—Br14173.0 (3)C31—C32—C33—C341.0 (7)
C153—C154—C155—C1562.6 (6)C32—C33—C34—C351.2 (7)
Br14—C154—C155—C156−173.3 (3)C32—C33—C34—Br3−178.5 (3)
C152—C151—C156—C155−2.1 (6)C33—C34—C35—C36−2.6 (8)
C15—C151—C156—C155175.0 (3)Br3—C34—C35—C36177.1 (4)
C154—C155—C156—C151−0.1 (6)C32—C31—C36—C350.5 (7)
C25—N21—N22—C230.3 (3)C37—C31—C36—C35178.1 (4)
N21—N22—C23—C24−1.6 (3)C34—C35—C36—C311.7 (8)
N21—N22—C23—N23172.3 (2)C36—C31—C37—C38176.4 (5)
N22—C23—N23—C231150.7 (3)C32—C31—C37—C38−6.1 (6)
C24—C23—N23—C231−36.7 (5)C36—C31—C37—Cl31−7.2 (5)
C23—N23—C231—C232−11.2 (5)C32—C31—C37—Cl31170.4 (3)
C23—N23—C231—C236168.2 (3)C31—C37—C38—C39177.1 (4)
N23—C231—C232—C233179.1 (3)Cl31—C37—C38—C390.7 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O13i0.861.962.801 (3)166
N13—H13···O230.862.022.880 (3)177
N21—H21···O23ii0.861.962.798 (3)164
N23—H23···N22iii0.862.163.009 (3)169
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x−1/2, y+1/2, z; (iii) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula2C17H18BrN3O·C9H5BrClN
Mr963.01
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)13.4390 (4), 13.8680 (4), 46.1620 (15)
β (°) 93.050 (2)
V (Å3)8591.1 (5)
Z8
Radiation typeMo Kα
µ (mm−1)2.92
Crystal size (mm)0.44 × 0.26 × 0.20
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.338, 0.557
No. of measured, independent and
observed [I > 2σ(I)] reflections		49869, 9729, 5997
Rint0.037
(sin θ/λ)max (Å−1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.136, 1.03
No. of reflections9729
No. of parameters505
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0539P)2 + 16.273P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å−3)0.62, −0.73

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, SIR2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected torsion angles (º) top
N11—C15—C151—C15217.8 (5)C32—C31—C37—C38−6.1 (6)
N21—C25—C251—C252−16.9 (5)C31—C37—C38—C39177.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O13i0.861.962.801 (3)166
N13—H13···O230.862.022.880 (3)177
N21—H21···O23ii0.861.962.798 (3)164
N23—H23···N22iii0.862.163.009 (3)169
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x−1/2, y+1/2, z; (iii) −x+1, y, −z+3/2.
 

Acknowledgements

X-ray data were collected at the EPSRC National Crystallography Service, University of Southampton, England; the authors thank the staff for all their help and advice. JC and JMT thank the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. JMT also thanks Universidad de Jaén for a scholarship grant supporting a short stay at the EPSRC National Crystallography Service, University of Southampton. JQ and SC thank COLCIENCIAS, UNIVALLE (Universidad del Valle, Colombia) and UDENAR (Universidad de Nariño, Colombia) for financial support.

References

First citationBernstein, J., Davis, R., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
 First citationBurla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science Google Scholar
 First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
 First citationHofmann, D. W. M. (2002). Acta Cryst. B58, 489–493.  Web of Science CrossRef CAS IUCr Journals Google Scholar
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 First citationMcArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.  Google Scholar
 First citationNonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
 First citationOtwinowski, 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.  Google Scholar
 First citationSheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
 First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2053-2296
Volume 62| Part 10| October 2006| Pages o608-o611
doi:10.1107/S0108270106033968
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