N-(o-Chloro­phenyl)-2,5-di­methyl­pyrrole-3-carb­aldehyde

Crystal structure analysis of the title compound, C₁₃H₁₂ClNO, reveals three crystallographically independent mol­ecules in the asymmetric unit. The main conformational difference between these mol­ecules is the orientation of the phenyl rings with respect to the pyrrole rings. The coplanar arrangement of the aldehyde groups attached to the pyrrole rings influences the pyrrole-ring geometry. The C2-C3 and N1-C5 bonds are noticeably longer than the C4-C5 and N1-C2 bonds. Two independent mol­ecules of the title compound form dimers via intermolecular C-H...O hydrogen bonds [D...A = 3.400 (3) Å and D-H...A = 157°]. The perpendicular orientation of the phenyl and pyrrole rings of one independent mol­ecule and its symmetry-related mol­ecule allows C-H...[pi] interactions, with an H...centroid distance of 2.85 Å and a C-H...[pi] angle of 155°. The distances between the H atom and the pyrrole-ring atoms indicate that the C-H bond points towards one of the bonds in the pyrrole ring.

S1. Comment

The substituted pyrrole ring, which is known to be an important unit in many kinds of useful π-electron systems (Evans, 1990; Yanai et al., 2000; Takeda et al., 2001), forms part of our research on substituted heterocyclic compounds (Jukić et al., 1999 & 2003). The synthesis of pyrrole rings has remained an extremely attractive domain in heterocyclic chemistry, as they constitute the core unit of many natural products (Fürstner et al., 2002) and serve as the building blocks for porphyrin synthesis (Dolušić et al., 2003; Guo et al., 2003; Naik et al., 2003). The present study forms part of our continuing interest in the synthesis, stereochemistry and structural analysis of N-aryl- and N-heteroaryl-2,5-dimethylpyrrole-3-carbaldehyde (Vorkapić-Furač et al., 1992) and in their usage as corrosion inhibitors of iron (Stupnišek-Lisac et al., 1988; Stupnišek-Lisac et al., 1992) or as synthetic plant growth factors (cytokinins; Bajrović et al., 1993).

The asymmetric unit of the title compound, (I), (Fig. 1) contains three crystallographically independent molecules, viz. A, B and C. The bond lengths in their pyrrole rings and attached aldehyde groups agree within standard uncertainties (Table 1), and the bond lengths in the rest of the molecules differ only slightly. The biggest conformational difference between these three molecules was observed in the orientation of the phenyl rings with respect to the pyrrole rings, the C2–N1–C9–C10 torsion angles being 92.4 (2), −82.9 (2) and −96.2 (2)°, respectively.

The aldehyde groups are coplanar with the pyrrole rings to which they are attached; the C4—C3—C6—O1 torsion angles are −4.0 (3), 0.7 (4) and −0.1 (4)°, respectively. A coplanar arrangement of the aldehyde groups allows the extension of the π conjugation of the ring over the carbonyl groups. The π-electron transfer is substantiated by the deviation of the pyrrole-ring geometry. The C2—C3 bond is slightly elongated compared with the average value for Csp²═Csp² bond distance in 1H-pyrroles (1.375 Å; Allen et al., 1987) and noticeably longer than the C4—C5 bond. Because of the C2—C3 and C4—C5 bond-length deviations, the N1—C5 bond is noticeably longer than the N1—C2 bond and the corresponding Csp²—N(3) bond distance in 1H-pyrroles (1.372 Å; Allen et al., 1987). The efficient π-systems spread from the pyrrole ring to the carbonyl group is confirmed by the shortening of the C3—C6 bond [Csp²—Csp²(conjugated) = 1.455 Å; Allen et al., 1987]. A survey the Cambridge Structural Database (Allen, 2002) revealed three structures that have an aldehyde group at the 3-position of the pyrrole ring (Conde et al., 1979; de la Figuera Gomez et al., 1985; Lokaj et al., 2001). In these structures, the pyrrole-ring geometry is significantly different because of the influence of the other ring substituents. The structure of (I) is the first example of an N-(o-chlorophenyl)-substituted pyrrole ring.

The sum of the angles around atom N1 is 360° (Table 1), assuming that the N atoms, whose lone electron pairs are included in the aromatic systems, posses an sp² planar arrangement. Consequently, the pyrrole rings are planar, and the largest observed deviation from their mean planes is 0.006 (2) Å for atom C2 in molecule A. The phenyl rings are almost perpendicular to the pyrrole rings [the dihedral angles are 86.9 (1), 83.8 (1) and 85.7 (1)°] and thus are not favourably disposed for inter-ring conjugation. Furthermore, the pyrrole and phenyl rings of molecules A and C are almost parallel to each other, the dihedral angles being 6.4 (1) and 7.0 (1)°, respectively.

In the crystal structure, two independent molecules of (I) form dimers via intermolecular C4A—H4A···O1Bⁱ hydrogen bonds [symmetry code (i): 1 − x, −y, 1 − z]. The D···A and H···A distances are 3.400 (3) and 2.53 Å, and the D–H···A angle is 157° (Fig. 2). We found molecules linked by such C_pyrrole—H···O(═CH) hydrogen bonds in only one structure (Adams et al., 1986). Surprisingly, molecule C is completely isolated and does not participate in hydrogen bonding. Its shortest intermolecular contacts are H14C···O1Bⁱ and H72C···O1Cⁱⁱ [symmetry codes (i): x, −1/2 − y, −1/2 + z; (ii): x, 1 + y, z], with distances of 2.62 and 2.63 Å, respectively. The phenyl and pyrrole rings of two neighbouring symmetry-related A molecules are perpendicularly oriented. Such molecular packing leads to C—H···π interaction between the phenyl H14A atom and the pyrrole ring, with an H···centroidⁱ distance of 2.85 Å and C—H···π angle of 155° [symmetry code (i): 1 − x, −y, 1 − z]. In fact, the H14A···C4A distance [2.70 Å] is shorter than the distance between the H atom and the pyrrole ring centroid. The second shortest H···C contact is that to atom C5A [2.87 Å], and all other H···C distances are larger than 3.05 Å. According to these observations, the C—H bond points more in the directions of? the C4A—C5A bond of the pyrrole ring than the ring as a whole (centroid). These C—H···π interactions connect hydrogen-bonded dimers in the ac plane.

S2. Experimental

N-(o-Chlorophenyl)-2,5-dimethylpyrrole-3-carbaldehyde was prepared by condensation of hexane-2,5-dione with 2-chloroaniline and subsequent Vilsmeier–Haack formylation of the pyrrole ring (Vorkapić-Furač et al., 1989), according to the modified procedure given for the preparation of? pyrrole-2-carbaldehyde and N-methylpyrrole-2-carbaldehyde (Silverstein et al., 1955). Compound (I) was recrystallized twice from a methanol–water (50:50, v/v) mixture and obtained as yellow crystals (yield 89%, m.p. 333 K). The structure of the compound was confirmed by elemental analysis and IR, UV, NMR and electron impact spectra (Vorkapić-Furač et al., 1989). A single-crystal was obtained by slow evaporation at room temperature from a methanol–water solution (50:50, v/v).

S3. Refinement

H atoms attached to C6 atoms were found in a difference Fourier map and the coordinates and isotropic thermal parameters were refined freely. All other H atoms were included in calculated positions as riding atoms, with C—H distances of 0.96 Å for methyl H atoms and 0.93 Å for the remaining H atoms.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. For clarity, only one of the three independent molecules from the asymmetric unit is presented. Displacement ellipsoids for non-H atoms have been drawn at the 20% probability level.
	Fig. 2. The crystal packing, viewed along the b axis. The three independent molecules are designated A, B and C. Intermolecular hydrogen bonds and C—H···π interactions are shown by dashed lines.

N-(2-chlorphenyl)-2,5-dimethylpyrrole-3-carbaldehyde

Crystal data

C13H12ClNO	F(000) = 1464
Mr = 233.69	Dx = 1.291 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8586 reflections
a = 21.6815 (3) Å	θ = 2.6–27.5°
b = 8.6127 (1) Å	µ = 0.30 mm^−1
c = 19.7231 (2) Å	T = 293 K
β = 101.6257 (5)°	Prismatic, yellow
V = 3607.46 (8) Å^3	0.35 × 0.35 × 0.15 mm
Z = 12

Data collection

Nonius KappaCCD area-detector diffractometer	8109 independent reflections
Radiation source: fine-focus sealed tube	5495 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ϕ and ω scans	θmax = 27.4°, θmin = 3.4°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −28→27
Tmin = 0.902, Tmax = 0.957	k = −11→10
43063 measured reflections	l = −25→25

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0706P)^2 + 1.2178P] where P = (Fo^2 + 2Fc^2)/3
8109 reflections	(Δ/σ)max = 0.001
451 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl1A	0.48046 (4)	0.03988 (10)	0.23429 (3)	0.0950 (3)
N1A	0.50037 (7)	0.08243 (19)	0.38620 (8)	0.0482 (4)
O1A	0.59812 (9)	0.5316 (2)	0.47022 (9)	0.0806 (5)
C2A	0.48663 (9)	0.2348 (2)	0.39532 (9)	0.0492 (4)
C3A	0.54292 (9)	0.3074 (2)	0.42339 (9)	0.0496 (4)
C4A	0.59147 (10)	0.1946 (2)	0.43005 (10)	0.0543 (5)
H4A	0.6341	0.2123	0.4473	0.065*
C5A	0.56522 (9)	0.0571 (2)	0.40701 (10)	0.0537 (5)
C6A	0.54944 (12)	0.4693 (3)	0.44217 (11)	0.0611 (5)
H6A	0.5102 (10)	0.530 (2)	0.4324 (10)	0.050 (5)*
C7A	0.59278 (12)	−0.0999 (3)	0.40252 (17)	0.0862 (8)
H71A	0.6374	−0.0959	0.4202	0.129*
H72A	0.5849	−0.1330	0.3551	0.129*
H73A	0.5739	−0.1719	0.4294	0.129*
C8A	0.42141 (11)	0.2953 (3)	0.37527 (14)	0.0735 (7)
H81A	0.4200	0.3999	0.3917	0.110*
H82A	0.3936	0.2314	0.3954	0.110*
H83A	0.4085	0.2937	0.3258	0.110*
C9A	0.45597 (9)	−0.0349 (2)	0.35823 (10)	0.0486 (4)
C10A	0.44351 (9)	−0.0687 (2)	0.28825 (10)	0.0530 (5)
C11A	0.40221 (11)	−0.1862 (3)	0.26169 (12)	0.0675 (6)
H11A	0.3949	−0.2101	0.2148	0.081*
C12A	0.37224 (11)	−0.2669 (3)	0.30552 (15)	0.0739 (7)
H12A	0.3442	−0.3459	0.2881	0.089*
C13A	0.38311 (13)	−0.2325 (3)	0.37480 (15)	0.0836 (8)
H13A	0.3618	−0.2864	0.4039	0.100*
C14A	0.42545 (12)	−0.1183 (3)	0.40117 (12)	0.0724 (7)
H14A	0.4336	−0.0971	0.4484	0.087*
Cl1B	0.13764 (4)	0.28273 (9)	0.23515 (3)	0.0901 (2)
N1B	0.16587 (7)	0.28089 (18)	0.38869 (8)	0.0462 (4)
O1B	0.25930 (8)	−0.1717 (2)	0.47523 (9)	0.0802 (5)
C2B	0.15079 (8)	0.1295 (2)	0.39870 (9)	0.0460 (4)
C3B	0.20599 (9)	0.0551 (2)	0.42895 (9)	0.0486 (4)
C4B	0.25548 (9)	0.1668 (2)	0.43633 (10)	0.0553 (5)
H4B	0.2977	0.1481	0.4551	0.066*
C5B	0.23064 (9)	0.3043 (2)	0.41153 (10)	0.0524 (5)
C6B	0.21092 (12)	−0.1062 (3)	0.44840 (11)	0.0598 (5)
H6B	0.1718 (10)	−0.164 (2)	0.4390 (10)	0.053 (6)*
C7B	0.26008 (11)	0.4580 (3)	0.40400 (15)	0.0759 (7)
H71B	0.3037	0.4550	0.4263	0.114*
H72B	0.2389	0.5368	0.4251	0.114*
H73B	0.2565	0.4811	0.3558	0.114*
C8B	0.08521 (10)	0.0713 (3)	0.37765 (12)	0.0617 (5)
H81B	0.0567	0.1454	0.3907	0.093*
H82B	0.0813	−0.0259	0.4002	0.093*
H83B	0.0753	0.0569	0.3284	0.093*
C9B	0.12261 (8)	0.3977 (2)	0.35786 (10)	0.0487 (4)
C10B	0.10606 (9)	0.4111 (3)	0.28617 (11)	0.0585 (5)
C11B	0.06506 (11)	0.5247 (3)	0.25593 (15)	0.0768 (7)
H11B	0.0545	0.5334	0.2080	0.092*
C12B	0.04009 (11)	0.6244 (3)	0.29674 (19)	0.0859 (9)
H12B	0.0124	0.7013	0.2763	0.103*
C13B	0.05515 (12)	0.6134 (3)	0.36765 (19)	0.0835 (8)
H13B	0.0373	0.6818	0.3947	0.100*
C14B	0.09717 (11)	0.4996 (3)	0.39897 (14)	0.0675 (6)
H14B	0.1079	0.4923	0.4470	0.081*
Cl1C	0.17611 (4)	−0.19303 (9)	0.26527 (3)	0.0955 (3)
N1C	0.16827 (7)	−0.26199 (17)	0.11563 (8)	0.0481 (4)
O1C	0.07458 (9)	−0.71643 (19)	0.03145 (10)	0.0893 (6)
C2C	0.18305 (9)	−0.4155 (2)	0.10940 (10)	0.0486 (4)
C3C	0.12867 (10)	−0.4890 (2)	0.07585 (10)	0.0501 (4)
C4C	0.08000 (10)	−0.3756 (2)	0.06230 (10)	0.0556 (5)
H4C	0.0385	−0.3934	0.0404	0.067*
C5C	0.10458 (9)	−0.2375 (2)	0.08680 (11)	0.0536 (5)
C6C	0.12301 (13)	−0.6522 (3)	0.05957 (12)	0.0652 (6)
H6C	0.1622 (11)	−0.711 (3)	0.0724 (11)	0.066 (7)*
C7C	0.07460 (12)	−0.0827 (3)	0.08900 (15)	0.0814 (7)
H71C	0.0324	−0.0858	0.0623	0.122*
H72C	0.0984	−0.0060	0.0700	0.122*
H73C	0.0736	−0.0566	0.1361	0.122*
C8C	0.24734 (11)	−0.4741 (3)	0.13670 (14)	0.0711 (6)
H81C	0.2774	−0.4096	0.1203	0.107*
H82C	0.2508	−0.5787	0.1211	0.107*
H83C	0.2556	−0.4720	0.1864	0.107*
C9C	0.21133 (9)	−0.1422 (2)	0.14413 (10)	0.0496 (4)
C10C	0.21797 (10)	−0.0969 (2)	0.21261 (11)	0.0566 (5)
C11C	0.25785 (11)	0.0235 (3)	0.23908 (13)	0.0700 (6)
H11C	0.2616	0.0544	0.2849	0.084*
C12C	0.29197 (11)	0.0968 (3)	0.19669 (15)	0.0739 (7)
H12C	0.3186	0.1785	0.2140	0.089*
C13C	0.28730 (12)	0.0515 (3)	0.12993 (16)	0.0772 (7)
H13C	0.3115	0.1006	0.1023	0.093*
C14C	0.24679 (11)	−0.0675 (3)	0.10263 (13)	0.0664 (6)
H14C	0.2434	−0.0973	0.0567	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1A	0.1319 (6)	0.1074 (6)	0.0542 (3)	−0.0403 (5)	0.0389 (4)	−0.0091 (3)
N1A	0.0496 (9)	0.0494 (9)	0.0451 (8)	−0.0045 (7)	0.0085 (7)	−0.0010 (7)
O1A	0.0899 (12)	0.0714 (11)	0.0765 (11)	−0.0241 (9)	0.0072 (9)	−0.0160 (9)
C2A	0.0552 (11)	0.0519 (11)	0.0418 (9)	−0.0031 (9)	0.0126 (8)	−0.0047 (8)
C3A	0.0593 (11)	0.0522 (11)	0.0373 (9)	−0.0082 (9)	0.0097 (8)	−0.0005 (8)
C4A	0.0516 (11)	0.0610 (12)	0.0481 (10)	−0.0083 (9)	0.0052 (8)	0.0046 (9)
C5A	0.0506 (11)	0.0554 (12)	0.0528 (11)	0.0002 (9)	0.0051 (9)	0.0064 (9)
C6A	0.0732 (15)	0.0601 (13)	0.0504 (11)	−0.0079 (12)	0.0131 (10)	−0.0062 (10)
C7A	0.0655 (15)	0.0616 (15)	0.123 (2)	0.0095 (12)	−0.0008 (14)	0.0029 (15)
C8A	0.0593 (13)	0.0682 (15)	0.0908 (17)	0.0043 (11)	0.0102 (12)	−0.0173 (13)
C9A	0.0495 (10)	0.0484 (10)	0.0483 (10)	−0.0045 (8)	0.0109 (8)	−0.0025 (8)
C10A	0.0570 (11)	0.0530 (11)	0.0498 (10)	−0.0015 (9)	0.0127 (9)	−0.0039 (9)
C11A	0.0712 (14)	0.0618 (13)	0.0644 (13)	−0.0025 (11)	0.0015 (11)	−0.0155 (11)
C12A	0.0636 (14)	0.0547 (13)	0.0982 (19)	−0.0144 (11)	0.0038 (13)	−0.0051 (13)
C13A	0.0868 (18)	0.0773 (17)	0.0906 (19)	−0.0314 (14)	0.0272 (14)	0.0045 (15)
C14A	0.0894 (17)	0.0746 (15)	0.0563 (12)	−0.0244 (13)	0.0223 (12)	−0.0010 (11)
Cl1B	0.1156 (6)	0.0991 (5)	0.0580 (3)	0.0189 (4)	0.0231 (3)	0.0101 (3)
N1B	0.0425 (8)	0.0443 (8)	0.0494 (8)	−0.0015 (6)	0.0037 (6)	0.0068 (7)
O1B	0.0829 (11)	0.0671 (10)	0.0852 (11)	0.0256 (9)	0.0044 (9)	0.0190 (9)
C2B	0.0492 (10)	0.0450 (10)	0.0425 (9)	−0.0029 (8)	0.0064 (8)	0.0048 (8)
C3B	0.0527 (11)	0.0497 (11)	0.0420 (9)	0.0047 (9)	0.0061 (8)	0.0056 (8)
C4B	0.0439 (10)	0.0607 (12)	0.0578 (11)	0.0038 (9)	0.0015 (9)	0.0067 (10)
C5B	0.0428 (10)	0.0533 (11)	0.0580 (11)	−0.0053 (8)	0.0028 (8)	0.0038 (9)
C6B	0.0710 (14)	0.0529 (12)	0.0544 (12)	0.0059 (11)	0.0099 (10)	0.0063 (10)
C7B	0.0553 (13)	0.0595 (14)	0.107 (2)	−0.0132 (11)	0.0028 (12)	0.0106 (13)
C8B	0.0549 (12)	0.0551 (12)	0.0708 (13)	−0.0080 (10)	0.0022 (10)	0.0096 (10)
C9B	0.0402 (9)	0.0444 (10)	0.0599 (11)	−0.0028 (8)	0.0063 (8)	0.0103 (9)
C10B	0.0500 (11)	0.0571 (12)	0.0662 (13)	−0.0017 (9)	0.0063 (9)	0.0165 (10)
C11B	0.0612 (14)	0.0717 (16)	0.0895 (17)	0.0040 (12)	−0.0039 (12)	0.0311 (14)
C12B	0.0541 (14)	0.0587 (15)	0.138 (3)	0.0047 (11)	0.0026 (15)	0.0330 (17)
C13B	0.0649 (15)	0.0511 (13)	0.141 (3)	0.0034 (11)	0.0350 (16)	−0.0002 (15)
C14B	0.0668 (14)	0.0534 (12)	0.0846 (16)	0.0030 (11)	0.0210 (12)	0.0010 (12)
Cl1C	0.1282 (6)	0.1010 (5)	0.0663 (4)	−0.0374 (5)	0.0415 (4)	−0.0145 (4)
N1C	0.0542 (9)	0.0388 (8)	0.0518 (9)	0.0008 (7)	0.0116 (7)	−0.0053 (7)
O1C	0.1110 (14)	0.0551 (10)	0.0895 (12)	−0.0281 (10)	−0.0093 (10)	−0.0030 (9)
C2C	0.0574 (11)	0.0394 (9)	0.0494 (10)	0.0027 (8)	0.0115 (8)	−0.0010 (8)
C3C	0.0626 (12)	0.0422 (10)	0.0454 (10)	−0.0055 (9)	0.0103 (8)	−0.0006 (8)
C4C	0.0532 (11)	0.0573 (12)	0.0552 (11)	−0.0032 (9)	0.0088 (9)	0.0012 (10)
C5C	0.0549 (11)	0.0489 (11)	0.0571 (11)	0.0043 (9)	0.0117 (9)	−0.0018 (9)
C6C	0.0872 (17)	0.0461 (12)	0.0585 (13)	−0.0063 (12)	0.0060 (12)	0.0009 (10)
C7C	0.0771 (16)	0.0630 (15)	0.1010 (19)	0.0215 (12)	0.0106 (14)	−0.0061 (14)
C8C	0.0665 (14)	0.0513 (12)	0.0907 (17)	0.0094 (10)	0.0042 (12)	−0.0034 (12)
C9C	0.0529 (11)	0.0380 (9)	0.0591 (11)	−0.0001 (8)	0.0146 (9)	−0.0067 (8)
C10C	0.0622 (12)	0.0486 (11)	0.0600 (12)	−0.0029 (9)	0.0144 (10)	−0.0068 (9)
C11C	0.0731 (14)	0.0558 (13)	0.0768 (15)	−0.0015 (11)	0.0047 (12)	−0.0185 (12)
C12C	0.0656 (14)	0.0458 (12)	0.106 (2)	−0.0073 (10)	0.0070 (13)	−0.0120 (13)
C13C	0.0755 (16)	0.0544 (13)	0.109 (2)	−0.0141 (12)	0.0350 (14)	0.0001 (14)
C14C	0.0816 (15)	0.0533 (12)	0.0705 (14)	−0.0076 (11)	0.0299 (12)	−0.0051 (11)

Geometric parameters (Å, º)

Cl1A—C10A	1.730 (2)	C7B—H73B	0.96
N1A—C2A	1.366 (2)	C8B—H81B	0.96
N1A—C5A	1.400 (2)	C8B—H82B	0.96
N1A—C9A	1.428 (2)	C8B—H83B	0.96
O1A—C6A	1.214 (3)	C9B—C14B	1.383 (3)
C2A—C3A	1.384 (3)	C9B—C10B	1.392 (3)
C2A—C8A	1.484 (3)	C10B—C11B	1.375 (3)
C3A—C4A	1.419 (3)	C11B—C12B	1.362 (4)
C3A—C6A	1.442 (3)	C11B—H11B	0.93
C4A—C5A	1.353 (3)	C12B—C13B	1.374 (4)
C4A—H4A	0.93	C12B—H12B	0.93
C5A—C7A	1.488 (3)	C13B—C14B	1.395 (4)
C6A—H6A	0.98 (2)	C13B—H13B	0.93
C7A—H71A	0.96	C14B—H14B	0.93
C7A—H72A	0.96	Cl1C—C10C	1.723 (2)
C7A—H73A	0.96	N1C—C2C	1.372 (2)
C8A—H81A	0.96	N1C—C5C	1.399 (2)
C8A—H82A	0.96	N1C—C9C	1.429 (2)
C8A—H83A	0.96	O1C—C6C	1.217 (3)
C9A—C14A	1.377 (3)	C2C—C3C	1.384 (3)
C9A—C10A	1.383 (3)	C2C—C8C	1.478 (3)
C10A—C11A	1.382 (3)	C3C—C4C	1.423 (3)
C11A—C12A	1.371 (3)	C3C—C6C	1.441 (3)
C11A—H11A	0.93	C4C—C5C	1.352 (3)
C12A—C13A	1.372 (4)	C4C—H4C	0.93
C12A—H12A	0.93	C5C—C7C	1.488 (3)
C13A—C14A	1.374 (3)	C6C—H6C	0.98 (2)
C13A—H13A	0.93	C7C—H71C	0.96
C14A—H14A	0.93	C7C—H72C	0.96
Cl1B—C10B	1.727 (2)	C7C—H73C	0.96
N1B—C2B	1.368 (2)	C8C—H81C	0.96
N1B—C5B	1.400 (2)	C8C—H82C	0.96
N1B—C9B	1.425 (2)	C8C—H83C	0.96
O1B—C6B	1.214 (3)	C9C—C10C	1.385 (3)
C2B—C3B	1.382 (3)	C9C—C14C	1.389 (3)
C2B—C8B	1.486 (3)	C10C—C11C	1.383 (3)
C3B—C4B	1.426 (3)	C11C—C12C	1.376 (4)
C3B—C6B	1.440 (3)	C11C—H11C	0.93
C4B—C5B	1.351 (3)	C12C—C13C	1.357 (4)
C4B—H4B	0.93	C12C—H12C	0.93
C5B—C7B	1.490 (3)	C13C—C14C	1.386 (3)
C6B—H6B	0.97 (2)	C13C—H13C	0.93
C7B—H71B	0.96	C14C—H14C	0.93
C7B—H72B	0.96
C2A—N1A—C5A	110.13 (16)	C2B—C8B—H81B	109.5
C2A—N1A—C9A	125.66 (16)	C2B—C8B—H82B	109.5
C5A—N1A—C9A	124.20 (16)	H81B—C8B—H82B	109.5
N1A—C2A—C3A	106.79 (17)	C2B—C8B—H83B	109.5
N1A—C2A—C8A	121.59 (18)	H81B—C8B—H83B	109.5
C3A—C2A—C8A	131.6 (2)	H82B—C8B—H83B	109.5
C2A—C3A—C4A	107.79 (17)	C14B—C9B—C10B	119.44 (19)
C2A—C3A—C6A	124.9 (2)	C14B—C9B—N1B	120.25 (18)
C4A—C3A—C6A	127.3 (2)	C10B—C9B—N1B	120.31 (18)
C5A—C4A—C3A	108.33 (18)	C11B—C10B—C9B	120.8 (2)
C5A—C4A—H4A	125.8	C11B—C10B—Cl1B	120.04 (19)
C3A—C4A—H4A	125.8	C9B—C10B—Cl1B	119.19 (15)
C4A—C5A—N1A	106.95 (18)	C12B—C11B—C10B	119.5 (2)
C4A—C5A—C7A	131.98 (19)	C12B—C11B—H11B	120.3
N1A—C5A—C7A	121.06 (18)	C10B—C11B—H11B	120.3
O1A—C6A—C3A	125.2 (2)	C11B—C12B—C13B	121.1 (2)
O1A—C6A—H6A	119.5 (12)	C11B—C12B—H12B	119.4
C3A—C6A—H6A	115.3 (12)	C13B—C12B—H12B	119.4
C5A—C7A—H71A	109.5	C12B—C13B—C14B	120.0 (3)
C5A—C7A—H72A	109.5	C12B—C13B—H13B	120.0
H71A—C7A—H72A	109.5	C14B—C13B—H13B	120.0
C5A—C7A—H73A	109.5	C9B—C14B—C13B	119.2 (2)
H71A—C7A—H73A	109.5	C9B—C14B—H14B	120.4
H72A—C7A—H73A	109.5	C13B—C14B—H14B	120.4
C2A—C8A—H81A	109.5	C2C—N1C—C5C	109.75 (16)
C2A—C8A—H82A	109.5	C2C—N1C—C9C	125.83 (16)
H81A—C8A—H82A	109.5	C5C—N1C—C9C	124.36 (15)
C2A—C8A—H83A	109.5	N1C—C2C—C3C	106.98 (17)
H81A—C8A—H83A	109.5	N1C—C2C—C8C	121.10 (17)
H82A—C8A—H83A	109.5	C3C—C2C—C8C	131.92 (18)
C14A—C9A—C10A	118.86 (19)	C2C—C3C—C4C	107.68 (17)
C14A—C9A—N1A	120.11 (17)	C2C—C3C—C6C	125.4 (2)
C10A—C9A—N1A	121.02 (17)	C4C—C3C—C6C	126.9 (2)
C11A—C10A—C9A	120.90 (19)	C5C—C4C—C3C	108.23 (18)
C11A—C10A—Cl1A	120.49 (16)	C5C—C4C—H4C	125.9
C9A—C10A—Cl1A	118.61 (15)	C3C—C4C—H4C	125.9
C12A—C11A—C10A	119.0 (2)	C4C—C5C—N1C	107.36 (17)
C12A—C11A—H11A	120.5	C4C—C5C—C7C	131.0 (2)
C10A—C11A—H11A	120.5	N1C—C5C—C7C	121.62 (19)
C13A—C12A—C11A	120.7 (2)	O1C—C6C—C3C	124.8 (2)
C13A—C12A—H12A	119.7	O1C—C6C—H6C	120.7 (14)
C11A—C12A—H12A	119.7	C3C—C6C—H6C	114.5 (14)
C12A—C13A—C14A	120.0 (2)	C5C—C7C—H71C	109.5
C12A—C13A—H13A	120.0	C5C—C7C—H72C	109.5
C14A—C13A—H13A	120.0	H71C—C7C—H72C	109.5
C13A—C14A—C9A	120.5 (2)	C5C—C7C—H73C	109.5
C13A—C14A—H14A	119.7	H71C—C7C—H73C	109.5
C9A—C14A—H14A	119.7	H72C—C7C—H73C	109.5
C2B—N1B—C5B	110.12 (15)	C2C—C8C—H81C	109.5
C2B—N1B—C9B	125.34 (15)	C2C—C8C—H82C	109.5
C5B—N1B—C9B	124.51 (15)	H81C—C8C—H82C	109.5
N1B—C2B—C3B	107.03 (16)	C2C—C8C—H83C	109.5
N1B—C2B—C8B	121.60 (17)	H81C—C8C—H83C	109.5
C3B—C2B—C8B	131.37 (18)	H82C—C8C—H83C	109.5
C2B—C3B—C4B	107.43 (17)	C10C—C9C—C14C	118.91 (19)
C2B—C3B—C6B	125.01 (19)	C10C—C9C—N1C	121.22 (17)
C4B—C3B—C6B	127.56 (19)	C14C—C9C—N1C	119.87 (18)
C5B—C4B—C3B	108.50 (17)	C11C—C10C—C9C	120.9 (2)
C5B—C4B—H4B	125.7	C11C—C10C—Cl1C	119.85 (18)
C3B—C4B—H4B	125.7	C9C—C10C—Cl1C	119.27 (15)
C4B—C5B—N1B	106.91 (17)	C12C—C11C—C10C	119.1 (2)
C4B—C5B—C7B	131.86 (18)	C12C—C11C—H11C	120.5
N1B—C5B—C7B	121.19 (17)	C10C—C11C—H11C	120.5
O1B—C6B—C3B	125.1 (2)	C13C—C12C—C11C	120.9 (2)
O1B—C6B—H6B	119.5 (12)	C13C—C12C—H12C	119.6
C3B—C6B—H6B	115.3 (12)	C11C—C12C—H12C	119.6
C5B—C7B—H71B	109.5	C12C—C13C—C14C	120.5 (2)
C5B—C7B—H72B	109.5	C12C—C13C—H13C	119.8
H71B—C7B—H72B	109.5	C14C—C13C—H13C	119.8
C5B—C7B—H73B	109.5	C13C—C14C—C9C	119.7 (2)
H71B—C7B—H73B	109.5	C13C—C14C—H14C	120.1
H72B—C7B—H73B	109.5	C9C—C14C—H14C	120.1
C5A—N1A—C2A—C3A	−1.1 (2)	C4B—C3B—C6B—O1B	0.7 (4)
C9A—N1A—C2A—C3A	−179.83 (16)	C2B—N1B—C9B—C14B	97.6 (2)
C5A—N1A—C2A—C8A	177.97 (19)	C5B—N1B—C9B—C14B	−84.1 (2)
C9A—N1A—C2A—C8A	−0.8 (3)	C2B—N1B—C9B—C10B	−82.9 (2)
N1A—C2A—C3A—C4A	0.9 (2)	C5B—N1B—C9B—C10B	95.3 (2)
C8A—C2A—C3A—C4A	−178.0 (2)	C14B—C9B—C10B—C11B	0.3 (3)
N1A—C2A—C3A—C6A	−178.97 (18)	N1B—C9B—C10B—C11B	−179.10 (18)
C8A—C2A—C3A—C6A	2.1 (3)	C14B—C9B—C10B—Cl1B	−179.60 (16)
C2A—C3A—C4A—C5A	−0.4 (2)	N1B—C9B—C10B—Cl1B	1.0 (2)
C6A—C3A—C4A—C5A	179.47 (19)	C9B—C10B—C11B—C12B	−0.5 (3)
C3A—C4A—C5A—N1A	−0.3 (2)	Cl1B—C10B—C11B—C12B	179.47 (19)
C3A—C4A—C5A—C7A	−179.2 (2)	C10B—C11B—C12B—C13B	0.0 (4)
C2A—N1A—C5A—C4A	0.8 (2)	C11B—C12B—C13B—C14B	0.7 (4)
C9A—N1A—C5A—C4A	179.63 (16)	C10B—C9B—C14B—C13B	0.3 (3)
C2A—N1A—C5A—C7A	179.9 (2)	N1B—C9B—C14B—C13B	179.71 (18)
C9A—N1A—C5A—C7A	−1.3 (3)	C12B—C13B—C14B—C9B	−0.8 (4)
C2A—C3A—C6A—O1A	175.8 (2)	C5C—N1C—C2C—C3C	0.6 (2)
C4A—C3A—C6A—O1A	−4.0 (3)	C9C—N1C—C2C—C3C	−176.74 (17)
C2A—N1A—C9A—C14A	−88.6 (3)	C5C—N1C—C2C—C8C	−179.01 (19)
C5A—N1A—C9A—C14A	92.8 (3)	C9C—N1C—C2C—C8C	3.7 (3)
C2A—N1A—C9A—C10A	92.4 (2)	N1C—C2C—C3C—C4C	−0.5 (2)
C5A—N1A—C9A—C10A	−86.2 (2)	C8C—C2C—C3C—C4C	179.0 (2)
C14A—C9A—C10A—C11A	−1.4 (3)	N1C—C2C—C3C—C6C	−179.12 (19)
N1A—C9A—C10A—C11A	177.62 (19)	C8C—C2C—C3C—C6C	0.4 (4)
C14A—C9A—C10A—Cl1A	178.34 (18)	C2C—C3C—C4C—C5C	0.2 (2)
N1A—C9A—C10A—Cl1A	−2.7 (3)	C6C—C3C—C4C—C5C	178.8 (2)
C9A—C10A—C11A—C12A	1.7 (3)	C3C—C4C—C5C—N1C	0.1 (2)
Cl1A—C10A—C11A—C12A	−178.04 (18)	C3C—C4C—C5C—C7C	−177.3 (2)
C10A—C11A—C12A—C13A	−0.3 (4)	C2C—N1C—C5C—C4C	−0.4 (2)
C11A—C12A—C13A—C14A	−1.4 (4)	C9C—N1C—C5C—C4C	176.94 (17)
C12A—C13A—C14A—C9A	1.7 (4)	C2C—N1C—C5C—C7C	177.2 (2)
C10A—C9A—C14A—C13A	−0.3 (4)	C9C—N1C—C5C—C7C	−5.4 (3)
N1A—C9A—C14A—C13A	−179.3 (2)	C2C—C3C—C6C—O1C	178.2 (2)
C5B—N1B—C2B—C3B	0.7 (2)	C4C—C3C—C6C—O1C	−0.1 (4)
C9B—N1B—C2B—C3B	179.16 (17)	C2C—N1C—C9C—C10C	−96.2 (2)
C5B—N1B—C2B—C8B	−178.68 (18)	C5C—N1C—C9C—C10C	86.9 (2)
C9B—N1B—C2B—C8B	−0.2 (3)	C2C—N1C—C9C—C14C	84.7 (3)
N1B—C2B—C3B—C4B	−0.6 (2)	C5C—N1C—C9C—C14C	−92.2 (2)
C8B—C2B—C3B—C4B	178.7 (2)	C14C—C9C—C10C—C11C	1.8 (3)
N1B—C2B—C3B—C6B	179.73 (18)	N1C—C9C—C10C—C11C	−177.32 (19)
C8B—C2B—C3B—C6B	−1.0 (3)	C14C—C9C—C10C—Cl1C	−177.90 (17)
C2B—C3B—C4B—C5B	0.3 (2)	N1C—C9C—C10C—Cl1C	3.0 (3)
C6B—C3B—C4B—C5B	179.9 (2)	C9C—C10C—C11C—C12C	−1.1 (3)
C3B—C4B—C5B—N1B	0.2 (2)	Cl1C—C10C—C11C—C12C	178.61 (18)
C3B—C4B—C5B—C7B	−177.6 (2)	C10C—C11C—C12C—C13C	−0.6 (4)
C2B—N1B—C5B—C4B	−0.5 (2)	C11C—C12C—C13C—C14C	1.6 (4)
C9B—N1B—C5B—C4B	−179.01 (18)	C12C—C13C—C14C—C9C	−0.8 (4)
C2B—N1B—C5B—C7B	177.5 (2)	C10C—C9C—C14C—C13C	−0.8 (3)
C9B—N1B—C5B—C7B	−0.9 (3)	N1C—C9C—C14C—C13C	178.28 (19)
C2B—C3B—C6B—O1B	−179.7 (2)