Structural study of the novel deuterated calix[4]pyrrole complex d₁₂-meso-tetra­kis­(4-meth­oxy­phenyl)-meso-tetra­methyl­calix[4]pyrrole–pyridine N-oxide–aceto­nitrile (1/1/1)

Calix[4]pyrroles act as powerful receptors for electron-rich neutral guests and anionic guests in organic solvents. For the electron-rich neutral guest pyridine N-oxide, calix[4]pyrrole, with a deep cavity, provides an appropriate environment. The ability of calix[4]pyrrole to host binding guest mol­ecules is the result of hydrogen bonding, π–π, C—H...π and hydro­phobic inter­actions of the cavity. The novel title complex, C₅₂H₄₀D₁₂N₄O₄·C₅H₅NO·C₂H₃N, based on d₁₂-meso-tetra­kis­(4-meth­oxy­phen­yl)-meso-tetra­methyl­calix[4]pyrrole, has been assembled using an excess of pyridine N-oxide and is the first deuterated com­plex of calix[4]pyrrole. A single-crystal X-ray study shows that the receptor adopts a cone conformation with the N-oxide fragment encapsulated deep within the cavity. ¹H NMR spectroscopy was used to probe the mol­ecular binding formation in CD₃CN. The results are consistent with the single-crystal X-ray study in identifying that the pyridine N-oxide mol­ecule occupies the cavity of the calix[4]pyrrole mol­ecule. UV–vis spectroscopy revealed that the calix[4]pyrrole receptor molecules are able to form 1:1 inclusion complexes in CH₃CN.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

d₁₂-meso-Tetrakis(4-methoxyphenyl)-meso-tetramethylcalix[4]pyrrole–pyridine N-oxide–acetonitrile (1/1/1)

Crystal data

C52H40D12N4O4·C5H5NO·C2H3N	F(000) = 992
Mr = 945.20	Dx = 1.257 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 10.9462 (3) Å	Cell parameters from 9878 reflections
b = 21.6003 (7) Å	θ = 3.0–28.4°
c = 10.9788 (4) Å	µ = 0.08 mm^−1
β = 105.796 (1)°	T = 200 K
V = 2497.81 (14) Å^3	Block, colorless
Z = 2	0.30 × 0.25 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer	10170 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.030
φ and ω scans	θmax = 28.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→12
Tmin = 0.976, Tmax = 0.980	k = −28→28
24960 measured reflections	l = −14→14
11969 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.044	w = 1/[σ^2(Fo^2) + (0.0473P)^2 + 0.4121P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.102	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.19 e Å^−3
11969 reflections	Δρmin = −0.26 e Å^−3
664 parameters	Absolute structure: Refined as an inversion twin
3 restraints	Absolute structure parameter: 0.3 (11)

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.

Refinement. Refined as a 2-component inversion twin. The C13 atom was disordered and refined over two sites with partial occupancies in the ratio of 0.54:0.46. D atoms bonded to C atoms were placed at calculated positions and refined using a riding-modeL,with Uiso(D) = 1.2Ueq(C). D atoms bonded to N atoms were located firstly in a difference Fourier map and were refined isotropically, with the isotropic displacement parameters coupled to the anisotropic displacement parameters (ADPs) of the parent N atoms, Uiso(D) = 1.2Ueq(N).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	1.1956 (2)	0.05064 (11)	0.3806 (3)	0.0814 (10)
O2	0.5318 (2)	0.07573 (9)	0.1860 (2)	0.0458 (5)
O3	0.6757 (2)	0.00426 (10)	0.7375 (2)	0.0541 (6)
O4	1.2924 (2)	0.01252 (10)	0.9401 (2)	0.0527 (6)
N1	1.14925 (18)	0.28577 (9)	0.69467 (18)	0.0224 (4)
D1A	1.101 (3)	0.2553 (14)	0.675 (3)	0.027*
N2	0.90713 (18)	0.30885 (9)	0.43194 (18)	0.0231 (4)
D2A	0.906 (3)	0.2777 (14)	0.478 (3)	0.028*
N3	0.70792 (19)	0.28931 (9)	0.59787 (18)	0.0230 (4)
D3A	0.757 (3)	0.2588 (14)	0.592 (3)	0.028*
N4	0.94725 (18)	0.26662 (9)	0.85973 (18)	0.0226 (4)
D4A	0.945 (3)	0.2439 (13)	0.794 (3)	0.027*
C1	1.2074 (2)	0.30493 (11)	0.8163 (2)	0.0234 (5)
C2	1.2783 (2)	0.35612 (12)	0.8067 (2)	0.0295 (5)
D2	1.327808	0.379913	0.875226	0.035*
C3	1.2648 (2)	0.36726 (12)	0.6767 (2)	0.0301 (5)
D3	1.303717	0.399826	0.642683	0.036*
C4	1.1856 (2)	0.32279 (11)	0.6083 (2)	0.0230 (5)
C5	1.1457 (2)	0.30887 (11)	0.4671 (2)	0.0231 (5)
C6	1.2398 (2)	0.34176 (12)	0.4065 (2)	0.0306 (5)
H6A	1.218717	0.331717	0.316137	0.046*
H6B	1.326391	0.327805	0.447915	0.046*
H6C	1.234209	0.386625	0.417072	0.046*
C7	1.1566 (2)	0.23900 (11)	0.4452 (2)	0.0246 (5)
C8	1.0736 (3)	0.20735 (13)	0.3455 (2)	0.0320 (6)
H8	1.005429	0.229146	0.289961	0.038*
C9	1.0888 (3)	0.14474 (14)	0.3258 (3)	0.0432 (7)
H9	1.031088	0.124009	0.257612	0.052*
C10	1.1885 (3)	0.11232 (13)	0.4058 (3)	0.0442 (7)
C11	1.2736 (3)	0.14295 (14)	0.5032 (3)	0.0409 (7)
H11	1.342822	0.121262	0.557448	0.049*
C12	1.2572 (3)	0.20577 (13)	0.5213 (3)	0.0325 (6)
H12	1.316697	0.226611	0.587892	0.039*
C13A	1.2862 (16)	0.0152 (5)	0.485 (2)	0.085 (6)	0.54 (3)
H13A	1.373564	0.027622	0.490468	0.128*	0.54 (3)
H13B	1.276321	−0.029273	0.467855	0.128*	0.54 (3)
H13C	1.267650	0.024216	0.566019	0.128*	0.54 (3)
C13B	1.3171 (11)	0.0194 (6)	0.4308 (19)	0.059 (4)	0.46 (3)
H13D	1.384435	0.043329	0.409454	0.088*	0.46 (3)
H13E	1.313123	−0.022066	0.393760	0.088*	0.46 (3)
H13F	1.335224	0.015956	0.523056	0.088*	0.46 (3)
C14	1.0139 (2)	0.33363 (10)	0.4072 (2)	0.0225 (5)
C15	0.9739 (2)	0.38223 (11)	0.3257 (2)	0.0267 (5)
D15	1.026662	0.408381	0.292340	0.032*
C16	0.8398 (2)	0.38666 (11)	0.3000 (2)	0.0263 (5)
D16	0.787024	0.416431	0.247062	0.032*
C17	0.8003 (2)	0.34017 (10)	0.3655 (2)	0.0229 (5)
C18	0.6676 (2)	0.32160 (11)	0.3680 (2)	0.0243 (5)
C19	0.5714 (3)	0.36436 (13)	0.2767 (2)	0.0330 (6)
H19A	0.588290	0.407512	0.303631	0.049*
H19B	0.484989	0.353196	0.278050	0.049*
H19C	0.579940	0.359465	0.190695	0.049*
C20	0.6366 (2)	0.25470 (11)	0.3197 (2)	0.0253 (5)
C21	0.5355 (2)	0.22264 (12)	0.3459 (2)	0.0309 (5)
H21	0.489304	0.241619	0.397602	0.037*
C22	0.5015 (3)	0.16398 (13)	0.2983 (3)	0.0342 (6)
H22	0.432378	0.143238	0.317403	0.041*
C23	0.5681 (3)	0.13512 (12)	0.2224 (2)	0.0326 (6)
C24	0.6661 (3)	0.16642 (13)	0.1926 (2)	0.0344 (6)
H24	0.711040	0.147630	0.139517	0.041*
C25	0.6991 (2)	0.22592 (12)	0.2409 (2)	0.0301 (5)
H25	0.766193	0.247185	0.219138	0.036*
C26	0.5936 (4)	0.04588 (17)	0.1031 (4)	0.0577 (9)
H26A	0.581541	0.070437	0.025661	0.087*
H26B	0.557117	0.004564	0.081495	0.087*
H26C	0.684509	0.042130	0.145189	0.087*
C27	0.6504 (2)	0.32856 (11)	0.4996 (2)	0.0233 (5)
C28	0.5757 (2)	0.36811 (11)	0.5454 (2)	0.0278 (5)
D28	0.525201	0.400697	0.499525	0.042*
C29	0.5867 (2)	0.35194 (12)	0.6730 (2)	0.0287 (5)
D29	0.545201	0.371838	0.727819	0.043*
C30	0.6676 (2)	0.30269 (10)	0.7033 (2)	0.0230 (5)
C31	0.7092 (2)	0.26560 (11)	0.8254 (2)	0.0235 (5)
C32	0.6166 (2)	0.28062 (13)	0.9055 (2)	0.0324 (6)
H32A	0.622886	0.324662	0.927831	0.049*
H32B	0.638615	0.255660	0.982987	0.049*
H32C	0.529578	0.271067	0.856513	0.049*
C33	0.7029 (2)	0.19528 (11)	0.7998 (2)	0.0257 (5)
C34	0.7788 (3)	0.15501 (12)	0.8877 (2)	0.0315 (5)
H34	0.836524	0.171695	0.961192	0.038*
C35	0.7727 (3)	0.09111 (12)	0.8711 (3)	0.0360 (6)
H35	0.825477	0.064691	0.932560	0.043*
C36	0.6893 (3)	0.06644 (12)	0.7645 (3)	0.0367 (6)
C37	0.6123 (3)	0.10576 (13)	0.6764 (3)	0.0402 (7)
H37	0.554934	0.088944	0.602773	0.048*
C38	0.6181 (3)	0.16922 (13)	0.6944 (3)	0.0343 (6)
H38	0.563269	0.195353	0.633927	0.041*
C39	0.7475 (5)	−0.03658 (15)	0.8308 (4)	0.0637 (11)
H39A	0.838092	−0.027296	0.846251	0.096*
H39B	0.731360	−0.079391	0.801252	0.096*
H39C	0.722774	−0.031319	0.909532	0.096*
C40	0.8427 (2)	0.28361 (11)	0.8993 (2)	0.0233 (5)
C41	0.8862 (3)	0.31507 (12)	1.0109 (2)	0.0302 (5)
D41	0.835592	0.332452	1.060090	0.045*
C42	1.0209 (2)	0.31702 (12)	1.0399 (2)	0.0313 (5)
D42	1.076354	0.336209	1.111777	0.047*
C43	1.0565 (2)	0.28648 (11)	0.9462 (2)	0.0244 (5)
C44	1.1875 (2)	0.27164 (11)	0.9314 (2)	0.0249 (5)
C45	1.2893 (2)	0.29500 (13)	1.0500 (2)	0.0335 (6)
H45A	1.374066	0.285854	1.040950	0.050*
H45B	1.278006	0.274125	1.125432	0.050*
H45C	1.280106	0.339797	1.058553	0.050*
C46	1.2071 (2)	0.20142 (11)	0.9256 (2)	0.0258 (5)
C47	1.2941 (2)	0.17607 (13)	0.8673 (2)	0.0309 (5)
H47	1.336483	0.202417	0.822686	0.037*
C48	1.3198 (3)	0.11326 (13)	0.8733 (3)	0.0364 (6)
H48	1.378338	0.096852	0.831847	0.044*
C49	1.2604 (3)	0.07415 (12)	0.9396 (3)	0.0379 (6)
C50	1.1746 (3)	0.09806 (14)	0.9994 (3)	0.0429 (7)
H50	1.133438	0.071643	1.045072	0.051*
C51	1.1495 (3)	0.16117 (13)	0.9919 (3)	0.0370 (6)
H51	1.090962	0.177424	1.033509	0.044*
C52	1.2524 (5)	−0.02646 (18)	1.0267 (5)	0.0782 (13)
H52A	1.275775	−0.007451	1.110904	0.117*
H52B	1.293884	−0.066905	1.030595	0.117*
H52C	1.160106	−0.031833	0.998073	0.117*
O5	0.92329 (17)	0.20583 (7)	0.61459 (16)	0.0274 (4)
N5	0.91979 (19)	0.14550 (9)	0.58743 (18)	0.0250 (4)
C53	0.8242 (3)	0.12292 (14)	0.4940 (3)	0.0435 (7)
H53	0.758612	0.149771	0.449123	0.052*
C54	0.8206 (4)	0.06110 (15)	0.4628 (3)	0.0572 (10)
H54	0.752639	0.045409	0.396643	0.069*
C55	0.9152 (4)	0.02211 (14)	0.5273 (3)	0.0501 (8)
H55	0.914879	−0.020460	0.505473	0.060*
C56	1.0102 (3)	0.04623 (15)	0.6242 (4)	0.0583 (10)
H56	1.075774	0.019963	0.671332	0.070*
C57	1.0113 (3)	0.10793 (13)	0.6533 (3)	0.0464 (8)
H57	1.077369	0.124148	0.720723	0.056*
N6	1.0653 (4)	0.50452 (19)	0.8580 (4)	0.0895 (13)
C58	0.9503 (3)	0.41361 (15)	0.7225 (4)	0.0521 (8)
H58A	0.913374	0.427881	0.635470	0.078*
H58B	0.882729	0.397819	0.757095	0.078*
H58C	1.011636	0.380533	0.722825	0.078*
C59	1.0138 (3)	0.46466 (17)	0.7992 (4)	0.0535 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0476 (15)	0.0328 (13)	0.139 (3)	0.0109 (11)	−0.0167 (16)	−0.0292 (15)
O2	0.0464 (12)	0.0365 (11)	0.0539 (13)	−0.0102 (9)	0.0128 (10)	−0.0149 (9)
O3	0.0755 (17)	0.0253 (11)	0.0576 (14)	−0.0069 (11)	0.0113 (12)	−0.0036 (9)
O4	0.0625 (15)	0.0279 (11)	0.0643 (15)	0.0094 (10)	0.0114 (12)	0.0053 (10)
N1	0.0211 (9)	0.0209 (10)	0.0239 (9)	−0.0032 (8)	0.0038 (8)	−0.0034 (7)
N2	0.0208 (9)	0.0228 (10)	0.0241 (10)	−0.0019 (8)	0.0036 (8)	0.0044 (8)
N3	0.0217 (9)	0.0234 (10)	0.0229 (9)	0.0044 (8)	0.0046 (8)	0.0001 (7)
N4	0.0230 (10)	0.0252 (10)	0.0189 (9)	0.0010 (8)	0.0044 (8)	−0.0038 (7)
C1	0.0180 (10)	0.0260 (12)	0.0244 (11)	0.0021 (9)	0.0024 (9)	−0.0033 (9)
C2	0.0258 (12)	0.0293 (13)	0.0299 (13)	−0.0070 (10)	0.0020 (10)	−0.0071 (10)
C3	0.0256 (12)	0.0289 (13)	0.0352 (13)	−0.0069 (10)	0.0072 (10)	−0.0014 (10)
C4	0.0190 (11)	0.0234 (11)	0.0265 (11)	0.0006 (9)	0.0059 (9)	−0.0011 (9)
C5	0.0213 (11)	0.0243 (11)	0.0245 (11)	−0.0032 (9)	0.0078 (9)	−0.0011 (9)
C6	0.0272 (13)	0.0358 (14)	0.0320 (13)	−0.0079 (11)	0.0134 (10)	−0.0023 (10)
C7	0.0232 (11)	0.0269 (12)	0.0262 (11)	0.0005 (9)	0.0112 (9)	−0.0018 (9)
C8	0.0285 (13)	0.0322 (14)	0.0321 (13)	0.0028 (11)	0.0027 (11)	−0.0047 (10)
C9	0.0337 (15)	0.0362 (16)	0.0526 (18)	−0.0003 (12)	−0.0004 (13)	−0.0183 (13)
C10	0.0324 (15)	0.0288 (15)	0.068 (2)	0.0027 (12)	0.0071 (14)	−0.0120 (13)
C11	0.0324 (14)	0.0365 (16)	0.0496 (17)	0.0122 (12)	0.0041 (12)	−0.0035 (12)
C12	0.0276 (13)	0.0349 (14)	0.0339 (13)	0.0029 (11)	0.0064 (11)	−0.0073 (11)
C13A	0.037 (6)	0.035 (4)	0.164 (14)	0.012 (4)	−0.007 (7)	−0.028 (7)
C13B	0.045 (6)	0.032 (4)	0.096 (10)	0.015 (4)	0.013 (5)	−0.005 (5)
C14	0.0241 (11)	0.0216 (11)	0.0218 (11)	−0.0048 (9)	0.0062 (9)	−0.0032 (8)
C15	0.0295 (12)	0.0252 (12)	0.0275 (12)	−0.0035 (10)	0.0112 (10)	0.0003 (9)
C16	0.0297 (12)	0.0231 (12)	0.0247 (12)	0.0012 (10)	0.0050 (10)	0.0014 (9)
C17	0.0242 (11)	0.0236 (12)	0.0196 (10)	−0.0001 (9)	0.0037 (9)	−0.0002 (8)
C18	0.0197 (11)	0.0266 (12)	0.0235 (11)	0.0000 (9)	0.0007 (9)	0.0036 (9)
C19	0.0276 (13)	0.0344 (14)	0.0309 (13)	0.0040 (11)	−0.0022 (10)	0.0072 (10)
C20	0.0229 (11)	0.0283 (12)	0.0203 (11)	−0.0028 (10)	−0.0018 (9)	0.0019 (9)
C21	0.0256 (12)	0.0349 (14)	0.0320 (13)	−0.0006 (11)	0.0072 (10)	−0.0020 (10)
C22	0.0256 (12)	0.0377 (16)	0.0391 (14)	−0.0063 (11)	0.0082 (11)	−0.0008 (11)
C23	0.0323 (13)	0.0317 (14)	0.0293 (12)	−0.0047 (11)	0.0007 (10)	−0.0028 (10)
C24	0.0357 (14)	0.0411 (16)	0.0264 (12)	−0.0021 (12)	0.0083 (11)	−0.0064 (11)
C25	0.0286 (13)	0.0380 (15)	0.0233 (11)	−0.0054 (11)	0.0061 (10)	0.0004 (10)
C26	0.054 (2)	0.049 (2)	0.069 (2)	−0.0061 (16)	0.0140 (18)	−0.0290 (17)
C27	0.0178 (10)	0.0224 (11)	0.0265 (11)	−0.0021 (9)	0.0006 (9)	0.0013 (9)
C28	0.0212 (11)	0.0249 (12)	0.0352 (13)	0.0039 (10)	0.0043 (10)	0.0023 (10)
C29	0.0245 (12)	0.0289 (13)	0.0343 (13)	0.0030 (10)	0.0105 (10)	−0.0015 (10)
C30	0.0195 (11)	0.0231 (11)	0.0265 (11)	−0.0016 (9)	0.0064 (9)	−0.0021 (9)
C31	0.0229 (11)	0.0252 (12)	0.0224 (11)	0.0006 (9)	0.0062 (9)	−0.0006 (9)
C32	0.0296 (13)	0.0388 (15)	0.0327 (13)	0.0013 (11)	0.0148 (11)	0.0017 (11)
C33	0.0255 (12)	0.0237 (12)	0.0297 (12)	−0.0026 (9)	0.0105 (10)	0.0015 (9)
C34	0.0345 (14)	0.0309 (13)	0.0276 (12)	−0.0007 (11)	0.0056 (10)	0.0028 (10)
C35	0.0403 (15)	0.0278 (14)	0.0380 (15)	0.0027 (11)	0.0076 (12)	0.0068 (11)
C36	0.0441 (16)	0.0250 (13)	0.0423 (15)	−0.0041 (11)	0.0143 (13)	−0.0007 (11)
C37	0.0394 (16)	0.0358 (15)	0.0393 (15)	−0.0113 (12)	0.0004 (12)	−0.0046 (11)
C38	0.0313 (13)	0.0305 (14)	0.0368 (14)	−0.0026 (11)	0.0020 (11)	0.0032 (11)
C39	0.108 (3)	0.0235 (15)	0.064 (2)	0.0058 (18)	0.029 (2)	0.0008 (14)
C40	0.0243 (11)	0.0235 (11)	0.0226 (11)	0.0019 (9)	0.0073 (9)	0.0020 (9)
C41	0.0331 (13)	0.0320 (13)	0.0266 (12)	0.0035 (11)	0.0101 (10)	−0.0037 (10)
C42	0.0322 (13)	0.0337 (14)	0.0251 (12)	0.0002 (11)	0.0031 (10)	−0.0075 (10)
C43	0.0247 (11)	0.0257 (12)	0.0211 (11)	0.0002 (9)	0.0031 (9)	0.0001 (9)
C44	0.0232 (11)	0.0282 (12)	0.0206 (11)	0.0002 (9)	0.0012 (9)	−0.0042 (9)
C45	0.0294 (13)	0.0421 (16)	0.0237 (12)	−0.0004 (11)	−0.0019 (10)	−0.0064 (10)
C46	0.0230 (12)	0.0269 (12)	0.0235 (11)	0.0013 (9)	−0.0005 (9)	0.0004 (9)
C47	0.0257 (12)	0.0342 (14)	0.0312 (13)	0.0015 (11)	0.0049 (10)	0.0006 (10)
C48	0.0326 (14)	0.0372 (15)	0.0377 (15)	0.0107 (12)	0.0066 (12)	−0.0017 (11)
C49	0.0398 (15)	0.0270 (14)	0.0391 (15)	0.0047 (12)	−0.0025 (12)	0.0017 (11)
C50	0.0430 (17)	0.0375 (16)	0.0489 (17)	0.0033 (13)	0.0138 (14)	0.0121 (13)
C51	0.0367 (14)	0.0386 (16)	0.0373 (14)	0.0062 (12)	0.0130 (12)	0.0072 (11)
C52	0.109 (4)	0.0341 (19)	0.093 (3)	0.010 (2)	0.031 (3)	0.0188 (19)
O5	0.0317 (9)	0.0196 (8)	0.0300 (9)	0.0010 (7)	0.0068 (7)	−0.0012 (6)
N5	0.0260 (10)	0.0224 (10)	0.0260 (10)	−0.0004 (8)	0.0063 (8)	0.0009 (8)
C53	0.0495 (18)	0.0301 (14)	0.0372 (15)	0.0023 (13)	−0.0114 (13)	−0.0001 (11)
C54	0.078 (3)	0.0323 (16)	0.0443 (18)	−0.0071 (16)	−0.0118 (17)	−0.0067 (13)
C55	0.073 (2)	0.0218 (14)	0.0533 (19)	0.0006 (14)	0.0129 (17)	−0.0041 (12)
C56	0.0483 (19)	0.0298 (16)	0.083 (3)	0.0110 (15)	−0.0059 (18)	0.0023 (16)
C57	0.0364 (16)	0.0296 (15)	0.0598 (19)	0.0030 (12)	−0.0095 (14)	0.0002 (13)
N6	0.083 (3)	0.071 (2)	0.093 (3)	0.003 (2)	−0.013 (2)	−0.019 (2)
C58	0.0451 (18)	0.0362 (17)	0.071 (2)	0.0054 (14)	0.0094 (16)	0.0035 (15)
C59	0.0477 (19)	0.047 (2)	0.058 (2)	0.0077 (16)	0.0021 (16)	0.0036 (16)

Geometric parameters (Å, º)

O1—C10	1.367 (4)	C25—H25	0.9500
O1—C13B	1.458 (9)	C26—H26A	0.9800
O1—C13A	1.507 (11)	C26—H26B	0.9800
O2—C23	1.370 (3)	C26—H26C	0.9800
O2—C26	1.427 (4)	C27—C28	1.370 (3)
O3—C36	1.375 (3)	C28—C29	1.417 (4)
O3—C39	1.417 (4)	C28—D28	0.9500
O4—C49	1.376 (3)	C29—C30	1.366 (3)
O4—C52	1.425 (5)	C29—D29	0.9500
N1—C1	1.377 (3)	C30—C31	1.522 (3)
N1—C4	1.379 (3)	C31—C40	1.516 (3)
N1—D1A	0.83 (3)	C31—C33	1.543 (3)
N2—C17	1.376 (3)	C31—C32	1.547 (3)
N2—C14	1.378 (3)	C32—H32A	0.9800
N2—D2A	0.84 (3)	C32—H32B	0.9800
N3—C30	1.377 (3)	C32—H32C	0.9800
N3—C27	1.382 (3)	C33—C38	1.391 (4)
N3—D3A	0.86 (3)	C33—C34	1.393 (3)
N4—C43	1.377 (3)	C34—C35	1.392 (4)
N4—C40	1.379 (3)	C34—H34	0.9500
N4—D4A	0.87 (3)	C35—C36	1.380 (4)
C1—C2	1.372 (3)	C35—H35	0.9500
C1—C44	1.520 (3)	C36—C37	1.387 (4)
C2—C3	1.414 (4)	C37—C38	1.384 (4)
C2—D2	0.9500	C37—H37	0.9500
C3—C4	1.373 (3)	C38—H38	0.9500
C3—D3	0.9500	C39—H39A	0.9800
C4—C5	1.522 (3)	C39—H39B	0.9800
C5—C14	1.511 (3)	C39—H39C	0.9800
C5—C7	1.538 (3)	C40—C41	1.369 (3)
C5—C6	1.544 (3)	C41—C42	1.422 (4)
C6—H6A	0.9800	C41—D41	0.9500
C6—H6B	0.9800	C42—C43	1.364 (3)
C6—H6C	0.9800	C42—D42	0.9500
C7—C12	1.387 (4)	C43—C44	1.522 (3)
C7—C8	1.396 (3)	C44—C46	1.536 (3)
C8—C9	1.387 (4)	C44—C45	1.549 (3)
C8—H8	0.9500	C45—H45A	0.9800
C9—C10	1.389 (4)	C45—H45B	0.9800
C9—H9	0.9500	C45—H45C	0.9800
C10—C11	1.381 (4)	C46—C51	1.391 (4)
C11—C12	1.390 (4)	C46—C47	1.396 (4)
C11—H11	0.9500	C47—C48	1.383 (4)
C12—H12	0.9500	C47—H47	0.9500
C13A—H13A	0.9800	C48—C49	1.387 (4)
C13A—H13B	0.9800	C48—H48	0.9500
C13A—H13C	0.9800	C49—C50	1.384 (4)
C13B—H13D	0.9800	C50—C51	1.389 (4)
C13B—H13E	0.9800	C50—H50	0.9500
C13B—H13F	0.9800	C51—H51	0.9500
C14—C15	1.371 (3)	C52—H52A	0.9800
C15—C16	1.421 (4)	C52—H52B	0.9800
C15—D15	0.9500	C52—H52C	0.9800
C16—C17	1.372 (3)	O5—N5	1.335 (2)
C16—D16	0.9500	N5—C57	1.338 (3)
C17—C18	1.514 (3)	N5—C53	1.341 (3)
C18—C27	1.514 (3)	C53—C54	1.377 (4)
C18—C20	1.545 (3)	C53—H53	0.9500
C18—C19	1.547 (3)	C54—C55	1.372 (5)
C19—H19A	0.9800	C54—H54	0.9500
C19—H19B	0.9800	C55—C56	1.372 (5)
C19—H19C	0.9800	C55—H55	0.9500
C20—C25	1.388 (4)	C56—C57	1.370 (4)
C20—C21	1.400 (4)	C56—H56	0.9500
C21—C22	1.382 (4)	C57—H57	0.9500
C21—H21	0.9500	N6—C59	1.130 (5)
C22—C23	1.396 (4)	C58—C59	1.446 (5)
C22—H22	0.9500	C58—H58A	0.9800
C23—C24	1.380 (4)	C58—H58B	0.9800
C24—C25	1.400 (4)	C58—H58C	0.9800
C24—H24	0.9500
C10—O1—C13B	118.1 (6)	C28—C27—C18	130.8 (2)
C10—O1—C13A	113.7 (5)	N3—C27—C18	122.4 (2)
C23—O2—C26	117.3 (2)	C27—C28—C29	108.1 (2)
C36—O3—C39	116.5 (3)	C27—C28—D28	126.0
C49—O4—C52	116.7 (3)	C29—C28—D28	126.0
C1—N1—C4	110.4 (2)	C30—C29—C28	107.9 (2)
C1—N1—D1A	125.7 (19)	C30—C29—D29	126.0
C4—N1—D1A	123.9 (19)	C28—C29—D29	126.0
C17—N2—C14	110.40 (19)	C29—C30—N3	107.1 (2)
C17—N2—D2A	124 (2)	C29—C30—C31	130.0 (2)
C14—N2—D2A	125 (2)	N3—C30—C31	122.9 (2)
C30—N3—C27	110.2 (2)	C40—C31—C30	110.47 (18)
C30—N3—D3A	124.6 (19)	C40—C31—C33	109.83 (19)
C27—N3—D3A	125.0 (19)	C30—C31—C33	111.71 (19)
C43—N4—C40	109.80 (19)	C40—C31—C32	109.14 (19)
C43—N4—D4A	125.0 (19)	C30—C31—C32	107.77 (19)
C40—N4—D4A	124.9 (19)	C33—C31—C32	107.8 (2)
C2—C1—N1	106.8 (2)	C31—C32—H32A	109.5
C2—C1—C44	131.1 (2)	C31—C32—H32B	109.5
N1—C1—C44	122.1 (2)	H32A—C32—H32B	109.5
C1—C2—C3	108.0 (2)	C31—C32—H32C	109.5
C1—C2—D2	126.0	H32A—C32—H32C	109.5
C3—C2—D2	126.0	H32B—C32—H32C	109.5
C4—C3—C2	108.0 (2)	C38—C33—C34	117.4 (2)
C4—C3—D3	126.0	C38—C33—C31	122.5 (2)
C2—C3—D3	126.0	C34—C33—C31	120.0 (2)
C3—C4—N1	106.7 (2)	C35—C34—C33	122.0 (2)
C3—C4—C5	131.2 (2)	C35—C34—H34	119.0
N1—C4—C5	122.0 (2)	C33—C34—H34	119.0
C14—C5—C4	110.41 (18)	C36—C35—C34	119.4 (3)
C14—C5—C7	112.63 (19)	C36—C35—H35	120.3
C4—C5—C7	109.90 (19)	C34—C35—H35	120.3
C14—C5—C6	108.65 (19)	O3—C36—C35	124.6 (3)
C4—C5—C6	107.94 (19)	O3—C36—C37	116.0 (3)
C7—C5—C6	107.15 (19)	C35—C36—C37	119.4 (2)
C5—C6—H6A	109.5	C38—C37—C36	120.7 (3)
C5—C6—H6B	109.5	C38—C37—H37	119.6
H6A—C6—H6B	109.5	C36—C37—H37	119.6
C5—C6—H6C	109.5	C37—C38—C33	120.9 (3)
H6A—C6—H6C	109.5	C37—C38—H38	119.5
H6B—C6—H6C	109.5	C33—C38—H38	119.5
C12—C7—C8	117.3 (2)	O3—C39—H39A	109.5
C12—C7—C5	119.7 (2)	O3—C39—H39B	109.5
C8—C7—C5	122.8 (2)	H39A—C39—H39B	109.5
C9—C8—C7	121.3 (3)	O3—C39—H39C	109.5
C9—C8—H8	119.3	H39A—C39—H39C	109.5
C7—C8—H8	119.3	H39B—C39—H39C	109.5
C8—C9—C10	120.0 (3)	C41—C40—N4	107.3 (2)
C8—C9—H9	120.0	C41—C40—C31	131.0 (2)
C10—C9—H9	120.0	N4—C40—C31	121.7 (2)
O1—C10—C11	124.0 (3)	C40—C41—C42	107.6 (2)
O1—C10—C9	116.2 (3)	C40—C41—D41	126.2
C11—C10—C9	119.8 (3)	C42—C41—D41	126.2
C10—C11—C12	119.5 (3)	C43—C42—C41	108.0 (2)
C10—C11—H11	120.3	C43—C42—D42	126.0
C12—C11—H11	120.3	C41—C42—D42	126.0
C7—C12—C11	122.1 (3)	C42—C43—N4	107.3 (2)
C7—C12—H12	119.0	C42—C43—C44	130.8 (2)
C11—C12—H12	119.0	N4—C43—C44	121.8 (2)
O1—C13A—H13A	109.5	C1—C44—C43	109.96 (19)
O1—C13A—H13B	109.5	C1—C44—C46	112.29 (19)
H13A—C13A—H13B	109.5	C43—C44—C46	111.0 (2)
O1—C13A—H13C	109.5	C1—C44—C45	108.2 (2)
H13A—C13A—H13C	109.5	C43—C44—C45	108.94 (19)
H13B—C13A—H13C	109.5	C46—C44—C45	106.3 (2)
O1—C13B—H13D	109.5	C44—C45—H45A	109.5
O1—C13B—H13E	109.5	C44—C45—H45B	109.5
H13D—C13B—H13E	109.5	H45A—C45—H45B	109.5
O1—C13B—H13F	109.5	C44—C45—H45C	109.5
H13D—C13B—H13F	109.5	H45A—C45—H45C	109.5
H13E—C13B—H13F	109.5	H45B—C45—H45C	109.5
C15—C14—N2	106.8 (2)	C51—C46—C47	117.2 (2)
C15—C14—C5	130.7 (2)	C51—C46—C44	120.5 (2)
N2—C14—C5	122.5 (2)	C47—C46—C44	121.8 (2)
C14—C15—C16	108.1 (2)	C48—C47—C46	121.2 (3)
C14—C15—D15	126.0	C48—C47—H47	119.4
C16—C15—D15	126.0	C46—C47—H47	119.4
C17—C16—C15	107.6 (2)	C47—C48—C49	120.3 (3)
C17—C16—D16	126.2	C47—C48—H48	119.9
C15—C16—D16	126.2	C49—C48—H48	119.9
C16—C17—N2	107.1 (2)	O4—C49—C50	124.3 (3)
C16—C17—C18	130.1 (2)	O4—C49—C48	115.8 (3)
N2—C17—C18	122.8 (2)	C50—C49—C48	119.8 (2)
C17—C18—C27	111.11 (18)	C49—C50—C51	119.1 (3)
C17—C18—C20	111.3 (2)	C49—C50—H50	120.4
C27—C18—C20	110.33 (19)	C51—C50—H50	120.4
C17—C18—C19	108.5 (2)	C50—C51—C46	122.3 (3)
C27—C18—C19	108.6 (2)	C50—C51—H51	118.8
C20—C18—C19	106.78 (19)	C46—C51—H51	118.8
C18—C19—H19A	109.5	O4—C52—H52A	109.5
C18—C19—H19B	109.5	O4—C52—H52B	109.5
H19A—C19—H19B	109.5	H52A—C52—H52B	109.5
C18—C19—H19C	109.5	O4—C52—H52C	109.5
H19A—C19—H19C	109.5	H52A—C52—H52C	109.5
H19B—C19—H19C	109.5	H52B—C52—H52C	109.5
C25—C20—C21	117.3 (2)	O5—N5—C57	120.0 (2)
C25—C20—C18	122.2 (2)	O5—N5—C53	119.6 (2)
C21—C20—C18	120.3 (2)	C57—N5—C53	120.4 (2)
C22—C21—C20	121.5 (2)	N5—C53—C54	120.4 (3)
C22—C21—H21	119.2	N5—C53—H53	119.8
C20—C21—H21	119.2	C54—C53—H53	119.8
C21—C22—C23	120.3 (2)	C55—C54—C53	120.0 (3)
C21—C22—H22	119.9	C55—C54—H54	120.0
C23—C22—H22	119.9	C53—C54—H54	120.0
O2—C23—C24	124.9 (3)	C56—C55—C54	118.2 (3)
O2—C23—C22	115.8 (2)	C56—C55—H55	120.9
C24—C23—C22	119.3 (2)	C54—C55—H55	120.9
C23—C24—C25	119.8 (2)	C57—C56—C55	120.5 (3)
C23—C24—H24	120.1	C57—C56—H56	119.8
C25—C24—H24	120.1	C55—C56—H56	119.8
C20—C25—C24	121.8 (2)	N5—C57—C56	120.4 (3)
C20—C25—H25	119.1	N5—C57—H57	119.8
C24—C25—H25	119.1	C56—C57—H57	119.8
O2—C26—H26A	109.5	C59—C58—H58A	109.5
O2—C26—H26B	109.5	C59—C58—H58B	109.5
H26A—C26—H26B	109.5	H58A—C58—H58B	109.5
O2—C26—H26C	109.5	C59—C58—H58C	109.5
H26A—C26—H26C	109.5	H58A—C58—H58C	109.5
H26B—C26—H26C	109.5	H58B—C58—H58C	109.5
C28—C27—N3	106.7 (2)	N6—C59—C58	178.6 (5)
C4—N1—C1—C2	2.0 (3)	C18—C27—C28—C29	175.1 (2)
C4—N1—C1—C44	−178.5 (2)	C27—C28—C29—C30	−0.2 (3)
N1—C1—C2—C3	−1.2 (3)	C28—C29—C30—N3	1.1 (3)
C44—C1—C2—C3	179.3 (2)	C28—C29—C30—C31	−177.6 (2)
C1—C2—C3—C4	0.1 (3)	C27—N3—C30—C29	−1.7 (3)
C2—C3—C4—N1	1.1 (3)	C27—N3—C30—C31	177.1 (2)
C2—C3—C4—C5	−174.6 (2)	C29—C30—C31—C40	−103.9 (3)
C1—N1—C4—C3	−1.9 (3)	N3—C30—C31—C40	77.6 (3)
C1—N1—C4—C5	174.3 (2)	C29—C30—C31—C33	133.6 (3)
C3—C4—C5—C14	−102.0 (3)	N3—C30—C31—C33	−45.0 (3)
N1—C4—C5—C14	82.8 (3)	C29—C30—C31—C32	15.3 (3)
C3—C4—C5—C7	133.1 (3)	N3—C30—C31—C32	−163.3 (2)
N1—C4—C5—C7	−42.0 (3)	C40—C31—C33—C38	−151.1 (2)
C3—C4—C5—C6	16.6 (3)	C30—C31—C33—C38	−28.2 (3)
N1—C4—C5—C6	−158.6 (2)	C32—C31—C33—C38	90.1 (3)
C14—C5—C7—C12	−161.9 (2)	C40—C31—C33—C34	32.7 (3)
C4—C5—C7—C12	−38.3 (3)	C30—C31—C33—C34	155.6 (2)
C6—C5—C7—C12	78.7 (3)	C32—C31—C33—C34	−86.1 (3)
C14—C5—C7—C8	22.6 (3)	C38—C33—C34—C35	1.0 (4)
C4—C5—C7—C8	146.1 (2)	C31—C33—C34—C35	177.4 (2)
C6—C5—C7—C8	−96.8 (3)	C33—C34—C35—C36	0.1 (4)
C12—C7—C8—C9	2.1 (4)	C39—O3—C36—C35	4.2 (5)
C5—C7—C8—C9	177.7 (3)	C39—O3—C36—C37	−175.9 (3)
C7—C8—C9—C10	−0.3 (5)	C34—C35—C36—O3	179.4 (3)
C13B—O1—C10—C11	−19.7 (11)	C34—C35—C36—C37	−0.5 (4)
C13A—O1—C10—C11	13.4 (12)	O3—C36—C37—C38	179.9 (3)
C13B—O1—C10—C9	159.6 (10)	C35—C36—C37—C38	−0.2 (4)
C13A—O1—C10—C9	−167.3 (12)	C36—C37—C38—C33	1.4 (4)
C8—C9—C10—O1	179.3 (3)	C34—C33—C38—C37	−1.7 (4)
C8—C9—C10—C11	−1.3 (5)	C31—C33—C38—C37	−178.0 (2)
O1—C10—C11—C12	−179.5 (3)	C43—N4—C40—C41	0.7 (3)
C9—C10—C11—C12	1.1 (5)	C43—N4—C40—C31	−177.4 (2)
C8—C7—C12—C11	−2.3 (4)	C30—C31—C40—C41	110.4 (3)
C5—C7—C12—C11	−178.1 (2)	C33—C31—C40—C41	−126.0 (3)
C10—C11—C12—C7	0.7 (5)	C32—C31—C40—C41	−7.9 (4)
C17—N2—C14—C15	1.2 (3)	C30—C31—C40—N4	−72.0 (3)
C17—N2—C14—C5	179.8 (2)	C33—C31—C40—N4	51.6 (3)
C4—C5—C14—C15	109.6 (3)	C32—C31—C40—N4	169.6 (2)
C7—C5—C14—C15	−127.2 (3)	N4—C40—C41—C42	−0.2 (3)
C6—C5—C14—C15	−8.6 (3)	C31—C40—C41—C42	177.7 (2)
C4—C5—C14—N2	−68.7 (3)	C40—C41—C42—C43	−0.4 (3)
C7—C5—C14—N2	54.6 (3)	C41—C42—C43—N4	0.8 (3)
C6—C5—C14—N2	173.2 (2)	C41—C42—C43—C44	−176.7 (2)
N2—C14—C15—C16	−0.4 (3)	C40—N4—C43—C42	−1.0 (3)
C5—C14—C15—C16	−178.8 (2)	C40—N4—C43—C44	176.9 (2)
C14—C15—C16—C17	−0.6 (3)	C2—C1—C44—C43	105.1 (3)
C15—C16—C17—N2	1.3 (3)	N1—C1—C44—C43	−74.4 (3)
C15—C16—C17—C18	−177.0 (2)	C2—C1—C44—C46	−130.8 (3)
C14—N2—C17—C16	−1.6 (3)	N1—C1—C44—C46	49.8 (3)
C14—N2—C17—C18	176.8 (2)	C2—C1—C44—C45	−13.8 (3)
C16—C17—C18—C27	−117.9 (3)	N1—C1—C44—C45	166.8 (2)
N2—C17—C18—C27	64.1 (3)	C42—C43—C44—C1	−115.8 (3)
C16—C17—C18—C20	118.7 (3)	N4—C43—C44—C1	67.0 (3)
N2—C17—C18—C20	−59.4 (3)	C42—C43—C44—C46	119.3 (3)
C16—C17—C18—C19	1.4 (3)	N4—C43—C44—C46	−57.9 (3)
N2—C17—C18—C19	−176.6 (2)	C42—C43—C44—C45	2.6 (4)
C17—C18—C20—C25	−23.0 (3)	N4—C43—C44—C45	−174.7 (2)
C27—C18—C20—C25	−146.9 (2)	C1—C44—C46—C51	−155.6 (2)
C19—C18—C20—C25	95.2 (3)	C43—C44—C46—C51	−32.1 (3)
C17—C18—C20—C21	162.5 (2)	C45—C44—C46—C51	86.3 (3)
C27—C18—C20—C21	38.6 (3)	C1—C44—C46—C47	32.2 (3)
C19—C18—C20—C21	−79.3 (3)	C43—C44—C46—C47	155.8 (2)
C25—C20—C21—C22	1.8 (4)	C45—C44—C46—C47	−85.9 (3)
C18—C20—C21—C22	176.6 (2)	C51—C46—C47—C48	1.3 (4)
C20—C21—C22—C23	0.1 (4)	C44—C46—C47—C48	173.7 (2)
C26—O2—C23—C24	−5.1 (4)	C46—C47—C48—C49	−1.0 (4)
C26—O2—C23—C22	176.9 (3)	C52—O4—C49—C50	−12.0 (5)
C21—C22—C23—O2	176.4 (2)	C52—O4—C49—C48	168.2 (3)
C21—C22—C23—C24	−1.7 (4)	C47—C48—C49—O4	−179.9 (3)
O2—C23—C24—C25	−176.6 (2)	C47—C48—C49—C50	0.3 (4)
C22—C23—C24—C25	1.4 (4)	O4—C49—C50—C51	−179.8 (3)
C21—C20—C25—C24	−2.1 (4)	C48—C49—C50—C51	0.0 (4)
C18—C20—C25—C24	−176.8 (2)	C49—C50—C51—C46	0.4 (5)
C23—C24—C25—C20	0.6 (4)	C47—C46—C51—C50	−1.0 (4)
C30—N3—C27—C28	1.6 (3)	C44—C46—C51—C50	−173.5 (3)
C30—N3—C27—C18	−174.8 (2)	O5—N5—C53—C54	178.5 (3)
C17—C18—C27—C28	113.2 (3)	C57—N5—C53—C54	−1.5 (5)
C20—C18—C27—C28	−122.8 (3)	N5—C53—C54—C55	−0.1 (6)
C19—C18—C27—C28	−6.1 (3)	C53—C54—C55—C56	1.4 (6)
C17—C18—C27—N3	−71.4 (3)	C54—C55—C56—C57	−1.3 (6)
C20—C18—C27—N3	52.6 (3)	O5—N5—C57—C56	−178.4 (3)
C19—C18—C27—N3	169.3 (2)	C53—N5—C57—C56	1.6 (5)
N3—C27—C28—C29	−0.8 (3)	C55—C56—C57—N5	−0.2 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—D4A···O5	0.87 (3)	2.09 (3)	2.941 (3)	168 (3)
N3—D3A···O5	0.86 (3)	2.11 (3)	2.934 (3)	160 (3)
N2—D2A···O5	0.84 (3)	2.13 (3)	2.968 (3)	172 (3)
N1—D1A···O5	0.83 (3)	2.16 (3)	2.947 (3)	157 (3)