Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107020628/sq3075sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107020628/sq3075Isup2.hkl |
CCDC reference: 652510
For related literature, see: Bernstein et al. (1995); Kornet et al. (1986); Wang et al. (2005); Wardell et al. (2006).
A solution of 4-nitrobenzoyl chloride (2 mmol) and phenylhydrazine (4 mmol) in 1,2-dichloroethane (25 ml) was heated under reflux for 3 h. The reaction mixture was cooled and the solvent was removed under reduced pressure. The solid product was then recrystallized from ethanol to give the title compound, (I) [m.p. 476–478 K; literature values: 476–478 K (Kornet et al., 1986); 471–473 K (Wang et al., 2005)].
The space group P212121 was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N). In the absence of significant resonant scattering, it was not possible to determine the absolute configuration of the molecules in the crystal selected for data collection. However, this has no chemical significance, and the Friedel-equivalent reflections were merged prior to the final refinements.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; 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).
C13H11N3O3 | F(000) = 536 |
Mr = 257.25 | Dx = 1.421 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1477 reflections |
a = 4.6982 (6) Å | θ = 3.1–27.6° |
b = 9.9532 (13) Å | µ = 0.10 mm−1 |
c = 25.719 (4) Å | T = 120 K |
V = 1202.7 (3) Å3 | Plate, yellow |
Z = 4 | 0.32 × 0.16 × 0.07 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 1477 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1314 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.6°, θmin = 3.1° |
ϕ and ω scans | h = −5→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→12 |
Tmin = 0.975, Tmax = 0.993 | l = −32→33 |
4443 measured reflections |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.061P)2 + 1.1588P] where P = (Fo2 + 2Fc2)/3 |
1477 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C13H11N3O3 | V = 1202.7 (3) Å3 |
Mr = 257.25 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 4.6982 (6) Å | µ = 0.10 mm−1 |
b = 9.9532 (13) Å | T = 120 K |
c = 25.719 (4) Å | 0.32 × 0.16 × 0.07 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 1477 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1314 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.993 | Rint = 0.037 |
4443 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.27 e Å−3 |
1477 reflections | Δρmin = −0.27 e Å−3 |
172 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.5301 (8) | 0.4619 (4) | 0.62844 (12) | 0.0233 (8) | |
C2 | 0.3233 (8) | 0.4257 (4) | 0.66448 (13) | 0.0281 (8) | |
C3 | 0.2294 (9) | 0.5166 (4) | 0.70126 (13) | 0.0326 (9) | |
C4 | 0.3444 (9) | 0.6445 (4) | 0.70033 (13) | 0.0303 (9) | |
N4 | 0.2407 (9) | 0.7426 (4) | 0.73870 (12) | 0.0410 (9) | |
O41 | 0.0836 (10) | 0.7033 (4) | 0.77368 (12) | 0.0619 (11) | |
O42 | 0.3102 (8) | 0.8603 (3) | 0.73315 (12) | 0.0468 (9) | |
C5 | 0.5504 (9) | 0.6830 (4) | 0.66527 (13) | 0.0292 (9) | |
C6 | 0.6447 (9) | 0.5911 (4) | 0.62919 (13) | 0.0281 (8) | |
C7 | 0.6417 (8) | 0.3675 (4) | 0.58886 (13) | 0.0242 (8) | |
O7 | 0.8892 (5) | 0.3774 (3) | 0.57235 (9) | 0.0287 (6) | |
N1 | 0.4676 (7) | 0.2685 (3) | 0.57330 (10) | 0.0249 (7) | |
N2 | 0.5636 (7) | 0.1789 (3) | 0.53576 (11) | 0.0316 (8) | |
C21 | 0.7356 (8) | 0.0726 (3) | 0.55066 (13) | 0.0225 (7) | |
C22 | 0.8580 (8) | 0.0630 (4) | 0.60011 (13) | 0.0270 (8) | |
C23 | 1.0473 (9) | −0.0398 (4) | 0.61098 (14) | 0.0329 (9) | |
C24 | 1.1178 (9) | −0.1335 (4) | 0.57367 (16) | 0.0346 (9) | |
C25 | 0.9950 (8) | −0.1248 (4) | 0.52475 (15) | 0.0304 (8) | |
C26 | 0.8070 (8) | −0.0236 (4) | 0.51305 (13) | 0.0252 (8) | |
H2 | 0.2458 | 0.3376 | 0.6638 | 0.034* | |
H3 | 0.0904 | 0.4921 | 0.7264 | 0.039* | |
H5 | 0.6260 | 0.7714 | 0.6660 | 0.035* | |
H6 | 0.7876 | 0.6156 | 0.6048 | 0.034* | |
H1 | 0.2858 | 0.2666 | 0.5815 | 0.030* | |
H2A | 0.4602 | 0.1733 | 0.5073 | 0.038* | |
H22 | 0.8113 | 0.1269 | 0.6262 | 0.032* | |
H23 | 1.1297 | −0.0459 | 0.6446 | 0.040* | |
H24 | 1.2491 | −0.2033 | 0.5814 | 0.042* | |
H25 | 1.0416 | −0.1896 | 0.4990 | 0.036* | |
H26 | 0.7250 | −0.0188 | 0.4793 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0196 (17) | 0.0312 (18) | 0.0191 (14) | 0.0018 (16) | −0.0020 (13) | 0.0014 (14) |
C2 | 0.0269 (19) | 0.0311 (19) | 0.0263 (16) | 0.0049 (18) | 0.0015 (15) | 0.0024 (15) |
C3 | 0.032 (2) | 0.043 (2) | 0.0230 (16) | 0.005 (2) | 0.0036 (16) | 0.0058 (17) |
C4 | 0.032 (2) | 0.036 (2) | 0.0222 (15) | 0.012 (2) | −0.0051 (16) | −0.0047 (15) |
N4 | 0.048 (2) | 0.046 (2) | 0.0290 (16) | 0.021 (2) | −0.0069 (17) | −0.0079 (16) |
O41 | 0.089 (3) | 0.059 (2) | 0.0379 (15) | 0.023 (2) | 0.0232 (19) | −0.0037 (16) |
O42 | 0.059 (2) | 0.0384 (17) | 0.0433 (16) | 0.0102 (18) | −0.0075 (16) | −0.0153 (14) |
C5 | 0.029 (2) | 0.0303 (19) | 0.0286 (16) | 0.0048 (18) | −0.0044 (16) | −0.0005 (16) |
C6 | 0.0222 (18) | 0.0333 (19) | 0.0287 (16) | 0.0029 (18) | 0.0004 (15) | 0.0025 (15) |
C7 | 0.0224 (18) | 0.0278 (17) | 0.0224 (14) | 0.0046 (18) | 0.0003 (14) | 0.0044 (14) |
O7 | 0.0194 (13) | 0.0384 (15) | 0.0284 (12) | 0.0012 (13) | 0.0056 (11) | 0.0016 (12) |
N1 | 0.0183 (15) | 0.0331 (17) | 0.0232 (12) | 0.0031 (14) | 0.0015 (12) | −0.0043 (13) |
N2 | 0.0338 (18) | 0.0382 (18) | 0.0226 (13) | 0.0157 (17) | −0.0069 (13) | −0.0061 (13) |
C21 | 0.0188 (17) | 0.0225 (17) | 0.0263 (16) | −0.0009 (16) | −0.0003 (14) | 0.0041 (14) |
C22 | 0.0252 (19) | 0.0279 (18) | 0.0278 (17) | 0.0003 (18) | −0.0024 (16) | −0.0033 (15) |
C23 | 0.032 (2) | 0.038 (2) | 0.0286 (16) | −0.001 (2) | −0.0064 (17) | 0.0099 (17) |
C24 | 0.032 (2) | 0.0260 (18) | 0.046 (2) | 0.005 (2) | −0.0067 (19) | 0.0069 (18) |
C25 | 0.029 (2) | 0.0260 (18) | 0.0362 (18) | 0.0005 (18) | 0.0005 (16) | −0.0027 (16) |
C26 | 0.0236 (19) | 0.0247 (17) | 0.0273 (15) | −0.0036 (16) | 0.0012 (15) | −0.0008 (14) |
C1—C2 | 1.390 (5) | N1—N2 | 1.390 (4) |
C1—C6 | 1.394 (5) | N1—H1 | 0.88 |
C1—C7 | 1.481 (5) | N2—C21 | 1.385 (5) |
C2—C3 | 1.381 (5) | N2—H2A | 0.88 |
C2—H2 | 0.95 | C21—C22 | 1.399 (5) |
C3—C4 | 1.383 (6) | C21—C26 | 1.402 (5) |
C3—H3 | 0.95 | C22—C23 | 1.385 (5) |
C4—C5 | 1.377 (5) | C22—H22 | 0.95 |
C4—N4 | 1.472 (5) | C23—C24 | 1.379 (6) |
N4—O42 | 1.224 (5) | C23—H23 | 0.95 |
N4—O41 | 1.228 (5) | C24—C25 | 1.387 (5) |
C5—C6 | 1.376 (5) | C24—H24 | 0.95 |
C5—H5 | 0.95 | C25—C26 | 1.373 (5) |
C6—H6 | 0.95 | C25—H25 | 0.95 |
C7—O7 | 1.242 (4) | C26—H26 | 0.95 |
C7—N1 | 1.342 (5) | ||
C2—C1—C6 | 119.9 (3) | C7—N1—N2 | 118.7 (3) |
C2—C1—C7 | 122.8 (3) | C7—N1—H1 | 122.4 |
C6—C1—C7 | 117.2 (3) | N2—N1—H1 | 117.9 |
C3—C2—C1 | 120.7 (4) | C21—N2—N1 | 119.2 (3) |
C3—C2—H2 | 119.6 | C21—N2—H2A | 120.2 |
C1—C2—H2 | 119.6 | N1—N2—H2A | 116.1 |
C2—C3—C4 | 117.8 (4) | N2—C21—C22 | 122.9 (3) |
C2—C3—H3 | 121.1 | N2—C21—C26 | 118.1 (3) |
C4—C3—H3 | 121.1 | C22—C21—C26 | 118.8 (3) |
C5—C4—C3 | 122.8 (4) | C23—C22—C21 | 119.9 (3) |
C5—C4—N4 | 119.1 (4) | C23—C22—H22 | 120.1 |
C3—C4—N4 | 118.1 (4) | C21—C22—H22 | 120.1 |
O42—N4—O41 | 123.5 (4) | C24—C23—C22 | 120.9 (3) |
O42—N4—C4 | 117.9 (4) | C24—C23—H23 | 119.5 |
O41—N4—C4 | 118.6 (4) | C22—C23—H23 | 119.5 |
C6—C5—C4 | 118.9 (4) | C23—C24—C25 | 119.3 (4) |
C6—C5—H5 | 120.6 | C23—C24—H24 | 120.4 |
C4—C5—H5 | 120.6 | C25—C24—H24 | 120.4 |
C5—C6—C1 | 119.9 (4) | C26—C25—C24 | 120.8 (4) |
C5—C6—H6 | 120.1 | C26—C25—H25 | 119.6 |
C1—C6—H6 | 120.1 | C24—C25—H25 | 119.6 |
O7—C7—N1 | 121.8 (3) | C25—C26—C21 | 120.3 (3) |
O7—C7—C1 | 121.1 (4) | C25—C26—H26 | 119.9 |
N1—C7—C1 | 117.1 (3) | C21—C26—H26 | 119.9 |
C6—C1—C2—C3 | 0.0 (6) | C6—C1—C7—N1 | −153.5 (3) |
C7—C1—C2—C3 | 178.9 (3) | O7—C7—N1—N2 | −3.3 (5) |
C1—C2—C3—C4 | 1.0 (6) | C1—C7—N1—N2 | 179.3 (3) |
C2—C3—C4—C5 | −1.4 (6) | C7—N1—N2—C21 | 81.7 (4) |
C2—C3—C4—N4 | 178.7 (3) | N1—N2—C21—C22 | −11.2 (5) |
C5—C4—N4—O42 | 10.7 (5) | C3—C4—N4—O41 | 8.7 (6) |
C3—C4—N4—O42 | −169.4 (4) | N1—N2—C21—C26 | 173.9 (3) |
C5—C4—N4—O41 | −171.2 (4) | N2—C21—C22—C23 | −174.4 (3) |
C3—C4—C5—C6 | 0.6 (6) | C26—C21—C22—C23 | 0.4 (5) |
N4—C4—C5—C6 | −179.4 (3) | C21—C22—C23—C24 | 0.0 (6) |
C4—C5—C6—C1 | 0.4 (5) | C22—C23—C24—C25 | −0.5 (6) |
C2—C1—C6—C5 | −0.7 (5) | C23—C24—C25—C26 | 0.6 (6) |
C7—C1—C6—C5 | −179.7 (3) | C24—C25—C26—C21 | −0.1 (6) |
C2—C1—C7—O7 | −150.0 (4) | N2—C21—C26—C25 | 174.7 (3) |
C6—C1—C7—O7 | 29.0 (5) | C22—C21—C26—C25 | −0.3 (5) |
C2—C1—C7—N1 | 27.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O7i | 0.88 | 2.18 | 2.926 (4) | 143 |
N2—H2A···O7ii | 0.88 | 2.14 | 2.952 (4) | 154 |
N2—H2A···N2ii | 0.88 | 2.62 | 3.302 (4) | 135 |
C3—H3···O42iii | 0.95 | 2.52 | 3.419 (5) | 158 |
C26—H26···O7ii | 0.95 | 2.50 | 3.285 (5) | 140 |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, −z+1; (iii) −x, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C13H11N3O3 |
Mr | 257.25 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 120 |
a, b, c (Å) | 4.6982 (6), 9.9532 (13), 25.719 (4) |
V (Å3) | 1202.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.32 × 0.16 × 0.07 |
Data collection | |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.975, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4443, 1477, 1314 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.149, 1.10 |
No. of reflections | 1477 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.27 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
C2—C1—C7—N1 | 27.5 (5) | N1—N2—C21—C22 | −11.2 (5) |
C1—C7—N1—N2 | 179.3 (3) | C3—C4—N4—O41 | 8.7 (6) |
C7—N1—N2—C21 | 81.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O7i | 0.88 | 2.18 | 2.926 (4) | 143 |
N2—H2A···O7ii | 0.88 | 2.14 | 2.952 (4) | 154 |
N2—H2A···N2ii | 0.88 | 2.62 | 3.302 (4) | 135 |
C3—H3···O42iii | 0.95 | 2.52 | 3.419 (5) | 158 |
C26—H26···O7ii | 0.95 | 2.50 | 3.285 (5) | 140 |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, −z+1; (iii) −x, y−1/2, −z+3/2. |
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As part of our continuing investigation of the supramolecular structures of acylhydrazines and acylhydrazones, we report here the structure of the title compound, (I) (Fig. 1), whose supramolecular structure we compare with that of the related compound N-(3,5-dinitrobenzoyl)-N'-phenylhydrazine, (II) (Wardell et al., 2006).
The configuration at each of the atoms N1 and N2 of (I) is almost co-planar. The central C—C(═O)—N—N unit adopts an almost planar trans conformation, and the remainder of the molecular conformation can be defined in terms of just four further torsion angles (Table 1). The large C7—N1—N2—C21 torsion angle reflects the tendency of the lone-pair orbitals on N1 and N2 to be nearly orthogonal, in order to minimize the corresponding overlap and resonance integrals. The molecules have no internal symmetry in the solid state and are thus conformationally chiral. The achiral space group ensures that each crystal contains only a single enantiomeric form.
The molecules of compound (I) are linked into a complex three-dimensional framework structure by a combination of one two-centre N—H···O hydrogen bond, one rather asymmetric three-centre N—H···(O,N) hydrogen bond and two independent two-centre C—H···O hydrogen bonds (Table 2). The formation of the sheet is readily analysed in terms of simple sub-structures.
In the first sub-structure, amide atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor to amide atom O7 in the molecule at (-1 + x, y, z), so generating by translation a C(4) (Bernstein et al., 1995) chain running parallel to the [100] direction (Fig. 2). In addition, atoms N2 and C26 in the molecule at (x, y, z) both act as hydrogen-bond donors to atom O7 in the molecule at (-1/2 + x, 1/2 - y, 1 - z), so forming a C(5)C(7)[R12(6)] chain of rings running parallel to the [100] direction and generated by the 21 screw axis along (x, 1/4, 1/2) (Fig. 3). Atom N2 at (x, y, z) also forms a rather long and probably fairly weak interaction with atom N2 at (-1/2 + x, 1/2 - y, 1 - z), so that N2 can be regarded as the donor in an asymmetric but almost planar three-centre N—H···(O,N) hydrogen bond. The combination of all these interactions generates a complex chain of rings running parallel to the [100] direction (Fig. 2).
The second sub-structure is built from a single C—H···O hydrogen bond. Aryl atom C3 in the molecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O42 in the molecule at (-x, -1/2 + y, 3/2 - z), so forming a C(5) chain running parallel to the [010] direction and generated by the 21 screw axis along (0, y, 3/4) (Fig. 3).
In combination, the N—H···O and C—H···O hydrogen bonds, which individually generate two independent C(5) helical chains running parallel to [100] and [010], respectively, together generate a C22(16) chain running parallel to the [001] direction (Fig. 4). The combined action of chains parallel to [100], [010] and [001] (Figs. 2–4) suffices to generate a single three-dimensional framework.
In the related 3,5-dinitro compound, (II) (Wardell et al., 2006), the molecules are again conformationally chiral, with a C7—N1—N2—C21 torsion angle of 84.2 (2)°, but the centrosymmetric space group P21/n accommodates equal numbers of the two enantiomeric forms. The molecules are linked into sheets by a combination of three independent two-centre hydrogen bonds, one each of N—H···O(carbonyl), N—H···O(nitro) and C—H···O(carbonyl) types.