Cyclo­propyl m-nitro­phenyl ketone

The title compound, C₁₀H₉NO₃, exhibits near coplanarity of the phenyl ring with the C=O bond and the nitro group. Through the O atoms of the carbonyl and nitro groups and the H atoms of the phenyl rings, a network of intermolecular hydrogen bonds involves each mol­ecule with four other mol­ecules. The result is a structure composed of discrete two-dimensional hydrogen-bonded molecular layers.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.040
• wR factor = 0.105
• Data-to-parameter ratio = 10.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



STRVAL_01
         From the CIF: _refine_ls_abs_structure_Flack    1.000
         From the CIF: _refine_ls_abs_structure_Flack_su    3.000
           Alert C Chirality of atom sites is inverted?

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.55
         From the CIF: _reflns_number_total               1296
         Count of symmetry unique reflns         1296
         Completeness (_total/calc)            100.00%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present           no
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

In virtually every organic chemistry textbook (e.g. Wade, 1999; Solomons & Fryhle, 2000), ketones are denoted as `meta directors' as opposed to `ortho-para directors' in electrophilic aromatic substitution reactions. Surprisingly, a systematic study of the nitration of aromatic ketones in this context has not apparently been reported. We have carried out the nitration of a series of alkyl phenyl ketones (alkyl is n-propyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl) with acetyl nitrate (fuming HNO₃–acetic anhydride; e.g. Kolb et al., 1984), as well as with the more commonly used `mixed acid' (concentrated HNO₃–H₂SO₄; e.g. Nimitz, 1991; Corson & Hazen, 1930) and identified the products by NMR, supported by GC–MS. While the extent of para nitration was very minor (except for the tert-butyl compound), these ketones unexpectedly underwent a high degree of ortho nitration, especially with acetyl nitrate, a phenomenon we attribute to complexation of the nitrating agent with the carbonyl group (Donahue, 1999; Kolb & Donahue, 1999; Kolb et al., 2002), as illustrated in the Scheme below. We assessed the steric and electronic interactions of the carbonyl group in our systems via a series of ab initio calculations (Kolb et al., 2002). Since no literature data are available for the X-ray structures of alkyl nitrophenyl ketones, we are now obtaining the X-ray structural parameters of our nitro products to get a reality check on the important parameters, e.g. the angle between the carbonyl group and the benzene ring. We now report the X-ray analysis of cyclopropyl m-nitrophenyl ketone, (I).

The structure of (I), with the atom numbering, is shown in Fig. 1. The molecule, excluding atoms C9 and C10 of the cyclopropyl group, is nearly planar. If all atoms, except C9 and C10, are included in a least-squares-plane calculation, the atoms with the largest deviations from the plane are C8, O3, and O1 with values of 0.307 (3), −0.283 (2) and 0.192 (3) Å, respectively. When atoms C9 and C10 are included in this calculation, their deviations from the least-squares plane are −0.299 (3) and 1.097 (3) Å, respectively. The carbonyl C═O vector is at an angle of 12.31 (17)° to the benzene-ring plane, and the angle between the benzene and cyclopropyl (C8–C10) rings is 75.1 (3)°. The molecules pack into infinite two-dimensional sheets made up of a network of C—H···O intermolecular interactions, as shown in Fig. 2. Within each sheet, each molecule is hydrogen bonded to four surrounding molecules. Three phenyl C atoms (C4, C5, and C6) act as donors, while the O atoms of the nitro and carbonyl groups act as acceptors. The hydrogen-bond geometry is given in Table 1. The two-dimensional planes stack normal to [001] with no bonding between the layers, as shown in Fig. 3. An examination of the data indicates that there are no close intra- or intermolecular contacts between non-H atoms.

S2. Experimental

The title compound, (I), was prepared according to a published procedure for the nitration of ketones with acetyl nitrate, prepared in situ from fuming nitric acid–acetic anhydride (e.g. Kolb et al., 1984). Cyclopropyl phenyl ketone, (II) (Aldrich; 2.080 g, 14.2 mmol), was thus converted into 2.373 g (87.2%) of a mixture of crude nitration products (a mixture of crystals and a yellow oil) shown by ¹H NMR to be composed of meta (I) (59%), ortho (III) (38%), and para (IV) (3%) nitro isomers. We obtained 30% ortho product with the `mixed acid' (e.g. Nimitz, 1991; Corson & Hazen, 1930) nitrating reagent. Trituration with light petroleum ether afforded a mass of white crystals, which, upon recrystallization from absolute EtOH, provided the pure meta isomer (I), m.p. 346–347 K [literature m.p. 345.5–346.5 K (Newman & Kaugars, 1966); 344–346 K (Thaisrivongs et al., 1995)]. The latter authors reported the IR and ¹H NMR spectra. We now report the ¹³C NMR spectrum (CDCl₃): 12.58, 17.51 122.68, 126.99, 130.07, 133.84, 138.99, 148.30, 198.41.

S3. Refinement

All H atoms were refined as riding.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: PROCESS in TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SIR92 (Burla et al., 1989); program(s) used to refine structure: LS in TEXSAN and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: TEXSAN, SHELXL97 and PLATON.

Figures

	Fig. 1. The molecular structure and atom-numbering scheme for (I), with displacement ellipsoids at the 50% probability level.
	Fig. 2. Hydrogen bonding in (I) and the resultant infinite two-dimensional molecular planes. [Symmetry codes: (i) 1/2 + x, 1/2 − y, 7/4 − z; (ii) 1/2 + x, −1/2 − y, 7/4 − z.]
	Fig. 3. Packing drawing of (I), showing the stacking of the two-dimensional molecular planes.

Cyclopropyl meta-nitrophenyl ketone

Crystal data

C10H9NO3	Melting point = 346–347 K
Mr = 191.18	Mo Kα radiation, λ = 0.71069 Å
Tetragonal, P41212	Cell parameters from 25 reflections
a = 11.438 (2) Å	θ = 11.1–12.1°
c = 14.284 (2) Å	µ = 0.10 mm^−1
V = 1868.8 (6) Å^3	T = 296 K
Z = 8	Tetragonal dipyramid, colorless
F(000) = 800	0.43 × 0.34 × 0.33 mm
Dx = 1.359 Mg m^−3

Data collection

Rigaku AFC-5S diffractometer	Rint = 0.059
Radiation source: fine-focus sealed tube	θmax = 27.6°, θmin = 2.3°
Graphite monochromator	h = 0→14
ω scans	k = 0→14
2438 measured reflections	l = 0→18
1296 independent reflections	3 standard reflections every 100 reflections
674 reflections with I > 2σ(I)	intensity decay: 6.8%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.049P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.105	(Δ/σ)max < 0.001
S = 0.98	Δρmax = 0.12 e Å^−3
1296 reflections	Δρmin = −0.15 e Å^−3
128 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.021 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: The absolute configuration could not be determined because of the lack of heavy atoms in the structure.
Secondary atom site location: difference Fourier map	Absolute structure parameter: 1 (3)

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

	x	y	z	Uiso*/Ueq
O1	0.5835 (2)	0.1546 (2)	0.8732 (2)	0.1100 (9)
O2	0.7178 (3)	0.2844 (2)	0.8664 (2)	0.1245 (11)
O3	0.67925 (16)	−0.25389 (17)	0.83853 (16)	0.0780 (7)
N1	0.6860 (3)	0.1832 (2)	0.8689 (2)	0.0815 (8)
C1	0.8225 (2)	−0.1111 (2)	0.86664 (18)	0.0478 (6)
C2	0.7393 (2)	−0.0229 (2)	0.8639 (2)	0.0537 (7)
C3	0.7758 (2)	0.0911 (2)	0.86886 (19)	0.0564 (7)
C4	0.8904 (3)	0.1220 (2)	0.8753 (2)	0.0650 (8)
C5	0.9728 (2)	0.0348 (2)	0.8778 (2)	0.0656 (8)
C6	0.9396 (2)	−0.0810 (2)	0.87492 (19)	0.0570 (7)
C7	0.7798 (2)	−0.2347 (2)	0.8628 (2)	0.0528 (7)
C8	0.8578 (3)	−0.3308 (2)	0.8892 (2)	0.0654 (8)
C9	0.8395 (4)	−0.4474 (2)	0.8436 (2)	0.0840 (11)
C10	0.8028 (3)	−0.4318 (3)	0.9397 (2)	0.0895 (11)
H2	0.6602	−0.0408	0.8589	0.064*
H4	0.9123	0.2002	0.8779	0.078*
H5	1.0517	0.0540	0.8814	0.079*
H6	0.9960	−0.1394	0.8786	0.068*
H8	0.9381	−0.3101	0.9067	0.078*
H9A	0.7791	−0.4532	0.7961	0.101*
H9B	0.9080	−0.4954	0.8321	0.101*
H10A	0.8484	−0.4700	0.9881	0.107*
H10B	0.7195	−0.4279	0.9521	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0686 (14)	0.0874 (17)	0.174 (3)	0.0262 (13)	−0.015 (2)	−0.0081 (19)
O2	0.126 (2)	0.0494 (13)	0.198 (3)	0.0129 (14)	−0.012 (2)	0.0056 (19)
O3	0.0561 (12)	0.0638 (13)	0.1141 (19)	−0.0121 (11)	−0.0099 (11)	−0.0032 (12)
N1	0.082 (2)	0.0588 (18)	0.104 (2)	0.0151 (16)	−0.006 (2)	−0.0040 (18)
C1	0.0435 (13)	0.0483 (14)	0.0515 (15)	−0.0035 (12)	0.0011 (14)	−0.0028 (12)
C2	0.0437 (14)	0.0530 (15)	0.0643 (18)	0.0017 (13)	0.0001 (15)	−0.0014 (15)
C3	0.0562 (16)	0.0493 (14)	0.0638 (17)	0.0065 (14)	0.0000 (16)	−0.0026 (16)
C4	0.0676 (19)	0.0539 (17)	0.073 (2)	−0.0099 (15)	0.0002 (19)	−0.0022 (18)
C5	0.0481 (16)	0.065 (2)	0.084 (2)	−0.0120 (15)	0.0000 (18)	−0.0061 (19)
C6	0.0438 (15)	0.0535 (16)	0.0737 (19)	−0.0010 (12)	0.0004 (16)	−0.0045 (17)
C7	0.0512 (15)	0.0501 (15)	0.0569 (17)	−0.0062 (14)	0.0053 (15)	−0.0003 (15)
C8	0.0629 (16)	0.0466 (15)	0.087 (2)	−0.0034 (14)	−0.0006 (17)	0.0041 (16)
C9	0.105 (3)	0.0519 (19)	0.095 (2)	0.0023 (18)	0.009 (2)	−0.0049 (17)
C10	0.112 (3)	0.064 (2)	0.092 (2)	−0.004 (2)	0.003 (2)	0.025 (2)

Geometric parameters (Å, º)

O1—N1	1.218 (3)	C8—C9	1.499 (4)
O2—N1	1.214 (3)	C8—C10	1.501 (4)
O3—C7	1.221 (3)	C9—C10	1.448 (5)
N1—C3	1.472 (3)	C2—H2	0.9300
C1—C2	1.387 (3)	C4—H4	0.9300
C1—C6	1.388 (3)	C5—H5	0.9300
C1—C7	1.497 (3)	C6—H6	0.9300
C2—C3	1.371 (4)	C8—H8	0.9800
C3—C4	1.360 (4)	C9—H9A	0.9700
C4—C5	1.373 (3)	C9—H9B	0.9700
C5—C6	1.379 (4)	C10—H10A	0.9700
C7—C8	1.465 (4)	C10—H10B	0.9700
O2—N1—O1	123.1 (3)	C3—C2—H2	120.6
O2—N1—C3	118.2 (3)	C1—C2—H2	120.6
O1—N1—C3	118.7 (3)	C3—C4—H4	120.8
C2—C1—C6	119.0 (2)	C5—C4—H4	120.8
C2—C1—C7	117.5 (2)	C4—C5—H5	119.7
C6—C1—C7	123.5 (2)	C6—C5—H5	119.7
C3—C2—C1	118.7 (2)	C5—C6—H6	119.8
C4—C3—C2	123.0 (2)	C1—C6—H6	119.8
C4—C3—N1	119.1 (3)	C7—C8—H8	117.1
C2—C3—N1	117.9 (3)	C9—C8—H8	117.1
C3—C4—C5	118.3 (3)	C10—C8—H8	117.1
C4—C5—C6	120.5 (3)	C10—C9—H9A	117.6
C5—C6—C1	120.4 (2)	C8—C9—H9A	117.6
O3—C7—C8	120.8 (3)	C10—C9—H9B	117.6
O3—C7—C1	119.2 (2)	C8—C9—H9B	117.6
C8—C7—C1	120.0 (2)	H9A—C9—H9B	114.8
C7—C8—C9	118.1 (3)	C9—C10—H10A	117.7
C7—C8—C10	116.5 (3)	C8—C10—H10A	117.7
C9—C8—C10	57.7 (2)	C9—C10—H10B	117.7
C10—C9—C8	61.2 (2)	C8—C10—H10B	117.7
C9—C10—C8	61.09 (19)	H10A—C10—H10B	114.8
C6—C1—C2—C3	0.5 (5)	C2—C1—C6—C5	−1.8 (4)
C7—C1—C2—C3	179.0 (2)	C7—C1—C6—C5	179.8 (3)
C1—C2—C3—C4	0.8 (5)	C2—C1—C7—O3	14.8 (4)
C1—C2—C3—N1	−178.1 (3)	C6—C1—C7—O3	−166.7 (3)
O2—N1—C3—C4	6.4 (5)	C2—C1—C7—C8	−164.3 (3)
O1—N1—C3—C4	−172.3 (3)	C6—C1—C7—C8	14.1 (4)
O2—N1—C3—C2	−174.8 (3)	O3—C7—C8—C9	30.2 (4)
O1—N1—C3—C2	6.6 (5)	C1—C7—C8—C9	−150.7 (3)
C2—C3—C4—C5	−0.6 (6)	O3—C7—C8—C10	−35.6 (4)
N1—C3—C4—C5	178.2 (3)	C1—C7—C8—C10	143.5 (3)
C3—C4—C5—C6	−0.7 (6)	C7—C8—C9—C10	−105.1 (3)
C4—C5—C6—C1	1.9 (5)	C7—C8—C10—C9	107.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1^i	0.93	2.57	3.378 (4)	146
C6—H6···O3^ii	0.93	2.47	3.369 (3)	163
C5—H5···O2^i	0.93	2.65	3.484 (4)	149

Symmetry codes: (i) x+1/2, −y+1/2, −z+7/4; (ii) x+1/2, −y−1/2, −z+7/4.