1-(4-Chloro­phen­yl)-3-(2-nitro­phenyl)propane-1,2-dione

Abstract

The title compound, C₁₅H₁₀ClNO₄, belongs to the class of 1,2-diketones, which have important applications in both synthetic organic chemistry and supra­molecular chemistry. A dihedral angle of 9.03 (1)° is found between the mean planes of the two benzene rings. C—H⋯O inter­actions help to stabilize the crystal structure.

Related literature

For the synthesis of the title compound, see: Barnes & Gist (1950 ▶). For applications of the title compound, see: Saalfrank et al. (1988 ▶); Schobert (1988 ▶); van Leusen & van Leusen (1977 ▶).

Experimental

Crystal data

• C₁₅H₁₀ClNO₄

• M _r = 303.69

• Monoclinic,

• a = 7.9995 (3) Å

• b = 6.3730 (2) Å

• c = 26.7750 (5) Å

• β = 91.340 (2)°

• V = 1364.64 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.29 mm⁻¹

• T = 298 (2) K

• 0.20 × 0.10 × 0.10 mm

Data collection

• Bruker SMART 4K CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.943, T _max = 0.971

• 8762 measured reflections

• 2408 independent reflections

• 1872 reflections with I > 2σ(I)

• R _int = 0.027

Refinement

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.133

• S = 1.07

• 2408 reflections

• 190 parameters

• H-atom parameters constrained

• Δρ_max = 0.38 e Å⁻³

• Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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
C5—H5⋯O3i	0.93	2.53	3.279 (3)	138
C15—H15⋯O1	0.93	2.59	3.244 (3)	128

Symmetry code: (i) .

supplementary crystallographic information

Comment

1,2-Diketones are important intermediates in the preparation of heterocyclic compounds in synthetic chemistry (van Leusen & van Leusen, 1977; Saalfrank et al., 1988). In addition, they can also be used as ligands in supramolecular chemistry (Schobert, 1988). The molecular structure of the title compound is shown in Fig. 1. The dihedral angle of the two benzene rings is 9.03 (1)°. Molecules are mainly connected by an intermolecular C—H···O interaction.

Experimental

The title compound was synthesized as previously described by Barnes & Gist (1950). Colorless crystals suitable for X-ray data collection were obtained by slow evaporation of a 5:2 ratio CH₂Cl₂:MeOH solution at 293 K.

Refinement

All H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined using a riding model, with U_iso(H) = 1.2 U_eq(C) (1.5U_eq(C) for methyl) of the parent atoms.

Figures

Fig. 1.

View of the title molecule showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by spheres of arbitrary radius.

Crystal data

C15H10ClNO4	F(000) = 624
Mr = 303.69	Dx = 1.478 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2433 reflections
a = 7.9995 (3) Å	θ = 2.6–23.4°
b = 6.3730 (2) Å	µ = 0.30 mm−1
c = 26.7750 (5) Å	T = 298 K
β = 91.340 (2)°	Block, colourless
V = 1364.64 (7) Å3	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection

Bruker SMART 4K CCD area-detector diffractometer	2408 independent reflections
Radiation source: fine-focus sealed tube	1872 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −9→9
Tmin = 0.943, Tmax = 0.971	k = −7→7
8762 measured reflections	l = −31→31

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0688P)2 + 0.2924P] where P = (Fo2 + 2Fc2)/3
2408 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.4590 (2)	0.5187 (3)	0.67527 (7)	0.0496 (5)
C2	0.4028 (3)	0.7133 (3)	0.65828 (7)	0.0498 (5)
C3	0.2727 (3)	0.8197 (4)	0.68005 (9)	0.0606 (6)
H3	0.2382	0.9492	0.6676	0.073*
C4	0.1952 (3)	0.7326 (5)	0.72019 (9)	0.0675 (7)
H4	0.1075	0.8028	0.7351	0.081*
C5	0.2471 (3)	0.5421 (4)	0.73831 (9)	0.0669 (7)
H5	0.1947	0.4829	0.7656	0.080*
C6	0.3771 (3)	0.4379 (4)	0.71616 (8)	0.0588 (6)
H6	0.4111	0.3089	0.7291	0.071*
C7	0.6000 (3)	0.3935 (4)	0.65391 (9)	0.0602 (6)
H7A	0.6018	0.2561	0.6695	0.072*
H7B	0.5777	0.3735	0.6185	0.072*
C8	0.7691 (3)	0.4913 (3)	0.66072 (7)	0.0504 (5)
C9	0.9136 (3)	0.3769 (4)	0.63586 (8)	0.0539 (5)
C10	1.0144 (2)	0.4879 (3)	0.59876 (7)	0.0471 (5)
C11	1.1423 (3)	0.3809 (4)	0.57538 (8)	0.0568 (6)
H11	1.1665	0.2433	0.5846	0.068*
C12	1.2338 (3)	0.4757 (4)	0.53865 (8)	0.0631 (6)
H12	1.3183	0.4029	0.5228	0.076*
C13	1.1976 (3)	0.6808 (4)	0.52582 (8)	0.0571 (6)
C14	1.0729 (3)	0.7893 (4)	0.54892 (8)	0.0572 (6)
H14	1.0505	0.9278	0.5401	0.069*
C15	0.9814 (3)	0.6933 (3)	0.58507 (8)	0.0536 (5)
H15	0.8965	0.7669	0.6005	0.064*
Cl1	1.31213 (9)	0.80635 (13)	0.48046 (2)	0.0813 (3)
N1	0.4783 (3)	0.8163 (4)	0.61492 (7)	0.0653 (6)
O1	0.5769 (2)	0.7162 (4)	0.58971 (7)	0.0969 (7)
O2	0.4318 (3)	0.9934 (3)	0.60410 (8)	0.0994 (7)
O3	0.79710 (19)	0.6406 (3)	0.68656 (6)	0.0693 (5)
O4	0.9394 (2)	0.1971 (3)	0.64872 (8)	0.0855 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0428 (11)	0.0539 (13)	0.0520 (11)	−0.0072 (9)	−0.0024 (9)	−0.0057 (10)
C2	0.0441 (11)	0.0588 (14)	0.0463 (11)	−0.0084 (10)	−0.0063 (9)	−0.0001 (10)
C3	0.0509 (13)	0.0614 (15)	0.0687 (15)	0.0020 (11)	−0.0109 (11)	−0.0052 (11)
C4	0.0447 (13)	0.0881 (19)	0.0697 (15)	0.0040 (12)	0.0022 (11)	−0.0143 (14)
C5	0.0516 (14)	0.0881 (19)	0.0614 (14)	−0.0112 (13)	0.0082 (11)	0.0013 (13)
C6	0.0538 (13)	0.0602 (14)	0.0623 (13)	−0.0091 (11)	−0.0032 (10)	0.0065 (11)
C7	0.0574 (14)	0.0606 (14)	0.0627 (13)	−0.0031 (11)	0.0040 (10)	−0.0117 (11)
C8	0.0533 (13)	0.0521 (13)	0.0461 (11)	0.0014 (10)	0.0050 (9)	0.0032 (10)
C9	0.0544 (13)	0.0497 (13)	0.0579 (12)	0.0040 (10)	0.0038 (10)	0.0016 (10)
C10	0.0448 (11)	0.0478 (12)	0.0485 (11)	0.0002 (9)	−0.0008 (9)	−0.0050 (9)
C11	0.0542 (13)	0.0491 (13)	0.0676 (14)	0.0044 (10)	0.0066 (10)	−0.0056 (10)
C12	0.0537 (14)	0.0705 (17)	0.0655 (14)	0.0015 (12)	0.0141 (11)	−0.0154 (12)
C13	0.0509 (13)	0.0724 (17)	0.0479 (12)	−0.0099 (11)	0.0004 (10)	−0.0030 (10)
C14	0.0580 (13)	0.0548 (13)	0.0589 (13)	−0.0014 (11)	0.0016 (10)	0.0049 (10)
C15	0.0492 (12)	0.0549 (14)	0.0568 (12)	0.0055 (10)	0.0047 (9)	0.0001 (10)
Cl1	0.0776 (5)	0.1050 (6)	0.0619 (4)	−0.0200 (4)	0.0179 (3)	0.0070 (3)
N1	0.0593 (12)	0.0772 (16)	0.0588 (12)	−0.0135 (11)	−0.0082 (10)	0.0125 (11)
O1	0.0753 (13)	0.143 (2)	0.0732 (13)	0.0231 (13)	0.0198 (10)	0.0355 (12)
O2	0.140 (2)	0.0620 (13)	0.0966 (14)	−0.0183 (13)	0.0092 (13)	0.0166 (11)
O3	0.0546 (9)	0.0763 (11)	0.0774 (11)	−0.0077 (8)	0.0083 (8)	−0.0257 (9)
O4	0.0905 (14)	0.0608 (12)	0.1068 (14)	0.0187 (10)	0.0394 (11)	0.0232 (10)

Geometric parameters (Å, °)

C1—C6	1.388 (3)	C8—C9	1.532 (3)
C1—C2	1.392 (3)	C9—O4	1.213 (3)
C1—C7	1.505 (3)	C9—C10	1.475 (3)
C2—C3	1.382 (3)	C10—C15	1.383 (3)
C2—N1	1.475 (3)	C10—C11	1.390 (3)
C3—C4	1.371 (3)	C11—C12	1.379 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.368 (4)	C12—C13	1.380 (3)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.380 (3)	C13—C14	1.373 (3)
C5—H5	0.9300	C13—Cl1	1.734 (2)
C6—H6	0.9300	C14—C15	1.371 (3)
C7—C8	1.497 (3)	C14—H14	0.9300
C7—H7A	0.9700	C15—H15	0.9300
C7—H7B	0.9700	N1—O2	1.221 (3)
C8—O3	1.195 (3)	N1—O1	1.229 (3)
C6—C1—C2	115.7 (2)	C7—C8—C9	115.99 (19)
C6—C1—C7	118.3 (2)	O4—C9—C10	123.5 (2)
C2—C1—C7	126.0 (2)	O4—C9—C8	116.8 (2)
C3—C2—C1	122.7 (2)	C10—C9—C8	119.63 (19)
C3—C2—N1	116.1 (2)	C15—C10—C11	118.9 (2)
C1—C2—N1	121.2 (2)	C15—C10—C9	121.91 (19)
C4—C3—C2	119.4 (2)	C11—C10—C9	119.2 (2)
C4—C3—H3	120.3	C12—C11—C10	120.9 (2)
C2—C3—H3	120.3	C12—C11—H11	119.5
C5—C4—C3	119.9 (2)	C10—C11—H11	119.5
C5—C4—H4	120.1	C11—C12—C13	118.7 (2)
C3—C4—H4	120.1	C11—C12—H12	120.6
C4—C5—C6	120.0 (2)	C13—C12—H12	120.6
C4—C5—H5	120.0	C14—C13—C12	121.0 (2)
C6—C5—H5	120.0	C14—C13—Cl1	119.0 (2)
C5—C6—C1	122.3 (2)	C12—C13—Cl1	119.99 (18)
C5—C6—H6	118.8	C15—C14—C13	119.9 (2)
C1—C6—H6	118.8	C15—C14—H14	120.0
C8—C7—C1	114.60 (19)	C13—C14—H14	120.0
C8—C7—H7A	108.6	C14—C15—C10	120.5 (2)
C1—C7—H7A	108.6	C14—C15—H15	119.7
C8—C7—H7B	108.6	C10—C15—H15	119.7
C1—C7—H7B	108.6	O2—N1—O1	123.0 (2)
H7A—C7—H7B	107.6	O2—N1—C2	118.0 (2)
O3—C8—C7	123.96 (19)	O1—N1—C2	118.8 (2)
O3—C8—C9	119.84 (19)
C6—C1—C2—C3	−0.7 (3)	O4—C9—C10—C15	−179.9 (2)
C7—C1—C2—C3	−179.6 (2)	C8—C9—C10—C15	−0.7 (3)
C6—C1—C2—N1	−179.61 (18)	O4—C9—C10—C11	2.6 (3)
C7—C1—C2—N1	1.4 (3)	C8—C9—C10—C11	−178.20 (19)
C1—C2—C3—C4	0.3 (3)	C15—C10—C11—C12	−0.9 (3)
N1—C2—C3—C4	179.30 (19)	C9—C10—C11—C12	176.7 (2)
C2—C3—C4—C5	0.1 (3)	C10—C11—C12—C13	0.8 (3)
C3—C4—C5—C6	−0.1 (4)	C11—C12—C13—C14	−0.1 (3)
C4—C5—C6—C1	−0.3 (4)	C11—C12—C13—Cl1	179.04 (17)
C2—C1—C6—C5	0.7 (3)	C12—C13—C14—C15	−0.5 (3)
C7—C1—C6—C5	179.7 (2)	Cl1—C13—C14—C15	−179.67 (17)
C6—C1—C7—C8	−112.2 (2)	C13—C14—C15—C10	0.4 (3)
C2—C1—C7—C8	66.7 (3)	C11—C10—C15—C14	0.2 (3)
C1—C7—C8—O3	9.9 (3)	C9—C10—C15—C14	−177.2 (2)
C1—C7—C8—C9	−175.36 (19)	C3—C2—N1—O2	6.2 (3)
O3—C8—C9—O4	115.7 (3)	C1—C2—N1—O2	−174.8 (2)
C7—C8—C9—O4	−59.3 (3)	C3—C2—N1—O1	−169.5 (2)
O3—C8—C9—C10	−63.5 (3)	C1—C2—N1—O1	9.5 (3)
C7—C8—C9—C10	121.5 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3i	0.93	2.53	3.279 (3)	138
C15—H15···O1	0.93	2.59	3.244 (3)	128

Symmetry codes: (i) −x+1, y−1/2, −z+3/2.