organic compounds
2-Nitrophenoxyacetanilide: a chain of rings generated by C—H⋯O hydrogen bonds
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
In molecules of the title compound, C14H12N2O4, the conformation is dominated by an intramolecular N—H⋯O hydrogen bond in which one of the nitro O atoms is the acceptor. The molecules are linked by paired C—H⋯O hydrogen bonds [H⋯O = 2.41 Å, C⋯O = 3.2990 (17) Å and C—H⋯O = 156°] into centrosymmetric (14) dimers; these dimers are linked weakly into chains of alternating (14) and (40) rings by a second C—H⋯O hydrogen bond [H⋯O = 2.55 Å, C⋯O = 3.5006 (15) Å and C—H⋯O = 162°].
Comment
The title compound, (I) (Fig. 1), was designed to contain a wide variety of potential donors and acceptors of both hard and soft (Braga et al., 1995; Desiraju & Steiner, 1999) hydrogen bonds. Thus, there are both N—H and C—H bonds to provide potential hydrogen-bond donors, and there are three types of O-atom sites as potential acceptors, namely the ether O, the carbonyl O and the nitro O atoms. In addition, the presence of two independent offers the possibility of N—H⋯π(arene) and C—H⋯π(arene) hydrogen bonding, as well as aromatic π–π stacking interactions.
In the event, the only hard hydrogen bond is intramolecular, and this appears to be the dominant influence on the overall S(9) motif (Bernstein et al., 1995). In addition, there is a short contact to atom O2, but this contact is probably just an adventitious consequence of the hydrogen bond to atom O11. The consequences of the intramolecular hydrogen bonding are firstly the nearly planar overall conformation (Table 1), with a cisoid O2—C27—C28—N2 fragment, and secondly the unavailability of the NH group for participation in intermolecular hydrogen bonds. The bond angles in the central spacer unit are indicative of the strongly attractive nature of the intramolecular hydrogen bond. The dihedral angle between the nitro group and the adjacent aryl ring is 11.8 (2)°.
Amine atom N2 acts as a donor to nitro atom O11 in a nearly linear N—H⋯O hydrogen bond, so forming anThe supramolecular aggregation is determined by two C—H⋯O hydrogen bonds, one weaker than the other (Table 2). In the stronger of these two interactions, aromatic atom C3 in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O28 in the molecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric S(9)[(14)]S(9) (Bernstein et al., 1995) dimer centred at (, , ) (Fig. 2). These dimers are linked by the longer of the two intermolecular hydrogen bonds; atom C27 in the molecule at (x, y, z) acts as a donor via atom H27A to nitro atom O11 in the molecule at (x, 1 + y, z), so forming by translation a C(7) chain parallel to [010]. Propagation of this hydrogen bond by translation and inversion then generates a complex chain of rings running parallel to the [010] direction, in which (14) rings centred at (, + n, ) (n = zero or integer) alternate with (40) rings centred at (, n, ) (n = zero or integer) (Fig. 3).
There are no direction-specific interactions between adjacent chains; in particular, there are no intermolecular hydrogen bonds involving the NH fragment, nor are there any C—H⋯π(arene) hydrogen bonds or aromatic π–π stacking interactions.
Experimental
For the preparation of (I), a suspension of PhNH2 (10 mmol) in cold NaOH solution (20 ml of 1 mol dm−3) was added to 2-nitrophenoxyacetyl chloride (10 mmol) (Minton & Stephen, 1922; Holley & Holley, 1952). The mixture was stirred for 1 h at 273 K and then allowed to reach ambient temperature. The precipitate that formed was collected after 16 h and recrystallized from ethanol, yielding the title compound [m.p. 394–395 K; literature m.p. 395–397 K (Kirk & Cohen, 1972)].
Crystal data
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Data collection
Refinement
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|
P21/n was uniquely assigned from the All H atoms were located from difference maps and treated as riding atoms, with C—H distances of 0.95 (aromatic) and 0.99 Å (CH2), and N—H distances of 0.88 Å, and with Uiso(H) values set at 1.2Ueq(C,N).
Data collection: KappaCCD Server Software (Nonius, 1997); cell DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; 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
10.1107/S010827010400513X/sk1709sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S010827010400513X/sk1709Isup2.hkl
For the preparation of (I), a suspension of PhNH2 (10 mmol) in cold NaOH solution (20 ml of 1 mol dm−3) was added to 2-nitrophenoxyacetyl chloride (10 mmol) (Minton & Stephen, 1922; Holley & Holley, 1952). After stirring for 1 h at 273 K, the mixture was allowed to reach ambient temperature, and the precipitate that formed was collected after 16 h. This was recrystallized from ethanol, yielding the title compound [m.p. 394–395 K; literature m.p. 395–397 K (Kirk & Cohen, 1972)].
Space group P21/n was uniquely assigned from the
All H atoms were located from difference maps and treated as riding atoms, with C—H distances of 0.95 (aromatic) and 0.99 Å (CH2), and N—H distances of 0.88 Å, and with Uiso(H) set at 1.2Ueq(C,N).Data collection: KappaCCD Server Software (Nonius, 1997); cell
DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; 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).Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. Part of the crystal structure of (I), showing the formation of a centrosymmetric hydrogen-bonded dimer. For clarity, the unit-cell box and H atoms bonded to C atoms but not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z). | |
Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a chain of alternating R22(14) and R44(40) rings along [010]. For clarity, H atoms bonded to C atoms but not involved in the motifs shown have been omitted. |
C14H12N2O4 | F(000) = 568 |
Mr = 272.26 | Dx = 1.447 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2869 reflections |
a = 8.5855 (3) Å | θ = 3.2–27.6° |
b = 6.6129 (2) Å | µ = 0.11 mm−1 |
c = 22.0221 (8) Å | T = 120 K |
β = 91.8330 (17)° | Block, colourless |
V = 1249.67 (7) Å3 | 0.40 × 0.30 × 0.10 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 2869 independent reflections |
Radiation source: rotating anode | 2048 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ scans, and ω scans with κ offsets | θmax = 27.6°, θmin = 3.2° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −11→11 |
Tmin = 0.951, Tmax = 0.989 | k = −8→8 |
5590 measured reflections | l = −28→28 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0596P)2 + 0.0301P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2869 reflections | Δρmax = 0.23 e Å−3 |
182 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.015 (2) |
C14H12N2O4 | V = 1249.67 (7) Å3 |
Mr = 272.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.5855 (3) Å | µ = 0.11 mm−1 |
b = 6.6129 (2) Å | T = 120 K |
c = 22.0221 (8) Å | 0.40 × 0.30 × 0.10 mm |
β = 91.8330 (17)° |
Nonius KappaCCD diffractometer | 2869 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 2048 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.989 | Rint = 0.028 |
5590 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.23 e Å−3 |
2869 reflections | Δρmin = −0.19 e Å−3 |
182 parameters |
x | y | z | Uiso*/Ueq | ||
O2 | 0.58655 (10) | 0.07786 (12) | 0.56272 (4) | 0.0273 (2) | |
O11 | 0.67330 (11) | −0.27857 (13) | 0.59281 (4) | 0.0352 (3) | |
O12 | 0.67431 (14) | −0.35883 (16) | 0.68733 (5) | 0.0538 (3) | |
O28 | 0.70165 (11) | 0.33007 (14) | 0.43088 (4) | 0.0362 (3) | |
N1 | 0.63677 (13) | −0.24551 (16) | 0.64546 (5) | 0.0317 (3) | |
N2 | 0.77220 (12) | 0.03034 (16) | 0.47565 (5) | 0.0264 (3) | |
C1 | 0.54833 (15) | −0.06453 (18) | 0.65985 (6) | 0.0278 (3) | |
C2 | 0.52726 (14) | 0.09548 (19) | 0.61855 (6) | 0.0249 (3) | |
C3 | 0.44553 (16) | 0.2652 (2) | 0.63713 (6) | 0.0318 (3) | |
C4 | 0.39037 (17) | 0.2747 (2) | 0.69490 (7) | 0.0419 (4) | |
C5 | 0.41105 (19) | 0.1180 (2) | 0.73528 (7) | 0.0461 (4) | |
C6 | 0.48921 (17) | −0.0531 (2) | 0.71761 (6) | 0.0384 (4) | |
C21 | 0.87765 (15) | −0.05310 (19) | 0.43475 (6) | 0.0263 (3) | |
C22 | 0.93602 (15) | 0.0529 (2) | 0.38626 (6) | 0.0316 (3) | |
C23 | 1.04188 (16) | −0.0409 (2) | 0.34902 (6) | 0.0360 (4) | |
C24 | 1.09038 (16) | −0.2371 (2) | 0.36001 (6) | 0.0361 (4) | |
C25 | 1.03025 (15) | −0.3423 (2) | 0.40782 (7) | 0.0352 (3) | |
C26 | 0.92444 (16) | −0.25263 (19) | 0.44513 (6) | 0.0313 (3) | |
C27 | 0.59236 (15) | 0.25291 (17) | 0.52486 (6) | 0.0274 (3) | |
C28 | 0.69471 (15) | 0.20731 (19) | 0.47213 (6) | 0.0270 (3) | |
H3 | 0.4279 | 0.3745 | 0.6098 | 0.038* | |
H4 | 0.3366 | 0.3926 | 0.7072 | 0.050* | |
H5 | 0.3718 | 0.1275 | 0.7750 | 0.055* | |
H6 | 0.5026 | −0.1632 | 0.7450 | 0.046* | |
H27A | 0.6353 | 0.3688 | 0.5484 | 0.033* | |
H27B | 0.4861 | 0.2887 | 0.5097 | 0.033* | |
H2 | 0.7545 | −0.0434 | 0.5080 | 0.032* | |
H22 | 0.9040 | 0.1882 | 0.3785 | 0.038* | |
H23 | 1.0815 | 0.0310 | 0.3155 | 0.043* | |
H24 | 1.1645 | −0.2987 | 0.3348 | 0.043* | |
H25 | 1.0620 | −0.4780 | 0.4152 | 0.042* | |
H26 | 0.8833 | −0.3267 | 0.4779 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0359 (5) | 0.0204 (5) | 0.0257 (5) | 0.0026 (4) | 0.0019 (4) | 0.0019 (4) |
O11 | 0.0411 (6) | 0.0276 (5) | 0.0366 (6) | 0.0061 (4) | −0.0015 (5) | −0.0029 (4) |
O12 | 0.0750 (8) | 0.0382 (6) | 0.0475 (7) | 0.0108 (6) | −0.0064 (6) | 0.0187 (5) |
O28 | 0.0390 (6) | 0.0288 (5) | 0.0408 (6) | 0.0015 (4) | 0.0033 (4) | 0.0108 (5) |
N1 | 0.0348 (7) | 0.0244 (6) | 0.0354 (7) | −0.0020 (5) | −0.0062 (5) | 0.0035 (5) |
N2 | 0.0288 (6) | 0.0223 (6) | 0.0280 (6) | 0.0000 (4) | −0.0011 (5) | 0.0023 (5) |
C1 | 0.0285 (7) | 0.0252 (7) | 0.0293 (7) | −0.0029 (5) | −0.0030 (6) | −0.0025 (6) |
C2 | 0.0227 (7) | 0.0259 (7) | 0.0258 (7) | −0.0017 (5) | −0.0032 (5) | −0.0034 (5) |
C3 | 0.0285 (7) | 0.0281 (7) | 0.0386 (8) | 0.0016 (6) | −0.0010 (6) | −0.0054 (6) |
C4 | 0.0350 (8) | 0.0399 (9) | 0.0514 (10) | −0.0030 (7) | 0.0101 (7) | −0.0151 (8) |
C5 | 0.0526 (10) | 0.0502 (10) | 0.0362 (9) | −0.0150 (8) | 0.0132 (7) | −0.0132 (8) |
C6 | 0.0469 (9) | 0.0397 (8) | 0.0285 (8) | −0.0128 (7) | −0.0002 (6) | 0.0000 (6) |
C21 | 0.0230 (7) | 0.0265 (7) | 0.0291 (7) | −0.0027 (5) | −0.0060 (5) | −0.0022 (6) |
C22 | 0.0314 (8) | 0.0293 (7) | 0.0338 (8) | −0.0015 (6) | −0.0027 (6) | 0.0008 (6) |
C23 | 0.0308 (8) | 0.0424 (9) | 0.0346 (8) | −0.0056 (6) | 0.0001 (6) | −0.0017 (7) |
C24 | 0.0277 (7) | 0.0445 (9) | 0.0357 (8) | −0.0001 (6) | −0.0031 (6) | −0.0124 (7) |
C25 | 0.0316 (8) | 0.0287 (7) | 0.0447 (9) | 0.0034 (6) | −0.0085 (6) | −0.0068 (6) |
C26 | 0.0306 (7) | 0.0270 (7) | 0.0358 (8) | −0.0013 (6) | −0.0046 (6) | −0.0001 (6) |
C27 | 0.0319 (7) | 0.0180 (7) | 0.0317 (7) | −0.0004 (5) | −0.0055 (6) | 0.0027 (5) |
C28 | 0.0265 (7) | 0.0222 (7) | 0.0318 (7) | −0.0046 (5) | −0.0061 (5) | 0.0029 (6) |
C1—C6 | 1.3867 (18) | C27—H27B | 0.99 |
C1—C2 | 1.4031 (18) | C28—O28 | 1.2211 (14) |
C1—N1 | 1.4577 (17) | C28—N2 | 1.3472 (16) |
C2—O2 | 1.3508 (15) | N2—C21 | 1.4098 (17) |
C2—C3 | 1.3919 (18) | N2—H2 | 0.88 |
C3—C4 | 1.373 (2) | C21—C22 | 1.3844 (18) |
C3—H3 | 0.95 | C21—C26 | 1.3960 (19) |
C4—C5 | 1.373 (2) | C22—C23 | 1.389 (2) |
C4—H4 | 0.95 | C22—H22 | 0.95 |
C5—C6 | 1.378 (2) | C23—C24 | 1.382 (2) |
C5—H5 | 0.95 | C23—H23 | 0.95 |
C6—H6 | 0.95 | C24—C25 | 1.376 (2) |
N1—O12 | 1.2234 (14) | C24—H24 | 0.95 |
N1—O11 | 1.2304 (14) | C25—C26 | 1.3784 (19) |
O2—C27 | 1.4283 (14) | C25—H25 | 0.95 |
C27—C28 | 1.5090 (18) | C26—H26 | 0.95 |
C27—H27A | 0.99 | ||
C6—C1—C2 | 120.66 (12) | C28—C27—H27B | 110.0 |
C6—C1—N1 | 116.92 (12) | H27A—C27—H27B | 108.3 |
C2—C1—N1 | 122.38 (11) | O28—C28—N2 | 125.78 (12) |
O2—C2—C3 | 123.04 (11) | O28—C28—C27 | 118.89 (11) |
O2—C2—C1 | 118.71 (11) | C27—C28—N2 | 115.33 (11) |
C3—C2—C1 | 118.25 (12) | C28—N2—C21 | 128.99 (11) |
C4—C3—C2 | 120.10 (13) | C28—N2—H2 | 115.5 |
C4—C3—H3 | 120.0 | C21—N2—H2 | 115.5 |
C2—C3—H3 | 120.0 | C22—C21—C26 | 119.69 (12) |
C3—C4—C5 | 121.60 (14) | C22—C21—N2 | 123.39 (12) |
C3—C4—H4 | 119.2 | C26—C21—N2 | 116.91 (12) |
C5—C4—H4 | 119.2 | C21—C22—C23 | 119.29 (14) |
C4—C5—C6 | 119.39 (14) | C21—C22—H22 | 120.4 |
C4—C5—H5 | 120.3 | C23—C22—H22 | 120.4 |
C6—C5—H5 | 120.3 | C24—C23—C22 | 120.97 (14) |
C5—C6—C1 | 119.99 (14) | C24—C23—H23 | 119.5 |
C5—C6—H6 | 120.0 | C22—C23—H23 | 119.5 |
C1—C6—H6 | 120.0 | C25—C24—C23 | 119.38 (13) |
O12—N1—O11 | 122.18 (11) | C25—C24—H24 | 120.3 |
O12—N1—C1 | 117.75 (12) | C23—C24—H24 | 120.3 |
O11—N1—C1 | 120.07 (10) | C24—C25—C26 | 120.60 (14) |
C2—O2—C27 | 118.86 (9) | C24—C25—H25 | 119.7 |
O2—C27—C28 | 108.62 (9) | C26—C25—H25 | 119.7 |
O2—C27—H27A | 110.0 | C25—C26—C21 | 120.05 (13) |
C28—C27—H27A | 110.0 | C25—C26—H26 | 120.0 |
O2—C27—H27B | 110.0 | C21—C26—H26 | 120.0 |
C6—C1—C2—O2 | −179.89 (11) | O2—C27—C28—N2 | −8.14 (15) |
N1—C1—C2—O2 | 2.36 (18) | O28—C28—N2—C21 | 0.8 (2) |
C6—C1—C2—C3 | −0.08 (19) | C27—C28—N2—C21 | −178.80 (12) |
N1—C1—C2—C3 | −177.83 (11) | C28—N2—C21—C22 | 9.4 (2) |
O2—C2—C3—C4 | −178.99 (12) | C28—C27—O2—C2 | 167.20 (10) |
C1—C2—C3—C4 | 1.21 (19) | C1—C2—O2—C27 | −168.01 (11) |
C2—C3—C4—C5 | −1.3 (2) | C2—C1—N1—O11 | −12.48 (18) |
C3—C4—C5—C6 | 0.1 (2) | C28—N2—C21—C26 | −171.10 (12) |
C4—C5—C6—C1 | 1.0 (2) | C26—C21—C22—C23 | −0.70 (19) |
C2—C1—C6—C5 | −1.1 (2) | N2—C21—C22—C23 | 178.77 (12) |
N1—C1—C6—C5 | 176.82 (12) | C21—C22—C23—C24 | −0.5 (2) |
C6—C1—N1—O12 | −11.43 (18) | C22—C23—C24—C25 | 1.4 (2) |
C2—C1—N1—O12 | 166.40 (12) | C23—C24—C25—C26 | −1.0 (2) |
C6—C1—N1—O11 | 169.69 (11) | C24—C25—C26—C21 | −0.2 (2) |
C3—C2—O2—C27 | 12.19 (17) | C22—C21—C26—C25 | 1.07 (19) |
O2—C27—C28—O28 | 172.24 (11) | N2—C21—C26—C25 | −178.43 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.88 | 2.07 | 2.5517 (13) | 113 |
N2—H2···O11 | 0.88 | 2.55 | 3.4191 (14) | 172 |
C3—H3···O28i | 0.95 | 2.41 | 3.2990 (17) | 156 |
C27—H27A···O11ii | 0.99 | 2.55 | 3.5006 (15) | 162 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C14H12N2O4 |
Mr | 272.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 120 |
a, b, c (Å) | 8.5855 (3), 6.6129 (2), 22.0221 (8) |
β (°) | 91.8330 (17) |
V (Å3) | 1249.67 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.40 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.951, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5590, 2869, 2048 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.108, 1.05 |
No. of reflections | 2869 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.19 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
C2—O2—C27 | 118.86 (9) | C27—C28—N2 | 115.33 (11) |
O2—C27—C28 | 108.62 (9) | C28—N2—C21 | 128.99 (11) |
O2—C27—C28—N2 | −8.14 (15) | C28—C27—O2—C2 | 167.20 (10) |
C27—C28—N2—C21 | −178.80 (12) | C1—C2—O2—C27 | −168.01 (11) |
C28—N2—C21—C22 | 9.4 (2) | C2—C1—N1—O11 | −12.48 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.88 | 2.07 | 2.5517 (13) | 113 |
N2—H2···O11 | 0.88 | 2.55 | 3.4191 (14) | 172 |
C3—H3···O28i | 0.95 | 2.41 | 3.2990 (17) | 156 |
C27—H27A···O11ii | 0.99 | 2.55 | 3.5006 (15) | 162 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z. |
Acknowledgements
X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants that have provided computing facilities for this work. JLW thanks CNPq and FAPERJ for financial support.
References
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The title compound, (I), was designed to contain a wide variety of potential donors and acceptors of both hard and soft (Braga et al., 1995; Desiraju & Steiner, 1999) hydrogen bonds. Thus there are both N—H and C—H bonds to provide potential hydrogen-bond donors, and there are three types of O sites as potential acceptors, namely the ether O, the carbonyl O and the nitro O atoms. In addition, the presence of two independent aryl groups offers the possibility of N—H···π(arene) and C—H···π(arene) hydrogen bonding, as well as aromatic π–π stacking interactions.
In the event, the only hard hydrogen bond is intramolecular, and this appears to be the dominant influence on the overall molecular conformation. Amine atom N2 acts as a donor to nitro atom O11 in a nearly linear N—H···O hydrogen bond, so forming an S(9) motif (Bernstein et al., 1995). In addition, there is a short contact to atom O2, but this contact is probably just an adventitious consequence of the hydrogen bond to atom O11. The consequences of the intramolecular hydrogen bonding are firstly the nearly planar overall conformation (Table 1), with a cisoid O2—C27—C28—N2 fragment, and secondly the unavailability of the NH unit for participation in intermolecular hydrogen bonds. The bond angles in the central spacer unit are indicative of the strongly attractive nature of the intramolecular hydrogen bond. The dihedral angle between the nitro group and the adjacent aryl ring is 11.8 (2) °.
The supramolecular aggregation is determined by two C—H···O hydrogen bonds, one weaker than the other (Table 2). In the stronger of these two interactions, aromatic atom C3 in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O28 in the molecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric S(9)[R22(14)]S(9) (Bernstein et al., 1995) dimer centred at (1/2, 1/2, 1/2) (Fig. 2). These dimers are linked by the longer of the two intermolecular hydrogen bonds; atom C27 in the molecule at (x, y, z) acts as a donor, via atom H27A, to nitro atom O11 in the molecule at (x, 1 + y, z), so forming by translation a C(7) chain parallel to [010]. Propagation of this hydrogen bond by translation and inversion then generates a complex chain of rings running parallel to the [010] direction, in which R22(14) rings centred at (1/2, 0.5 + n, 1/2) (n = zero or integer) alternate with R44(40) rings centred at (1/2, n, 1/2) (n = zero or integer) (Fig. 3).
There are no direction-specific interactions between adjacent chains; in particular, there are no intermolecular hydrogen bonds involving the NH fragment, nor are there any C—H···π(arene) hydrogen bonds or aromatic π–π stacking interactions.