[3-Benzoyl-2,4-bis­(3-nitro­phen­yl)cyclo­but­yl](phen­yl)methanone

Prakash S Nayak; Badiadka Narayana; Hemmige S Yathirajan; Thomas Gerber; Eric Hosten; Richard Betz

doi:10.1107/S1600536812044650

. 2012 Nov 3;68(Pt 12):o3272–o3273. doi: 10.1107/S1600536812044650

[3-Benzoyl-2,4-bis(3-nitrophenyl)cyclobutyl](phenyl)methanone

Prakash S Nayak ^a, Badiadka Narayana ^a, Hemmige S Yathirajan ^b, Thomas Gerber ^c, Eric Hosten ^c, Richard Betz ^c,^*

PMCID: PMC3588821 PMID: 23468786

Abstract

The asymmetric unit of the title compound, C₃₀H₂₂N₂O₆, comprises a half-molecule of the cyclobutane derivative. The least-squares planes defined by the respective C atoms of the aromatic substituents intersect at angles of 76.81 (7) and 89.22 (8)° with the least-squares plane defined by the C atoms of the cyclobutane ring. In the crystal, C—H⋯O contacts connect the molecules into a three-dimensional network. The shortest centroid–centroid distance between the two different aromatic rings is 3.9601 (8) Å.

Related literature

For the biological activity of chalcones and cyclobutane-derived compounds, see: Dimmock et al. (1999 ▶); Marais et al. (2005 ▶); Katerere et al. (2004 ▶); Seidel et al. (2000 ▶). For the crystal structures of similar compounds, see: Zheng et al. (2001 ▶); Zhuang & Zheng (2002 ▶). For general information about the dimerization of chalcones, see: Stobbe & Bremer (1929 ▶); Mustafa (1952 ▶). For puckering analysis of cyclic motifs, see: Cremer & Pople (1975 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₃₀H₂₂N₂O₆
M _r = 506.50
Monoclinic,
a = 5.7850 (1) Å
b = 14.7824 (3) Å
c = 14.3589 (3) Å
β = 104.858 (1)°
V = 1186.86 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.33 × 0.14 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.968, T _max = 0.989
11005 measured reflections
2945 independent reflections
2387 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.111
S = 1.03
2945 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(21.1KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812044650/fj2603sup1.cif

e-68-o3272-sup1.cif^{(21.1KB, cif)}

Click here for additional data file.^{(3.8KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536812044650/fj2603Isup2.cdx

Click here for additional data file.^{(144.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044650/fj2603Isup3.hkl

e-68-o3272-Isup3.hkl^{(144.6KB, hkl)}

Click here for additional data file.^{(9.3KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812044650/fj2603Isup4.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	1.00	2.56	3.3957 (15)	141
C14—H14⋯O2ⁱⁱ	0.95	2.56	3.3666 (19)	142
C2—H2⋯O3ⁱⁱⁱ	1.00	2.61	3.5009 (17)	148

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

Acknowledgments

BN thanks the UGC for financial assistance through a BSR one-time grant for the purchase of chemicals. PSN thanks Mangalore University for research facilities and the DST–PURSE for financial assistance.

supplementary crystallographic information

Comment

Chalcones comprise one of the most commonly occurring classes of medicinally important natural compounds, since they show various biological activities (Dimmock et al., 1999; Marais et al.,. 2005). Cyclobutane-containing natural products have, e.g., been reported for Combretum albopunctatum (Katerere et al., 2004) and Goniothalamus thwaitesii (Seidel et al. 2000). Because of the various biological activities of these natural compounds, the synthesis of cyclobutane-derived compounds is one of the most intensively studied photochemical reactions of chalcone derivatives. These reactions can be carried out in solution, solid state and molten state by sunlight or UV-vis irradiation, with variable results in terms of yield and product composition (Stobbe & Bremer, 1929; Mustafa, 1952). The crystal structures of some dimerized chalcones such as r-1,c-2,t-3,t-4- 1,3-bis(4-methoxyphenyl)-2,4-bis(5-phenyl-1,3,4-oxadiazol-2-yl) cyclobutane 1,4-dioxane solvate (Zheng et al., 2001) and r-1,c-2,t- 3,t-4–1,2-bis(4-methoxyphenyl)-3,4-bis(5-phenyl-1,3,4-oxadiazol-2-yl) cyclobutane (Zhuang & Zheng, 2002) have been reported. In view of the pharmacological importance of chalcone derivatives, the synthesis of such a compound was attempted. Upon the determination of the reaction product's crystal structure, the unintentional formation of the corresponding dimer in the wake of the reaction sequence was revealed.

The title compound, [3-benzoyl-2,4-bis(3-nitrophenyl)cyclobutyl](phenyl)methanone, features a central cyclobutane moiety that bears one aromatic substituent on each carbon atom. Due to the centrosymmetry of the molecule, the relative orientation of these substituents corresponds to cis-trans-cis-trans. The small puckering amplitude precludes a puckering analysis of this ring (Cremer & Pople, 1975). The least-squares planes defined by the respective carbon atoms of the aromatic substituents intersect with the least-squares plane defined the carbon atoms of the cyclobutane ring at angles of 76.81 (7) ° and 89.22 (8) °. The aforementioned planes of the two different aromatic moieties in the asymmetric unit enclose an angle of 24.09 (6) ° (Fig. 1).

In the crystal, intermolecular C–H···O contacts whose range falls by more than 0.1 Å below the sum of van-der-Waals radii of the respective atoms can be observed. These are supported by the hydrogen atom in para position of the non-substituted phenyl group as well as all methine-type hydrogen atoms while the hydrogen atoms of the nitrophenyl moiety do not take part in such contacts. All oxygen atoms present in the molecule act as acceptors. Furthermore, one intramolecular C–H···O contact between a carbonyl group and a methine-type hydrogen atom is apparent. In total, the molecules are connected to a three-dimensional network. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for these contacts is S(5)C¹₁(8)C¹₁(13)R²₂(10) on the unary level. Metrical parameters as well as information about the symmetry of these contacts are summarized in Table 1. The shortest intercentroid distance between two aromatic systems was measured at 3.9601 (8) Å and is apparent between the two different aromatic substituents (Fig. 2).

The packing of the title compound in the crystal structure is shown in Figure 3.

Experimental

To a mixture of 3-nitrobenzaldehyde (1.51 g, 0.01 mol) and acetophenone (1.16 ml, 0.01 mol) in ethanol (50 ml), a sodium hydroxide solution (10%, 10 ml) was added. The mixture was stirred at 278–283 K for 3 h. The precipitate formed was collected by filtration and purified by recrystallization from ethanol. Single crystals suitable for the X-ray diffraction study were grown from methanol by slow evaporation at room temperature. The synthesized chalcone was dimerized during crystallization.