2,4,5-Tri­phenyl-4H-imidazol-4-yl hydro­peroxide-di­chloro­methane (2/1)

The structure of lophine peroxide was confirmed to be 2,4,5-tri­phenyl-4H-imidazol-4-yl hydro­peroxide and not the 2,5-endoperoxide. The asymmetric unit is composed of an O-H...N hydrogen-bonded dimer of lophine peroxide with an R/R or S/S configuration and a CH₂Cl₂ solvent mol­ecule, i.e. 2C₂₁H₁₆N₂O₂·CH₂Cl₂.

S1. Comment

In lophine chemiluminescence, the peroxide is known to be the critical intermediate. Lophine peroxide was originally formulated as the 2,5-endoperoxide, (II), by Dufraisse et al. (1957), but this structure is invalidated by the ¹H NMR and UV spectra, and the hydroperoxide structure (I) was established by White & Harding (1964). X-ray analysis of the lophine peroxide has long been required for structure confirmation. However, only silk-hair-type crystals have grown from ethanol solution. Recently, we obtained prismatic crystals from a CH₂Cl₂ solution. The melting point of the crystals is higher (388 K) than that of silk-hair-type crystals (383 K). We report here the structure of the prismatic crystal and discuss the structure of lophine peroxide, (I).

The S/S dimer is bonded by two hydrogen bonds and the π–π stacking between the phenyl groups (A and A') on the second position of each imidazole ring. The angle between the planes of rings A and A' is 11.19 (4)°. The center-to-center distance between rings A and A' is 3.84 (5) Å. The bond lengths of 1.470 (2) Å for O1—O2 and 1.464 (2) Å for O1'—O2' agree with the average value for RO—OH of 1.465 Å (Boche et al., 1996), and are shorter than the range 1.496–1.550 Å for R₁O—OR₂ (Suzuki et al., 2000; Izuoka et al., 1997; Coughlin et al., 1979; Sander et al., 1997; Adam et al., 1983). The C2—O1 [1.419 (3) Å] and C2'—O1' bond lengths [1.418 (2) Å] are shorter than the mean value of those of R—OOR (1.455 Å; Suzuki et al., 2000).

The unit cell consists of an S/S domain and an R/R domain. These domains are formed by two kinds of inter-domain π–π stacking. An intra-domain π–π stacking center-to-center distance between the phenyl groups (B) of an R/R dimer or an S/S dimer is 3.99 (4) Å along the a axis. Another inter-domain π–π stacking is observed between the phenyl group (A) of an R/R dimer and the phenyl group (A') of an S/S dimer. The angle between the molecular axes of a lophine peroxide moiety between adjacent R/R or S/S dimers is about 60°.

S2. Experimental

The title compound was prepared according to the method of White et al. (1964). Crystallization from CH₂Cl₂ yielded colorless needles (89%) which showed identical ¹H NMR, IR, and UV spectral data to those of a verified sample obtained from ethanol (Kimura et al., 1993; White et al., 1964). The melting point of this crystals is higher (388 K) than that of silk-hair-type crystals obtained from ethanol (383 K). HRMS (FAB) m/z: calculated for C₂₁H₁₆N₂O₂ 329.1290; found 329.1265.

S3. Refinement

The positional parameters of the H atoms attached to C atoms were calculated geometrically and fixed with U_iso = 0.048 Ų. The H atoms of the peroxide groups were found by difference syntheses and their positional parameters were somewhat refined and fixed.

Computing details

Data collection: MSC/RAXIS-RAPID Imaging Plate Diffractometer Control Software (Molecular Structure Corporation, 1996); cell refinement: MSC/RAXIS-RAPID Imaging Plate Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

2,4,5-Triphenyl-4H-imidazol-4-yl-hydroperoxide dichloromethane solvate (2:1)

Crystal data

2C21H16N2O2·CH2Cl2	F(000) = 3088
Mr = 741.67	Dx = 1.361 Mg m^−3
Monoclinic, C2/c	Melting point: 115 K
Hall symbol: -C 2yc	Cu Kα radiation, λ = 1.5418 Å
a = 19.519 (1) Å	Cell parameters from 14799 reflections
b = 14.269 (1) Å	θ = 4.1–68.0°
c = 26.068 (2) Å	µ = 2.02 mm^−1
β = 94.456 (2)°	T = 123 K
V = 7238.5 (8) Å^3	Prism, colorless
Z = 8	0.34 × 0.33 × 0.32 mm

Data collection

Rigaku RAXIS-RAPID Imaging Plate diffractometer	6464 independent reflections
Radiation source: X-ray tube	4887 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
ω scans	θmax = 68.0°, θmin = 4.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −22→23
Tmin = 0.460, Tmax = 0.524	k = −17→17
33961 measured reflections	l = −31→31

Refinement

Refinement on F^2	H-atom parameters not refined
Least-squares matrix: full	Calculated w = 1/[σ^2(Fo^2) + (0.06000(Max(Fo^2,0) + 2Fc^2)/3)^2])
R[F^2 > 2σ(F^2)] = 0.051	(Δ/σ)max = 0.001
wR(F^2) = 0.142	Δρmax = 0.65 e Å^−3
S = 1.15	Δρmin = −0.99 e Å^−3
6464 reflections	Extinction correction: Zachariasen (1967) type 2 Gaussian isotropic
479 parameters	Extinction coefficient: 0.0048 (6)

Special details

Refinement. Refinement using reflections with F² > −10.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Cl1	0.40322 (4)	0.17763 (5)	0.01415 (3)	0.0485 (2)
Cl2	0.51833 (5)	0.29661 (9)	−0.00407 (4)	0.0780 (3)
O1	−0.05768 (8)	0.8611 (1)	0.32699 (5)	0.0208 (4)
O1'	−0.10842 (8)	1.0736 (1)	0.29438 (5)	0.0204 (4)
O2	−0.04542 (8)	0.8810 (1)	0.38227 (6)	0.0243 (4)
O2'	−0.18213 (8)	1.0535 (1)	0.29260 (6)	0.0232 (4)
N1	−0.17736 (10)	0.8765 (1)	0.33548 (7)	0.0211 (4)
N1'	−0.10067 (10)	1.0596 (1)	0.38635 (7)	0.0203 (4)
N2	−0.1765 (1)	0.7424 (1)	0.38580 (7)	0.0227 (5)
N2'	−0.16336 (10)	1.1959 (1)	0.39420 (7)	0.0217 (4)
C1	−0.2046 (1)	0.8330 (2)	0.37215 (8)	0.0205 (5)
C1'	−0.1398 (1)	1.1072 (2)	0.41426 (8)	0.0210 (5)
C2	−0.1223 (1)	0.8156 (1)	0.31965 (8)	0.0194 (5)
C2'	−0.0898 (1)	1.1198 (1)	0.34156 (8)	0.0192 (5)
C3	−0.1273 (1)	0.7304 (1)	0.35590 (8)	0.0204 (5)
C3'	−0.1354 (1)	1.2045 (1)	0.35116 (8)	0.0191 (5)
C4	−0.2593 (1)	0.8701 (2)	0.40186 (8)	0.0222 (5)
C4'	−0.1597 (1)	1.0783 (2)	0.46517 (8)	0.0235 (5)
C5	−0.2918 (1)	0.9548 (2)	0.38770 (9)	0.0262 (6)
C5'	−0.1264 (2)	1.0034 (2)	0.49082 (10)	0.0402 (7)
C6	−0.3422 (1)	0.9897 (2)	0.41671 (9)	0.0300 (6)
C6'	−0.1448 (2)	0.9783 (2)	0.5394 (1)	0.0485 (9)
C7	−0.3605 (1)	0.9423 (2)	0.45990 (10)	0.0335 (7)
C7'	−0.1960 (2)	1.0264 (2)	0.56199 (10)	0.0415 (7)
C8	−0.3283 (1)	0.8582 (2)	0.47438 (10)	0.0364 (7)
C8'	−0.2295 (1)	1.1001 (2)	0.53637 (10)	0.0362 (7)
C9	−0.2780 (1)	0.8221 (2)	0.44524 (9)	0.0295 (6)
C9'	−0.2114 (1)	1.1264 (2)	0.48804 (9)	0.0284 (6)
C10	−0.1323 (1)	0.7922 (2)	0.26245 (8)	0.0191 (5)
C10'	−0.0135 (1)	1.1402 (2)	0.34167 (8)	0.0214 (5)
C11	−0.0997 (1)	0.8456 (2)	0.22715 (9)	0.0264 (6)
C12'	0.0299 (1)	1.0750 (2)	0.32130 (8)	0.0250 (5)
C12	−0.1089 (1)	0.8247 (2)	0.17486 (9)	0.0308 (6)
C12'	0.1002 (1)	1.0908 (2)	0.32342 (9)	0.0266 (6)
C13	−0.1516 (1)	0.7515 (2)	0.15802 (9)	0.0273 (6)
C13'	0.1277 (1)	1.1717 (2)	0.34617 (9)	0.0288 (6)
C14	−0.1850 (1)	0.6991 (2)	0.19318 (9)	0.0270 (6)
C14'	0.0846 (1)	1.2362 (2)	0.36662 (10)	0.0293 (6)
C15	−0.1751 (1)	0.7193 (2)	0.24562 (9)	0.0247 (6)
C15'	0.0142 (1)	1.2218 (2)	0.36444 (9)	0.0267 (6)
C16	−0.0840 (1)	0.6478 (2)	0.35662 (8)	0.0216 (5)
C16'	−0.1454 (1)	1.2858 (2)	0.31740 (8)	0.0197 (5)
C17	−0.0309 (1)	0.6397 (2)	0.32381 (9)	0.0260 (6)
C17'	−0.1115 (1)	1.2946 (2)	0.27269 (9)	0.0264 (6)
C18	0.0084 (1)	0.5586 (2)	0.32408 (10)	0.0306 (6)
C18'	−0.1210 (2)	1.3742 (2)	0.24224 (9)	0.0328 (6)
C19	−0.0045 (1)	0.4860 (2)	0.3572 (1)	0.0328 (6)
C19'	−0.1651 (1)	1.4444 (2)	0.25566 (9)	0.0329 (6)
C20	−0.0562 (1)	0.4941 (2)	0.39064 (10)	0.0317 (6)
C20'	−0.2001 (1)	1.4358 (2)	0.29952 (9)	0.0299 (6)
C21	−0.0960 (1)	0.5742 (2)	0.39048 (9)	0.0277 (6)
C21'	−0.1906 (1)	1.3574 (2)	0.33045 (8)	0.0253 (6)
C22	0.4581 (1)	0.2665 (2)	0.03932 (10)	0.0352 (7)
H5	−0.2822	0.9848	0.3558	0.0480*
H5'	−0.0843	0.9747	0.4784	0.0480*
H6	−0.3665	1.0452	0.4060	0.0480*
H6'	−0.1222	0.9279	0.5565	0.0480*
H7	−0.3999	0.9652	0.4803	0.0480*
H7'	−0.2101	1.0080	0.5970	0.0480*
H8	−0.3433	0.8216	0.5056	0.0480*
H8'	−0.2655	1.1397	0.5525	0.0480*
H9	−0.2569	0.7626	0.4556	0.0480*
H9'	−0.2379	1.1768	0.4673	0.0480*
H11	−0.0695	0.8965	0.2363	0.0480*
H11'	0.0119	1.0182	0.3059	0.0480*
H12	−0.0856	0.8595	0.1519	0.0480*
H12'	0.1298	1.0438	0.3091	0.0480*
H13	−0.1647	0.7395	0.1211	0.0480*
H13'	0.1779	1.1825	0.3447	0.0480*
H14	−0.2155	0.6487	0.1819	0.0480*
H14'	0.1065	1.2905	0.3839	0.0480*
H15	−0.2028	0.6834	0.2668	0.0480*
H15'	−0.0195	1.2696	0.3773	0.0480*
H17	−0.0198	0.6893	0.2987	0.0480*
H17'	−0.0787	1.2451	0.2626	0.0480*
H18	0.0436	0.5526	0.2991	0.0480*
H18'	−0.0981	1.3766	0.2122	0.0480*
H19	0.0245	0.4289	0.3582	0.0480*
H19'	−0.1709	1.4991	0.2361	0.0480*
H20	−0.0575	0.4477	0.4185	0.0480*
H20'	−0.2299	1.4826	0.3111	0.0480*
H21	−0.1363	0.5815	0.4154	0.0480*
H21'	−0.2153	1.3544	0.3618	0.0480*
H22	0.4796	0.2454	0.0695	0.0480*
H22'	0.4337	0.3267	0.0454	0.0480*
H2o'	−0.1840	0.9893	0.3085	0.0480*
H2o	−0.0660	0.9448	0.3852	0.0480*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0581 (5)	0.0375 (4)	0.0495 (4)	−0.0204 (3)	0.0015 (3)	−0.0035 (3)
Cl2	0.0741 (6)	0.1016 (8)	0.0636 (5)	−0.0521 (6)	0.0391 (5)	−0.0310 (5)
O1	0.0220 (8)	0.0207 (8)	0.0194 (7)	−0.0006 (6)	0.0003 (6)	−0.0027 (6)
O1'	0.0214 (7)	0.0187 (8)	0.0213 (7)	−0.0006 (6)	0.0034 (6)	−0.0029 (6)
O2	0.0291 (8)	0.0216 (8)	0.0215 (7)	0.0027 (7)	−0.0038 (6)	−0.0031 (6)
O2'	0.0211 (8)	0.0192 (8)	0.0294 (8)	0.0003 (6)	0.0017 (6)	0.0029 (6)
N1	0.0221 (9)	0.0175 (9)	0.0236 (9)	0.0016 (7)	0.0013 (7)	−0.0008 (7)
N1'	0.0258 (9)	0.0157 (9)	0.0196 (8)	−0.0012 (7)	0.0039 (7)	−0.0001 (7)
N2	0.0265 (9)	0.0175 (9)	0.0246 (9)	0.0021 (8)	0.0047 (7)	0.0007 (7)
N2'	0.0270 (10)	0.0175 (9)	0.0209 (8)	0.0013 (8)	0.0036 (7)	−0.0004 (7)
C1	0.023 (1)	0.017 (1)	0.0210 (10)	0.0017 (8)	0.0006 (8)	0.0001 (8)
C1'	0.026 (1)	0.016 (1)	0.0212 (10)	0.0001 (9)	0.0019 (8)	−0.0025 (8)
C2	0.0188 (10)	0.0152 (10)	0.024 (1)	0.0000 (8)	0.0017 (8)	0.0020 (8)
C2'	0.026 (1)	0.0133 (10)	0.0186 (9)	−0.0004 (8)	0.0023 (8)	0.0004 (7)
C3	0.024 (1)	0.016 (1)	0.0215 (9)	−0.0014 (9)	0.0018 (8)	0.0005 (8)
C3'	0.022 (1)	0.0151 (10)	0.0196 (9)	−0.0029 (8)	−0.0009 (8)	−0.0020 (7)
C4	0.021 (1)	0.022 (1)	0.0230 (10)	0.0000 (9)	0.0008 (8)	−0.0027 (8)
C4'	0.030 (1)	0.022 (1)	0.0188 (10)	−0.0017 (10)	0.0028 (9)	−0.0013 (8)
C5	0.028 (1)	0.023 (1)	0.028 (1)	0.0017 (10)	0.0018 (9)	0.0000 (9)
C5'	0.063 (2)	0.033 (1)	0.027 (1)	0.017 (1)	0.015 (1)	0.007 (1)
C6	0.031 (1)	0.027 (1)	0.032 (1)	0.009 (1)	0.0014 (10)	−0.0036 (9)
C6'	0.083 (2)	0.036 (2)	0.029 (1)	0.020 (2)	0.016 (1)	0.013 (1)
C7	0.030 (1)	0.036 (1)	0.036 (1)	0.010 (1)	0.010 (1)	−0.007 (1)
C7'	0.060 (2)	0.044 (2)	0.023 (1)	0.006 (1)	0.012 (1)	0.008 (1)
C8	0.038 (1)	0.044 (2)	0.029 (1)	0.011 (1)	0.011 (1)	0.003 (1)
C8'	0.039 (1)	0.045 (2)	0.026 (1)	0.005 (1)	0.010 (1)	0.002 (1)
C9	0.031 (1)	0.032 (1)	0.026 (1)	0.007 (1)	0.0034 (10)	0.0029 (9)
C9'	0.032 (1)	0.032 (1)	0.022 (1)	0.006 (1)	0.0032 (9)	0.0019 (9)
C10	0.0172 (10)	0.017 (1)	0.0225 (10)	0.0030 (8)	−0.0005 (8)	−0.0011 (8)
C10'	0.027 (1)	0.018 (1)	0.0198 (9)	0.0025 (9)	0.0031 (8)	0.0013 (8)
C11	0.029 (1)	0.023 (1)	0.028 (1)	−0.0062 (9)	0.0032 (9)	−0.0003 (9)
C11'	0.030 (1)	0.023 (1)	0.0224 (10)	0.0015 (10)	0.0023 (9)	−0.0040 (8)
C12	0.030 (1)	0.037 (1)	0.026 (1)	−0.004 (1)	0.0054 (10)	0.0028 (10)
C12'	0.025 (1)	0.030 (1)	0.025 (1)	0.0043 (10)	0.0048 (9)	0.0015 (9)
C13	0.029 (1)	0.029 (1)	0.024 (1)	0.0036 (10)	0.0003 (9)	−0.0033 (9)
C13'	0.026 (1)	0.028 (1)	0.032 (1)	0.0004 (10)	0.0018 (10)	0.0067 (9)
C14	0.029 (1)	0.018 (1)	0.033 (1)	−0.0012 (9)	−0.0014 (10)	−0.0029 (9)
C14'	0.027 (1)	0.019 (1)	0.040 (1)	−0.0021 (10)	−0.002 (1)	0.0014 (9)
C15	0.023 (1)	0.019 (1)	0.033 (1)	−0.0014 (9)	0.0031 (9)	0.0015 (9)
C15'	0.029 (1)	0.018 (1)	0.034 (1)	0.0019 (9)	0.0021 (10)	−0.0001 (9)
C16	0.026 (1)	0.015 (1)	0.0234 (10)	−0.0014 (9)	0.0005 (9)	−0.0023 (8)
C16'	0.021 (1)	0.016 (1)	0.0225 (10)	0.0002 (8)	−0.0019 (8)	−0.0020 (8)
C17	0.027 (1)	0.020 (1)	0.031 (1)	0.0022 (9)	0.0034 (9)	0.0009 (9)
C17'	0.035 (1)	0.021 (1)	0.024 (1)	0.0034 (10)	0.0045 (9)	0.0022 (8)
C18	0.026 (1)	0.026 (1)	0.040 (1)	0.006 (1)	0.005 (1)	−0.0043 (10)
C18'	0.052 (2)	0.023 (1)	0.024 (1)	0.001 (1)	0.009 (1)	0.0046 (9)
C19	0.030 (1)	0.019 (1)	0.049 (1)	0.0066 (10)	0.000 (1)	0.001 (1)
C19'	0.052 (2)	0.019 (1)	0.028 (1)	−0.001 (1)	−0.001 (1)	0.0048 (9)
C20	0.042 (1)	0.018 (1)	0.034 (1)	0.003 (1)	0.000 (1)	0.0061 (9)
C20'	0.036 (1)	0.021 (1)	0.033 (1)	0.009 (1)	0.0015 (10)	0.0009 (9)
C21	0.033 (1)	0.021 (1)	0.029 (1)	0.0030 (10)	0.0052 (10)	0.0037 (9)
C21'	0.032 (1)	0.021 (1)	0.024 (1)	0.0041 (10)	0.0048 (9)	0.0009 (8)
C22	0.039 (1)	0.036 (1)	0.030 (1)	−0.013 (1)	0.003 (1)	−0.004 (1)

Geometric parameters (Å, º)

Cl1—C22	1.754 (3)	C10—C11	1.387 (3)
Cl2—C22	1.747 (3)	C10—C15	1.385 (3)
O1—O2	1.470 (2)	C10'—C11'	1.390 (3)
O1—C2	1.419 (3)	C10'—C15'	1.397 (3)
O1'—O2'	1.464 (2)	C11—C12	1.393 (3)
O1'—C2'	1.418 (2)	C11—H11	0.953
O2—H2o	1.001	C11'—C12'	1.388 (4)
O2'—H2o'	1.007	C11'—H11'	0.959
N1—C1	1.288 (3)	C12—C13	1.386 (4)
N1—C2	1.465 (3)	C12—H12	0.925
N1'—C1'	1.288 (3)	C12'—C13'	1.387 (4)
N1'—C2'	1.477 (3)	C12'—H12'	0.979
N2—C1	1.438 (3)	C13—C14	1.385 (4)
N2—C3	1.293 (3)	C13—H13	0.991
N2'—C1'	1.432 (3)	C13'—C14'	1.380 (4)
N2'—C3'	1.291 (3)	C13'—H13'	0.996
C1—C4	1.467 (3)	C14—C15	1.396 (3)
C1'—C4'	1.470 (3)	C14—H14	0.964
C2—C3	1.548 (3)	C14'—C15'	1.387 (4)
C2—C10	1.526 (3)	C14'—H14'	0.978
C2'—C3'	1.534 (3)	C15—H15	0.950
C2'—C10'	1.518 (3)	C15'—H15'	1.022
C3—C16	1.451 (3)	C16—C17	1.398 (3)
C3'—C16'	1.459 (3)	C16—C21	1.404 (3)
C4—C5	1.400 (3)	C16'—C17'	1.390 (3)
C4—C9	1.394 (3)	C16'—C21'	1.409 (3)
C4'—C5'	1.394 (4)	C17—C18	1.388 (3)
C4'—C9'	1.393 (3)	C17—H17	0.998
C5—C6	1.381 (3)	C17'—C18'	1.390 (3)
C5—H5	0.968	C17'—H17'	1.003
C5'—C6'	1.390 (4)	C18—C19	1.384 (4)
C5'—H5'	0.994	C18—H18	0.987
C6—C7	1.384 (4)	C18'—C19'	1.384 (4)
C6—H6	0.953	C18'—H18'	0.930
C6'—C7'	1.382 (4)	C19—C20	1.388 (4)
C6'—H6'	0.938	C19—H19	0.991
C7—C8	1.393 (4)	C19'—C20'	1.382 (4)
C7—H7	1.020	C19'—H19'	0.934
C7'—C8'	1.383 (4)	C20—C21	1.382 (4)
C7'—H7'	1.009	C20—H20	0.984
C8—C9	1.386 (4)	C20'—C21'	1.382 (3)
C8—H8	1.027	C20'—H20'	0.950
C8'—C9'	1.387 (3)	C21—H21	1.064
C8'—H8'	1.018	C21'—H21'	0.981
C9—H9	0.973	C22—H22	0.912
C9'—H9'	1.017	C22—H22'	1.002
O1···O1'	3.282 (2)	O2···C22^ii	3.035 (3)
O1···C12^i	3.296 (3)	O2'···N1	2.760 (2)
O1'···C12'^i	3.097 (3)	N1···N1'	3.243 (3)
O2···N1'	2.773 (2)
O2—O1—C2	107.2 (1)	C11'—C10'—C15'	119.5 (2)
O2'—O1'—C2'	107.7 (1)	C10—C11—C12	120.1 (2)
O1—O2—H2o	102.5	C10—C11—H11	123.9
O1'—O2'—H2o'	103.4	C12—C11—H11	116.0
C1—N1—C2	106.0 (2)	C10'—C11'—C12'	120.4 (2)
C1'—N1'—C2'	105.5 (2)	C10'—C11'—H11'	120.7
C1—N2—C3	104.9 (2)	C11'—C12'—H11'	118.9
C1'—N2'—C3'	104.8 (2)	C11—C12—C13	120.0 (2)
N1—C1—N2	116.5 (2)	C11—C12—H12	119.2
N1—C1—C4	125.2 (2)	C13—C12—H12	120.8
N2—C1—C4	118.3 (2)	C11'—C12'—C13'	120.0 (2)
N1'—C1'—N2'	116.6 (2)	C11'—C12'—H12'	119.0
N1'—C1'—C4'	124.9 (2)	C13'—C12'—H12'	121.0
N2'—C1'—C4'	118.5 (2)	C12—C13—C14	120.0 (2)
O1—C2—N1	110.8 (2)	C12—C13—H13	122.8
O1—C2—C3	112.0 (2)	C14—C13—H13	116.7
O1—C2—C10	106.1 (2)	C12'—C13'—C14'	119.6 (2)
N1—C2—C3	102.2 (2)	C12'—C13'—H13'	117.4
N1—C2—C10	111.4 (2)	C14'—C13'—H13'	122.9
C3—C2—C10	114.6 (2)	C13—C14—C15	120.0 (2)
O1'—C2'—N1'	111.9 (2)	C13—C14—H14	120.9
O1'—C2'—C3'	113.3 (2)	C15—C14—H14	119.1
O1'—C2'—C10'	106.0 (2)	C13'—C14'—C15'	121.1 (2)
N1'—C2'—C3'	102.0 (2)	C13'—C14'—H14'	116.6
N1'—C2'—C10'	108.1 (2)	C15'—C14'—H14'	122.2
C3'—C2'—C10'	115.5 (2)	C10—C15—C14	120.0 (2)
N2—C3—C2	110.4 (2)	C10—C15—H15	125.3
N2—C3—C16	124.0 (2)	C14—C15—H15	114.5
C2—C3—C16	125.6 (2)	C10'—C15'—C14'	119.4 (2)
N2'—C3'—C2'	110.9 (2)	C10'—C15'—H15'	117.3
N2'—C3'—C16'	123.7 (2)	C14'—C15'—H15'	123.2
C2'—C3'—C16'	125.4 (2)	C3—C16—C17	121.2 (2)
C1—C4—C5	120.4 (2)	C3—C16—C21	119.3 (2)
C1—C4—C9	119.8 (2)	C17—C16—C21	119.4 (2)
C5—C4—C9	119.8 (2)	C3'—C16'—C17'	121.8 (2)
C1'—C4'—C5'	120.1 (2)	C3'—C16'—C21'	119.2 (2)
C1'—C4'—C9'	120.0 (2)	C17'—C16'—C21'	119.0 (2)
C5'—C4'—C9'	119.9 (2)	C16—C17—C18	120.1 (2)
C4—C5—C6	119.6 (2)	C16—C17—H17	123.4
C4—C5—H5	119.7	C18—C17—H17	116.5
C6—C5—H5	120.3	C16'—C17'—C18'	120.1 (2)
C4'—C5'—C6'	119.4 (2)	C16'—C17'—H17'	120.8
C4'—C5'—H5'	121.7	C18'—C17'—H17'	119.0
C6'—C5'—H5'	118.0	C17—C18—C19	120.0 (2)
C5—C6—C7	120.6 (2)	C17—C18—H18	118.8
C5—C6—H6	120.0	C19—C18—H18	121.1
C7—C6—H6	119.3	C17'—C18'—C19'	120.3 (2)
C5'—C6'—C7'	120.5 (3)	C17'—C18'—H18'	117.4
C5'—C6'—H6'	118.9	C19'—C18'—H18'	122.2
C7'—C6'—H6'	120.6	C18—C19—C20	120.4 (2)
C6—C7—C8	120.1 (2)	C18—C19—H19	120.0
C6—C7—H7	121.2	C20—C19—H19	119.5
C8—C7—H7	118.5	C18'—C19'—C20'	120.1 (2)
C6'—C7'—C8'	120.2 (2)	C18'—C19'—H19'	121.2
C6'—C7'—H7'	120.9	C20'—C19'—H19'	118.7
C8'—C7'—H7'	118.9	C19—C20—C21	120.2 (2)
C7—C8—C9	119.7 (2)	C19—C20—H20	118.0
C7—C8—H8	120.0	C21—C20—H20	120.8
C9—C8—H8	120.2	C19'—C20'—C21'	120.2 (2)
C7'—C8'—C9'	120.0 (2)	C19'—C20'—H20'	123.6
C7'—C8'—H8'	122.6	C21'—C20'—H20'	116.2
C9'—C8'—H8'	117.2	C16—C21—C20	119.9 (2)
C4—C9—C8	120.2 (2)	C16—C21—H21	118.6
C4—C9—H9	121.5	C20—C21—H21	121.4
C8—C9—H9	118.3	C16'—C21'—C20'	120.3 (2)
C4'—C9'—C8'	120.0 (2)	C16'—C21'—H21'	121.8
C4'—C9'—H9'	118.5	C20'—C21'—H21'	117.9
C8'—C9'—H9'	121.3	Cl1—C22—Cl2	111.0 (1)
C2—C10—C11	119.9 (2)	Cl1—C22—H22	108.1
C2—C10—C15	120.1 (2)	Cl1—C22—H22'	113.3
C11—C10—C15	120.0 (2)	Cl2—C22—H22	110.7
C2'—C10'—C11'	119.9 (2)	Cl2—C22—H22'	104.1
C2'—C10'—C15'	120.5 (2)	H22—C22—H22'	109.8
O1—C2—N1—C1	−119.0 (2)	C6—C7—C8—C9	−0.3 (4)
O1—C2—C3—N2	119.0 (2)	C6—C7—C8—H8	−177.5 (3)
O1—C2—C3—C16	−61.4 (3)	C6'—C5'—C4'—C9'	−0.9 (4)
O1—C2—C10—C11	−26.1 (3)	C6'—C7'—C8'—C9'	−0.4 (5)
O1—C2—C10—C15	155.5 (2)	C6'—C7'—C8'—H8'	−176.3 (3)
O1'—C2'—N1'—C1'	−125.0 (2)	C7—C6—C5—H5	174.1 (2)
O1'—C2'—C3'—N2'	123.4 (2)	C7—C8—C9—H9	−178.6 (3)
O1'—C2'—C3'—C16'	−58.1 (3)	C7'—C6'—C5'—H5'	169.8 (3)
O1'—C2'—C10'—C11'	−38.0 (2)	C7'—C8'—C9'—H9'	175.0 (3)
O1'—C2'—C10'—C15'	145.3 (2)	C8—C7—C6—H6	176.3 (3)
O2—O1—C2—N1	61.3 (2)	C8'—C7'—C6'—H6'	−179.4 (3)
O2—O1—C2—C3	−52.1 (2)	C9—C4—C5—H5	−173.9 (2)
O2—O1—C2—C10	−177.7 (1)	C9—C8—C7—H7	175.5 (3)
O2'—O1'—C2'—N1'	62.9 (2)	C9'—C4'—C5'—H5'	−169.5 (3)
O2'—O1'—C2'—C3'	−51.7 (2)	C9'—C8'—C7'—H7'	−179.6 (3)
O2'—O1'—C2'—C10'	−179.5 (1)	C10—C2—C3—C16	59.4 (3)
N1—C1—N2—C3	1.4 (3)	C10—C11—C12—C13	1.1 (4)
N1—C1—C4—C5	7.3 (3)	C10—C11—C12—H12	−177.8 (2)
N1—C1—C4—C9	−171.0 (2)	C10—C15—C14—C13	0.5 (3)
N1—C2—C3—N2	0.4 (2)	C10—C15—C14—H14	−179.0 (2)
N1—C2—C3—C16	179.9 (2)	C10'—C2'—C3'—C16'	64.5 (3)
N1—C2—C10—C11	94.5 (2)	C10'—C11'—C12'—C13'	0.3 (3)
N1—C2—C10—C15	−84.0 (2)	C10'—C11'—C12'—H12'	179.6 (2)
N1'—C1'—N2'—C3'	−1.5 (3)	C10'—C15'—C14'—C13'	0.7 (4)
N1'—C1'—C4'—C5'	11.9 (4)	C10'—C15'—C14'—H14'	−176.6 (2)
N1'—C1'—C4'—C9'	−168.7 (2)	C11—C10—C15—C14	0.5 (3)
N1'—C2'—C3'—N2'	3.0 (2)	C11—C10—C15—H15	−173.5 (2)
N1'—C2'—C3'—C16'	−178.5 (2)	C11—C12—C13—C14	−0.2 (4)
N1'—C2'—C10'—C11'	82.2 (2)	C11—C12—C13—H13	171.4 (2)
N1'—C2'—C10'—C15'	−94.6 (2)	C11'—C10'—C15'—C14'	−0.4 (3)
N2—C1—N1—C2	−1.1 (2)	C11'—C10'—C15'—H15'	176.9 (2)
N2—C1—C4—C5	−175.3 (2)	C11'—C12'—C13'—C14'	0.0 (3)
N2—C1—C4—C9	6.4 (3)	C11'—C12'—C13'—H13'	−175.7 (2)
N2—C3—C2—C10	−120.2 (2)	C12—C11—C10—C15	−1.3 (4)
N2—C3—C16—C17	−179.0 (2)	C12—C13—C14—C15	−0.6 (4)
N2—C3—C16—C21	1.8 (3)	C12—C13—C14—H14	178.8 (2)
N2'—C1'—N1'—C2'	3.4 (2)	C11'—C12'—C10'—C15'	−0.1 (3)
N2'—C1'—C4'—C5'	−166.2 (2)	C12'—C13'—C14'—C15'	−0.5 (4)
N2'—C1'—C4'—C9'	13.3 (3)	C12'—C13'—C14'—H14'	176.9 (2)
N2'—C3'—C2'—C10'	−114.1 (2)	C13—C12—C11—H11	179.6 (2)
N2'—C3'—C16'—C17'	176.5 (2)	C13—C14—C15—H15	175.1 (2)
N2'—C3'—C16'—C21'	−3.4 (3)	C13'—C12'—C11'—H11'	−179.1 (2)
C1—N1—C2—C3	0.5 (2)	C13'—C14'—C15'—H15'	−176.4 (2)
C1—N1—C2—C10	123.2 (2)	C14—C13—C12—H12	178.8 (3)
C1—N2—C3—C2	−0.9 (2)	C14'—C13'—C12'—H12'	−179.2 (2)
C1—N2—C3—C16	179.5 (2)	C15—C10—C11—H11	−179.6 (2)
C1—C4—C5—C6	−178.6 (2)	C15—C14—C13—H13	−172.7 (2)
C1—C4—C5—H5	7.8 (3)	C15'—C10'—C11'—H11'	179.3 (2)
C1—C4—C9—C8	178.1 (2)	C15'—C14'—C13'—H13'	175.0 (2)
C1—C4—C9—H9	−2.8 (4)	C16—C17—C18—C19	−0.6 (4)
C1'—N1'—C2'—C3'	−3.6 (2)	C16—C17—C18—H18	176.2 (2)
C1'—N1'—C2'—C10'	118.7 (2)	C16—C21—C20—C19	−0.3 (4)
C1'—N2'—C3'—C2'	−1.2 (2)	C16—C21—C20—H20	167.5 (2)
C1'—N2'—C3'—C16'	−179.7 (2)	C16'—C17'—C18'—C19'	−1.2 (4)
C1'—C4'—C5'—C6'	178.5 (3)	C16'—C17'—C18'—H18'	−178.6 (2)
C1'—C4'—C5'—H5'	10.0 (5)	C16'—C21'—C20'—C19'	−0.2 (4)
C1'—C4'—C9'—C8'	−179.0 (2)	C16'—C21'—C20'—H20'	−177.8 (2)
C1'—C4'—C9'—H9'	6.1 (4)	C17—C16—C21—C20	−0.9 (3)
C2—O1—O2—H2o	−90.2 (2)	C17—C16—C21—H21	179.5 (2)
C2—N1—C1—C4	176.3 (2)	C17—C18—C19—C20	−0.6 (4)
C2—C3—C16—C17	1.5 (3)	C17—C18—C19—H19	−178.1 (2)
C2—C3—C16—C21	−177.7 (2)	C17'—C16'—C21'—C20'	−1.0 (3)
C2—C10—C11—C12	−179.8 (2)	C17'—C16'—C21'—H21'	−179.5 (2)
C2—C10—C11—H11	1.9 (4)	C17'—C18'—C19'—C20'	0.0 (4)
C2—C10—C15—C14	179.0 (2)	C17'—C18'—C19'—H19'	178.1 (3)
C2—C10—C15—H15	5.0 (4)	C18—C17—C16—C21	1.3 (3)
C2'—O1'—O2'—H2o'	−90.6 (2)	C18—C19—C20—C21	1.1 (4)
C2'—N1'—C1'—C4'	−174.7 (2)	C18—C19—C20—H20	−167.1 (2)
C2'—C3'—C16'—C17'	−1.8 (3)	C18'—C17'—C16'—C21'	1.7 (3)
C2'—C3'—C16'—C21'	178.2 (2)	C18'—C19'—C20'—C21'	0.7 (4)
C2'—C10'—C11'—C12'	−176.9 (2)	C18'—C19'—C20'—H20'	178.1 (3)
C2'—C10'—C11'—H11'	2.5 (3)	C19—C18—C17—H17	−179.1 (2)
C2'—C10'—C15'—C14'	176.3 (2)	C19—C20—C21—H21	179.2 (2)
C2'—C10'—C15'—H15'	−6.4 (3)	C19'—C18'—C17'—H17'	−178.9 (2)
C3—N2—C1—C4	−176.3 (2)	C19'—C20'—C21'—H21'	178.4 (2)
C3—C2—C10—C11	−150.1 (2)	C20—C19—C18—H18	−177.3 (2)
C3—C2—C10—C15	31.4 (3)	C20'—C19'—C18'—H18'	177.3 (3)
C3—C16—C17—C18	−177.9 (2)	C21—C16—C17—H17	179.7 (2)
C3—C16—C17—H17	0.5 (4)	C21—C20—C19—H19	178.6 (2)
C3—C16—C21—C20	178.4 (2)	C21'—C16'—C17'—H17'	179.3 (2)
C3—C16—C21—H21	−1.2 (3)	C21'—C20'—C19'—H19'	−177.4 (2)
C3'—N2'—C1'—C4'	176.7 (2)	H5—C5—C6—H6	−2.5 (4)
C3'—C2'—C10'—C11'	−164.3 (2)	H5'—C5'—C6'—H6'	−10.9 (6)
C3'—C2'—C10'—C15'	19.0 (3)	H6—C6—C7—H7	0.6 (4)
C3'—C16'—C17'—C18'	−178.3 (2)	H6'—C6'—C7'—H7'	−0.2 (6)
C3'—C16'—C17'—H17'	−0.7 (4)	H7—C7—C8—H8	−1.7 (4)
C3'—C16'—C21'—C20'	179.0 (2)	H7'—C7'—C8'—H8'	4.5 (5)
C3'—C16'—C21'—H21'	0.4 (3)	H8—C8—C9—H9	−1.4 (4)
C4—C5—C6—C7	0.6 (4)	H8'—C8'—C9'—H9'	−9.0 (4)
C4—C5—C6—H6	−176.0 (2)	H11—C11—C12—H12	0.6 (4)
C4—C9—C8—C7	0.5 (4)	H11'—C11'—C12'—H12'	0.2 (4)
C4—C9—C8—H8	177.7 (2)	H12—C12—C13—H13	−9.7 (4)
C4'—C5'—C6'—C7'	0.7 (5)	H12'—C12'—C13'—H13'	5.0 (4)
C4'—C5'—C6'—H6'	−180.0 (3)	H13—C13—C14—H14	6.8 (4)
C4'—C9'—C8'—C7'	0.3 (4)	H13'—C13'—C14'—H14'	−7.6 (4)
C4'—C9'—C8'—H8'	176.3 (2)	H14—C14—C15—H15	−4.4 (4)
C5—C4—C9—C8	−0.2 (4)	H14'—C14'—C15'—H15'	6.3 (4)
C5—C4—C9—H9	178.8 (2)	H17—C17—C18—H18	−2.3 (4)
C5—C6—C7—C8	−0.3 (4)	H17'—C17'—C18'—H18'	3.8 (4)
C5—C6—C7—H7	−176.0 (2)	H18—C18—C19—H19	5.2 (4)
C5'—C4'—C9'—C8'	0.4 (4)	H18'—C18'—C19'—H19'	−4.7 (5)
C5'—C4'—C9'—H9'	−174.5 (3)	H19—C19—C20—H20	10.4 (4)
C5'—C6'—C7'—C8'	−0.1 (5)	H19'—C19'—C20'—H20'	0.0 (5)
C5'—C6'—C7'—H7'	179.1 (3)	H20—C20—C21—H21	−12.9 (4)
C6—C5—C4—C9	−0.3 (3)	H20'—C20'—C21'—H21'	0.8 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2′—H2o′···N1	1.00	1.76	2.760 (2)	173.6 (1)
O2—H2o···N1′	1.01	1.77	2.773 (2)	176.2 (1)