Three new N-benzylideneaniline derivatives [p-nitrobenzylidene-p-phenylamineaniline (I), 2,4-dinitrobenzylidene-p-phenylamineaniline (II) and p-dinitrobenzylidene-p-diethylamineaniline (III)] containing electron–push–pull groups have been prepared. They present a planar N-benzylideneaniline core and neighbouring functional atoms, which are related through an efficient intramolecular charge transfer (CT). Two of the derivatives crystallize in non-centrosymmetric space groups, a necessary condition for non-linear optical (NLO) responses. The NLO properties were calculated for the molecular conformations determined by single-crystal X-ray diffraction as well as for the four molecules packed into each corresponding unit cell, using a quantum-chemical method at the cam-B3LYP/NLO-V level of theory. As expected from antiparallel face-to-face stacking through centrosymmetry, the main NLO descriptors – namely, the first hyperpolarizability (βtot) and its projection on the dipole moment direction (βvec) – are almost zero for the tetramer of derivative III. Interestingly, the calculated first hyperpolarizability decreases in the non-centrosymmetric unit-cell content of derivative II when compared to its single molecule, which may be related to its molecular pillaring, similar to that observed in derivative III. On the other hand, a desirable magnification of the NLO properties was found for packed units of derivative I, which may be a consequence of its parallel face-to-tail stacking with the CT vectors of all molecules pointing in the same direction. Moreover, the CT vector of compound I makes an angle of θ = 33.6° with its crystal polar axis, resulting in a higher-order parameter (cos3θ = 0.6) compared with the other derivatives. This is in line with the higher macroscopic second-order NLO response predicted for derivative I, βtot = 120.4 × 10−30 e.s.u.
Supporting information
CCDC references: 991743; 991744; 991745
For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008).
(I)
N-[4-(4-Nitrobenzylideneamino)phenyl]phenylamine
top
Crystal data top
C19H15N3O2 | F(000) = 664 |
Mr = 317.34 | Dx = 1.369 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3885 (3) Å | Cell parameters from 7992 reflections |
b = 16.7902 (4) Å | θ = 3.1–29.5° |
c = 8.9064 (2) Å | µ = 0.09 mm−1 |
β = 97.704 (2)° | T = 150 K |
V = 1539.48 (7) Å3 | Prism, red |
Z = 4 | 0.83 × 0.41 × 0.02 mm |
Data collection top
Xcalibur, Atlas, Gemini ultra diffractometer | 3037 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 10.4186 pixels mm-1 | θmax = 29.5°, θmin = 3.1° |
ω scans | h = −13→14 |
15522 measured reflections | k = −22→22 |
3793 independent reflections | l = −11→12 |
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)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0511P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
3793 reflections | Δρmax = 0.18 e Å−3 |
220 parameters | Δρmin = −0.19 e Å−3 |
2 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.2 (10) |
Crystal data top
C19H15N3O2 | V = 1539.48 (7) Å3 |
Mr = 317.34 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 10.3885 (3) Å | µ = 0.09 mm−1 |
b = 16.7902 (4) Å | T = 150 K |
c = 8.9064 (2) Å | 0.83 × 0.41 × 0.02 mm |
β = 97.704 (2)° | |
Data collection top
Xcalibur, Atlas, Gemini ultra diffractometer | 3037 reflections with I > 2σ(I) |
15522 measured reflections | Rint = 0.034 |
3793 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | Δρmax = 0.18 e Å−3 |
S = 1.00 | Δρmin = −0.19 e Å−3 |
3793 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
220 parameters | Absolute structure parameter: −0.2 (10) |
2 restraints | |
Special details top
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell s.u.'s are taken into
account individually in the estimation of s.u.'s in distances, angles and
torsion angles; correlations between s.u.'s in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'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 >
2σ(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 | 1.05627 (14) | 0.86269 (9) | 1.47754 (17) | 0.0265 (3) | |
C6 | 1.08414 (14) | 0.79395 (9) | 1.40314 (17) | 0.0292 (3) | |
H6 | 1.1406 | 0.7547 | 1.4525 | 0.035* | |
C5 | 1.02775 (14) | 0.78394 (9) | 1.25526 (16) | 0.0297 (3) | |
H5 | 1.0432 | 0.7363 | 1.2031 | 0.036* | |
C4 | 0.94843 (13) | 0.84263 (8) | 1.18104 (16) | 0.0257 (3) | |
C3 | 0.92257 (14) | 0.91191 (8) | 1.26046 (16) | 0.0270 (3) | |
H3 | 0.8683 | 0.9521 | 1.2108 | 0.032* | |
C2 | 0.97516 (14) | 0.92196 (8) | 1.40943 (17) | 0.0274 (3) | |
H2 | 0.9565 | 0.9682 | 1.4642 | 0.033* | |
C7 | 0.89574 (14) | 0.83072 (9) | 1.02239 (17) | 0.0282 (3) | |
H7 | 0.9147 | 0.7825 | 0.9741 | 0.034* | |
C8 | 0.77705 (13) | 0.86987 (8) | 0.79143 (16) | 0.0237 (3) | |
C13 | 0.81637 (14) | 0.80893 (8) | 0.70024 (16) | 0.0275 (3) | |
H13 | 0.8815 | 0.7724 | 0.7418 | 0.033* | |
C12 | 0.76246 (13) | 0.80116 (8) | 0.55208 (16) | 0.0279 (3) | |
H12 | 0.7903 | 0.7592 | 0.4926 | 0.033* | |
C11 | 0.66684 (13) | 0.85425 (8) | 0.48699 (16) | 0.0255 (3) | |
C10 | 0.62932 (14) | 0.91627 (9) | 0.57647 (16) | 0.0270 (3) | |
H10 | 0.5661 | 0.9538 | 0.5344 | 0.032* | |
C9 | 0.68416 (14) | 0.92301 (8) | 0.72616 (16) | 0.0255 (3) | |
H9 | 0.6574 | 0.9653 | 0.7858 | 0.031* | |
C14 | 0.50850 (15) | 0.87688 (8) | 0.24986 (16) | 0.0253 (3) | |
C15 | 0.50800 (15) | 0.88379 (9) | 0.09377 (17) | 0.0295 (3) | |
H15 | 0.5841 | 0.8709 | 0.0504 | 0.035* | |
C16 | 0.39828 (16) | 0.90915 (9) | 0.00154 (18) | 0.0348 (4) | |
H16 | 0.3985 | 0.912 | −0.1049 | 0.042* | |
C17 | 0.28812 (17) | 0.93035 (9) | 0.06324 (18) | 0.0365 (4) | |
H17 | 0.2128 | 0.9484 | 0 | 0.044* | |
C18 | 0.28882 (15) | 0.92501 (9) | 0.21836 (18) | 0.0319 (3) | |
H18 | 0.2138 | 0.9403 | 0.2617 | 0.038* | |
C19 | 0.39729 (15) | 0.89765 (9) | 0.31139 (18) | 0.0286 (3) | |
H19 | 0.3956 | 0.8931 | 0.4174 | 0.034* | |
N1 | 1.11300 (14) | 0.87181 (8) | 1.63661 (15) | 0.0334 (3) | |
N2 | 0.82556 (11) | 0.88247 (7) | 0.94651 (14) | 0.0266 (3) | |
N3 | 0.61950 (13) | 0.84406 (9) | 0.33503 (14) | 0.0333 (3) | |
O2 | 1.19138 (14) | 0.82128 (8) | 1.69197 (14) | 0.0540 (4) | |
O1 | 1.07907 (13) | 0.92866 (7) | 1.70810 (13) | 0.0456 (3) | |
HN3 | 0.665 (2) | 0.8122 (12) | 0.290 (2) | 0.055* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0264 (7) | 0.0284 (8) | 0.0250 (7) | −0.0027 (6) | 0.0038 (6) | 0.0016 (6) |
C6 | 0.0277 (7) | 0.0271 (8) | 0.0324 (8) | 0.0051 (6) | 0.0021 (6) | 0.0048 (6) |
C5 | 0.0291 (8) | 0.0268 (7) | 0.0328 (8) | 0.0060 (6) | 0.0033 (6) | 0.0005 (6) |
C4 | 0.0224 (7) | 0.0254 (7) | 0.0299 (8) | −0.0009 (6) | 0.0053 (6) | 0.0030 (6) |
C3 | 0.0239 (7) | 0.0236 (7) | 0.0334 (9) | 0.0032 (6) | 0.0031 (6) | 0.0043 (6) |
C2 | 0.0284 (8) | 0.0227 (7) | 0.0322 (8) | 0.0002 (6) | 0.0084 (6) | 0.0006 (6) |
C7 | 0.0266 (8) | 0.0246 (8) | 0.0325 (8) | 0.0023 (6) | 0.0009 (6) | −0.0015 (6) |
C8 | 0.0207 (7) | 0.0225 (7) | 0.0283 (8) | −0.0007 (5) | 0.0045 (6) | 0.0043 (6) |
C13 | 0.0238 (7) | 0.0247 (7) | 0.0346 (8) | 0.0059 (6) | 0.0065 (6) | 0.0066 (6) |
C12 | 0.0271 (8) | 0.0241 (7) | 0.0343 (8) | 0.0039 (6) | 0.0107 (6) | 0.0003 (6) |
C11 | 0.0245 (8) | 0.0250 (7) | 0.0279 (8) | −0.0012 (6) | 0.0065 (6) | 0.0029 (6) |
C10 | 0.0256 (7) | 0.0214 (7) | 0.0329 (8) | 0.0041 (5) | 0.0002 (6) | 0.0035 (6) |
C9 | 0.0269 (8) | 0.0190 (7) | 0.0307 (8) | 0.0012 (6) | 0.0040 (6) | 0.0000 (6) |
C14 | 0.0259 (7) | 0.0221 (7) | 0.0275 (8) | −0.0025 (6) | 0.0021 (6) | −0.0006 (6) |
C15 | 0.0335 (8) | 0.0251 (8) | 0.0311 (8) | −0.0047 (6) | 0.0093 (7) | −0.0033 (6) |
C16 | 0.0445 (10) | 0.0322 (8) | 0.0272 (8) | −0.0055 (7) | 0.0022 (7) | 0.0012 (6) |
C17 | 0.0352 (8) | 0.0339 (9) | 0.0382 (9) | −0.0009 (7) | −0.0034 (7) | 0.0010 (7) |
C18 | 0.0265 (7) | 0.0309 (8) | 0.0379 (9) | −0.0025 (6) | 0.0032 (6) | −0.0010 (7) |
C19 | 0.0304 (8) | 0.0290 (8) | 0.0268 (7) | −0.0047 (6) | 0.0054 (6) | −0.0022 (6) |
N1 | 0.0377 (7) | 0.0326 (7) | 0.0291 (7) | −0.0055 (6) | 0.0011 (6) | 0.0026 (6) |
N2 | 0.0242 (7) | 0.0268 (7) | 0.0285 (7) | 0.0017 (5) | 0.0030 (5) | 0.0029 (5) |
N3 | 0.0317 (7) | 0.0386 (8) | 0.0293 (7) | 0.0102 (6) | 0.0030 (6) | −0.0063 (6) |
O2 | 0.0720 (9) | 0.0452 (8) | 0.0389 (7) | 0.0122 (7) | −0.0149 (6) | 0.0034 (6) |
O1 | 0.0534 (7) | 0.0457 (7) | 0.0365 (7) | −0.0015 (6) | 0.0020 (5) | −0.0114 (6) |
Geometric parameters (Å, º) top
C1—C6 | 1.381 (2) | C11—N3 | 1.3873 (19) |
C1—C2 | 1.390 (2) | C11—C10 | 1.398 (2) |
C1—N1 | 1.468 (2) | C10—C9 | 1.382 (2) |
C6—C5 | 1.378 (2) | C10—H10 | 0.95 |
C6—H6 | 0.95 | C9—H9 | 0.95 |
C5—C4 | 1.393 (2) | C14—C19 | 1.388 (2) |
C5—H5 | 0.95 | C14—C15 | 1.394 (2) |
C4—C3 | 1.406 (2) | C14—N3 | 1.405 (2) |
C4—C7 | 1.459 (2) | C15—C16 | 1.380 (2) |
C3—C2 | 1.376 (2) | C15—H15 | 0.95 |
C3—H3 | 0.95 | C16—C17 | 1.381 (2) |
C2—H2 | 0.95 | C16—H16 | 0.95 |
C7—N2 | 1.2693 (18) | C17—C18 | 1.383 (2) |
C7—H7 | 0.95 | C17—H17 | 0.95 |
C8—C9 | 1.384 (2) | C18—C19 | 1.385 (2) |
C8—C13 | 1.401 (2) | C18—H18 | 0.95 |
C8—N2 | 1.4212 (19) | C19—H19 | 0.95 |
C13—C12 | 1.369 (2) | N1—O1 | 1.2252 (18) |
C13—H13 | 0.95 | N1—O2 | 1.2321 (18) |
C12—C11 | 1.401 (2) | N3—HN3 | 0.85 (2) |
C12—H12 | 0.95 | | |
| | | |
C6—C1—C2 | 122.89 (14) | C10—C11—C12 | 118.32 (13) |
C6—C1—N1 | 117.87 (13) | C9—C10—C11 | 120.02 (13) |
C2—C1—N1 | 119.22 (14) | C9—C10—H10 | 120 |
C5—C6—C1 | 118.09 (14) | C11—C10—H10 | 120 |
C5—C6—H6 | 121 | C10—C9—C8 | 121.76 (13) |
C1—C6—H6 | 121 | C10—C9—H9 | 119.1 |
C6—C5—C4 | 121.06 (14) | C8—C9—H9 | 119.1 |
C6—C5—H5 | 119.5 | C19—C14—C15 | 118.73 (14) |
C4—C5—H5 | 119.5 | C19—C14—N3 | 123.48 (14) |
C5—C4—C3 | 119.16 (13) | C15—C14—N3 | 117.65 (13) |
C5—C4—C7 | 118.94 (13) | C16—C15—C14 | 120.77 (14) |
C3—C4—C7 | 121.90 (12) | C16—C15—H15 | 119.6 |
C2—C3—C4 | 120.58 (13) | C14—C15—H15 | 119.6 |
C2—C3—H3 | 119.7 | C15—C16—C17 | 120.34 (15) |
C4—C3—H3 | 119.7 | C15—C16—H16 | 119.8 |
C3—C2—C1 | 118.18 (13) | C17—C16—H16 | 119.8 |
C3—C2—H2 | 120.9 | C16—C17—C18 | 119.14 (15) |
C1—C2—H2 | 120.9 | C16—C17—H17 | 120.4 |
N2—C7—C4 | 122.41 (13) | C18—C17—H17 | 120.4 |
N2—C7—H7 | 118.8 | C17—C18—C19 | 120.93 (15) |
C4—C7—H7 | 118.8 | C17—C18—H18 | 119.5 |
C9—C8—C13 | 117.94 (13) | C19—C18—H18 | 119.5 |
C9—C8—N2 | 116.66 (12) | C18—C19—C14 | 120.06 (15) |
C13—C8—N2 | 125.40 (12) | C18—C19—H19 | 120 |
C12—C13—C8 | 121.00 (13) | C14—C19—H19 | 120 |
C12—C13—H13 | 119.5 | O1—N1—O2 | 123.31 (14) |
C8—C13—H13 | 119.5 | O1—N1—C1 | 118.46 (14) |
C13—C12—C11 | 120.93 (13) | O2—N1—C1 | 118.22 (13) |
C13—C12—H12 | 119.5 | C7—N2—C8 | 121.27 (12) |
C11—C12—H12 | 119.5 | C11—N3—C14 | 129.51 (13) |
N3—C11—C10 | 123.95 (13) | C11—N3—HN3 | 113.4 (13) |
N3—C11—C12 | 117.66 (13) | C14—N3—HN3 | 117.0 (13) |
| | | |
C2—C1—C6—C5 | −0.5 (2) | N2—C8—C9—C10 | −179.51 (12) |
N1—C1—C6—C5 | 177.94 (13) | C19—C14—C15—C16 | −1.4 (2) |
C1—C6—C5—C4 | 2.2 (2) | N3—C14—C15—C16 | 174.48 (14) |
C6—C5—C4—C3 | −2.1 (2) | C14—C15—C16—C17 | 1.9 (2) |
C6—C5—C4—C7 | 177.28 (13) | C15—C16—C17—C18 | −0.7 (2) |
C5—C4—C3—C2 | 0.2 (2) | C16—C17—C18—C19 | −1.0 (2) |
C7—C4—C3—C2 | −179.06 (13) | C17—C18—C19—C14 | 1.5 (2) |
C4—C3—C2—C1 | 1.3 (2) | C15—C14—C19—C18 | −0.3 (2) |
C6—C1—C2—C3 | −1.2 (2) | N3—C14—C19—C18 | −175.92 (14) |
N1—C1—C2—C3 | −179.66 (12) | C6—C1—N1—O1 | −172.99 (14) |
C5—C4—C7—N2 | −178.16 (13) | C2—C1—N1—O1 | 5.5 (2) |
C3—C4—C7—N2 | 1.1 (2) | C6—C1—N1—O2 | 6.2 (2) |
C9—C8—C13—C12 | −1.4 (2) | C2—C1—N1—O2 | −175.25 (14) |
N2—C8—C13—C12 | 179.17 (13) | C4—C7—N2—C8 | 179.06 (13) |
C8—C13—C12—C11 | 0.4 (2) | C9—C8—N2—C7 | 169.30 (13) |
C13—C12—C11—N3 | 178.13 (13) | C13—C8—N2—C7 | −11.3 (2) |
C13—C12—C11—C10 | 1.1 (2) | C10—C11—N3—C14 | −17.3 (3) |
N3—C11—C10—C9 | −178.30 (13) | C12—C11—N3—C14 | 165.86 (14) |
C12—C11—C10—C9 | −1.4 (2) | C19—C14—N3—C11 | −29.1 (2) |
C11—C10—C9—C8 | 0.4 (2) | C15—C14—N3—C11 | 155.26 (14) |
C13—C8—C9—C10 | 1.0 (2) | | |
(II)
N-[4-(2,4-dinitrobenzylideneamino)phenyl]phenylamine
top
Crystal data top
C19H14N4O4 | Dx = 1.426 Mg m−3 |
Mr = 362.34 | Cu Kα radiation, λ = 1.5418 Å |
Orthorhombic, P212121 | Cell parameters from 3724 reflections |
a = 6.5715 (2) Å | θ = 2.6–66.5° |
b = 15.0533 (4) Å | µ = 0.86 mm−1 |
c = 17.0598 (5) Å | T = 150 K |
V = 1687.60 (8) Å3 | Prism, red |
Z = 4 | 0.90 × 0.11 × 0.08 mm |
F(000) = 752 | |
Data collection top
Xcalibur, Atlas, Gemini ultra diffractometer | 2612 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 10.4186 pixels mm-1 | θmax = 66.6°, θmin = 3.9° |
ω scans | h = −4→7 |
6008 measured reflections | k = −16→17 |
2905 independent reflections | l = −17→20 |
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)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.0533P)2 + 0.0662P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2905 reflections | Δρmax = 0.12 e Å−3 |
247 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.2 (2) |
Crystal data top
C19H14N4O4 | V = 1687.60 (8) Å3 |
Mr = 362.34 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 6.5715 (2) Å | µ = 0.86 mm−1 |
b = 15.0533 (4) Å | T = 150 K |
c = 17.0598 (5) Å | 0.90 × 0.11 × 0.08 mm |
Data collection top
Xcalibur, Atlas, Gemini ultra diffractometer | 2612 reflections with I > 2σ(I) |
6008 measured reflections | Rint = 0.021 |
2905 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.084 | Δρmax = 0.12 e Å−3 |
S = 1.05 | Δρmin = −0.17 e Å−3 |
2905 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
247 parameters | Absolute structure parameter: 0.2 (2) |
0 restraints | |
Special details top
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell s.u.'s are taken into
account individually in the estimation of s.u.'s in distances, angles and
torsion angles; correlations between s.u.'s in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'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 >
2σ(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 | |
O4 | 0.2931 (2) | 0.35218 (8) | 0.71549 (7) | 0.0458 (3) | |
N4 | 0.3510 (2) | 0.32847 (9) | 0.65055 (8) | 0.0323 (3) | |
O3 | 0.4211 (2) | 0.37961 (8) | 0.60149 (7) | 0.0419 (3) | |
N3 | 0.2920 (3) | 0.43762 (10) | 0.14072 (8) | 0.0354 (3) | |
N1 | 0.3118 (2) | 0.02368 (11) | 0.74303 (10) | 0.0431 (4) | |
N2 | 0.36409 (19) | 0.23825 (9) | 0.41748 (8) | 0.0287 (3) | |
C8 | 0.3440 (2) | 0.29283 (11) | 0.35041 (9) | 0.0266 (3) | |
O2 | 0.3226 (2) | 0.05278 (10) | 0.80974 (8) | 0.0527 (4) | |
C9 | 0.3521 (2) | 0.24951 (11) | 0.27839 (9) | 0.0300 (4) | |
H9 | 0.3699 | 0.1869 | 0.2772 | 0.036* | |
C5 | 0.3360 (2) | 0.23373 (10) | 0.63102 (9) | 0.0271 (3) | |
C12 | 0.3088 (2) | 0.43196 (10) | 0.28126 (9) | 0.0287 (3) | |
H12 | 0.296 | 0.4948 | 0.2824 | 0.034* | |
O1 | 0.2914 (3) | −0.05488 (10) | 0.72680 (10) | 0.0685 (5) | |
C7 | 0.3105 (2) | 0.26609 (11) | 0.48485 (9) | 0.0273 (3) | |
H7 | 0.2599 | 0.3248 | 0.4913 | 0.033* | |
C11 | 0.3131 (2) | 0.38779 (10) | 0.20887 (9) | 0.0286 (3) | |
C13 | 0.3229 (2) | 0.38544 (10) | 0.35097 (9) | 0.0273 (3) | |
H13 | 0.3182 | 0.4164 | 0.3994 | 0.033* | |
C4 | 0.3279 (2) | 0.20607 (10) | 0.55278 (9) | 0.0274 (3) | |
C1 | 0.3212 (3) | 0.08660 (11) | 0.67714 (9) | 0.0323 (4) | |
C3 | 0.3219 (3) | 0.11400 (11) | 0.53990 (10) | 0.0318 (4) | |
H3 | 0.3199 | 0.0924 | 0.4876 | 0.038* | |
C10 | 0.3349 (3) | 0.29527 (11) | 0.20890 (10) | 0.0319 (4) | |
H10 | 0.3378 | 0.2639 | 0.1606 | 0.038* | |
C6 | 0.3308 (2) | 0.17592 (11) | 0.69367 (9) | 0.0305 (4) | |
H6 | 0.3336 | 0.197 | 0.7462 | 0.037* | |
C14 | 0.3144 (3) | 0.40395 (11) | 0.06443 (9) | 0.0362 (4) | |
C2 | 0.3189 (3) | 0.05418 (12) | 0.60095 (11) | 0.0362 (4) | |
H2 | 0.3153 | −0.0079 | 0.5912 | 0.043* | |
C19 | 0.4903 (3) | 0.35710 (13) | 0.04370 (11) | 0.0459 (5) | |
H19 | 0.5948 | 0.3477 | 0.0813 | 0.055* | |
C15 | 0.1651 (4) | 0.41896 (13) | 0.00849 (10) | 0.0476 (5) | |
H15 | 0.0455 | 0.451 | 0.0219 | 0.057* | |
C18 | 0.5118 (4) | 0.32436 (14) | −0.03202 (12) | 0.0605 (7) | |
H18 | 0.6297 | 0.2914 | −0.0458 | 0.073* | |
C16 | 0.1915 (5) | 0.38694 (14) | −0.06729 (11) | 0.0616 (7) | |
H16 | 0.09 | 0.3979 | −0.1057 | 0.074* | |
C17 | 0.3629 (5) | 0.33957 (15) | −0.08723 (12) | 0.0702 (8) | |
H17 | 0.3785 | 0.3174 | −0.139 | 0.084* | |
H3N | 0.218 (5) | 0.483 (2) | 0.1436 (15) | 0.084* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O4 | 0.0620 (8) | 0.0414 (7) | 0.0340 (7) | 0.0019 (7) | 0.0031 (6) | −0.0062 (6) |
N4 | 0.0357 (7) | 0.0291 (7) | 0.0320 (7) | 0.0028 (6) | −0.0033 (6) | 0.0027 (6) |
O3 | 0.0547 (7) | 0.0299 (7) | 0.0411 (7) | −0.0058 (6) | 0.0011 (6) | 0.0058 (5) |
N3 | 0.0497 (9) | 0.0320 (8) | 0.0245 (7) | 0.0076 (7) | −0.0013 (7) | 0.0022 (6) |
N1 | 0.0327 (8) | 0.0425 (9) | 0.0541 (10) | 0.0033 (8) | 0.0061 (8) | 0.0206 (8) |
N2 | 0.0269 (7) | 0.0301 (7) | 0.0290 (7) | −0.0045 (6) | −0.0019 (5) | 0.0019 (6) |
C8 | 0.0234 (7) | 0.0306 (8) | 0.0257 (8) | −0.0006 (7) | −0.0022 (7) | 0.0023 (6) |
O2 | 0.0522 (8) | 0.0633 (9) | 0.0426 (8) | 0.0035 (8) | 0.0027 (7) | 0.0244 (7) |
C9 | 0.0312 (8) | 0.0268 (8) | 0.0320 (8) | −0.0012 (7) | −0.0033 (7) | −0.0014 (7) |
C5 | 0.0218 (7) | 0.0281 (8) | 0.0313 (8) | 0.0024 (7) | 0.0010 (7) | 0.0037 (7) |
C12 | 0.0274 (7) | 0.0271 (8) | 0.0316 (8) | 0.0012 (7) | 0.0002 (7) | −0.0001 (7) |
O1 | 0.0913 (12) | 0.0352 (8) | 0.0791 (11) | −0.0018 (8) | 0.0135 (10) | 0.0234 (7) |
C7 | 0.0226 (7) | 0.0287 (9) | 0.0306 (9) | 0.0002 (7) | −0.0022 (6) | 0.0028 (7) |
C11 | 0.0285 (7) | 0.0298 (8) | 0.0277 (8) | 0.0013 (7) | −0.0011 (7) | 0.0020 (6) |
C13 | 0.0248 (7) | 0.0316 (9) | 0.0256 (7) | −0.0010 (7) | −0.0003 (7) | −0.0031 (6) |
C4 | 0.0209 (7) | 0.0300 (8) | 0.0314 (8) | 0.0013 (7) | −0.0001 (7) | 0.0028 (6) |
C1 | 0.0244 (8) | 0.0328 (9) | 0.0396 (9) | 0.0016 (7) | 0.0027 (7) | 0.0135 (7) |
C3 | 0.0283 (8) | 0.0316 (9) | 0.0356 (9) | −0.0011 (8) | 0.0007 (8) | 0.0014 (7) |
C10 | 0.0370 (8) | 0.0327 (8) | 0.0261 (8) | −0.0020 (8) | −0.0010 (8) | −0.0048 (7) |
C6 | 0.0230 (7) | 0.0376 (9) | 0.0308 (8) | 0.0010 (7) | 0.0003 (7) | 0.0060 (7) |
C14 | 0.0561 (11) | 0.0260 (8) | 0.0266 (8) | −0.0018 (9) | −0.0004 (8) | 0.0036 (6) |
C2 | 0.0309 (8) | 0.0270 (9) | 0.0508 (10) | −0.0015 (8) | 0.0023 (9) | 0.0040 (7) |
C19 | 0.0636 (12) | 0.0389 (11) | 0.0352 (10) | 0.0022 (10) | 0.0087 (9) | 0.0035 (8) |
C15 | 0.0736 (13) | 0.0327 (10) | 0.0366 (10) | −0.0053 (11) | −0.0109 (11) | 0.0060 (8) |
C18 | 0.1033 (19) | 0.0414 (12) | 0.0367 (11) | 0.0043 (13) | 0.0241 (12) | 0.0033 (9) |
C16 | 0.115 (2) | 0.0374 (11) | 0.0321 (10) | −0.0110 (14) | −0.0193 (13) | 0.0073 (8) |
C17 | 0.149 (3) | 0.0355 (11) | 0.0263 (10) | −0.0128 (15) | 0.0105 (14) | −0.0008 (9) |
Geometric parameters (Å, º) top
O4—N4 | 1.2245 (18) | C11—C10 | 1.400 (2) |
N4—O3 | 1.2269 (18) | C13—H13 | 0.95 |
N4—C5 | 1.468 (2) | C4—C3 | 1.404 (2) |
N3—C11 | 1.390 (2) | C1—C6 | 1.375 (2) |
N3—C14 | 1.405 (2) | C1—C2 | 1.388 (2) |
N3—H3N | 0.84 (3) | C3—C2 | 1.377 (2) |
N1—O2 | 1.221 (2) | C3—H3 | 0.95 |
N1—O1 | 1.222 (2) | C10—H10 | 0.95 |
N1—C1 | 1.471 (2) | C6—H6 | 0.95 |
N2—C7 | 1.273 (2) | C14—C15 | 1.387 (3) |
N2—C8 | 1.415 (2) | C14—C19 | 1.399 (3) |
C8—C9 | 1.392 (2) | C2—H2 | 0.95 |
C8—C13 | 1.401 (2) | C19—C18 | 1.390 (3) |
C9—C10 | 1.376 (2) | C19—H19 | 0.95 |
C9—H9 | 0.95 | C15—C16 | 1.391 (3) |
C5—C6 | 1.379 (2) | C15—H15 | 0.95 |
C5—C4 | 1.399 (2) | C18—C17 | 1.378 (4) |
C12—C13 | 1.383 (2) | C18—H18 | 0.95 |
C12—C11 | 1.403 (2) | C16—C17 | 1.375 (4) |
C12—H12 | 0.95 | C16—H16 | 0.95 |
C7—C4 | 1.474 (2) | C17—H17 | 0.95 |
C7—H7 | 0.95 | | |
| | | |
O4—N4—O3 | 123.43 (14) | C6—C1—C2 | 122.41 (15) |
O4—N4—C5 | 117.88 (13) | C6—C1—N1 | 118.35 (15) |
O3—N4—C5 | 118.69 (13) | C2—C1—N1 | 119.24 (16) |
C11—N3—C14 | 124.74 (14) | C2—C3—C4 | 121.85 (15) |
C11—N3—H3N | 116.6 (19) | C2—C3—H3 | 119.1 |
C14—N3—H3N | 114.1 (18) | C4—C3—H3 | 119.1 |
O2—N1—O1 | 124.37 (16) | C9—C10—C11 | 120.45 (15) |
O2—N1—C1 | 118.58 (16) | C9—C10—H10 | 119.8 |
O1—N1—C1 | 117.04 (17) | C11—C10—H10 | 119.8 |
C7—N2—C8 | 120.87 (14) | C1—C6—C5 | 117.35 (15) |
C9—C8—C13 | 118.42 (14) | C1—C6—H6 | 121.3 |
C9—C8—N2 | 115.99 (14) | C5—C6—H6 | 121.3 |
C13—C8—N2 | 125.56 (14) | C15—C14—C19 | 119.51 (17) |
C10—C9—C8 | 121.52 (14) | C15—C14—N3 | 120.29 (18) |
C10—C9—H9 | 119.2 | C19—C14—N3 | 120.18 (17) |
C8—C9—H9 | 119.2 | C3—C2—C1 | 118.56 (16) |
C6—C5—C4 | 123.42 (15) | C3—C2—H2 | 120.7 |
C6—C5—N4 | 116.04 (14) | C1—C2—H2 | 120.7 |
C4—C5—N4 | 120.54 (13) | C18—C19—C14 | 119.8 (2) |
C13—C12—C11 | 121.04 (14) | C18—C19—H19 | 120.1 |
C13—C12—H12 | 119.5 | C14—C19—H19 | 120.1 |
C11—C12—H12 | 119.5 | C14—C15—C16 | 119.6 (2) |
N2—C7—C4 | 119.12 (14) | C14—C15—H15 | 120.2 |
N2—C7—H7 | 120.4 | C16—C15—H15 | 120.2 |
C4—C7—H7 | 120.4 | C17—C18—C19 | 120.3 (2) |
N3—C11—C10 | 123.16 (15) | C17—C18—H18 | 119.9 |
N3—C11—C12 | 118.58 (14) | C19—C18—H18 | 119.9 |
C10—C11—C12 | 118.24 (15) | C17—C16—C15 | 120.8 (2) |
C12—C13—C8 | 120.30 (14) | C17—C16—H16 | 119.6 |
C12—C13—H13 | 119.9 | C15—C16—H16 | 119.6 |
C8—C13—H13 | 119.9 | C16—C17—C18 | 119.90 (19) |
C5—C4—C3 | 116.37 (14) | C16—C17—H17 | 120 |
C5—C4—C7 | 124.80 (14) | C18—C17—H17 | 120 |
C3—C4—C7 | 118.67 (14) | | |
| | | |
C7—N2—C8—C9 | −162.76 (14) | O2—N1—C1—C2 | 176.92 (16) |
C7—N2—C8—C13 | 19.2 (2) | O1—N1—C1—C2 | −3.8 (2) |
C13—C8—C9—C10 | −1.6 (2) | C5—C4—C3—C2 | 1.6 (3) |
N2—C8—C9—C10 | −179.85 (15) | C7—C4—C3—C2 | −174.05 (15) |
O4—N4—C5—C6 | −23.1 (2) | C8—C9—C10—C11 | 1.5 (3) |
O3—N4—C5—C6 | 156.63 (15) | N3—C11—C10—C9 | −179.04 (15) |
O4—N4—C5—C4 | 156.91 (15) | C12—C11—C10—C9 | −0.2 (3) |
O3—N4—C5—C4 | −23.3 (2) | C2—C1—C6—C5 | 0.7 (3) |
C8—N2—C7—C4 | 178.06 (13) | N1—C1—C6—C5 | −178.94 (14) |
C14—N3—C11—C10 | −8.1 (3) | C4—C5—C6—C1 | 1.3 (2) |
C14—N3—C11—C12 | 173.04 (18) | N4—C5—C6—C1 | −178.62 (14) |
C13—C12—C11—N3 | 178.04 (16) | C11—N3—C14—C15 | 128.94 (19) |
C13—C12—C11—C10 | −0.9 (2) | C11—N3—C14—C19 | −52.8 (3) |
C11—C12—C13—C8 | 0.7 (2) | C4—C3—C2—C1 | 0.2 (3) |
C9—C8—C13—C12 | 0.6 (2) | C6—C1—C2—C3 | −1.4 (3) |
N2—C8—C13—C12 | 178.58 (13) | N1—C1—C2—C3 | 178.18 (16) |
C6—C5—C4—C3 | −2.4 (2) | C15—C14—C19—C18 | −1.5 (3) |
N4—C5—C4—C3 | 177.52 (14) | N3—C14—C19—C18 | −179.69 (18) |
C6—C5—C4—C7 | 172.92 (15) | C19—C14—C15—C16 | 0.3 (3) |
N4—C5—C4—C7 | −7.1 (2) | N3—C14—C15—C16 | 178.55 (17) |
N2—C7—C4—C5 | 159.28 (15) | C14—C19—C18—C17 | 1.5 (3) |
N2—C7—C4—C3 | −25.5 (2) | C14—C15—C16—C17 | 0.8 (3) |
O2—N1—C1—C6 | −3.5 (2) | C15—C16—C17—C18 | −0.8 (3) |
O1—N1—C1—C6 | 175.85 (18) | C19—C18—C17—C16 | −0.4 (3) |
(III)
N-[4-(4-Nitrobenzylideneamino)phenyl]diethylamine
top
Crystal data top
C17H19N3O2 | F(000) = 632 |
Mr = 297.35 | Dx = 1.306 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.1019 (5) Å | Cell parameters from 4763 reflections |
b = 7.6028 (3) Å | θ = 2.1–29.4° |
c = 12.3616 (4) Å | µ = 0.09 mm−1 |
β = 91.615 (3)° | T = 120 K |
V = 1512.70 (9) Å3 | Prism, red |
Z = 4 | 0.69 × 0.39 × 0.30 mm |
Data collection top
Oxford Diffraction Xcalibur, Atlas, Gemini Ultra diffractometer | 2893 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 10.4186 pixels mm-1 | θmax = 29.5°, θmin = 2.5° |
ω scans | h = −20→20 |
13092 measured reflections | k = −7→9 |
3700 independent reflections | l = −16→15 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0607P)2 + 0.3666P] where P = (Fo2 + 2Fc2)/3 |
3700 reflections | (Δ/σ)max < 0.001 |
201 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C17H19N3O2 | V = 1512.70 (9) Å3 |
Mr = 297.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.1019 (5) Å | µ = 0.09 mm−1 |
b = 7.6028 (3) Å | T = 120 K |
c = 12.3616 (4) Å | 0.69 × 0.39 × 0.30 mm |
β = 91.615 (3)° | |
Data collection top
Oxford Diffraction Xcalibur, Atlas, Gemini Ultra diffractometer | 2893 reflections with I > 2σ(I) |
13092 measured reflections | Rint = 0.031 |
3700 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.23 e Å−3 |
3700 reflections | Δρmin = −0.27 e Å−3 |
201 parameters | |
Special details top
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell s.u.'s are taken into
account individually in the estimation of s.u.'s in distances, angles and
torsion angles; correlations between s.u.'s in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'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 >
2σ(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 | |
O1 | 0.85206 (6) | 0.00583 (14) | 1.10158 (8) | 0.0358 (3) | |
N2 | 0.47371 (6) | 0.15482 (13) | 0.82784 (8) | 0.0222 (2) | |
N1 | 0.80569 (7) | 0.12102 (15) | 1.13418 (9) | 0.0282 (3) | |
O2 | 0.82431 (7) | 0.22062 (16) | 1.20897 (9) | 0.0450 (3) | |
C8 | 0.39387 (7) | 0.17600 (16) | 0.77967 (10) | 0.0212 (3) | |
N3 | 0.15534 (6) | 0.19441 (15) | 0.62889 (8) | 0.0237 (2) | |
C13 | 0.33222 (7) | 0.28987 (16) | 0.81622 (10) | 0.0222 (3) | |
H13 | 0.3439 | 0.3632 | 0.877 | 0.027* | |
C6 | 0.66496 (8) | 0.24437 (17) | 1.12905 (10) | 0.0258 (3) | |
H6 | 0.6767 | 0.3001 | 1.1965 | 0.031* | |
C11 | 0.23361 (7) | 0.18855 (16) | 0.67641 (10) | 0.0203 (3) | |
C7 | 0.48925 (7) | 0.20761 (16) | 0.92443 (10) | 0.0223 (3) | |
H7 | 0.4465 | 0.2632 | 0.9632 | 0.027* | |
C5 | 0.58793 (8) | 0.26322 (17) | 1.07758 (10) | 0.0246 (3) | |
H5 | 0.5459 | 0.3302 | 1.111 | 0.029* | |
C9 | 0.37452 (7) | 0.07394 (17) | 0.68881 (10) | 0.0232 (3) | |
H9 | 0.4161 | −0.0004 | 0.6605 | 0.028* | |
C12 | 0.25475 (7) | 0.29748 (16) | 0.76552 (10) | 0.0225 (3) | |
H12 | 0.2147 | 0.378 | 0.7912 | 0.027* | |
C3 | 0.63288 (8) | 0.08144 (17) | 0.92978 (10) | 0.0228 (3) | |
H3 | 0.6219 | 0.0267 | 0.8618 | 0.027* | |
C1 | 0.72428 (7) | 0.14265 (16) | 1.07999 (10) | 0.0225 (3) | |
C10 | 0.29657 (7) | 0.07740 (17) | 0.63837 (10) | 0.0230 (3) | |
H10 | 0.2854 | 0.004 | 0.5775 | 0.028* | |
C2 | 0.70932 (8) | 0.05892 (17) | 0.98155 (10) | 0.0238 (3) | |
H2 | 0.7508 | −0.0124 | 0.9504 | 0.029* | |
C4 | 0.57135 (7) | 0.18473 (16) | 0.97704 (10) | 0.0210 (3) | |
C16 | 0.06796 (9) | 0.46199 (19) | 0.65100 (12) | 0.0347 (3) | |
H16A | 0.1151 | 0.5357 | 0.6743 | 0.052* | |
H16B | 0.0175 | 0.5033 | 0.6855 | 0.052* | |
H16C | 0.0604 | 0.4692 | 0.5722 | 0.052* | |
C15 | 0.08482 (8) | 0.27271 (18) | 0.68354 (11) | 0.0270 (3) | |
H15A | 0.0957 | 0.2678 | 0.7627 | 0.032* | |
H15B | 0.0345 | 0.2017 | 0.667 | 0.032* | |
C17 | 0.10650 (9) | −0.0838 (2) | 0.54181 (13) | 0.0363 (4) | |
H17A | 0.1517 | −0.1537 | 0.5747 | 0.054* | |
H17B | 0.0905 | −0.1336 | 0.4711 | 0.054* | |
H17C | 0.0586 | −0.0855 | 0.589 | 0.054* | |
C14 | 0.13551 (8) | 0.10433 (18) | 0.52733 (10) | 0.0276 (3) | |
H14A | 0.1854 | 0.1041 | 0.4824 | 0.033* | |
H14B | 0.0915 | 0.171 | 0.4877 | 0.033* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0297 (5) | 0.0394 (6) | 0.0381 (6) | 0.0075 (4) | −0.0039 (4) | 0.0041 (5) |
N2 | 0.0212 (5) | 0.0201 (5) | 0.0254 (6) | −0.0031 (4) | 0.0004 (4) | 0.0019 (4) |
N1 | 0.0294 (6) | 0.0293 (6) | 0.0257 (6) | −0.0047 (5) | −0.0046 (4) | 0.0047 (5) |
O2 | 0.0450 (7) | 0.0511 (7) | 0.0379 (6) | −0.0039 (5) | −0.0164 (5) | −0.0112 (5) |
C8 | 0.0205 (6) | 0.0198 (6) | 0.0234 (6) | −0.0029 (4) | 0.0016 (5) | 0.0019 (5) |
N3 | 0.0226 (5) | 0.0267 (6) | 0.0216 (5) | 0.0012 (4) | −0.0010 (4) | −0.0044 (4) |
C13 | 0.0258 (6) | 0.0201 (6) | 0.0208 (6) | −0.0029 (5) | 0.0002 (5) | −0.0019 (5) |
C6 | 0.0356 (7) | 0.0216 (7) | 0.0199 (6) | −0.0021 (5) | −0.0021 (5) | −0.0017 (5) |
C11 | 0.0213 (6) | 0.0200 (6) | 0.0198 (6) | −0.0025 (4) | 0.0017 (4) | 0.0020 (5) |
C7 | 0.0222 (6) | 0.0201 (6) | 0.0249 (6) | −0.0019 (4) | 0.0041 (5) | 0.0020 (5) |
C5 | 0.0286 (7) | 0.0213 (6) | 0.0241 (7) | 0.0012 (5) | 0.0040 (5) | −0.0010 (5) |
C9 | 0.0216 (6) | 0.0232 (6) | 0.0251 (6) | −0.0004 (5) | 0.0048 (5) | −0.0016 (5) |
C12 | 0.0244 (6) | 0.0207 (6) | 0.0226 (6) | 0.0014 (5) | 0.0027 (5) | −0.0011 (5) |
C3 | 0.0261 (6) | 0.0221 (6) | 0.0204 (6) | −0.0027 (5) | 0.0009 (5) | −0.0020 (5) |
C1 | 0.0251 (6) | 0.0193 (6) | 0.0228 (6) | −0.0038 (5) | −0.0026 (5) | 0.0044 (5) |
C10 | 0.0257 (6) | 0.0227 (6) | 0.0208 (6) | −0.0028 (5) | 0.0025 (5) | −0.0036 (5) |
C2 | 0.0252 (6) | 0.0221 (6) | 0.0241 (6) | −0.0002 (5) | 0.0022 (5) | −0.0009 (5) |
C4 | 0.0233 (6) | 0.0178 (6) | 0.0219 (6) | −0.0040 (4) | 0.0018 (5) | 0.0037 (5) |
C16 | 0.0309 (7) | 0.0362 (8) | 0.0368 (8) | 0.0086 (6) | −0.0029 (6) | −0.0062 (6) |
C15 | 0.0215 (6) | 0.0351 (8) | 0.0244 (7) | −0.0009 (5) | 0.0009 (5) | −0.0041 (5) |
C17 | 0.0342 (8) | 0.0331 (8) | 0.0411 (9) | 0.0004 (6) | −0.0076 (6) | −0.0105 (7) |
C14 | 0.0264 (7) | 0.0340 (8) | 0.0220 (7) | 0.0020 (5) | −0.0034 (5) | −0.0039 (5) |
Geometric parameters (Å, º) top
O1—N1 | 1.2262 (15) | C9—C10 | 1.3859 (17) |
N2—C7 | 1.2776 (16) | C9—H9 | 0.95 |
N2—C8 | 1.4107 (15) | C12—H12 | 0.95 |
N1—O2 | 1.2258 (15) | C3—C2 | 1.3818 (17) |
N1—C1 | 1.4644 (16) | C3—C4 | 1.4043 (17) |
C8—C9 | 1.3932 (17) | C3—H3 | 0.95 |
C8—C13 | 1.4015 (17) | C1—C2 | 1.3883 (17) |
N3—C11 | 1.3762 (15) | C10—H10 | 0.95 |
N3—C14 | 1.4576 (16) | C2—H2 | 0.95 |
N3—C15 | 1.4639 (16) | C16—C15 | 1.517 (2) |
C13—C12 | 1.3814 (17) | C16—H16A | 0.98 |
C13—H13 | 0.95 | C16—H16B | 0.98 |
C6—C1 | 1.3824 (19) | C16—H16C | 0.98 |
C6—C5 | 1.3854 (18) | C15—H15A | 0.99 |
C6—H6 | 0.95 | C15—H15B | 0.99 |
C11—C10 | 1.4106 (17) | C17—C14 | 1.517 (2) |
C11—C12 | 1.4120 (17) | C17—H17A | 0.98 |
C7—C4 | 1.4671 (17) | C17—H17B | 0.98 |
C7—H7 | 0.95 | C17—H17C | 0.98 |
C5—C4 | 1.3976 (17) | C14—H14A | 0.99 |
C5—H5 | 0.95 | C14—H14B | 0.99 |
| | | |
C7—N2—C8 | 120.71 (11) | C6—C1—N1 | 118.87 (11) |
O2—N1—O1 | 123.43 (11) | C2—C1—N1 | 118.72 (11) |
O2—N1—C1 | 118.18 (11) | C9—C10—C11 | 120.77 (11) |
O1—N1—C1 | 118.38 (11) | C9—C10—H10 | 119.6 |
C9—C8—C13 | 117.36 (11) | C11—C10—H10 | 119.6 |
C9—C8—N2 | 117.21 (11) | C3—C2—C1 | 118.65 (12) |
C13—C8—N2 | 125.44 (11) | C3—C2—H2 | 120.7 |
C11—N3—C14 | 121.88 (10) | C1—C2—H2 | 120.7 |
C11—N3—C15 | 121.94 (10) | C5—C4—C3 | 119.31 (11) |
C14—N3—C15 | 115.76 (10) | C5—C4—C7 | 119.39 (11) |
C12—C13—C8 | 121.22 (11) | C3—C4—C7 | 121.28 (11) |
C12—C13—H13 | 119.4 | C15—C16—H16A | 109.5 |
C8—C13—H13 | 119.4 | C15—C16—H16B | 109.5 |
C1—C6—C5 | 118.50 (12) | H16A—C16—H16B | 109.5 |
C1—C6—H6 | 120.8 | C15—C16—H16C | 109.5 |
C5—C6—H6 | 120.8 | H16A—C16—H16C | 109.5 |
N3—C11—C10 | 122.36 (11) | H16B—C16—H16C | 109.5 |
N3—C11—C12 | 120.78 (11) | N3—C15—C16 | 113.51 (11) |
C10—C11—C12 | 116.86 (11) | N3—C15—H15A | 108.9 |
N2—C7—C4 | 121.83 (11) | C16—C15—H15A | 108.9 |
N2—C7—H7 | 119.1 | N3—C15—H15B | 108.9 |
C4—C7—H7 | 119.1 | C16—C15—H15B | 108.9 |
C6—C5—C4 | 120.68 (12) | H15A—C15—H15B | 107.7 |
C6—C5—H5 | 119.7 | C14—C17—H17A | 109.5 |
C4—C5—H5 | 119.7 | C14—C17—H17B | 109.5 |
C10—C9—C8 | 122.09 (11) | H17A—C17—H17B | 109.5 |
C10—C9—H9 | 119 | C14—C17—H17C | 109.5 |
C8—C9—H9 | 119 | H17A—C17—H17C | 109.5 |
C13—C12—C11 | 121.61 (11) | H17B—C17—H17C | 109.5 |
C13—C12—H12 | 119.2 | N3—C14—C17 | 113.71 (11) |
C11—C12—H12 | 119.2 | N3—C14—H14A | 108.8 |
C2—C3—C4 | 120.41 (12) | C17—C14—H14A | 108.8 |
C2—C3—H3 | 119.8 | N3—C14—H14B | 108.8 |
C4—C3—H3 | 119.8 | C17—C14—H14B | 108.8 |
C6—C1—C2 | 122.41 (11) | H14A—C14—H14B | 107.7 |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C19H15N3O2 | C19H14N4O4 | C17H19N3O2 |
Mr | 317.34 | 362.34 | 297.35 |
Crystal system, space group | Monoclinic, Cc | Orthorhombic, P212121 | Monoclinic, P21/c |
Temperature (K) | 150 | 150 | 120 |
a, b, c (Å) | 10.3885 (3), 16.7902 (4), 8.9064 (2) | 6.5715 (2), 15.0533 (4), 17.0598 (5) | 16.1019 (5), 7.6028 (3), 12.3616 (4) |
α, β, γ (°) | 90, 97.704 (2), 90 | 90, 90, 90 | 90, 91.615 (3), 90 |
V (Å3) | 1539.48 (7) | 1687.60 (8) | 1512.70 (9) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Cu Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.86 | 0.09 |
Crystal size (mm) | 0.83 × 0.41 × 0.02 | 0.90 × 0.11 × 0.08 | 0.69 × 0.39 × 0.30 |
|
Data collection |
Diffractometer | Xcalibur, Atlas, Gemini ultra diffractometer | Xcalibur, Atlas, Gemini ultra diffractometer | Oxford Diffraction Xcalibur, Atlas, Gemini Ultra diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15522, 3793, 3037 | 6008, 2905, 2612 | 13092, 3700, 2893 |
Rint | 0.034 | 0.021 | 0.031 |
(sin θ/λ)max (Å−1) | 0.693 | 0.595 | 0.692 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.087, 1.00 | 0.032, 0.084, 1.05 | 0.046, 0.126, 1.03 |
No. of reflections | 3793 | 2905 | 3700 |
No. of parameters | 220 | 247 | 201 |
No. of restraints | 2 | 0 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.19 | 0.12, −0.17 | 0.23, −0.27 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack H D (1983), Acta Cryst. A39, 876-881 | ? |
Absolute structure parameter | −0.2 (10) | 0.2 (2) | ? |