Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107053619/ln3061sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107053619/ln3061IVsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107053619/ln3061Vsup3.hkl |
CCDC references: 672558; 672559
Compound (III) was prepared following the literature protocol (Huisgen et al., 1977); compounds (IV) and (V) were synthesized from (III) and commercial norbornene (Huisgen & Eckell, 1977a) or methyl α-chloroarylate (Huisgen & Eckell, 1977b), respectively, according to the procedure reported by Huisgen et al. (1977)??. Crystals suitable for X-ray measurement were obtained by slow evaporation from a dichloromethane/methanol (1:3) mixture. The melting points are 458–459 K for (IV) and 454–455 K for (V) [the previously reported melting points were 461–462 K for (IV) (Huisgen & Eckell, 1977a) and 456–457 K for (V) (Huisgen & Eckell, 1977b)]. The melting points were determined in a capillary using a MELT-TEMP II aparatus (Aldrich) and are uncorrected.
All H atoms were positioned geometrically and refined with a riding model. In (IV), Uiso(H) values were constrained to 1.2Ueq(C), with C—H distances of 0.98, 0.97 and 0.93 Å for methine, methylene and aromatic groups, respectively. In (V), for methyl H atoms, Uiso(H) values were constrained to 1.5Ueq(C), with C—H distances of 0.98 Å; the C—H distances are 0.95 and 0.99 Å for the aromatic and methylene groups, respectively, with Uiso(H) values constrained to 1.2Ueq(C).
Azomethine imines, (I), belong to the class of well known and widely applied 1,3-dipoles (Grashey, 1984). They undergo (2 + 3)-cycloadditions with both electron-rich and electron-deficient ethylene derivatives to yield the corresponding 1,2-pyrazolidine derivatives of type (II). N-cyano substituted pyrazolidines are of interest because of their expected biological activity; for example, some of them were tested as cathepsin K inhibitors for the treatment of osteoporosis (Deaton et al., 2005). The mechanism of the (2 + 3)-cycloaddition in the case of azomethine imines is believed to follow the concerted pathway that results in stereospecific formation of the final cycloadducts (Huisgen & Eckell, 1977a). For the purposes of organic synthesis, an especially attractive group is the relatively stable and reactive azomethine imines of type (III) prepared from 4-chlorophenyldiazocyanide and diaryl derivatives of diazomethane, described for the first time by Huisgen et al. (1977). The yellow crystalline C-(2,2'-biphenylylene)-Nα-(4-chlorophenyl)-Nβ-cyanoazomthine imine, (III), reacts smoothly with norbornene and methyl α-chloroacrylate to affort the expected (2 + 3)-cycloadducts (IV) and (V), respectively, in high yields. The streochemical structures of the isolated products were initially established by Huisgen and co-workers on the basis of the spectroscopic data (Huisgen et al., 1977; Huisgen & Eckell, 1977b). The (2 + 3)-cycloaddition with norbornene was reported to give the exo-oriented cycloadduct (Huisgen & Eckell, 1977a). In the case of the product obtained from methyl α-chloroacrylate, the reaction was reported to lead mainly to the sterically more crowded regioisomer (V); the minor product corresponding to the structure (VI) was found in the mother liquor after separation of (V) (Huisgen & Eckell, 1977b). The goal of the present work was to resynthesize pyrazolidines (IV) and (V) and to confirm their structures and the predicted substitution pattern in the pyrazolidine ring by X-ray diffraction analysis. Other features related to the intermolecular interactions were also of interest.
Compound (IV) (Fig. 1) crystalizes with one molecule and compound (V) (Fig. 2) with two independent molecules in the asymmetric unit [(V-A) and (V-B)]. The weighted r.m.s. fit of the non-H atoms from the two molecules of (V) is 2.88 Å (Mackay, 1984). The largest deviation from perfect overlap is observed for the fluorene group. The molecules of both compounds contain the pyrazolidine ring as a relevant fragment of the structure. The substituents at atoms C3, N1 and N2 in both compounds are identical, as they originate from the same 1,3-dipole, (IIIa). In the molecule of (IV), the norbornane ring is fused with the heterocyclic ring, and in the case of (V), the Cl atom and ester group are bonded to atom C4. Thus, the regiochemical structure attributed to (V) by Huisgen & Eckell (1977a) was correct. Moreover, the structure of (IV) shows that the pyrazolidine ring is exo-oriented with respect to the norbornane skeleton. It is worth mentioning that an analogous orientation was proposed for (2 + 3)-cycloadducts obtained from norbornene and other 1,3-dipoles, for example, diphenylnitrilimine, benzonitrile N-oxide (Huisgen et al., 1967) and methyl diazoacetate (Gorpinchenko et al., 2006).
The sums of the bond angles around atom N1 [atom N101 in (V-B)] are 343 (1), 336 (1) and 336 (1)° for (IV), (V-A) and (V-B), respectively, while the corresponding angle sums around atom N2 [atom N102 in (V-B)] are 324 (1), 342 (1) and 343 (1)°, respectively. These values indicate significant pyramidalization at these N atoms. A similar pyramidalization about the N-cyano N atom is found in other heterocyclic compounds containing the –N—C≡N group (Bird et al., 1995). In contrast, the amine N atom of the parent cyanamide, CH2N2, has a geometry that is somewhat flatter; the sums of the bond angles were found to be 356 (2)° in a low-temperature X-ray study (Denner et al., 1988), and 349.3 (7) and 349.6 (7)° in a study based on neutron data and an X-ray multipole refinement, respectively, for a host–guest complex of cyanamide in 18-crown-6 (Koritsanszky et al., 1991).
The pyrazolidine ring in each compound is nonplanar, as the three C atoms and two N atoms are sp3-hybridized. In (IV), this ring adopts a twisted conformation, with the pseudo-twofold axis passing through the mid-point of the N2—C3 bond and atom C5. For (IV), the puckering parameters (Cremer & Pople, 1975) for the atom sequence N1—N2—C3—C4—C5 are q2 = 0.385 (1) Å and φ2 = 229.8 (2)° [asymmetry parameter (Nardelli, 1983) Δ2 = 0.019 (1)]. The substituents at atoms N1 and N2 occupy equatorial positions, while atoms C41 and C44 are in axial positions with respect to the pyrazolidine ring. The pyrazolidine ring of (V) adopts an envelope conformation in molecule A, with a pseudo-mirror passing through atom C4 and the mid-point of the N1—N2 bond. In molecule B, the ring has a twisted conformation, with the pseudo-twofold axis passing through the mid-point of the C104—C105 bond and atom N102. For (V-A), the puckering parameters for the atom sequence N1—N2—C3—C4—C5 are q2 = 0.400 (2) Å and φ2 = 295.1 (3)° [asymmetry parameter Δs = 0.041 (1)], while for (V-B) the puckering parameters for the atom sequence N101—N102—C103—C104—C105 are q2 = 0.389 (2) Å and φ2 = 128.4 (3)° [Δ2 = 0.013 (1)]. The different puckering of the pyrazolidine rings of molecules A and B causes differences in the orientations of the substituents. The cyano group at atom N1 is nearly axial and perfectly axial at atom N101. In both molecules of compound (V), the chlorophenyl substituent at atom N2 (N102) occupies a nearly equatorial position, while the Cl and ester substituents at atom C4 (C104) occupy axial and equatorial positions, respectively.
The bonds distances and angles in both molecules are mostly in good agreement with expected values (Allen et al., 1987). However, the N—N bond distances are longer than expected. The long N1—N2 bond of 1.4785 (15) Å in (IV) and 1.458 (3) and 1.445 (3) Å for (V-A) and (V-B), respectively, may be caused by the influence of the cyano and chlorophenyl substituents on the pyrazolidine ring. Moreover, a search of the Cambridge Structural Database (Version 5.28 of November 2006; Allen, 2002) for structures containing the pyrazolidine fragment (Scheme 2), revealed a range of N—N bond lengths from 1.387 to 1.514 Å for 42 structures. The search was limited to ordered structures, without errors, with R less than 0.05 and an average bond length s.u. smaller than 0.005 Å.
In (IV), atom N7i [symmetry code: (i) x - 1, y, z] is involved in an unconventional C17—H17···N7i hydrogen bond, which links the molecules into chains along the [100] direction (Fig. 2). This generates a graph-set motif of C(9) (Etter et al., 1990). In contrast, molecules A and B in (V) are linked into dimers by a weak C5—H5B···N107 interaction; atom N7 does not act as an acceptor in any interaction. In addition, some weak nonclassical intermolecular C—H···O, C—H···Cl and C—H···π interactions are observed. For (IV), a C—H···π interaction (see Table 1, where Cg1 is defined by atoms C8–C13 in one of the six-membered rings of the fluorene group) involves pairs of molecules related by a centre of inversion. For (V) (see Table 2, where Cg2 is defined by atoms C121–C126 in the chlorophenyl ring of molecule B), all interactions emanate from H atoms solely in molecule A and the acceptor atoms are in one adjacent molecule A and three different B molecules.
For related literature, see: Allen et al. (1987); Bird et al. (1995); Cremer & Pople (1975); Deaton et al. (2005); Denner et al. (1988); Etter et al. (1990); Gorpinchenko et al. (2006); Grashey (1984); Huisgen & Eckell (1977a, 1977b); Huisgen et al. (1967, 1977); Koritsanszky et al. (1991); Mackay (1984); Nardelli (1983).
For both compounds, data collection: X-AREA (Stoe & Cie, 2000); cell refinement: X-AREA (Stoe & Cie, 2000); data reduction: X-AREA (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and WinGX (Farrugia, 1999).
C27H22ClN3 | F(000) = 888 |
Mr = 423.93 | Dx = 1.330 Mg m−3 |
Monoclinic, P21/n | Melting point = 458–459 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0914 (9) Å | Cell parameters from 17870 reflections |
b = 12.6225 (9) Å | θ = 2.0–28.0° |
c = 18.5025 (17) Å | µ = 0.20 mm−1 |
β = 94.576 (8)° | T = 173 K |
V = 2116.5 (3) Å3 | Plate, colorless |
Z = 4 | 0.35 × 0.15 × 0.10 mm |
Stoe IPDSII image-plate diffractometer | 3437 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.046 |
Graphite monochromator | θmax = 28.0°, θmin = 2.0° |
Detector resolution: 150 pixels mm-1 | h = −12→11 |
phi–scan | k = −16→16 |
17870 measured reflections | l = −24→24 |
5071 independent reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 0.85 | w = 1/[σ2(Fo2) + (0.048P)2P] where P = (Fo2 + 2Fc2)/3 |
5071 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C27H22ClN3 | V = 2116.5 (3) Å3 |
Mr = 423.93 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.0914 (9) Å | µ = 0.20 mm−1 |
b = 12.6225 (9) Å | T = 173 K |
c = 18.5025 (17) Å | 0.35 × 0.15 × 0.10 mm |
β = 94.576 (8)° |
Stoe IPDSII image-plate diffractometer | 3437 reflections with I > 2σ(I) |
17870 measured reflections | Rint = 0.046 |
5071 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 0.85 | Δρmax = 0.24 e Å−3 |
5071 reflections | Δρmin = −0.30 e Å−3 |
280 parameters |
Experimental. The melting points were determined in a capillary using a MELT-TEMP II aparatus (Aldrich) and are uncorrected. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.87311 (5) | 0.11946 (3) | −0.00430 (2) | 0.05128 (12) | |
N1 | 0.98927 (12) | 0.52950 (9) | 0.22082 (6) | 0.0268 (2) | |
N2 | 0.98726 (11) | 0.41725 (9) | 0.24356 (6) | 0.0257 (2) | |
N7 | 1.16985 (13) | 0.57955 (11) | 0.13209 (7) | 0.0395 (3) | |
C3 | 0.88134 (13) | 0.41965 (10) | 0.30181 (7) | 0.0258 (3) | |
C4 | 0.92074 (14) | 0.52415 (10) | 0.34305 (7) | 0.0263 (3) | |
C5 | 0.97717 (14) | 0.59945 (10) | 0.28499 (7) | 0.0278 (3) | |
C6 | 1.09251 (14) | 0.55351 (11) | 0.17522 (7) | 0.0289 (3) | |
C8 | 0.88944 (14) | 0.32163 (10) | 0.34974 (7) | 0.0258 (3) | |
C9 | 1.01144 (14) | 0.26909 (11) | 0.38226 (7) | 0.0295 (3) | |
C10 | 0.98917 (16) | 0.18330 (11) | 0.42741 (7) | 0.0335 (3) | |
C11 | 0.84759 (17) | 0.15246 (11) | 0.44121 (8) | 0.0356 (3) | |
C12 | 0.72473 (15) | 0.20380 (11) | 0.40816 (7) | 0.0319 (3) | |
C13 | 0.74640 (14) | 0.28726 (10) | 0.36132 (7) | 0.0267 (3) | |
C14 | 0.64008 (14) | 0.34921 (10) | 0.31423 (7) | 0.0264 (3) | |
C15 | 0.48729 (14) | 0.34112 (11) | 0.30279 (7) | 0.0309 (3) | |
C16 | 0.41476 (14) | 0.40404 (11) | 0.24961 (8) | 0.0320 (3) | |
C17 | 0.49150 (15) | 0.47640 (11) | 0.21067 (8) | 0.0326 (3) | |
C18 | 0.64356 (14) | 0.48758 (11) | 0.22397 (7) | 0.0299 (3) | |
C19 | 0.71749 (13) | 0.42251 (10) | 0.27511 (7) | 0.0261 (3) | |
C21 | 0.94928 (13) | 0.34853 (11) | 0.18262 (7) | 0.0267 (3) | |
C22 | 0.89651 (15) | 0.38424 (12) | 0.11386 (7) | 0.0329 (3) | |
C23 | 0.87376 (15) | 0.31408 (12) | 0.05658 (8) | 0.0362 (3) | |
C24 | 0.89965 (14) | 0.20786 (12) | 0.06802 (8) | 0.0342 (3) | |
C25 | 0.94877 (15) | 0.17005 (12) | 0.13625 (8) | 0.0332 (3) | |
C26 | 0.97558 (14) | 0.24055 (11) | 0.19278 (7) | 0.0299 (3) | |
C41 | 1.04854 (14) | 0.52596 (11) | 0.40332 (7) | 0.0282 (3) | |
C42 | 1.04121 (16) | 0.63363 (11) | 0.44139 (7) | 0.0337 (3) | |
C43 | 1.08754 (18) | 0.71289 (12) | 0.38289 (8) | 0.0410 (4) | |
C44 | 1.12461 (15) | 0.63977 (11) | 0.32058 (7) | 0.0338 (3) | |
C45 | 1.18516 (14) | 0.54153 (12) | 0.36118 (7) | 0.0330 (3) | |
H4 | 0.8317 | 0.5540 | 0.3617 | 0.032* | |
H5 | 0.9080 | 0.6579 | 0.2738 | 0.033* | |
H9 | 1.1064 | 0.2908 | 0.3740 | 0.035* | |
H10 | 1.0700 | 0.1463 | 0.4485 | 0.040* | |
H11 | 0.8347 | 0.0967 | 0.4730 | 0.043* | |
H12 | 0.6300 | 0.1827 | 0.4173 | 0.038* | |
H15 | 0.4349 | 0.2947 | 0.3301 | 0.037* | |
H16 | 0.3132 | 0.3975 | 0.2400 | 0.038* | |
H17 | 0.4409 | 0.5179 | 0.1753 | 0.039* | |
H18 | 0.6946 | 0.5378 | 0.1990 | 0.036* | |
H22 | 0.8765 | 0.4559 | 0.1065 | 0.040* | |
H23 | 0.8412 | 0.3386 | 0.0107 | 0.043* | |
H25 | 0.9635 | 0.0978 | 0.1438 | 0.040* | |
H26 | 1.0116 | 0.2158 | 0.2381 | 0.036* | |
H41 | 1.0527 | 0.4645 | 0.4358 | 0.034* | |
H42A | 1.1090 | 0.6363 | 0.4846 | 0.040* | |
H42B | 0.9421 | 0.6483 | 0.4546 | 0.040* | |
H43A | 1.0073 | 0.7606 | 0.3677 | 0.049* | |
H43B | 1.1728 | 0.7541 | 0.4008 | 0.049* | |
H44 | 1.1907 | 0.6707 | 0.2870 | 0.041* | |
H45B | 1.2736 | 0.5561 | 0.3925 | 0.040* | |
H45A | 1.2020 | 0.4828 | 0.3291 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0585 (3) | 0.0538 (3) | 0.0408 (2) | 0.00231 (19) | −0.00080 (17) | −0.02135 (19) |
N1 | 0.0300 (5) | 0.0277 (6) | 0.0234 (5) | −0.0006 (4) | 0.0053 (4) | 0.0024 (5) |
N2 | 0.0282 (5) | 0.0262 (6) | 0.0229 (5) | 0.0003 (4) | 0.0040 (4) | 0.0010 (4) |
N7 | 0.0352 (6) | 0.0487 (8) | 0.0356 (7) | 0.0021 (6) | 0.0086 (5) | 0.0090 (6) |
C3 | 0.0262 (6) | 0.0281 (7) | 0.0236 (6) | 0.0013 (5) | 0.0041 (5) | 0.0007 (5) |
C4 | 0.0275 (6) | 0.0270 (7) | 0.0249 (6) | 0.0008 (5) | 0.0053 (5) | 0.0003 (5) |
C5 | 0.0321 (7) | 0.0268 (7) | 0.0249 (6) | 0.0015 (5) | 0.0040 (5) | −0.0001 (5) |
C6 | 0.0280 (6) | 0.0324 (7) | 0.0261 (6) | 0.0018 (5) | 0.0005 (5) | 0.0032 (6) |
C8 | 0.0310 (6) | 0.0256 (7) | 0.0211 (6) | 0.0001 (5) | 0.0034 (5) | −0.0029 (5) |
C9 | 0.0310 (7) | 0.0314 (7) | 0.0260 (6) | 0.0015 (5) | 0.0017 (5) | −0.0026 (6) |
C10 | 0.0425 (8) | 0.0293 (7) | 0.0276 (7) | 0.0057 (6) | −0.0035 (6) | −0.0008 (6) |
C11 | 0.0520 (9) | 0.0269 (7) | 0.0276 (7) | −0.0037 (6) | 0.0013 (6) | 0.0007 (6) |
C12 | 0.0387 (7) | 0.0297 (7) | 0.0278 (7) | −0.0058 (6) | 0.0052 (6) | −0.0012 (6) |
C13 | 0.0309 (7) | 0.0263 (7) | 0.0234 (6) | −0.0003 (5) | 0.0040 (5) | −0.0036 (5) |
C14 | 0.0302 (6) | 0.0252 (6) | 0.0243 (6) | 0.0007 (5) | 0.0048 (5) | −0.0049 (5) |
C15 | 0.0300 (7) | 0.0316 (7) | 0.0318 (7) | −0.0026 (5) | 0.0076 (5) | −0.0058 (6) |
C16 | 0.0248 (6) | 0.0355 (8) | 0.0356 (7) | 0.0019 (5) | 0.0022 (5) | −0.0090 (6) |
C17 | 0.0312 (7) | 0.0338 (8) | 0.0325 (7) | 0.0066 (6) | −0.0004 (5) | −0.0017 (6) |
C18 | 0.0310 (7) | 0.0289 (7) | 0.0298 (7) | 0.0019 (5) | 0.0032 (5) | 0.0007 (6) |
C19 | 0.0266 (6) | 0.0263 (6) | 0.0257 (6) | 0.0012 (5) | 0.0036 (5) | −0.0032 (5) |
C21 | 0.0234 (6) | 0.0313 (7) | 0.0256 (6) | 0.0013 (5) | 0.0028 (5) | −0.0025 (5) |
C22 | 0.0346 (7) | 0.0340 (8) | 0.0296 (7) | 0.0047 (6) | −0.0018 (6) | −0.0002 (6) |
C23 | 0.0378 (7) | 0.0446 (9) | 0.0254 (7) | 0.0042 (6) | −0.0028 (6) | −0.0033 (6) |
C24 | 0.0301 (7) | 0.0411 (8) | 0.0314 (7) | −0.0008 (6) | 0.0029 (5) | −0.0109 (6) |
C25 | 0.0330 (7) | 0.0309 (7) | 0.0363 (7) | 0.0012 (6) | 0.0075 (6) | −0.0033 (6) |
C26 | 0.0309 (7) | 0.0336 (7) | 0.0258 (6) | 0.0029 (5) | 0.0046 (5) | 0.0010 (6) |
C41 | 0.0328 (7) | 0.0293 (7) | 0.0225 (6) | −0.0020 (5) | 0.0030 (5) | 0.0006 (6) |
C42 | 0.0422 (8) | 0.0333 (7) | 0.0257 (7) | −0.0049 (6) | 0.0042 (6) | −0.0020 (6) |
C43 | 0.0586 (10) | 0.0329 (8) | 0.0316 (7) | −0.0104 (7) | 0.0051 (7) | −0.0010 (7) |
C44 | 0.0380 (7) | 0.0372 (8) | 0.0268 (7) | −0.0106 (6) | 0.0068 (5) | 0.0009 (6) |
C45 | 0.0287 (7) | 0.0419 (8) | 0.0281 (7) | −0.0028 (6) | −0.0001 (5) | −0.0022 (6) |
Cl1—C24 | 1.7442 (14) | C44—H44 | 0.9800 |
N2—C21 | 1.4425 (17) | C21—C26 | 1.3939 (19) |
N2—N1 | 1.4785 (15) | C41—C45 | 1.5311 (18) |
N2—C3 | 1.5019 (16) | C41—C42 | 1.5345 (19) |
N1—C6 | 1.3458 (17) | C41—H41 | 0.9800 |
N1—C5 | 1.4907 (16) | C24—C23 | 1.375 (2) |
C4—C41 | 1.5451 (18) | C24—C25 | 1.390 (2) |
C4—C3 | 1.5515 (18) | C23—H23 | 0.9300 |
C4—C5 | 1.5518 (18) | C26—C25 | 1.3801 (19) |
C4—H4 | 0.9800 | C26—H26 | 0.9300 |
C13—C12 | 1.3882 (19) | C11—C10 | 1.388 (2) |
C13—C8 | 1.4035 (17) | C11—H11 | 0.9300 |
C13—C14 | 1.4732 (18) | C9—C8 | 1.3876 (18) |
C19—C18 | 1.3858 (18) | C9—C10 | 1.3923 (19) |
C19—C14 | 1.3987 (18) | C9—H9 | 0.9300 |
C19—C3 | 1.5319 (17) | C42—C43 | 1.5565 (19) |
C5—C44 | 1.5325 (18) | C42—H42A | 0.9700 |
C5—H5 | 0.9800 | C42—H42B | 0.9700 |
C3—C8 | 1.5205 (18) | C18—C17 | 1.3918 (19) |
C6—N7 | 1.1527 (17) | C18—H18 | 0.9300 |
C12—C11 | 1.390 (2) | C16—C17 | 1.386 (2) |
C12—H12 | 0.9300 | C16—H16 | 0.9300 |
C22—C23 | 1.384 (2) | C17—H17 | 0.9300 |
C22—C21 | 1.3980 (18) | C10—H10 | 0.9300 |
C22—H22 | 0.9300 | C25—H25 | 0.9300 |
C15—C16 | 1.389 (2) | C43—H43A | 0.9700 |
C15—C14 | 1.3920 (18) | C43—H43B | 0.9700 |
C15—H15 | 0.9300 | C45—H45B | 0.9700 |
C44—C45 | 1.529 (2) | C45—H45A | 0.9700 |
C44—C43 | 1.535 (2) | ||
C21—N2—N1 | 111.19 (9) | C23—C24—C25 | 120.90 (13) |
C21—N2—C3 | 116.47 (10) | C23—C24—Cl1 | 119.62 (11) |
N1—N2—C3 | 102.01 (9) | C25—C24—Cl1 | 119.47 (11) |
C6—N1—N2 | 114.78 (10) | C24—C23—C22 | 119.53 (13) |
C6—N1—C5 | 117.74 (11) | C24—C23—H23 | 120.2 |
N2—N1—C5 | 109.73 (9) | C22—C23—H23 | 120.2 |
C41—C4—C3 | 119.89 (11) | C25—C26—C21 | 120.67 (13) |
C41—C4—C5 | 102.68 (10) | C25—C26—H26 | 119.7 |
C3—C4—C5 | 104.86 (10) | C21—C26—H26 | 119.7 |
C41—C4—H4 | 109.6 | C10—C11—C12 | 120.86 (13) |
C3—C4—H4 | 109.6 | C10—C11—H11 | 119.6 |
C5—C4—H4 | 109.6 | C12—C11—H11 | 119.6 |
C12—C13—C8 | 120.62 (12) | C8—C9—C10 | 118.85 (12) |
C12—C13—C14 | 130.76 (12) | C8—C9—H9 | 120.6 |
C8—C13—C14 | 108.53 (11) | C10—C9—H9 | 120.6 |
C18—C19—C14 | 120.58 (12) | C41—C42—C43 | 103.06 (11) |
C18—C19—C3 | 129.82 (12) | C41—C42—H42A | 111.2 |
C14—C19—C3 | 109.51 (11) | C43—C42—H42A | 111.2 |
N1—C5—C44 | 114.92 (11) | C41—C42—H42B | 111.2 |
N1—C5—C4 | 103.77 (10) | C43—C42—H42B | 111.2 |
C44—C5—C4 | 103.42 (10) | H42A—C42—H42B | 109.1 |
N1—C5—H5 | 111.4 | C19—C18—C17 | 118.78 (12) |
C44—C5—H5 | 111.4 | C19—C18—H18 | 120.6 |
C4—C5—H5 | 111.4 | C17—C18—H18 | 120.6 |
N2—C3—C8 | 113.46 (10) | C17—C16—C15 | 120.98 (12) |
N2—C3—C19 | 115.58 (10) | C17—C16—H16 | 119.5 |
C8—C3—C19 | 102.00 (10) | C15—C16—H16 | 119.5 |
N2—C3—C4 | 103.53 (10) | C9—C8—C13 | 120.29 (12) |
C8—C3—C4 | 113.98 (10) | C9—C8—C3 | 129.92 (11) |
C19—C3—C4 | 108.60 (10) | C13—C8—C3 | 109.76 (11) |
N7—C6—N1 | 173.07 (14) | C16—C17—C18 | 120.60 (13) |
C13—C12—C11 | 118.64 (12) | C16—C17—H17 | 119.7 |
C13—C12—H12 | 120.7 | C18—C17—H17 | 119.7 |
C11—C12—H12 | 120.7 | C11—C10—C9 | 120.65 (13) |
C23—C22—C21 | 120.66 (13) | C11—C10—H10 | 119.7 |
C23—C22—H22 | 119.7 | C9—C10—H10 | 119.7 |
C21—C22—H22 | 119.7 | C15—C14—C19 | 120.46 (12) |
C16—C15—C14 | 118.50 (12) | C15—C14—C13 | 130.59 (12) |
C16—C15—H15 | 120.7 | C19—C14—C13 | 108.89 (11) |
C14—C15—H15 | 120.7 | C26—C25—C24 | 119.45 (13) |
C45—C44—C5 | 102.12 (11) | C26—C25—H25 | 120.3 |
C45—C44—C43 | 102.15 (11) | C24—C25—H25 | 120.3 |
C5—C44—C43 | 106.59 (12) | C44—C43—C42 | 102.93 (11) |
C45—C44—H44 | 114.8 | C44—C43—H43A | 111.2 |
C5—C44—H44 | 114.8 | C42—C43—H43A | 111.2 |
C43—C44—H44 | 114.8 | C44—C43—H43B | 111.2 |
C26—C21—C22 | 118.74 (12) | C42—C43—H43B | 111.2 |
C26—C21—N2 | 117.05 (11) | H43A—C43—H43B | 109.1 |
C22—C21—N2 | 124.10 (12) | C44—C45—C41 | 94.55 (10) |
C45—C41—C42 | 100.77 (11) | C44—C45—H45B | 112.8 |
C45—C41—C4 | 103.19 (10) | C41—C45—H45B | 112.8 |
C42—C41—C4 | 106.66 (11) | C44—C45—H45A | 112.8 |
C45—C41—H41 | 114.9 | C41—C45—H45A | 112.8 |
C42—C41—H41 | 114.9 | H45B—C45—H45A | 110.3 |
C4—C41—H41 | 114.9 | ||
C21—N2—N1—C6 | −64.03 (13) | Cl1—C24—C23—C22 | −179.26 (11) |
C3—N2—N1—C6 | 171.13 (10) | C21—C22—C23—C24 | 1.8 (2) |
C21—N2—N1—C5 | 160.72 (10) | C22—C21—C26—C25 | −0.59 (19) |
C3—N2—N1—C5 | 35.87 (11) | N2—C21—C26—C25 | −176.97 (11) |
C6—N1—C5—C44 | −38.12 (16) | C13—C12—C11—C10 | −0.4 (2) |
N2—N1—C5—C44 | 95.65 (12) | C45—C41—C42—C43 | 37.96 (13) |
C6—N1—C5—C4 | −150.30 (11) | C4—C41—C42—C43 | −69.45 (13) |
N2—N1—C5—C4 | −16.53 (12) | C14—C19—C18—C17 | −1.94 (19) |
C41—C4—C5—N1 | 117.15 (10) | C3—C19—C18—C17 | −178.09 (13) |
C3—C4—C5—N1 | −8.88 (12) | C14—C15—C16—C17 | −2.56 (19) |
C41—C4—C5—C44 | −3.15 (13) | C10—C9—C8—C13 | −1.16 (18) |
C3—C4—C5—C44 | −129.18 (10) | C10—C9—C8—C3 | 176.52 (12) |
C21—N2—C3—C8 | 74.93 (13) | C12—C13—C8—C9 | 3.22 (19) |
N1—N2—C3—C8 | −163.82 (10) | C14—C13—C8—C9 | −173.71 (11) |
C21—N2—C3—C19 | −42.39 (15) | C12—C13—C8—C3 | −174.89 (11) |
N1—N2—C3—C19 | 78.86 (12) | C14—C13—C8—C3 | 8.18 (14) |
C21—N2—C3—C4 | −161.01 (10) | N2—C3—C8—C9 | 45.86 (18) |
N1—N2—C3—C4 | −39.75 (11) | C19—C3—C8—C9 | 170.85 (13) |
C18—C19—C3—N2 | −49.41 (18) | C4—C3—C8—C9 | −72.31 (16) |
C14—C19—C3—N2 | 134.10 (11) | N2—C3—C8—C13 | −136.26 (11) |
C18—C19—C3—C8 | −172.98 (13) | C19—C3—C8—C13 | −11.27 (13) |
C14—C19—C3—C8 | 10.53 (13) | C4—C3—C8—C13 | 105.56 (12) |
C18—C19—C3—C4 | 66.36 (17) | C15—C16—C17—C18 | 0.1 (2) |
C14—C19—C3—C4 | −110.13 (12) | C19—C18—C17—C16 | 2.2 (2) |
C41—C4—C3—N2 | −84.11 (13) | C12—C11—C10—C9 | 2.5 (2) |
C5—C4—C3—N2 | 30.38 (12) | C8—C9—C10—C11 | −1.65 (19) |
C41—C4—C3—C8 | 39.62 (15) | C16—C15—C14—C19 | 2.78 (19) |
C5—C4—C3—C8 | 154.11 (10) | C16—C15—C14—C13 | −174.00 (13) |
C41—C4—C3—C19 | 152.56 (11) | C18—C19—C14—C15 | −0.55 (19) |
C5—C4—C3—C19 | −92.95 (11) | C3—C19—C14—C15 | 176.32 (11) |
C8—C13—C12—C11 | −2.39 (19) | C18—C19—C14—C13 | 176.87 (12) |
C14—C13—C12—C11 | 173.77 (13) | C3—C19—C14—C13 | −6.26 (14) |
N1—C5—C44—C45 | −75.37 (13) | C12—C13—C14—C15 | −0.6 (2) |
C4—C5—C44—C45 | 37.01 (12) | C8—C13—C14—C15 | 175.91 (13) |
N1—C5—C44—C43 | 177.85 (11) | C12—C13—C14—C19 | −177.67 (13) |
C4—C5—C44—C43 | −69.76 (13) | C8—C13—C14—C19 | −1.16 (14) |
C23—C22—C21—C26 | −1.36 (19) | C21—C26—C25—C24 | 2.11 (19) |
C23—C22—C21—N2 | 174.74 (12) | C23—C24—C25—C26 | −1.7 (2) |
N1—N2—C21—C26 | 165.83 (10) | Cl1—C24—C25—C26 | 177.34 (10) |
C3—N2—C21—C26 | −77.91 (14) | C45—C44—C43—C42 | −32.57 (14) |
N1—N2—C21—C22 | −10.33 (16) | C5—C44—C43—C42 | 74.18 (14) |
C3—N2—C21—C22 | 105.93 (14) | C41—C42—C43—C44 | −3.34 (14) |
C3—C4—C41—C45 | 83.87 (13) | C5—C44—C45—C41 | −55.09 (11) |
C5—C4—C41—C45 | −31.76 (13) | C43—C44—C45—C41 | 55.09 (12) |
C3—C4—C41—C42 | −170.45 (10) | C42—C41—C45—C44 | −56.92 (11) |
C5—C4—C41—C42 | 73.93 (12) | C4—C41—C45—C44 | 53.22 (12) |
C25—C24—C23—C22 | −0.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17···N7i | 0.93 | 2.65 | 3.418 (1) | 141 |
C42—H42B···Cg1ii | 0.97 | 2.74 | 3.484 (2) | 134 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+1. |
C24H17Cl2N3O2 | F(000) = 1856 |
Mr = 450.31 | Dx = 1.444 Mg m−3 |
Monoclinic, P21/c | Melting point = 454–455 K |
Hall symbol: -P2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 11.1818 (5) Å | Cell parameters from 23396 reflections |
b = 13.2534 (4) Å | θ = 1.5–25.0° |
c = 28.1265 (11) Å | µ = 0.34 mm−1 |
β = 96.363 (3)° | T = 120 K |
V = 4142.6 (3) Å3 | Plate, colorless |
Z = 8 | 0.37 × 0.37 × 0.08 mm |
Stoe IPDSII image-plate diffractometer | 4866 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.045 |
Graphite monochromator | θmax = 25.0°, θmin = 1.5° |
Detector resolution: 150 pixels mm-1 | h = −13→13 |
phi–scan | k = −15→13 |
23396 measured reflections | l = −29→33 |
7295 independent reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.02 |
[exp(2.00(sinθ/λ)2)]/
[σ2(Fo2) + (0.0404P)2]
where P = 0.33333Fo2 + 0.66667Fc2 |
7295 reflections | (Δ/σ)max = 0.001 |
559 parameters | Δρmax = 0.84 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C24H17Cl2N3O2 | V = 4142.6 (3) Å3 |
Mr = 450.31 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.1818 (5) Å | µ = 0.34 mm−1 |
b = 13.2534 (4) Å | T = 120 K |
c = 28.1265 (11) Å | 0.37 × 0.37 × 0.08 mm |
β = 96.363 (3)° |
Stoe IPDSII image-plate diffractometer | 4866 reflections with I > 2σ(I) |
23396 measured reflections | Rint = 0.045 |
7295 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.84 e Å−3 |
7295 reflections | Δρmin = −0.41 e Å−3 |
559 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.19062 (6) | 0.29108 (7) | −0.19441 (2) | 0.04582 (19) | |
Cl2 | 0.16398 (5) | 0.21353 (5) | 0.11089 (2) | 0.02777 (14) | |
O42 | −0.03896 (18) | 0.42321 (14) | 0.13806 (7) | 0.0443 (5) | |
O43 | −0.05242 (15) | 0.25933 (14) | 0.15557 (6) | 0.0337 (4) | |
N1 | 0.13052 (15) | 0.34045 (15) | 0.01889 (7) | 0.0235 (4) | |
N2 | 0.03496 (15) | 0.26720 (14) | 0.00639 (7) | 0.0207 (4) | |
N7 | 0.33242 (17) | 0.26889 (17) | 0.00682 (8) | 0.0343 (5) | |
C3 | −0.03988 (18) | 0.25762 (17) | 0.04691 (8) | 0.0202 (5) | |
C4 | 0.04764 (18) | 0.30204 (17) | 0.08939 (8) | 0.0218 (5) | |
C5 | 0.11071 (19) | 0.38595 (18) | 0.06505 (9) | 0.0245 (5) | |
C6 | 0.2398 (2) | 0.29813 (18) | 0.01484 (9) | 0.0249 (5) | |
C8 | −0.08308 (19) | 0.15019 (17) | 0.05501 (8) | 0.0208 (5) | |
C9 | −0.0201 (2) | 0.06051 (19) | 0.05753 (9) | 0.0277 (5) | |
C10 | −0.0814 (2) | −0.02777 (19) | 0.06602 (10) | 0.0341 (6) | |
C11 | −0.2029 (2) | −0.0268 (2) | 0.07142 (10) | 0.0349 (6) | |
C12 | −0.2679 (2) | 0.06282 (19) | 0.06741 (9) | 0.0270 (5) | |
C13 | −0.20753 (19) | 0.15122 (17) | 0.05916 (8) | 0.0212 (5) | |
C14 | −0.25432 (18) | 0.25389 (17) | 0.04983 (8) | 0.0208 (5) | |
C15 | −0.37180 (19) | 0.28903 (18) | 0.04468 (8) | 0.0235 (5) | |
C16 | −0.3931 (2) | 0.38780 (19) | 0.03009 (9) | 0.0282 (5) | |
C17 | −0.2990 (2) | 0.45054 (19) | 0.02063 (9) | 0.0296 (5) | |
C18 | −0.18093 (19) | 0.41529 (17) | 0.02576 (9) | 0.0238 (5) | |
C19 | −0.15874 (18) | 0.31695 (17) | 0.04065 (8) | 0.0196 (5) | |
C21 | −0.02069 (18) | 0.27844 (17) | −0.04112 (8) | 0.0206 (5) | |
C22 | 0.03237 (19) | 0.33527 (19) | −0.07485 (9) | 0.0252 (5) | |
C23 | −0.0188 (2) | 0.3390 (2) | −0.12205 (9) | 0.0297 (6) | |
C24 | −0.1233 (2) | 0.2859 (2) | −0.13532 (9) | 0.0284 (5) | |
C25 | −0.17731 (19) | 0.22963 (19) | −0.10255 (9) | 0.0276 (5) | |
C26 | −0.12646 (18) | 0.22486 (18) | −0.05564 (8) | 0.0234 (5) | |
C41 | −0.0180 (2) | 0.33600 (19) | 0.13058 (9) | 0.0265 (5) | |
C44 | −0.1166 (2) | 0.2836 (2) | 0.19602 (10) | 0.0410 (7) | |
H5A | 0.0593 | 0.4468 | 0.0605 | 0.029* | |
H5B | 0.1879 | 0.4044 | 0.0837 | 0.029* | |
H9 | 0.0632 | 0.0591 | 0.0536 | 0.033* | |
H10 | −0.0391 | −0.0900 | 0.0681 | 0.041* | |
H11 | −0.2422 | −0.0880 | 0.0779 | 0.042* | |
H12 | −0.3518 | 0.0634 | 0.0703 | 0.032* | |
H15 | −0.4363 | 0.2463 | 0.0510 | 0.028* | |
H16 | −0.4732 | 0.4130 | 0.0265 | 0.034* | |
H17 | −0.3154 | 0.5180 | 0.0106 | 0.036* | |
H18 | −0.1167 | 0.4581 | 0.0191 | 0.029* | |
H22 | 0.1042 | 0.3718 | −0.0654 | 0.030* | |
H23 | 0.0177 | 0.3777 | −0.1450 | 0.036* | |
H25 | −0.2497 | 0.1940 | −0.1123 | 0.033* | |
H26 | −0.1632 | 0.1852 | −0.0331 | 0.028* | |
H44A | −0.1375 | 0.2212 | 0.2118 | 0.062* | |
H44B | −0.1903 | 0.3207 | 0.1849 | 0.062* | |
H44C | −0.0655 | 0.3255 | 0.2187 | 0.062* | |
Cl10 | 0.38337 (5) | 1.05566 (5) | 0.06729 (2) | 0.03142 (14) | |
Cl20 | 0.59140 (5) | 0.44562 (4) | 0.21560 (2) | 0.02571 (13) | |
O142 | 0.88978 (14) | 0.55891 (15) | 0.21929 (7) | 0.0373 (4) | |
O143 | 0.77694 (13) | 0.53999 (13) | 0.28001 (6) | 0.0295 (4) | |
N101 | 0.56634 (16) | 0.58986 (14) | 0.12830 (7) | 0.0233 (4) | |
N102 | 0.52678 (16) | 0.66505 (14) | 0.16034 (7) | 0.0212 (4) | |
N107 | 0.39892 (19) | 0.46855 (16) | 0.10314 (8) | 0.0352 (5) | |
C103 | 0.60186 (18) | 0.65814 (17) | 0.20784 (8) | 0.0209 (5) | |
C104 | 0.67443 (18) | 0.55739 (18) | 0.20260 (8) | 0.0221 (5) | |
C105 | 0.6853 (2) | 0.55400 (19) | 0.14912 (9) | 0.0265 (5) | |
C106 | 0.4775 (2) | 0.52116 (19) | 0.11662 (9) | 0.0266 (5) | |
C108 | 0.68960 (18) | 0.74592 (17) | 0.21934 (8) | 0.0216 (5) | |
C109 | 0.76794 (19) | 0.79090 (19) | 0.19067 (9) | 0.0281 (5) | |
C110 | 0.8362 (2) | 0.8723 (2) | 0.20904 (10) | 0.0345 (6) | |
C111 | 0.8273 (2) | 0.90848 (19) | 0.25489 (10) | 0.0338 (6) | |
C112 | 0.7478 (2) | 0.86407 (18) | 0.28362 (9) | 0.0288 (6) | |
C113 | 0.67825 (18) | 0.78260 (17) | 0.26526 (8) | 0.0228 (5) | |
C114 | 0.58043 (18) | 0.72768 (17) | 0.28501 (8) | 0.0215 (5) | |
C115 | 0.5323 (2) | 0.73906 (18) | 0.32810 (9) | 0.0257 (5) | |
C116 | 0.4319 (2) | 0.68254 (19) | 0.33569 (9) | 0.0275 (5) | |
C117 | 0.3798 (2) | 0.61718 (18) | 0.30117 (9) | 0.0261 (5) | |
C118 | 0.42796 (18) | 0.60483 (17) | 0.25806 (8) | 0.0222 (5) | |
C119 | 0.52974 (18) | 0.65980 (17) | 0.25058 (8) | 0.0197 (5) | |
C121 | 0.50120 (18) | 0.76035 (17) | 0.13817 (8) | 0.0213 (5) | |
C122 | 0.50433 (19) | 0.77323 (18) | 0.08901 (8) | 0.0244 (5) | |
C123 | 0.4699 (2) | 0.86510 (19) | 0.06776 (9) | 0.0277 (5) | |
C124 | 0.43247 (19) | 0.94295 (18) | 0.09512 (9) | 0.0245 (5) | |
C125 | 0.43103 (18) | 0.93175 (17) | 0.14411 (8) | 0.0225 (5) | |
C126 | 0.46445 (18) | 0.83985 (18) | 0.16532 (8) | 0.0223 (5) | |
C141 | 0.79375 (19) | 0.55304 (18) | 0.23463 (9) | 0.0260 (5) | |
C144 | 0.8833 (2) | 0.5201 (2) | 0.31279 (10) | 0.0403 (7) | |
H10A | 0.7502 | 0.5991 | 0.1406 | 0.032* | |
H10B | 0.7010 | 0.4845 | 0.1385 | 0.032* | |
H109 | 0.7746 | 0.7666 | 0.1593 | 0.034* | |
H110 | 0.8901 | 0.9039 | 0.1899 | 0.041* | |
H111 | 0.8756 | 0.9639 | 0.2668 | 0.041* | |
H112 | 0.7412 | 0.8887 | 0.3149 | 0.035* | |
H115 | 0.5673 | 0.7845 | 0.3518 | 0.031* | |
H116 | 0.3983 | 0.6889 | 0.3651 | 0.033* | |
H117 | 0.3101 | 0.5802 | 0.3070 | 0.031* | |
H118 | 0.3921 | 0.5599 | 0.2343 | 0.027* | |
H122 | 0.5299 | 0.7195 | 0.0702 | 0.029* | |
H123 | 0.4721 | 0.8742 | 0.0344 | 0.033* | |
H125 | 0.4075 | 0.9863 | 0.1629 | 0.027* | |
H126 | 0.4622 | 0.8312 | 0.1987 | 0.027* | |
H14A | 0.8605 | 0.5117 | 0.3452 | 0.060* | |
H14B | 0.9394 | 0.5768 | 0.3123 | 0.060* | |
H14C | 0.9222 | 0.4583 | 0.3031 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0386 (3) | 0.0757 (5) | 0.0220 (3) | −0.0065 (3) | −0.0020 (3) | 0.0084 (4) |
Cl2 | 0.0255 (3) | 0.0294 (3) | 0.0279 (3) | 0.0027 (2) | 0.0007 (2) | 0.0019 (3) |
O42 | 0.0648 (12) | 0.0307 (11) | 0.0410 (12) | 0.0043 (9) | 0.0213 (9) | −0.0057 (9) |
O43 | 0.0413 (9) | 0.0339 (10) | 0.0282 (10) | −0.0056 (8) | 0.0136 (8) | −0.0006 (8) |
N1 | 0.0184 (9) | 0.0267 (11) | 0.0256 (11) | −0.0027 (8) | 0.0025 (8) | −0.0033 (9) |
N2 | 0.0183 (8) | 0.0231 (10) | 0.0207 (10) | −0.0050 (7) | 0.0021 (7) | −0.0015 (8) |
N7 | 0.0264 (11) | 0.0361 (13) | 0.0414 (14) | −0.0021 (9) | 0.0089 (9) | 0.0013 (11) |
C3 | 0.0216 (10) | 0.0210 (12) | 0.0182 (12) | 0.0000 (9) | 0.0028 (9) | 0.0012 (10) |
C4 | 0.0220 (10) | 0.0230 (12) | 0.0203 (12) | 0.0002 (9) | 0.0018 (9) | −0.0002 (10) |
C5 | 0.0220 (11) | 0.0257 (13) | 0.0257 (13) | −0.0020 (9) | 0.0020 (9) | −0.0027 (11) |
C6 | 0.0243 (12) | 0.0274 (13) | 0.0227 (12) | −0.0041 (10) | 0.0019 (9) | 0.0018 (11) |
C8 | 0.0228 (10) | 0.0215 (12) | 0.0181 (12) | −0.0038 (9) | 0.0024 (9) | 0.0031 (10) |
C9 | 0.0270 (11) | 0.0253 (13) | 0.0310 (13) | 0.0026 (10) | 0.0037 (10) | 0.0004 (12) |
C10 | 0.0407 (14) | 0.0208 (13) | 0.0413 (16) | 0.0026 (10) | 0.0066 (12) | 0.0015 (12) |
C11 | 0.0400 (14) | 0.0232 (13) | 0.0424 (17) | −0.0082 (11) | 0.0082 (12) | 0.0035 (12) |
C12 | 0.0263 (11) | 0.0249 (13) | 0.0307 (14) | −0.0057 (10) | 0.0066 (10) | −0.0001 (11) |
C13 | 0.0248 (11) | 0.0217 (12) | 0.0177 (12) | −0.0011 (9) | 0.0039 (9) | 0.0005 (10) |
C14 | 0.0234 (11) | 0.0237 (12) | 0.0155 (12) | −0.0014 (9) | 0.0036 (8) | 0.0003 (10) |
C15 | 0.0216 (10) | 0.0272 (13) | 0.0224 (12) | −0.0017 (9) | 0.0050 (9) | −0.0012 (11) |
C16 | 0.0225 (11) | 0.0316 (14) | 0.0310 (14) | 0.0053 (10) | 0.0047 (10) | 0.0005 (12) |
C17 | 0.0335 (12) | 0.0219 (12) | 0.0330 (14) | 0.0046 (10) | 0.0013 (10) | 0.0033 (12) |
C18 | 0.0239 (11) | 0.0231 (12) | 0.0249 (13) | −0.0014 (9) | 0.0042 (9) | 0.0032 (10) |
C19 | 0.0201 (10) | 0.0239 (12) | 0.0154 (11) | −0.0001 (9) | 0.0049 (8) | −0.0010 (10) |
C21 | 0.0219 (10) | 0.0216 (12) | 0.0184 (11) | 0.0040 (9) | 0.0025 (9) | −0.0004 (10) |
C22 | 0.0247 (11) | 0.0264 (12) | 0.0248 (13) | −0.0030 (9) | 0.0046 (9) | 0.0020 (11) |
C23 | 0.0308 (12) | 0.0343 (14) | 0.0250 (13) | −0.0020 (11) | 0.0081 (10) | 0.0041 (11) |
C24 | 0.0255 (11) | 0.0382 (14) | 0.0213 (13) | 0.0035 (10) | 0.0024 (9) | −0.0001 (12) |
C25 | 0.0211 (11) | 0.0359 (14) | 0.0258 (13) | −0.0023 (10) | 0.0020 (9) | −0.0020 (11) |
C26 | 0.0196 (10) | 0.0289 (13) | 0.0222 (12) | −0.0013 (9) | 0.0046 (9) | 0.0020 (11) |
C41 | 0.0271 (11) | 0.0278 (14) | 0.0245 (13) | −0.0030 (10) | 0.0026 (10) | −0.0041 (11) |
C44 | 0.0446 (15) | 0.0478 (17) | 0.0349 (16) | −0.0067 (13) | 0.0231 (12) | −0.0065 (14) |
Cl10 | 0.0342 (3) | 0.0237 (3) | 0.0355 (3) | 0.0033 (2) | 0.0000 (2) | 0.0056 (3) |
Cl20 | 0.0295 (3) | 0.0193 (3) | 0.0288 (3) | −0.0016 (2) | 0.0054 (2) | 0.0000 (3) |
O142 | 0.0255 (8) | 0.0448 (11) | 0.0428 (11) | 0.0026 (8) | 0.0094 (8) | −0.0032 (10) |
O143 | 0.0266 (8) | 0.0344 (10) | 0.0270 (10) | 0.0069 (7) | 0.0005 (7) | −0.0016 (8) |
N101 | 0.0281 (10) | 0.0199 (10) | 0.0225 (11) | −0.0015 (8) | 0.0052 (8) | −0.0037 (8) |
N102 | 0.0265 (9) | 0.0193 (10) | 0.0182 (10) | 0.0010 (8) | 0.0039 (7) | −0.0039 (8) |
N107 | 0.0360 (11) | 0.0298 (12) | 0.0381 (13) | −0.0007 (10) | −0.0025 (10) | −0.0041 (10) |
C103 | 0.0230 (10) | 0.0203 (12) | 0.0196 (12) | −0.0005 (9) | 0.0037 (9) | −0.0006 (10) |
C104 | 0.0238 (10) | 0.0188 (11) | 0.0248 (12) | −0.0013 (9) | 0.0069 (9) | −0.0008 (11) |
C105 | 0.0288 (11) | 0.0245 (12) | 0.0275 (13) | 0.0023 (10) | 0.0089 (9) | −0.0033 (11) |
C106 | 0.0320 (12) | 0.0243 (13) | 0.0234 (13) | 0.0040 (10) | 0.0021 (10) | −0.0008 (11) |
C108 | 0.0205 (10) | 0.0187 (11) | 0.0256 (13) | 0.0020 (9) | 0.0018 (9) | 0.0007 (10) |
C109 | 0.0241 (11) | 0.0271 (13) | 0.0337 (14) | 0.0001 (10) | 0.0067 (10) | 0.0023 (12) |
C110 | 0.0257 (12) | 0.0332 (15) | 0.0448 (17) | −0.0054 (10) | 0.0045 (11) | 0.0067 (13) |
C111 | 0.0267 (12) | 0.0247 (13) | 0.0474 (17) | −0.0065 (10) | −0.0071 (11) | 0.0019 (12) |
C112 | 0.0297 (12) | 0.0229 (13) | 0.0317 (14) | 0.0010 (10) | −0.0063 (10) | −0.0013 (11) |
C113 | 0.0201 (10) | 0.0196 (12) | 0.0273 (13) | 0.0028 (9) | −0.0030 (9) | 0.0016 (10) |
C114 | 0.0213 (10) | 0.0171 (11) | 0.0252 (13) | 0.0052 (9) | −0.0014 (9) | 0.0005 (10) |
C115 | 0.0318 (12) | 0.0234 (13) | 0.0213 (12) | 0.0081 (10) | 0.0007 (10) | −0.0020 (10) |
C116 | 0.0317 (12) | 0.0305 (14) | 0.0219 (13) | 0.0109 (10) | 0.0098 (10) | 0.0055 (11) |
C117 | 0.0242 (11) | 0.0250 (13) | 0.0305 (14) | 0.0053 (9) | 0.0088 (10) | 0.0053 (11) |
C118 | 0.0217 (10) | 0.0207 (12) | 0.0240 (13) | 0.0015 (9) | 0.0013 (9) | 0.0005 (10) |
C119 | 0.0212 (10) | 0.0182 (11) | 0.0197 (12) | 0.0046 (9) | 0.0019 (8) | 0.0029 (10) |
C121 | 0.0207 (10) | 0.0205 (12) | 0.0230 (12) | −0.0024 (9) | 0.0036 (9) | 0.0007 (10) |
C122 | 0.0293 (11) | 0.0225 (12) | 0.0226 (12) | 0.0001 (10) | 0.0081 (9) | −0.0020 (10) |
C123 | 0.0321 (12) | 0.0293 (13) | 0.0224 (13) | −0.0015 (10) | 0.0058 (10) | 0.0011 (11) |
C124 | 0.0243 (10) | 0.0208 (12) | 0.0279 (13) | −0.0024 (9) | 0.0010 (9) | 0.0021 (11) |
C125 | 0.0193 (10) | 0.0214 (12) | 0.0269 (13) | −0.0004 (9) | 0.0025 (9) | −0.0047 (11) |
C126 | 0.0222 (10) | 0.0243 (12) | 0.0206 (12) | 0.0002 (9) | 0.0029 (9) | −0.0021 (10) |
C141 | 0.0272 (12) | 0.0174 (11) | 0.0340 (14) | 0.0015 (10) | 0.0061 (10) | −0.0040 (11) |
C144 | 0.0373 (14) | 0.0434 (16) | 0.0374 (16) | 0.0113 (12) | −0.0081 (12) | −0.0067 (13) |
O42—C41 | 1.202 (3) | C103—N102 | 1.500 (3) |
O43—C41 | 1.317 (3) | C103—C119 | 1.520 (3) |
O43—C44 | 1.447 (3) | C103—C108 | 1.533 (3) |
Cl2—C4 | 1.806 (2) | C103—C104 | 1.578 (3) |
Cl1—C24 | 1.748 (2) | C104—C105 | 1.523 (3) |
N1—C6 | 1.361 (3) | C104—C141 | 1.526 (3) |
N1—N2 | 1.458 (2) | C104—Cl20 | 1.807 (2) |
N1—C5 | 1.470 (3) | C105—N101 | 1.471 (3) |
N2—C21 | 1.418 (3) | C105—H10A | 0.9900 |
N2—C3 | 1.492 (3) | C105—H10B | 0.9900 |
N7—C6 | 1.151 (3) | C106—N107 | 1.152 (3) |
C3—C8 | 1.529 (3) | C106—N101 | 1.361 (3) |
C3—C19 | 1.538 (3) | C119—C118 | 1.387 (3) |
C3—C4 | 1.572 (3) | C119—C114 | 1.395 (3) |
C4—C41 | 1.508 (3) | C118—C117 | 1.390 (3) |
C4—C5 | 1.520 (3) | C118—H118 | 0.9500 |
C5—H5A | 0.9900 | C117—C116 | 1.381 (4) |
C5—H5B | 0.9900 | C117—H117 | 0.9500 |
C8—C9 | 1.379 (3) | C116—C115 | 1.386 (3) |
C8—C13 | 1.409 (3) | C116—H116 | 0.9500 |
C9—C10 | 1.390 (4) | C115—C114 | 1.388 (3) |
C9—H9 | 0.9500 | C115—H115 | 0.9500 |
C10—C11 | 1.383 (4) | C114—C113 | 1.473 (3) |
C10—H10 | 0.9500 | C113—C112 | 1.396 (3) |
C11—C12 | 1.391 (4) | C113—C108 | 1.399 (3) |
C11—H11 | 0.9500 | C112—C111 | 1.396 (4) |
C12—C13 | 1.385 (3) | C112—H112 | 0.9500 |
C12—H12 | 0.9500 | C111—C110 | 1.390 (4) |
C13—C14 | 1.471 (3) | C111—H111 | 0.9500 |
C14—C15 | 1.386 (3) | C110—C109 | 1.387 (4) |
C14—C19 | 1.403 (3) | C110—H110 | 0.9500 |
C15—C16 | 1.385 (3) | C109—C108 | 1.389 (3) |
C15—H15 | 0.9500 | C109—H109 | 0.9500 |
C16—C17 | 1.390 (3) | C121—C126 | 1.390 (3) |
C16—H16 | 0.9500 | C121—C122 | 1.398 (3) |
C17—C18 | 1.393 (3) | C121—N102 | 1.424 (3) |
C17—H17 | 0.9500 | C126—C125 | 1.389 (3) |
C18—C19 | 1.383 (3) | C126—H126 | 0.9500 |
C18—H18 | 0.9500 | C125—C124 | 1.388 (3) |
C21—C22 | 1.394 (3) | C125—H125 | 0.9500 |
C21—C26 | 1.401 (3) | C124—C123 | 1.379 (3) |
C26—C25 | 1.379 (3) | C124—Cl10 | 1.746 (2) |
C26—H26 | 0.9500 | C123—C122 | 1.392 (3) |
C25—C24 | 1.376 (4) | C123—H123 | 0.9500 |
C25—H25 | 0.9500 | C122—H122 | 0.9500 |
C24—C23 | 1.379 (3) | C141—O142 | 1.203 (3) |
C23—C22 | 1.387 (3) | C141—O143 | 1.322 (3) |
C23—H23 | 0.9500 | C144—O143 | 1.446 (3) |
C22—H22 | 0.9500 | C144—H14A | 0.9800 |
C44—H44A | 0.9800 | C144—H14B | 0.9800 |
C44—H44B | 0.9800 | C144—H14C | 0.9800 |
C44—H44C | 0.9800 | N101—N102 | 1.445 (3) |
C41—O43—C44 | 116.6 (2) | N102—C103—C119 | 114.20 (17) |
C6—N1—N2 | 110.27 (18) | N102—C103—C108 | 115.06 (19) |
C6—N1—C5 | 117.88 (18) | C119—C103—C108 | 101.85 (18) |
N2—N1—C5 | 107.94 (16) | N102—C103—C104 | 102.20 (17) |
C21—N2—N1 | 113.00 (17) | C119—C103—C104 | 114.17 (18) |
C21—N2—C3 | 120.27 (16) | C108—C103—C104 | 109.76 (16) |
N1—N2—C3 | 109.30 (16) | C105—C104—C141 | 114.95 (18) |
N2—C3—C8 | 113.97 (18) | C105—C104—C103 | 102.43 (18) |
N2—C3—C19 | 114.82 (18) | C141—C104—C103 | 113.70 (18) |
C8—C3—C19 | 102.13 (16) | C105—C104—Cl20 | 105.94 (16) |
N2—C3—C4 | 101.19 (16) | C141—C104—Cl20 | 106.55 (16) |
C8—C3—C4 | 114.57 (18) | C103—C104—Cl20 | 113.19 (14) |
C19—C3—C4 | 110.66 (18) | N101—C105—C104 | 102.49 (17) |
C41—C4—C5 | 114.7 (2) | N101—C105—H10A | 111.3 |
C41—C4—C3 | 112.36 (17) | C104—C105—H10A | 111.3 |
C5—C4—C3 | 102.27 (18) | N101—C105—H10B | 111.3 |
C41—C4—Cl2 | 109.32 (16) | C104—C105—H10B | 111.3 |
C5—C4—Cl2 | 105.85 (14) | H10A—C105—H10B | 109.2 |
C3—C4—Cl2 | 112.07 (15) | N107—C106—N101 | 173.7 (3) |
N1—C5—C4 | 102.74 (18) | C118—C119—C114 | 120.7 (2) |
N1—C5—H5A | 111.2 | C118—C119—C103 | 128.9 (2) |
C4—C5—H5A | 111.2 | C114—C119—C103 | 110.36 (18) |
N1—C5—H5B | 111.2 | C119—C118—C117 | 118.3 (2) |
C4—C5—H5B | 111.2 | C119—C118—H118 | 120.8 |
H5A—C5—H5B | 109.1 | C117—C118—H118 | 120.8 |
N7—C6—N1 | 172.2 (3) | C116—C117—C118 | 120.9 (2) |
C9—C8—C13 | 120.5 (2) | C116—C117—H117 | 119.6 |
C9—C8—C3 | 129.95 (19) | C118—C117—H117 | 119.6 |
C13—C8—C3 | 109.54 (19) | C117—C116—C115 | 121.1 (2) |
C8—C9—C10 | 118.4 (2) | C117—C116—H116 | 119.4 |
C8—C9—H9 | 120.8 | C115—C116—H116 | 119.4 |
C10—C9—H9 | 120.8 | C116—C115—C114 | 118.4 (2) |
C11—C10—C9 | 121.4 (2) | C116—C115—H115 | 120.8 |
C11—C10—H10 | 119.3 | C114—C115—H115 | 120.8 |
C9—C10—H10 | 119.3 | C115—C114—C119 | 120.6 (2) |
C10—C11—C12 | 120.6 (2) | C115—C114—C113 | 130.7 (2) |
C10—C11—H11 | 119.7 | C119—C114—C113 | 108.6 (2) |
C12—C11—H11 | 119.7 | C112—C113—C108 | 120.4 (2) |
C13—C12—C11 | 118.4 (2) | C112—C113—C114 | 130.5 (2) |
C13—C12—H12 | 120.8 | C108—C113—C114 | 108.88 (19) |
C11—C12—H12 | 120.8 | C113—C112—C111 | 118.4 (2) |
C12—C13—C8 | 120.7 (2) | C113—C112—H112 | 120.8 |
C12—C13—C14 | 130.0 (2) | C111—C112—H112 | 120.8 |
C8—C13—C14 | 109.22 (19) | C110—C111—C112 | 120.5 (2) |
C15—C14—C19 | 120.9 (2) | C110—C111—H111 | 119.8 |
C15—C14—C13 | 130.1 (2) | C112—C111—H111 | 119.8 |
C19—C14—C13 | 108.70 (18) | C109—C110—C111 | 121.4 (2) |
C16—C15—C14 | 118.6 (2) | C109—C110—H110 | 119.3 |
C16—C15—H15 | 120.7 | C111—C110—H110 | 119.3 |
C14—C15—H15 | 120.7 | C110—C109—C108 | 118.3 (2) |
C15—C16—C17 | 120.9 (2) | C110—C109—H109 | 120.9 |
C15—C16—H16 | 119.6 | C108—C109—H109 | 120.9 |
C17—C16—H16 | 119.6 | C109—C108—C113 | 121.0 (2) |
C16—C17—C18 | 120.6 (2) | C109—C108—C103 | 129.3 (2) |
C16—C17—H17 | 119.7 | C113—C108—C103 | 109.70 (19) |
C18—C17—H17 | 119.7 | C126—C121—C122 | 119.5 (2) |
C19—C18—C17 | 118.9 (2) | C126—C121—N102 | 119.3 (2) |
C19—C18—H18 | 120.5 | C122—C121—N102 | 121.1 (2) |
C17—C18—H18 | 120.5 | C125—C126—C121 | 120.7 (2) |
C18—C19—C14 | 120.15 (19) | C125—C126—H126 | 119.7 |
C18—C19—C3 | 129.83 (19) | C121—C126—H126 | 119.7 |
C14—C19—C3 | 109.92 (19) | C124—C125—C126 | 119.2 (2) |
C22—C21—C26 | 119.0 (2) | C124—C125—H125 | 120.4 |
C22—C21—N2 | 121.51 (19) | C126—C125—H125 | 120.4 |
C26—C21—N2 | 119.3 (2) | C123—C124—C125 | 120.8 (2) |
C25—C26—C21 | 120.1 (2) | C123—C124—Cl10 | 119.30 (19) |
C25—C26—H26 | 120.0 | C125—C124—Cl10 | 119.92 (18) |
C21—C26—H26 | 120.0 | C124—C123—C122 | 120.1 (2) |
C24—C25—C26 | 120.0 (2) | C124—C123—H123 | 120.0 |
C24—C25—H25 | 120.0 | C122—C123—H123 | 120.0 |
C26—C25—H25 | 120.0 | C123—C122—C121 | 119.7 (2) |
C25—C24—C23 | 121.1 (2) | C123—C122—H122 | 120.1 |
C25—C24—Cl1 | 118.90 (18) | C121—C122—H122 | 120.1 |
C23—C24—Cl1 | 119.99 (19) | O142—C141—O143 | 125.6 (2) |
C24—C23—C22 | 119.2 (2) | O142—C141—C104 | 122.9 (2) |
C24—C23—H23 | 120.4 | O143—C141—C104 | 111.48 (18) |
C22—C23—H23 | 120.4 | O143—C144—H14A | 109.5 |
C23—C22—C21 | 120.6 (2) | O143—C144—H14B | 109.5 |
C23—C22—H22 | 119.7 | H14A—C144—H14B | 109.5 |
C21—C22—H22 | 119.7 | O143—C144—H14C | 109.5 |
O42—C41—O43 | 125.1 (2) | H14A—C144—H14C | 109.5 |
O42—C41—C4 | 122.8 (2) | H14B—C144—H14C | 109.5 |
O43—C41—C4 | 112.1 (2) | C106—N101—N102 | 110.25 (17) |
O43—C44—H44A | 109.5 | C106—N101—C105 | 118.91 (19) |
O43—C44—H44B | 109.5 | N102—N101—C105 | 107.47 (17) |
H44A—C44—H44B | 109.5 | C121—N102—N101 | 113.52 (18) |
O43—C44—H44C | 109.5 | C121—N102—C103 | 120.65 (18) |
H44A—C44—H44C | 109.5 | N101—N102—C103 | 109.49 (16) |
H44B—C44—H44C | 109.5 | C141—O143—C144 | 116.39 (19) |
C6—N1—N2—C21 | −98.9 (2) | N102—C103—C104—C105 | 30.1 (2) |
C5—N1—N2—C21 | 131.06 (19) | C119—C103—C104—C105 | 153.97 (18) |
C6—N1—N2—C3 | 124.32 (19) | C108—C103—C104—C105 | −92.4 (2) |
C5—N1—N2—C3 | −5.7 (2) | N102—C103—C104—C141 | 154.77 (18) |
C21—N2—C3—C8 | 84.2 (2) | C119—C103—C104—C141 | −81.4 (2) |
N1—N2—C3—C8 | −142.63 (18) | C108—C103—C104—C141 | 32.2 (3) |
C21—N2—C3—C19 | −33.1 (3) | N102—C103—C104—Cl20 | −83.46 (18) |
N1—N2—C3—C19 | 100.1 (2) | C119—C103—C104—Cl20 | 40.4 (2) |
C21—N2—C3—C4 | −152.28 (19) | C108—C103—C104—Cl20 | 153.98 (16) |
N1—N2—C3—C4 | −19.1 (2) | C141—C104—C105—N101 | −163.45 (19) |
N2—C3—C4—C41 | 159.53 (19) | C103—C104—C105—N101 | −39.6 (2) |
C8—C3—C4—C41 | −77.4 (2) | Cl20—C104—C105—N101 | 79.19 (18) |
C19—C3—C4—C41 | 37.4 (3) | N102—C103—C119—C118 | 47.6 (3) |
N2—C3—C4—C5 | 36.0 (2) | C108—C103—C119—C118 | 172.3 (2) |
C8—C3—C4—C5 | 159.13 (18) | C104—C103—C119—C118 | −69.5 (3) |
C19—C3—C4—C5 | −86.1 (2) | N102—C103—C119—C114 | −132.75 (19) |
N2—C3—C4—Cl2 | −76.90 (18) | C108—C103—C119—C114 | −8.1 (2) |
C8—C3—C4—Cl2 | 46.2 (2) | C104—C103—C119—C114 | 110.1 (2) |
C19—C3—C4—Cl2 | 160.97 (15) | C114—C119—C118—C117 | −1.6 (3) |
C6—N1—C5—C4 | −96.6 (2) | C103—C119—C118—C117 | 178.0 (2) |
N2—N1—C5—C4 | 29.1 (2) | C119—C118—C117—C116 | 0.0 (3) |
C41—C4—C5—N1 | −161.98 (17) | C118—C117—C116—C115 | 1.2 (3) |
C3—C4—C5—N1 | −40.1 (2) | C117—C116—C115—C114 | −0.7 (3) |
Cl2—C4—C5—N1 | 77.41 (17) | C116—C115—C114—C119 | −0.9 (3) |
N2—C3—C8—C9 | 47.3 (3) | C116—C115—C114—C113 | 174.1 (2) |
C19—C3—C8—C9 | 171.8 (2) | C118—C119—C114—C115 | 2.1 (3) |
C4—C3—C8—C9 | −68.6 (3) | C103—C119—C114—C115 | −177.52 (19) |
N2—C3—C8—C13 | −131.35 (19) | C118—C119—C114—C113 | −173.9 (2) |
C19—C3—C8—C13 | −6.9 (2) | C103—C119—C114—C113 | 6.5 (2) |
C4—C3—C8—C13 | 112.7 (2) | C115—C114—C113—C112 | −2.4 (4) |
C13—C8—C9—C10 | −2.4 (4) | C119—C114—C113—C112 | 173.1 (2) |
C3—C8—C9—C10 | 179.1 (2) | C115—C114—C113—C108 | −177.3 (2) |
C8—C9—C10—C11 | 0.6 (4) | C119—C114—C113—C108 | −1.8 (2) |
C9—C10—C11—C12 | 1.5 (4) | C108—C113—C112—C111 | 0.8 (3) |
C10—C11—C12—C13 | −1.7 (4) | C114—C113—C112—C111 | −173.6 (2) |
C11—C12—C13—C8 | −0.1 (4) | C113—C112—C111—C110 | 0.2 (4) |
C11—C12—C13—C14 | 174.7 (2) | C112—C111—C110—C109 | −0.7 (4) |
C9—C8—C13—C12 | 2.1 (3) | C111—C110—C109—C108 | 0.0 (4) |
C3—C8—C13—C12 | −179.0 (2) | C110—C109—C108—C113 | 1.0 (3) |
C9—C8—C13—C14 | −173.7 (2) | C110—C109—C108—C103 | 178.0 (2) |
C3—C8—C13—C14 | 5.2 (3) | C112—C113—C108—C109 | −1.5 (3) |
C12—C13—C14—C15 | −3.2 (4) | C114—C113—C108—C109 | 174.0 (2) |
C8—C13—C14—C15 | 172.1 (2) | C112—C113—C108—C103 | −179.0 (2) |
C12—C13—C14—C19 | −176.2 (2) | C114—C113—C108—C103 | −3.5 (2) |
C8—C13—C14—C19 | −0.9 (3) | N102—C103—C108—C109 | −46.3 (3) |
C19—C14—C15—C16 | 0.2 (3) | C119—C103—C108—C109 | −170.3 (2) |
C13—C14—C15—C16 | −172.0 (2) | C104—C103—C108—C109 | 68.3 (3) |
C14—C15—C16—C17 | 0.2 (4) | N102—C103—C108—C113 | 131.0 (2) |
C15—C16—C17—C18 | −0.2 (4) | C119—C103—C108—C113 | 6.9 (2) |
C16—C17—C18—C19 | −0.3 (4) | C104—C103—C108—C113 | −114.4 (2) |
C17—C18—C19—C14 | 0.7 (3) | C122—C121—C126—C125 | −0.1 (3) |
C17—C18—C19—C3 | 176.7 (2) | N102—C121—C126—C125 | −175.64 (18) |
C15—C14—C19—C18 | −0.7 (3) | C121—C126—C125—C124 | 1.2 (3) |
C13—C14—C19—C18 | 173.1 (2) | C126—C125—C124—C123 | −1.9 (3) |
C15—C14—C19—C3 | −177.4 (2) | C126—C125—C124—Cl10 | 176.69 (16) |
C13—C14—C19—C3 | −3.7 (2) | C125—C124—C123—C122 | 1.4 (3) |
N2—C3—C19—C18 | −46.1 (3) | Cl10—C124—C123—C122 | −177.20 (17) |
C8—C3—C19—C18 | −170.0 (2) | C124—C123—C122—C121 | −0.2 (3) |
C4—C3—C19—C18 | 67.7 (3) | C126—C121—C122—C123 | −0.5 (3) |
N2—C3—C19—C14 | 130.2 (2) | N102—C121—C122—C123 | 175.04 (19) |
C8—C3—C19—C14 | 6.4 (2) | C105—C104—C141—O142 | 8.7 (3) |
C4—C3—C19—C14 | −116.0 (2) | C103—C104—C141—O142 | −108.9 (3) |
N1—N2—C21—C22 | 15.7 (3) | Cl20—C104—C141—O142 | 125.7 (2) |
C3—N2—C21—C22 | 147.2 (2) | C105—C104—C141—O143 | −169.9 (2) |
N1—N2—C21—C26 | −169.51 (19) | C103—C104—C141—O143 | 72.5 (2) |
C3—N2—C21—C26 | −37.9 (3) | Cl20—C104—C141—O143 | −52.9 (2) |
C22—C21—C26—C25 | −0.7 (3) | C104—C105—N101—C106 | −91.2 (2) |
N2—C21—C26—C25 | −175.7 (2) | C104—C105—N101—N102 | 34.8 (2) |
C21—C26—C25—C24 | 0.9 (4) | C126—C121—N102—N101 | −178.80 (17) |
C26—C25—C24—C23 | −0.6 (4) | C122—C121—N102—N101 | 5.7 (3) |
C26—C25—C24—Cl1 | −179.58 (19) | C126—C121—N102—C103 | −45.9 (3) |
C25—C24—C23—C22 | 0.0 (4) | C122—C121—N102—C103 | 138.6 (2) |
Cl1—C24—C23—C22 | 179.04 (19) | C106—N101—N102—C121 | −106.5 (2) |
C24—C23—C22—C21 | 0.2 (4) | C105—N101—N102—C121 | 122.51 (19) |
C26—C21—C22—C23 | 0.2 (3) | C106—N101—N102—C103 | 115.5 (2) |
N2—C21—C22—C23 | 175.0 (2) | C105—N101—N102—C103 | −15.5 (2) |
C44—O43—C41—O42 | −2.3 (3) | C119—C103—N102—C121 | 91.9 (2) |
C44—O43—C41—C4 | −179.93 (19) | C108—C103—N102—C121 | −25.4 (3) |
C5—C4—C41—O42 | 13.6 (3) | C104—C103—N102—C121 | −144.28 (18) |
C3—C4—C41—O42 | −102.6 (3) | C119—C103—N102—N101 | −133.52 (19) |
Cl2—C4—C41—O42 | 132.3 (2) | C108—C103—N102—N101 | 109.2 (2) |
C5—C4—C41—O43 | −168.66 (19) | C104—C103—N102—N101 | −9.7 (2) |
C3—C4—C41—O43 | 75.1 (2) | O142—C141—O143—C144 | −7.2 (4) |
Cl2—C4—C41—O43 | −50.0 (2) | C104—C141—O143—C144 | 171.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···N107 | 0.99 | 2.51 | 3.459 (3) | 160 |
C23—H23···O142i | 0.95 | 2.57 | 3.502 (3) | 166 |
C25—H25···Cg2ii | 0.95 | 2.50 | 3.400 (2) | 158 |
C44—H44A···Cl1iii | 0.98 | 2.77 | 3.425 (3) | 125 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z; (iii) x, −y+1/2, z+1/2. |
Experimental details
(IV) | (V) | |
Crystal data | ||
Chemical formula | C27H22ClN3 | C24H17Cl2N3O2 |
Mr | 423.93 | 450.31 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 173 | 120 |
a, b, c (Å) | 9.0914 (9), 12.6225 (9), 18.5025 (17) | 11.1818 (5), 13.2534 (4), 28.1265 (11) |
β (°) | 94.576 (8) | 96.363 (3) |
V (Å3) | 2116.5 (3) | 4142.6 (3) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.20 | 0.34 |
Crystal size (mm) | 0.35 × 0.15 × 0.10 | 0.37 × 0.37 × 0.08 |
Data collection | ||
Diffractometer | Stoe IPDSII image-plate | Stoe IPDSII image-plate |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17870, 5071, 3437 | 23396, 7295, 4866 |
Rint | 0.046 | 0.045 |
(sin θ/λ)max (Å−1) | 0.660 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.081, 0.85 | 0.036, 0.079, 1.02 |
No. of reflections | 5071 | 7295 |
No. of parameters | 280 | 559 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.30 | 0.84, −0.41 |
Computer programs: X-AREA (Stoe & Cie, 2000), SHELXS86 (Sheldrick, 1990), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17···N7i | 0.93 | 2.65 | 3.418 (1) | 141 |
C42—H42B···Cg1ii | 0.97 | 2.74 | 3.484 (2) | 134 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···N107 | 0.99 | 2.51 | 3.459 (3) | 160 |
C23—H23···O142i | 0.95 | 2.57 | 3.502 (3) | 166 |
C25—H25···Cg2ii | 0.95 | 2.50 | 3.400 (2) | 158 |
C44—H44A···Cl1iii | 0.98 | 2.77 | 3.425 (3) | 125 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z; (iii) x, −y+1/2, z+1/2. |
Azomethine imines, (I), belong to the class of well known and widely applied 1,3-dipoles (Grashey, 1984). They undergo (2 + 3)-cycloadditions with both electron-rich and electron-deficient ethylene derivatives to yield the corresponding 1,2-pyrazolidine derivatives of type (II). N-cyano substituted pyrazolidines are of interest because of their expected biological activity; for example, some of them were tested as cathepsin K inhibitors for the treatment of osteoporosis (Deaton et al., 2005). The mechanism of the (2 + 3)-cycloaddition in the case of azomethine imines is believed to follow the concerted pathway that results in stereospecific formation of the final cycloadducts (Huisgen & Eckell, 1977a). For the purposes of organic synthesis, an especially attractive group is the relatively stable and reactive azomethine imines of type (III) prepared from 4-chlorophenyldiazocyanide and diaryl derivatives of diazomethane, described for the first time by Huisgen et al. (1977). The yellow crystalline C-(2,2'-biphenylylene)-Nα-(4-chlorophenyl)-Nβ-cyanoazomthine imine, (III), reacts smoothly with norbornene and methyl α-chloroacrylate to affort the expected (2 + 3)-cycloadducts (IV) and (V), respectively, in high yields. The streochemical structures of the isolated products were initially established by Huisgen and co-workers on the basis of the spectroscopic data (Huisgen et al., 1977; Huisgen & Eckell, 1977b). The (2 + 3)-cycloaddition with norbornene was reported to give the exo-oriented cycloadduct (Huisgen & Eckell, 1977a). In the case of the product obtained from methyl α-chloroacrylate, the reaction was reported to lead mainly to the sterically more crowded regioisomer (V); the minor product corresponding to the structure (VI) was found in the mother liquor after separation of (V) (Huisgen & Eckell, 1977b). The goal of the present work was to resynthesize pyrazolidines (IV) and (V) and to confirm their structures and the predicted substitution pattern in the pyrazolidine ring by X-ray diffraction analysis. Other features related to the intermolecular interactions were also of interest.
Compound (IV) (Fig. 1) crystalizes with one molecule and compound (V) (Fig. 2) with two independent molecules in the asymmetric unit [(V-A) and (V-B)]. The weighted r.m.s. fit of the non-H atoms from the two molecules of (V) is 2.88 Å (Mackay, 1984). The largest deviation from perfect overlap is observed for the fluorene group. The molecules of both compounds contain the pyrazolidine ring as a relevant fragment of the structure. The substituents at atoms C3, N1 and N2 in both compounds are identical, as they originate from the same 1,3-dipole, (IIIa). In the molecule of (IV), the norbornane ring is fused with the heterocyclic ring, and in the case of (V), the Cl atom and ester group are bonded to atom C4. Thus, the regiochemical structure attributed to (V) by Huisgen & Eckell (1977a) was correct. Moreover, the structure of (IV) shows that the pyrazolidine ring is exo-oriented with respect to the norbornane skeleton. It is worth mentioning that an analogous orientation was proposed for (2 + 3)-cycloadducts obtained from norbornene and other 1,3-dipoles, for example, diphenylnitrilimine, benzonitrile N-oxide (Huisgen et al., 1967) and methyl diazoacetate (Gorpinchenko et al., 2006).
The sums of the bond angles around atom N1 [atom N101 in (V-B)] are 343 (1), 336 (1) and 336 (1)° for (IV), (V-A) and (V-B), respectively, while the corresponding angle sums around atom N2 [atom N102 in (V-B)] are 324 (1), 342 (1) and 343 (1)°, respectively. These values indicate significant pyramidalization at these N atoms. A similar pyramidalization about the N-cyano N atom is found in other heterocyclic compounds containing the –N—C≡N group (Bird et al., 1995). In contrast, the amine N atom of the parent cyanamide, CH2N2, has a geometry that is somewhat flatter; the sums of the bond angles were found to be 356 (2)° in a low-temperature X-ray study (Denner et al., 1988), and 349.3 (7) and 349.6 (7)° in a study based on neutron data and an X-ray multipole refinement, respectively, for a host–guest complex of cyanamide in 18-crown-6 (Koritsanszky et al., 1991).
The pyrazolidine ring in each compound is nonplanar, as the three C atoms and two N atoms are sp3-hybridized. In (IV), this ring adopts a twisted conformation, with the pseudo-twofold axis passing through the mid-point of the N2—C3 bond and atom C5. For (IV), the puckering parameters (Cremer & Pople, 1975) for the atom sequence N1—N2—C3—C4—C5 are q2 = 0.385 (1) Å and φ2 = 229.8 (2)° [asymmetry parameter (Nardelli, 1983) Δ2 = 0.019 (1)]. The substituents at atoms N1 and N2 occupy equatorial positions, while atoms C41 and C44 are in axial positions with respect to the pyrazolidine ring. The pyrazolidine ring of (V) adopts an envelope conformation in molecule A, with a pseudo-mirror passing through atom C4 and the mid-point of the N1—N2 bond. In molecule B, the ring has a twisted conformation, with the pseudo-twofold axis passing through the mid-point of the C104—C105 bond and atom N102. For (V-A), the puckering parameters for the atom sequence N1—N2—C3—C4—C5 are q2 = 0.400 (2) Å and φ2 = 295.1 (3)° [asymmetry parameter Δs = 0.041 (1)], while for (V-B) the puckering parameters for the atom sequence N101—N102—C103—C104—C105 are q2 = 0.389 (2) Å and φ2 = 128.4 (3)° [Δ2 = 0.013 (1)]. The different puckering of the pyrazolidine rings of molecules A and B causes differences in the orientations of the substituents. The cyano group at atom N1 is nearly axial and perfectly axial at atom N101. In both molecules of compound (V), the chlorophenyl substituent at atom N2 (N102) occupies a nearly equatorial position, while the Cl and ester substituents at atom C4 (C104) occupy axial and equatorial positions, respectively.
The bonds distances and angles in both molecules are mostly in good agreement with expected values (Allen et al., 1987). However, the N—N bond distances are longer than expected. The long N1—N2 bond of 1.4785 (15) Å in (IV) and 1.458 (3) and 1.445 (3) Å for (V-A) and (V-B), respectively, may be caused by the influence of the cyano and chlorophenyl substituents on the pyrazolidine ring. Moreover, a search of the Cambridge Structural Database (Version 5.28 of November 2006; Allen, 2002) for structures containing the pyrazolidine fragment (Scheme 2), revealed a range of N—N bond lengths from 1.387 to 1.514 Å for 42 structures. The search was limited to ordered structures, without errors, with R less than 0.05 and an average bond length s.u. smaller than 0.005 Å.
In (IV), atom N7i [symmetry code: (i) x - 1, y, z] is involved in an unconventional C17—H17···N7i hydrogen bond, which links the molecules into chains along the [100] direction (Fig. 2). This generates a graph-set motif of C(9) (Etter et al., 1990). In contrast, molecules A and B in (V) are linked into dimers by a weak C5—H5B···N107 interaction; atom N7 does not act as an acceptor in any interaction. In addition, some weak nonclassical intermolecular C—H···O, C—H···Cl and C—H···π interactions are observed. For (IV), a C—H···π interaction (see Table 1, where Cg1 is defined by atoms C8–C13 in one of the six-membered rings of the fluorene group) involves pairs of molecules related by a centre of inversion. For (V) (see Table 2, where Cg2 is defined by atoms C121–C126 in the chlorophenyl ring of molecule B), all interactions emanate from H atoms solely in molecule A and the acceptor atoms are in one adjacent molecule A and three different B molecules.