Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104000678/sk1695sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104000678/sk1695Isup2.hkl |
CCDC reference: 235342
A suspension of equimolar amounts (16 mmol) of 4-nitrophenylhydrazine and 4,4-dimethyl-3-oxopentanenitrile in concentrated HCl (10 ml) and water (20 ml) was stirred at room temperature for 10 min. The volume was then reduced to half the original, concentrated HCl (20 ml) was added, and the resulting mixture was heated with stirring for 15 min. The mixture was then cooled and neutralized with aqueous ammonia. The solid product, (I), was collected and recrystallized from water (yield 90%, m.p. 445 K).
Space group P21/c was uniquely assigned from the systematic absences. All H atoms were located from difference maps, which showed clearly the pyramidal nature of the amine group based on atom N5, and all H atoms then treated as riding atoms, with C—H 0.distances of 95 (aromatic) or 0.98 Å (methyl), and N—H distances of 0.88 Å.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: 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: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
C13H16N4O2 | F(000) = 552 |
Mr = 260.30 | Dx = 1.315 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3001 reflections |
a = 5.9581 (2) Å | θ = 3.4–27.5° |
b = 18.3064 (11) Å | µ = 0.09 mm−1 |
c = 12.0776 (7) Å | T = 120 K |
β = 93.4150 (12)° | Lath, yellow |
V = 1314.98 (12) Å3 | 0.20 × 0.10 × 0.04 mm |
Z = 4 |
KappaCCD diffractometer | 3001 independent reflections |
Radiation source: rotating anode | 1700 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.4° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −7→7 |
Tmin = 0.977, Tmax = 0.996 | k = −23→21 |
14938 measured reflections | l = −15→15 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0613P)2] where P = (Fo2 + 2Fc2)/3 |
3001 reflections | (Δ/σ)max < 0.001 |
175 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C13H16N4O2 | V = 1314.98 (12) Å3 |
Mr = 260.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.9581 (2) Å | µ = 0.09 mm−1 |
b = 18.3064 (11) Å | T = 120 K |
c = 12.0776 (7) Å | 0.20 × 0.10 × 0.04 mm |
β = 93.4150 (12)° |
KappaCCD diffractometer | 3001 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 1700 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.996 | Rint = 0.071 |
14938 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.22 e Å−3 |
3001 reflections | Δρmin = −0.28 e Å−3 |
175 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1283 (2) | 0.28405 (8) | 0.47981 (12) | 0.0220 (4) | |
N2 | −0.0010 (2) | 0.24448 (9) | 0.55116 (12) | 0.0230 (4) | |
C3 | −0.1270 (3) | 0.20118 (10) | 0.48495 (16) | 0.0224 (4) | |
C4 | −0.0870 (3) | 0.21303 (11) | 0.37242 (16) | 0.0249 (5) | |
C5 | 0.0753 (3) | 0.26618 (11) | 0.37125 (15) | 0.0237 (4) | |
N5 | 0.1812 (3) | 0.29677 (10) | 0.28533 (13) | 0.0306 (4) | |
C11 | 0.2811 (3) | 0.33687 (10) | 0.52501 (15) | 0.0216 (4) | |
C12 | 0.4827 (3) | 0.35070 (11) | 0.47563 (16) | 0.0243 (4) | |
C13 | 0.6273 (3) | 0.40335 (10) | 0.51985 (16) | 0.0252 (5) | |
C14 | 0.5694 (3) | 0.44051 (10) | 0.61374 (16) | 0.0233 (4) | |
N14 | 0.7185 (3) | 0.49841 (9) | 0.65867 (15) | 0.0299 (4) | |
O141 | 0.8857 (2) | 0.51414 (8) | 0.60916 (13) | 0.0390 (4) | |
O142 | 0.6673 (3) | 0.52972 (9) | 0.74362 (14) | 0.0451 (4) | |
C15 | 0.3728 (3) | 0.42629 (11) | 0.66465 (17) | 0.0267 (5) | |
C16 | 0.2286 (3) | 0.37361 (11) | 0.62040 (15) | 0.0236 (5) | |
C31 | −0.2820 (3) | 0.14534 (10) | 0.53212 (16) | 0.0252 (5) | |
C32 | −0.1497 (4) | 0.07485 (12) | 0.5542 (2) | 0.0397 (6) | |
C33 | −0.3742 (4) | 0.17272 (13) | 0.63963 (18) | 0.0373 (6) | |
C34 | −0.4792 (4) | 0.12980 (13) | 0.44822 (19) | 0.0408 (6) | |
H4 | −0.1581 | 0.1891 | 0.3100 | 0.030* | |
H5A | 0.1182 | 0.2843 | 0.2203 | 0.037* | |
H5B | 0.2177 | 0.3433 | 0.2910 | 0.037* | |
H12 | 0.5201 | 0.3240 | 0.4119 | 0.029* | |
H13 | 0.7641 | 0.4139 | 0.4865 | 0.030* | |
H15 | 0.3373 | 0.4524 | 0.7293 | 0.032* | |
H16 | 0.0938 | 0.3625 | 0.6551 | 0.028* | |
H32A | −0.0937 | 0.0568 | 0.4846 | 0.059* | |
H32B | −0.2480 | 0.0380 | 0.5848 | 0.059* | |
H32C | −0.0224 | 0.0845 | 0.6073 | 0.059* | |
H33A | −0.2501 | 0.1791 | 0.6958 | 0.056* | |
H33B | −0.4812 | 0.1370 | 0.6661 | 0.056* | |
H33C | −0.4505 | 0.2196 | 0.6261 | 0.056* | |
H34A | −0.5587 | 0.1755 | 0.4297 | 0.061* | |
H34B | −0.5828 | 0.0953 | 0.4805 | 0.061* | |
H34C | −0.4223 | 0.1087 | 0.3808 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0240 (8) | 0.0251 (10) | 0.0169 (8) | −0.0029 (7) | 0.0014 (6) | 0.0017 (7) |
N2 | 0.0227 (8) | 0.0241 (10) | 0.0226 (9) | −0.0014 (7) | 0.0029 (6) | 0.0032 (7) |
C3 | 0.0201 (10) | 0.0216 (11) | 0.0255 (11) | 0.0047 (8) | 0.0007 (8) | −0.0016 (9) |
C4 | 0.0256 (10) | 0.0273 (12) | 0.0217 (11) | −0.0007 (8) | 0.0005 (8) | −0.0045 (9) |
C5 | 0.0250 (10) | 0.0265 (12) | 0.0197 (10) | 0.0016 (8) | 0.0018 (7) | 0.0003 (9) |
N5 | 0.0375 (10) | 0.0350 (11) | 0.0192 (9) | −0.0100 (8) | 0.0019 (7) | −0.0014 (8) |
C11 | 0.0231 (10) | 0.0215 (11) | 0.0199 (10) | 0.0009 (8) | −0.0020 (7) | 0.0017 (8) |
C12 | 0.0243 (10) | 0.0248 (12) | 0.0238 (10) | 0.0029 (8) | 0.0017 (8) | 0.0000 (9) |
C13 | 0.0216 (10) | 0.0248 (12) | 0.0292 (12) | 0.0021 (8) | 0.0012 (8) | 0.0037 (9) |
C14 | 0.0245 (10) | 0.0187 (11) | 0.0259 (11) | 0.0007 (8) | −0.0052 (8) | −0.0017 (9) |
N14 | 0.0292 (10) | 0.0244 (10) | 0.0354 (11) | 0.0018 (7) | −0.0046 (8) | −0.0023 (8) |
O141 | 0.0293 (8) | 0.0360 (10) | 0.0518 (10) | −0.0064 (7) | 0.0038 (7) | −0.0028 (8) |
O142 | 0.0492 (10) | 0.0425 (11) | 0.0436 (10) | −0.0092 (8) | 0.0036 (7) | −0.0178 (9) |
C15 | 0.0289 (11) | 0.0267 (12) | 0.0242 (11) | 0.0039 (9) | −0.0011 (8) | −0.0027 (9) |
C16 | 0.0228 (10) | 0.0254 (12) | 0.0228 (11) | 0.0021 (8) | 0.0020 (7) | 0.0023 (9) |
C31 | 0.0264 (11) | 0.0219 (11) | 0.0276 (11) | −0.0012 (8) | 0.0037 (8) | 0.0008 (9) |
C32 | 0.0395 (13) | 0.0270 (13) | 0.0534 (15) | 0.0045 (10) | 0.0097 (10) | 0.0070 (11) |
C33 | 0.0372 (12) | 0.0377 (14) | 0.0385 (13) | −0.0059 (10) | 0.0140 (10) | −0.0021 (11) |
C34 | 0.0332 (12) | 0.0425 (15) | 0.0464 (15) | −0.0121 (10) | −0.0008 (10) | 0.0031 (12) |
N1—N2 | 1.393 (2) | C14—N14 | 1.466 (2) |
N2—C3 | 1.327 (2) | N14—O141 | 1.226 (2) |
C3—C4 | 1.411 (3) | N14—O142 | 1.229 (2) |
C4—C5 | 1.373 (3) | C15—C16 | 1.378 (3) |
C5—N1 | 1.370 (2) | C15—H15 | 0.95 |
N1—C11 | 1.415 (2) | C16—H16 | 0.95 |
C3—C31 | 1.512 (3) | C31—C33 | 1.524 (3) |
C4—H4 | 0.95 | C31—C32 | 1.527 (3) |
C5—N5 | 1.366 (2) | C31—C34 | 1.532 (3) |
N5—H5A | 0.88 | C32—H32A | 0.98 |
N5—H5B | 0.88 | C32—H32B | 0.98 |
C11—C16 | 1.386 (3) | C32—H32C | 0.98 |
C11—C12 | 1.396 (3) | C33—H33A | 0.98 |
C12—C13 | 1.379 (3) | C33—H33B | 0.98 |
C12—H12 | 0.95 | C33—H33C | 0.98 |
C13—C14 | 1.384 (3) | C34—H34A | 0.98 |
C13—H13 | 0.95 | C34—H34B | 0.98 |
C14—C15 | 1.380 (3) | C34—H34C | 0.98 |
C5—N1—N2 | 111.32 (14) | C16—C15—C14 | 119.04 (18) |
C5—N1—C11 | 129.70 (16) | C16—C15—H15 | 120.5 |
N2—N1—C11 | 118.91 (14) | C14—C15—H15 | 120.5 |
C3—N2—N1 | 104.59 (15) | C15—C16—C11 | 119.71 (18) |
N2—C3—C4 | 111.52 (17) | C15—C16—H16 | 120.1 |
N2—C3—C31 | 120.89 (17) | C11—C16—H16 | 120.1 |
C4—C3—C31 | 127.54 (17) | C3—C31—C33 | 110.97 (17) |
C5—C4—C3 | 106.18 (16) | C3—C31—C32 | 108.45 (15) |
C5—C4—H4 | 126.9 | C33—C31—C32 | 109.74 (17) |
C3—C4—H4 | 126.9 | C3—C31—C34 | 109.75 (16) |
N5—C5—N1 | 122.59 (17) | C33—C31—C34 | 108.88 (17) |
N5—C5—C4 | 130.99 (18) | C32—C31—C34 | 109.03 (18) |
N1—C5—C4 | 106.37 (16) | C31—C32—H32A | 109.5 |
C5—N5—H5A | 112.3 | C31—C32—H32B | 109.5 |
C5—N5—H5B | 117.4 | H32A—C32—H32B | 109.5 |
H5A—N5—H5B | 114.2 | C31—C32—H32C | 109.5 |
C16—C11—C12 | 120.66 (18) | H32A—C32—H32C | 109.5 |
C16—C11—N1 | 118.72 (17) | H32B—C32—H32C | 109.5 |
C12—C11—N1 | 120.61 (17) | C31—C33—H33A | 109.5 |
C13—C12—C11 | 119.68 (18) | C31—C33—H33B | 109.5 |
C13—C12—H12 | 120.2 | H33A—C33—H33B | 109.5 |
C11—C12—H12 | 120.2 | C31—C33—H33C | 109.5 |
C12—C13—C14 | 118.71 (18) | H33A—C33—H33C | 109.5 |
C12—C13—H13 | 120.6 | H33B—C33—H33C | 109.5 |
C14—C13—H13 | 120.6 | C31—C34—H34A | 109.5 |
C15—C14—C13 | 122.16 (18) | C31—C34—H34B | 109.5 |
C15—C14—N14 | 118.89 (18) | H34A—C34—H34B | 109.5 |
C13—C14—N14 | 118.92 (17) | C31—C34—H34C | 109.5 |
O141—N14—O142 | 123.13 (17) | H34A—C34—H34C | 109.5 |
O141—N14—C14 | 118.76 (17) | H34B—C34—H34C | 109.5 |
O142—N14—C14 | 118.10 (17) | ||
C5—N1—N2—C3 | 1.83 (19) | C11—C12—C13—C14 | 1.0 (3) |
C11—N1—N2—C3 | 179.06 (15) | C12—C13—C14—C15 | 0.4 (3) |
N1—N2—C3—C4 | −1.56 (19) | C12—C13—C14—N14 | −177.76 (16) |
N1—N2—C3—C31 | 175.96 (15) | C15—C14—N14—O141 | −175.34 (17) |
N2—C3—C4—C5 | 0.8 (2) | C13—C14—N14—O141 | 2.8 (3) |
C31—C3—C4—C5 | −176.55 (17) | C15—C14—N14—O142 | 3.5 (3) |
N2—N1—C5—N5 | −179.03 (17) | C13—C14—N14—O142 | −178.3 (2) |
C11—N1—C5—N5 | 4.1 (3) | C13—C14—C15—C16 | −0.3 (3) |
N2—N1—C5—C4 | −1.4 (2) | N14—C14—C15—C16 | 177.82 (17) |
C11—N1—C5—C4 | −178.24 (17) | C14—C15—C16—C11 | −1.1 (3) |
C3—C4—C5—N5 | 177.8 (2) | C12—C11—C16—C15 | 2.5 (3) |
C3—C4—C5—N1 | 0.4 (2) | N1—C11—C16—C15 | −178.74 (16) |
C5—N1—C11—C16 | 145.19 (19) | N2—C3—C31—C33 | 32.8 (2) |
N2—N1—C11—C16 | −31.5 (2) | C4—C3—C31—C33 | −150.16 (19) |
N2—N1—C11—C12 | 147.35 (17) | N2—C3—C31—C32 | −87.9 (2) |
C5—N1—C11—C12 | −36.0 (3) | C4—C3—C31—C32 | 89.2 (2) |
C16—C11—C12—C13 | −2.4 (3) | N2—C3—C31—C34 | 153.14 (18) |
N1—C11—C12—C13 | 178.82 (16) | C4—C3—C31—C34 | −29.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N2i | 0.88 | 2.19 | 3.063 (2) | 173 |
N5—H5B···O142ii | 0.88 | 2.47 | 3.326 (2) | 166 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C13H16N4O2 |
Mr | 260.30 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 5.9581 (2), 18.3064 (11), 12.0776 (7) |
β (°) | 93.4150 (12) |
V (Å3) | 1314.98 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.10 × 0.04 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.977, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14938, 3001, 1700 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.124, 0.96 |
No. of reflections | 3001 |
No. of parameters | 175 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.28 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
N1—N2 | 1.393 (2) | N1—C11 | 1.415 (2) |
N2—C3 | 1.327 (2) | C5—N5 | 1.366 (2) |
C3—C4 | 1.411 (3) | C14—N14 | 1.466 (2) |
C4—C5 | 1.373 (3) | N14—O141 | 1.226 (2) |
C5—N1 | 1.370 (2) | N14—O142 | 1.229 (2) |
N2—N1—C11—C12 | 147.35 (17) | C13—C14—N14—O141 | 2.8 (3) |
C5—N1—C11—C12 | −36.0 (3) | C13—C14—N14—O142 | −178.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N2i | 0.88 | 2.19 | 3.063 (2) | 173 |
N5—H5B···O142ii | 0.88 | 2.47 | 3.326 (2) | 166 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1. |
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The title compound, (I), is a frequently used intermediate for the synthesis of interesting fused pyrazolo[3,4-b]pyridine or similar derivatives. In the molecules of the title compound (Fig. 1), the dihedral angle between the aryl and heterocyclic rings is 33.7 (2)°, possibly controlled in part by the tendency of atom H12 and the amine group bonded to atom C5 to avoid one another. On the other hand, the nitro group is almost coplanar with the adjacent aryl ring, with a dihedral angle between the aryl plane and the C/NO2 plane of only 2.2 (2). Associated with the dihedral angle between the rings, there is negligible evidence for any delocalization of the lone pair at atom N1 into the nitro group to form the polarized structure (Ia). In particular, the C—N distances exocyclic to the aryl ring (Table 1) are typical of their type (Allen et al., 1987), while the C—C bond distances in the aryl ring span the small range 1.378 (3)–1.396 (3) Å, with no sign of quinonoid-type bond fixation. However, there is marked bond fixation within the heterocyclic ring (Table 1), where the C3—C4 and C4—C5 distances differ significantly, as do the N2—C3 and N1—C5 distances. Consistent with the pyramidal nature of atom N5, the bond C5—N5 bond is long for its type. The dihedral angle between the two rings and the conformation adopted by the tert-butyl group render the molecules chiral; however, the space group accommodates equal numbers of the two enantiomeric forms.
The molecules of (I) are linked into sheets by one N—H···O hydrogen bond and one N—H···N hydrogen bond (Table 1), and the sheet-formation is readily analysed by considering the action of each of these hydrogen bonds in turn.
Amine atom N5 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H5B, to nitro atom O142 in the molecule at (1 − x, 1 − y, 1 − z), thereby generating a centrosymmetric R22(20) (Bernstein et al., 1995) dimer centred at (1/2, 1/2, 1/2). The action of the N—H···N hydrogen bond is to link each of these dimers to four adjacent dimers, thereby forming a continuous sheet. Amine atoms N5 at (x, y, z) and (1 − x, 1 − y, 1 − z) both lie in the dimer centred at (1/2, 1/2, 1/2), and these atoms act as hydrogen-bond donors, this time via atom H5A, to atoms N52 in the molecules at (x, 0.5 − y, −0.5 + z) and (1 − x, 0.5 + y, 1.5 − z), respectively, which themselves lie in the dimers centred at (1/2, 0, 0) and (1/2, 1, 1), respectively. Likewise, atoms N52 at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms N5 in the molecules at (x, 0.5 − y, 0.5 + z) and (1 − x, 0.5 + y, 0.5 − z), which themselves lie in the dimers centred at (1/2, 0, 1) and (1/2, 1, 0). Propagation by the space group of these two hydrogen bonds then generates a (100) sheet built from alternating R22(20) and R66(32) rings, where both ring types are centrosymmetric (Fig. 2). If the R22 dimers are regarded as the nodes of the resulting net then this is of (4,4) type (Batten & Robson, 1998).
There are no direction-specific interactions between adjacent sheets; in particular, there are neither C—H···π(arene) hydrogen bonds nor aromatic π···π stacking interactions present in the structure. The R66(32) rings are largely occupied by a pair of tert-butyl groups, one pendent from each of the adjacent (100) sheets, and there are no solvent-accessible voids within the structure.