Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102022758/na1587sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102022758/na1587Isup2.hkl |
CCDC reference: 208028
The title compound was obtained by the nitrosation of the corresponding amine with NaNO2/HCl in ethanol. Diffraction quality crystals of (I) were obtained by recrystallization from ethanol. The parent amine, 1,3-diphenyl-1,2,3,4-tetrahydrobenzo[b][1,6]naphthyridine, was obtained by the action of NaN3/H2SO4 on 2,4,6,8-tetraphenyl-3,7-diazabicyclo[3.3.1]nonan-9-one (Sivakumar, 2000) as a non-crystalline product.
All H atoms were geometrically fixed and allowed to ride on their parent atoms, with C—H distances in the range 0.86–0.96 Å, and Uiso = 1.5eq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: SHELX97 and PARST (Nardelli, 1995).
C24H19N3O | F(000) = 768 |
Mr = 365.42 | Dx = 1.290 Mg m−3 |
Monoclinic, P21/a | Cu Kα radiation, λ = 1.54180 Å |
a = 9.713 (6) Å | Cell parameters from 25 reflections |
b = 19.265 (8) Å | θ = 4.4–68.0° |
c = 10.450 (2) Å | µ = 0.64 mm−1 |
β = 105.74 (3)° | T = 293 K |
V = 1882.1 (14) Å3 | Plate, pale yellow |
Z = 4 | 0.2 × 0.2 × 0.15 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.052 |
Radiation source: fine-focus sealed tube | θmax = 68.0°, θmin = 4.4° |
Graphite monochromator | h = −11→11 |
non–profiled w/2θ scans | k = 0→23 |
3876 measured reflections | l = −12→12 |
3435 independent reflections | 3 standard reflections every 100 reflections |
2660 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.172 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1135P)2 + 0.167P] where P = (Fo2 + 2Fc2)/3 |
3435 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C24H19N3O | V = 1882.1 (14) Å3 |
Mr = 365.42 | Z = 4 |
Monoclinic, P21/a | Cu Kα radiation |
a = 9.713 (6) Å | µ = 0.64 mm−1 |
b = 19.265 (8) Å | T = 293 K |
c = 10.450 (2) Å | 0.2 × 0.2 × 0.15 mm |
β = 105.74 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.052 |
3876 measured reflections | 3 standard reflections every 100 reflections |
3435 independent reflections | intensity decay: none |
2660 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.172 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.23 e Å−3 |
3435 reflections | Δρmin = −0.20 e Å−3 |
253 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O | −0.2538 (2) | 0.74971 (9) | −0.15540 (15) | 0.0822 (5) | |
N1 | 0.26428 (18) | 0.85872 (8) | 0.22203 (15) | 0.0560 (4) | |
N2 | −0.14707 (17) | 0.81452 (8) | 0.00869 (15) | 0.0519 (4) | |
N3 | −0.2456 (2) | 0.76712 (9) | −0.04006 (17) | 0.0672 (5) | |
C1 | 0.0730 (2) | 0.88174 (11) | 0.02359 (18) | 0.0566 (5) | |
H1A | 0.1525 | 0.8831 | −0.0160 | 0.068* | |
H1B | 0.0397 | 0.9290 | 0.0268 | 0.068* | |
C2 | −0.0481 (2) | 0.83912 (9) | −0.06702 (18) | 0.0510 (4) | |
H2 | −0.0053 | 0.7982 | −0.0967 | 0.061* | |
C3 | −0.1325 (2) | 0.83110 (10) | 0.15039 (18) | 0.0536 (5) | |
H3 | −0.1762 | 0.7925 | 0.1863 | 0.064* | |
C4 | 0.0682 (2) | 0.81396 (10) | 0.3577 (2) | 0.0571 (5) | |
H4 | 0.0027 | 0.7977 | 0.4010 | 0.069* | |
C5 | 0.2679 (3) | 0.80539 (12) | 0.5640 (2) | 0.0682 (6) | |
H5 | 0.2064 | 0.7903 | 0.6126 | 0.082* | |
C6 | 0.4089 (3) | 0.81350 (11) | 0.6254 (2) | 0.0716 (6) | |
H6 | 0.4427 | 0.8043 | 0.7159 | 0.086* | |
C7 | 0.5048 (3) | 0.83554 (11) | 0.5549 (2) | 0.0681 (6) | |
H7 | 0.6014 | 0.8407 | 0.5983 | 0.082* | |
C8 | 0.4556 (2) | 0.84951 (11) | 0.4216 (2) | 0.0636 (5) | |
H8 | 0.5194 | 0.8643 | 0.3751 | 0.076* | |
C9 | 0.3103 (2) | 0.84176 (9) | 0.35445 (19) | 0.0538 (5) | |
C10 | 0.2133 (2) | 0.81961 (9) | 0.42672 (19) | 0.0561 (5) | |
C11 | 0.1265 (2) | 0.85525 (10) | 0.16292 (18) | 0.0518 (4) | |
C12 | 0.0236 (2) | 0.83237 (9) | 0.22719 (18) | 0.0515 (4) | |
C13 | −0.2166 (2) | 0.89604 (10) | 0.16495 (17) | 0.0532 (5) | |
C14 | −0.3646 (2) | 0.89194 (13) | 0.1294 (2) | 0.0685 (6) | |
H14 | −0.4091 | 0.8505 | 0.0961 | 0.082* | |
C15 | −0.4473 (3) | 0.94873 (15) | 0.1426 (3) | 0.0781 (7) | |
H15 | −0.5466 | 0.9454 | 0.1186 | 0.094* | |
C16 | −0.3817 (3) | 1.00969 (14) | 0.1911 (3) | 0.0796 (7) | |
H16 | −0.4367 | 1.0480 | 0.2001 | 0.095* | |
C17 | −0.2354 (3) | 1.01483 (13) | 0.2266 (2) | 0.0729 (6) | |
H17 | −0.1918 | 1.0567 | 0.2588 | 0.087* | |
C18 | −0.1518 (2) | 0.95774 (11) | 0.2149 (2) | 0.0613 (5) | |
H18 | −0.0526 | 0.9612 | 0.2406 | 0.074* | |
C19 | −0.12092 (19) | 0.88110 (9) | −0.18879 (17) | 0.0487 (4) | |
C20 | −0.0778 (2) | 0.87241 (11) | −0.30400 (19) | 0.0610 (5) | |
H20 | −0.0128 | 0.8377 | −0.3084 | 0.073* | |
C21 | −0.1313 (3) | 0.91526 (13) | −0.4122 (2) | 0.0713 (6) | |
H21 | −0.1010 | 0.9093 | −0.4887 | 0.086* | |
C22 | −0.2287 (3) | 0.96660 (12) | −0.4083 (2) | 0.0689 (6) | |
H22 | −0.2635 | 0.9955 | −0.4813 | 0.083* | |
C23 | −0.2742 (2) | 0.97476 (11) | −0.2953 (2) | 0.0634 (5) | |
H23 | −0.3417 | 1.0085 | −0.2925 | 0.076* | |
C24 | −0.2195 (2) | 0.93276 (10) | −0.18588 (19) | 0.0558 (5) | |
H24 | −0.2492 | 0.9393 | −0.1093 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O | 0.0965 (13) | 0.0837 (11) | 0.0689 (10) | −0.0292 (9) | 0.0266 (9) | −0.0193 (8) |
N1 | 0.0563 (10) | 0.0551 (9) | 0.0562 (9) | −0.0051 (7) | 0.0148 (7) | 0.0006 (7) |
N2 | 0.0516 (9) | 0.0517 (8) | 0.0536 (8) | −0.0102 (7) | 0.0163 (7) | −0.0031 (6) |
N3 | 0.0756 (12) | 0.0641 (10) | 0.0609 (10) | −0.0189 (9) | 0.0168 (9) | −0.0077 (8) |
C1 | 0.0520 (11) | 0.0630 (11) | 0.0554 (10) | −0.0091 (9) | 0.0156 (9) | 0.0051 (8) |
C2 | 0.0517 (11) | 0.0504 (9) | 0.0540 (10) | −0.0011 (8) | 0.0196 (8) | −0.0020 (7) |
C3 | 0.0583 (12) | 0.0568 (10) | 0.0494 (10) | −0.0075 (8) | 0.0207 (8) | 0.0039 (8) |
C4 | 0.0651 (12) | 0.0527 (10) | 0.0556 (10) | −0.0024 (9) | 0.0196 (9) | 0.0070 (8) |
C5 | 0.0779 (15) | 0.0669 (13) | 0.0562 (11) | 0.0001 (11) | 0.0121 (10) | 0.0109 (9) |
C6 | 0.0878 (17) | 0.0592 (12) | 0.0579 (12) | −0.0039 (11) | 0.0029 (11) | 0.0046 (9) |
C7 | 0.0636 (13) | 0.0549 (11) | 0.0753 (13) | 0.0004 (9) | 0.0005 (11) | 0.0001 (9) |
C8 | 0.0603 (13) | 0.0588 (11) | 0.0673 (12) | −0.0019 (9) | 0.0097 (10) | 0.0008 (9) |
C9 | 0.0573 (11) | 0.0432 (9) | 0.0585 (10) | −0.0005 (8) | 0.0117 (9) | −0.0008 (7) |
C10 | 0.0635 (12) | 0.0467 (9) | 0.0563 (11) | −0.0020 (8) | 0.0134 (9) | 0.0048 (8) |
C11 | 0.0541 (11) | 0.0490 (9) | 0.0534 (10) | −0.0029 (8) | 0.0167 (8) | 0.0003 (7) |
C12 | 0.0549 (11) | 0.0479 (9) | 0.0521 (10) | −0.0045 (8) | 0.0153 (8) | 0.0012 (7) |
C13 | 0.0539 (11) | 0.0636 (11) | 0.0475 (9) | −0.0037 (8) | 0.0231 (8) | 0.0041 (8) |
C14 | 0.0547 (12) | 0.0814 (14) | 0.0752 (13) | −0.0093 (10) | 0.0274 (10) | −0.0064 (11) |
C15 | 0.0491 (12) | 0.1019 (18) | 0.0882 (16) | 0.0055 (12) | 0.0269 (11) | −0.0037 (14) |
C16 | 0.0764 (16) | 0.0807 (16) | 0.0917 (16) | 0.0113 (13) | 0.0399 (13) | −0.0009 (13) |
C17 | 0.0743 (15) | 0.0663 (13) | 0.0873 (15) | 0.0003 (11) | 0.0376 (13) | −0.0034 (11) |
C18 | 0.0534 (11) | 0.0657 (12) | 0.0686 (12) | −0.0046 (9) | 0.0228 (9) | −0.0019 (9) |
C19 | 0.0461 (10) | 0.0514 (9) | 0.0494 (9) | −0.0049 (7) | 0.0144 (8) | −0.0027 (7) |
C20 | 0.0687 (13) | 0.0633 (11) | 0.0575 (11) | −0.0006 (10) | 0.0281 (10) | −0.0051 (9) |
C21 | 0.0887 (17) | 0.0784 (14) | 0.0544 (11) | −0.0057 (12) | 0.0322 (11) | 0.0018 (10) |
C22 | 0.0809 (15) | 0.0644 (12) | 0.0605 (12) | −0.0058 (11) | 0.0176 (11) | 0.0099 (10) |
C23 | 0.0666 (13) | 0.0534 (11) | 0.0700 (12) | 0.0066 (9) | 0.0180 (10) | 0.0060 (9) |
C24 | 0.0574 (11) | 0.0573 (11) | 0.0556 (10) | 0.0024 (8) | 0.0204 (9) | −0.0024 (8) |
O—N3 | 1.233 (2) | C8—H8 | 0.9300 |
N1—C11 | 1.315 (3) | C9—C10 | 1.423 (3) |
N1—C9 | 1.373 (2) | C11—C12 | 1.417 (3) |
N2—N3 | 1.321 (2) | C13—C18 | 1.380 (3) |
N2—C2 | 1.479 (2) | C13—C14 | 1.386 (3) |
N2—C3 | 1.484 (2) | C14—C15 | 1.386 (3) |
C1—C11 | 1.497 (3) | C14—H14 | 0.9300 |
C1—C2 | 1.533 (3) | C15—C16 | 1.366 (4) |
C1—H1A | 0.9700 | C15—H15 | 0.9300 |
C1—H1B | 0.9700 | C16—C17 | 1.372 (4) |
C2—C19 | 1.512 (3) | C16—H16 | 0.9300 |
C2—H2 | 0.9800 | C17—C18 | 1.392 (3) |
C3—C12 | 1.511 (3) | C17—H17 | 0.9300 |
C3—C13 | 1.524 (3) | C18—H18 | 0.9300 |
C3—H3 | 0.9800 | C19—C24 | 1.387 (3) |
C4—C12 | 1.361 (3) | C19—C20 | 1.388 (2) |
C4—C10 | 1.402 (3) | C20—C21 | 1.383 (3) |
C4—H4 | 0.9300 | C20—H20 | 0.9300 |
C5—C6 | 1.355 (4) | C21—C22 | 1.377 (3) |
C5—C10 | 1.414 (3) | C21—H21 | 0.9300 |
C5—H5 | 0.9300 | C22—C23 | 1.377 (3) |
C6—C7 | 1.401 (4) | C22—H22 | 0.9300 |
C6—H6 | 0.9300 | C23—C24 | 1.384 (3) |
C7—C8 | 1.371 (3) | C23—H23 | 0.9300 |
C7—H7 | 0.9300 | C24—H24 | 0.9300 |
C8—C9 | 1.404 (3) | ||
C11—N1—C9 | 118.22 (17) | C5—C10—C9 | 118.4 (2) |
N3—N2—C2 | 121.6 (2) | N1—C11—C12 | 123.51 (17) |
N3—N2—C3 | 113.4 (2) | N1—C11—C1 | 118.72 (17) |
C2—N2—C3 | 124.43 (15) | C12—C11—C1 | 117.60 (18) |
O—N3—N2 | 114.4 (2) | C4—C12—C11 | 118.81 (19) |
C11—C1—C2 | 115.09 (16) | C4—C12—C3 | 121.92 (18) |
C11—C1—H1A | 108.5 | C11—C12—C3 | 119.25 (17) |
C2—C1—H1A | 108.5 | C18—C13—C14 | 118.97 (19) |
C11—C1—H1B | 108.5 | C18—C13—C3 | 122.89 (18) |
C2—C1—H1B | 108.5 | C14—C13—C3 | 118.12 (18) |
H1A—C1—H1B | 107.5 | C13—C14—C15 | 121.0 (2) |
N2—C2—C19 | 113.48 (16) | C13—C14—H14 | 119.5 |
N2—C2—C1 | 110.02 (15) | C15—C14—H14 | 119.5 |
C19—C2—C1 | 109.79 (15) | C16—C15—C14 | 119.4 (2) |
N2—C2—H2 | 107.8 | C16—C15—H15 | 120.3 |
C19—C2—H2 | 107.8 | C14—C15—H15 | 120.3 |
C1—C2—H2 | 107.8 | C15—C16—C17 | 120.5 (2) |
N2—C3—C12 | 110.1 (2) | C15—C16—H16 | 119.8 |
N2—C3—C13 | 111.6 (2) | C17—C16—H16 | 119.8 |
C12—C3—C13 | 114.93 (16) | C16—C17—C18 | 120.3 (2) |
N2—C3—H3 | 106.6 | C16—C17—H17 | 119.8 |
C12—C3—H3 | 106.6 | C18—C17—H17 | 119.8 |
C13—C3—H3 | 106.6 | C13—C18—C17 | 119.8 (2) |
C12—C4—C10 | 119.84 (19) | C13—C18—H18 | 120.1 |
C12—C4—H4 | 120.1 | C17—C18—H18 | 120.1 |
C10—C4—H4 | 120.1 | C24—C19—C20 | 118.55 (18) |
C6—C5—C10 | 120.8 (2) | C24—C19—C2 | 122.24 (16) |
C6—C5—H5 | 119.6 | C20—C19—C2 | 118.91 (17) |
C10—C5—H5 | 119.6 | C21—C20—C19 | 120.2 (2) |
C5—C6—C7 | 121.1 (2) | C21—C20—H20 | 119.9 |
C5—C6—H6 | 119.5 | C19—C20—H20 | 119.9 |
C7—C6—H6 | 119.5 | C22—C21—C20 | 120.86 (19) |
C8—C7—C6 | 119.7 (2) | C22—C21—H21 | 119.6 |
C8—C7—H7 | 120.1 | C20—C21—H21 | 119.6 |
C6—C7—H7 | 120.1 | C23—C22—C21 | 119.3 (2) |
C7—C8—C9 | 120.9 (2) | C23—C22—H22 | 120.3 |
C7—C8—H8 | 119.6 | C21—C22—H22 | 120.3 |
C9—C8—H8 | 119.6 | C22—C23—C24 | 120.1 (2) |
N1—C9—C8 | 119.12 (19) | C22—C23—H23 | 120.0 |
N1—C9—C10 | 121.65 (18) | C24—C23—H23 | 120.0 |
C8—C9—C10 | 119.16 (18) | C23—C24—C19 | 120.94 (18) |
C4—C10—C5 | 123.7 (2) | C23—C24—H24 | 119.5 |
C4—C10—C9 | 117.89 (18) | C19—C24—H24 | 119.5 |
C2—N2—N3—O | −5.0 (3) | N1—C11—C12—C4 | 1.1 (3) |
C3—N2—N3—O | −176.1 (2) | C1—C11—C12—C4 | −174.12 (17) |
N3—N2—C2—C19 | 68.4 (2) | N1—C11—C12—C3 | 179.35 (17) |
C3—N2—C2—C19 | −121.55 (19) | C1—C11—C12—C3 | 4.1 (3) |
N3—N2—C2—C1 | −168.15 (18) | N2—C3—C12—C4 | −148.61 (17) |
C3—N2—C2—C1 | 1.9 (2) | C13—C3—C12—C4 | 84.4 (2) |
C11—C1—C2—N2 | 38.0 (2) | N2—C3—C12—C11 | 33.2 (2) |
C11—C1—C2—C19 | 163.6 (2) | C13—C3—C12—C11 | −93.8 (2) |
N3—N2—C3—C12 | 133.87 (17) | N2—C3—C13—C18 | −110.5 (2) |
C2—N2—C3—C12 | −36.9 (2) | C12—C3—C13—C18 | 15.8 (2) |
N3—N2—C3—C13 | −97.3 (2) | N2—C3—C13—C14 | 71.2 (2) |
C2—N2—C3—C13 | 92.0 (2) | C12—C3—C13—C14 | −162.57 (17) |
C10—C5—C6—C7 | −0.6 (4) | C18—C13—C14—C15 | 0.4 (3) |
C5—C6—C7—C8 | 0.3 (3) | C3—C13—C14—C15 | 178.8 (2) |
C6—C7—C8—C9 | −0.2 (3) | C13—C14—C15—C16 | 0.2 (4) |
C11—N1—C9—C8 | −175.84 (17) | C14—C15—C16—C17 | −0.1 (4) |
C11—N1—C9—C10 | 1.2 (3) | C15—C16—C17—C18 | −0.6 (4) |
C7—C8—C9—N1 | 177.61 (18) | C14—C13—C18—C17 | −1.0 (3) |
C7—C8—C9—C10 | 0.5 (3) | C3—C13—C18—C17 | −179.34 (18) |
C12—C4—C10—C5 | 176.35 (19) | C16—C17—C18—C13 | 1.2 (3) |
C12—C4—C10—C9 | −2.8 (3) | N2—C2—C19—C24 | 45.2 (2) |
C6—C5—C10—C4 | −178.4 (2) | C1—C2—C19—C24 | −78.4 (2) |
C6—C5—C10—C9 | 0.8 (3) | N2—C2—C19—C20 | −141.18 (17) |
N1—C9—C10—C4 | 1.4 (3) | C1—C2—C19—C20 | 95.2 (2) |
C8—C9—C10—C4 | 178.49 (18) | C24—C19—C20—C21 | 0.9 (3) |
N1—C9—C10—C5 | −177.79 (18) | C2—C19—C20—C21 | −173.01 (19) |
C8—C9—C10—C5 | −0.7 (3) | C19—C20—C21—C22 | −0.7 (3) |
C9—N1—C11—C12 | −2.5 (3) | C20—C21—C22—C23 | −0.6 (4) |
C9—N1—C11—C1 | 172.66 (16) | C21—C22—C23—C24 | 1.5 (3) |
C2—C1—C11—N1 | 142.07 (18) | C22—C23—C24—C19 | −1.3 (3) |
C2—C1—C11—C12 | −42.5 (2) | C20—C19—C24—C23 | 0.1 (3) |
C10—C4—C12—C11 | 1.7 (3) | C2—C19—C24—C23 | 173.79 (18) |
C10—C4—C12—C3 | −176.49 (17) |
Experimental details
Crystal data | |
Chemical formula | C24H19N3O |
Mr | 365.42 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 293 |
a, b, c (Å) | 9.713 (6), 19.265 (8), 10.450 (2) |
β (°) | 105.74 (3) |
V (Å3) | 1882.1 (14) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.2 × 0.2 × 0.15 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3876, 3435, 2660 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.172, 1.07 |
No. of reflections | 3435 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.20 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997) and PLATON (Spek, 2000), SHELX97 and PARST (Nardelli, 1995).
O—N3 | 1.233 (2) | N2—C3 | 1.484 (2) |
N1—C11 | 1.315 (3) | C1—C11 | 1.497 (3) |
N1—C9 | 1.373 (2) | C2—C19 | 1.512 (3) |
N2—N3 | 1.321 (2) | C3—C13 | 1.524 (3) |
N2—C2 | 1.479 (2) | ||
N3—N2—C2 | 121.6 (2) | N2—C3—C12 | 110.1 (2) |
N3—N2—C3 | 113.4 (2) | N2—C3—C13 | 111.6 (2) |
O—N3—N2 | 114.4 (2) | ||
C2—N2—N3—O | −5.0 (3) | C1—C11—C12—C3 | 4.1 (3) |
C3—N2—N3—O | −176.1 (2) | C13—C3—C12—C11 | −93.8 (2) |
C11—C1—C2—C19 | 163.6 (2) | C1—C2—C19—C24 | −78.4 (2) |
N1—C11—C12—C4 | 1.1 (3) |
Nitrosamines are known to exhibit carcinogenic properties (Magee et al., 1976; Ferguson, 1975). Ever since the first demonstration of carcinogenicity in N-nitroso compounds (Magee & Barnes, 1956), there have been extensive biochemical and physicochemical studies on their structure-activity relationships (Lijinsky, 1984; Magee et al., 1976). However, there is little information on the detailed geometries of N-nitroso compounds, although several solution NMR spectroscopic investigations have been carried out (Fraser & Grindley, 1975; Forrest et al., 1974; Ellis et al., 1974; Priya et al., 1992). Certain N-nitrosoureas are used as antitumour agents or antibiotics (Sapse et al., 1988).
1,6-Naphthyridines have extensive pharmacological properties. These derivatives have antiinflammatory (Di Braccio et al., 1997), antibacterial (Hong et al., 1997), antitumour (Chen et al.., 1997), cardiotonic (Mohan & Mishra, 1997), and anticonvulsant and insecticidal (Damon & Nadelson, 1981) properties. They exhibit unique photophysical, photochemical and optical properties due to the charge-transfer interaction between the donor and acceptor substituents. They can behave as nonlinear optical materials, which have various applications in the field of telecommunications (Murugan, 1997). In addition, 1,6-naphthyridine derivatives are also used as novel potent adenosine 3',5'-cyclic phosphate phosphodiesterase III inhibitors (Singh et al., 1995).
We have undertaken the synthesis and structural analysis of a series of cyclic nitrosamines (Senthilkumar et al., 1992, 1995; Ravinderan et al., 1992; Priya et al., 1992). The 1,6-naphthyridine system is known (Reed et al., 1988; Vinick, 1989), but only a few structural data have been reported to date (Balogh et al., 1986; Goméz de Andérez et al., 1992; Govindasamy et al., 2000). Against this background, and in order to obtain detailed information about stereochemical and conformational changes induced by the substituents on the title compound, (I), in the solid state, its X-ray structure determination has been carried out and the results are presented here. \sch
Fig. 1 shows a view of (I) with the atom-numbering scheme. The N2—N3 and N3═O bond lengths and the N2—N3—O bond angle are comparable with the previously reported values of 1.331 (2) Å, 1.231 (2) Å and 115.3 (1)°, respectively (Priya et al., 1992). The N2—N3 bond exhibits partial double-bond character, which leads to restricted rotation about the bond, as also found from solution NMR studies (Cooney & Brownstein, 1974). The N—C distances in (I) agree well with the literature values (Allen et al., 1987).
The nitroso group of (I) has a coplanar orientation with respect to atoms C2 and C3, as is evident from the C3—N2—N3—O and C2—N2—N3—O torsion angles, respectively. The C11—C1—C2—C19 torsion angle shows that the phenyl ring attached at C2 is equatorially disposed in the naphthyridine system. The C11—C12—C3—C13 torsion angle shows that the phenyl group attached at C3 is axially oriented in the naphthyridine system. A similar effect has also been observed by Lavaanya et al. (2001). The dihedral angle between the fused pyridine rings is 16.2 (1)°. The interplanar angle formed between the fused tetrahydropyridine and benzo planes is 13.4 (1)°. The angle between the planes of the C13—C18 and C19—C24 phenyl rings is 88.9 (1)°.
The substitution of a methyl or nitroso group at the N2 position has been shown to exert a large influence on the conformation of the ring and the orientation of the ring substituents (Vierhapper, 1980; Baliah & Natarajan, 1989). The tetrahydropyridine ring of (I) has a boat conformation, with a total puckering amplitude (Cremer & Pople, 1975) of QT = 0.520 (2) Å and with values of the lowest displacement asymmetry parameters (Nardelli, 1983) of ΔS(C1) = 0.015 (1) and ΔS(N2—C2) = 0.019 (1).
In addition to van der Waals interactions, the crystal packing of (I) is stabilized by an C—H···O intermolecular hydrogen bond, with C5—H5 0.93, H5—Oi 2.47 and C5···Oi 3.179 (3) Å, and C5—H5···Oi 133° [symmetry code: (i) x + 1/2, 3/2 − y, 1 + z]. This intermolecular hydrogen bond forms a C(9) (Bernstein et al., 1995) graph-set chain, O—N3—N2—C3—C12—C4—C10—C5—H5, running along the [001] direction (Fig. 2).