2-Methoxy­carbonyl-4-nitro­acetanilide: π-stacked chains linked in pairs by C—H⋯O hydrogen bonds

Glidewell, C.; Low, J.N.; Skakle, J.M.S.; Wardell, J.L.

doi:10.1107/S1600536804009195

organic compounds

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ISSN: 2056-9890

Volume 60| Part 5| May 2004| Pages o852-o854

https://doi.org/10.1107/S1600536804009195

2-Methoxycarbonyl-4-nitroacetanilide: π-stacked chains linked in pairs by C—H⋯O hydrogen bonds

Christopher Glidewell,^a ^* John N. Low,^b Janet M. S. Skakle ^b and James L. Wardell ^c

^aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 15 April 2004; accepted 19 April 2004; online 24 April 2004)

Molecules of the title compound, C₁₀H₁₀N₂O₅, lie on mirror planes in space group Ibam. The molecules are linked into [001] chains by an aromatic π–π stacking interaction, and pairs of these chains are linked by a single C—H⋯O hydrogen bond.

Comment

The title compound (I) (Fig. 1), crystallizes in the uncommon space group Ibam with Z′ = 0.5: all of the atoms apart from the methyl H atoms lie on a mirror plane, chosen for the reference molecule as that at z = 0.5. Each of the H atoms in the methyl groups is disordered over two sites with equal occupancy. The inter-bond angles at N1, at C11 and at C21 (Table 1) show marked deviations from 120°, possibly indicative of repulsive non-bonded intramolecular contacts (Table 2). The bond distances show no unusual values.

The molecules of compound (I) are linked into chains by a single aromatic π–π stacking interaction, and these chains are weakly linked in pairs by a C—H⋯O hydrogen bond. The reference molecule at (x, y, 0.5) forms π-stacking interactions with the two molecules at (1 − x, y, 0) and (1 − x, y, 1). The common interplanar spacing is c/2 and the ring-centroid separation is 3.634 (2) Å, corresponding to a near-ideal centroid offset of 1.341 (2) Å. Propagation of this interaction thus produces a chain running parallel to the [001] direction and generated by the c-glide plane at x = 0.5 (Fig. 2). Four chains of this type run through each unit cell; two are generated by the c-glide plane at x = 0.5 and lie wholly within the domain 0.25 < y < 0.75, while the two others generated by the c-glide plane at x = 0.0 lie within the domain −0.25 < x < 0.25.

Within each domain of x, the pairs of [001] chains in the domains 0 < y < 0.5 and 0.5 < y < 1.0 are linked by a single C—H⋯O hydrogen bond which, although it is rather long, is effectively linear (Table 2). Atom C3 in the molecule at (x, y, 0.5) acts as donor to nitro atom O41 in the molecule at (1 − x, 1 − y, 0.5), so forming an R₂²(10) motif generated by the twofold rotation axis along (0.5, 0.5, z) (Fig. 3).

Figure 1
The molecule of compound (I

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. For the sake of clarity, only one orientation is shown for each methyl group.

Figure 2
Stereoview of part of the crystal structure of compound (I

), showing the formation of a π-stacked chain along [001]. For the sake of clarity, the H atoms have all been omitted.

Figure 3
Part of the crystal structure of compound (I

), showing the formation of the R²₂(10) motif which links the [001] chains into pairs. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 0.5).

Experimental

2-Carboxymethylacetanilide was nitrated using fuming nitric acid at 273 K, following a published procedure (Adams et al., 1954 ). The reaction mixture was poured on to ice and the resulting solid (I) was collected. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in acetone (m.p. 447–449 K).

Crystal data

C₁₀H₁₀N₂O₅
M_r = 238.20
Orthorhombic, Ibam
a = 16.4482 (14) Å
b = 19.9095 (17) Å
c = 6.7549 (6) Å
V = 2212.1 (3) Å³
Z = 8
D_x = 1.430 Mg m⁻³
Mo Kα radiation
Cell parameters from 1384 reflections
θ = 2.1–27.5°
μ = 0.12 mm⁻¹
T = 291 (2) K
Prism, colourless
0.43 × 0.18 × 0.13 mm

Data collection

Bruker SMART 1000 CCD area detector diffractometer
φ–ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.930, T_max = 0.985
7820 measured reflections
1384 independent reflections
828 reflections with I > 2σ(I)
R_int = 0.057
θ_max = 27.5°
h = −21 → 21
k = −24 → 25
l = −8 → 6

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.130
S = 1.01
1384 reflections
105 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0672P)² + 0.1650P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Selected bond angles (°)

C1—N1—C11	129.6 (2)
N1—C11—O11	122.8 (2)
N1—C11—C12	114.1 (2)
O11—C11—C12	123.1 (2)
C2—C21—O21	111.55 (19)
C2—C21—O22	125.9 (2)
O21—C21—O22	122.5 (2)
C21—O21—C22	117.2 (2)

Table 2
Geometric parameters (Å, °) for hydrogen bonds and short intramolecular contacts

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O22	0.86	1.98	2.691 (2)	139
C3—H3⋯O41ⁱ	0.93	2.51	3.440 (3)	180
C3—H3⋯O21	0.93	2.32	2.660 (3)	101
C6—H6⋯O11	0.93	2.23	2.854 (3)	124
Symmetry code: (i) 1-x,1-y,z.

All of the non-H atoms lie on mirror planes and the reference molecule was chosen to lie on the mirror plane at z = 0.5. The H atoms were located in difference maps and then treated as riding atoms, with C—H distances 0.93 (aromatic) or 0.95 Å (methyl) and an N—H distance of 0.86 Å, and with U_iso(H) = 1.2U_eq(C,N), or 1.5U_eq(C) for the methyl groups. Each methyl group was modelled using six H-atom sites, each with 0.5 occupancy, offset by 60° intervals.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536804009195/lh6206sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804009195/lh6206Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

2-Methoxycarbonyl-4-nitroacetanilide top

Crystal data top

C₁₀H₁₀N₂O₅	F(000) = 992
M_r = 238.20	D_x = 1.430 Mg m⁻³
Orthorhombic, Ibam	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2 2c	Cell parameters from 1384 reflections
a = 16.4482 (14) Å	θ = 2.1–27.5°
b = 19.9095 (17) Å	µ = 0.12 mm⁻¹
c = 6.7549 (6) Å	T = 291 K
V = 2212.1 (3) Å³	Prism, colourless
Z = 8	0.43 × 0.18 × 0.13 mm

Data collection top

Bruker SMART 1000 CCD area detector diffractometer	1384 independent reflections
Radiation source: fine-focus sealed X-ray tube	828 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
φ–ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −21→21
T_min = 0.930, T_max = 0.985	k = −24→25
7820 measured reflections	l = −8→6

Refinement top

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0672P)² + 0.165P] where P = (F_o² + 2F_c²)/3
1384 reflections	(Δ/σ)_max < 0.001
105 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O11	0.45219 (11)	0.10453 (9)	0.5000	0.0744 (6)
O21	0.66067 (10)	0.37614 (9)	0.5000	0.0692 (6)
O22	0.68212 (10)	0.26564 (8)	0.5000	0.0616 (6)
O41	0.40462 (14)	0.47898 (12)	0.5000	0.1634 (16)
O42	0.29482 (11)	0.42449 (11)	0.5000	0.0958 (8)
N1	0.54959 (11)	0.18637 (9)	0.5000	0.0489 (5)
N4	0.36872 (14)	0.42739 (12)	0.5000	0.0729 (8)
C1	0.50391 (14)	0.24555 (11)	0.5000	0.0416 (6)
C2	0.54480 (12)	0.30844 (11)	0.5000	0.0408 (5)
C3	0.49928 (13)	0.36756 (12)	0.5000	0.0470 (6)
C4	0.41495 (13)	0.36446 (12)	0.5000	0.0490 (6)
C5	0.37413 (14)	0.30371 (13)	0.5000	0.0507 (6)
C6	0.41814 (14)	0.24511 (12)	0.5000	0.0504 (6)
C11	0.52385 (16)	0.12038 (12)	0.5000	0.0512 (6)
C12	0.59167 (17)	0.07005 (13)	0.5000	0.0689 (8)
C21	0.63546 (13)	0.31282 (11)	0.5000	0.0450 (6)
C22	0.74801 (15)	0.38759 (15)	0.5000	0.0832 (10)
H1	0.6015	0.1919	0.5000	0.059*
H3	0.5254	0.4090	0.5000	0.056*
H5	0.3176	0.3026	0.5000	0.061*
H6	0.3908	0.2042	0.5000	0.061*
H12A	0.6364	0.0871	0.4236	0.103*	0.50
H12B	0.5729	0.0287	0.4428	0.103*	0.50
H12C	0.6092	0.0621	0.6335	0.103*	0.50
H22A	0.7726	0.3620	0.6046	0.125*	0.50
H22B	0.7587	0.4345	0.5202	0.125*	0.50
H22C	0.7704	0.3738	0.3752	0.125*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11	0.0529 (12)	0.0586 (11)	0.1116 (18)	−0.0126 (8)	0.000	0.000
O21	0.0310 (8)	0.0527 (10)	0.1239 (18)	−0.0032 (7)	0.000	0.000
O22	0.0367 (9)	0.0546 (10)	0.0936 (16)	0.0063 (8)	0.000	0.000
O41	0.0541 (13)	0.0527 (14)	0.383 (5)	0.0054 (10)	0.000	0.000
O42	0.0394 (11)	0.0895 (15)	0.158 (3)	0.0176 (10)	0.000	0.000
N1	0.0394 (10)	0.0479 (11)	0.0593 (14)	−0.0033 (8)	0.000	0.000
N4	0.0402 (12)	0.0643 (15)	0.114 (2)	0.0088 (11)	0.000	0.000
C1	0.0381 (12)	0.0490 (12)	0.0376 (14)	−0.0013 (9)	0.000	0.000
C2	0.0325 (11)	0.0494 (12)	0.0404 (14)	−0.0020 (9)	0.000	0.000
C3	0.0358 (12)	0.0497 (12)	0.0556 (16)	−0.0024 (10)	0.000	0.000
C4	0.0351 (12)	0.0541 (14)	0.0580 (17)	0.0029 (10)	0.000	0.000
C5	0.0314 (11)	0.0679 (16)	0.0527 (17)	−0.0019 (11)	0.000	0.000
C6	0.0369 (13)	0.0590 (15)	0.0554 (17)	−0.0090 (10)	0.000	0.000
C11	0.0522 (15)	0.0485 (14)	0.0530 (16)	−0.0055 (11)	0.000	0.000
C12	0.0604 (16)	0.0521 (16)	0.094 (2)	0.0014 (12)	0.000	0.000
C21	0.0365 (12)	0.0479 (13)	0.0504 (16)	−0.0031 (10)	0.000	0.000
C22	0.0301 (13)	0.0730 (18)	0.147 (3)	−0.0092 (13)	0.000	0.000

Geometric parameters (Å, º) top

C1—N1	1.397 (3)	O21—C22	1.454 (3)
C1—C6	1.411 (3)	C22—H22A	0.96
C1—C2	1.421 (3)	C22—H22B	0.96
N1—C11	1.380 (3)	C22—H22C	0.96
N1—H1	0.86	C3—C4	1.388 (3)
C11—O11	1.220 (3)	C3—H3	0.93
C11—C12	1.499 (4)	C4—C5	1.383 (3)
C12—H12A	0.96	C4—N4	1.466 (3)
C12—H12B	0.96	N4—O41	1.185 (3)
C12—H12C	0.96	N4—O42	1.217 (3)
C2—C3	1.395 (3)	C5—C6	1.373 (3)
C2—C21	1.494 (3)	C5—H5	0.93
C21—O22	1.213 (3)	C6—H6	0.93
C21—O21	1.327 (3)

N1—C1—C6	122.2 (2)	O21—C22—H22A	109.5
N1—C1—C2	119.24 (19)	O21—C22—H22B	109.5
C6—C1—C2	118.6 (2)	H22A—C22—H22B	109.5
C1—N1—C11	129.6 (2)	O21—C22—H22C	109.5
C11—N1—H1	115.2	H22A—C22—H22C	109.5
C1—N1—H1	115.2	H22B—C22—H22C	109.5
N1—C11—O11	122.8 (2)	C4—C3—C2	119.9 (2)
N1—C11—C12	114.1 (2)	C4—C3—H3	120.0
O11—C11—C12	123.1 (2)	C2—C3—H3	120.0
C11—C12—H12A	109.5	C5—C4—C3	121.6 (2)
C11—C12—H12B	109.5	C5—C4—N4	119.7 (2)
H12A—C12—H12B	109.5	C3—C4—N4	118.7 (2)
C11—C12—H12C	109.5	O41—N4—O42	122.6 (2)
H12A—C12—H12C	109.5	O41—N4—C4	118.8 (2)
H12B—C12—H12C	109.5	O42—N4—C4	118.5 (2)
C3—C2—C1	119.3 (2)	C6—C5—C4	119.1 (2)
C3—C2—C21	119.1 (2)	C6—C5—H5	120.4
C1—C2—C21	121.58 (19)	C4—C5—H5	120.4
C2—C21—O21	111.55 (19)	C5—C6—C1	121.5 (2)
C2—C21—O22	125.9 (2)	C5—C6—H6	119.3
O21—C21—O22	122.5 (2)	C1—C6—H6	119.3
C21—O21—C22	117.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O22	0.86	1.98	2.691 (2)	139
C3—H3···O41ⁱ	0.93	2.51	3.440 (3)	180
C3—H3···O21	0.93	2.32	2.660 (3)	101
C6—H6···O11	0.93	2.23	2.854 (3)	124

Symmetry code: (i) −x+1, −y+1, z.

Acknowledgements

X-ray data were collected at the University of Aberdeen using a Bruker SMART 1000 CCD diffractometer; the authors thank the University of Aberdeen for funding the purchase of the diffractometer. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work. JLW thanks CNPq and FAPERJ for financial support.

References

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