A one-dimensional manganese(III)–porphyrin coordination polymer: crystal structure and photophysical properties

A novel manganese(III)–porphyrin com­plex, namely, catena-poly[[chlorido­manganese(III)]-μ₂-5,10,15,20-tetra­kis­(pyridin-3-yl)-21H,23H-porphinato(2−)-κ⁵N²¹,N²²,N²³,N²⁴:N⁵], [MnCl(C₄₀H₂₄N₈)]_n, 1, was prepared by the hydro­thermal reaction of manganese chloride with 5,10,15,20-tetra­kis­(pyridin-3-yl)-21H,23H-porphine. The crystal structure was determined by single-crystal X-ray diffraction. The porphyrin macrocycle exhibits a saddle-like distortion geometry. The Mn^III atom has a six-coordination geometry. Each porphyrin unit links to two neighbouring units to yield a one-dimensional coordination polymer. These chains are further inter­linked by hydrogen bonds to form a two-dimensional network. The com­plex shows red photoluminescence emission bands in ethanol solution, which can be attributed to ligand-to-ligand charge transfer (LLCT) accom­panied by partial metal-to-ligand charge transfer (MLCT), as revealed by TDDFT calculations.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2005) and ASP (Chen, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

catena-Poly[[chloridomanganese(III)]-µ₂-5,10,15,20-tetrakis(pyridin-3-yl)-21H,23H-porphinato(2-)-κ⁵N²¹,N²²,N²³,N²⁴:N⁵]

Crystal data

[MnCl(C40H24N8)]	Dx = 1.488 Mg m^−3
Mr = 707.06	Melting point: not measured K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.5189 (4) Å	Cell parameters from 6010 reflections
b = 14.2450 (5) Å	θ = 3.8–28.8°
c = 23.4079 (9) Å	µ = 0.55 mm^−1
β = 95.920 (3)°	T = 293 K
V = 3157.1 (2) Å^3	Block, black
Z = 4	0.21 × 0.15 × 0.13 mm
F(000) = 1448

Data collection

Rigaku OD SuperNova (Mo) X-ray Source diffractometer	5560 independent reflections
Radiation source: micro-focus sealed X-ray tube	4759 reflections with I > 2σ(I)
Detector resolution: 8.0894 pixels mm^-1	Rint = 0.018
ω scans	θmax = 25.0°, θmin = 3.5°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −11→11
Tmin = 0.906, Tmax = 0.931	k = −14→16
12826 measured reflections	l = −27→19

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0448P)^2 + 1.8589P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
5560 reflections	Δρmax = 0.42 e Å^−3
451 parameters	Δρmin = −0.36 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Mn1	0.53315 (3)	0.51127 (2)	0.18745 (2)	0.02493 (11)
Cl1	0.30211 (6)	0.57552 (5)	0.14745 (3)	0.04700 (18)
N1	0.46986 (18)	0.38903 (12)	0.22076 (7)	0.0261 (4)
N2	0.57766 (18)	0.44246 (12)	0.11624 (7)	0.0261 (4)
N3	0.61812 (18)	0.62870 (12)	0.15821 (7)	0.0248 (4)
N4	0.51138 (19)	0.57451 (12)	0.26256 (7)	0.0269 (4)
N5	0.5870 (3)	0.03307 (18)	0.11457 (13)	0.0700 (8)
N6	1.0321 (2)	0.63201 (17)	0.00385 (9)	0.0474 (6)
N7	0.72104 (19)	0.96742 (13)	0.27828 (8)	0.0308 (4)
N8	0.5205 (4)	0.38846 (19)	0.47868 (10)	0.0693 (8)
C1	0.4436 (2)	0.37197 (16)	0.27688 (9)	0.0290 (5)
C2	0.4086 (3)	0.27496 (16)	0.28289 (10)	0.0365 (6)
H2A	0.387585	0.245471	0.316413	0.044*
C3	0.4118 (3)	0.23446 (16)	0.23143 (10)	0.0372 (6)
H3A	0.390298	0.172147	0.222485	0.045*
C4	0.4540 (2)	0.30382 (15)	0.19282 (9)	0.0285 (5)
C5	0.4900 (2)	0.28457 (16)	0.13776 (10)	0.0304 (5)
C6	0.5500 (2)	0.34957 (16)	0.10322 (9)	0.0294 (5)
C7	0.6006 (3)	0.32772 (17)	0.04943 (10)	0.0386 (6)
H7A	0.591766	0.270236	0.030574	0.046*
C8	0.6632 (3)	0.40463 (17)	0.03091 (10)	0.0379 (6)
H8A	0.706655	0.410062	−0.002742	0.045*
C9	0.6506 (2)	0.47688 (16)	0.07259 (9)	0.0285 (5)
C10	0.7038 (2)	0.56732 (16)	0.06973 (9)	0.0276 (5)
C11	0.6788 (2)	0.63898 (15)	0.10799 (9)	0.0282 (5)
C12	0.7061 (3)	0.73639 (17)	0.09892 (10)	0.0379 (6)
H12A	0.748395	0.761748	0.068313	0.045*
C13	0.6597 (3)	0.78459 (16)	0.14264 (10)	0.0364 (6)
H13A	0.661286	0.849422	0.147317	0.044*
C14	0.6071 (2)	0.71704 (15)	0.18080 (9)	0.0269 (5)
C15	0.5596 (2)	0.73716 (15)	0.23377 (9)	0.0266 (5)
C16	0.5190 (2)	0.66947 (15)	0.27223 (9)	0.0282 (5)
C17	0.4865 (3)	0.68838 (17)	0.32943 (10)	0.0403 (6)
H17A	0.483226	0.747261	0.346399	0.048*
C18	0.4615 (3)	0.60598 (18)	0.35418 (10)	0.0422 (6)
H18A	0.438947	0.597175	0.391532	0.051*
C19	0.4760 (2)	0.53402 (17)	0.31243 (9)	0.0314 (5)
C20	0.4498 (2)	0.43856 (16)	0.32072 (9)	0.0314 (5)
C21	0.5840 (3)	0.1212 (2)	0.13315 (14)	0.0592 (8)
H21A	0.658100	0.141035	0.159378	0.071*
C22	0.4790 (3)	0.18577 (16)	0.11645 (10)	0.0347 (5)
C23	0.3685 (3)	0.15530 (19)	0.07808 (11)	0.0470 (7)
H23A	0.294807	0.195670	0.065721	0.056*
C24	0.3691 (4)	0.0643 (2)	0.05841 (13)	0.0597 (8)
H24A	0.295726	0.042024	0.032681	0.072*
C25	0.4798 (4)	0.0073 (2)	0.07744 (15)	0.0632 (9)
H25A	0.479674	−0.053741	0.063298	0.076*
C26	0.9382 (3)	0.61381 (18)	0.04065 (10)	0.0388 (6)
H26A	0.967888	0.617434	0.079698	0.047*
C27	0.7982 (2)	0.58969 (16)	0.02431 (9)	0.0299 (5)
C28	0.7557 (3)	0.58433 (18)	−0.03354 (10)	0.0384 (6)
H28A	0.663564	0.567166	−0.046451	0.046*
C29	0.8517 (3)	0.60483 (19)	−0.07231 (10)	0.0440 (6)
H29A	0.824931	0.603038	−0.111644	0.053*
C30	0.9860 (3)	0.62764 (19)	−0.05162 (11)	0.0462 (7)
H30A	1.049841	0.641059	−0.078018	0.055*
C31	0.6987 (2)	0.87867 (16)	0.26209 (9)	0.0309 (5)
H31A	0.777197	0.842164	0.256587	0.037*
C32	0.5673 (2)	0.83681 (15)	0.25286 (9)	0.0265 (5)
C33	0.4513 (2)	0.89075 (17)	0.26223 (10)	0.0347 (5)
H33A	0.361051	0.865089	0.257610	0.042*
C34	0.4714 (3)	0.98318 (17)	0.27852 (11)	0.0394 (6)
H34A	0.394757	1.021074	0.284625	0.047*
C35	0.6069 (3)	1.01845 (16)	0.28560 (10)	0.0346 (5)
H35A	0.619310	1.081127	0.296038	0.041*
C36	0.5316 (3)	0.4174 (2)	0.42459 (11)	0.0520 (7)
H36A	0.615005	0.446732	0.416956	0.062*
C37	0.4264 (3)	0.40624 (16)	0.37959 (10)	0.0372 (6)
C38	0.3029 (3)	0.3627 (2)	0.39138 (12)	0.0507 (7)
H38A	0.229239	0.354387	0.362502	0.061*
C39	0.2900 (4)	0.3319 (2)	0.44624 (14)	0.0680 (10)
H39A	0.208529	0.301258	0.454838	0.082*
C40	0.3987 (5)	0.3469 (2)	0.48775 (13)	0.0743 (11)
H40A	0.387552	0.327000	0.524851	0.089*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0295 (2)	0.01878 (18)	0.02758 (19)	−0.00305 (14)	0.00787 (13)	−0.00290 (13)
Cl1	0.0322 (3)	0.0521 (4)	0.0564 (4)	0.0018 (3)	0.0033 (3)	−0.0009 (3)
N1	0.0264 (10)	0.0223 (10)	0.0305 (10)	−0.0027 (8)	0.0071 (7)	−0.0019 (7)
N2	0.0260 (10)	0.0235 (10)	0.0293 (10)	−0.0011 (8)	0.0062 (7)	−0.0010 (7)
N3	0.0272 (10)	0.0203 (9)	0.0275 (9)	−0.0004 (8)	0.0061 (7)	−0.0025 (7)
N4	0.0324 (10)	0.0211 (10)	0.0281 (10)	−0.0013 (8)	0.0072 (7)	−0.0019 (7)
N5	0.0755 (19)	0.0336 (14)	0.100 (2)	0.0084 (13)	0.0019 (16)	−0.0176 (14)
N6	0.0384 (12)	0.0551 (15)	0.0503 (14)	−0.0078 (11)	0.0126 (10)	0.0051 (11)
N7	0.0322 (11)	0.0228 (10)	0.0370 (11)	−0.0006 (8)	0.0020 (8)	−0.0031 (8)
N8	0.118 (3)	0.0507 (16)	0.0372 (14)	0.0126 (17)	−0.0033 (14)	0.0029 (12)
C1	0.0275 (12)	0.0277 (12)	0.0327 (12)	−0.0002 (10)	0.0072 (9)	0.0022 (9)
C2	0.0467 (15)	0.0249 (12)	0.0393 (13)	−0.0031 (11)	0.0106 (11)	0.0051 (10)
C3	0.0465 (15)	0.0204 (12)	0.0455 (14)	−0.0043 (11)	0.0090 (11)	−0.0008 (10)
C4	0.0273 (12)	0.0222 (11)	0.0363 (12)	−0.0024 (9)	0.0047 (9)	−0.0014 (9)
C5	0.0286 (12)	0.0248 (12)	0.0380 (13)	−0.0017 (10)	0.0045 (9)	−0.0045 (10)
C6	0.0285 (12)	0.0241 (12)	0.0365 (12)	−0.0019 (9)	0.0073 (9)	−0.0062 (9)
C7	0.0434 (15)	0.0306 (13)	0.0447 (14)	−0.0056 (11)	0.0190 (11)	−0.0149 (11)
C8	0.0395 (14)	0.0374 (14)	0.0398 (13)	−0.0060 (11)	0.0192 (10)	−0.0115 (11)
C9	0.0256 (12)	0.0277 (12)	0.0330 (12)	0.0002 (9)	0.0065 (9)	−0.0035 (9)
C10	0.0276 (12)	0.0276 (12)	0.0282 (11)	0.0000 (9)	0.0063 (9)	−0.0011 (9)
C11	0.0298 (12)	0.0243 (12)	0.0313 (12)	−0.0015 (10)	0.0067 (9)	0.0008 (9)
C12	0.0528 (16)	0.0269 (13)	0.0364 (13)	−0.0066 (11)	0.0163 (11)	0.0023 (10)
C13	0.0512 (15)	0.0189 (12)	0.0405 (13)	−0.0021 (11)	0.0116 (11)	0.0004 (10)
C14	0.0288 (12)	0.0200 (11)	0.0322 (12)	−0.0004 (9)	0.0042 (9)	−0.0010 (9)
C15	0.0258 (11)	0.0199 (11)	0.0341 (12)	−0.0005 (9)	0.0030 (9)	−0.0034 (9)
C16	0.0317 (12)	0.0236 (12)	0.0300 (12)	−0.0012 (9)	0.0058 (9)	−0.0042 (9)
C17	0.0579 (17)	0.0284 (13)	0.0367 (13)	−0.0016 (12)	0.0152 (11)	−0.0088 (10)
C18	0.0624 (17)	0.0350 (14)	0.0316 (13)	−0.0012 (13)	0.0168 (11)	−0.0028 (11)
C19	0.0373 (13)	0.0295 (13)	0.0285 (12)	−0.0021 (10)	0.0081 (9)	−0.0017 (9)
C20	0.0353 (13)	0.0289 (13)	0.0310 (12)	−0.0004 (10)	0.0078 (9)	0.0017 (9)
C21	0.0568 (19)	0.0362 (16)	0.082 (2)	0.0036 (14)	−0.0059 (15)	−0.0185 (15)
C22	0.0420 (14)	0.0238 (12)	0.0403 (13)	−0.0071 (11)	0.0132 (10)	−0.0066 (10)
C23	0.0535 (17)	0.0330 (14)	0.0536 (16)	−0.0068 (13)	0.0015 (12)	−0.0070 (12)
C24	0.074 (2)	0.0425 (18)	0.0601 (19)	−0.0190 (16)	−0.0029 (15)	−0.0162 (14)
C25	0.087 (3)	0.0304 (16)	0.075 (2)	−0.0073 (16)	0.0180 (18)	−0.0195 (15)
C26	0.0401 (14)	0.0426 (15)	0.0342 (13)	−0.0088 (12)	0.0066 (10)	−0.0013 (11)
C27	0.0342 (13)	0.0232 (11)	0.0335 (12)	−0.0002 (10)	0.0087 (9)	−0.0003 (9)
C28	0.0352 (14)	0.0431 (15)	0.0367 (13)	0.0001 (11)	0.0030 (10)	0.0031 (11)
C29	0.0535 (17)	0.0494 (17)	0.0301 (13)	0.0024 (13)	0.0091 (11)	0.0053 (11)
C30	0.0510 (17)	0.0476 (17)	0.0432 (16)	0.0010 (13)	0.0201 (12)	0.0110 (12)
C31	0.0293 (12)	0.0259 (12)	0.0376 (13)	0.0014 (10)	0.0043 (9)	−0.0055 (10)
C32	0.0300 (12)	0.0220 (11)	0.0280 (11)	−0.0016 (9)	0.0056 (9)	−0.0014 (9)
C33	0.0261 (12)	0.0318 (13)	0.0467 (14)	−0.0022 (10)	0.0068 (10)	−0.0063 (11)
C34	0.0354 (14)	0.0304 (13)	0.0529 (15)	0.0082 (11)	0.0076 (11)	−0.0065 (11)
C35	0.0417 (14)	0.0216 (12)	0.0404 (13)	0.0008 (11)	0.0045 (10)	−0.0051 (10)
C36	0.075 (2)	0.0388 (15)	0.0416 (16)	0.0048 (14)	0.0030 (13)	−0.0013 (12)
C37	0.0554 (16)	0.0242 (12)	0.0337 (13)	0.0062 (11)	0.0123 (11)	0.0019 (10)
C38	0.0622 (19)	0.0489 (17)	0.0439 (15)	0.0008 (14)	0.0191 (13)	0.0110 (13)
C39	0.097 (3)	0.058 (2)	0.055 (2)	0.0047 (19)	0.0357 (19)	0.0192 (16)
C40	0.137 (4)	0.051 (2)	0.0378 (18)	0.015 (2)	0.022 (2)	0.0139 (15)

Geometric parameters (Å, º)

Mn1—N4	2.0053 (17)	C13—H13A	0.9300
Mn1—N3	2.0087 (17)	C14—C15	1.393 (3)
Mn1—N2	2.0159 (17)	C15—C16	1.400 (3)
Mn1—N1	2.0249 (18)	C15—C32	1.488 (3)
Mn1—N7^i	2.4741 (18)	C16—C17	1.431 (3)
Mn1—Cl1	2.4752 (7)	C17—C18	1.341 (3)
N1—C4	1.380 (3)	C17—H17A	0.9300
N1—C1	1.384 (3)	C18—C19	1.433 (3)
N2—C6	1.377 (3)	C18—H18A	0.9300
N2—C9	1.383 (3)	C19—C20	1.400 (3)
N3—C11	1.370 (3)	C20—C37	1.491 (3)
N3—C14	1.373 (3)	C21—C22	1.384 (4)
N4—C16	1.372 (3)	C21—H21A	0.9300
N4—C19	1.375 (3)	C22—C23	1.380 (4)
N5—C25	1.322 (4)	C23—C24	1.376 (4)
N5—C21	1.330 (4)	C23—H23A	0.9300
N6—C30	1.328 (3)	C24—C25	1.368 (5)
N6—C26	1.330 (3)	C24—H24A	0.9300
N7—C31	1.331 (3)	C25—H25A	0.9300
N7—C35	1.333 (3)	C26—C27	1.391 (3)
N8—C40	1.338 (5)	C26—H26A	0.9300
N8—C36	1.346 (4)	C27—C28	1.375 (3)
C1—C20	1.394 (3)	C28—C29	1.384 (3)
C1—C2	1.432 (3)	C28—H28A	0.9300
C2—C3	1.339 (3)	C29—C30	1.359 (4)
C2—H2A	0.9300	C29—H29A	0.9300
C3—C4	1.425 (3)	C30—H30A	0.9300
C3—H3A	0.9300	C31—C32	1.383 (3)
C4—C5	1.394 (3)	C31—H31A	0.9300
C5—C6	1.390 (3)	C32—C33	1.381 (3)
C5—C22	1.493 (3)	C33—C34	1.379 (3)
C6—C7	1.428 (3)	C33—H33A	0.9300
C7—C8	1.340 (3)	C34—C35	1.378 (3)
C7—H7A	0.9300	C34—H34A	0.9300
C8—C9	1.432 (3)	C35—H35A	0.9300
C8—H8A	0.9300	C36—C37	1.386 (4)
C9—C10	1.389 (3)	C36—H36A	0.9300
C10—C11	1.395 (3)	C37—C38	1.382 (4)
C10—C27	1.495 (3)	C38—C39	1.375 (4)
C11—C12	1.432 (3)	C38—H38A	0.9300
C12—C13	1.344 (3)	C39—C40	1.361 (5)
C12—H12A	0.9300	C39—H39A	0.9300
C13—C14	1.438 (3)	C40—H40A	0.9300
N4—Mn1—N3	90.36 (7)	C16—C15—C32	118.18 (19)
N4—Mn1—N2	173.18 (7)	N4—C16—C15	125.89 (19)
N3—Mn1—N2	89.82 (7)	N4—C16—C17	109.09 (19)
N4—Mn1—N1	89.25 (7)	C15—C16—C17	124.9 (2)
N3—Mn1—N1	173.52 (7)	C18—C17—C16	107.7 (2)
N2—Mn1—N1	89.80 (7)	C18—C17—H17A	126.1
N4—Mn1—N7^i	90.51 (7)	C16—C17—H17A	126.1
N3—Mn1—N7^i	85.42 (7)	C17—C18—C19	107.3 (2)
N2—Mn1—N7^i	82.71 (7)	C17—C18—H18A	126.3
N1—Mn1—N7^i	88.11 (7)	C19—C18—H18A	126.3
N4—Mn1—Cl1	89.85 (6)	N4—C19—C20	126.0 (2)
N3—Mn1—Cl1	86.36 (5)	N4—C19—C18	109.2 (2)
N2—Mn1—Cl1	96.97 (5)	C20—C19—C18	124.7 (2)
N1—Mn1—Cl1	100.11 (5)	C1—C20—C19	123.6 (2)
N7^i—Mn1—Cl1	171.77 (5)	C1—C20—C37	118.1 (2)
C4—N1—C1	105.91 (18)	C19—C20—C37	118.3 (2)
C4—N1—Mn1	126.60 (14)	N5—C21—C22	125.0 (3)
C1—N1—Mn1	127.34 (14)	N5—C21—H21A	117.5
C6—N2—C9	106.02 (17)	C22—C21—H21A	117.5
C6—N2—Mn1	126.76 (14)	C23—C22—C21	117.0 (2)
C9—N2—Mn1	127.07 (15)	C23—C22—C5	122.4 (2)
C11—N3—C14	106.76 (17)	C21—C22—C5	120.5 (2)
C11—N3—Mn1	126.98 (14)	C24—C23—C22	119.0 (3)
C14—N3—Mn1	125.62 (14)	C24—C23—H23A	120.5
C16—N4—C19	106.68 (17)	C22—C23—H23A	120.5
C16—N4—Mn1	125.38 (14)	C25—C24—C23	118.7 (3)
C19—N4—Mn1	127.77 (15)	C25—C24—H24A	120.6
C25—N5—C21	115.9 (3)	C23—C24—H24A	120.6
C30—N6—C26	116.6 (2)	N5—C25—C24	124.4 (3)
C31—N7—C35	116.5 (2)	N5—C25—H25A	117.8
C31—N7—Mn1^ii	116.75 (15)	C24—C25—H25A	117.8
C35—N7—Mn1^ii	125.23 (15)	N6—C26—C27	124.0 (2)
C40—N8—C36	116.0 (3)	N6—C26—H26A	118.0
N1—C1—C20	125.5 (2)	C27—C26—H26A	118.0
N1—C1—C2	109.23 (19)	C28—C27—C26	117.5 (2)
C20—C1—C2	125.2 (2)	C28—C27—C10	123.4 (2)
C3—C2—C1	107.5 (2)	C26—C27—C10	119.1 (2)
C3—C2—H2A	126.3	C27—C28—C29	119.1 (2)
C1—C2—H2A	126.3	C27—C28—H28A	120.4
C2—C3—C4	107.8 (2)	C29—C28—H28A	120.4
C2—C3—H3A	126.1	C30—C29—C28	118.5 (2)
C4—C3—H3A	126.1	C30—C29—H29A	120.7
N1—C4—C5	125.9 (2)	C28—C29—H29A	120.7
N1—C4—C3	109.48 (19)	N6—C30—C29	124.3 (2)
C5—C4—C3	124.2 (2)	N6—C30—H30A	117.9
C6—C5—C4	124.1 (2)	C29—C30—H30A	117.9
C6—C5—C22	116.89 (19)	N7—C31—C32	124.7 (2)
C4—C5—C22	118.6 (2)	N7—C31—H31A	117.6
N2—C6—C5	126.3 (2)	C32—C31—H31A	117.6
N2—C6—C7	109.29 (19)	C33—C32—C31	117.4 (2)
C5—C6—C7	124.3 (2)	C33—C32—C15	124.3 (2)
C8—C7—C6	108.0 (2)	C31—C32—C15	118.31 (19)
C8—C7—H7A	126.0	C34—C33—C32	119.1 (2)
C6—C7—H7A	126.0	C34—C33—H33A	120.5
C7—C8—C9	107.2 (2)	C32—C33—H33A	120.5
C7—C8—H8A	126.4	C35—C34—C33	118.8 (2)
C9—C8—H8A	126.4	C35—C34—H34A	120.6
N2—C9—C10	125.32 (19)	C33—C34—H34A	120.6
N2—C9—C8	109.43 (19)	N7—C35—C34	123.4 (2)
C10—C9—C8	125.3 (2)	N7—C35—H35A	118.3
C9—C10—C11	124.09 (19)	C34—C35—H35A	118.3
C9—C10—C27	118.77 (19)	N8—C36—C37	124.0 (3)
C11—C10—C27	117.11 (19)	N8—C36—H36A	118.0
N3—C11—C10	126.0 (2)	C37—C36—H36A	118.0
N3—C11—C12	109.27 (19)	C38—C37—C36	117.6 (2)
C10—C11—C12	124.6 (2)	C38—C37—C20	122.3 (2)
C13—C12—C11	107.6 (2)	C36—C37—C20	120.1 (2)
C13—C12—H12A	126.2	C39—C38—C37	119.3 (3)
C11—C12—H12A	126.2	C39—C38—H38A	120.3
C12—C13—C14	107.1 (2)	C37—C38—H38A	120.3
C12—C13—H13A	126.4	C40—C39—C38	118.8 (3)
C14—C13—H13A	126.4	C40—C39—H39A	120.6
N3—C14—C15	125.19 (19)	C38—C39—H39A	120.6
N3—C14—C13	109.18 (18)	N8—C40—C39	124.3 (3)
C15—C14—C13	125.5 (2)	N8—C40—H40A	117.9
C14—C15—C16	124.5 (2)	C39—C40—H40A	117.9
C14—C15—C32	116.95 (19)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C34—H34A···Cl1^iii	0.93	2.69	3.527 (3)	150

Symmetry code: (iii) −x+1/2, y+1/2, −z+1/2.