1,1',1''-{[4-(3,4-Ethyl-ene-dioxy-thio-phen-2-yl)phen-yl]methane-tri-yl}tris-(1H-pyra-zole).

In the title complex, C(22)H(18)N(6)O(2)S, two of the pyrazole rings are disordered over two sets of sites with ratios of refined occupancies of 0.58 (2):0.42 (2) and 0.517 (12):0.483 (12). The dioxane ring is in a half-chair conformation and the two -CH(2)- groups of this ring are disordered over two sets of sites, the ratio of refined occupancies being 0.855 (19):0.145 (19). The essentially planar thio-phene ring [largest deviation = 0.0444 (2) Å] forms a dihedral angle of 19.59 (3)° with the benzene ring.

Related literature

For the preparation and coordination chemistry of tris­(pyrazol­yl)borates and tris­(pyrazol­yl)methanes, see: Trofimenko (1999 ▶); Pettinari & Pettinari (2005 ▶); Reger et al. (2000 ▶). For the chemistry of tris­(pyrazol­yl)methane derivatives, see: Humphrey et al. (1999 ▶). For a general Stille coupling procedure, see: Sankaran et al. (2001 ▶). For similar structures, see: Liddle & Gardinier (2007 ▶).

Experimental

Crystal data

C22H18N6O2S

M = 430.48

Triclinic,

a = 7.2356 (14) Å

b = 8.1104 (16) Å

c = 18.626 (4) Å

α = 95.05 (3)°

β = 99.20 (2)°

γ = 112.14 (3)°

V = 986.2 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.20 mm−1

T = 153 K

0.16 × 0.15 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: gaussian (SHELXTL; Sheldrick, 2008 ▶) T min = 0.969, T max = 0.979

5461 measured reflections

3466 independent reflections

2749 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.148

S = 1.12

3466 reflections

294 parameters

9 restraints

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.46 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: COLLECT; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997) ▶; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶) within WinGX (Farrugia, 1999 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and POV-RAY (Persistence of Vision, 2004 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681104253X/lh5310sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104253X/lh5310Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681104253X/lh5310Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C22H18N6O2S	Z = 2
Mr = 430.48	F(000) = 448
Triclinic, P1	Dx = 1.450 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2356 (14) Å	Cell parameters from 3640 reflections
b = 8.1104 (16) Å	θ = 2.9–30.5°
c = 18.626 (4) Å	µ = 0.20 mm−1
α = 95.05 (3)°	T = 153 K
β = 99.20 (2)°	Block, colourless
γ = 112.14 (3)°	0.16 × 0.15 × 0.11 mm
V = 986.2 (3) Å3

Nonius KappaCCD diffractometer	3466 independent reflections
Radiation source: fine-focus sealed tube	2749 reflections with I > 2σ(I)
graphite	Rint = 0.025
ω scans	θmax = 25.0°, θmin = 3.1°
Absorption correction: gaussian (SHELXTL; Sheldrick, 2008)	h = −8→8
Tmin = 0.969, Tmax = 0.979	k = −8→9
5461 measured reflections	l = −22→22

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148	H-atom parameters constrained
S = 1.12	w = 1/[σ2(Fo2) + (0.0645P)2 + 1.0306P] where P = (Fo2 + 2Fc2)/3
3466 reflections	(Δ/σ)max < 0.001
294 parameters	Δρmax = 0.43 e Å−3
9 restraints	Δρmin = −0.46 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.70254 (12)	0.81579 (11)	0.44453 (4)	0.0321 (2)
O1	0.5573 (3)	0.7026 (3)	0.63060 (11)	0.0330 (5)
O2	0.2139 (3)	0.6959 (3)	0.52420 (11)	0.0270 (5)
N4	−0.3420 (4)	0.5741 (3)	0.20905 (14)	0.0304 (6)
N5	−0.1013 (3)	0.9898 (3)	0.19286 (12)	0.0211 (5)
N6	−0.2521 (4)	1.0130 (4)	0.14646 (14)	0.0353 (7)
C1	0.7421 (5)	0.7770 (4)	0.53348 (17)	0.0316 (7)
H1	0.8682	0.7828	0.5604	0.038*
C2	0.5699 (5)	0.7370 (4)	0.56037 (15)	0.0243 (7)
C3	0.3742 (8)	0.7069 (13)	0.6507 (3)	0.0310 (15)	0.855 (19)
H3A	0.3921	0.8339	0.6635	0.037*	0.855 (19)
H3B	0.3511	0.6484	0.6948	0.037*	0.855 (19)
C4	0.1914 (9)	0.6121 (11)	0.5890 (3)	0.0289 (15)	0.855 (19)
H4A	0.1721	0.4846	0.5768	0.035*	0.855 (19)
H4B	0.0682	0.6137	0.6052	0.035*	0.855 (19)
C3A	0.359 (5)	0.615 (6)	0.6379 (19)	0.039 (9)	0.145 (19)
H3C	0.3554	0.6129	0.6907	0.047*	0.145 (19)
H3D	0.3040	0.4890	0.6122	0.047*	0.145 (19)
C4A	0.232 (5)	0.709 (7)	0.6058 (15)	0.032 (8)	0.145 (19)
H4C	0.2937	0.8381	0.6288	0.038*	0.145 (19)
H4D	0.0938	0.6549	0.6168	0.038*	0.145 (19)
C5	0.4023 (4)	0.7346 (3)	0.50830 (15)	0.0195 (6)
C6	0.4478 (4)	0.7732 (4)	0.44105 (15)	0.0210 (6)
C7	0.3179 (4)	0.7824 (3)	0.37400 (15)	0.0208 (6)
C8	0.3706 (5)	0.7717 (4)	0.30513 (16)	0.0265 (7)
H8A	0.4919	0.7548	0.3015	0.032*
C9	0.2494 (5)	0.7853 (4)	0.24205 (15)	0.0250 (7)
H9A	0.2896	0.7797	0.1961	0.030*
C10	0.0697 (4)	0.8068 (3)	0.24590 (15)	0.0213 (6)
C11	0.0162 (4)	0.8172 (4)	0.31440 (15)	0.0236 (6)
H11A	−0.1064	0.8321	0.3178	0.028*
C12	0.1377 (4)	0.8061 (4)	0.37725 (15)	0.0224 (6)
H12	0.0985	0.8147	0.4233	0.027*
C13	−0.0677 (4)	0.8237 (4)	0.17826 (15)	0.0234 (7)
C14	0.1425 (4)	0.9858 (4)	0.09120 (15)	0.0242 (7)
H14A	0.1559	1.1045	0.1082	0.029*
N1	0.0423 (14)	0.8309 (8)	0.1170 (4)	0.012 (3)*	0.42 (2)
N2	0.0684 (18)	0.6899 (7)	0.0800 (3)	0.018 (2)*	0.42 (2)
C15	0.180 (2)	0.7485 (7)	0.0295 (4)	0.028 (3)*	0.42 (2)
H15A	0.2229	0.6793	−0.0028	0.033*	0.42 (2)
N1A	0.0096 (11)	0.8381 (6)	0.1101 (3)	0.019 (2)*	0.58 (2)
N2A	−0.0119 (14)	0.6789 (6)	0.0712 (3)	0.0246 (17)*	0.58 (2)
C15A	0.1144 (15)	0.7421 (5)	0.0252 (3)	0.0270 (19)*	0.58 (2)
H15B	0.1313	0.6633	−0.0116	0.032*	0.58 (2)
C16	0.2206 (5)	0.9305 (4)	0.03417 (16)	0.0307 (7)
H16A	0.2915	1.0069	0.0030	0.037*
N3	−0.2502 (8)	0.6548 (7)	0.1554 (3)	0.0144 (16)*	0.483 (12)
C17	−0.3761 (10)	0.6025 (8)	0.0880 (3)	0.0231 (19)*	0.483 (12)
H17A	−0.3440	0.6460	0.0439	0.028*	0.483 (12)
C18	−0.5556 (11)	0.4771 (9)	0.0952 (4)	0.030 (2)*	0.483 (12)
H18A	−0.6694	0.4060	0.0568	0.036*	0.483 (12)
C19	−0.5387 (17)	0.4739 (15)	0.1706 (5)	0.029 (4)*	0.483 (12)
H19A	−0.6490	0.4107	0.1927	0.035*	0.483 (12)
N3A	−0.2799 (7)	0.6848 (8)	0.1619 (3)	0.0165 (16)*	0.517 (12)
C17A	−0.4363 (10)	0.6444 (9)	0.1030 (4)	0.036 (2)*	0.517 (12)
H17B	−0.4336	0.7065	0.0620	0.043*	0.517 (12)
C18A	−0.5959 (10)	0.5005 (7)	0.1130 (4)	0.0243 (17)*	0.517 (12)
H18B	−0.7279	0.4424	0.0821	0.029*	0.517 (12)
C19A	−0.5217 (15)	0.4570 (14)	0.1794 (4)	0.026 (3)*	0.517 (12)
H19B	−0.5945	0.3545	0.1999	0.032*	0.517 (12)
C20	0.0224 (4)	1.1452 (4)	0.24024 (15)	0.0228 (6)
H20A	0.1386	1.1618	0.2767	0.027*
C21	−0.2231 (6)	1.1819 (5)	0.16671 (19)	0.0413 (9)
H21A	−0.3072	1.2373	0.1445	0.050*
C22	−0.0533 (5)	1.2711 (4)	0.22500 (18)	0.0331 (8)
H22A	−0.0025	1.3930	0.2486	0.040*

	U11	U22	U33	U12	U13	U23
S1	0.0269 (4)	0.0472 (5)	0.0283 (4)	0.0194 (4)	0.0107 (3)	0.0060 (3)
O1	0.0304 (12)	0.0432 (13)	0.0218 (11)	0.0125 (10)	−0.0015 (9)	0.0090 (9)
O2	0.0222 (11)	0.0382 (12)	0.0208 (11)	0.0095 (9)	0.0063 (8)	0.0138 (9)
N4	0.0240 (14)	0.0293 (14)	0.0288 (14)	−0.0008 (11)	0.0073 (11)	0.0075 (11)
N5	0.0183 (12)	0.0281 (13)	0.0142 (12)	0.0065 (10)	0.0032 (10)	0.0032 (10)
N6	0.0291 (15)	0.0603 (19)	0.0214 (14)	0.0252 (14)	0.0003 (11)	0.0054 (13)
C1	0.0266 (17)	0.0429 (18)	0.0266 (17)	0.0178 (14)	0.0005 (13)	0.0041 (14)
C2	0.0296 (17)	0.0216 (14)	0.0192 (15)	0.0102 (12)	−0.0007 (12)	0.0010 (11)
C3	0.031 (3)	0.036 (4)	0.022 (2)	0.009 (3)	0.006 (2)	0.010 (2)
C4	0.030 (3)	0.035 (3)	0.021 (3)	0.011 (3)	0.005 (2)	0.012 (3)
C3A	0.045 (17)	0.014 (16)	0.042 (17)	−0.007 (14)	0.013 (12)	0.007 (13)
C4A	0.025 (14)	0.04 (2)	0.020 (14)	0.005 (14)	0.002 (11)	−0.004 (13)
C5	0.0222 (15)	0.0149 (13)	0.0209 (15)	0.0073 (11)	0.0035 (12)	0.0021 (11)
C6	0.0219 (15)	0.0197 (13)	0.0239 (15)	0.0102 (11)	0.0077 (12)	0.0023 (11)
C7	0.0262 (16)	0.0152 (13)	0.0196 (14)	0.0067 (12)	0.0049 (12)	0.0032 (11)
C8	0.0320 (17)	0.0284 (15)	0.0236 (15)	0.0157 (13)	0.0100 (13)	0.0026 (12)
C9	0.0371 (18)	0.0235 (15)	0.0154 (14)	0.0113 (13)	0.0106 (13)	0.0023 (11)
C10	0.0267 (16)	0.0151 (13)	0.0180 (14)	0.0033 (11)	0.0055 (12)	0.0035 (11)
C11	0.0236 (15)	0.0301 (15)	0.0195 (15)	0.0107 (12)	0.0085 (12)	0.0088 (12)
C12	0.0256 (16)	0.0262 (15)	0.0161 (14)	0.0082 (12)	0.0093 (12)	0.0073 (11)
C13	0.0281 (16)	0.0201 (14)	0.0134 (14)	0.0005 (12)	0.0032 (12)	0.0030 (11)
C14	0.0272 (16)	0.0226 (14)	0.0236 (15)	0.0090 (12)	0.0089 (12)	0.0065 (12)
C16	0.0335 (18)	0.0406 (18)	0.0229 (16)	0.0177 (15)	0.0096 (14)	0.0099 (13)
C20	0.0225 (15)	0.0240 (15)	0.0204 (14)	0.0068 (12)	0.0058 (12)	0.0045 (11)
C21	0.047 (2)	0.065 (2)	0.0311 (18)	0.0402 (19)	0.0115 (16)	0.0143 (17)
C22	0.043 (2)	0.0348 (17)	0.0298 (17)	0.0202 (15)	0.0160 (15)	0.0096 (14)

S1—C1	1.713 (3)	C10—C13	1.526 (4)
S1—C6	1.732 (3)	C11—C12	1.378 (4)
O1—C2	1.371 (4)	C11—H11A	0.9500
O1—C3A	1.37 (3)	C12—H12	0.9500
O1—C3	1.445 (5)	C13—N1A	1.463 (4)
O2—C5	1.366 (3)	C13—N3	1.468 (4)
O2—C4	1.439 (4)	C13—N3A	1.485 (4)
O2—C4A	1.50 (3)	C13—N1	1.486 (5)
N4—C19A	1.283 (10)	C14—N1A	1.341 (5)
N4—N3A	1.320 (5)	C14—N1	1.366 (6)
N4—N3	1.366 (6)	C14—C16	1.396 (3)
N4—C19	1.378 (11)	C14—H14A	0.9500
N5—N6	1.362 (3)	N1—N2	1.372 (5)
N5—C20	1.367 (4)	N2—C15	1.340 (6)
N5—C13	1.466 (4)	C15—C16	1.385 (5)
N6—C21	1.316 (5)	C15—H15A	0.9500
C1—C2	1.354 (4)	N1A—N2A	1.366 (5)
C1—H1	0.9500	N2A—C15A	1.344 (6)
C2—C5	1.420 (4)	C15A—C16	1.408 (5)
C3—C4	1.501 (11)	C15A—H15B	0.9500
C3—H3A	0.9900	C16—H16A	0.9500
C3—H3B	0.9900	N3—C17	1.355 (5)
C4—H4A	0.9900	C17—C18	1.350 (7)
C4—H4B	0.9900	C17—H17A	0.9500
C3A—C4A	1.49 (7)	C18—C19	1.394 (7)
C3A—H3C	0.9900	C18—H18A	0.9500
C3A—H3D	0.9900	C19—H19A	0.9500
C4A—H4C	0.9900	N3A—C17A	1.361 (5)
C4A—H4D	0.9900	C17A—C18A	1.350 (6)
C5—C6	1.378 (4)	C17A—H17B	0.9500
C6—C7	1.463 (4)	C18A—C19A	1.396 (7)
C7—C12	1.398 (4)	C18A—H18B	0.9500
C7—C8	1.400 (4)	C19A—H19B	0.9500
C8—C9	1.388 (4)	C20—C22	1.359 (4)
C8—H8A	0.9500	C20—H20A	0.9500
C9—C10	1.387 (4)	C21—C22	1.406 (5)
C9—H9A	0.9500	C21—H21A	0.9500
C10—C11	1.396 (4)	C22—H22A	0.9500
C1—S1—C6	93.25 (15)	N1A—C13—N3	100.5 (4)
C2—O1—C3A	112.4 (13)	N5—C13—N3	116.8 (4)
C2—O1—C3	112.3 (3)	N1A—C13—N3A	108.9 (4)
C5—O2—C4	112.3 (3)	N5—C13—N3A	101.5 (4)
C5—O2—C4A	109.3 (11)	N5—C13—N1	110.7 (4)
C19A—N4—N3A	108.0 (4)	N3—C13—N1	104.0 (4)
C19A—N4—N3	109.2 (4)	N3A—C13—N1	114.7 (4)
N3A—N4—C19	98.7 (5)	N1A—C13—C10	117.0 (4)
N3—N4—C19	101.9 (4)	N5—C13—C10	109.3 (2)
N6—N5—C20	111.7 (2)	N3—C13—C10	109.2 (3)
N6—N5—C13	118.9 (2)	N3A—C13—C10	114.4 (3)
C20—N5—C13	128.3 (2)	N1—C13—C10	106.2 (5)
C21—N6—N5	104.4 (3)	N1A—C14—C16	108.1 (3)
C2—C1—S1	111.0 (2)	N1—C14—C16	104.5 (3)
C2—C1—H1	124.5	N1A—C14—H14A	123.1
S1—C1—H1	124.5	N1—C14—H14A	127.8
C1—C2—O1	123.9 (3)	C16—C14—H14A	127.8
C1—C2—C5	113.0 (3)	C14—N1—N2	109.4 (4)
O1—C2—C5	123.1 (3)	C14—N1—C13	123.8 (4)
O1—C3—C4	111.5 (6)	N2—N1—C13	126.8 (6)
O1—C3—H3A	109.3	C15—N2—N1	109.8 (5)
C4—C3—H3A	109.3	N2—C15—C16	105.8 (5)
O1—C3—H3B	109.3	N2—C15—H15A	127.1
C4—C3—H3B	109.3	C16—C15—H15A	127.1
H3A—C3—H3B	108.0	C14—N1A—N2A	114.6 (3)
O2—C4—C3	111.7 (6)	C14—N1A—C13	127.5 (4)
O2—C4—H4A	109.3	N2A—N1A—C13	115.4 (4)
C3—C4—H4A	109.3	C15A—N2A—N1A	99.8 (4)
O2—C4—H4B	109.3	N2A—C15A—C16	116.9 (5)
C3—C4—H4B	109.3	N2A—C15A—H15B	121.5
H4A—C4—H4B	108.0	C16—C15A—H15B	121.5
O1—C3A—C4A	110 (3)	C15—C16—C14	110.3 (4)
O1—C3A—H3C	109.7	C14—C16—C15A	100.5 (4)
C4A—C3A—H3C	109.7	C14—C16—H16A	124.9
O1—C3A—H3D	109.7	C15A—C16—H16A	132.0
C4A—C3A—H3D	109.7	C17—N3—N4	113.1 (4)
H3C—C3A—H3D	108.2	C17—N3—C13	125.0 (4)
C3A—C4A—O2	111 (4)	N4—N3—C13	118.0 (4)
C3A—C4A—H4C	109.4	C18—C17—N3	107.2 (5)
O2—C4A—H4C	109.4	C18—C17—H17A	126.4
C3A—C4A—H4D	109.4	N3—C17—H17A	126.4
O2—C4A—H4D	109.4	C17—C18—C19	105.6 (7)
H4C—C4A—H4D	108.0	C17—C18—H18A	127.2
O2—C5—C6	123.9 (3)	C19—C18—H18A	127.2
O2—C5—C2	122.4 (2)	N4—C19—C18	111.4 (8)
C6—C5—C2	113.7 (3)	N4—C19—H19A	124.3
C5—C6—C7	130.1 (3)	C18—C19—H19A	124.3
C5—C6—S1	109.0 (2)	N4—N3A—C17A	108.9 (4)
C7—C6—S1	120.9 (2)	N4—N3A—C13	120.0 (3)
C12—C7—C8	117.7 (3)	C17A—N3A—C13	131.1 (4)
C12—C7—C6	120.5 (2)	C18A—C17A—N3A	108.0 (5)
C8—C7—C6	121.8 (3)	C18A—C17A—H17B	126.0
C9—C8—C7	121.5 (3)	N3A—C17A—H17B	126.0
C9—C8—H8A	119.3	C17A—C18A—C19A	103.9 (6)
C7—C8—H8A	119.3	C17A—C18A—H18B	128.1
C10—C9—C8	120.2 (3)	C19A—C18A—H18B	128.1
C10—C9—H9A	119.9	N4—C19A—C18A	110.8 (7)
C8—C9—H9A	119.9	N4—C19A—H19B	124.6
C9—C10—C11	118.6 (3)	C18A—C19A—H19B	124.6
C9—C10—C13	122.2 (2)	C22—C20—N5	106.7 (3)
C11—C10—C13	119.2 (3)	C22—C20—H20A	126.7
C12—C11—C10	121.3 (3)	N5—C20—H20A	126.7
C12—C11—H11A	119.4	N6—C21—C22	112.3 (3)
C10—C11—H11A	119.4	N6—C21—H21A	123.9
C11—C12—C7	120.7 (3)	C22—C21—H21A	123.9
C11—C12—H12	119.6	C20—C22—C21	105.0 (3)
C7—C12—H12	119.6	C20—C22—H22A	127.5
N1A—C13—N5	104.1 (3)	C21—C22—H22A	127.5
C20—N5—N6—C21	−1.4 (3)	C10—C13—N1—N2	73.6 (8)
C13—N5—N6—C21	−170.4 (2)	C14—N1—N2—C15	−1.1 (10)
C6—S1—C1—C2	−1.3 (3)	C13—N1—N2—C15	−178.4 (8)
S1—C1—C2—O1	−178.9 (2)	N1—N2—C15—C16	−1.5 (10)
S1—C1—C2—C5	0.9 (3)	N1—C14—N1A—N2A	−73.0 (14)
C3A—O1—C2—C1	−162 (2)	C16—C14—N1A—N2A	0.8 (6)
C3—O1—C2—C1	166.0 (5)	N1—C14—N1A—C13	88.3 (16)
C3A—O1—C2—C5	18 (2)	C16—C14—N1A—C13	162.1 (6)
C3—O1—C2—C5	−13.8 (5)	N5—C13—N1A—C14	40.3 (8)
C2—O1—C3—C4	42.9 (8)	N3—C13—N1A—C14	161.6 (7)
C3A—O1—C3—C4	−54 (3)	N3A—C13—N1A—C14	147.9 (7)
C5—O2—C4—C3	45.3 (8)	N1—C13—N1A—C14	−88 (2)
C4A—O2—C4—C3	−45 (2)	C10—C13—N1A—C14	−80.5 (8)
O1—C3—C4—O2	−61.0 (9)	N5—C13—N1A—N2A	−158.6 (5)
C2—O1—C3A—C4A	−49 (4)	N3—C13—N1A—N2A	−37.3 (6)
C3—O1—C3A—C4A	47 (4)	N3A—C13—N1A—N2A	−50.9 (7)
O1—C3A—C4A—O2	66 (5)	N1—C13—N1A—N2A	72.8 (19)
C5—O2—C4A—C3A	−46 (4)	C10—C13—N1A—N2A	80.7 (6)
C4—O2—C4A—C3A	55 (4)	C14—N1A—N2A—C15A	−1.9 (7)
C4—O2—C5—C6	163.5 (4)	C13—N1A—N2A—C15A	−165.5 (6)
C4A—O2—C5—C6	−165 (2)	N1A—N2A—C15A—C16	2.3 (7)
C4—O2—C5—C2	−16.0 (5)	N2—C15—C16—C14	3.5 (8)
C4A—O2—C5—C2	15 (2)	N2—C15—C16—C15A	−57.3 (11)
C1—C2—C5—O2	179.5 (3)	N1A—C14—C16—C15	−15.9 (6)
O1—C2—C5—O2	−0.7 (4)	N1—C14—C16—C15	−4.1 (7)
C1—C2—C5—C6	0.0 (4)	N1A—C14—C16—C15A	0.6 (5)
O1—C2—C5—C6	179.8 (2)	N1—C14—C16—C15A	12.3 (5)
O2—C5—C6—C7	0.0 (5)	N2A—C15A—C16—C15	121.7 (15)
C2—C5—C6—C7	179.4 (3)	N2A—C15A—C16—C14	−1.9 (7)
O2—C5—C6—S1	179.5 (2)	C19A—N4—N3—C17	5.3 (8)
C2—C5—C6—S1	−1.0 (3)	N3A—N4—N3—C17	−83.7 (10)
C1—S1—C6—C5	1.3 (2)	C19—N4—N3—C17	−3.0 (8)
C1—S1—C6—C7	−179.1 (2)	C19A—N4—N3—C13	164.3 (7)
C5—C6—C7—C12	20.3 (4)	N3A—N4—N3—C13	75.3 (8)
S1—C6—C7—C12	−159.3 (2)	C19—N4—N3—C13	156.0 (7)
C5—C6—C7—C8	−161.1 (3)	N1A—C13—N3—C17	−37.6 (8)
S1—C6—C7—C8	19.4 (4)	N5—C13—N3—C17	74.2 (7)
C12—C7—C8—C9	0.4 (4)	N3A—C13—N3—C17	86.6 (13)
C6—C7—C8—C9	−178.3 (2)	N1—C13—N3—C17	−48.1 (8)
C7—C8—C9—C10	−1.1 (4)	C10—C13—N3—C17	−161.2 (6)
C8—C9—C10—C11	0.9 (4)	N1A—C13—N3—N4	166.1 (6)
C8—C9—C10—C13	179.5 (2)	N5—C13—N3—N4	−82.1 (6)
C9—C10—C11—C12	−0.1 (4)	N3A—C13—N3—N4	−69.7 (12)
C13—C10—C11—C12	−178.7 (2)	N1—C13—N3—N4	155.6 (6)
C10—C11—C12—C7	−0.6 (4)	C10—C13—N3—N4	42.6 (7)
C8—C7—C12—C11	0.5 (4)	N4—N3—C17—C18	−2.7 (9)
C6—C7—C12—C11	179.2 (3)	C13—N3—C17—C18	−159.9 (7)
N6—N5—C13—N1A	67.9 (4)	N3—C17—C18—C19	7.0 (10)
C20—N5—C13—N1A	−99.1 (4)	C19A—N4—C19—C18	−126 (4)
N6—N5—C13—N3	−41.8 (4)	N3A—N4—C19—C18	24.6 (9)
C20—N5—C13—N3	151.2 (3)	N3—N4—C19—C18	7.5 (9)
N6—N5—C13—N3A	−45.2 (3)	C17—C18—C19—N4	−9.4 (11)
C20—N5—C13—N3A	147.8 (3)	C19A—N4—N3A—C17A	5.9 (8)
N6—N5—C13—N1	76.9 (5)	N3—N4—N3A—C17A	102.7 (10)
C20—N5—C13—N1	−90.1 (5)	C19—N4—N3A—C17A	0.4 (7)
N6—N5—C13—C10	−166.4 (2)	C19A—N4—N3A—C13	−173.8 (7)
C20—N5—C13—C10	26.6 (4)	N3—N4—N3A—C13	−77.0 (8)
C9—C10—C13—N1A	−7.2 (4)	C19—N4—N3A—C13	−179.3 (7)
C11—C10—C13—N1A	171.4 (3)	N1A—C13—N3A—N4	141.0 (6)
C9—C10—C13—N5	−125.1 (3)	N5—C13—N3A—N4	−109.6 (6)
C11—C10—C13—N5	53.5 (3)	N3—C13—N3A—N4	81.7 (13)
C9—C10—C13—N3	106.0 (4)	N1—C13—N3A—N4	131.0 (7)
C11—C10—C13—N3	−75.4 (4)	C10—C13—N3A—N4	8.0 (8)
C9—C10—C13—N3A	121.9 (4)	N1A—C13—N3A—C17A	−38.7 (9)
C11—C10—C13—N3A	−59.5 (5)	N5—C13—N3A—C17A	70.8 (8)
C9—C10—C13—N1	−5.6 (4)	N3—C13—N3A—C17A	−98.0 (14)
C11—C10—C13—N1	173.0 (3)	N1—C13—N3A—C17A	−48.6 (9)
N1A—C14—N1—N2	112.6 (17)	C10—C13—N3A—C17A	−171.6 (6)
C16—C14—N1—N2	3.2 (7)	N4—N3A—C17A—C18A	−2.4 (8)
N1A—C14—N1—C13	−70.0 (13)	C13—N3A—C17A—C18A	177.2 (7)
C16—C14—N1—C13	−179.4 (7)	N3A—C17A—C18A—C19A	−1.7 (9)
N1A—C13—N1—C14	69.4 (19)	N3A—N4—C19A—C18A	−7.1 (9)
N5—C13—N1—C14	15.3 (10)	N3—N4—C19A—C18A	−25.2 (9)
N3—C13—N1—C14	141.6 (8)	C19—N4—C19A—C18A	23 (3)
N3A—C13—N1—C14	129.4 (8)	C17A—C18A—C19A—N4	5.5 (10)
C10—C13—N1—C14	−103.3 (8)	N6—N5—C20—C22	1.3 (3)
N1A—C13—N1—N2	−114 (2)	C13—N5—C20—C22	169.0 (3)
N5—C13—N1—N2	−167.8 (7)	N5—N6—C21—C22	1.0 (4)
N3—C13—N1—N2	−41.5 (9)	N5—C20—C22—C21	−0.6 (3)
N3A—C13—N1—N2	−53.7 (10)	N6—C21—C22—C20	−0.2 (4)