Crystal structure of 1′,1′′-dimethyl-4′-(4-cholorophen­yl)di­spiro­[11H-indeno[1,2-b]quinoxaline-11,2′-pyrrolidine-3′,3′′-piperidin]-4′′-one

In the title compound, C₃₀H₂₇ClN₄O, the central pyrrolidine ring adopts an envelope conformation with the methyl­ene C atom being the flap. The quinoxaline and indane rings are each essentially planar, with r.m.s. deviations of 0.027 (1) and 0.0417 (1) Å, respectively. The pyrrolidine ring forms dihedral angles of 88.25 (1) and 83.76 (1)° with the quinoxaline and indane rings, respectively. A weak intra­molecular C—H...N inter­action is observed. In the crystal, C—H...π inter­actions lead to supra­molecular chains along [101] that assemble in the ac plane. Connections along the b axis are of the type Cl...Cl [3.6538 (16) Å].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.116
• Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level B
THETM01_ALERT_3_B  The value of sine(theta_max)/wavelength is less than 0.575
            Calculated sin(theta_max)/wavelength =    0.5681

Author Response: In this particular structure determination, the crystals did not diffract out that far. Inclusion of the very weak data beyond 23.8 Deg did not enhance the structure refinement. However, the structure was solved with out ambiguity.

PLAT019_ALERT_1_B  _diffrn_measured_fraction_theta_full/_max < 1.0      0.851 Report

Author Response: The best crystal investigated was still of poor quality and very weakly diffracting, with no usable data obtanied above 23.8 Deg. Nonetheless the structure solved readily and refined to give acceptable uncertainties on the metrical data.

PLAT023_ALERT_3_B Resolution (too) Low [sin(theta)/Lambda < 0.6]..      23.82 Degree

Alert level C
PLAT241_ALERT_2_C High      Ueq as Compared to Neighbors for .....        C35 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        C31 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        C34 Check
PLAT334_ALERT_2_C Small Average Benzene  C-C Dist. C31    -C36           1.37 Ang.
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.839 Report
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.568         25 Report

Alert level G
PLAT128_ALERT_4_G Alternate Setting for Input Space Group     C2/c       I2/a Note
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT793_ALERT_4_G The Model has Chirality at C3      .............          R Verify
PLAT793_ALERT_4_G The Model has Chirality at C4      .............          S Verify
PLAT793_ALERT_4_G The Model has Chirality at C5      .............          R Verify
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          43 %
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          2 Report

   0 ALERT level A = Most likely a serious problem - resolve or explain
   3 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Chemical context

Quinoxaline derivatives are an important class of benzoheterocycles. They have found applications as anti-cancer, anti-viral, and anti-bacterial agents (Seitz et al., 2002), and dyes (Dailey et al., 2001). Quinoxaline derivatives were found to exhibit anti-microbial (Kleim et al. 1995), anti­tumor (Abasolo et al., 1987), and anti-tuberculous activity (Rodrigo et al., 2002). Our inter­est in preparing pharmacologically active quinoxaline derivatives led us to the title compound, and we have undertaken X-ray crystal structure determination in order to establish its conformation.

S2. Structural commentary

In the title compound (Fig. 1), C₃₀H₂₇ClN₄O, the central pyrrolidine ring is an envelope on C2 with the asymmetry parameters ΔC_s(C2) = 7.6 (2) Å and puckering parameters q₂ = 0.433 (2) Å and ϕ₂ = 31.2 (3)°. The pyrrolidine ring is almost equatorial with the quinoxaline and indane rings making dihedral angles of 88.34 (1)° and 83.71 (1)°, respectively. The quinoxaline ring system (C12—C17/N3,N4) is planar, with r.m.s. deviation of 0.027 (1) Å. The indane group is also planar with r.m.s.deviation 0.0417 (1)°. The dihedral angle between the mean planes of the fused quinoxaline and the indane groups is 8.39 (1) °, which indicates that the fused rings are slightly twisted about the C12—C13 bond. The C—C bond lengths in the pyrrolidine ring in particular, at two spiro junctions (C3—C4 = 1.558 (3) Å and C4—C5 = 1.605 (3) Å) are somewhat longer than the normal values (C—C = 1.54 Å), as found in a similar structure (Selvanayagam et al., 2011). This may be due to the the steric inter­actions of the bulky substituents at atoms C4 and C5 of the pyrrolidine ring. The short contact H32 ··· H2b of 2.18 Å results in substantial widening of the bond angle C3—C31—C32 to 123.67 (1) °. The sum of the bond angles around N1 (339.87 (1)°) and N2 (330.97 (1)°) indicate that the atoms N1 and N2 exhibit a pyramidal geometry. The six membered ring N2/C41—C45 exhibits a twisted chair conformation, as indicated by the assymetrical parameters ΔC_s(N2) = 7.4 (2)°, ΔC_s(C45) = 7.4 (2) ° and with the puckering parameters Q = 0.559 (3) Å, θ = 17.4 (3)° and Φ = 24.6 (9)°. The torsion angle C4—C41—N2—C42 is -167.50 ° corresponds to an anti­periplanar conformation.

A weak intra-molecular C—H···N inter­action is observed (Table 1). In the crystal, C—H···π inter­actions lead to supra­molecular chains along [101] that assemble in the ac plane. Connections along the b axis are of the type Cl···Cl (3.6538 (16) Å).

S3. Synthesis and crystallization

A mixture of 1-methyl-3-[E-(4-chloro­phenyl)­methyl­idene]tetra­hydro-2(1H)- pyridinone (1 mmol), ninhydrin (1 mmol), o-phenyl­enedi­amine (1 mmol) and sarcosine (1 mmol) in methanol was refluxed for 3-4 h. After completion of the reaction as indicated by TLC the reaction mixture was poured into cold water. The solid precipitate obtained was filtered and dried. The product was purified by colum chromatography using petroleum ether:ethyl­acetate mixture (90:10 V/V). Suitable crystals for the single crystal-X-ray studies were obtained by recrystalizing the product from methanol. Yield: 42%, Melting point: 450-452 K.

S4. Refinement

All the H atoms were placed at calculated positions and allowed to ride on their carrier atoms with C—H = 0.93–0.98 Å, and with U_iso = 1.2U_eq(C) for CH₂ and CH groups, and U_iso = 1.5U_eq(C) for CH₃ groups. The (-1 1 1), (1 1 0) reflections were affected by the beam-stop and were removed from the final refinement. The best crystal investigated was still of poor quality and very weakly diffracting, with no usable data obtanied above θ = 23.8°. Nonetheless, the structure was solved readily and refined to give acceptable uncertainties on the metrical data.

Related literature

For the importance of quinoxaline derivatives, see: Abasolo et al. (1987); Kleim et al. (1995); Dailey et al. (2001); Rodrigo et al. (2002); Seitz et al. (2002). For a related structure, see: Selvanayagam et al. (2011).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. H-atoms are omitted for clarity.
	Fig. 2. The partial packing diagram showing C—H···π interactions as dashed lines. All H-atoms are omitted for clarity except for the H atom involved in the intermolecular interaction.

1',1''-Dimethyl-4'-(4-cholorophenyl)dispiro[11H- indeno[1,2-b]quinoxaline-11,2'-pyrrolidine-3',3''-piperidin]-4''-one

Crystal data

C30H27ClN4O	F(000) = 2080
Mr = 495.00	Dx = 1.326 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.4220 (13) Å	Cell parameters from 2000 reflections
b = 14.3498 (9) Å	θ = 2–31°
c = 17.2811 (9) Å	µ = 0.19 mm^−1
β = 116.847 (2)°	T = 293 K
V = 4960.9 (5) Å^3	Block, colourless
Z = 8	0.21 × 0.19 × 0.18 mm

Data collection

Bruker Kappa APEXII diffractometer	2758 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
ω and ϕ scans	θmax = 23.8°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→25
Tmin = 0.967, Tmax = 0.974	k = −16→16
18093 measured reflections	l = −19→13
3791 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.052P)^2 + 2.7359P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3791 reflections	Δρmax = 0.22 e Å^−3
325 parameters	Δρmin = −0.26 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.

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

	x	y	z	Uiso*/Ueq
C1	0.30822 (11)	0.05687 (16)	0.33108 (14)	0.0608 (6)
H1A	0.3191	0.0297	0.2883	0.091*
H1B	0.3481	0.0807	0.3781	0.091*
H1C	0.2888	0.0103	0.3526	0.091*
C2	0.23954 (11)	0.18035 (15)	0.34879 (13)	0.0523 (5)
H2A	0.2767	0.2104	0.3965	0.063*
H2B	0.2174	0.1385	0.3717	0.063*
C3	0.19136 (10)	0.25089 (14)	0.28740 (12)	0.0459 (5)
H3	0.2184	0.2962	0.2746	0.055*
C4	0.15164 (10)	0.19405 (14)	0.20256 (12)	0.0457 (5)
C5	0.20122 (9)	0.10932 (14)	0.21204 (12)	0.0439 (5)
C6	0.22053 (10)	0.09623 (14)	0.13862 (12)	0.0466 (5)
C7	0.19965 (10)	0.01074 (15)	0.09751 (12)	0.0492 (5)
C8	0.21358 (12)	−0.01455 (18)	0.03003 (14)	0.0630 (6)
H8	0.1994	−0.0717	0.0024	0.076*
C9	0.24862 (13)	0.0464 (2)	0.00475 (16)	0.0714 (7)
H9	0.2575	0.0308	−0.0413	0.086*
C10	0.27083 (12)	0.13009 (18)	0.04655 (14)	0.0650 (6)
H10	0.2953	0.1699	0.0292	0.078*
C11	0.25718 (10)	0.15583 (16)	0.11420 (13)	0.0556 (6)
H11	0.2725	0.2124	0.1426	0.067*
C12	0.17122 (9)	0.01365 (14)	0.21185 (12)	0.0447 (5)
C13	0.16878 (10)	−0.04160 (14)	0.14202 (12)	0.0462 (5)
C14	0.12375 (10)	−0.15970 (15)	0.18401 (13)	0.0513 (5)
C15	0.12990 (10)	−0.10743 (15)	0.25619 (13)	0.0506 (5)
C16	0.11002 (11)	−0.14672 (17)	0.31511 (15)	0.0628 (6)
H16	0.1147	−0.1130	0.3635	0.075*
C17	0.08385 (12)	−0.23439 (19)	0.30153 (17)	0.0719 (7)
H17	0.0710	−0.2604	0.3410	0.086*
C18	0.07626 (12)	−0.28531 (18)	0.22925 (18)	0.0737 (7)
H18	0.0576	−0.3446	0.2202	0.088*
C19	0.09589 (11)	−0.24923 (16)	0.17162 (15)	0.0623 (6)
H19	0.0908	−0.2842	0.1237	0.075*
C31	0.15093 (10)	0.30600 (14)	0.32168 (13)	0.0483 (5)
C32	0.14179 (12)	0.27914 (17)	0.39179 (14)	0.0640 (6)
H32	0.1598	0.2228	0.4188	0.077*
C33	0.10678 (13)	0.3330 (2)	0.42345 (15)	0.0742 (7)
H33	0.1012	0.3126	0.4709	0.089*
C34	0.08049 (13)	0.4154 (2)	0.38554 (17)	0.0752 (7)
C35	0.08847 (17)	0.4439 (2)	0.3162 (2)	0.1013 (10)
H35	0.0704	0.5005	0.2898	0.122*
C36	0.12311 (15)	0.38969 (18)	0.28474 (18)	0.0839 (8)
H36	0.1278	0.4104	0.2368	0.101*
C41	0.08396 (10)	0.16135 (16)	0.19371 (13)	0.0539 (5)
H41A	0.0908	0.1229	0.2432	0.065*
H41B	0.0576	0.2151	0.1934	0.065*
C42	−0.00945 (13)	0.0602 (2)	0.1155 (2)	0.0974 (10)
H42A	0.0060	0.0193	0.1647	0.146*
H42B	−0.0396	0.1053	0.1193	0.146*
H42C	−0.0322	0.0244	0.0632	0.146*
C43	0.02670 (14)	0.1710 (2)	0.04037 (16)	0.0857 (9)
H43A	−0.0012	0.2199	0.0455	0.103*
H43B	0.0004	0.1369	−0.0128	0.103*
C44	0.08668 (14)	0.2140 (2)	0.03617 (14)	0.0824 (8)
H44A	0.1079	0.1672	0.0164	0.099*
H44B	0.0716	0.2639	−0.0063	0.099*
C45	0.13753 (13)	0.25230 (18)	0.12140 (14)	0.0612 (6)
N1	0.26100 (8)	0.13210 (12)	0.29228 (10)	0.0486 (4)
N2	0.04763 (9)	0.10806 (14)	0.11417 (12)	0.0668 (5)
N3	0.15437 (8)	−0.01733 (12)	0.27018 (10)	0.0499 (4)
N4	0.14498 (8)	−0.12662 (12)	0.12568 (11)	0.0532 (5)
O1	0.16569 (11)	0.32522 (13)	0.12566 (11)	0.0874 (6)
Cl1	0.03708 (5)	0.48362 (8)	0.42608 (6)	0.1348 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0526 (13)	0.0683 (16)	0.0540 (13)	0.0102 (11)	0.0175 (11)	0.0012 (11)
C2	0.0550 (13)	0.0562 (13)	0.0397 (11)	0.0015 (10)	0.0160 (10)	−0.0042 (10)
C3	0.0513 (12)	0.0446 (12)	0.0423 (11)	−0.0033 (9)	0.0215 (10)	−0.0010 (9)
C4	0.0502 (12)	0.0497 (13)	0.0360 (10)	0.0035 (10)	0.0185 (9)	0.0018 (9)
C5	0.0458 (11)	0.0479 (12)	0.0362 (10)	0.0004 (9)	0.0168 (9)	−0.0014 (9)
C6	0.0451 (11)	0.0539 (13)	0.0382 (11)	0.0029 (10)	0.0164 (9)	0.0037 (10)
C7	0.0484 (12)	0.0581 (14)	0.0380 (11)	0.0033 (10)	0.0167 (10)	−0.0017 (10)
C8	0.0732 (16)	0.0713 (16)	0.0464 (13)	−0.0009 (13)	0.0287 (12)	−0.0120 (11)
C9	0.0785 (17)	0.094 (2)	0.0515 (14)	0.0000 (15)	0.0383 (13)	−0.0059 (14)
C10	0.0638 (15)	0.0843 (19)	0.0534 (14)	−0.0014 (13)	0.0322 (12)	0.0078 (13)
C11	0.0566 (13)	0.0617 (15)	0.0488 (12)	−0.0004 (11)	0.0241 (11)	0.0025 (11)
C12	0.0424 (11)	0.0516 (13)	0.0371 (11)	0.0039 (9)	0.0153 (9)	0.0017 (9)
C13	0.0440 (11)	0.0480 (13)	0.0402 (11)	0.0032 (10)	0.0133 (9)	0.0003 (10)
C14	0.0428 (11)	0.0502 (14)	0.0500 (12)	0.0033 (10)	0.0112 (10)	0.0067 (10)
C15	0.0408 (11)	0.0565 (14)	0.0470 (12)	−0.0002 (10)	0.0133 (10)	0.0055 (10)
C16	0.0532 (13)	0.0751 (17)	0.0574 (14)	−0.0066 (12)	0.0226 (11)	0.0095 (12)
C17	0.0577 (15)	0.0799 (19)	0.0707 (17)	−0.0117 (13)	0.0223 (13)	0.0178 (14)
C18	0.0583 (15)	0.0604 (16)	0.0869 (19)	−0.0086 (12)	0.0190 (14)	0.0120 (15)
C19	0.0554 (14)	0.0506 (14)	0.0665 (15)	−0.0019 (11)	0.0149 (12)	0.0030 (11)
C31	0.0535 (12)	0.0455 (13)	0.0454 (12)	−0.0062 (10)	0.0218 (10)	−0.0037 (9)
C32	0.0822 (17)	0.0618 (15)	0.0521 (13)	0.0109 (13)	0.0339 (13)	0.0044 (11)
C33	0.0803 (17)	0.098 (2)	0.0518 (14)	0.0089 (16)	0.0364 (14)	−0.0049 (14)
C34	0.0730 (17)	0.085 (2)	0.0645 (16)	0.0170 (15)	0.0286 (14)	−0.0128 (14)
C35	0.143 (3)	0.0686 (19)	0.120 (3)	0.0444 (19)	0.084 (2)	0.0252 (18)
C36	0.122 (2)	0.0625 (17)	0.096 (2)	0.0280 (16)	0.0741 (19)	0.0268 (15)
C41	0.0477 (12)	0.0577 (14)	0.0505 (12)	0.0040 (10)	0.0170 (10)	−0.0077 (10)
C42	0.0565 (16)	0.100 (2)	0.111 (2)	−0.0149 (15)	0.0164 (16)	−0.0301 (18)
C43	0.0708 (18)	0.103 (2)	0.0537 (15)	0.0192 (16)	0.0022 (14)	−0.0080 (15)
C44	0.090 (2)	0.103 (2)	0.0409 (13)	0.0323 (17)	0.0177 (14)	0.0129 (13)
C45	0.0720 (16)	0.0648 (16)	0.0493 (13)	0.0192 (13)	0.0295 (12)	0.0092 (12)
N1	0.0462 (10)	0.0531 (11)	0.0410 (9)	0.0039 (8)	0.0148 (8)	−0.0023 (8)
N2	0.0516 (11)	0.0734 (14)	0.0582 (12)	0.0014 (10)	0.0096 (10)	−0.0157 (10)
N3	0.0496 (10)	0.0564 (12)	0.0424 (10)	−0.0024 (8)	0.0198 (8)	0.0016 (8)
N4	0.0516 (10)	0.0521 (11)	0.0475 (10)	0.0005 (9)	0.0151 (9)	−0.0010 (9)
O1	0.1327 (17)	0.0656 (12)	0.0729 (12)	0.0032 (12)	0.0542 (12)	0.0171 (10)
Cl1	0.1370 (8)	0.1672 (9)	0.1083 (7)	0.0676 (7)	0.0626 (6)	−0.0185 (6)

Geometric parameters (Å, º)

C1—N1	1.447 (3)	C15—C16	1.401 (3)
C1—H1A	0.9600	C16—C17	1.363 (3)
C1—H1B	0.9600	C16—H16	0.9300
C1—H1C	0.9600	C17—C18	1.390 (4)
C2—N1	1.445 (2)	C17—H17	0.9300
C2—C3	1.511 (3)	C18—C19	1.360 (3)
C2—H2A	0.9700	C18—H18	0.9300
C2—H2B	0.9700	C19—H19	0.9300
C3—C31	1.511 (3)	C31—C36	1.371 (3)
C3—C4	1.558 (3)	C31—C32	1.372 (3)
C3—H3	0.9800	C32—C33	1.379 (3)
C4—C41	1.529 (3)	C32—H32	0.9300
C4—C45	1.538 (3)	C33—C34	1.352 (4)
C4—C5	1.605 (3)	C33—H33	0.9300
C5—N1	1.466 (2)	C34—C35	1.352 (4)
C5—C6	1.526 (3)	C34—Cl1	1.736 (2)
C5—C12	1.528 (3)	C35—C36	1.374 (4)
C6—C11	1.378 (3)	C35—H35	0.9300
C6—C7	1.389 (3)	C36—H36	0.9300
C7—C8	1.385 (3)	C41—N2	1.458 (3)
C7—C13	1.455 (3)	C41—H41A	0.9700
C8—C9	1.372 (3)	C41—H41B	0.9700
C8—H8	0.9300	C42—N2	1.462 (3)
C9—C10	1.374 (3)	C42—H42A	0.9600
C9—H9	0.9300	C42—H42B	0.9600
C10—C11	1.386 (3)	C42—H42C	0.9600
C10—H10	0.9300	C43—N2	1.457 (3)
C11—H11	0.9300	C43—C44	1.511 (4)
C12—N3	1.304 (2)	C43—H43A	0.9700
C12—C13	1.424 (3)	C43—H43B	0.9700
C13—N4	1.310 (3)	C44—C45	1.501 (4)
C14—N4	1.379 (3)	C44—H44A	0.9700
C14—C19	1.402 (3)	C44—H44B	0.9700
C14—C15	1.408 (3)	C45—O1	1.207 (3)
C15—N3	1.382 (3)
N1—C1—H1A	109.5	C16—C17—C18	120.6 (2)
N1—C1—H1B	109.5	C16—C17—H17	119.7
H1A—C1—H1B	109.5	C18—C17—H17	119.7
N1—C1—H1C	109.5	C19—C18—C17	120.6 (2)
H1A—C1—H1C	109.5	C19—C18—H18	119.7
H1B—C1—H1C	109.5	C17—C18—H18	119.7
N1—C2—C3	101.37 (15)	C18—C19—C14	120.4 (2)
N1—C2—H2A	111.5	C18—C19—H19	119.8
C3—C2—H2A	111.5	C14—C19—H19	119.8
N1—C2—H2B	111.5	C36—C31—C32	116.1 (2)
C3—C2—H2B	111.5	C36—C31—C3	120.23 (19)
H2A—C2—H2B	109.3	C32—C31—C3	123.67 (19)
C2—C3—C31	116.15 (16)	C31—C32—C33	122.1 (2)
C2—C3—C4	103.51 (15)	C31—C32—H32	118.9
C31—C3—C4	116.98 (16)	C33—C32—H32	118.9
C2—C3—H3	106.5	C34—C33—C32	120.0 (2)
C31—C3—H3	106.5	C34—C33—H33	120.0
C4—C3—H3	106.5	C32—C33—H33	120.0
C41—C4—C45	106.83 (17)	C35—C34—C33	119.4 (2)
C41—C4—C3	112.00 (15)	C35—C34—Cl1	120.6 (2)
C45—C4—C3	111.62 (17)	C33—C34—Cl1	119.9 (2)
C41—C4—C5	112.83 (16)	C34—C35—C36	120.3 (3)
C45—C4—C5	110.64 (15)	C34—C35—H35	119.9
C3—C4—C5	103.02 (15)	C36—C35—H35	119.9
N1—C5—C6	109.41 (15)	C31—C36—C35	122.1 (2)
N1—C5—C12	114.58 (15)	C31—C36—H36	118.9
C6—C5—C12	100.23 (15)	C35—C36—H36	118.9
N1—C5—C4	102.88 (14)	N2—C41—C4	111.24 (16)
C6—C5—C4	116.86 (15)	N2—C41—H41A	109.4
C12—C5—C4	113.36 (15)	C4—C41—H41A	109.4
C11—C6—C7	120.10 (18)	N2—C41—H41B	109.4
C11—C6—C5	127.65 (19)	C4—C41—H41B	109.4
C7—C6—C5	112.17 (17)	H41A—C41—H41B	108.0
C8—C7—C6	120.7 (2)	N2—C42—H42A	109.5
C8—C7—C13	130.7 (2)	N2—C42—H42B	109.5
C6—C7—C13	108.46 (17)	H42A—C42—H42B	109.5
C9—C8—C7	118.7 (2)	N2—C42—H42C	109.5
C9—C8—H8	120.6	H42A—C42—H42C	109.5
C7—C8—H8	120.6	H42B—C42—H42C	109.5
C8—C9—C10	120.9 (2)	N2—C43—C44	110.7 (2)
C8—C9—H9	119.6	N2—C43—H43A	109.5
C10—C9—H9	119.6	C44—C43—H43A	109.5
C9—C10—C11	120.7 (2)	N2—C43—H43B	109.5
C9—C10—H10	119.6	C44—C43—H43B	109.5
C11—C10—H10	119.6	H43A—C43—H43B	108.1
C6—C11—C10	118.9 (2)	C45—C44—C43	113.6 (2)
C6—C11—H11	120.6	C45—C44—H44A	108.8
C10—C11—H11	120.6	C43—C44—H44A	108.8
N3—C12—C13	123.48 (19)	C45—C44—H44B	108.8
N3—C12—C5	125.84 (17)	C43—C44—H44B	108.8
C13—C12—C5	110.51 (16)	H44A—C44—H44B	107.7
N4—C13—C12	123.85 (18)	O1—C45—C44	121.4 (2)
N4—C13—C7	127.70 (18)	O1—C45—C4	121.9 (2)
C12—C13—C7	108.38 (18)	C44—C45—C4	116.6 (2)
N4—C14—C19	118.7 (2)	C2—N1—C1	116.20 (16)
N4—C14—C15	122.43 (19)	C2—N1—C5	107.75 (15)
C19—C14—C15	118.8 (2)	C1—N1—C5	115.92 (16)
N3—C15—C16	118.7 (2)	C43—N2—C41	108.79 (19)
N3—C15—C14	121.71 (18)	C43—N2—C42	111.5 (2)
C16—C15—C14	119.6 (2)	C41—N2—C42	110.65 (19)
C17—C16—C15	120.0 (2)	C12—N3—C15	114.47 (17)
C17—C16—H16	120.0	C13—N4—C14	113.86 (17)
C15—C16—H16	120.0
N1—C2—C3—C31	171.55 (16)	C14—C15—C16—C17	−1.1 (3)
N1—C2—C3—C4	41.92 (19)	C15—C16—C17—C18	−0.4 (4)
C2—C3—C4—C41	98.92 (19)	C16—C17—C18—C19	1.2 (4)
C31—C3—C4—C41	−30.2 (2)	C17—C18—C19—C14	−0.4 (4)
C2—C3—C4—C45	−141.35 (17)	N4—C14—C19—C18	178.0 (2)
C31—C3—C4—C45	89.5 (2)	C15—C14—C19—C18	−1.1 (3)
C2—C3—C4—C5	−22.61 (18)	C2—C3—C31—C36	158.8 (2)
C31—C3—C4—C5	−151.73 (16)	C4—C3—C31—C36	−78.4 (3)
C41—C4—C5—N1	−125.30 (16)	C2—C3—C31—C32	−18.6 (3)
C45—C4—C5—N1	115.08 (18)	C4—C3—C31—C32	104.2 (2)
C3—C4—C5—N1	−4.34 (18)	C36—C31—C32—C33	−0.1 (4)
C41—C4—C5—C6	114.83 (18)	C3—C31—C32—C33	177.4 (2)
C45—C4—C5—C6	−4.8 (2)	C31—C32—C33—C34	−0.4 (4)
C3—C4—C5—C6	−124.21 (17)	C32—C33—C34—C35	0.5 (4)
C41—C4—C5—C12	−1.0 (2)	C32—C33—C34—Cl1	−179.4 (2)
C45—C4—C5—C12	−120.61 (19)	C33—C34—C35—C36	−0.1 (5)
C3—C4—C5—C12	119.97 (16)	Cl1—C34—C35—C36	179.8 (3)
N1—C5—C6—C11	−51.1 (3)	C32—C31—C36—C35	0.4 (4)
C12—C5—C6—C11	−171.90 (19)	C3—C31—C36—C35	−177.1 (3)
C4—C5—C6—C11	65.2 (3)	C34—C35—C36—C31	−0.3 (5)
N1—C5—C6—C7	125.62 (18)	C45—C4—C41—N2	57.7 (2)
C12—C5—C6—C7	4.8 (2)	C3—C4—C41—N2	−179.81 (16)
C4—C5—C6—C7	−118.06 (19)	C5—C4—C41—N2	−64.1 (2)
C11—C6—C7—C8	−1.9 (3)	N2—C43—C44—C45	−47.8 (3)
C5—C6—C7—C8	−178.92 (18)	C43—C44—C45—O1	−139.5 (3)
C11—C6—C7—C13	173.82 (18)	C43—C44—C45—C4	40.4 (3)
C5—C6—C7—C13	−3.2 (2)	C41—C4—C45—O1	136.3 (2)
C6—C7—C8—C9	0.2 (3)	C3—C4—C45—O1	13.6 (3)
C13—C7—C8—C9	−174.4 (2)	C5—C4—C45—O1	−100.5 (2)
C7—C8—C9—C10	1.4 (4)	C41—C4—C45—C44	−43.6 (2)
C8—C9—C10—C11	−1.3 (4)	C3—C4—C45—C44	−166.30 (19)
C7—C6—C11—C10	2.0 (3)	C5—C4—C45—C44	79.6 (2)
C5—C6—C11—C10	178.47 (19)	C3—C2—N1—C1	−179.25 (17)
C9—C10—C11—C6	−0.4 (3)	C3—C2—N1—C5	−47.3 (2)
N1—C5—C12—N3	53.5 (3)	C6—C5—N1—C2	156.77 (16)
C6—C5—C12—N3	170.50 (18)	C12—C5—N1—C2	−91.62 (19)
C4—C5—C12—N3	−64.2 (2)	C4—C5—N1—C2	31.88 (19)
N1—C5—C12—C13	−121.80 (17)	C6—C5—N1—C1	−71.1 (2)
C6—C5—C12—C13	−4.8 (2)	C12—C5—N1—C1	40.5 (2)
C4—C5—C12—C13	120.51 (17)	C4—C5—N1—C1	164.01 (16)
N3—C12—C13—N4	5.1 (3)	C44—C43—N2—C41	62.2 (3)
C5—C12—C13—N4	−179.49 (18)	C44—C43—N2—C42	−175.5 (2)
N3—C12—C13—C7	−172.11 (18)	C4—C41—N2—C43	−69.7 (2)
C5—C12—C13—C7	3.3 (2)	C4—C41—N2—C42	167.5 (2)
C8—C7—C13—N4	−2.0 (4)	C13—C12—N3—C15	−3.6 (3)
C6—C7—C13—N4	−177.16 (19)	C5—C12—N3—C15	−178.36 (17)
C8—C7—C13—C12	175.1 (2)	C16—C15—N3—C12	−179.58 (18)
C6—C7—C13—C12	−0.1 (2)	C14—C15—N3—C12	−0.4 (3)
N4—C14—C15—N3	3.6 (3)	C12—C13—N4—C14	−1.7 (3)
C19—C14—C15—N3	−177.29 (19)	C7—C13—N4—C14	174.96 (18)
N4—C14—C15—C16	−177.21 (19)	C19—C14—N4—C13	178.54 (19)
C19—C14—C15—C16	1.9 (3)	C15—C14—N4—C13	−2.4 (3)
N3—C15—C16—C17	178.0 (2)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C14–C19 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C41—H41A···N3	0.97	2.39	2.988 (3)	120
C11—H11···Cg1^i	0.93	2.89	3.655 (2)	140

Symmetry code: (i) x, −y, z−1/2.