Hydro­gen-bonded adducts of ferrocene-1,1'-diyl­bis­(di­phenyl­methanol): a finite cyclic 1:1 adduct with 2,2'-dipyridyl­amine

In ferrocene-1,1'-diyl­bis­(di­phenyl­methanol)-2,2'-dipyridyl­amine (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₀H₉N₃, (I), there is an intramolecular O-H...O hydrogen bond [H...O 2.03 Å, O...O 2.775 (2) Å and O-H...O 147°] in the ferrocenediol component, and the two neutral molecular components are linked by one O-H...N hydrogen bond [H...N 1.96 Å, O...N 2.755 (2) Å and O-H...N, 157°] and one N-H...O hydrogen bond [H...O 2.26 Å, N...O 3.112 (2) Å and N-H...O 164°] forming a cyclic R(8) motif. One of the pyridyl N atoms plays no part in the intermolecular hydrogen bonding, but participates in a short intramolecular C-H...N contact [H...N 2.31 Å, C...N 2.922 (2) Å and C-H...N 122°].

S1. Comment

Ferrocene-1,1'-diylbis(diphenylmethanol), [Fe(C₅H₄CPh₂OH)₂], forms hydrogen-bonded adducts with a wide range of amines, particularly heteroaromatic amines and diamines. Thus with pyridine, this diol forms an adduct of stoichiometry (diol).(amine)₂ (Ferguson et al., 1993), in which the number of hydrogen bond donor hydroxyl groups is equal to the number of amine N acceptors: despite this, the molecular aggregate contains disordered O—H···O and O—H···N hydrogen bonds indicative of mobile hydroxyl H atoms.

Similarly, in the 1: 1 adduct formed by the diol with 4,4'-bipyridyl (Glidewell et al., 1994), the number of hydroxyl groups is equal to the number of N atoms but only half of the bipyridyl molecules are involved in the supramolecular aggregation, which takes the form of the centrosymmetric three-component aggregate (diol)-(diamine)-(diol), while the remainder of the bipyridyl molecules simply occupy isolated sites in the structure (Glidewell et al., 1994). By contrast, in each of the similar 1:1 adducts formed with 1,2-bis(4'-pyridyl)ethane (Zakaria et al., 2001) and 1,2-bis(4'-pyridyl)ethene (Zakaria et al., 2002), there is a finite two-component aggregate containing one intramolecular O—H···O hydrogen bond and one intermolecular O—H···N hydrogen bond, while the second N plays no part in the hydrogen bonding. Continuing this theme, we have now synthesized and characterized a 1:1 adduct [C₃₆H₃₀FeO₂]·[C₁₀H₉N₃], (I), formed between the ferrocenediol and 2,2'-dipyridylamine, which was selected in order to increase the ratio of hydrogen-bond donors to acceptors in the expectation of forcing both pyridyl N atoms to participate in the supramolecular aggregation.

Compound (I) forms a finite 1:1 aggregate (Fig. 1) and, in addition to the intramolecular O—H···O hydrogen bond so commonly found in adducts involving this diol (Ferguson et al., 1993; 1995; Glidewell et al., 1994; Zakaria et al., 2001, 2002), there are two other hydrogen bonds, one each of O—H···N and N—H···O types, linking the two molecular components by forming an R³₃(8) ring (Table 2, Fig. 1). It is striking that both of the hydroxyl O atoms act as both hydrogen-bond donors and acceptors, while pyridyl N3 forms no intermolecular hydrogen bonds. Moreover the conformation of the nearly planar diamine (Table 1) is such that N2 is on the same edge of the diamine as the N11—H1 bond, while N3 is on the opposite edge. Atom N3 does, however, participate in a short intramolecular C—H···N contact (Table 2). In order to investigate whether this contact makes any significant contribution to the preferred conformation of the amine, we have undertaken SCF-MO calculations using the AM1 technique (Dewar et al., 1985; Stewart, 1990), for the three possible near-planar conformers (A) - (C) (Scheme 1). Conformers (A) and (C) were both calculated to have C₂ symmetry, with torsional angles N—C—N—C of 155.0° and -24.3° respectively, suggestive of repulsion between the ortho C—H bonds in (A) and between the pyridyl N lone pairs in (C), and with enthalpies of formation respectively 1.5 kJ mol^-1 and 2.2 kJ mol^-1 higher than that of the planar conformer (B). Clearly these energy differences are insufficient to determine the overall conformation.

However, it is interesting to note that pure 2,2'-dipyridylamine crystallizes in three polymorphs: orthorhombic Pccn with Z' = 1 (Johnson & Jacobson, 1973); triclinic P-1 with Z' = 2 (Pyrka & Pinkerton, 1992); and monoclinic P2₁/c with Z' = 2 (Schödel et al., 1996), and that in each of these forms, the molecules adopt the same overall conformation as that observed here in (I). In the orthorhombic and triclinic forms, the molecules are linked into dimeric units by means of paired N—H···N hydrogen bonds forming an R²₂(8) motif, with no involvement in the supramolecular aggregation of the N on the opposite edge of each molecule. On the other hand, in the monoclinic polymorph where the molecules are linked into tetrameric aggregates, half of the molecules utilize all of their N atoms in the hydrogen bonding, acting as single donors and double acceptors, while the other half act as single donors only, leaving both pyridyl N atoms in these molecules uninvolved in the hydrogen bonding.

S2. Experimental

Equimolar quantities of the two components were separately dissolved in methanol: the solutions were mixed and the mixture was then set aside to crystallize, producing analytically pure (I). Analysis: found C 77.1, H 5.4, N 5.7%; C₄₆H₃₉FeN₃O₂ requires C 76.6, H 5.4, N 5.8%. Crystals suitable for single-crystal X-ray diffraction were selected directly from the analytical sample.

S3. Refinement

Compound (I) crystallized in the monoclinic system; the space group P2₁/c was uniquely assigned from the systematic absences. H atoms were treated as riding atoms with distances C—H 0.95 Å, N—H 0.88 Å and O—H 0.84 Å.

Computing details

Data collection: Kappa-CCD server software (Nonius, 1997); 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, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Figures

Fig. 1. The molecular components of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Ferrocene-1,1'-diylbis(diphenylmethanol)–2,2'-dipyridylamine (1/1)

Crystal data

C36H30FeO2·C10H9N3	F(000) = 1512
Mr = 721.65	Dx = 1.322 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8310 reflections
a = 13.3507 (1) Å	θ = 2.7–27.5°
b = 16.8198 (2) Å	µ = 0.46 mm^−1
c = 17.6306 (2) Å	T = 150 K
β = 113.6410 (7)°	Block, colourless
V = 3626.80 (7) Å^3	0.35 × 0.32 × 0.30 mm
Z = 4

Data collection

Kappa-CCD diffractometer	8294 independent reflections
Radiation source: fine-focus sealed X-ray tube	7142 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→17
Tmin = 0.856, Tmax = 0.874	k = −21→0
32220 measured reflections	l = −22→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0352P)^2 + 2.0419P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
8294 reflections	Δρmax = 0.34 e Å^−3
472 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0049 (8)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
Fe1	0.045060 (17)	−0.084402 (12)	0.207326 (12)	0.02114 (8)
O1	0.23510 (9)	0.07110 (7)	0.28146 (7)	0.0305 (3)
O2	0.03877 (8)	0.10551 (7)	0.29356 (6)	0.0249 (2)
C11	0.18101 (12)	−0.04398 (9)	0.19363 (9)	0.0228 (3)
C12	0.08563 (12)	−0.00649 (9)	0.13432 (9)	0.0246 (3)
C13	0.01421 (13)	−0.06650 (10)	0.08470 (9)	0.0284 (3)
C14	0.06504 (13)	−0.14147 (10)	0.11203 (10)	0.0293 (3)
C15	0.16814 (13)	−0.12796 (9)	0.17914 (10)	0.0263 (3)
C16	0.27662 (12)	0.00100 (9)	0.25646 (9)	0.0237 (3)
C41	0.34308 (13)	−0.05025 (11)	0.33177 (10)	0.0314 (4)
C42	0.40371 (15)	−0.11411 (12)	0.32292 (13)	0.0435 (5)
C43	0.46390 (18)	−0.16147 (16)	0.39134 (18)	0.0668 (7)
C44	0.46474 (19)	−0.1429 (2)	0.46854 (16)	0.0773 (10)
C45	0.40805 (18)	−0.0784 (2)	0.47764 (13)	0.0685 (9)
C46	0.34689 (15)	−0.03199 (14)	0.40995 (11)	0.0453 (5)
C31	0.35319 (12)	0.03387 (9)	0.21811 (10)	0.0260 (3)
C32	0.33558 (14)	0.02205 (10)	0.13593 (10)	0.0300 (3)
C33	0.40530 (16)	0.05694 (11)	0.10404 (12)	0.0376 (4)
C34	0.49201 (16)	0.10283 (12)	0.15336 (13)	0.0428 (5)
C35	0.51188 (16)	0.11328 (13)	0.23608 (14)	0.0472 (5)
C36	0.44287 (14)	0.07898 (12)	0.26826 (12)	0.0382 (4)
C24	0.05373 (13)	−0.14473 (10)	0.31086 (10)	0.0285 (3)
C23	−0.04668 (13)	−0.16119 (10)	0.24317 (10)	0.0296 (3)
C22	−0.10340 (13)	−0.08806 (9)	0.21506 (10)	0.0266 (3)
C21	−0.03730 (12)	−0.02520 (9)	0.26575 (9)	0.0222 (3)
C25	0.05928 (12)	−0.06139 (9)	0.32545 (9)	0.0244 (3)
C26	−0.06313 (12)	0.06269 (9)	0.26519 (9)	0.0216 (3)
C51	−0.11991 (12)	0.08036 (9)	0.32396 (9)	0.0229 (3)
C52	−0.14965 (13)	0.15837 (9)	0.33107 (9)	0.0261 (3)
C53	−0.19582 (14)	0.17801 (10)	0.38667 (10)	0.0300 (3)
C54	−0.21276 (15)	0.11995 (11)	0.43577 (11)	0.0349 (4)
C55	−0.18580 (17)	0.04228 (11)	0.42799 (12)	0.0411 (4)
C56	−0.13967 (15)	0.02203 (10)	0.37220 (11)	0.0343 (4)
C61	−0.13319 (12)	0.09287 (9)	0.17821 (9)	0.0231 (3)
C62	−0.08970 (14)	0.14282 (9)	0.13628 (10)	0.0276 (3)
C63	−0.15347 (15)	0.16938 (10)	0.05656 (10)	0.0352 (4)
C64	−0.26197 (16)	0.14683 (12)	0.01843 (11)	0.0408 (4)
C65	−0.30682 (15)	0.09836 (12)	0.06025 (11)	0.0391 (4)
C66	−0.24306 (13)	0.07165 (10)	0.13974 (10)	0.0303 (3)
N1	0.26014 (11)	0.21590 (8)	0.39752 (8)	0.0286 (3)
N2	0.14606 (11)	0.16261 (8)	0.45231 (8)	0.0298 (3)
C71	0.21649 (13)	0.22138 (9)	0.45669 (9)	0.0269 (3)
C73	0.09999 (14)	0.16259 (11)	0.50760 (10)	0.0332 (4)
C74	0.12027 (15)	0.21891 (11)	0.56817 (10)	0.0370 (4)
C75	0.19201 (16)	0.28001 (12)	0.57154 (11)	0.0396 (4)
C76	0.24093 (15)	0.28200 (11)	0.51593 (10)	0.0345 (4)
C81	0.31651 (12)	0.27194 (9)	0.37130 (10)	0.0260 (3)
N3	0.35893 (11)	0.33620 (8)	0.41723 (8)	0.0285 (3)
C83	0.40947 (13)	0.38892 (10)	0.38696 (11)	0.0310 (3)
C84	0.42006 (16)	0.38102 (11)	0.31333 (12)	0.0408 (4)
C85	0.37664 (19)	0.31289 (13)	0.26699 (14)	0.0524 (6)
C86	0.32443 (16)	0.25778 (11)	0.29573 (12)	0.0410 (4)
H1	0.1723	0.0617	0.2795	0.046*
H2	0.0617	0.1129	0.3449	0.037*
H12	0.0722	0.0491	0.1289	0.030*
H13	−0.0553	−0.0580	0.0410	0.034*
H14	0.0356	−0.1918	0.0896	0.035*
H15	0.2193	−0.1677	0.2090	0.032*
H42	0.4043	−0.1256	0.2703	0.052*
H43	0.5039	−0.2059	0.3852	0.080*
H44	0.5048	−0.1752	0.5151	0.093*
H45	0.4107	−0.0653	0.5308	0.082*
H46	0.3074	0.0124	0.4169	0.054*
H32	0.2760	−0.0098	0.1013	0.036*
H33	0.3926	0.0488	0.0476	0.045*
H34	0.5382	0.1273	0.1309	0.051*
H35	0.5728	0.1439	0.2708	0.057*
H36	0.4569	0.0863	0.3250	0.046*
H24	0.1077	−0.1827	0.3411	0.034*
H23	−0.0718	−0.2122	0.2205	0.035*
H22	−0.1728	−0.0820	0.1705	0.032*
H25	0.1174	−0.0342	0.3678	0.029*
H52	−0.1383	0.1987	0.2976	0.031*
H53	−0.2158	0.2315	0.3909	0.036*
H54	−0.2428	0.1336	0.4746	0.042*
H55	−0.1987	0.0021	0.4609	0.049*
H56	−0.1217	−0.0318	0.3672	0.041*
H62	−0.0155	0.1591	0.1624	0.033*
H63	−0.1224	0.2030	0.0284	0.042*
H64	−0.3055	0.1645	−0.0361	0.049*
H65	−0.3815	0.0833	0.0345	0.047*
H66	−0.2747	0.0387	0.1680	0.036*
H1A	0.2508	0.1696	0.3724	0.034*
H73	0.0504	0.1210	0.5045	0.040*
H74	0.0866	0.2163	0.6064	0.044*
H75	0.2074	0.3205	0.6122	0.048*
H76	0.2901	0.3235	0.5177	0.041*
H83	0.4400	0.4350	0.4191	0.037*
H84	0.4557	0.4205	0.2946	0.049*
H85	0.3831	0.3046	0.2158	0.063*
H86	0.2943	0.2110	0.2649	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.02265 (12)	0.01971 (12)	0.02113 (12)	−0.00083 (8)	0.00885 (8)	−0.00129 (8)
O1	0.0272 (6)	0.0299 (6)	0.0391 (6)	−0.0069 (5)	0.0183 (5)	−0.0123 (5)
O2	0.0239 (5)	0.0277 (5)	0.0250 (5)	−0.0070 (4)	0.0119 (4)	−0.0049 (4)
C11	0.0252 (7)	0.0235 (7)	0.0221 (7)	−0.0002 (6)	0.0120 (6)	−0.0009 (5)
C12	0.0281 (8)	0.0240 (7)	0.0232 (7)	0.0014 (6)	0.0120 (6)	0.0020 (6)
C13	0.0303 (8)	0.0333 (8)	0.0202 (7)	−0.0010 (6)	0.0087 (6)	−0.0015 (6)
C14	0.0338 (8)	0.0282 (8)	0.0277 (8)	−0.0029 (6)	0.0143 (6)	−0.0084 (6)
C15	0.0299 (8)	0.0237 (7)	0.0284 (7)	0.0024 (6)	0.0149 (6)	−0.0021 (6)
C16	0.0230 (7)	0.0244 (7)	0.0246 (7)	−0.0006 (6)	0.0106 (6)	−0.0016 (6)
C41	0.0222 (7)	0.0409 (9)	0.0287 (8)	−0.0058 (7)	0.0078 (6)	0.0075 (7)
C42	0.0302 (9)	0.0458 (11)	0.0502 (11)	0.0050 (8)	0.0115 (8)	0.0180 (9)
C43	0.0352 (11)	0.0661 (16)	0.0883 (19)	0.0107 (10)	0.0136 (11)	0.0418 (14)
C44	0.0387 (12)	0.118 (2)	0.0594 (15)	−0.0045 (14)	0.0032 (11)	0.0580 (16)
C45	0.0320 (11)	0.130 (3)	0.0335 (10)	−0.0167 (13)	0.0027 (8)	0.0290 (13)
C46	0.0275 (9)	0.0773 (15)	0.0274 (8)	−0.0144 (9)	0.0071 (7)	0.0068 (9)
C31	0.0232 (7)	0.0270 (8)	0.0300 (8)	0.0030 (6)	0.0130 (6)	0.0054 (6)
C32	0.0334 (8)	0.0278 (8)	0.0337 (8)	0.0077 (6)	0.0185 (7)	0.0056 (6)
C33	0.0464 (10)	0.0357 (9)	0.0431 (10)	0.0155 (8)	0.0310 (8)	0.0141 (8)
C34	0.0376 (10)	0.0408 (10)	0.0631 (13)	0.0095 (8)	0.0340 (9)	0.0188 (9)
C35	0.0317 (9)	0.0529 (12)	0.0587 (12)	−0.0092 (9)	0.0198 (9)	0.0061 (10)
C36	0.0302 (9)	0.0478 (11)	0.0367 (9)	−0.0087 (8)	0.0135 (7)	0.0022 (8)
C24	0.0338 (8)	0.0249 (8)	0.0301 (8)	0.0019 (6)	0.0161 (7)	0.0063 (6)
C23	0.0324 (8)	0.0235 (7)	0.0377 (9)	−0.0054 (6)	0.0191 (7)	−0.0015 (6)
C22	0.0229 (7)	0.0261 (8)	0.0313 (8)	−0.0044 (6)	0.0113 (6)	−0.0034 (6)
C21	0.0235 (7)	0.0223 (7)	0.0229 (7)	−0.0023 (6)	0.0116 (6)	−0.0014 (5)
C25	0.0263 (7)	0.0272 (7)	0.0211 (7)	−0.0009 (6)	0.0109 (6)	0.0007 (6)
C26	0.0209 (7)	0.0218 (7)	0.0232 (7)	−0.0031 (5)	0.0101 (5)	−0.0020 (5)
C51	0.0224 (7)	0.0261 (7)	0.0215 (7)	−0.0024 (6)	0.0100 (6)	−0.0015 (5)
C52	0.0286 (8)	0.0259 (7)	0.0269 (7)	−0.0019 (6)	0.0143 (6)	−0.0009 (6)
C53	0.0341 (8)	0.0286 (8)	0.0325 (8)	−0.0011 (7)	0.0188 (7)	−0.0055 (6)
C54	0.0417 (10)	0.0377 (9)	0.0359 (9)	−0.0035 (7)	0.0265 (8)	−0.0038 (7)
C55	0.0592 (12)	0.0343 (9)	0.0462 (10)	−0.0002 (8)	0.0382 (10)	0.0064 (8)
C56	0.0472 (10)	0.0259 (8)	0.0405 (9)	0.0009 (7)	0.0287 (8)	0.0027 (7)
C61	0.0261 (7)	0.0221 (7)	0.0229 (7)	0.0026 (6)	0.0116 (6)	−0.0009 (5)
C62	0.0335 (8)	0.0246 (7)	0.0286 (8)	0.0011 (6)	0.0165 (6)	0.0000 (6)
C63	0.0477 (10)	0.0321 (9)	0.0291 (8)	0.0051 (8)	0.0187 (7)	0.0060 (7)
C64	0.0477 (11)	0.0454 (11)	0.0246 (8)	0.0088 (8)	0.0097 (7)	0.0055 (7)
C65	0.0308 (9)	0.0501 (11)	0.0302 (9)	0.0025 (8)	0.0058 (7)	−0.0016 (8)
C66	0.0276 (8)	0.0370 (9)	0.0262 (8)	−0.0013 (7)	0.0106 (6)	−0.0003 (6)
N1	0.0333 (7)	0.0235 (6)	0.0290 (7)	−0.0059 (5)	0.0123 (6)	−0.0049 (5)
N2	0.0314 (7)	0.0297 (7)	0.0248 (6)	−0.0067 (6)	0.0078 (5)	0.0000 (5)
C71	0.0264 (7)	0.0268 (8)	0.0233 (7)	−0.0024 (6)	0.0055 (6)	0.0009 (6)
C73	0.0339 (9)	0.0355 (9)	0.0277 (8)	−0.0052 (7)	0.0099 (7)	0.0057 (7)
C74	0.0424 (10)	0.0425 (10)	0.0284 (8)	−0.0031 (8)	0.0165 (7)	0.0020 (7)
C75	0.0505 (11)	0.0394 (10)	0.0287 (8)	−0.0065 (8)	0.0156 (8)	−0.0065 (7)
C76	0.0407 (9)	0.0328 (9)	0.0293 (8)	−0.0102 (7)	0.0133 (7)	−0.0057 (7)
C81	0.0222 (7)	0.0243 (7)	0.0293 (8)	−0.0002 (6)	0.0078 (6)	−0.0004 (6)
N3	0.0262 (6)	0.0269 (7)	0.0297 (7)	−0.0041 (5)	0.0083 (5)	−0.0026 (5)
C83	0.0258 (8)	0.0271 (8)	0.0372 (9)	−0.0047 (6)	0.0095 (7)	−0.0036 (7)
C84	0.0451 (10)	0.0384 (10)	0.0456 (10)	−0.0145 (8)	0.0252 (9)	−0.0064 (8)
C85	0.0691 (14)	0.0536 (12)	0.0514 (12)	−0.0251 (11)	0.0418 (11)	−0.0174 (10)
C86	0.0513 (11)	0.0364 (10)	0.0428 (10)	−0.0154 (8)	0.0269 (9)	−0.0146 (8)

Geometric parameters (Å, º)

Fe1—C15	2.0344 (15)	C22—C21	1.436 (2)
Fe1—C11	2.0412 (15)	C22—H22	0.95
Fe1—C22	2.0415 (15)	C21—C25	1.433 (2)
Fe1—C21	2.0421 (14)	C21—C26	1.517 (2)
Fe1—C14	2.0433 (15)	C25—H25	0.95
Fe1—C23	2.0465 (15)	C26—C61	1.528 (2)
Fe1—C24	2.0508 (15)	C26—C51	1.538 (2)
Fe1—C25	2.0509 (15)	C51—C52	1.391 (2)
Fe1—C13	2.0544 (15)	C51—C56	1.391 (2)
Fe1—C12	2.0559 (15)	C52—C53	1.391 (2)
O1—C16	1.4449 (18)	C52—H52	0.95
O1—H1	0.84	C53—C54	1.383 (2)
O2—C26	1.4400 (17)	C53—H53	0.95
O2—H2	0.84	C54—C55	1.377 (3)
C11—C12	1.430 (2)	C54—H54	0.95
C11—C15	1.433 (2)	C55—C56	1.396 (2)
C11—C16	1.515 (2)	C55—H55	0.95
C12—C13	1.423 (2)	C56—H56	0.95
C12—H12	0.95	C61—C62	1.391 (2)
C13—C14	1.421 (2)	C61—C66	1.393 (2)
C13—H13	0.95	C62—C63	1.393 (2)
C14—C15	1.428 (2)	C62—H62	0.95
C14—H14	0.95	C63—C64	1.383 (3)
C15—H15	0.95	C63—H63	0.95
C16—C41	1.533 (2)	C64—C65	1.386 (3)
C16—C31	1.537 (2)	C64—H64	0.95
C41—C42	1.391 (3)	C65—C66	1.390 (2)
C41—C46	1.393 (3)	C65—H65	0.95
C42—C43	1.399 (3)	C66—H66	0.95
C42—H42	0.95	N1—C71	1.387 (2)
C43—C44	1.392 (4)	N1—C81	1.396 (2)
C43—H43	0.95	N1—H1A	0.88
C44—C45	1.370 (4)	N2—C71	1.345 (2)
C44—H44	0.95	N2—C73	1.345 (2)
C45—C46	1.385 (3)	C71—C76	1.401 (2)
C45—H45	0.95	C73—C74	1.371 (3)
C46—H46	0.95	C73—H73	0.95
C31—C32	1.386 (2)	C74—C75	1.390 (3)
C31—C36	1.394 (2)	C74—H74	0.95
C32—C33	1.395 (2)	C75—C76	1.379 (2)
C32—H32	0.95	C75—H75	0.95
C33—C34	1.373 (3)	C76—H76	0.95
C33—H33	0.95	C81—N3	1.333 (2)
C34—C35	1.385 (3)	C81—C86	1.399 (2)
C34—H34	0.95	N3—C83	1.347 (2)
C35—C36	1.387 (3)	C83—C84	1.367 (2)
C35—H35	0.95	C83—H83	0.95
C36—H36	0.95	C84—C85	1.392 (3)
C24—C23	1.420 (2)	C84—H84	0.95
C24—C25	1.422 (2)	C85—C86	1.373 (3)
C24—H24	0.95	C85—H85	0.95
C23—C22	1.425 (2)	C86—H86	0.95
C23—H23	0.95
C16—O1—H1	109.5	C21—C26—C61	112.10 (12)
C26—O2—H2	109.5	O2—C26—C51	108.76 (11)
C12—C11—C15	107.23 (13)	C21—C26—C51	110.85 (12)
C12—C11—C16	123.82 (13)	C61—C26—C51	110.07 (12)
C15—C11—C16	128.91 (13)	C52—C51—C56	118.63 (14)
C13—C12—C11	108.51 (13)	C52—C51—C26	118.58 (13)
C13—C12—H12	125.7	C56—C51—C26	122.75 (14)
C11—C12—H12	125.7	C51—C52—C53	120.71 (15)
C14—C13—C12	108.05 (14)	C51—C52—H52	119.6
C14—C13—H13	126.0	C53—C52—H52	119.6
C12—C13—H13	126.0	C54—C53—C52	120.23 (15)
C13—C14—C15	108.07 (14)	C54—C53—H53	119.9
C13—C14—H14	126.0	C52—C53—H53	119.9
C15—C14—H14	126.0	C55—C54—C53	119.54 (15)
C14—C15—C11	108.14 (14)	C55—C54—H54	120.2
C14—C15—H15	125.9	C53—C54—H54	120.2
C11—C15—H15	125.9	C54—C55—C56	120.57 (16)
O1—C16—C11	108.47 (12)	C54—C55—H55	119.7
O1—C16—C41	110.75 (13)	C56—C55—H55	119.7
C11—C16—C41	112.20 (13)	C51—C56—C55	120.27 (16)
O1—C16—C31	104.18 (12)	C51—C56—H56	119.9
C11—C16—C31	111.84 (12)	C55—C56—H56	119.9
C41—C16—C31	109.11 (12)	C62—C61—C66	118.59 (14)
C42—C41—C46	119.30 (17)	C62—C61—C26	121.08 (14)
C42—C41—C16	119.86 (15)	C66—C61—C26	120.32 (13)
C46—C41—C16	120.80 (17)	C61—C62—C63	120.91 (16)
C41—C42—C43	120.1 (2)	C61—C62—H62	119.5
C41—C42—H42	119.9	C63—C62—H62	119.5
C43—C42—H42	119.9	C64—C63—C62	119.98 (16)
C44—C43—C42	119.5 (3)	C64—C63—H63	120.0
C44—C43—H43	120.3	C62—C63—H63	120.0
C42—C43—H43	120.3	C63—C64—C65	119.63 (16)
C45—C44—C43	120.3 (2)	C63—C64—H64	120.2
C45—C44—H44	119.9	C65—C64—H64	120.2
C43—C44—H44	119.9	C64—C65—C66	120.38 (17)
C44—C45—C46	120.6 (2)	C64—C65—H65	119.8
C44—C45—H45	119.7	C66—C65—H65	119.8
C46—C45—H45	119.7	C65—C66—C61	120.49 (16)
C45—C46—C41	120.2 (2)	C65—C66—H66	119.8
C45—C46—H46	119.9	C61—C66—H66	119.8
C41—C46—H46	119.9	C71—N1—C81	130.49 (14)
C32—C31—C36	118.94 (15)	C71—N1—H1A	114.8
C32—C31—C16	122.98 (14)	C81—N1—H1A	114.8
C36—C31—C16	118.07 (14)	C71—N2—C73	118.10 (14)
C31—C32—C33	120.01 (17)	N2—C71—N1	113.76 (14)
C31—C32—H32	120.0	N2—C71—C76	121.74 (15)
C33—C32—H32	120.0	N1—C71—C76	124.49 (15)
C34—C33—C32	120.70 (17)	N2—C73—C74	124.02 (16)
C34—C33—H33	119.6	N2—C73—H73	118.0
C32—C33—H33	119.6	C74—C73—H73	118.0
C33—C34—C35	119.68 (16)	C73—C74—C75	117.50 (16)
C33—C34—H34	120.2	C73—C74—H74	121.3
C35—C34—H34	120.2	C75—C74—H74	121.3
C34—C35—C36	120.00 (19)	C76—C75—C74	120.15 (17)
C34—C35—H35	120.0	C76—C75—H75	119.9
C36—C35—H35	120.0	C74—C75—H75	119.9
C35—C36—C31	120.64 (18)	C75—C76—C71	118.48 (16)
C35—C36—H36	119.7	C75—C76—H76	120.8
C31—C36—H36	119.7	C71—C76—H76	120.8
C23—C24—C25	107.90 (14)	N3—C81—N1	120.04 (14)
C23—C24—H24	126.0	N3—C81—C86	122.73 (15)
C25—C24—H24	126.0	N1—C81—C86	117.22 (14)
C24—C23—C22	108.37 (14)	C81—N3—C83	116.83 (14)
C24—C23—H23	125.8	N3—C83—C84	124.81 (16)
C22—C23—H23	125.8	N3—C83—H83	117.6
C23—C22—C21	108.10 (14)	C84—C83—H83	117.6
C23—C22—H22	125.9	C83—C84—C85	117.39 (17)
C21—C22—H22	125.9	C83—C84—H84	121.3
C25—C21—C22	106.97 (13)	C85—C84—H84	121.3
C25—C21—C26	123.64 (13)	C86—C85—C84	119.53 (18)
C22—C21—C26	129.19 (13)	C86—C85—H85	120.2
C24—C25—C21	108.65 (13)	C84—C85—H85	120.2
C24—C25—H25	125.7	C85—C86—C81	118.69 (17)
C21—C25—H25	125.7	C85—C86—H86	120.7
O2—C26—C21	107.72 (12)	C81—C86—H86	120.7
O2—C26—C61	107.18 (11)
C15—C11—C12—C13	0.81 (16)	C22—C21—C26—C61	−34.2 (2)
C16—C11—C12—C13	178.92 (13)	C25—C21—C26—C51	−84.94 (16)
C11—C12—C13—C14	−0.69 (17)	C22—C21—C26—C51	89.26 (18)
C12—C13—C14—C15	0.30 (18)	O2—C26—C51—C52	61.81 (17)
C13—C14—C15—C11	0.21 (17)	C21—C26—C51—C52	−179.93 (13)
C12—C11—C15—C14	−0.62 (16)	C61—C26—C51—C52	−55.33 (17)
C16—C11—C15—C14	−178.60 (14)	O2—C26—C51—C56	−116.13 (16)
C12—C11—C16—O1	34.27 (18)	C21—C26—C51—C56	2.1 (2)
C15—C11—C16—O1	−148.06 (14)	C61—C26—C51—C56	126.73 (16)
C12—C11—C16—C41	156.94 (14)	C56—C51—C52—C53	1.5 (2)
C15—C11—C16—C41	−25.4 (2)	C26—C51—C52—C53	−176.52 (14)
C12—C11—C16—C31	−80.06 (17)	C51—C52—C53—C54	0.0 (2)
C15—C11—C16—C31	97.61 (17)	C52—C53—C54—C55	−1.4 (3)
O1—C16—C41—C42	−170.43 (15)	C53—C54—C55—C56	1.2 (3)
C11—C16—C41—C42	68.20 (19)	C52—C51—C56—C55	−1.7 (3)
C31—C16—C41—C42	−56.33 (19)	C26—C51—C56—C55	176.29 (16)
O1—C16—C41—C46	7.2 (2)	C54—C55—C56—C51	0.3 (3)
C11—C16—C41—C46	−114.20 (17)	O2—C26—C61—C62	9.20 (18)
C31—C16—C41—C46	121.28 (16)	C21—C26—C61—C62	−108.80 (15)
C46—C41—C42—C43	2.8 (3)	C51—C26—C61—C62	127.32 (14)
C16—C41—C42—C43	−179.53 (17)	O2—C26—C61—C66	−169.78 (13)
C41—C42—C43—C44	−1.6 (3)	C21—C26—C61—C66	72.22 (17)
C42—C43—C44—C45	−0.7 (4)	C51—C26—C61—C66	−51.66 (18)
C43—C44—C45—C46	1.7 (4)	C66—C61—C62—C63	−1.8 (2)
C44—C45—C46—C41	−0.5 (3)	C26—C61—C62—C63	179.16 (14)
C42—C41—C46—C45	−1.8 (3)	C61—C62—C63—C64	0.8 (3)
C16—C41—C46—C45	−179.41 (17)	C62—C63—C64—C65	0.5 (3)
O1—C16—C31—C32	−117.66 (15)	C63—C64—C65—C66	−0.7 (3)
C11—C16—C31—C32	−0.7 (2)	C64—C65—C66—C61	−0.4 (3)
C41—C16—C31—C32	124.02 (16)	C62—C61—C66—C65	1.6 (2)
O1—C16—C31—C36	60.90 (18)	C26—C61—C66—C65	−179.36 (15)
C11—C16—C31—C36	177.85 (14)	C73—N2—C71—N1	179.57 (14)
C41—C16—C31—C36	−57.41 (19)	C73—N2—C71—C76	−0.9 (2)
C36—C31—C32—C33	−1.8 (2)	C81—N1—C71—N2	165.27 (15)
C16—C31—C32—C33	176.77 (14)	C81—N1—C71—C76	−14.2 (3)
C31—C32—C33—C34	0.3 (2)	C71—N2—C73—C74	0.1 (3)
C32—C33—C34—C35	1.4 (3)	N2—C73—C74—C75	0.8 (3)
C33—C34—C35—C36	−1.5 (3)	C73—C74—C75—C76	−0.8 (3)
C34—C35—C36—C31	0.0 (3)	C74—C75—C76—C71	0.0 (3)
C32—C31—C36—C35	1.6 (3)	N2—C71—C76—C75	0.9 (3)
C16—C31—C36—C35	−176.97 (17)	N1—C71—C76—C75	−179.67 (16)
C25—C24—C23—C22	0.48 (18)	C71—N1—C81—N3	16.4 (2)
C24—C23—C22—C21	0.17 (18)	C71—N1—C81—C86	−162.74 (17)
C23—C22—C21—C25	−0.75 (17)	N1—C81—N3—C83	−178.12 (14)
C23—C22—C21—C26	−175.70 (14)	C86—C81—N3—C83	1.0 (2)
C23—C24—C25—C21	−0.95 (17)	C81—N3—C83—C84	0.0 (3)
C22—C21—C25—C24	1.05 (16)	N3—C83—C84—C85	−0.9 (3)
C26—C21—C25—C24	176.35 (13)	C83—C84—C85—C86	0.9 (3)
C25—C21—C26—O2	33.94 (18)	C84—C85—C86—C81	0.0 (3)
C22—C21—C26—O2	−151.86 (14)	N3—C81—C86—C85	−1.0 (3)
C25—C21—C26—C61	151.62 (13)	N1—C81—C86—C85	178.16 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84	2.03	2.7748 (15)	147
O2—H2···N2	0.84	1.96	2.7556 (17)	158
N1—H1A···O1	0.88	2.26	3.1116 (17)	164
C76—H76···N3	0.95	2.31	2.922 (2)	122