The three pyran structures 6-methylamino-5-nitro-2,4-diphenyl-4
H-pyran-3-carbonitrile, C
19H
15N
3O
3, (I), 4-(3-fluorophenyl)-6-methylamino-5-nitro-2-phenyl-4
H-pyran-3-carbonitrile, C
19H
14FN
3O
3, (II), and 4-(4-chlorophenyl)-6-methylamino-5-nitro-2-phenyl-4
H-pyran-3-carbonitrile, C
19H
14ClN
3O
3, (III), differ in the nature of the aryl group at the 4-position. The heterocyclic ring in all three structures adopts a flattened boat conformation. The dihedral angle between the pseudo-axial phenyl substituent and the flat part of the pyran ring is 89.97 (1)° in (I), 80.11 (1)° in (II) and 87.77 (1)° in (III). In all three crystal structures, a strong intramolecular N-H
O hydrogen bond links the flat conjugated H-N-C=C-N-O fragment into a six-membered ring. In (II), molecules are linked into dimeric aggregates by N-H
O(nitro) hydrogen bonds, generating an
R22(12) graph-set motif. In (III), intermolecular N-H
N and C-H
N hydrogen bonds link the molecules into a linear chain pattern generating
C(8) and
C(9) graph-set motifs, respectively.
Supporting information
CCDC references: 950439; 950440; 950441
For the preparation of (I), a mixture of benzoylacetonitrile (1.0 mmol),
benzaldehyde (1.0 mmol) and Et3N (1.0 mmol) was dissolved in EtOH (10 ml) in
a 50 ml round-bottomed flask. The reaction mixture was stirred at room
temperature for 5–10 min.
(E)-N-Methyl-1-methylsulfanyl-2-nitroethenamine (1.0 mmol) was
then added and the reaction mixture was refluxed at 353 K. Consumption of the
starting materials was monitored by thin-layer chromatography (TLC). After 90 min, the precipated solid was filtered off, washed with diethyl ether (5–7 ml) and dried under vacuum to obtain the product as a yellow solid. The
compound was further recrystallized from EtOH to obtain crystals of (I)
suitable for single-crystal X-ray studies (m.p. 513 K, yield 93%).
For the preparation of (II), a mixture of benzoylacetonitrile (1.0 mmol),
3-fluorobenzaldehyde (1.0 mmol) and Et3N (1.0 mmol) was dissolved in EtOH
(10 ml) in a 50 ml round-bottomed flask. The reaction mixture was stirred at
room temperature for 5–10 min.
(E)-N-Methyl-1-methylsulfanyl-2-nitroethenamine (1.0 mmol) was
then added and the reaction mixture was refluxed at 353 K. Consumption of the
starting materials was monitored by TLC. After 90 min, the precipated solid
was filtered off, washed with diethyl ether (5–7 ml) and dried under vacuum
to obtain the product as yellow solid. The compound was further recrystallized
from EtOH to obtain crystals of (II) suitable for the single-crystal X-ray
studies (m.p. 463 K, yield 91%).
For the preparation of (III), a mixture of benzoylacetonitrile (1.0 mmol),
4-chlorobenzaldehyde (1.0 mmol) and Et3N (1.0 mmol) was dissolved in EtOH
(10 ml) in a 50 ml round-bottomed flask. The reaction mixture was stirred at
room temperature for 5–10 min.
(E)-N-Methyl-1-methylsulfanyl-2-nitroethenamine (1.0 mmol) was
then added and the reaction mixture was refluxed at 353 K. Consumption of the
starting materials was monitored by TLC. After 90 min, the precipated solid
was filtered off, washed with diethyl ether (5–7 ml) and dried under vacuum
to obtain the product as yellow solid. The compound was further recrystallized
from EtOH to obtain crystals of (III) suitable for the single-crystal X-ray
studies (m.p. 481 K, yield 95%).
H atoms were placed in calculated positions and allowed to ride on their parent
atoms, with C—H = 0.93–0.98 Å and N—H = 0.86 Å, and with
Uiso(H) = 1.2Ueq(C,N) for amide, methylene and methyne H
atoms, or 1.5Ueq(C) for methyl H atoms.
For all compounds, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(I) 6-Methylamino-5-nitro-2,4-diphenyl-4
H-pyran-3-carbonitrile
top
Crystal data top
C19H15N3O3 | F(000) = 1392 |
Mr = 333.34 | Dx = 1.372 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2000 reflections |
a = 18.6202 (12) Å | θ = 2–27° |
b = 11.7427 (7) Å | µ = 0.10 mm−1 |
c = 14.9474 (9) Å | T = 293 K |
β = 98.999 (2)° | Block, colourless |
V = 3228.0 (3) Å3 | 0.24 × 0.22 × 0.20 mm |
Z = 8 | |
Data collection top
Bruker Kappa APEXII area-detector diffractometer | 3513 independent reflections |
Radiation source: fine-focus sealed tube | 2904 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 0 pixels mm-1 | θmax = 27.0°, θmin = 2.1° |
ω and ϕ scans | h = −21→23 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→14 |
Tmin = 0.977, Tmax = 0.981 | l = −12→19 |
15966 measured reflections | |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0455P)2 + 1.730P] where P = (Fo2 + 2Fc2)/3 |
3513 reflections | (Δ/σ)max < 0.001 |
227 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C19H15N3O3 | V = 3228.0 (3) Å3 |
Mr = 333.34 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.6202 (12) Å | µ = 0.10 mm−1 |
b = 11.7427 (7) Å | T = 293 K |
c = 14.9474 (9) Å | 0.24 × 0.22 × 0.20 mm |
β = 98.999 (2)° | |
Data collection top
Bruker Kappa APEXII area-detector diffractometer | 3513 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2904 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.981 | Rint = 0.026 |
15966 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.20 e Å−3 |
3513 reflections | Δρmin = −0.20 e Å−3 |
227 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.10766 (7) | −0.00323 (10) | 0.06890 (8) | 0.0283 (3) | |
C2 | 0.06562 (7) | 0.08020 (10) | 0.09280 (8) | 0.0285 (3) | |
C3 | 0.08190 (7) | 0.20502 (10) | 0.07944 (8) | 0.0295 (3) | |
H3 | 0.0357 | 0.2446 | 0.0603 | 0.035* | |
C4 | 0.12640 (7) | 0.21377 (10) | 0.00439 (8) | 0.0310 (3) | |
C5 | 0.16529 (7) | 0.12278 (10) | −0.02210 (8) | 0.0304 (3) | |
C6 | 0.24148 (9) | 0.01907 (13) | −0.11414 (12) | 0.0515 (4) | |
H6A | 0.2709 | −0.0157 | −0.0629 | 0.077* | |
H6B | 0.2716 | 0.0395 | −0.1582 | 0.077* | |
H6C | 0.2048 | −0.0337 | −0.1405 | 0.077* | |
C11 | 0.10243 (7) | −0.12612 (10) | 0.08579 (8) | 0.0298 (3) | |
C12 | 0.08385 (8) | −0.16461 (12) | 0.16724 (10) | 0.0400 (3) | |
H12 | 0.0767 | −0.1130 | 0.2122 | 0.048* | |
C13 | 0.07610 (9) | −0.28038 (13) | 0.18086 (12) | 0.0511 (4) | |
H13 | 0.0641 | −0.3066 | 0.2354 | 0.061* | |
C14 | 0.08605 (9) | −0.35693 (12) | 0.11394 (12) | 0.0508 (4) | |
H14 | 0.0790 | −0.4343 | 0.1227 | 0.061* | |
C15 | 0.10621 (8) | −0.31954 (12) | 0.03468 (10) | 0.0438 (3) | |
H15 | 0.1136 | −0.3718 | −0.0097 | 0.053* | |
C16 | 0.11558 (7) | −0.20446 (11) | 0.02032 (9) | 0.0348 (3) | |
H16 | 0.1306 | −0.1795 | −0.0328 | 0.042* | |
C21 | 0.00120 (7) | 0.05365 (10) | 0.12976 (8) | 0.0311 (3) | |
C31 | 0.11889 (7) | 0.25881 (10) | 0.16804 (8) | 0.0297 (3) | |
C32 | 0.18603 (7) | 0.21957 (12) | 0.21042 (9) | 0.0377 (3) | |
H32 | 0.2080 | 0.1584 | 0.1860 | 0.045* | |
C33 | 0.22042 (9) | 0.27119 (14) | 0.28904 (10) | 0.0488 (4) | |
H33 | 0.2653 | 0.2444 | 0.3173 | 0.059* | |
C34 | 0.18817 (10) | 0.36206 (15) | 0.32535 (10) | 0.0545 (4) | |
H34 | 0.2117 | 0.3975 | 0.3774 | 0.065* | |
C35 | 0.12130 (10) | 0.40032 (14) | 0.28477 (11) | 0.0534 (4) | |
H35 | 0.0993 | 0.4610 | 0.3098 | 0.064* | |
C36 | 0.08652 (8) | 0.34835 (12) | 0.20619 (10) | 0.0407 (3) | |
H36 | 0.0411 | 0.3742 | 0.1792 | 0.049* | |
N1 | 0.12821 (7) | 0.31884 (9) | −0.03759 (8) | 0.0387 (3) | |
N2 | 0.20709 (6) | 0.12040 (10) | −0.08505 (8) | 0.0384 (3) | |
H2 | 0.2147 | 0.1837 | −0.1110 | 0.046* | |
N3 | −0.05244 (7) | 0.03673 (12) | 0.15504 (8) | 0.0453 (3) | |
O1 | 0.16361 (5) | 0.02091 (7) | 0.02094 (6) | 0.0326 (2) | |
O3 | 0.09247 (7) | 0.39827 (8) | −0.01189 (8) | 0.0526 (3) | |
O2 | 0.16606 (7) | 0.33349 (9) | −0.09958 (7) | 0.0533 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0290 (6) | 0.0280 (6) | 0.0272 (6) | −0.0033 (5) | 0.0024 (5) | 0.0014 (5) |
C2 | 0.0296 (6) | 0.0265 (6) | 0.0286 (6) | −0.0032 (5) | 0.0015 (5) | −0.0001 (5) |
C3 | 0.0291 (6) | 0.0243 (5) | 0.0341 (6) | 0.0003 (5) | 0.0018 (5) | 0.0002 (5) |
C4 | 0.0378 (7) | 0.0254 (6) | 0.0288 (6) | −0.0031 (5) | 0.0020 (5) | 0.0023 (5) |
C5 | 0.0318 (6) | 0.0282 (6) | 0.0300 (6) | −0.0054 (5) | 0.0015 (5) | 0.0021 (5) |
C6 | 0.0547 (9) | 0.0446 (8) | 0.0614 (10) | 0.0019 (7) | 0.0281 (8) | −0.0016 (7) |
C11 | 0.0297 (6) | 0.0262 (6) | 0.0327 (6) | 0.0003 (5) | 0.0023 (5) | 0.0038 (5) |
C12 | 0.0463 (8) | 0.0364 (7) | 0.0394 (7) | 0.0056 (6) | 0.0128 (6) | 0.0072 (6) |
C13 | 0.0561 (10) | 0.0428 (8) | 0.0583 (10) | 0.0047 (7) | 0.0217 (8) | 0.0217 (7) |
C14 | 0.0529 (9) | 0.0274 (7) | 0.0725 (11) | −0.0004 (6) | 0.0114 (8) | 0.0120 (7) |
C15 | 0.0510 (9) | 0.0280 (6) | 0.0503 (8) | 0.0044 (6) | 0.0012 (7) | −0.0020 (6) |
C16 | 0.0396 (7) | 0.0302 (6) | 0.0336 (7) | 0.0041 (5) | 0.0029 (5) | 0.0035 (5) |
C21 | 0.0337 (7) | 0.0304 (6) | 0.0278 (6) | 0.0008 (5) | 0.0004 (5) | 0.0017 (5) |
C31 | 0.0340 (6) | 0.0249 (6) | 0.0311 (6) | −0.0057 (5) | 0.0079 (5) | 0.0004 (5) |
C32 | 0.0377 (7) | 0.0355 (7) | 0.0392 (7) | −0.0026 (6) | 0.0035 (6) | −0.0008 (5) |
C33 | 0.0461 (8) | 0.0566 (9) | 0.0407 (8) | −0.0127 (7) | −0.0031 (7) | 0.0031 (7) |
C34 | 0.0688 (11) | 0.0605 (10) | 0.0341 (7) | −0.0248 (9) | 0.0076 (7) | −0.0118 (7) |
C35 | 0.0730 (11) | 0.0448 (8) | 0.0468 (9) | −0.0081 (8) | 0.0231 (8) | −0.0159 (7) |
C36 | 0.0450 (8) | 0.0351 (7) | 0.0443 (8) | −0.0003 (6) | 0.0141 (6) | −0.0044 (6) |
N1 | 0.0523 (7) | 0.0278 (5) | 0.0348 (6) | −0.0027 (5) | 0.0033 (5) | 0.0031 (4) |
N2 | 0.0457 (7) | 0.0325 (6) | 0.0399 (6) | −0.0039 (5) | 0.0155 (5) | 0.0025 (5) |
N3 | 0.0365 (7) | 0.0586 (8) | 0.0412 (7) | −0.0012 (6) | 0.0074 (5) | 0.0110 (6) |
O1 | 0.0335 (5) | 0.0264 (4) | 0.0393 (5) | 0.0008 (4) | 0.0101 (4) | 0.0049 (4) |
O3 | 0.0710 (7) | 0.0276 (5) | 0.0604 (7) | 0.0080 (5) | 0.0136 (6) | 0.0055 (5) |
O2 | 0.0800 (8) | 0.0387 (5) | 0.0451 (6) | −0.0035 (5) | 0.0223 (6) | 0.0122 (5) |
Geometric parameters (Å, º) top
C1—C2 | 1.3370 (18) | C13—H13 | 0.9300 |
C1—O1 | 1.3833 (15) | C14—C15 | 1.370 (2) |
C1—C11 | 1.4708 (16) | C14—H14 | 0.9300 |
C2—C21 | 1.4312 (18) | C15—C16 | 1.3836 (19) |
C2—C3 | 1.5162 (16) | C15—H15 | 0.9300 |
C3—C4 | 1.4988 (18) | C16—H16 | 0.9300 |
C3—C31 | 1.5303 (17) | C21—N3 | 1.1393 (17) |
C3—H3 | 0.9800 | C31—C36 | 1.3788 (18) |
C4—C5 | 1.3829 (18) | C31—C32 | 1.3888 (18) |
C4—N1 | 1.3870 (16) | C32—C33 | 1.387 (2) |
C5—N2 | 1.3120 (17) | C32—H32 | 0.9300 |
C5—O1 | 1.3608 (14) | C33—C34 | 1.377 (2) |
C6—N2 | 1.4498 (19) | C33—H33 | 0.9300 |
C6—H6A | 0.9600 | C34—C35 | 1.373 (3) |
C6—H6B | 0.9600 | C34—H34 | 0.9300 |
C6—H6C | 0.9600 | C35—C36 | 1.391 (2) |
C11—C12 | 1.3921 (18) | C35—H35 | 0.9300 |
C11—C16 | 1.3924 (18) | C36—H36 | 0.9300 |
C12—C13 | 1.385 (2) | N1—O3 | 1.2412 (15) |
C12—H12 | 0.9300 | N1—O2 | 1.2606 (16) |
C13—C14 | 1.379 (2) | N2—H2 | 0.8600 |
| | | |
C2—C1—O1 | 120.54 (11) | C15—C14—H14 | 119.8 |
C2—C1—C11 | 128.02 (12) | C13—C14—H14 | 119.8 |
O1—C1—C11 | 111.43 (10) | C14—C15—C16 | 120.37 (14) |
C1—C2—C21 | 120.30 (11) | C14—C15—H15 | 119.8 |
C1—C2—C3 | 122.39 (11) | C16—C15—H15 | 119.8 |
C21—C2—C3 | 117.28 (11) | C15—C16—C11 | 119.73 (13) |
C4—C3—C2 | 108.07 (10) | C15—C16—H16 | 120.1 |
C4—C3—C31 | 113.13 (10) | C11—C16—H16 | 120.1 |
C2—C3—C31 | 110.93 (10) | N3—C21—C2 | 175.68 (13) |
C4—C3—H3 | 108.2 | C36—C31—C32 | 119.00 (12) |
C2—C3—H3 | 108.2 | C36—C31—C3 | 120.40 (12) |
C31—C3—H3 | 108.2 | C32—C31—C3 | 120.59 (11) |
C5—C4—N1 | 120.46 (12) | C33—C32—C31 | 120.33 (14) |
C5—C4—C3 | 122.47 (11) | C33—C32—H32 | 119.8 |
N1—C4—C3 | 117.06 (11) | C31—C32—H32 | 119.8 |
N2—C5—O1 | 112.36 (11) | C34—C33—C32 | 120.05 (15) |
N2—C5—C4 | 128.15 (12) | C34—C33—H33 | 120.0 |
O1—C5—C4 | 119.48 (11) | C32—C33—H33 | 120.0 |
N2—C6—H6A | 109.5 | C35—C34—C33 | 120.06 (14) |
N2—C6—H6B | 109.5 | C35—C34—H34 | 120.0 |
H6A—C6—H6B | 109.5 | C33—C34—H34 | 120.0 |
N2—C6—H6C | 109.5 | C34—C35—C36 | 120.00 (15) |
H6A—C6—H6C | 109.5 | C34—C35—H35 | 120.0 |
H6B—C6—H6C | 109.5 | C36—C35—H35 | 120.0 |
C12—C11—C16 | 119.68 (12) | C31—C36—C35 | 120.54 (15) |
C12—C11—C1 | 120.05 (12) | C31—C36—H36 | 119.7 |
C16—C11—C1 | 120.26 (11) | C35—C36—H36 | 119.7 |
C13—C12—C11 | 119.54 (14) | O3—N1—O2 | 120.89 (11) |
C13—C12—H12 | 120.2 | O3—N1—C4 | 118.45 (12) |
C11—C12—H12 | 120.2 | O2—N1—C4 | 120.66 (12) |
C14—C13—C12 | 120.28 (14) | C5—N2—C6 | 124.89 (12) |
C14—C13—H13 | 119.9 | C5—N2—H2 | 117.6 |
C12—C13—H13 | 119.9 | C6—N2—H2 | 117.6 |
C15—C14—C13 | 120.30 (13) | C5—O1—C1 | 119.99 (10) |
| | | |
O1—C1—C2—C21 | 170.28 (10) | C14—C15—C16—C11 | −1.8 (2) |
C11—C1—C2—C21 | −8.58 (19) | C12—C11—C16—C15 | 3.5 (2) |
O1—C1—C2—C3 | −7.59 (17) | C1—C11—C16—C15 | −176.09 (12) |
C11—C1—C2—C3 | 173.56 (11) | C4—C3—C31—C36 | 119.21 (13) |
C1—C2—C3—C4 | 24.38 (15) | C2—C3—C31—C36 | −119.16 (13) |
C21—C2—C3—C4 | −153.54 (10) | C4—C3—C31—C32 | −59.70 (15) |
C1—C2—C3—C31 | −100.17 (14) | C2—C3—C31—C32 | 61.93 (15) |
C21—C2—C3—C31 | 81.90 (13) | C36—C31—C32—C33 | −1.1 (2) |
C2—C3—C4—C5 | −20.51 (16) | C3—C31—C32—C33 | 177.79 (12) |
C31—C3—C4—C5 | 102.72 (13) | C31—C32—C33—C34 | −0.2 (2) |
C2—C3—C4—N1 | 160.47 (10) | C32—C33—C34—C35 | 1.2 (2) |
C31—C3—C4—N1 | −76.30 (14) | C33—C34—C35—C36 | −0.9 (2) |
N1—C4—C5—N2 | 0.5 (2) | C32—C31—C36—C35 | 1.5 (2) |
C3—C4—C5—N2 | −178.49 (12) | C3—C31—C36—C35 | −177.46 (13) |
N1—C4—C5—O1 | 179.01 (11) | C34—C35—C36—C31 | −0.5 (2) |
C3—C4—C5—O1 | 0.02 (18) | C5—C4—N1—O3 | 179.91 (12) |
C2—C1—C11—C12 | −37.61 (19) | C3—C4—N1—O3 | −1.05 (17) |
O1—C1—C11—C12 | 143.44 (12) | C5—C4—N1—O2 | −1.00 (19) |
C2—C1—C11—C16 | 141.99 (13) | C3—C4—N1—O2 | 178.05 (11) |
O1—C1—C11—C16 | −36.96 (15) | O1—C5—N2—C6 | 6.75 (18) |
C16—C11—C12—C13 | −2.3 (2) | C4—C5—N2—C6 | −174.65 (14) |
C1—C11—C12—C13 | 177.30 (13) | N2—C5—O1—C1 | −160.86 (10) |
C11—C12—C13—C14 | −0.6 (2) | C4—C5—O1—C1 | 20.41 (16) |
C12—C13—C14—C15 | 2.3 (3) | C2—C1—O1—C5 | −16.76 (16) |
C13—C14—C15—C16 | −1.1 (2) | C11—C1—O1—C5 | 162.27 (10) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.86 | 2.00 | 2.6154 (16) | 128 |
(II) 4-(3-Fluorophenyl)-6-methylamino-5-nitro-2-phenyl-4
H-pyran-3-carbonitrile
top
Crystal data top
C19H14FN3O3 | Z = 2 |
Mr = 351.33 | F(000) = 364 |
Triclinic, P1 | Dx = 1.405 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6736 (14) Å | Cell parameters from 2000 reflections |
b = 8.6808 (15) Å | θ = 1–27° |
c = 13.152 (2) Å | µ = 0.11 mm−1 |
α = 81.498 (11)° | T = 293 K |
β = 75.721 (11)° | Block, colourless |
γ = 79.851 (11)° | 0.23 × 0.21 × 0.19 mm |
V = 830.8 (3) Å3 | |
Data collection top
Bruker Kappa APEXII area-detector diffractometer | 3597 independent reflections |
Radiation source: fine-focus sealed tube | 2829 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 0 pixels mm-1 | θmax = 27.0°, θmin = 1.6° |
ω and ϕ scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −11→10 |
Tmin = 0.976, Tmax = 0.980 | l = −16→16 |
12513 measured reflections | |
Refinement top
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) = 0.136 | w = 1/[σ2(Fo2) + (0.0768P)2 + 0.1237P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3597 reflections | Δρmax = 0.22 e Å−3 |
237 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.054 (6) |
Crystal data top
C19H14FN3O3 | γ = 79.851 (11)° |
Mr = 351.33 | V = 830.8 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.6736 (14) Å | Mo Kα radiation |
b = 8.6808 (15) Å | µ = 0.11 mm−1 |
c = 13.152 (2) Å | T = 293 K |
α = 81.498 (11)° | 0.23 × 0.21 × 0.19 mm |
β = 75.721 (11)° | |
Data collection top
Bruker Kappa APEXII area-detector diffractometer | 3597 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2829 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.980 | Rint = 0.038 |
12513 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.22 e Å−3 |
3597 reflections | Δρmin = −0.19 e Å−3 |
237 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | −0.04183 (18) | 0.25859 (17) | 0.28829 (11) | 0.0355 (3) | |
C2 | −0.08146 (18) | 0.11563 (16) | 0.28764 (11) | 0.0352 (3) | |
C3 | 0.04007 (18) | −0.03395 (16) | 0.31565 (11) | 0.0344 (3) | |
H3 | −0.0367 | −0.1077 | 0.3611 | 0.041* | |
C4 | 0.16379 (18) | 0.00630 (16) | 0.37773 (10) | 0.0344 (3) | |
C5 | 0.20049 (17) | 0.15838 (17) | 0.37405 (10) | 0.0348 (3) | |
C6 | 0.3585 (2) | 0.3670 (2) | 0.39809 (15) | 0.0529 (4) | |
H6A | 0.4082 | 0.3926 | 0.3242 | 0.079* | |
H6B | 0.4456 | 0.3754 | 0.4376 | 0.079* | |
H6C | 0.2496 | 0.4388 | 0.4203 | 0.079* | |
C11 | −0.14315 (18) | 0.41106 (16) | 0.25639 (12) | 0.0373 (3) | |
C12 | −0.1687 (2) | 0.4470 (2) | 0.15451 (14) | 0.0529 (4) | |
H12 | −0.1210 | 0.3752 | 0.1052 | 0.063* | |
C13 | −0.2656 (3) | 0.5904 (2) | 0.12646 (16) | 0.0643 (5) | |
H13 | −0.2825 | 0.6150 | 0.0580 | 0.077* | |
C14 | −0.3372 (2) | 0.6971 (2) | 0.19893 (16) | 0.0579 (5) | |
H14 | −0.4033 | 0.7928 | 0.1796 | 0.069* | |
C15 | −0.3111 (2) | 0.66202 (19) | 0.29966 (15) | 0.0533 (4) | |
H15 | −0.3594 | 0.7342 | 0.3487 | 0.064* | |
C16 | −0.2133 (2) | 0.51997 (18) | 0.32857 (13) | 0.0462 (4) | |
H16 | −0.1944 | 0.4973 | 0.3967 | 0.055* | |
C21 | −0.24361 (19) | 0.09982 (17) | 0.25715 (11) | 0.0392 (3) | |
C31 | 0.14277 (18) | −0.11054 (17) | 0.21553 (11) | 0.0365 (3) | |
C32 | 0.1658 (2) | −0.27203 (18) | 0.21524 (12) | 0.0427 (4) | |
H32 | 0.1205 | −0.3359 | 0.2759 | 0.051* | |
C33 | 0.2571 (2) | −0.3370 (2) | 0.12377 (14) | 0.0506 (4) | |
C34 | 0.3244 (2) | −0.2490 (2) | 0.03192 (13) | 0.0551 (4) | |
H34 | 0.3836 | −0.2959 | −0.0289 | 0.066* | |
C35 | 0.3015 (3) | −0.0891 (2) | 0.03283 (14) | 0.0628 (5) | |
H35 | 0.3461 | −0.0261 | −0.0284 | 0.075* | |
C36 | 0.2128 (3) | −0.0196 (2) | 0.12361 (13) | 0.0541 (4) | |
H36 | 0.2002 | 0.0890 | 0.1229 | 0.065* | |
N1 | 0.24545 (17) | −0.11560 (14) | 0.43778 (9) | 0.0401 (3) | |
N2 | 0.31636 (16) | 0.20741 (14) | 0.41642 (10) | 0.0406 (3) | |
H2 | 0.3707 | 0.1404 | 0.4577 | 0.049* | |
N3 | −0.37260 (19) | 0.08219 (18) | 0.23414 (12) | 0.0544 (4) | |
O1 | 0.10934 (13) | 0.27976 (11) | 0.32151 (8) | 0.0406 (3) | |
O2 | 0.35908 (16) | −0.09167 (14) | 0.48660 (9) | 0.0516 (3) | |
O3 | 0.20321 (18) | −0.24970 (13) | 0.44459 (10) | 0.0570 (3) | |
F1 | 0.28240 (19) | −0.49606 (13) | 0.12553 (10) | 0.0838 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0337 (7) | 0.0366 (7) | 0.0366 (7) | −0.0019 (5) | −0.0120 (5) | −0.0023 (6) |
C2 | 0.0340 (7) | 0.0355 (7) | 0.0359 (7) | −0.0020 (5) | −0.0095 (5) | −0.0045 (6) |
C3 | 0.0352 (7) | 0.0304 (7) | 0.0360 (7) | −0.0046 (5) | −0.0069 (5) | −0.0011 (5) |
C4 | 0.0363 (7) | 0.0330 (7) | 0.0315 (7) | 0.0006 (5) | −0.0086 (5) | −0.0010 (5) |
C5 | 0.0314 (6) | 0.0376 (7) | 0.0326 (7) | 0.0009 (5) | −0.0072 (5) | −0.0018 (5) |
C6 | 0.0575 (10) | 0.0465 (9) | 0.0630 (10) | −0.0099 (7) | −0.0262 (8) | −0.0079 (8) |
C11 | 0.0349 (7) | 0.0332 (7) | 0.0449 (8) | −0.0034 (5) | −0.0141 (6) | −0.0013 (6) |
C12 | 0.0641 (11) | 0.0470 (9) | 0.0504 (9) | 0.0038 (8) | −0.0258 (8) | −0.0069 (7) |
C13 | 0.0799 (13) | 0.0558 (11) | 0.0625 (11) | 0.0039 (9) | −0.0400 (10) | 0.0009 (9) |
C14 | 0.0573 (10) | 0.0386 (9) | 0.0806 (13) | 0.0032 (7) | −0.0332 (9) | 0.0024 (8) |
C15 | 0.0550 (10) | 0.0387 (9) | 0.0653 (11) | 0.0020 (7) | −0.0152 (8) | −0.0108 (8) |
C16 | 0.0525 (9) | 0.0388 (8) | 0.0473 (9) | −0.0009 (6) | −0.0153 (7) | −0.0045 (7) |
C21 | 0.0396 (7) | 0.0373 (8) | 0.0410 (8) | −0.0015 (6) | −0.0108 (6) | −0.0072 (6) |
C31 | 0.0346 (7) | 0.0391 (8) | 0.0363 (7) | −0.0036 (5) | −0.0101 (5) | −0.0045 (6) |
C32 | 0.0452 (8) | 0.0399 (8) | 0.0432 (8) | −0.0070 (6) | −0.0085 (6) | −0.0069 (6) |
C33 | 0.0522 (9) | 0.0460 (9) | 0.0567 (10) | −0.0028 (7) | −0.0125 (7) | −0.0205 (8) |
C34 | 0.0539 (10) | 0.0691 (12) | 0.0433 (9) | −0.0038 (8) | −0.0078 (7) | −0.0213 (8) |
C35 | 0.0735 (12) | 0.0695 (13) | 0.0384 (9) | −0.0130 (9) | −0.0001 (8) | −0.0019 (8) |
C36 | 0.0685 (11) | 0.0431 (9) | 0.0435 (9) | −0.0089 (8) | −0.0012 (8) | −0.0008 (7) |
N1 | 0.0463 (7) | 0.0361 (7) | 0.0351 (6) | 0.0019 (5) | −0.0108 (5) | −0.0020 (5) |
N2 | 0.0405 (6) | 0.0397 (7) | 0.0443 (7) | −0.0017 (5) | −0.0177 (5) | −0.0040 (5) |
N3 | 0.0469 (8) | 0.0616 (9) | 0.0609 (9) | −0.0074 (6) | −0.0190 (7) | −0.0156 (7) |
O1 | 0.0403 (5) | 0.0333 (5) | 0.0512 (6) | −0.0052 (4) | −0.0213 (4) | 0.0039 (4) |
O2 | 0.0562 (7) | 0.0516 (7) | 0.0509 (6) | 0.0008 (5) | −0.0290 (5) | 0.0004 (5) |
O3 | 0.0816 (9) | 0.0350 (6) | 0.0575 (7) | −0.0039 (5) | −0.0297 (6) | 0.0034 (5) |
F1 | 0.1108 (10) | 0.0499 (7) | 0.0839 (8) | −0.0052 (6) | −0.0002 (7) | −0.0309 (6) |
Geometric parameters (Å, º) top
C1—C2 | 1.330 (2) | C13—H13 | 0.9300 |
C1—O1 | 1.3853 (16) | C14—C15 | 1.370 (3) |
C1—C11 | 1.4718 (19) | C14—H14 | 0.9300 |
C2—C21 | 1.4319 (19) | C15—C16 | 1.380 (2) |
C2—C3 | 1.5141 (19) | C15—H15 | 0.9300 |
C3—C4 | 1.5079 (19) | C16—H16 | 0.9300 |
C3—C31 | 1.5361 (19) | C21—N3 | 1.1444 (19) |
C3—H3 | 0.9800 | C31—C32 | 1.382 (2) |
C4—N1 | 1.3782 (17) | C31—C36 | 1.386 (2) |
C4—C5 | 1.389 (2) | C32—C33 | 1.379 (2) |
C5—N2 | 1.3154 (18) | C32—H32 | 0.9300 |
C5—O1 | 1.3567 (16) | C33—F1 | 1.358 (2) |
C6—N2 | 1.450 (2) | C33—C34 | 1.367 (3) |
C6—H6A | 0.9600 | C34—C35 | 1.370 (3) |
C6—H6B | 0.9600 | C34—H34 | 0.9300 |
C6—H6C | 0.9600 | C35—C36 | 1.385 (2) |
C11—C12 | 1.384 (2) | C35—H35 | 0.9300 |
C11—C16 | 1.385 (2) | C36—H36 | 0.9300 |
C12—C13 | 1.383 (2) | N1—O3 | 1.2474 (17) |
C12—H12 | 0.9300 | N1—O2 | 1.2630 (16) |
C13—C14 | 1.375 (3) | N2—H2 | 0.8600 |
| | | |
C2—C1—O1 | 121.53 (12) | C15—C14—H14 | 120.1 |
C2—C1—C11 | 127.61 (13) | C13—C14—H14 | 120.1 |
O1—C1—C11 | 110.87 (11) | C14—C15—C16 | 120.19 (16) |
C1—C2—C21 | 119.50 (13) | C14—C15—H15 | 119.9 |
C1—C2—C3 | 122.92 (12) | C16—C15—H15 | 119.9 |
C21—C2—C3 | 117.57 (12) | C15—C16—C11 | 120.20 (15) |
C4—C3—C2 | 108.09 (11) | C15—C16—H16 | 119.9 |
C4—C3—C31 | 113.40 (11) | C11—C16—H16 | 119.9 |
C2—C3—C31 | 110.35 (11) | N3—C21—C2 | 177.78 (16) |
C4—C3—H3 | 108.3 | C32—C31—C36 | 118.64 (14) |
C2—C3—H3 | 108.3 | C32—C31—C3 | 120.45 (12) |
C31—C3—H3 | 108.3 | C36—C31—C3 | 120.90 (13) |
N1—C4—C5 | 119.97 (12) | C33—C32—C31 | 119.03 (15) |
N1—C4—C3 | 117.38 (12) | C33—C32—H32 | 120.5 |
C5—C4—C3 | 122.63 (12) | C31—C32—H32 | 120.5 |
N2—C5—O1 | 111.37 (12) | F1—C33—C34 | 118.58 (15) |
N2—C5—C4 | 128.89 (13) | F1—C33—C32 | 118.29 (16) |
O1—C5—C4 | 119.75 (12) | C34—C33—C32 | 123.13 (16) |
N2—C6—H6A | 109.5 | C33—C34—C35 | 117.52 (15) |
N2—C6—H6B | 109.5 | C33—C34—H34 | 121.2 |
H6A—C6—H6B | 109.5 | C35—C34—H34 | 121.2 |
N2—C6—H6C | 109.5 | C34—C35—C36 | 121.03 (16) |
H6A—C6—H6C | 109.5 | C34—C35—H35 | 119.5 |
H6B—C6—H6C | 109.5 | C36—C35—H35 | 119.5 |
C12—C11—C16 | 119.52 (14) | C35—C36—C31 | 120.63 (16) |
C12—C11—C1 | 120.54 (13) | C35—C36—H36 | 119.7 |
C16—C11—C1 | 119.93 (13) | C31—C36—H36 | 119.7 |
C13—C12—C11 | 119.59 (16) | O3—N1—O2 | 120.41 (12) |
C13—C12—H12 | 120.2 | O3—N1—C4 | 118.95 (12) |
C11—C12—H12 | 120.2 | O2—N1—C4 | 120.63 (12) |
C14—C13—C12 | 120.59 (17) | C5—N2—C6 | 124.30 (13) |
C14—C13—H13 | 119.7 | C5—N2—H2 | 117.9 |
C12—C13—H13 | 119.7 | C6—N2—H2 | 117.9 |
C15—C14—C13 | 119.89 (15) | C5—O1—C1 | 120.39 (11) |
| | | |
O1—C1—C2—C21 | 177.20 (12) | C12—C11—C16—C15 | 1.3 (2) |
C11—C1—C2—C21 | −2.7 (2) | C1—C11—C16—C15 | −178.87 (14) |
O1—C1—C2—C3 | −4.2 (2) | C4—C3—C31—C32 | 99.19 (15) |
C11—C1—C2—C3 | 175.88 (13) | C2—C3—C31—C32 | −139.38 (13) |
C1—C2—C3—C4 | 19.64 (18) | C4—C3—C31—C36 | −81.32 (17) |
C21—C2—C3—C4 | −161.73 (12) | C2—C3—C31—C36 | 40.11 (18) |
C1—C2—C3—C31 | −104.89 (15) | C36—C31—C32—C33 | −0.2 (2) |
C21—C2—C3—C31 | 73.74 (15) | C3—C31—C32—C33 | 179.34 (13) |
C2—C3—C4—N1 | 160.79 (11) | C31—C32—C33—F1 | 178.44 (14) |
C31—C3—C4—N1 | −76.53 (15) | C31—C32—C33—C34 | −1.0 (3) |
C2—C3—C4—C5 | −20.86 (17) | F1—C33—C34—C35 | −178.30 (16) |
C31—C3—C4—C5 | 101.82 (15) | C32—C33—C34—C35 | 1.1 (3) |
N1—C4—C5—N2 | 4.7 (2) | C33—C34—C35—C36 | −0.1 (3) |
C3—C4—C5—N2 | −173.60 (13) | C34—C35—C36—C31 | −0.9 (3) |
N1—C4—C5—O1 | −174.93 (11) | C32—C31—C36—C35 | 1.1 (3) |
C3—C4—C5—O1 | 6.8 (2) | C3—C31—C36—C35 | −178.42 (16) |
C2—C1—C11—C12 | −60.1 (2) | C5—C4—N1—O3 | 176.16 (13) |
O1—C1—C11—C12 | 120.01 (15) | C3—C4—N1—O3 | −5.45 (18) |
C2—C1—C11—C16 | 120.12 (17) | C5—C4—N1—O2 | −2.7 (2) |
O1—C1—C11—C16 | −59.81 (17) | C3—C4—N1—O2 | 175.69 (12) |
C16—C11—C12—C13 | −0.7 (3) | O1—C5—N2—C6 | −7.4 (2) |
C1—C11—C12—C13 | 179.46 (16) | C4—C5—N2—C6 | 172.91 (14) |
C11—C12—C13—C14 | −0.2 (3) | N2—C5—O1—C1 | −167.83 (12) |
C12—C13—C14—C15 | 0.6 (3) | C4—C5—O1—C1 | 11.87 (19) |
C13—C14—C15—C16 | 0.0 (3) | C2—C1—O1—C5 | −13.4 (2) |
C14—C15—C16—C11 | −0.9 (3) | C11—C1—O1—C5 | 166.56 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.86 | 2.01 | 2.6155 (17) | 127 |
N2—H2···O2i | 0.86 | 2.32 | 3.0241 (17) | 140 |
Symmetry code: (i) −x+1, −y, −z+1. |
(III) 4-(4-Chlorophenyl)-6-methylamino-5-nitro-2-phenyl-4
H-pyran-3-carbonitrile
top
Crystal data top
C19H14ClN3O3 | Z = 2 |
Mr = 367.78 | F(000) = 380 |
Triclinic, P1 | Dx = 1.370 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4556 (2) Å | Cell parameters from 2000 reflections |
b = 9.9562 (2) Å | θ = 2–28° |
c = 11.1806 (3) Å | µ = 0.24 mm−1 |
α = 95.810 (1)° | T = 293 K |
β = 111.785 (1)° | Block, colourless |
γ = 109.362 (1)° | 0.23 × 0.21 × 0.18 mm |
V = 891.38 (4) Å3 | |
Data collection top
Bruker Kappa APEXII area-detector diffractometer | 4420 independent reflections |
Radiation source: fine-focus sealed tube | 3554 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 0 pixels mm-1 | θmax = 28.3°, θmin = 2.0° |
ω and ϕ scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −11→13 |
Tmin = 0.947, Tmax = 0.958 | l = −14→14 |
16021 measured reflections | |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0624P)2 + 0.2375P] where P = (Fo2 + 2Fc2)/3 |
4420 reflections | (Δ/σ)max < 0.001 |
236 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
Crystal data top
C19H14ClN3O3 | γ = 109.362 (1)° |
Mr = 367.78 | V = 891.38 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.4556 (2) Å | Mo Kα radiation |
b = 9.9562 (2) Å | µ = 0.24 mm−1 |
c = 11.1806 (3) Å | T = 293 K |
α = 95.810 (1)° | 0.23 × 0.21 × 0.18 mm |
β = 111.785 (1)° | |
Data collection top
Bruker Kappa APEXII area-detector diffractometer | 4420 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3554 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.958 | Rint = 0.029 |
16021 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.42 e Å−3 |
4420 reflections | Δρmin = −0.50 e Å−3 |
236 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.60184 (16) | 0.26728 (15) | 0.49536 (13) | 0.0348 (3) | |
C2 | 0.51351 (16) | 0.31464 (15) | 0.39939 (13) | 0.0334 (3) | |
C3 | 0.55526 (16) | 0.35478 (15) | 0.28609 (13) | 0.0335 (3) | |
H3 | 0.5667 | 0.4566 | 0.2880 | 0.040* | |
C4 | 0.72108 (17) | 0.35033 (16) | 0.31183 (13) | 0.0367 (3) | |
C5 | 0.80705 (17) | 0.30018 (16) | 0.41388 (14) | 0.0365 (3) | |
C6 | 1.0321 (2) | 0.2367 (2) | 0.55371 (18) | 0.0559 (4) | |
H6A | 1.0262 | 0.2783 | 0.6321 | 0.084* | |
H6B | 1.1464 | 0.2639 | 0.5704 | 0.084* | |
H6C | 0.9770 | 0.1314 | 0.5311 | 0.084* | |
C11 | 0.57577 (18) | 0.23797 (16) | 0.61391 (14) | 0.0379 (3) | |
C12 | 0.4217 (2) | 0.14573 (19) | 0.60158 (17) | 0.0487 (4) | |
H12 | 0.3356 | 0.0943 | 0.5176 | 0.058* | |
C13 | 0.3964 (2) | 0.1306 (2) | 0.7148 (2) | 0.0603 (5) | |
H13 | 0.2932 | 0.0691 | 0.7069 | 0.072* | |
C14 | 0.5241 (3) | 0.2064 (2) | 0.83869 (19) | 0.0598 (5) | |
H14 | 0.5060 | 0.1979 | 0.9144 | 0.072* | |
C15 | 0.6781 (3) | 0.2946 (2) | 0.85164 (17) | 0.0570 (4) | |
H15 | 0.7642 | 0.3441 | 0.9360 | 0.068* | |
C16 | 0.7055 (2) | 0.31027 (19) | 0.73942 (15) | 0.0482 (4) | |
H16 | 0.8103 | 0.3689 | 0.7482 | 0.058* | |
C21 | 0.37636 (17) | 0.34091 (15) | 0.40609 (14) | 0.0376 (3) | |
C31 | 0.41364 (17) | 0.25690 (15) | 0.15294 (13) | 0.0344 (3) | |
C32 | 0.3707 (2) | 0.10743 (17) | 0.12027 (16) | 0.0496 (4) | |
H32 | 0.4324 | 0.0661 | 0.1785 | 0.060* | |
C33 | 0.2370 (2) | 0.01769 (18) | 0.00190 (18) | 0.0566 (4) | |
H33 | 0.2092 | −0.0832 | −0.0198 | 0.068* | |
C34 | 0.1464 (2) | 0.07923 (19) | −0.08268 (15) | 0.0493 (4) | |
C35 | 0.1868 (2) | 0.2275 (2) | −0.05303 (17) | 0.0578 (4) | |
H35 | 0.1246 | 0.2683 | −0.1115 | 0.069* | |
C36 | 0.3213 (2) | 0.31618 (18) | 0.06511 (16) | 0.0503 (4) | |
H36 | 0.3498 | 0.4172 | 0.0855 | 0.060* | |
N1 | 0.79234 (16) | 0.41021 (16) | 0.23030 (13) | 0.0468 (3) | |
N2 | 0.95153 (16) | 0.29208 (16) | 0.44394 (14) | 0.0473 (3) | |
H2 | 1.0019 | 0.3215 | 0.3954 | 0.057* | |
N3 | 0.26940 (16) | 0.36726 (16) | 0.40904 (15) | 0.0515 (3) | |
O1 | 0.74240 (12) | 0.25073 (12) | 0.49902 (10) | 0.0411 (2) | |
O2 | 0.92913 (17) | 0.40985 (19) | 0.24227 (15) | 0.0734 (4) | |
O3 | 0.71758 (16) | 0.46488 (15) | 0.14702 (12) | 0.0571 (3) | |
Cl1 | −0.02116 (6) | −0.03401 (7) | −0.23113 (5) | 0.0798 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0313 (6) | 0.0412 (7) | 0.0342 (6) | 0.0127 (5) | 0.0186 (5) | 0.0075 (5) |
C2 | 0.0295 (6) | 0.0390 (7) | 0.0315 (6) | 0.0117 (5) | 0.0156 (5) | 0.0053 (5) |
C3 | 0.0328 (7) | 0.0365 (6) | 0.0320 (6) | 0.0130 (5) | 0.0155 (5) | 0.0092 (5) |
C4 | 0.0335 (7) | 0.0458 (7) | 0.0344 (7) | 0.0141 (6) | 0.0193 (6) | 0.0122 (6) |
C5 | 0.0325 (7) | 0.0448 (7) | 0.0357 (7) | 0.0140 (6) | 0.0197 (6) | 0.0091 (5) |
C6 | 0.0442 (9) | 0.0810 (12) | 0.0539 (10) | 0.0348 (9) | 0.0220 (8) | 0.0264 (9) |
C11 | 0.0408 (7) | 0.0453 (7) | 0.0368 (7) | 0.0192 (6) | 0.0236 (6) | 0.0140 (6) |
C12 | 0.0420 (8) | 0.0597 (9) | 0.0482 (9) | 0.0167 (7) | 0.0249 (7) | 0.0206 (7) |
C13 | 0.0570 (11) | 0.0772 (12) | 0.0691 (12) | 0.0277 (9) | 0.0449 (10) | 0.0372 (10) |
C14 | 0.0830 (13) | 0.0758 (12) | 0.0540 (10) | 0.0426 (11) | 0.0502 (10) | 0.0327 (9) |
C15 | 0.0716 (12) | 0.0654 (11) | 0.0371 (8) | 0.0276 (9) | 0.0262 (8) | 0.0140 (7) |
C16 | 0.0467 (9) | 0.0567 (9) | 0.0393 (8) | 0.0149 (7) | 0.0216 (7) | 0.0127 (7) |
C21 | 0.0313 (7) | 0.0412 (7) | 0.0357 (7) | 0.0103 (6) | 0.0147 (6) | 0.0038 (5) |
C31 | 0.0337 (7) | 0.0398 (7) | 0.0312 (6) | 0.0143 (5) | 0.0159 (5) | 0.0093 (5) |
C32 | 0.0551 (10) | 0.0424 (8) | 0.0435 (8) | 0.0201 (7) | 0.0125 (7) | 0.0115 (6) |
C33 | 0.0644 (11) | 0.0392 (8) | 0.0492 (9) | 0.0101 (7) | 0.0182 (8) | 0.0037 (7) |
C34 | 0.0392 (8) | 0.0580 (9) | 0.0336 (7) | 0.0041 (7) | 0.0134 (6) | 0.0035 (6) |
C35 | 0.0524 (10) | 0.0662 (11) | 0.0425 (9) | 0.0241 (9) | 0.0067 (7) | 0.0159 (8) |
C36 | 0.0538 (9) | 0.0444 (8) | 0.0442 (8) | 0.0214 (7) | 0.0108 (7) | 0.0110 (7) |
N1 | 0.0413 (7) | 0.0606 (8) | 0.0431 (7) | 0.0163 (6) | 0.0250 (6) | 0.0195 (6) |
N2 | 0.0376 (7) | 0.0713 (9) | 0.0474 (7) | 0.0276 (6) | 0.0257 (6) | 0.0233 (6) |
N3 | 0.0364 (7) | 0.0568 (8) | 0.0603 (9) | 0.0170 (6) | 0.0240 (6) | 0.0056 (7) |
O1 | 0.0383 (5) | 0.0597 (6) | 0.0409 (5) | 0.0260 (5) | 0.0251 (4) | 0.0225 (5) |
O2 | 0.0541 (8) | 0.1213 (12) | 0.0796 (9) | 0.0429 (8) | 0.0502 (7) | 0.0555 (9) |
O3 | 0.0575 (7) | 0.0733 (8) | 0.0500 (7) | 0.0252 (6) | 0.0293 (6) | 0.0334 (6) |
Cl1 | 0.0573 (3) | 0.0891 (4) | 0.0450 (3) | −0.0041 (3) | 0.0077 (2) | −0.0054 (2) |
Geometric parameters (Å, º) top
C1—C2 | 1.3303 (19) | C13—H13 | 0.9300 |
C1—O1 | 1.3789 (16) | C14—C15 | 1.371 (3) |
C1—C11 | 1.4751 (18) | C14—H14 | 0.9300 |
C2—C21 | 1.4314 (18) | C15—C16 | 1.386 (2) |
C2—C3 | 1.5130 (17) | C15—H15 | 0.9300 |
C3—C4 | 1.5023 (18) | C16—H16 | 0.9300 |
C3—C31 | 1.5232 (18) | C21—N3 | 1.1366 (18) |
C3—H3 | 0.9800 | C31—C32 | 1.376 (2) |
C4—C5 | 1.381 (2) | C31—C36 | 1.378 (2) |
C4—N1 | 1.3928 (17) | C32—C33 | 1.385 (2) |
C5—N2 | 1.3129 (18) | C32—H32 | 0.9300 |
C5—O1 | 1.3599 (16) | C33—C34 | 1.367 (3) |
C6—N2 | 1.453 (2) | C33—H33 | 0.9300 |
C6—H6A | 0.9600 | C34—C35 | 1.367 (3) |
C6—H6B | 0.9600 | C34—Cl1 | 1.7382 (16) |
C6—H6C | 0.9600 | C35—C36 | 1.383 (2) |
C11—C12 | 1.387 (2) | C35—H35 | 0.9300 |
C11—C16 | 1.387 (2) | C36—H36 | 0.9300 |
C12—C13 | 1.386 (2) | N1—O3 | 1.2378 (17) |
C12—H12 | 0.9300 | N1—O2 | 1.2512 (17) |
C13—C14 | 1.375 (3) | N2—H2 | 0.8600 |
| | | |
C2—C1—O1 | 121.66 (11) | C15—C14—H14 | 119.7 |
C2—C1—C11 | 126.91 (12) | C13—C14—H14 | 119.7 |
O1—C1—C11 | 111.24 (11) | C14—C15—C16 | 120.18 (17) |
C1—C2—C21 | 119.33 (12) | C14—C15—H15 | 119.9 |
C1—C2—C3 | 124.34 (12) | C16—C15—H15 | 119.9 |
C21—C2—C3 | 116.16 (12) | C15—C16—C11 | 119.61 (16) |
C4—C3—C2 | 108.26 (11) | C15—C16—H16 | 120.2 |
C4—C3—C31 | 115.00 (11) | C11—C16—H16 | 120.2 |
C2—C3—C31 | 110.22 (11) | N3—C21—C2 | 176.80 (16) |
C4—C3—H3 | 107.7 | C32—C31—C36 | 118.67 (14) |
C2—C3—H3 | 107.7 | C32—C31—C3 | 121.01 (13) |
C31—C3—H3 | 107.7 | C36—C31—C3 | 120.26 (13) |
C5—C4—N1 | 120.09 (12) | C31—C32—C33 | 120.92 (15) |
C5—C4—C3 | 124.17 (11) | C31—C32—H32 | 119.5 |
N1—C4—C3 | 115.62 (12) | C33—C32—H32 | 119.5 |
N2—C5—O1 | 111.38 (12) | C34—C33—C32 | 119.17 (15) |
N2—C5—C4 | 128.48 (12) | C34—C33—H33 | 120.4 |
O1—C5—C4 | 120.14 (12) | C32—C33—H33 | 120.4 |
N2—C6—H6A | 109.5 | C33—C34—C35 | 121.14 (15) |
N2—C6—H6B | 109.5 | C33—C34—Cl1 | 118.93 (13) |
H6A—C6—H6B | 109.5 | C35—C34—Cl1 | 119.93 (14) |
N2—C6—H6C | 109.5 | C34—C35—C36 | 119.16 (16) |
H6A—C6—H6C | 109.5 | C34—C35—H35 | 120.4 |
H6B—C6—H6C | 109.5 | C36—C35—H35 | 120.4 |
C12—C11—C16 | 119.89 (13) | C31—C36—C35 | 120.94 (15) |
C12—C11—C1 | 120.94 (14) | C31—C36—H36 | 119.5 |
C16—C11—C1 | 119.08 (13) | C35—C36—H36 | 119.5 |
C13—C12—C11 | 119.76 (16) | O3—N1—O2 | 121.14 (12) |
C13—C12—H12 | 120.1 | O3—N1—C4 | 118.22 (13) |
C11—C12—H12 | 120.1 | O2—N1—C4 | 120.64 (13) |
C14—C13—C12 | 119.97 (16) | C5—N2—C6 | 124.45 (13) |
C14—C13—H13 | 120.0 | C5—N2—H2 | 117.8 |
C12—C13—H13 | 120.0 | C6—N2—H2 | 117.8 |
C15—C14—C13 | 120.53 (15) | C5—O1—C1 | 120.48 (11) |
| | | |
O1—C1—C2—C21 | −175.10 (12) | C12—C11—C16—C15 | −2.8 (2) |
C11—C1—C2—C21 | −0.5 (2) | C1—C11—C16—C15 | 173.82 (15) |
O1—C1—C2—C3 | 0.0 (2) | C4—C3—C31—C32 | 58.45 (18) |
C11—C1—C2—C3 | 174.66 (13) | C2—C3—C31—C32 | −64.24 (17) |
C1—C2—C3—C4 | −7.15 (18) | C4—C3—C31—C36 | −124.33 (15) |
C21—C2—C3—C4 | 168.13 (11) | C2—C3—C31—C36 | 112.97 (15) |
C1—C2—C3—C31 | 119.42 (14) | C36—C31—C32—C33 | −0.3 (2) |
C21—C2—C3—C31 | −65.31 (15) | C3—C31—C32—C33 | 176.95 (15) |
C2—C3—C4—C5 | 7.13 (19) | C31—C32—C33—C34 | −0.4 (3) |
C31—C3—C4—C5 | −116.61 (15) | C32—C33—C34—C35 | 0.8 (3) |
C2—C3—C4—N1 | −168.74 (12) | C32—C33—C34—Cl1 | 179.96 (14) |
C31—C3—C4—N1 | 67.53 (16) | C33—C34—C35—C36 | −0.3 (3) |
N1—C4—C5—N2 | −4.4 (2) | Cl1—C34—C35—C36 | −179.52 (14) |
C3—C4—C5—N2 | 179.95 (14) | C32—C31—C36—C35 | 0.7 (2) |
N1—C4—C5—O1 | 175.64 (13) | C3—C31—C36—C35 | −176.53 (15) |
C3—C4—C5—O1 | −0.1 (2) | C34—C35—C36—C31 | −0.4 (3) |
C2—C1—C11—C12 | 53.2 (2) | C5—C4—N1—O3 | −174.20 (14) |
O1—C1—C11—C12 | −131.75 (15) | C3—C4—N1—O3 | 1.8 (2) |
C2—C1—C11—C16 | −123.41 (17) | C5—C4—N1—O2 | 5.1 (2) |
O1—C1—C11—C16 | 51.69 (18) | C3—C4—N1—O2 | −178.89 (15) |
C16—C11—C12—C13 | 2.4 (2) | O1—C5—N2—C6 | 0.3 (2) |
C1—C11—C12—C13 | −174.14 (15) | C4—C5—N2—C6 | −179.72 (16) |
C11—C12—C13—C14 | −0.2 (3) | N2—C5—O1—C1 | 171.71 (13) |
C12—C13—C14—C15 | −1.6 (3) | C4—C5—O1—C1 | −8.3 (2) |
C13—C14—C15—C16 | 1.2 (3) | C2—C1—O1—C5 | 8.4 (2) |
C14—C15—C16—C11 | 1.0 (3) | C11—C1—O1—C5 | −166.99 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.86 | 2.00 | 2.6171 (18) | 128 |
N2—H2···N3i | 0.86 | 2.36 | 3.0305 (18) | 135 |
C6—H6B···N3i | 0.96 | 2.61 | 3.244 (2) | 124 |
Symmetry code: (i) x+1, y, z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C19H15N3O3 | C19H14FN3O3 | C19H14ClN3O3 |
Mr | 333.34 | 351.33 | 367.78 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 18.6202 (12), 11.7427 (7), 14.9474 (9) | 7.6736 (14), 8.6808 (15), 13.152 (2) | 9.4556 (2), 9.9562 (2), 11.1806 (3) |
α, β, γ (°) | 90, 98.999 (2), 90 | 81.498 (11), 75.721 (11), 79.851 (11) | 95.810 (1), 111.785 (1), 109.362 (1) |
V (Å3) | 3228.0 (3) | 830.8 (3) | 891.38 (4) |
Z | 8 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.11 | 0.24 |
Crystal size (mm) | 0.24 × 0.22 × 0.20 | 0.23 × 0.21 × 0.19 | 0.23 × 0.21 × 0.18 |
|
Data collection |
Diffractometer | Bruker Kappa APEXII area-detector diffractometer | Bruker Kappa APEXII area-detector diffractometer | Bruker Kappa APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.977, 0.981 | 0.976, 0.980 | 0.947, 0.958 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15966, 3513, 2904 | 12513, 3597, 2829 | 16021, 4420, 3554 |
Rint | 0.026 | 0.038 | 0.029 |
(sin θ/λ)max (Å−1) | 0.639 | 0.639 | 0.668 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.102, 1.05 | 0.040, 0.136, 1.05 | 0.045, 0.130, 1.05 |
No. of reflections | 3513 | 3597 | 4420 |
No. of parameters | 227 | 237 | 236 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.20 | 0.22, −0.19 | 0.42, −0.50 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.86 | 2.00 | 2.6154 (16) | 128 |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.86 | 2.01 | 2.6155 (17) | 127 |
N2—H2···O2i | 0.86 | 2.32 | 3.0241 (17) | 140 |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.86 | 2.00 | 2.6171 (18) | 128 |
N2—H2···N3i | 0.86 | 2.36 | 3.0305 (18) | 135 |
C6—H6B···N3i | 0.96 | 2.61 | 3.244 (2) | 124 |
Symmetry code: (i) x+1, y, z. |
Comparison of ring folding in (I), (II), (III) topCompound | O1 displacement (Å) | C3 displacement (Å) |
(I) | 0.190 (2) | 0.284 (2) |
(II) | -0.128 (2) | -0.259 (2) |
(III) | -0.085 (2) | -0.091 (2) |
Selected torsion angles (°) in (I), (II), (III) topCompound | C12—C11—C1—C2 | C4—C3—C31—C32 | N1—C4—C5—N2 |
(I) | -37.62 (2) | -59.72 (2) | 0.5 (2) |
(II) | -60.1 (2) | 99.2 (2) | 4.7 (2) |
(III) | 53.2 (2) | 58.42 (2) | -4.3 (2) |
Selected bond lengths (Å) in (I), (II) and (III) topCompound | C5—N2 | C4—N1 | N1—O2 | C2—C21 |
(I) | 1.3120 (17) | 1.3870 (16) | 1.2606 (16) | 1.4312 (18) |
(II) | 1.3154 (18) | 1.3782 (17) | 1.2630 (16) | 1.4319 (19) |
(III) | 1.3129 (18) | 1.3928 (17) | 1.2512 (17) | 1.4314 (18) |
The synthesis of hydrogenated compounds has been extensively studied due to their interesting biological properties. For example, derivatives of 1,4-dihydropyridine exhibit high biological activities as calcium channel blockers (Bossert et al., 1981) and as calcium agonists or antagonists (Triggle et al., 1980; Kokubun & Reuter, 1984; Bossert & Vater, 1989; Wang et al., 1989; Alajarin et al., 1995). 4H-Pyran derivatives have structures similar to those of 1,4-dihydropyridine and elicit the interest of organic chemists as well as of crystallographers. The title compounds, 6-methylamino-5-nitro-2,4-diphenyl-4H-pyran-3-carbonitrile, (I), 4-(3-fluorophenyl)-6-methylamino-5-nitro-2-phenyl-4H-pyran-3-carbonitrile, (II), and 4-(4-chlorophenyl)-6-methylamino-5-nitro-2-phenyl-4H-pyran-3-carbonitrile, (III), and some related compounds are widely used as organic intermediates in organic chemistry (Liang et al., 2009). Much interest has recently been paid to the design of polyfunctionalized substituted pyran derivatives, owing to their wide range of biological activities (Lokaj et al., 1990; Marco et al., 1993). 4H-Pyran derivatives are potential bioactive compounds and can be used as calcium antagonists (Suarez et al., 2002). Thus, there has been a growing interest in the structures of 4H-pyran derivatives. The high biological activities of these compounds, in conjunction with our research interests, prompted us to synthesize and establish the structures of compounds (I)–(III).
The central six-membered pyran ring in all three molecules has a boat conformation, with atoms O1 and C3 displaced diagonally opposite to the C1/C2/C4/C5 mean plane (Table 1). The puckering parameters (Cremer & Pople, 1975) for this ring are q2 = 0.2768 (12) Å, θ = 97.8 (3)° and ϕ = 352.1 (3)° for (I), q2 = 0.2261 Å, θ = 103.10° and ϕ = 3.5845° for (II), and q2 = 0.1011 Å, θ = 88.67° and ϕ = 180.0° for (III). Atoms C1/C2/C4/C5 are coplanar to within 0.0193 (1) Å for (I), 0.0064 (1) Å for (II) and 0.0001 (1) Å for (III). The differences in the deviations are due to the steric hindrance of the different substituents at the C3 position of the pyran ring. The heterocycles in (I), (II) and (III) have similar conformations to those in pyrans with comparable structures, and in derivatives of1,4-dihydropyridine, for example, 3,5-dimethyl 2,6-dimethyl-4-(2-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate (nifedipine; Triggle et al., 1980), 3-(2-methoxyethyl) 5-propan-2-yl 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate (nimodipine; Wang et al., 1989) and 5-O-methyl 3-O-(oxolan-2-ylmethyl) 2,6-dimethyl-4-(2-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate (furnidipine; Alajarin et al., 1995).
The phenyl ring is attached to the pyran ring by a (-)-synclinal conformation in (I) and (II) and by a (+)-synclinal conformation in (III), which is evidenced by the C12—C11—C1—C2 torsion angles (Table 2). Similarly, the methoxybenzene ring is attached to the pyran ring by (-)-synclinal, (+)-anticlinal and (+)-synclinal conformations in (I), (II) and (III), respectively, as evidenced by the C4—C3—C31—C32 torsion angles (Table 2). The orientation of nitro atom N1 with respect to atom N2 bearing the methyl group is described by the N1—C4—C5—N2 torsion angles (Table 2), indicating a (+)-synperiplanar conformation in (I) and (II), and a (-)-synperiplanar conformation in (III). These conformations and deviations from the ideal value of 0° in all three structures may be due to the significant difference in the mode of participation of atom N2 in the hydrogen bonding.
The dihedral angles between the pseudo-axial aryl substituent and the C1/C2/C4/C5 plane of the boat of the heterocycle are 89.97 (1)° in (I), 80.11 (1)° in (II) and 87.77 (1)° in (III), minimizing possible intramolecular steric contacts in all three molecules. Similar orientations of sterically demanding substituents were found in all previously determined derivatives of 4H-pyrans (Sharanina et al., 1986; Klokol et al., 1987; Shestopalov et al., 1991; Samet et al., 1996; Florencio & García-Blanco, (1987); Bellanato et al., 1988; Lokaj et al., 1990; Marco et al., 1993). The value of the angle is close to 90° in practically all known 4H-pyran derivatives containing sterically demanding substituents in the 4-position of the heterocycle.
As was described previously for related compounds (Nesterov et al., 2004, 2006), there is conjugation in all three title compounds between the donor (NH) and acceptor (C—NO2) groups via the C4═C5 double bond (Tables 3, 4 and 5). Thus, in all three molecules, the C5—N2 distances are shorter than the average conjugated C—N single bond (1.370 Å) found in the Cambridge Structural Database (Version?; Allen, 2002) (Table 6). In contrast, the C1═C2 bonds are elongated in comparison with the C4═C5 bond and the standard value (Allen et al., 1987). The C4—N1 bonds are considerably shorter than usual for C—NO2 bonds (1.468 Å; Allen et al., 1987) (Table 6) and the N1—O2 bonds are distinctly longer than the standard value (1.239 Å; Allen et al., 1987), which may be due to the intramolecular N—H···O hydrogen bond found in all three structures (Table 6). There is a long Csp2—Csp1 bond (C2—C21; Table 6) in all three structures due to conjugation.
An intramolecular N2—H2···O2 hydrogen bond, which stabilizes the crystal structure, exists in all three molecules and links the flat conjugated H—N—C═C—N—O fragment into a six-membered ring, generating an S(6) graph-set motif (Bernstein et al., 1995). This seems to be a common feature in related structures (Nesterov et al., 2004, 2006; Nesterov & Viltchinskaia, 2001).
In the crystal structure of (I), the molecules appear to pack as a molecular species and the structure contains some weak C—H···π interactions.
The crystal structure of (II) has the above-mentioned bifurcated intramolecular N—H···O(nitro) and N—H···N(nitro) hydrogen bonds. The H atom of the N—H group participates in both inter- and intramolecular N—H···O interactions. The intermolecular N2—H2···O2i hydrogen bond (see Table 4 for symmetry code) links inversion-related molecules into an aggregate, forming an R22(12) ring motif (Fig. 2). This ring motif is linked through van der Waals interactions, stabilizing the crystal structure.
The crystal structure of (III) appears to form normal intramolecular N—H···O(nitro) and intermolecular N—H···N(cyano) contacts, resulting in one-dimensional chains that lie parallel to the [100] direction, in addition to some weak C—H···N and C—H···π interactions. The N2—H2···N3 and C6—H6B···N3ii hydrogen bonds (see Table 5 for symmetry code) together form a linear chain, generating C(8) and C(9) motifs, respectively (Fig. 3).