Conformational analyses and a structural comparison of the four spiro compounds 3-bromo-1,9-diphenyl-4-p-tolyl-7-oxa-1,2,8-triazaspiro[4.4]nona-2,8-dien-6-one, (I), C24H18BrN3O2, 3-bromo-4-(4-methoxyphenyl)-1,9-diphenyl-7-oxa-1,2,8-triazaspiro[4.4]nona-2,8-dien-6-one, (II), C24H18BrN3O3, 3-bromo-4-(4-chlorophenyl)-1,7,9-triphenyl-1,2,7,8-tetraazaspiro[4.4]nona-2,8-dien-6-one, (III), C29H20BrClN4O, and 3-bromo-1,7,9-triphenyl-4-p-tolyl-1,2,7,8-tetraazaspiro[4.4]nona-2,8-dien-6-one, (IV), C30H22.89Br1.11N4O, are presented. The molecular structures are rather similar, which is as expected since the compounds are all products of concerted 1,3-dipolar attack on (Z)-4-arylidene oxazolone and pyrazolone derivatives. The observed conformations tend to favour extended π conjugation of the benzene rings and other π systems, as shown by a comparison of selected geometric parameters of the four structures.
Supporting information
CCDC references: 259040; 259041; 259042; 259043
Products (I) and (II) were obtained by C-bromo-N-phenylnitrilimine, generated in situ, and (Z)-4-(arylmethylidene)oxazol-5-ones, as previously described by Foti et al. (2001). The same procedure with (Z)-4-(arylmethylidene)pyrazol-5-ones led to the formation of (III) and (IV). After purification of the products, crystals suitable for X-ray analysis were obtained by slow evaporation of chloroform solutions.
X-ray diffraction analysis gave an orthorhombic crystal system for (I), and monoclinic for (II), (III) and (IV). These space groups were hypothesized to be centrosymmetric during the data-reduction procedure and finally confirmed by the subsequent analyses. All H atoms were treated as riding, with alkyl C—H distances of 0.98, methyl C—H distances of 0.96 and aromatic C—H distances of 0.93 Å, and with Uiso(H) = 1.2Ueq(C). Please check added text. All data were measured at 298 (2) K. For disordered methyl groups, the special SHELXL97 (Sheldrick, 1997) instruction, defining six sites with fractional occupancy factors (AFIX 127), was applied. Intensities, which in some cases were calculated by profile fitting (Lehman & Larsen, 1974), were corrected for absorption using the ψ-scan procedure (North et al., 1968). During the refinement of the structure of (IV), we observed a consistent electron density (3.5 e Å−3) 1.7 Å from atom C25. It is known that, during the reaction, C25 could be brominated, leading to a known side-product. Thus, despite the relatively short distance, the model was refined by optimizing the occupancy factor of a Br atom partially replacing atom H25. Although the resulting C—Br distance of 1.707 (8) Å is more reminiscent of a C—Cl distance, the mass spectrum of (IV) clearly showed the presence of the second Br substituent and unambiguously ruled out the presence of Cl. In the final refinement, the occupancy factor of atom Br2 was found to be 0.11 and was fixed in order to reduce the number of parameters, so that in the solid state there are 11% of dibrominated molecules.
For all compounds, data collection: XSCANS (Siemens, 1989); cell refinement: XSCANS; data reduction: XPREPW (Bruker, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (Bruker, 1997); software used to prepare material for publication: PARST97 (Nardelli, 1995) and WinGX-PC (Version 1.6.4.05; Farrugia, 1999).
(I) 3-Bromo-1,9-diphenyl-4-
p-tolyl-7-oxa-1,2,8-triazaspiro[4.4]nona-2,8-dien-6-one
top
Crystal data top
C24H18BrN3O2 | F(000) = 1872 |
Mr = 460.32 | Dx = 1.457 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 30 reflections |
a = 14.180 (2) Å | θ = 5.3–12.5° |
b = 16.076 (2) Å | µ = 1.98 mm−1 |
c = 18.413 (2) Å | T = 298 K |
V = 4197.4 (9) Å3 | Irregular, light yellow |
Z = 8 | 0.4 × 0.32 × 0.28 mm |
Data collection top
Bruker P4 diffractometer | Rint = 0.043 |
2θ/ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: ψ scan (North et al., 1968) | h = −1→17 |
Tmin = 0.414, Tmax = 0.573 | k = −1→20 |
5243 measured reflections | l = −1→23 |
4267 independent reflections | 3 standard reflections every 197 reflections |
1805 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0333P)2 + 1.0734P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.053 | (Δ/σ)max = 0.003 |
wR(F2) = 0.105 | Δρmax = 0.26 e Å−3 |
S = 1.00 | Δρmin = −0.27 e Å−3 |
4267 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
273 parameters | Extinction coefficient: 0.00148 (12) |
0 restraints | |
Crystal data top
C24H18BrN3O2 | V = 4197.4 (9) Å3 |
Mr = 460.32 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.180 (2) Å | µ = 1.98 mm−1 |
b = 16.076 (2) Å | T = 298 K |
c = 18.413 (2) Å | 0.4 × 0.32 × 0.28 mm |
Data collection top
Bruker P4 diffractometer | 1805 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.043 |
Tmin = 0.414, Tmax = 0.573 | 3 standard reflections every 197 reflections |
5243 measured reflections | intensity decay: none |
4267 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.26 e Å−3 |
4267 reflections | Δρmin = −0.27 e Å−3 |
273 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.74636 (4) | 0.10933 (3) | 0.60520 (3) | 0.0786 (2) | |
O1 | 0.9070 (2) | 0.34324 (19) | 0.70273 (16) | 0.0662 (10) | |
C1 | 0.9035 (3) | 0.3692 (3) | 0.6424 (3) | 0.0505 (13) | |
O2 | 0.9021 (2) | 0.45240 (19) | 0.62686 (16) | 0.0603 (9) | |
N3 | 0.9102 (2) | 0.4648 (2) | 0.54887 (19) | 0.0544 (10) | |
C4 | 0.9156 (3) | 0.3936 (3) | 0.5174 (2) | 0.0398 (10) | |
C5 | 0.9043 (3) | 0.3226 (3) | 0.5701 (2) | 0.0410 (11) | |
N6 | 0.9702 (2) | 0.2522 (2) | 0.57065 (17) | 0.0447 (9) | |
N7 | 0.9217 (3) | 0.1796 (2) | 0.59324 (19) | 0.0522 (10) | |
C8 | 0.8336 (3) | 0.1937 (3) | 0.5878 (2) | 0.0479 (11) | |
C9 | 0.8079 (3) | 0.2773 (2) | 0.5559 (2) | 0.0428 (11) | |
H9 | 0.8027 | 0.2695 | 0.5032 | 0.051* | |
C10 | 0.9186 (3) | 0.3879 (3) | 0.4385 (2) | 0.0415 (10) | |
C11 | 0.8694 (3) | 0.4474 (3) | 0.3986 (3) | 0.0581 (12) | |
H11 | 0.8347 | 0.4881 | 0.4226 | 0.07* | |
C12 | 0.8720 (3) | 0.4464 (3) | 0.3236 (3) | 0.0700 (15) | |
H12 | 0.8396 | 0.4866 | 0.2971 | 0.084* | |
C13 | 0.9223 (3) | 0.3861 (3) | 0.2884 (3) | 0.0700 (14) | |
H13 | 0.9239 | 0.3852 | 0.2379 | 0.084* | |
C14 | 0.9703 (3) | 0.3269 (3) | 0.3272 (3) | 0.0677 (14) | |
H14 | 1.0042 | 0.2859 | 0.3028 | 0.081* | |
C15 | 0.9689 (3) | 0.3275 (3) | 0.4018 (2) | 0.0531 (11) | |
H15 | 1.0018 | 0.2872 | 0.4277 | 0.064* | |
C16 | 1.0621 (3) | 0.2619 (2) | 0.6003 (2) | 0.0438 (10) | |
C17 | 1.0991 (3) | 0.2054 (3) | 0.6496 (2) | 0.0555 (12) | |
H17 | 1.0626 | 0.1612 | 0.666 | 0.067* | |
C18 | 1.1900 (3) | 0.2153 (3) | 0.6741 (2) | 0.0652 (14) | |
H18 | 1.2149 | 0.1767 | 0.7065 | 0.078* | |
C19 | 1.2445 (4) | 0.2808 (3) | 0.6518 (2) | 0.0648 (13) | |
H19 | 1.3057 | 0.2871 | 0.6691 | 0.078* | |
C20 | 1.2079 (3) | 0.3364 (3) | 0.6038 (3) | 0.0650 (14) | |
H20 | 1.2445 | 0.3812 | 0.5888 | 0.078* | |
C21 | 1.1173 (3) | 0.3278 (3) | 0.5768 (2) | 0.0568 (13) | |
H21 | 1.0938 | 0.3657 | 0.5432 | 0.068* | |
C22 | 0.7201 (3) | 0.3217 (3) | 0.5799 (2) | 0.0427 (11) | |
C23 | 0.6669 (3) | 0.3636 (2) | 0.5295 (2) | 0.0495 (11) | |
H23 | 0.6859 | 0.3641 | 0.4811 | 0.059* | |
C24 | 0.5857 (3) | 0.4052 (3) | 0.5493 (3) | 0.0596 (14) | |
H24 | 0.5501 | 0.432 | 0.5139 | 0.071* | |
C25 | 0.5563 (3) | 0.4076 (3) | 0.6210 (3) | 0.0533 (12) | |
C26 | 0.6104 (3) | 0.3663 (3) | 0.6715 (2) | 0.0546 (12) | |
H26 | 0.5921 | 0.3671 | 0.72 | 0.066* | |
C27 | 0.6907 (3) | 0.3240 (3) | 0.6520 (2) | 0.0535 (12) | |
H27 | 0.7258 | 0.2966 | 0.6873 | 0.064* | |
C28 | 0.4679 (3) | 0.4545 (3) | 0.6420 (3) | 0.0826 (16) | |
H28A | 0.4199 | 0.4451 | 0.6062 | 0.099* | |
H28B | 0.4815 | 0.5129 | 0.6447 | 0.099* | |
H28C | 0.4461 | 0.4353 | 0.6884 | 0.099* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0749 (4) | 0.0555 (3) | 0.1056 (4) | −0.0227 (3) | −0.0047 (4) | 0.0131 (3) |
O1 | 0.071 (2) | 0.083 (3) | 0.0438 (19) | 0.004 (2) | −0.0061 (18) | −0.0076 (19) |
C1 | 0.037 (3) | 0.062 (4) | 0.053 (3) | −0.004 (2) | −0.002 (3) | −0.011 (3) |
O2 | 0.066 (2) | 0.052 (2) | 0.063 (2) | −0.0013 (18) | 0.0017 (17) | −0.0226 (17) |
N3 | 0.057 (3) | 0.047 (2) | 0.060 (3) | 0.000 (2) | 0.003 (2) | −0.009 (2) |
C4 | 0.032 (2) | 0.036 (2) | 0.051 (3) | −0.001 (2) | −0.002 (2) | −0.004 (3) |
C5 | 0.040 (3) | 0.041 (2) | 0.042 (3) | 0.000 (2) | −0.001 (2) | −0.008 (2) |
N6 | 0.043 (2) | 0.039 (2) | 0.052 (2) | 0.0007 (19) | 0.0027 (19) | 0.0013 (18) |
N7 | 0.055 (2) | 0.0395 (19) | 0.062 (3) | −0.006 (2) | 0.001 (2) | 0.002 (2) |
C8 | 0.049 (3) | 0.041 (3) | 0.053 (3) | −0.008 (2) | 0.001 (3) | −0.005 (2) |
C9 | 0.045 (3) | 0.044 (3) | 0.038 (3) | −0.006 (2) | 0.001 (2) | −0.001 (2) |
C10 | 0.042 (3) | 0.038 (2) | 0.044 (3) | −0.008 (2) | −0.002 (2) | 0.004 (2) |
C11 | 0.060 (3) | 0.050 (3) | 0.064 (3) | −0.002 (3) | 0.001 (3) | 0.002 (3) |
C12 | 0.071 (4) | 0.072 (4) | 0.067 (4) | 0.002 (3) | −0.010 (3) | 0.027 (3) |
C13 | 0.067 (3) | 0.090 (4) | 0.052 (3) | −0.007 (3) | 0.003 (3) | 0.010 (3) |
C14 | 0.069 (4) | 0.082 (4) | 0.053 (3) | 0.006 (3) | 0.009 (3) | −0.004 (3) |
C15 | 0.048 (3) | 0.054 (3) | 0.058 (3) | 0.006 (2) | 0.003 (3) | 0.002 (3) |
C16 | 0.039 (3) | 0.050 (3) | 0.043 (3) | 0.006 (2) | 0.001 (2) | −0.012 (3) |
C17 | 0.058 (3) | 0.061 (3) | 0.047 (3) | 0.007 (3) | 0.001 (3) | −0.002 (3) |
C18 | 0.060 (4) | 0.084 (4) | 0.053 (3) | 0.024 (3) | −0.002 (3) | −0.002 (3) |
C19 | 0.042 (3) | 0.084 (4) | 0.069 (3) | 0.020 (3) | −0.014 (3) | −0.023 (3) |
C20 | 0.041 (3) | 0.061 (3) | 0.093 (4) | −0.002 (2) | −0.007 (3) | −0.010 (3) |
C21 | 0.045 (3) | 0.050 (3) | 0.075 (3) | 0.003 (2) | −0.009 (3) | 0.001 (3) |
C22 | 0.040 (3) | 0.046 (3) | 0.042 (3) | −0.008 (2) | 0.002 (2) | 0.002 (2) |
C23 | 0.050 (3) | 0.055 (3) | 0.044 (3) | −0.003 (3) | −0.003 (2) | 0.003 (3) |
C24 | 0.056 (3) | 0.061 (3) | 0.062 (3) | 0.005 (3) | −0.008 (3) | 0.010 (3) |
C25 | 0.042 (3) | 0.050 (3) | 0.068 (3) | −0.003 (2) | 0.005 (3) | −0.004 (3) |
C26 | 0.051 (3) | 0.069 (3) | 0.043 (3) | −0.004 (3) | 0.008 (3) | 0.003 (3) |
C27 | 0.047 (3) | 0.065 (3) | 0.048 (3) | 0.000 (3) | −0.007 (3) | 0.010 (3) |
C28 | 0.069 (4) | 0.075 (3) | 0.104 (4) | 0.012 (3) | 0.015 (3) | 0.012 (3) |
Geometric parameters (Å, º) top
Br1—C8 | 1.864 (4) | C15—H15 | 0.93 |
O1—C1 | 1.189 (5) | C16—C21 | 1.386 (5) |
C1—O2 | 1.368 (5) | C16—C17 | 1.387 (5) |
C1—C5 | 1.527 (5) | C17—C18 | 1.375 (6) |
O2—N3 | 1.454 (4) | C17—H17 | 0.93 |
N3—C4 | 1.286 (4) | C18—C19 | 1.370 (6) |
C4—C10 | 1.455 (5) | C18—H18 | 0.93 |
C4—C5 | 1.506 (5) | C19—C20 | 1.360 (5) |
C5—N6 | 1.468 (5) | C19—H19 | 0.93 |
C5—C9 | 1.571 (5) | C20—C21 | 1.385 (5) |
N6—N7 | 1.418 (4) | C20—H20 | 0.93 |
N6—C16 | 1.422 (5) | C21—H21 | 0.93 |
N7—C8 | 1.273 (5) | C22—C23 | 1.373 (5) |
C8—C9 | 1.511 (5) | C22—C27 | 1.392 (5) |
C9—C22 | 1.501 (5) | C23—C24 | 1.380 (5) |
C9—H9 | 0.98 | C23—H23 | 0.93 |
C10—C15 | 1.381 (5) | C24—C25 | 1.384 (6) |
C10—C11 | 1.394 (5) | C24—H24 | 0.93 |
C11—C12 | 1.382 (6) | C25—C26 | 1.375 (5) |
C11—H11 | 0.93 | C25—C28 | 1.514 (5) |
C12—C13 | 1.366 (6) | C26—C27 | 1.375 (5) |
C12—H12 | 0.93 | C26—H26 | 0.93 |
C13—C14 | 1.372 (6) | C27—H27 | 0.93 |
C13—H13 | 0.93 | C28—H28A | 0.96 |
C14—C15 | 1.374 (5) | C28—H28B | 0.96 |
C14—H14 | 0.93 | C28—H28C | 0.96 |
| | | |
O1—C1—O2 | 122.6 (4) | C10—C15—H15 | 119.9 |
O1—C1—C5 | 130.0 (5) | C21—C16—C17 | 119.4 (4) |
O2—C1—C5 | 107.3 (4) | C21—C16—N6 | 118.8 (4) |
C1—O2—N3 | 109.8 (3) | C17—C16—N6 | 121.8 (4) |
C4—N3—O2 | 109.2 (3) | C18—C17—C16 | 119.6 (4) |
N3—C4—C10 | 120.5 (4) | C18—C17—H17 | 120.2 |
N3—C4—C5 | 112.1 (4) | C16—C17—H17 | 120.2 |
C10—C4—C5 | 126.8 (4) | C19—C18—C17 | 121.3 (5) |
N6—C5—C4 | 121.3 (3) | C19—C18—H18 | 119.4 |
N6—C5—C1 | 112.1 (3) | C17—C18—H18 | 119.4 |
C4—C5—C1 | 101.0 (3) | C20—C19—C18 | 119.0 (5) |
N6—C5—C9 | 101.4 (3) | C20—C19—H19 | 120.5 |
C4—C5—C9 | 109.7 (3) | C18—C19—H19 | 120.5 |
C1—C5—C9 | 111.5 (3) | C19—C20—C21 | 121.5 (5) |
N7—N6—C16 | 115.0 (3) | C19—C20—H20 | 119.2 |
N7—N6—C5 | 109.2 (3) | C21—C20—H20 | 119.2 |
C16—N6—C5 | 120.1 (3) | C20—C21—C16 | 119.2 (4) |
C8—N7—N6 | 107.8 (3) | C20—C21—H21 | 120.4 |
N7—C8—C9 | 115.3 (4) | C16—C21—H21 | 120.4 |
N7—C8—Br1 | 120.5 (3) | C23—C22—C27 | 117.9 (4) |
C9—C8—Br1 | 123.6 (3) | C23—C22—C9 | 119.4 (4) |
C22—C9—C8 | 120.6 (3) | C27—C22—C9 | 122.8 (4) |
C22—C9—C5 | 116.9 (3) | C22—C23—C24 | 121.1 (4) |
C8—C9—C5 | 97.9 (3) | C22—C23—H23 | 119.4 |
C22—C9—H9 | 106.8 | C24—C23—H23 | 119.4 |
C8—C9—H9 | 106.8 | C23—C24—C25 | 121.1 (4) |
C5—C9—H9 | 106.8 | C23—C24—H24 | 119.4 |
C15—C10—C11 | 118.8 (4) | C25—C24—H24 | 119.4 |
C15—C10—C4 | 123.2 (4) | C26—C25—C24 | 117.6 (4) |
C11—C10—C4 | 118.0 (4) | C26—C25—C28 | 121.9 (4) |
C12—C11—C10 | 120.4 (4) | C24—C25—C28 | 120.5 (4) |
C12—C11—H11 | 119.8 | C25—C26—C27 | 121.6 (4) |
C10—C11—H11 | 119.8 | C25—C26—H26 | 119.2 |
C13—C12—C11 | 119.7 (5) | C27—C26—H26 | 119.2 |
C13—C12—H12 | 120.2 | C26—C27—C22 | 120.7 (4) |
C11—C12—H12 | 120.2 | C26—C27—H27 | 119.7 |
C12—C13—C14 | 120.4 (5) | C22—C27—H27 | 119.7 |
C12—C13—H13 | 119.8 | C25—C28—H28A | 109.5 |
C14—C13—H13 | 119.8 | C25—C28—H28B | 109.5 |
C13—C14—C15 | 120.5 (5) | H28A—C28—H28B | 109.5 |
C13—C14—H14 | 119.8 | C25—C28—H28C | 109.5 |
C15—C14—H14 | 119.8 | H28A—C28—H28C | 109.5 |
C14—C15—C10 | 120.2 (4) | H28B—C28—H28C | 109.5 |
C14—C15—H15 | 119.9 | | |
| | | |
O1—C1—O2—N3 | 172.6 (4) | C5—C4—C10—C15 | −43.2 (6) |
C5—C1—O2—N3 | −5.0 (5) | N3—C4—C10—C11 | −32.6 (6) |
C1—O2—N3—C4 | 0.5 (5) | C5—C4—C10—C11 | 138.0 (4) |
O2—N3—C4—C10 | 176.3 (3) | C15—C10—C11—C12 | −0.7 (6) |
O2—N3—C4—C5 | 4.4 (5) | C4—C10—C11—C12 | 178.2 (4) |
N3—C4—C5—N6 | −131.6 (4) | C10—C11—C12—C13 | 0.7 (7) |
C10—C4—C5—N6 | 57.2 (6) | C11—C12—C13—C14 | −0.2 (7) |
N3—C4—C5—C1 | −7.0 (4) | C12—C13—C14—C15 | −0.3 (7) |
C10—C4—C5—C1 | −178.3 (4) | C13—C14—C15—C10 | 0.2 (7) |
N3—C4—C5—C9 | 110.8 (4) | C11—C10—C15—C14 | 0.3 (6) |
C10—C4—C5—C9 | −60.4 (5) | C4—C10—C15—C14 | −178.6 (4) |
O1—C1—C5—N6 | −39.8 (7) | N7—N6—C16—C21 | 175.0 (3) |
O2—C1—C5—N6 | 137.6 (3) | C5—N6—C16—C21 | −51.4 (5) |
O1—C1—C5—C4 | −170.4 (5) | N7—N6—C16—C17 | −2.1 (5) |
O2—C1—C5—C4 | 6.9 (4) | C5—N6—C16—C17 | 131.4 (4) |
O1—C1—C5—C9 | 73.1 (6) | C21—C16—C17—C18 | −0.3 (6) |
O2—C1—C5—C9 | −109.6 (4) | N6—C16—C17—C18 | 176.9 (4) |
C4—C5—N6—N7 | −149.3 (3) | C16—C17—C18—C19 | 1.1 (7) |
C1—C5—N6—N7 | 91.4 (4) | C17—C18—C19—C20 | −0.7 (7) |
C9—C5—N6—N7 | −27.6 (4) | C18—C19—C20—C21 | −0.6 (7) |
C4—C5—N6—C16 | 74.7 (5) | C19—C20—C21—C16 | 1.4 (7) |
C1—C5—N6—C16 | −44.5 (5) | C17—C16—C21—C20 | −0.9 (6) |
C9—C5—N6—C16 | −163.6 (3) | N6—C16—C21—C20 | −178.2 (4) |
C16—N6—N7—C8 | 154.8 (3) | C8—C9—C22—C23 | −141.0 (4) |
C5—N6—N7—C8 | 16.3 (5) | C5—C9—C22—C23 | 100.4 (4) |
N6—N7—C8—C9 | 3.6 (5) | C8—C9—C22—C27 | 40.5 (6) |
N6—N7—C8—Br1 | 174.8 (2) | C5—C9—C22—C27 | −78.1 (5) |
N7—C8—C9—C22 | −147.6 (4) | C27—C22—C23—C24 | −1.5 (6) |
Br1—C8—C9—C22 | 41.5 (5) | C9—C22—C23—C24 | 180.0 (4) |
N7—C8—C9—C5 | −19.9 (4) | C22—C23—C24—C25 | 1.6 (7) |
Br1—C8—C9—C5 | 169.3 (3) | C23—C24—C25—C26 | −0.8 (7) |
N6—C5—C9—C22 | 156.7 (3) | C23—C24—C25—C28 | 179.1 (4) |
C4—C5—C9—C22 | −73.8 (4) | C24—C25—C26—C27 | −0.1 (7) |
C1—C5—C9—C22 | 37.2 (5) | C28—C25—C26—C27 | −179.9 (4) |
N6—C5—C9—C8 | 26.4 (3) | C25—C26—C27—C22 | 0.1 (7) |
C4—C5—C9—C8 | 155.9 (3) | C23—C22—C27—C26 | 0.7 (6) |
C1—C5—C9—C8 | −93.0 (4) | C9—C22—C27—C26 | 179.2 (4) |
N3—C4—C10—C15 | 146.3 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C28—H28C···O1i | 0.96 | 2.55 | 3.482 (5) | 163 |
Symmetry code: (i) x−1/2, y, −z+3/2. |
(II) 3-Bromo-1,9-diphenyl-4-(4-methoxy-phenyl)-7-oxa-1,2,8-triazaspiro[4.4]nona- 2,8-dien-6-one
top
Crystal data top
C24H18BrN3O3 | F(000) = 1936 |
Mr = 476.32 | Dx = 1.524 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yC | Cell parameters from 44 reflections |
a = 35.375 (3) Å | θ = 5.2–15.4° |
b = 9.200 (1) Å | µ = 2.01 mm−1 |
c = 12.807 (2) Å | T = 298 K |
β = 94.81 (1)° | Prismatic, yellow |
V = 4153.2 (9) Å3 | 0.50 × 0.23 × 0.15 mm |
Z = 8 | |
Data collection top
Bruker P4 diffractometer | Rint = 0.061 |
ω scans | θmax = 26°, θmin = 2.3° |
Absorption correction: ψ scan (North et al., 1968) | h = −1→43 |
Tmin = 0.388, Tmax = 0.739 | k = −11→1 |
4814 measured reflections | l = −15→15 |
4047 independent reflections | 3 standard reflections every 197 reflections |
2153 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.067 | w = 1/[σ2(Fo2) + (0.1P)2 where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.200 | (Δ/σ)max < 0.001 |
S = 1.08 | Δρmax = 1.46 e Å−3 |
4047 reflections | Δρmin = −0.38 e Å−3 |
282 parameters | |
Crystal data top
C24H18BrN3O3 | V = 4153.2 (9) Å3 |
Mr = 476.32 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 35.375 (3) Å | µ = 2.01 mm−1 |
b = 9.200 (1) Å | T = 298 K |
c = 12.807 (2) Å | 0.50 × 0.23 × 0.15 mm |
β = 94.81 (1)° | |
Data collection top
Bruker P4 diffractometer | 2153 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.061 |
Tmin = 0.388, Tmax = 0.739 | 3 standard reflections every 197 reflections |
4814 measured reflections | intensity decay: none |
4047 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.200 | H-atom parameters constrained |
S = 1.08 | Δρmax = 1.46 e Å−3 |
4047 reflections | Δρmin = −0.38 e Å−3 |
282 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.05103 (2) | 0.24132 (9) | 0.33395 (6) | 0.0624 (3) | |
O1 | 0.08859 (13) | 0.0665 (5) | −0.0252 (3) | 0.0567 (12) | |
C1 | 0.11327 (19) | 0.0205 (7) | 0.0335 (4) | 0.0412 (15) | |
O2 | 0.13410 (13) | −0.0997 (5) | 0.0104 (3) | 0.0562 (12) | |
N3 | 0.16605 (15) | −0.1145 (6) | 0.0885 (4) | 0.0529 (14) | |
C4 | 0.16483 (16) | −0.0119 (6) | 0.1550 (4) | 0.0378 (14) | |
C5 | 0.12974 (16) | 0.0763 (6) | 0.1398 (4) | 0.0362 (14) | |
N6 | 0.13357 (14) | 0.2355 (5) | 0.1437 (4) | 0.0412 (12) | |
N7 | 0.10485 (15) | 0.2986 (6) | 0.1990 (4) | 0.0425 (13) | |
C8 | 0.08810 (17) | 0.1958 (7) | 0.2430 (4) | 0.0398 (15) | |
C9 | 0.10110 (15) | 0.0443 (6) | 0.2256 (4) | 0.0350 (14) | |
H9 | 0.116 | 0.0124 | 0.2895 | 0.06* | |
C10 | 0.19654 (17) | 0.0053 (8) | 0.2375 (5) | 0.0481 (16) | |
C11 | 0.19377 (18) | 0.1052 (7) | 0.3193 (5) | 0.0492 (17) | |
H11 | 0.1725 | 0.1643 | 0.3211 | 0.06* | |
C12 | 0.2230 (2) | 0.1144 (9) | 0.3967 (5) | 0.064 (2) | |
H12 | 0.2209 | 0.1777 | 0.4526 | 0.06* | |
C13 | 0.2550 (2) | 0.0325 (11) | 0.3930 (7) | 0.083 (3) | |
H13 | 0.2746 | 0.0403 | 0.4456 | 0.06* | |
C14 | 0.2579 (2) | −0.0634 (10) | 0.3095 (7) | 0.083 (3) | |
H14 | 0.2798 | −0.1183 | 0.3061 | 0.06* | |
C15 | 0.2291 (2) | −0.0772 (9) | 0.2334 (6) | 0.064 (2) | |
H15 | 0.2312 | −0.1421 | 0.1785 | 0.06* | |
C16 | 0.14448 (17) | 0.3164 (7) | 0.0567 (4) | 0.0385 (14) | |
C17 | 0.1695 (2) | 0.2565 (8) | −0.0092 (5) | 0.0572 (18) | |
H17 | 0.1794 | 0.1639 | 0.0035 | 0.06* | |
C18 | 0.1794 (2) | 0.3369 (10) | −0.0944 (6) | 0.069 (2) | |
H18 | 0.1961 | 0.296 | −0.1386 | 0.06* | |
C19 | 0.1660 (2) | 0.4715 (9) | −0.1157 (6) | 0.067 (2) | |
H19 | 0.1723 | 0.5217 | −0.1748 | 0.06* | |
C20 | 0.1430 (2) | 0.5314 (8) | −0.0481 (6) | 0.063 (2) | |
H20 | 0.1342 | 0.6257 | −0.0604 | 0.06* | |
C21 | 0.13189 (19) | 0.4574 (7) | 0.0389 (5) | 0.0492 (17) | |
H21 | 0.1163 | 0.5019 | 0.0843 | 0.06* | |
C22 | 0.07192 (16) | −0.0711 (6) | 0.1963 (4) | 0.0357 (14) | |
C23 | 0.03716 (16) | −0.0388 (7) | 0.1440 (4) | 0.0401 (15) | |
H23 | 0.031 | 0.0579 | 0.1296 | 0.06* | |
C24 | 0.01124 (17) | −0.1459 (7) | 0.1126 (5) | 0.0427 (15) | |
H24 | −0.0119 | −0.1216 | 0.0772 | 0.06* | |
C25 | 0.02025 (17) | −0.2903 (7) | 0.1347 (5) | 0.0414 (15) | |
C26 | 0.05436 (18) | −0.3246 (7) | 0.1881 (5) | 0.0448 (15) | |
H26 | 0.0604 | −0.4211 | 0.2033 | 0.06* | |
C27 | 0.07987 (18) | −0.2155 (7) | 0.2194 (5) | 0.0419 (15) | |
H27 | 0.1027 | −0.2398 | 0.2565 | 0.06* | |
O3 | −0.00298 (13) | −0.4052 (5) | 0.1071 (3) | 0.0550 (12) | |
C28 | −0.0372 (2) | −0.3767 (8) | 0.0428 (6) | 0.061 (2) | |
H28A | −0.0503 | −0.4664 | 0.0272 | 0.06* | |
H28B | −0.0311 | −0.3314 | −0.0212 | 0.06* | |
H28C | −0.0531 | −0.313 | 0.0793 | 0.06* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0511 (4) | 0.0661 (5) | 0.0730 (5) | 0.0020 (4) | 0.0218 (3) | −0.0184 (4) |
O1 | 0.060 (3) | 0.063 (3) | 0.044 (2) | −0.001 (3) | −0.013 (2) | −0.002 (2) |
C1 | 0.048 (4) | 0.043 (4) | 0.033 (3) | −0.003 (3) | 0.002 (3) | −0.009 (3) |
O2 | 0.065 (3) | 0.050 (3) | 0.053 (3) | 0.005 (2) | 0.001 (2) | −0.019 (2) |
N3 | 0.050 (3) | 0.048 (4) | 0.059 (3) | 0.008 (3) | 0.004 (3) | −0.004 (3) |
C4 | 0.039 (4) | 0.031 (3) | 0.043 (3) | 0.003 (3) | 0.004 (3) | −0.001 (3) |
C5 | 0.037 (3) | 0.033 (3) | 0.039 (3) | 0.000 (3) | 0.001 (3) | −0.007 (3) |
N6 | 0.042 (3) | 0.034 (3) | 0.049 (3) | 0.004 (2) | 0.005 (2) | −0.006 (2) |
N7 | 0.042 (3) | 0.038 (3) | 0.047 (3) | 0.002 (2) | 0.002 (2) | −0.009 (2) |
C8 | 0.038 (3) | 0.045 (4) | 0.036 (3) | 0.005 (3) | 0.004 (3) | −0.012 (3) |
C9 | 0.030 (3) | 0.038 (4) | 0.036 (3) | 0.001 (3) | −0.004 (2) | 0.001 (3) |
C10 | 0.035 (4) | 0.057 (4) | 0.053 (4) | 0.001 (3) | 0.003 (3) | 0.017 (3) |
C11 | 0.036 (4) | 0.063 (5) | 0.048 (4) | −0.005 (3) | 0.000 (3) | −0.008 (3) |
C12 | 0.050 (5) | 0.086 (6) | 0.054 (4) | −0.014 (4) | −0.004 (4) | −0.003 (4) |
C13 | 0.049 (5) | 0.113 (8) | 0.082 (6) | −0.010 (5) | −0.026 (4) | 0.012 (6) |
C14 | 0.045 (5) | 0.096 (7) | 0.106 (7) | 0.022 (5) | 0.000 (5) | 0.021 (6) |
C15 | 0.042 (4) | 0.075 (6) | 0.073 (5) | 0.019 (4) | 0.001 (4) | 0.003 (4) |
C16 | 0.037 (3) | 0.036 (4) | 0.041 (3) | −0.007 (3) | −0.004 (3) | 0.003 (3) |
C17 | 0.062 (4) | 0.049 (4) | 0.062 (4) | −0.001 (4) | 0.013 (3) | 0.001 (4) |
C18 | 0.072 (5) | 0.072 (6) | 0.067 (5) | −0.021 (5) | 0.025 (4) | −0.007 (4) |
C19 | 0.070 (5) | 0.061 (5) | 0.069 (5) | −0.014 (4) | 0.006 (4) | 0.017 (4) |
C20 | 0.063 (5) | 0.044 (4) | 0.080 (5) | −0.003 (4) | 0.004 (4) | 0.012 (4) |
C21 | 0.047 (4) | 0.046 (4) | 0.054 (4) | −0.003 (3) | −0.002 (3) | −0.002 (3) |
C22 | 0.038 (3) | 0.034 (3) | 0.035 (3) | −0.003 (3) | 0.000 (3) | −0.003 (3) |
C23 | 0.040 (4) | 0.036 (4) | 0.043 (3) | 0.006 (3) | −0.004 (3) | 0.001 (3) |
C24 | 0.032 (3) | 0.045 (4) | 0.049 (4) | 0.007 (3) | −0.006 (3) | −0.002 (3) |
C25 | 0.035 (3) | 0.048 (4) | 0.041 (3) | −0.008 (3) | 0.005 (3) | −0.005 (3) |
C26 | 0.051 (4) | 0.034 (4) | 0.049 (4) | 0.006 (3) | 0.001 (3) | 0.006 (3) |
C27 | 0.034 (3) | 0.047 (4) | 0.045 (3) | 0.003 (3) | 0.002 (3) | 0.003 (3) |
O3 | 0.050 (3) | 0.042 (3) | 0.071 (3) | −0.007 (2) | −0.009 (2) | −0.006 (2) |
C28 | 0.049 (4) | 0.053 (5) | 0.080 (5) | −0.005 (4) | −0.006 (4) | −0.012 (4) |
Geometric parameters (Å, º) top
Br1—C8 | 1.873 (6) | C16—C21 | 1.384 (9) |
O1—C1 | 1.181 (7) | C16—C17 | 1.387 (9) |
C1—O2 | 1.374 (7) | C17—C18 | 1.388 (10) |
C1—C5 | 1.524 (8) | C17—H17 | 0.93 |
O2—N3 | 1.451 (7) | C18—C19 | 1.346 (11) |
N3—C4 | 1.275 (7) | C18—H18 | 0.93 |
C4—C5 | 1.482 (8) | C19—C20 | 1.354 (10) |
C4—C10 | 1.483 (8) | C19—H19 | 0.93 |
C5—N6 | 1.471 (7) | C20—C21 | 1.390 (9) |
C5—C9 | 1.584 (8) | C20—H20 | 0.93 |
N6—N7 | 1.412 (7) | C21—H21 | 0.93 |
N6—C16 | 1.420 (8) | C22—C23 | 1.382 (8) |
N7—C8 | 1.272 (8) | C22—C27 | 1.385 (8) |
C8—C9 | 1.490 (8) | C23—C24 | 1.383 (8) |
C9—C22 | 1.506 (8) | C23—H23 | 0.93 |
C9—H9 | 0.98 | C24—C25 | 1.390 (9) |
C10—C15 | 1.383 (9) | C24—H24 | 0.93 |
C10—C11 | 1.404 (9) | C25—O3 | 1.367 (7) |
C11—C12 | 1.374 (9) | C25—C26 | 1.373 (8) |
C11—H11 | 0.93 | C26—C27 | 1.386 (9) |
C12—C13 | 1.364 (11) | C26—H26 | 0.93 |
C12—H12 | 0.93 | C27—H27 | 0.93 |
C13—C14 | 1.397 (12) | O3—C28 | 1.430 (8) |
C13—H13 | 0.93 | C28—H28A | 0.96 |
C14—C15 | 1.357 (10) | C28—H28B | 0.96 |
C14—H14 | 0.93 | C28—H28C | 0.96 |
C15—H15 | 0.93 | | |
| | | |
O1—C1—O2 | 122.2 (5) | C10—C15—H15 | 120 |
O1—C1—C5 | 130.9 (6) | C21—C16—C17 | 119.0 (6) |
O2—C1—C5 | 106.9 (5) | C21—C16—N6 | 121.1 (6) |
C1—O2—N3 | 109.2 (4) | C17—C16—N6 | 119.9 (6) |
C4—N3—O2 | 108.8 (5) | C16—C17—C18 | 118.9 (7) |
N3—C4—C5 | 113.1 (5) | C16—C17—H17 | 120.5 |
N3—C4—C10 | 119.2 (6) | C18—C17—H17 | 120.5 |
C5—C4—C10 | 127.6 (5) | C19—C18—C17 | 122.7 (8) |
N6—C5—C4 | 117.8 (5) | C19—C18—H18 | 118.6 |
N6—C5—C1 | 113.1 (5) | C17—C18—H18 | 118.6 |
C4—C5—C1 | 100.8 (5) | C18—C19—C20 | 117.8 (7) |
N6—C5—C9 | 102.9 (4) | C18—C19—H19 | 121.1 |
C4—C5—C9 | 112.6 (5) | C20—C19—H19 | 121.1 |
C1—C5—C9 | 109.8 (4) | C19—C20—C21 | 122.6 (7) |
N7—N6—C16 | 115.6 (5) | C19—C20—H20 | 118.7 |
N7—N6—C5 | 111.0 (5) | C21—C20—H20 | 118.7 |
C16—N6—C5 | 121.7 (5) | C16—C21—C20 | 118.9 (7) |
C8—N7—N6 | 107.3 (5) | C16—C21—H21 | 120.6 |
N7—C8—C9 | 117.9 (5) | C20—C21—H21 | 120.6 |
N7—C8—Br1 | 119.0 (5) | C23—C22—C27 | 117.8 (5) |
C9—C8—Br1 | 122.9 (5) | C23—C22—C9 | 122.2 (5) |
C8—C9—C22 | 118.9 (5) | C27—C22—C9 | 120.0 (5) |
C8—C9—C5 | 98.8 (5) | C22—C23—C24 | 121.9 (6) |
C22—C9—C5 | 115.0 (4) | C22—C23—H23 | 119 |
C8—C9—H9 | 107.8 | C24—C23—H23 | 119 |
C22—C9—H9 | 107.8 | C23—C24—C25 | 119.1 (5) |
C5—C9—H9 | 107.8 | C23—C24—H24 | 120.4 |
C15—C10—C11 | 119.9 (6) | C25—C24—H24 | 120.4 |
C15—C10—C4 | 119.8 (6) | O3—C25—C26 | 115.8 (6) |
C11—C10—C4 | 120.4 (6) | O3—C25—C24 | 124.4 (6) |
C12—C11—C10 | 119.0 (7) | C26—C25—C24 | 119.9 (5) |
C12—C11—H11 | 120.5 | C25—C26—C27 | 120.1 (6) |
C10—C11—H11 | 120.5 | C25—C26—H26 | 120 |
C13—C12—C11 | 121.1 (8) | C27—C26—H26 | 120 |
C13—C12—H12 | 119.4 | C22—C27—C26 | 121.2 (6) |
C11—C12—H12 | 119.4 | C22—C27—H27 | 119.4 |
C12—C13—C14 | 119.4 (7) | C26—C27—H27 | 119.4 |
C12—C13—H13 | 120.3 | C25—O3—C28 | 117.9 (5) |
C14—C13—H13 | 120.3 | O3—C28—H28A | 109.5 |
C15—C14—C13 | 120.7 (8) | O3—C28—H28B | 109.5 |
C15—C14—H14 | 119.7 | H28A—C28—H28B | 109.5 |
C13—C14—H14 | 119.7 | O3—C28—H28C | 109.5 |
C14—C15—C10 | 119.9 (8) | H28A—C28—H28C | 109.5 |
C14—C15—H15 | 120 | H28B—C28—H28C | 109.5 |
| | | |
O1—C1—O2—N3 | 170.4 (6) | N3—C4—C10—C11 | −171.9 (6) |
C5—C1—O2—N3 | −7.2 (6) | C5—C4—C10—C11 | 6.5 (9) |
C1—O2—N3—C4 | 0.4 (7) | C15—C10—C11—C12 | −2.9 (10) |
O2—N3—C4—C5 | 7.1 (7) | C4—C10—C11—C12 | 177.4 (6) |
O2—N3—C4—C10 | −174.3 (5) | C10—C11—C12—C13 | 2.5 (11) |
N3—C4—C5—N6 | −134.4 (6) | C11—C12—C13—C14 | −0.6 (13) |
C10—C4—C5—N6 | 47.1 (8) | C12—C13—C14—C15 | −1.1 (13) |
N3—C4—C5—C1 | −10.9 (6) | C13—C14—C15—C10 | 0.7 (12) |
C10—C4—C5—C1 | 170.6 (6) | C11—C10—C15—C14 | 1.3 (11) |
N3—C4—C5—C9 | 106.0 (6) | C4—C10—C15—C14 | −179.0 (7) |
C10—C4—C5—C9 | −72.5 (7) | N7—N6—C16—C21 | 9.8 (8) |
O1—C1—C5—N6 | −40.3 (9) | C5—N6—C16—C21 | 149.6 (6) |
O2—C1—C5—N6 | 137.1 (5) | N7—N6—C16—C17 | −173.1 (5) |
O1—C1—C5—C4 | −167.0 (7) | C5—N6—C16—C17 | −33.3 (8) |
O2—C1—C5—C4 | 10.4 (6) | C21—C16—C17—C18 | −3.5 (10) |
O1—C1—C5—C9 | 74.1 (8) | N6—C16—C17—C18 | 179.3 (6) |
O2—C1—C5—C9 | −108.6 (5) | C16—C17—C18—C19 | 0.4 (11) |
C4—C5—N6—N7 | −138.9 (5) | C17—C18—C19—C20 | 2.5 (12) |
C1—C5—N6—N7 | 104.1 (5) | C18—C19—C20—C21 | −2.3 (11) |
C9—C5—N6—N7 | −14.3 (6) | C17—C16—C21—C20 | 3.7 (9) |
C4—C5—N6—C16 | 79.7 (7) | N6—C16—C21—C20 | −179.2 (6) |
C1—C5—N6—C16 | −37.3 (7) | C19—C20—C21—C16 | −0.8 (11) |
C9—C5—N6—C16 | −155.8 (5) | C8—C9—C22—C23 | 27.2 (8) |
C16—N6—N7—C8 | 154.3 (5) | C5—C9—C22—C23 | −89.5 (7) |
C5—N6—N7—C8 | 10.3 (6) | C8—C9—C22—C27 | −154.4 (5) |
N6—N7—C8—C9 | −1.1 (7) | C5—C9—C22—C27 | 88.9 (6) |
N6—N7—C8—Br1 | 174.4 (4) | C27—C22—C23—C24 | −1.8 (9) |
N7—C8—C9—C22 | −132.5 (6) | C9—C22—C23—C24 | 176.7 (5) |
Br1—C8—C9—C22 | 52.3 (7) | C22—C23—C24—C25 | 0.4 (9) |
N7—C8—C9—C5 | −7.5 (6) | C23—C24—C25—O3 | −179.6 (5) |
Br1—C8—C9—C5 | 177.3 (4) | C23—C24—C25—C26 | 0.7 (9) |
N6—C5—C9—C8 | 12.1 (5) | O3—C25—C26—C27 | 179.9 (5) |
C4—C5—C9—C8 | 140.0 (5) | C24—C25—C26—C27 | −0.4 (9) |
C1—C5—C9—C8 | −108.6 (5) | C23—C22—C27—C26 | 2.1 (9) |
N6—C5—C9—C22 | 139.8 (5) | C9—C22—C27—C26 | −176.4 (5) |
C4—C5—C9—C22 | −92.3 (6) | C25—C26—C27—C22 | −1.0 (9) |
C1—C5—C9—C22 | 19.1 (7) | C26—C25—O3—C28 | −174.1 (6) |
N3—C4—C10—C15 | 8.4 (9) | C24—C25—O3—C28 | 6.2 (9) |
C5—C4—C10—C15 | −173.2 (6) | | |
(III) 3-bromo-4-(4-chlorophenyl)-1,7,9-triphenyl-1,2,7,8-tetraazaspiro[4.4]nona- 2,8-dien-6-one
top
Crystal data top
C29H20BrClN4O | F(000) = 2256 |
Mr = 555.85 | Dx = 1.467 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 52 reflections |
a = 16.735 (1) Å | θ = 2.9–15.4° |
b = 21.454 (2) Å | µ = 1.77 mm−1 |
c = 14.254 (1) Å | T = 298 K |
β = 100.498 (6)° | Irregular, pale yellow |
V = 5032.3 (7) Å3 | 0.39 × 0.3 × 0.19 mm |
Z = 8 | |
Data collection top
Bruker P4 diffractometer | Rint = 0.023 |
ω scans | θmax = 25°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | h = −1→19 |
Tmin = 0.577, Tmax = 0.714 | k = −1→25 |
5121 measured reflections | l = −16→16 |
4365 independent reflections | 3 standard reflections every 197 reflections |
2467 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0238P)2 + 11.4647P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
4365 reflections | Δρmax = 0.37 e Å−3 |
327 parameters | Δρmin = −0.32 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00045 (7) |
Crystal data top
C29H20BrClN4O | V = 5032.3 (7) Å3 |
Mr = 555.85 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.735 (1) Å | µ = 1.77 mm−1 |
b = 21.454 (2) Å | T = 298 K |
c = 14.254 (1) Å | 0.39 × 0.3 × 0.19 mm |
β = 100.498 (6)° | |
Data collection top
Bruker P4 diffractometer | 2467 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.023 |
Tmin = 0.577, Tmax = 0.714 | 3 standard reflections every 197 reflections |
5121 measured reflections | intensity decay: none |
4365 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 1 restraint |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0238P)2 + 11.4647P] where P = (Fo2 + 2Fc2)/3 |
4365 reflections | Δρmax = 0.37 e Å−3 |
327 parameters | Δρmin = −0.32 e Å−3 |
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 | |
Br1 | 0.04863 (4) | 0.47337 (2) | 0.13965 (4) | 0.0793 (2) | |
Cl1 | −0.09079 (9) | 0.72080 (6) | −0.15718 (9) | 0.0822 (5) | |
O1 | 0.10192 (18) | 0.68384 (13) | 0.2765 (2) | 0.0553 (8) | |
C1 | 0.1574 (3) | 0.68136 (19) | 0.2336 (3) | 0.0439 (10) | |
N2 | 0.1922 (2) | 0.72896 (15) | 0.1917 (2) | 0.0480 (9) | |
N3 | 0.2646 (2) | 0.71140 (16) | 0.1618 (2) | 0.0476 (9) | |
C4 | 0.2756 (2) | 0.65260 (19) | 0.1773 (3) | 0.0439 (10) | |
C5 | 0.2047 (2) | 0.62347 (18) | 0.2125 (3) | 0.0429 (10) | |
N6 | 0.2188 (2) | 0.57874 (16) | 0.2919 (2) | 0.0499 (9) | |
N7 | 0.1601 (2) | 0.53112 (16) | 0.2777 (3) | 0.0527 (9) | |
C8 | 0.1240 (3) | 0.53418 (19) | 0.1912 (3) | 0.0509 (11) | |
C9 | 0.1523 (3) | 0.58328 (18) | 0.1313 (3) | 0.0468 (11) | |
H9 | 0.1901 | 0.5635 | 0.0953 | 0.07* | |
C10 | 0.1677 (3) | 0.7925 (2) | 0.1796 (3) | 0.0478 (11) | |
C11 | 0.2243 (3) | 0.8379 (2) | 0.1738 (3) | 0.0590 (13) | |
H11 | 0.2787 | 0.8274 | 0.1777 | 0.07* | |
C12 | 0.1999 (4) | 0.8994 (2) | 0.1621 (4) | 0.0761 (16) | |
H12 | 0.2381 | 0.9303 | 0.1582 | 0.07* | |
C13 | 0.1201 (4) | 0.9149 (3) | 0.1562 (4) | 0.0854 (18) | |
H13 | 0.1037 | 0.9563 | 0.1481 | 0.07* | |
C14 | 0.0645 (4) | 0.8692 (3) | 0.1623 (4) | 0.0859 (17) | |
H14 | 0.0102 | 0.8801 | 0.1587 | 0.07* | |
C15 | 0.0867 (3) | 0.8077 (2) | 0.1737 (3) | 0.0666 (14) | |
H15 | 0.0481 | 0.777 | 0.1774 | 0.07* | |
C16 | 0.3466 (3) | 0.6211 (2) | 0.1521 (3) | 0.0474 (11) | |
C17 | 0.3589 (3) | 0.5576 (2) | 0.1637 (4) | 0.0714 (15) | |
H17 | 0.322 | 0.5336 | 0.1895 | 0.07* | |
C18 | 0.4259 (4) | 0.5298 (3) | 0.1372 (4) | 0.0936 (19) | |
H18 | 0.4336 | 0.4871 | 0.1448 | 0.07* | |
C19 | 0.4804 (3) | 0.5643 (3) | 0.1002 (4) | 0.0840 (17) | |
H19 | 0.5249 | 0.5451 | 0.0818 | 0.07* | |
C20 | 0.4700 (3) | 0.6273 (3) | 0.0900 (4) | 0.0843 (17) | |
H20 | 0.5083 | 0.6513 | 0.0667 | 0.07* | |
C21 | 0.4029 (3) | 0.6549 (2) | 0.1142 (4) | 0.0673 (14) | |
H21 | 0.3951 | 0.6975 | 0.1048 | 0.07* | |
C22 | 0.2442 (3) | 0.5986 (2) | 0.3884 (3) | 0.0486 (11) | |
C23 | 0.2189 (3) | 0.5683 (2) | 0.4625 (3) | 0.0670 (14) | |
H23 | 0.1835 | 0.5346 | 0.4509 | 0.07* | |
C24 | 0.2466 (4) | 0.5885 (3) | 0.5541 (4) | 0.0868 (18) | |
H24 | 0.2286 | 0.5684 | 0.6043 | 0.07* | |
C25 | 0.2997 (3) | 0.6371 (3) | 0.5739 (4) | 0.0755 (16) | |
H25 | 0.3185 | 0.6497 | 0.6365 | 0.07* | |
C26 | 0.3241 (3) | 0.6667 (3) | 0.4999 (4) | 0.0836 (17) | |
H26 | 0.3596 | 0.7003 | 0.5119 | 0.07* | |
C27 | 0.2970 (3) | 0.6477 (2) | 0.4070 (3) | 0.0768 (16) | |
H27 | 0.3147 | 0.6682 | 0.3571 | 0.07* | |
C28 | 0.0905 (3) | 0.61822 (19) | 0.0607 (3) | 0.0474 (11) | |
C29 | 0.1096 (3) | 0.6355 (2) | −0.0257 (3) | 0.0561 (12) | |
H29 | 0.1604 | 0.6255 | −0.0392 | 0.07* | |
C30 | 0.0543 (3) | 0.6677 (2) | −0.0927 (3) | 0.0604 (13) | |
H30 | 0.0674 | 0.679 | −0.1511 | 0.07* | |
C31 | −0.0197 (3) | 0.6825 (2) | −0.0714 (3) | 0.0565 (12) | |
C32 | −0.0409 (3) | 0.6663 (2) | 0.0139 (3) | 0.0568 (12) | |
H32 | −0.0917 | 0.6767 | 0.027 | 0.07* | |
C33 | 0.0149 (3) | 0.6340 (2) | 0.0801 (3) | 0.0512 (12) | |
H33 | 0.0014 | 0.6229 | 0.1383 | 0.07* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0963 (5) | 0.0606 (3) | 0.0785 (4) | −0.0295 (3) | 0.0092 (3) | −0.0152 (3) |
Cl1 | 0.0875 (10) | 0.0827 (9) | 0.0679 (8) | 0.0267 (8) | −0.0080 (7) | 0.0008 (7) |
O1 | 0.050 (2) | 0.064 (2) | 0.0572 (19) | −0.0080 (16) | 0.0234 (17) | −0.0078 (16) |
C1 | 0.042 (3) | 0.050 (3) | 0.040 (2) | −0.008 (2) | 0.008 (2) | −0.006 (2) |
N2 | 0.048 (2) | 0.041 (2) | 0.058 (2) | 0.0007 (18) | 0.0195 (19) | −0.0019 (18) |
N3 | 0.044 (2) | 0.045 (2) | 0.056 (2) | 0.0009 (18) | 0.0159 (18) | 0.0007 (18) |
C4 | 0.041 (3) | 0.046 (3) | 0.045 (3) | −0.001 (2) | 0.009 (2) | 0.001 (2) |
C5 | 0.044 (3) | 0.038 (2) | 0.047 (3) | −0.002 (2) | 0.010 (2) | 0.001 (2) |
N6 | 0.053 (2) | 0.045 (2) | 0.053 (2) | −0.0099 (18) | 0.0142 (19) | 0.0012 (18) |
N7 | 0.060 (2) | 0.045 (2) | 0.054 (2) | −0.005 (2) | 0.012 (2) | 0.0009 (19) |
C8 | 0.059 (3) | 0.039 (2) | 0.056 (3) | −0.007 (2) | 0.012 (2) | −0.008 (2) |
C9 | 0.051 (3) | 0.043 (2) | 0.048 (3) | −0.001 (2) | 0.013 (2) | −0.002 (2) |
C10 | 0.049 (3) | 0.047 (3) | 0.049 (3) | 0.004 (2) | 0.013 (2) | −0.007 (2) |
C11 | 0.060 (3) | 0.048 (3) | 0.070 (3) | 0.006 (3) | 0.014 (3) | 0.003 (2) |
C12 | 0.099 (5) | 0.047 (3) | 0.086 (4) | 0.001 (3) | 0.028 (3) | 0.003 (3) |
C13 | 0.109 (5) | 0.053 (4) | 0.093 (4) | 0.029 (4) | 0.016 (4) | 0.007 (3) |
C14 | 0.078 (4) | 0.078 (4) | 0.101 (5) | 0.030 (4) | 0.015 (4) | 0.003 (4) |
C15 | 0.056 (3) | 0.061 (3) | 0.081 (4) | 0.009 (3) | 0.008 (3) | −0.006 (3) |
C16 | 0.039 (3) | 0.052 (3) | 0.053 (3) | 0.003 (2) | 0.012 (2) | 0.001 (2) |
C17 | 0.061 (4) | 0.058 (3) | 0.100 (4) | 0.013 (3) | 0.027 (3) | 0.021 (3) |
C18 | 0.086 (4) | 0.065 (4) | 0.136 (5) | 0.035 (4) | 0.038 (4) | 0.019 (4) |
C19 | 0.059 (4) | 0.091 (5) | 0.107 (5) | 0.023 (3) | 0.030 (3) | 0.001 (4) |
C20 | 0.060 (4) | 0.087 (4) | 0.118 (5) | 0.003 (3) | 0.048 (3) | 0.005 (4) |
C21 | 0.054 (3) | 0.059 (3) | 0.096 (4) | 0.002 (3) | 0.032 (3) | −0.006 (3) |
C22 | 0.047 (3) | 0.050 (3) | 0.050 (3) | 0.003 (2) | 0.010 (2) | 0.000 (2) |
C23 | 0.083 (4) | 0.062 (3) | 0.054 (3) | −0.017 (3) | 0.008 (3) | 0.007 (3) |
C24 | 0.120 (5) | 0.087 (4) | 0.054 (3) | −0.020 (4) | 0.017 (3) | 0.012 (3) |
C25 | 0.089 (4) | 0.089 (4) | 0.045 (3) | −0.011 (3) | 0.003 (3) | −0.006 (3) |
C26 | 0.094 (4) | 0.091 (4) | 0.062 (4) | −0.040 (3) | 0.003 (3) | −0.014 (3) |
C27 | 0.086 (4) | 0.092 (4) | 0.051 (3) | −0.045 (3) | 0.010 (3) | 0.002 (3) |
C28 | 0.051 (3) | 0.045 (3) | 0.049 (3) | −0.002 (2) | 0.014 (2) | −0.006 (2) |
C29 | 0.054 (3) | 0.061 (3) | 0.057 (3) | 0.001 (3) | 0.019 (3) | −0.001 (3) |
C30 | 0.068 (4) | 0.062 (3) | 0.054 (3) | 0.008 (3) | 0.016 (3) | 0.006 (3) |
C31 | 0.061 (3) | 0.046 (3) | 0.056 (3) | 0.005 (2) | −0.005 (3) | −0.005 (2) |
C32 | 0.051 (3) | 0.061 (3) | 0.057 (3) | 0.005 (2) | 0.005 (3) | −0.008 (3) |
C33 | 0.054 (3) | 0.054 (3) | 0.048 (3) | −0.002 (2) | 0.015 (2) | −0.005 (2) |
Geometric parameters (Å, º) top
Br1—C8 | 1.870 (4) | C17—C18 | 1.382 (6) |
Cl1—C31 | 1.748 (4) | C17—H17 | 0.93 |
O1—C1 | 1.201 (4) | C18—C19 | 1.352 (7) |
C1—N2 | 1.366 (5) | C18—H18 | 0.93 |
C1—C5 | 1.532 (5) | C19—C20 | 1.368 (7) |
N2—N3 | 1.408 (4) | C19—H19 | 0.93 |
N2—C10 | 1.425 (5) | C20—C21 | 1.368 (6) |
N3—C4 | 1.288 (5) | C20—H20 | 0.93 |
C4—C16 | 1.467 (5) | C21—H21 | 0.93 |
C4—C5 | 1.506 (5) | C22—C27 | 1.369 (6) |
C5—N6 | 1.470 (5) | C22—C23 | 1.372 (6) |
C5—C9 | 1.576 (5) | C23—C24 | 1.374 (6) |
N6—N7 | 1.406 (4) | C23—H23 | 0.93 |
N6—C22 | 1.428 (5) | C24—C25 | 1.367 (7) |
N7—C8 | 1.272 (5) | C24—H24 | 0.93 |
C8—C9 | 1.487 (5) | C25—C26 | 1.357 (7) |
C9—C28 | 1.505 (6) | C25—H25 | 0.93 |
C9—H9 | 0.98 | C26—C27 | 1.380 (6) |
C10—C11 | 1.372 (6) | C26—H26 | 0.93 |
C10—C15 | 1.382 (6) | C27—H27 | 0.93 |
C11—C12 | 1.381 (6) | C28—C29 | 1.378 (6) |
C11—H11 | 0.93 | C28—C33 | 1.386 (6) |
C12—C13 | 1.365 (7) | C29—C30 | 1.388 (6) |
C12—H12 | 0.93 | C29—H29 | 0.93 |
C13—C14 | 1.365 (7) | C30—C31 | 1.366 (6) |
C13—H13 | 0.93 | C30—H30 | 0.93 |
C14—C15 | 1.373 (7) | C31—C32 | 1.372 (6) |
C14—H14 | 0.93 | C32—C33 | 1.385 (6) |
C15—H15 | 0.93 | C32—H32 | 0.93 |
C16—C21 | 1.376 (6) | C33—H33 | 0.93 |
C16—C17 | 1.382 (6) | | |
| | | |
O1—C1—N2 | 128.3 (4) | C16—C17—H17 | 119.9 |
O1—C1—C5 | 127.6 (4) | C18—C17—H17 | 119.9 |
N2—C1—C5 | 104.1 (3) | C19—C18—C17 | 120.6 (5) |
C1—N2—N3 | 113.1 (3) | C19—C18—H18 | 119.7 |
C1—N2—C10 | 129.2 (4) | C17—C18—H18 | 119.7 |
N3—N2—C10 | 117.7 (3) | C18—C19—C20 | 120.0 (5) |
C4—N3—N2 | 108.3 (3) | C18—C19—H19 | 120 |
N3—C4—C16 | 120.4 (4) | C20—C19—H19 | 120 |
N3—C4—C5 | 111.5 (4) | C19—C20—C21 | 119.7 (5) |
C16—C4—C5 | 127.8 (4) | C19—C20—H20 | 120.1 |
N6—C5—C4 | 120.1 (3) | C21—C20—H20 | 120.1 |
N6—C5—C1 | 113.3 (3) | C20—C21—C16 | 121.5 (5) |
C4—C5—C1 | 101.3 (3) | C20—C21—H21 | 119.2 |
N6—C5—C9 | 101.5 (3) | C16—C21—H21 | 119.2 |
C4—C5—C9 | 110.4 (3) | C27—C22—C23 | 119.6 (4) |
C1—C5—C9 | 110.4 (3) | C27—C22—N6 | 119.0 (4) |
N7—N6—C22 | 115.7 (3) | C23—C22—N6 | 121.3 (4) |
N7—N6—C5 | 110.7 (3) | C22—C23—C24 | 119.0 (5) |
C22—N6—C5 | 121.6 (3) | C22—C23—H23 | 120.5 |
C8—N7—N6 | 107.4 (3) | C24—C23—H23 | 120.5 |
N7—C8—C9 | 116.7 (4) | C25—C24—C23 | 122.1 (5) |
N7—C8—Br1 | 120.8 (3) | C25—C24—H24 | 119 |
C9—C8—Br1 | 122.1 (3) | C23—C24—H24 | 119 |
C8—C9—C28 | 119.0 (4) | C26—C25—C24 | 118.2 (5) |
C8—C9—C5 | 99.1 (3) | C26—C25—H25 | 120.9 |
C28—C9—C5 | 116.2 (3) | C24—C25—H25 | 120.9 |
C8—C9—H9 | 107.2 | C25—C26—C27 | 121.1 (5) |
C28—C9—H9 | 107.2 | C25—C26—H26 | 119.5 |
C5—C9—H9 | 107.2 | C27—C26—H26 | 119.5 |
C11—C10—C15 | 120.6 (4) | C22—C27—C26 | 120.0 (5) |
C11—C10—N2 | 120.0 (4) | C22—C27—H27 | 120 |
C15—C10—N2 | 119.4 (4) | C26—C27—H27 | 120 |
C10—C11—C12 | 119.6 (5) | C29—C28—C33 | 118.8 (4) |
C10—C11—H11 | 120.2 | C29—C28—C9 | 119.2 (4) |
C12—C11—H11 | 120.2 | C33—C28—C9 | 122.0 (4) |
C13—C12—C11 | 120.3 (5) | C28—C29—C30 | 121.0 (4) |
C13—C12—H12 | 119.8 | C28—C29—H29 | 119.5 |
C11—C12—H12 | 119.8 | C30—C29—H29 | 119.5 |
C14—C13—C12 | 119.4 (5) | C31—C30—C29 | 118.7 (4) |
C14—C13—H13 | 120.3 | C31—C30—H30 | 120.6 |
C12—C13—H13 | 120.3 | C29—C30—H30 | 120.6 |
C13—C14—C15 | 121.7 (6) | C30—C31—C32 | 122.0 (4) |
C13—C14—H14 | 119.2 | C30—C31—Cl1 | 118.9 (4) |
C15—C14—H14 | 119.2 | C32—C31—Cl1 | 119.1 (4) |
C14—C15—C10 | 118.4 (5) | C31—C32—C33 | 118.6 (4) |
C14—C15—H15 | 120.8 | C31—C32—H32 | 120.7 |
C10—C15—H15 | 120.8 | C33—C32—H32 | 120.7 |
C21—C16—C17 | 118.0 (4) | C32—C33—C28 | 120.9 (4) |
C21—C16—C4 | 119.7 (4) | C32—C33—H33 | 119.6 |
C17—C16—C4 | 122.3 (4) | C28—C33—H33 | 119.6 |
C16—C17—C18 | 120.1 (5) | | |
| | | |
O1—C1—N2—N3 | 169.7 (4) | N2—C10—C11—C12 | −179.9 (4) |
C5—C1—N2—N3 | −10.9 (4) | C10—C11—C12—C13 | −0.1 (8) |
O1—C1—N2—C10 | −6.7 (7) | C11—C12—C13—C14 | 0.2 (9) |
C5—C1—N2—C10 | 172.7 (4) | C12—C13—C14—C15 | −0.4 (9) |
C1—N2—N3—C4 | 4.1 (5) | C13—C14—C15—C10 | 0.4 (8) |
C10—N2—N3—C4 | −179.1 (4) | C11—C10—C15—C14 | −0.2 (7) |
N2—N3—C4—C16 | 179.5 (3) | N2—C10—C15—C14 | 179.8 (4) |
N2—N3—C4—C5 | 5.1 (5) | N3—C4—C16—C21 | 1.8 (6) |
N3—C4—C5—N6 | −136.7 (4) | C5—C4—C16—C21 | 175.2 (4) |
C16—C4—C5—N6 | 49.5 (6) | N3—C4—C16—C17 | −177.2 (4) |
N3—C4—C5—C1 | −11.1 (4) | C5—C4—C16—C17 | −3.8 (7) |
C16—C4—C5—C1 | 175.1 (4) | C21—C16—C17—C18 | −0.3 (8) |
N3—C4—C5—C9 | 105.9 (4) | C4—C16—C17—C18 | 178.7 (5) |
C16—C4—C5—C9 | −67.9 (5) | C16—C17—C18—C19 | 0.5 (9) |
O1—C1—C5—N6 | −38.1 (6) | C17—C18—C19—C20 | 0.8 (10) |
N2—C1—C5—N6 | 142.5 (3) | C18—C19—C20—C21 | −2.3 (9) |
O1—C1—C5—C4 | −168.1 (4) | C19—C20—C21—C16 | 2.4 (9) |
N2—C1—C5—C4 | 12.5 (4) | C17—C16—C21—C20 | −1.1 (7) |
O1—C1—C5—C9 | 74.9 (5) | C4—C16—C21—C20 | 179.8 (5) |
N2—C1—C5—C9 | −104.5 (4) | N7—N6—C22—C27 | −175.6 (4) |
C4—C5—N6—N7 | −143.2 (4) | C5—N6—C22—C27 | −36.5 (6) |
C1—C5—N6—N7 | 97.0 (4) | N7—N6—C22—C23 | 6.6 (6) |
C9—C5—N6—N7 | −21.3 (4) | C5—N6—C22—C23 | 145.7 (4) |
C4—C5—N6—C22 | 75.9 (5) | C27—C22—C23—C24 | 0.8 (7) |
C1—C5—N6—C22 | −43.9 (5) | N6—C22—C23—C24 | 178.6 (4) |
C9—C5—N6—C22 | −162.2 (4) | C22—C23—C24—C25 | −1.2 (9) |
C22—N6—N7—C8 | 157.3 (4) | C23—C24—C25—C26 | 1.2 (9) |
C5—N6—N7—C8 | 13.9 (5) | C24—C25—C26—C27 | −0.9 (9) |
N6—N7—C8—C9 | 1.0 (5) | C23—C22—C27—C26 | −0.5 (8) |
N6—N7—C8—Br1 | 173.5 (3) | N6—C22—C27—C26 | −178.3 (5) |
N7—C8—C9—C28 | −140.5 (4) | C25—C26—C27—C22 | 0.6 (9) |
Br1—C8—C9—C28 | 47.0 (5) | C8—C9—C28—C29 | −144.0 (4) |
N7—C8—C9—C5 | −13.7 (5) | C5—C9—C28—C29 | 97.7 (5) |
Br1—C8—C9—C5 | 173.9 (3) | C8—C9—C28—C33 | 36.5 (6) |
N6—C5—C9—C8 | 19.4 (4) | C5—C9—C28—C33 | −81.8 (5) |
C4—C5—C9—C8 | 147.8 (3) | C33—C28—C29—C30 | −0.6 (6) |
C1—C5—C9—C8 | −101.0 (4) | C9—C28—C29—C30 | 179.9 (4) |
N6—C5—C9—C28 | 148.1 (4) | C28—C29—C30—C31 | 0.5 (7) |
C4—C5—C9—C28 | −83.4 (4) | C29—C30—C31—C32 | −0.4 (7) |
C1—C5—C9—C28 | 27.8 (5) | C29—C30—C31—Cl1 | −177.9 (3) |
C1—N2—C10—C11 | 152.6 (4) | C30—C31—C32—C33 | 0.2 (7) |
N3—N2—C10—C11 | −23.7 (6) | Cl1—C31—C32—C33 | 177.8 (3) |
C1—N2—C10—C15 | −27.4 (7) | C31—C32—C33—C28 | −0.2 (6) |
N3—N2—C10—C15 | 156.3 (4) | C29—C28—C33—C32 | 0.4 (6) |
C15—C10—C11—C12 | 0.1 (7) | C9—C28—C33—C32 | 179.9 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O1 | 0.93 | 2.52 | 3.022 (6) | 114 |
C21—H21···N3 | 0.93 | 2.48 | 2.802 (6) | 100 |
C23—H23···N7 | 0.93 | 2.43 | 2.756 (6) | 101 |
(IV) 3-Bromo-1,7,9-triphenyl-4-
p-tolyl-1,2,7,8-tetraazaspiro[4.4]nona-2,8-dien-6-one
top
Crystal data top
C30H22.89Br1.11N4O | F(000) = 1111 |
Mr = 544.11 | Dx = 1.391 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 10.107 (1) Å | θ = 4.4–16.0° |
b = 13.578 (3) Å | µ = 1.78 mm−1 |
c = 19.146 (3) Å | T = 298 K |
β = 98.50 (1)° | Prismatic, colourless |
V = 2598.6 (8) Å3 | 0.36 × 0.34 × 0.18 mm |
Z = 4 | |
Data collection top
Bruker P4 diffractometer | Rint = 0.037 |
ω scans | θmax = 25°, θmin = 1.9° |
Absorption correction: ψ scan (North et al., 1968) | h = −1→12 |
Tmin = 0.459, Tmax = 0.726 | k = −16→1 |
5812 measured reflections | l = −22→22 |
4510 independent reflections | 3 standard reflections every 197 reflections |
2455 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.057 | w = 1/[σ2(Fo2) + (0.0641P)2 + 0.8649P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.149 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.36 e Å−3 |
4510 reflections | Δρmin = −0.45 e Å−3 |
335 parameters | |
Crystal data top
C30H22.89Br1.11N4O | V = 2598.6 (8) Å3 |
Mr = 544.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.107 (1) Å | µ = 1.78 mm−1 |
b = 13.578 (3) Å | T = 298 K |
c = 19.146 (3) Å | 0.36 × 0.34 × 0.18 mm |
β = 98.50 (1)° | |
Data collection top
Bruker P4 diffractometer | 2455 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.037 |
Tmin = 0.459, Tmax = 0.726 | 3 standard reflections every 197 reflections |
5812 measured reflections | intensity decay: none |
4510 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.36 e Å−3 |
4510 reflections | Δρmin = −0.45 e Å−3 |
335 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Br1 | 0.62209 (7) | 1.11856 (5) | 0.06638 (3) | 0.0769 (3) | |
O1 | 0.8674 (4) | 0.9128 (3) | 0.24928 (19) | 0.0677 (10) | |
C1 | 0.7609 (5) | 0.9008 (4) | 0.2683 (3) | 0.0550 (13) | |
N2 | 0.7171 (4) | 0.8218 (3) | 0.3048 (2) | 0.0539 (10) | |
N3 | 0.5898 (4) | 0.8361 (3) | 0.3232 (2) | 0.0510 (10) | |
C4 | 0.5451 (5) | 0.9219 (3) | 0.3009 (2) | 0.0451 (11) | |
C5 | 0.6400 (4) | 0.9715 (3) | 0.2578 (2) | 0.0451 (11) | |
N6 | 0.6819 (4) | 1.0746 (3) | 0.2728 (2) | 0.0547 (11) | |
N7 | 0.6944 (4) | 1.1241 (3) | 0.2100 (2) | 0.0576 (11) | |
C8 | 0.6392 (5) | 1.0721 (4) | 0.1597 (3) | 0.0541 (13) | |
C9 | 0.5723 (5) | 0.9797 (3) | 0.1790 (2) | 0.0502 (12) | |
H9 | 0.4777 | 0.9952 | 0.1792 | 0.06* | |
C10 | 0.7911 (5) | 0.7366 (4) | 0.3333 (3) | 0.0602 (14) | |
C11 | 0.7323 (6) | 0.6741 (4) | 0.3764 (3) | 0.0788 (18) | |
H11 | 0.6477 | 0.6876 | 0.3876 | 0.095* | |
C12 | 0.8022 (8) | 0.5904 (5) | 0.4030 (4) | 0.109 (2) | |
H12 | 0.7639 | 0.5476 | 0.4322 | 0.131* | |
C13 | 0.9256 (8) | 0.5707 (6) | 0.3866 (5) | 0.124 (3) | |
H13 | 0.9721 | 0.5153 | 0.4053 | 0.148* | |
C14 | 0.9810 (7) | 0.6315 (6) | 0.3431 (5) | 0.115 (3) | |
H14 | 1.0647 | 0.6164 | 0.3312 | 0.137* | |
C15 | 0.9154 (6) | 0.7162 (5) | 0.3159 (3) | 0.0826 (18) | |
H15 | 0.9547 | 0.7582 | 0.2865 | 0.099* | |
C16 | 0.4132 (5) | 0.9544 (3) | 0.3121 (2) | 0.0480 (12) | |
C17 | 0.3749 (5) | 1.0528 (4) | 0.3059 (3) | 0.0589 (14) | |
H17 | 0.4339 | 1.1001 | 0.2936 | 0.071* | |
C18 | 0.2500 (6) | 1.0796 (4) | 0.3180 (3) | 0.0729 (16) | |
H18 | 0.2258 | 1.1457 | 0.3141 | 0.087* | |
C19 | 0.1597 (6) | 1.0129 (5) | 0.3356 (3) | 0.0830 (19) | |
H19 | 0.0749 | 1.0325 | 0.3435 | 0.1* | |
C20 | 0.1976 (6) | 0.9163 (5) | 0.3414 (3) | 0.0846 (19) | |
H20 | 0.1374 | 0.8699 | 0.3536 | 0.102* | |
C21 | 0.3213 (5) | 0.8859 (4) | 0.3299 (3) | 0.0692 (15) | |
H21 | 0.3442 | 0.8195 | 0.334 | 0.083* | |
C22 | 0.7690 (5) | 1.1041 (4) | 0.3332 (3) | 0.0514 (12) | |
C23 | 0.8372 (5) | 1.1921 (4) | 0.3352 (3) | 0.0641 (15) | |
H23 | 0.8311 | 1.2307 | 0.2947 | 0.077* | |
C24 | 0.9144 (6) | 1.2238 (5) | 0.3965 (4) | 0.0865 (19) | |
H24 | 0.9598 | 1.2835 | 0.3971 | 0.104* | |
C25 | 0.9243 (6) | 1.1681 (5) | 0.4562 (3) | 0.0866 (19) | |
H25 | 0.9761 | 1.1899 | 0.4975 | 0.104* | 0.89 |
Br2 | 1.0110 (6) | 1.2117 (6) | 0.5333 (3) | 0.097 (2) | 0.11 |
C26 | 0.8592 (6) | 1.0810 (5) | 0.4556 (3) | 0.0754 (17) | |
H26 | 0.8668 | 1.043 | 0.4964 | 0.091* | |
C27 | 0.7813 (5) | 1.0481 (4) | 0.3946 (3) | 0.0649 (15) | |
H27 | 0.7368 | 0.9882 | 0.3946 | 0.078* | |
C28 | 0.5780 (5) | 0.8881 (4) | 0.1336 (2) | 0.0524 (12) | |
C29 | 0.4679 (5) | 0.8280 (4) | 0.1215 (3) | 0.0623 (14) | |
H29 | 0.3917 | 0.8436 | 0.1412 | 0.075* | |
C30 | 0.4693 (7) | 0.7447 (4) | 0.0803 (3) | 0.0775 (18) | |
H30 | 0.3946 | 0.704 | 0.0733 | 0.093* | |
C31 | 0.5799 (8) | 0.7209 (4) | 0.0496 (3) | 0.0761 (18) | |
C32 | 0.6902 (7) | 0.7816 (5) | 0.0617 (3) | 0.0751 (17) | |
H32 | 0.7662 | 0.7657 | 0.0419 | 0.09* | |
C33 | 0.6904 (5) | 0.8656 (4) | 0.1026 (3) | 0.0635 (14) | |
H33 | 0.7649 | 0.9066 | 0.1094 | 0.076* | |
C34 | 0.5829 (9) | 0.6280 (5) | 0.0055 (4) | 0.120 (3) | |
H34A | 0.6673 | 0.6235 | −0.0117 | 0.18* | |
H34B | 0.5119 | 0.6304 | −0.0338 | 0.18* | |
H34C | 0.5713 | 0.5714 | 0.034 | 0.18* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.1023 (5) | 0.0707 (4) | 0.0578 (3) | 0.0026 (4) | 0.0125 (3) | 0.0143 (3) |
O1 | 0.051 (2) | 0.080 (3) | 0.075 (2) | −0.002 (2) | 0.0210 (19) | 0.010 (2) |
C1 | 0.058 (4) | 0.055 (3) | 0.052 (3) | −0.006 (3) | 0.009 (3) | 0.000 (3) |
N2 | 0.049 (3) | 0.051 (3) | 0.064 (3) | 0.006 (2) | 0.014 (2) | 0.003 (2) |
N3 | 0.047 (3) | 0.049 (3) | 0.059 (2) | 0.002 (2) | 0.013 (2) | 0.003 (2) |
C4 | 0.053 (3) | 0.038 (3) | 0.045 (3) | −0.002 (2) | 0.009 (2) | −0.003 (2) |
C5 | 0.042 (3) | 0.045 (3) | 0.048 (3) | −0.001 (2) | 0.005 (2) | −0.001 (2) |
N6 | 0.061 (3) | 0.050 (2) | 0.052 (2) | −0.013 (2) | 0.007 (2) | 0.002 (2) |
N7 | 0.070 (3) | 0.050 (2) | 0.054 (2) | −0.006 (2) | 0.014 (2) | 0.002 (2) |
C8 | 0.062 (3) | 0.052 (3) | 0.049 (3) | 0.001 (3) | 0.013 (3) | 0.012 (3) |
C9 | 0.049 (3) | 0.055 (3) | 0.046 (3) | −0.003 (3) | 0.005 (2) | −0.001 (2) |
C10 | 0.061 (4) | 0.056 (3) | 0.065 (3) | 0.007 (3) | 0.013 (3) | 0.000 (3) |
C11 | 0.073 (4) | 0.066 (4) | 0.103 (5) | 0.021 (3) | 0.031 (4) | 0.018 (4) |
C12 | 0.113 (6) | 0.070 (5) | 0.147 (7) | 0.022 (4) | 0.029 (5) | 0.035 (5) |
C13 | 0.106 (6) | 0.099 (6) | 0.171 (8) | 0.055 (5) | 0.038 (6) | 0.048 (6) |
C14 | 0.087 (5) | 0.097 (6) | 0.164 (8) | 0.040 (5) | 0.033 (5) | 0.032 (5) |
C15 | 0.058 (4) | 0.092 (5) | 0.101 (5) | 0.016 (4) | 0.021 (3) | 0.015 (4) |
C16 | 0.047 (3) | 0.047 (3) | 0.051 (3) | 0.005 (3) | 0.013 (2) | −0.008 (2) |
C17 | 0.063 (4) | 0.050 (3) | 0.065 (3) | 0.005 (3) | 0.010 (3) | −0.003 (3) |
C18 | 0.072 (4) | 0.061 (4) | 0.086 (4) | 0.019 (3) | 0.011 (3) | −0.014 (3) |
C19 | 0.059 (4) | 0.102 (5) | 0.088 (4) | 0.013 (4) | 0.012 (3) | −0.017 (4) |
C20 | 0.063 (4) | 0.082 (5) | 0.113 (5) | −0.004 (4) | 0.028 (4) | −0.005 (4) |
C21 | 0.061 (4) | 0.060 (3) | 0.090 (4) | −0.005 (3) | 0.020 (3) | −0.007 (3) |
C22 | 0.044 (3) | 0.052 (3) | 0.058 (3) | −0.005 (3) | 0.006 (2) | −0.003 (3) |
C23 | 0.058 (4) | 0.061 (4) | 0.072 (4) | −0.008 (3) | 0.005 (3) | −0.001 (3) |
C24 | 0.085 (5) | 0.075 (4) | 0.095 (5) | −0.030 (4) | 0.000 (4) | −0.012 (4) |
C25 | 0.085 (5) | 0.091 (5) | 0.076 (4) | −0.023 (4) | −0.014 (3) | −0.018 (4) |
Br2 | 0.090 (4) | 0.133 (6) | 0.065 (3) | −0.053 (4) | 0.000 (3) | −0.024 (4) |
C26 | 0.071 (4) | 0.089 (5) | 0.062 (4) | 0.000 (4) | −0.005 (3) | 0.002 (3) |
C27 | 0.072 (4) | 0.055 (3) | 0.066 (4) | −0.009 (3) | 0.003 (3) | −0.003 (3) |
C28 | 0.060 (3) | 0.052 (3) | 0.045 (3) | −0.001 (3) | 0.005 (2) | 0.004 (3) |
C29 | 0.069 (4) | 0.060 (3) | 0.060 (3) | −0.016 (3) | 0.013 (3) | −0.001 (3) |
C30 | 0.119 (5) | 0.057 (4) | 0.055 (3) | −0.036 (4) | 0.006 (4) | 0.005 (3) |
C31 | 0.124 (6) | 0.054 (4) | 0.050 (3) | 0.001 (4) | 0.010 (4) | 0.002 (3) |
C32 | 0.094 (5) | 0.072 (4) | 0.062 (4) | 0.017 (4) | 0.017 (3) | −0.006 (3) |
C33 | 0.066 (4) | 0.062 (4) | 0.063 (3) | −0.005 (3) | 0.008 (3) | −0.004 (3) |
C34 | 0.211 (8) | 0.070 (4) | 0.077 (4) | 0.003 (5) | 0.013 (5) | −0.024 (4) |
Geometric parameters (Å, º) top
Br1—C8 | 1.878 (5) | C18—H18 | 0.93 |
O1—C1 | 1.198 (5) | C19—C20 | 1.366 (8) |
C1—N2 | 1.389 (6) | C19—H19 | 0.93 |
C1—C5 | 1.543 (6) | C20—C21 | 1.366 (7) |
N2—N3 | 1.397 (5) | C20—H20 | 0.93 |
N2—C10 | 1.441 (6) | C21—H21 | 0.93 |
N3—C4 | 1.298 (6) | C22—C23 | 1.377 (7) |
C4—C16 | 1.450 (6) | C22—C27 | 1.390 (7) |
C4—C5 | 1.512 (6) | C23—C24 | 1.379 (7) |
C5—N6 | 1.478 (6) | C23—H23 | 0.93 |
C5—C9 | 1.567 (6) | C24—C25 | 1.362 (8) |
N6—N7 | 1.398 (5) | C24—H24 | 0.93 |
N6—C22 | 1.404 (6) | C25—C26 | 1.353 (8) |
N7—C8 | 1.257 (6) | C25—Br2 | 1.707 (8) |
C8—C9 | 1.497 (7) | C25—H25 | 0.93 |
C9—C28 | 1.522 (6) | C26—C27 | 1.383 (7) |
C9—H9 | 0.98 | C26—H26 | 0.93 |
C10—C15 | 1.375 (7) | C27—H27 | 0.93 |
C10—C11 | 1.377 (7) | C28—C29 | 1.372 (7) |
C11—C12 | 1.395 (8) | C28—C33 | 1.391 (7) |
C11—H11 | 0.93 | C29—C30 | 1.380 (7) |
C12—C13 | 1.357 (9) | C29—H29 | 0.93 |
C12—H12 | 0.93 | C30—C31 | 1.376 (8) |
C13—C14 | 1.351 (9) | C30—H30 | 0.93 |
C13—H13 | 0.93 | C31—C32 | 1.378 (8) |
C14—C15 | 1.390 (8) | C31—C34 | 1.521 (8) |
C14—H14 | 0.93 | C32—C33 | 1.384 (7) |
C15—H15 | 0.93 | C32—H32 | 0.93 |
C16—C17 | 1.391 (7) | C33—H33 | 0.93 |
C16—C21 | 1.393 (7) | C34—H34A | 0.96 |
C17—C18 | 1.366 (7) | C34—H34B | 0.96 |
C17—H17 | 0.93 | C34—H34C | 0.96 |
C18—C19 | 1.364 (8) | | |
| | | |
O1—C1—N2 | 128.7 (5) | C17—C18—H18 | 118.9 |
O1—C1—C5 | 127.4 (5) | C18—C19—C20 | 117.9 (6) |
N2—C1—C5 | 103.9 (4) | C18—C19—H19 | 121.1 |
C1—N2—N3 | 113.2 (4) | C20—C19—H19 | 121.1 |
C1—N2—C10 | 128.7 (4) | C21—C20—C19 | 122.0 (6) |
N3—N2—C10 | 117.6 (4) | C21—C20—H20 | 119 |
C4—N3—N2 | 109.3 (4) | C19—C20—H20 | 119 |
N3—C4—C16 | 120.4 (4) | C20—C21—C16 | 119.8 (5) |
N3—C4—C5 | 111.2 (4) | C20—C21—H21 | 120.1 |
C16—C4—C5 | 128.1 (4) | C16—C21—H21 | 120.1 |
N6—C5—C4 | 120.2 (4) | C23—C22—C27 | 117.9 (5) |
N6—C5—C1 | 111.4 (4) | C23—C22—N6 | 121.4 (5) |
C4—C5—C1 | 101.9 (4) | C27—C22—N6 | 120.5 (4) |
N6—C5—C9 | 101.0 (4) | C22—C23—C24 | 120.9 (5) |
C4—C5—C9 | 109.6 (4) | C22—C23—H23 | 119.6 |
C1—C5—C9 | 113.2 (4) | C24—C23—H23 | 119.6 |
N7—N6—C22 | 116.4 (4) | C25—C24—C23 | 120.2 (6) |
N7—N6—C5 | 110.4 (4) | C25—C24—H24 | 119.9 |
C22—N6—C5 | 123.8 (4) | C23—C24—H24 | 119.9 |
C8—N7—N6 | 107.6 (4) | C26—C25—C24 | 120.2 (6) |
N7—C8—C9 | 116.6 (4) | C26—C25—Br2 | 119.8 (6) |
N7—C8—Br1 | 120.6 (4) | C24—C25—Br2 | 119.8 (6) |
C9—C8—Br1 | 122.3 (4) | C26—C25—H25 | 119.9 |
C8—C9—C28 | 119.2 (4) | C24—C25—H25 | 119.9 |
C8—C9—C5 | 98.5 (4) | Br2—C25—H25 | 3.4 |
C28—C9—C5 | 116.3 (4) | C25—C26—C27 | 120.3 (6) |
C8—C9—H9 | 107.3 | C25—C26—H26 | 119.9 |
C28—C9—H9 | 107.3 | C27—C26—H26 | 119.9 |
C5—C9—H9 | 107.3 | C26—C27—C22 | 120.5 (5) |
C15—C10—C11 | 120.8 (5) | C26—C27—H27 | 119.8 |
C15—C10—N2 | 120.7 (5) | C22—C27—H27 | 119.8 |
C11—C10—N2 | 118.4 (5) | C29—C28—C33 | 119.3 (5) |
C10—C11—C12 | 118.7 (6) | C29—C28—C9 | 119.0 (5) |
C10—C11—H11 | 120.6 | C33—C28—C9 | 121.7 (5) |
C12—C11—H11 | 120.6 | C28—C29—C30 | 120.5 (5) |
C13—C12—C11 | 120.6 (7) | C28—C29—H29 | 119.8 |
C13—C12—H12 | 119.7 | C30—C29—H29 | 119.8 |
C11—C12—H12 | 119.7 | C31—C30—C29 | 121.0 (6) |
C14—C13—C12 | 120.1 (7) | C31—C30—H30 | 119.5 |
C14—C13—H13 | 120 | C29—C30—H30 | 119.5 |
C12—C13—H13 | 120 | C30—C31—C32 | 118.4 (5) |
C13—C14—C15 | 121.2 (7) | C30—C31—C34 | 121.1 (7) |
C13—C14—H14 | 119.4 | C32—C31—C34 | 120.5 (7) |
C15—C14—H14 | 119.4 | C31—C32—C33 | 121.4 (6) |
C10—C15—C14 | 118.5 (6) | C31—C32—H32 | 119.3 |
C10—C15—H15 | 120.7 | C33—C32—H32 | 119.3 |
C14—C15—H15 | 120.7 | C32—C33—C28 | 119.4 (5) |
C17—C16—C21 | 118.4 (5) | C32—C33—H33 | 120.3 |
C17—C16—C4 | 122.0 (5) | C28—C33—H33 | 120.3 |
C21—C16—C4 | 119.6 (5) | C31—C34—H34A | 109.5 |
C18—C17—C16 | 119.6 (5) | C31—C34—H34B | 109.5 |
C18—C17—H17 | 120.2 | H34A—C34—H34B | 109.5 |
C16—C17—H17 | 120.2 | C31—C34—H34C | 109.5 |
C19—C18—C17 | 122.3 (6) | H34A—C34—H34C | 109.5 |
C19—C18—H18 | 118.9 | H34B—C34—H34C | 109.5 |
| | | |
O1—C1—N2—N3 | 175.3 (5) | C10—C11—C12—C13 | −0.1 (11) |
C5—C1—N2—N3 | −4.4 (5) | C11—C12—C13—C14 | −1.2 (13) |
O1—C1—N2—C10 | 4.4 (8) | C12—C13—C14—C15 | 1.7 (14) |
C5—C1—N2—C10 | −175.2 (4) | C11—C10—C15—C14 | −0.5 (9) |
C1—N2—N3—C4 | −0.2 (5) | N2—C10—C15—C14 | −178.1 (6) |
C10—N2—N3—C4 | 171.7 (4) | C13—C14—C15—C10 | −0.9 (12) |
N2—N3—C4—C16 | 178.9 (4) | N3—C4—C16—C17 | 163.2 (5) |
N2—N3—C4—C5 | 5.0 (5) | C5—C4—C16—C17 | −24.1 (7) |
N3—C4—C5—N6 | −131.0 (4) | N3—C4—C16—C21 | −16.5 (7) |
C16—C4—C5—N6 | 55.7 (6) | C5—C4—C16—C21 | 156.2 (5) |
N3—C4—C5—C1 | −7.3 (5) | C21—C16—C17—C18 | 0.6 (8) |
C16—C4—C5—C1 | 179.4 (4) | C4—C16—C17—C18 | −179.1 (4) |
N3—C4—C5—C9 | 112.8 (4) | C16—C17—C18—C19 | −0.5 (9) |
C16—C4—C5—C9 | −60.5 (6) | C17—C18—C19—C20 | 0.3 (9) |
O1—C1—C5—N6 | −43.7 (7) | C18—C19—C20—C21 | −0.3 (10) |
N2—C1—C5—N6 | 136.0 (4) | C19—C20—C21—C16 | 0.4 (10) |
O1—C1—C5—C4 | −173.1 (5) | C17—C16—C21—C20 | −0.6 (8) |
N2—C1—C5—C4 | 6.6 (4) | C4—C16—C21—C20 | 179.1 (5) |
O1—C1—C5—C9 | 69.4 (6) | N7—N6—C22—C23 | 16.4 (7) |
N2—C1—C5—C9 | −110.9 (4) | C5—N6—C22—C23 | 159.7 (4) |
C4—C5—N6—N7 | −143.6 (4) | N7—N6—C22—C27 | −168.2 (4) |
C1—C5—N6—N7 | 97.4 (4) | C5—N6—C22—C27 | −24.9 (7) |
C9—C5—N6—N7 | −23.1 (5) | C27—C22—C23—C24 | −0.5 (8) |
C4—C5—N6—C22 | 71.3 (6) | N6—C22—C23—C24 | 175.0 (5) |
C1—C5—N6—C22 | −47.7 (6) | C22—C23—C24—C25 | 0.1 (9) |
C9—C5—N6—C22 | −168.2 (4) | C23—C24—C25—C26 | 0.4 (10) |
C22—N6—N7—C8 | 161.7 (4) | C23—C24—C25—Br2 | −175.7 (5) |
C5—N6—N7—C8 | 13.7 (5) | C24—C25—C26—C27 | −0.4 (10) |
N6—N7—C8—C9 | 3.1 (6) | Br2—C25—C26—C27 | 175.6 (6) |
N6—N7—C8—Br1 | 174.8 (3) | C25—C26—C27—C22 | 0.0 (9) |
N7—C8—C9—C28 | −143.6 (5) | C23—C22—C27—C26 | 0.4 (8) |
Br1—C8—C9—C28 | 44.9 (6) | N6—C22—C27—C26 | −175.1 (5) |
N7—C8—C9—C5 | −16.9 (6) | C8—C9—C28—C29 | −142.4 (5) |
Br1—C8—C9—C5 | 171.6 (3) | C5—C9—C28—C29 | 99.8 (5) |
N6—C5—C9—C8 | 21.8 (4) | C8—C9—C28—C33 | 35.7 (7) |
C4—C5—C9—C8 | 149.6 (4) | C5—C9—C28—C33 | −82.1 (6) |
C1—C5—C9—C8 | −97.4 (4) | C33—C28—C29—C30 | 1.5 (7) |
N6—C5—C9—C28 | 150.4 (4) | C9—C28—C29—C30 | 179.7 (4) |
C4—C5—C9—C28 | −81.8 (5) | C28—C29—C30—C31 | −1.2 (8) |
C1—C5—C9—C28 | 31.2 (6) | C29—C30—C31—C32 | 1.0 (8) |
C1—N2—C10—C15 | −11.4 (8) | C29—C30—C31—C34 | 178.7 (5) |
N3—N2—C10—C15 | 178.1 (5) | C30—C31—C32—C33 | −1.2 (8) |
C1—N2—C10—C11 | 170.8 (5) | C34—C31—C32—C33 | −178.9 (5) |
N3—N2—C10—C11 | 0.4 (7) | C31—C32—C33—C28 | 1.6 (8) |
C15—C10—C11—C12 | 0.9 (9) | C29—C28—C33—C32 | −1.7 (7) |
N2—C10—C11—C12 | 178.7 (6) | C9—C28—C33—C32 | −179.8 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O1 | 0.93 | 2.35 | 2.967 (7) | 124 |
C11—H11···N3 | 0.93 | 2.39 | 2.742 (7) | 102 |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | C24H18BrN3O2 | C24H18BrN3O3 | C29H20BrClN4O | C30H22.89Br1.11N4O |
Mr | 460.32 | 476.32 | 555.85 | 544.11 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, C2/c | Monoclinic, C2/c | Monoclinic, P21/c |
Temperature (K) | 298 | 298 | 298 | 298 |
a, b, c (Å) | 14.180 (2), 16.076 (2), 18.413 (2) | 35.375 (3), 9.200 (1), 12.807 (2) | 16.735 (1), 21.454 (2), 14.254 (1) | 10.107 (1), 13.578 (3), 19.146 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 94.81 (1), 90 | 90, 100.498 (6), 90 | 90, 98.50 (1), 90 |
V (Å3) | 4197.4 (9) | 4153.2 (9) | 5032.3 (7) | 2598.6 (8) |
Z | 8 | 8 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.98 | 2.01 | 1.77 | 1.78 |
Crystal size (mm) | 0.4 × 0.32 × 0.28 | 0.50 × 0.23 × 0.15 | 0.39 × 0.3 × 0.19 | 0.36 × 0.34 × 0.18 |
|
Data collection |
Diffractometer | Bruker P4 diffractometer | Bruker P4 diffractometer | Bruker P4 diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) | Empirical (using intensity measurements) (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.414, 0.573 | 0.388, 0.739 | 0.577, 0.714 | 0.459, 0.726 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5243, 4267, 1805 | 4814, 4047, 2153 | 5121, 4365, 2467 | 5812, 4510, 2455 |
Rint | 0.043 | 0.061 | 0.023 | 0.037 |
(sin θ/λ)max (Å−1) | 0.625 | 0.617 | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.105, 1.00 | 0.067, 0.200, 1.08 | 0.049, 0.104, 1.03 | 0.057, 0.149, 1.02 |
No. of reflections | 4267 | 4047 | 4365 | 4510 |
No. of parameters | 273 | 282 | 327 | 335 |
No. of restraints | 0 | 0 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
| w = 1/[σ2(Fo2) + (0.0333P)2 + 1.0734P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.1P)2 where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0238P)2 + 11.4647P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0641P)2 + 0.8649P] where P = (Fo2 + 2Fc2)/3 |
Δρmax, Δρmin (e Å−3) | 0.26, −0.27 | 1.46, −0.38 | 0.37, −0.32 | 0.36, −0.45 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C28—H28C···O1i | 0.96 | 2.55 | 3.482 (5) | 163 |
Symmetry code: (i) x−1/2, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O1 | 0.93 | 2.52 | 3.022 (6) | 114 |
C21—H21···N3 | 0.93 | 2.48 | 2.802 (6) | 100 |
C23—H23···N7 | 0.93 | 2.43 | 2.756 (6) | 101 |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O1 | 0.93 | 2.35 | 2.967 (7) | 124 |
C11—H11···N3 | 0.93 | 2.39 | 2.742 (7) | 102 |
Comparison of selected distances, torsion angles and angles between mean planes (Å and °) for (I), (II), (III) and (IV) topGeometric parameter | (I) | (II) | (III) | (IV) |
Br1-C8 | 1.864 (4) | 1.873 (6) | 1.870 (4) | 1.878 (5) |
O1-C1 | 1.189 (5) | 1.181 (7) | 1.201 (4) | 1.198 (5) |
N3-O2[N2] | 1.454 (4) | 1.451 (7) | 1.408 (4) | 1.397 (5) |
N3-C4 | 1.286 (4) | 1.275 (7) | 1.288 (5) | 1.298 (6) |
C4-C10[C16] | 1.455 (5) | 1.483 (8) | 1.467 (5) | 1.450 (6) |
N6-N7 | 1.418 (4) | 1.412 (7) | 1.406 (4) | 1.398 (5) |
N6-C16[C22] | 1.422 (5) | 1.420 (8) | 1.428 (6) | 1.404 (6) |
N7-C8 | 1.273 (5) | 1.272 (8) | 1.272 (5) | 1.257 (6) |
N3-C4-C10[C16]-C15[C21] | 146.3 (4) | 8.4 (9) | 1.8 (6) | -16.5 (7) |
C5-C4-C10[C16]-C15[C21] | -43.2 (6) | -173.2 (6) | 175.2 (4) | 156.2 (5) |
N3-C4-C10[C16]-C11[C21] | -32.6 (6) | -171.9 (6) | -177.2 (4) | 163.2 (5) |
C5-C4-C10[C16]-C11[C21] | 138.0 (4) | 6.5 (9) | -3.8 (7) | -24.1 (7) |
N7-N6-C16[22]-C21[C23] | 175.0 (3) | 9.8 (8) | 6.6 (6) | 16.4 (7) |
C5-N6-C16[22]-C21[C23] | -51.4 (5) | 149.6 (6) | 145.7 (4) | 159.7 (4) |
N7-N6-C16[22]-C17[C27] | -2.2 (5) | -173.1 (5) | -175.6 (4) | -168.2 (4) |
C5-N6-C16[22]-C17[C27] | 131.4 (4) | -33.3 (8) | -36.5 (6) | -24.9 (7) |
O2[N2]-N3-C4-C5 | 4.5 (5) | 7.1 (7) | 5.1 (5) | 5.0 (5) |
O2[N3]-N3-C4-C10[C16] | 176.3 (3) | -174.3 (5) | 179.5 (3) | 178.9 (4) |
pyrazolone-N3Ph | | | 23.8 (2) | 5.2 (2) |
isox[pyr]azolone-C4Ph | 36.9 (1) | 9.2 (2) | 0.9 (2) | 19.7 (2) |
pyrazoline-N6Ph | 27.7 (1) | 24.2 (2) | 20.4 (2) | 9.9 (2) |
Numbers in square brackets indicate the corresponding atom numbers for (III) and (IV), when these differ from (I) and (II). |
Spirans are organic compounds often present in natural products (Oh et al., 2003). The creation of stereogenic quaternary C centres is a challenging task in organic chemistry, especially for spiro-centres (Hughes et al., 2001). Because of their ability to generate a surrounding asymmetrical space, spirans have been exploited for asymmetric synthesis, molecular recognition and catalysis. The synthesis of biologically active heterocyclic spiro compounds (Negoro et al., 1998) has mainly been addressed toward structures mimicking peptide β-turn secondary structures (Braña et al., 2002). This is of particular interest when the rigidly mimicked conformation is also the bioactive one. Furthermore, the non-peptide nature of spiro-compounds may prevent possible unwanted side-effects (Khalil et al., 1999).
The synthesis of a new dipolar intermediate, C-bromo-N-phenylnitrilimine, (Foti et al., 1999), enabled us to obtain, by cycloaddition with selected dipolarophiles, 3-bromopyrazoles with interesting biopharmacological properties. The introduction of a Br substituent might increase the biological activity of related derivatives. In this context, we report the crystal structures of the four title bromo compounds, (I)-(IV). These spiro compounds are composed of substituted isoxazolinone or pyrazolinone rings, connected to pyrazoline rings through the asymmetric spiro-centre C5. Beyond the spiro-centre, another asymmetric atom, C9, is present (Figs. 1–4). The CIP Please define configuration of this atom is always inverted with respect to the other asymmetric centre, C9. Therefore, the crystals of these compounds are (5R,9S)-(5S,9R) racemic mixtures, and all crystallize in centrosymmetric space groups. \sch
The structures of (I) and (II) are very similar, as are those of (III) and (IV), as they differ only in the para-substituent of the aromatic ring attached to C9. Since the four conformations are reasonably similar, we will discuss these two pairs together, reporting the four respective values for each mentioned geometric parameter or referring to the comparative table listed below (Table 4). The two core rings are oriented almost perpendicular to one another, with the angles between their mean planes being 89.0 (1), 88.5 (2), 87.7 (1) and 88.6 (2)°, respectively.
The isoxazolinone rings, in (I) and (II), and the pyrazolinone rings, in (III) and (IV), are less puckered [maximum deviations from the mean plane for atom C1 are 0.045 (4), 0.066 (6), 0.081 (4) and 0.040 (4) Å, respectively] than the corresponding pyrazoline rings, which show a slight envelope-like distortion: atom C5 is always above the mean plane, by 0.197 (4), 0.094 (6), 0.142 (4) and 0.143 (4) Å, respectively. Cremer & Pople (1975) puckering parameters for the C5/N6/N7/C8/C9 ring are q2 = 0.287 (3), 0.142 (5), 0.214 (4) and 0.239 (4) Å, respectively, and ϕ2 = −5.9 (7), 5(2), −2(1) and −6(1)°, respectively. This is expected because of the further chiral sp3-hybridized endocyclic C atom present in pyrazolines.
The aromatic rings conjugated with endocyclic double bonds or sp2-hybridized atoms tend to lie on the same plane of the attached core rings, developing extended π conjugations. On the other hand, these are partially hampered because of steric hindrance (see Table 4 for a comparison of torsion angles and angles between mean planes). These quasi-coplanar orientations of the aromatic rings are also supported by intramolecular dipolar interactions between aromatic ortho-H and electronegative N3, O1 and N7 atoms, which are sometimes cited as intramolecular hydrogen bonds (see Tables 1–3).
In compound (I), the packing is mainly characterized by an unusual intermolecular interaction between atom Br1 and the N3—O2 bond [Br1···O2i 3.310 (3) and Br1···N3i 3.377 (3) Å; symmetry code: (i) 3/2 − x, y − 1/2, z], which may be interpreted as a stabilizing intermolecular combination between a Br atomic orbital and the lowest unoccupied molecular anti-bonding orbital centred on the C═N—O system of the next molecule along the crystallographic screw b axis (Fig. 4). Other weak dipolar interactions and a hydrogen bond (Table 1) contribute to the three-dimensional packing.
In compound (II), the three-dimensional structure is generated by weak intermolecular dipolar interactions. As usual for these systems, there is an interaction between the carbonyl O atom and the methyl group of another molecule. Although it is too weak to be considered as a hydrogen bond [C28···O1 3.376 (9) and H28···O1 2.644 (5) Å, and C28—H28···O1 133.3 (4)°], it is doubled because it occurs between objects related by a symmetry inversion centre, thus sorting dimers with an R22(22) first-order graph-set (Fig. 5).
The crystal packing of (III) is dominated by dipolar interactions. Among these, we mention the intermolecular interaction between atom H27 and the Cl atom of another molecule, which could be interpreted as a weak hydrogen-bond interaction creating one-dimensional C(11) chains along the [101] axis (Fig. 6).
The structure of (IV) presented more refinement problems, because of the presence of small amounts (about 10–15%, varying across the several tested samples) of a side product which occupy the same crystallographic site, but bearing another Br atom substituted on the aromatic C25 atom (Fig. 3). These molecules are embedded in the lattice packing (atom Br2 interacts with the aromatic π system of other molecules). Several polar and dipolar interactions support the overall crystal packing.
Table 1. Hydrogen-bonding geometry for (I) (Å, °).
Table 2. Short intramolecular contacts for (III) (Å, °).
Table 3. Short intramolecular contacts for (IV) (Å, °).
Table 4. Comparison of selected distances, torsion angles and angles between mean planes (Å, °) for (I), (II), (III) and (IV).