2'-(4-Chloro­phen­yl)-2,3,4,5,6,7-hexa­hydro-4',7'-methano­spiro­[9H-fluorene-9,3'-1H-indazole]-1'-carbo­nitrile and methyl 4'-chloro-2'-(4-chloro­phen­yl)-1'-cyano­spiro­[9H-fluorene-9,3'-pyrazolidine]-4'-carboxyl­ate

The title compounds, C₂₇H₂₂ClN₃, (IV), and C₂₄H₁₇Cl₂N₃O₂, (V), were synthesized as part of our ongoing studies on (2+3)-cyclo­addition reactions. Compound (V) crystallizes with two mol­ecules in the asymmetric unit. The pyrazolidine ring of compound (IV) adopts a twisted conformation, while in compound (V) it adopts a twisted and an envolope conformation in the two molecules. There are short inter­molecular contacts, which can be recognized as unconventional hydrogen bonds, in both structures.

S1. Comment

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)-N^α-(4-chlorophenyl)-N^β-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 Δ_s = 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.

Related literature

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).

S2. Experimental

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.

S3. Refinement

All H atoms were positioned geometrically and refined with a riding model. In (IV), U_iso(H) values were constrained to 1.2U_eq(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, U_iso(H) values were constrained to 1.5U_eq(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 U_iso(H) values constrained to 1.2U_eq(C).

Computing details

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).

Figures

	Fig. 1. The molecular structure of (IV), with the atomic numbering scheme and 40% probability displacement ellipsoids. H atoms have been omitted for clarity.
	Fig. 2. The molecular structure of the two symmetry-independent molecules of (V), with the atomic numbering scheme and 40% probability displacement ellipsoids. The C—H···N interaction forming dimers between molecules A and B is shown as a dashed line. The other H atoms have been omitted for clarity.
	Fig. 3. Part of the crystal structure of (IV), showing the C—H···N interaction forming chains along the a axis. The symmetry code is given in Table 1.

(IV) 2'-(4-Chlorophenyl)-2,3,4,5,6,7-hexahydro-4',7'-methanospiro[9H-fluorene- 9,3'-1H-indazole]-1'-carbonitrile

Crystal data

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) Å^3	Plate, colorless
Z = 4	0.35 × 0.15 × 0.10 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 0.85	w = 1/[σ^2(Fo^2) + (0.048P)^2P] where P = (Fo^2 + 2Fc^2)/3
5071 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···N7^i	0.93	2.65	3.418 (1)	141
C42—H42B···Cg1^ii	0.97	2.74	3.484 (2)	134

Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+1.

(V) methyl 4'-chloro-2'-(4-chlorophenyl)-1'-cyanospiro[9H-fluorene-9,3'-pyrazolidine]- 4'-carboxylate

Crystal data

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) Å^3	Plate, colorless
Z = 8	0.37 × 0.37 × 0.08 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.079	H-atom parameters constrained
S = 1.02	[exp(2.00(sinθ/λ)^2)]/ [σ^2(Fo^2) + (0.0404P)^2] where P = 0.33333Fo^2 + 0.66667Fc^2
7295 reflections	(Δ/σ)max = 0.001
559 parameters	Δρmax = 0.84 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···O142^i	0.95	2.57	3.502 (3)	166
C25—H25···Cg2^ii	0.95	2.50	3.400 (2)	158
C44—H44A···Cl1^iii	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.