2,6-Bis­[bis­(pyridin-2-yl­methyl)­amino­methyl]-4-tert-butyl­phenol

The title compound (Hbpbp), C₃₆H₄₀N₆O, is a phenol with one intramolecular bifurcated hydrogen bond. This result furnishes an explanation as to why the otherwise symmetric deprotonated ligand shows a propensity for forming asymmetric, e.g. heterovalent and heterometallic, coordination compounds.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.051
• wR factor = 0.138
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT027_ALERT_3_A _diffrn_reflns_theta_full too Low ............      24.70 Deg.

Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) .       3.98 Ratio

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.753     0.989
            Tmin' and Tmax expected:      0.964     0.989
            RR' =      0.781
            Please check that your absorption correction is appropriate.
THETM01_ALERT_3_C  The value of sine(theta_max)/wavelength is less than 0.590
            Calculated sin(theta_max)/wavelength =    0.5880
PLAT023_ALERT_3_C Resolution (too) Low [sin(th)/Lambda < 0.6]...      24.70 Deg.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ...........       0.78
PLAT220_ALERT_2_C Large Non-Solvent    N     Ueq(max)/Ueq(min) .       2.62 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) .       3.58 Ratio

   1 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

We have used the phenolate-hinged dinucleating ligand bpbp⁻ for the synthesis of dimetallic coordination compounds and have succeeded in crystallizing the parent phenol, Hbpbp, (I). This together with the dichloride diperchlorate tetraprotonated double salt of H₅bpbp⁴⁺ (Gomez et al., 2000) has given us further insight in the mechanism of the ligand coordination.

The conformation of (I) (Fig. 1) is dominated by an intramolecular bifurcated hydrogen bond from the phenol O1—H1 group to N2 [2.11 (2) Å] of one arm and N221 [2.43 (2) Å] of one pyridine of that same arm. The angles around H1 sum to 255 (3)°. This hydrogen bond gives a C1—C2—C20—N2 torsion angle of −47.7 (3)° (syn). The C1—C6—C60—N6 torsion angle on the other hand is 174.48 (17)° (anti). This can be explained by a 2.53 Å hydrogen bond from C5—H5 of the phenol ring to N6 of the other ligand arm. In addition, atoms H613 and H623 of the attached pyridine rings form similar hydrogen bonds to N6 (2.53 and 2.55 Å, respectively). In the previously investigated H₅bpbp⁴⁺ cation, these C—H donors have been displaced by N—H donors from the protonated pyridines. As a result, both amines are oriented syn to the O—H group.

The molecular packing is dominated by C—H···N [shortest contacts 2.61 Å for H8a···N621ⁱ and H626···N611ⁱⁱ; symmetry codes: (i): 1 + x, y, 1 + z; (ii) x, y, −1 + z] and C—H···π bonding [shortest contacts are to the central phenol ring (centroid = PC): H216···PCⁱⁱⁱ = 2.85 Å and H224···PC^iv; symmetry codes: (iii) −1/2 + x, 1/2 − y, 1/2 + z; (iv) 1/2 + x, 1/2 − y, −1/2 + z].

We propose that the asymmetry between the bis(pyridin-2-ylmethyl)aminomethyl arms, one hydrogen-bonded, one dangling, can account for the observed asymmetric coordination chemistry of the bpbp⁻ ligand (Ghiladi et al., 1997, 1999). A stepwise insertion of two metal ions seems likely because the dangling arm is more available for coordination.

S2. Experimental

Compound (I) was synthesized according to a published procedure (Ghiladi et al., 1997). The raw product was subjected to column chromatography with acetone as eluent. Prismatic crystals suitable for diffraction were formed by subsequent recrystallization from acetone.

S3. Refinement

All H atoms could be located from a Fourier difference map. The phenol proton was refined isotropically in the riding mode, with U_iso(H1) = 1.2U_eq(O1) and the bond length O1—H1 restrained to 0.90 (5) Å. The remaining ligand H atoms were constrained to ideal positions with U_iso = 1.2U_eq(parent atom).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. View of (I) (50% probability displacement ellipsoids). Only the phenolic H atom is included. The excluded atom numbers are consecutive to those included.

(I)

Crystal data

C36H40N6O	F(000) = 1224
Mr = 572.74	Dx = 1.199 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 16912 reflections
a = 9.892 (5) Å	θ = 3.7–24.7°
b = 31.185 (5) Å	µ = 0.07 mm^−1
c = 10.524 (5) Å	T = 180 K
β = 102.188 (5)°	Prism, colourless
V = 3173 (2) Å^3	0.48 × 0.35 × 0.15 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	3501 reflections with I > 2σ(I)
Narrow–frame ϕ and ω scans	Rint = 0.052
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 24.7°, θmin = 3.7°
Tmin = 0.753, Tmax = 0.989	h = −11→11
16542 measured reflections	k = −36→27
5388 independent reflections	l = −12→12

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0705P)^2 + 0.1173P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.051	(Δ/σ)max = 0.001
wR(F^2) = 0.138	Δρmax = 0.32 e Å^−3
S = 1.02	Δρmin = −0.18 e Å^−3
5388 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
392 parameters	Extinction coefficient: 0.0053 (9)
1 restraint

Special details

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.

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

	x	y	z	Uiso*/Ueq
C1	0.5137 (2)	0.31570 (6)	0.57854 (19)	0.0279 (5)
C2	0.6341 (2)	0.30429 (6)	0.66721 (19)	0.0281 (5)
C3	0.7047 (2)	0.33577 (6)	0.7494 (2)	0.0306 (5)
H3	0.7851	0.3278	0.8117	0.037*
C4	0.6621 (2)	0.37820 (6)	0.74369 (19)	0.0281 (5)
C5	0.5430 (2)	0.38842 (6)	0.6520 (2)	0.0297 (5)
H5	0.513	0.4174	0.6444	0.036*
C6	0.46649 (19)	0.35799 (6)	0.57161 (19)	0.0271 (5)
C7	0.7375 (2)	0.41262 (7)	0.8354 (2)	0.0351 (5)
C8	0.8608 (3)	0.39482 (8)	0.9322 (3)	0.0588 (7)
H8A	0.9057	0.418	0.9885	0.088*
H8B	0.9269	0.3823	0.8852	0.088*
H8C	0.8293	0.3727	0.9854	0.088*
C9	0.7857 (3)	0.44876 (7)	0.7585 (3)	0.0570 (7)
H9A	0.7063	0.4604	0.6963	0.086*
H9B	0.8538	0.4377	0.7114	0.086*
H9C	0.8279	0.4715	0.8182	0.086*
C10	0.6362 (3)	0.43104 (8)	0.9138 (3)	0.0562 (7)
H10A	0.555	0.4427	0.8541	0.084*
H10B	0.682	0.4539	0.9711	0.084*
H10C	0.6071	0.4082	0.9663	0.084*
C20	0.6933 (2)	0.25973 (6)	0.6688 (2)	0.0347 (5)
H20A	0.7364	0.2561	0.5927	0.042*
H20B	0.7664	0.256	0.7483	0.042*
C60	0.3339 (2)	0.36825 (6)	0.4758 (2)	0.0325 (5)
H60A	0.3482	0.363	0.3868	0.039*
H60B	0.2611	0.3483	0.4908	0.039*
C211	0.5445 (2)	0.22486 (7)	0.7908 (2)	0.0440 (6)
H21A	0.5342	0.2545	0.821	0.053*
H21B	0.6187	0.2109	0.8553	0.053*
C212	0.4117 (3)	0.20117 (7)	0.7865 (3)	0.0522 (7)
C213	0.3070 (3)	0.19958 (8)	0.6781 (3)	0.0670 (8)
H213	0.3186	0.2123	0.5991	0.08*
C214	0.1843 (3)	0.17943 (10)	0.6846 (4)	0.0917 (12)
H214	0.1106	0.178	0.6104	0.11*
C215	0.1712 (5)	0.16162 (12)	0.7997 (6)	0.1076 (17)
H215	0.0878	0.1477	0.8073	0.129*
C216	0.2772 (5)	0.16401 (10)	0.9017 (5)	0.0994 (15)
H216	0.2659	0.1514	0.9809	0.119*
C221	0.6357 (2)	0.18476 (6)	0.6305 (2)	0.0371 (5)
H22A	0.565	0.1627	0.6352	0.045*
H22B	0.7214	0.1769	0.6935	0.045*
C222	0.6642 (2)	0.18537 (6)	0.4957 (2)	0.0335 (5)
C223	0.7856 (2)	0.16950 (7)	0.4706 (3)	0.0458 (6)
H223	0.852	0.1565	0.538	0.055*
C224	0.8099 (3)	0.17258 (8)	0.3469 (3)	0.0586 (8)
H224	0.8933	0.1619	0.3277	0.07*
C225	0.7122 (3)	0.19128 (8)	0.2525 (3)	0.0595 (7)
H225	0.7267	0.1944	0.1666	0.071*
C226	0.5929 (3)	0.20538 (8)	0.2846 (3)	0.0581 (7)
H226	0.5241	0.2176	0.2176	0.07*
C611	0.2245 (2)	0.41865 (6)	0.5967 (2)	0.0335 (5)
H61A	0.2825	0.4038	0.672	0.04*
H61B	0.1313	0.4055	0.5805	0.04*
C612	0.2127 (2)	0.46535 (7)	0.6302 (2)	0.0314 (5)
C613	0.2735 (2)	0.49812 (7)	0.5739 (2)	0.0377 (5)
H613	0.3275	0.4918	0.5115	0.045*
C614	0.2554 (2)	0.53993 (7)	0.6087 (2)	0.0430 (6)
H614	0.2948	0.5628	0.5694	0.052*
C615	0.1790 (2)	0.54801 (7)	0.7015 (2)	0.0440 (6)
H615	0.1652	0.5765	0.7284	0.053*
C616	0.1236 (2)	0.51353 (7)	0.7540 (2)	0.0434 (6)
H616	0.0722	0.5191	0.819	0.052*
C621	0.1816 (2)	0.42173 (7)	0.36475 (19)	0.0312 (5)
H62A	0.1275	0.4471	0.381	0.037*
H62B	0.117	0.3972	0.345	0.037*
C622	0.2430 (2)	0.43048 (6)	0.2480 (2)	0.0296 (5)
C623	0.3810 (2)	0.44006 (7)	0.2575 (2)	0.0375 (5)
H623	0.4435	0.44	0.3395	0.045*
C624	0.4266 (2)	0.44976 (7)	0.1458 (2)	0.0459 (6)
H624	0.5211	0.4564	0.1495	0.055*
C625	0.3331 (2)	0.44972 (7)	0.0291 (2)	0.0441 (6)
H625	0.3613	0.4567	−0.0492	0.053*
C626	0.1985 (2)	0.43950 (7)	0.0279 (2)	0.0405 (6)
H626	0.1348	0.4392	−0.0534	0.049*
N2	0.58677 (18)	0.22663 (5)	0.66572 (17)	0.0328 (4)
N6	0.28431 (16)	0.41209 (5)	0.48279 (16)	0.0292 (4)
N211	0.3999 (3)	0.18311 (7)	0.9004 (2)	0.0767 (8)
N221	0.5666 (2)	0.20307 (6)	0.4039 (2)	0.0473 (5)
N611	0.13705 (18)	0.47286 (6)	0.71994 (17)	0.0390 (5)
N621	0.15145 (18)	0.42993 (5)	0.13452 (17)	0.0354 (4)
O1	0.43944 (14)	0.28727 (4)	0.49318 (14)	0.0369 (4)
H1	0.470 (2)	0.2615 (6)	0.509 (2)	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0305 (11)	0.0295 (11)	0.0233 (12)	−0.0045 (9)	0.0050 (9)	−0.0032 (9)
C2	0.0292 (11)	0.0296 (11)	0.0253 (12)	0.0000 (9)	0.0052 (9)	0.0008 (9)
C3	0.0282 (11)	0.0363 (12)	0.0256 (12)	0.0012 (9)	0.0019 (9)	0.0030 (9)
C4	0.0286 (11)	0.0321 (11)	0.0243 (12)	−0.0011 (9)	0.0071 (9)	0.0004 (9)
C5	0.0334 (12)	0.0273 (11)	0.0284 (12)	0.0024 (9)	0.0066 (10)	0.0002 (9)
C6	0.0281 (11)	0.0303 (11)	0.0218 (12)	0.0014 (9)	0.0029 (9)	0.0018 (8)
C7	0.0346 (12)	0.0359 (12)	0.0327 (13)	−0.0032 (9)	0.0024 (10)	−0.0046 (9)
C8	0.0576 (16)	0.0527 (15)	0.0534 (18)	−0.0077 (13)	−0.0169 (14)	−0.0122 (12)
C9	0.0638 (17)	0.0492 (15)	0.0575 (19)	−0.0184 (13)	0.0116 (14)	−0.0031 (13)
C10	0.0575 (16)	0.0631 (17)	0.0480 (17)	−0.0062 (13)	0.0108 (14)	−0.0213 (13)
C20	0.0332 (12)	0.0322 (12)	0.0364 (14)	0.0015 (9)	0.0024 (10)	−0.0010 (9)
C60	0.0347 (12)	0.0333 (12)	0.0265 (12)	0.0026 (9)	−0.0003 (10)	−0.0007 (9)
C211	0.0613 (16)	0.0387 (13)	0.0351 (15)	0.0027 (11)	0.0172 (12)	0.0003 (10)
C212	0.0758 (19)	0.0337 (13)	0.0601 (19)	0.0023 (12)	0.0436 (17)	−0.0019 (12)
C213	0.0631 (19)	0.0626 (18)	0.082 (2)	−0.0084 (15)	0.0300 (18)	0.0016 (16)
C214	0.065 (2)	0.084 (2)	0.139 (4)	−0.0145 (17)	0.050 (2)	−0.011 (2)
C215	0.113 (3)	0.074 (2)	0.169 (5)	−0.025 (2)	0.105 (4)	−0.030 (3)
C216	0.154 (4)	0.059 (2)	0.122 (4)	−0.023 (3)	0.114 (3)	−0.011 (2)
C221	0.0429 (13)	0.0276 (12)	0.0419 (14)	0.0032 (10)	0.0111 (11)	0.0036 (10)
C222	0.0380 (12)	0.0231 (11)	0.0404 (14)	−0.0017 (9)	0.0102 (11)	−0.0050 (9)
C223	0.0415 (14)	0.0460 (14)	0.0514 (17)	0.0059 (11)	0.0129 (13)	−0.0057 (11)
C224	0.0571 (17)	0.0565 (17)	0.070 (2)	0.0039 (13)	0.0307 (17)	−0.0135 (14)
C225	0.083 (2)	0.0545 (16)	0.0502 (18)	0.0003 (15)	0.0345 (17)	−0.0077 (13)
C226	0.0695 (18)	0.0668 (18)	0.0403 (17)	0.0095 (14)	0.0169 (15)	0.0072 (13)
C611	0.0332 (12)	0.0412 (13)	0.0258 (13)	0.0029 (10)	0.0060 (10)	0.0028 (9)
C612	0.0283 (11)	0.0408 (13)	0.0231 (12)	0.0056 (9)	0.0006 (10)	0.0002 (9)
C613	0.0370 (12)	0.0404 (13)	0.0368 (14)	0.0014 (10)	0.0104 (11)	−0.0023 (10)
C614	0.0407 (13)	0.0427 (14)	0.0446 (16)	−0.0010 (11)	0.0068 (12)	−0.0007 (11)
C615	0.0405 (13)	0.0419 (14)	0.0449 (16)	0.0074 (11)	−0.0014 (12)	−0.0103 (11)
C616	0.0405 (13)	0.0561 (16)	0.0338 (14)	0.0134 (12)	0.0081 (11)	−0.0055 (11)
C621	0.0277 (11)	0.0374 (12)	0.0263 (13)	0.0037 (9)	0.0006 (10)	0.0016 (9)
C622	0.0348 (12)	0.0280 (11)	0.0242 (12)	0.0037 (9)	0.0018 (10)	−0.0001 (9)
C623	0.0327 (12)	0.0492 (14)	0.0289 (13)	0.0016 (10)	0.0024 (10)	0.0017 (10)
C624	0.0368 (13)	0.0610 (16)	0.0407 (16)	0.0001 (11)	0.0099 (12)	0.0008 (12)
C625	0.0478 (14)	0.0559 (15)	0.0302 (14)	0.0015 (12)	0.0119 (12)	0.0037 (11)
C626	0.0453 (14)	0.0487 (14)	0.0244 (14)	0.0007 (11)	0.0003 (11)	0.0012 (10)
N2	0.0400 (10)	0.0272 (9)	0.0328 (11)	0.0006 (8)	0.0115 (9)	0.0002 (7)
N6	0.0312 (9)	0.0349 (10)	0.0194 (10)	0.0058 (7)	0.0007 (8)	−0.0003 (7)
N211	0.127 (2)	0.0517 (14)	0.0702 (18)	−0.0082 (14)	0.0647 (17)	−0.0038 (12)
N221	0.0487 (12)	0.0536 (12)	0.0416 (13)	0.0098 (10)	0.0141 (10)	0.0081 (10)
N611	0.0401 (11)	0.0484 (12)	0.0286 (11)	0.0086 (9)	0.0075 (9)	0.0012 (9)
N621	0.0373 (10)	0.0425 (11)	0.0238 (11)	−0.0004 (8)	0.0006 (9)	0.0018 (8)
O1	0.0410 (9)	0.0290 (8)	0.0350 (9)	0.0016 (7)	−0.0048 (7)	−0.0061 (7)

Geometric parameters (Å, º)

C1—O1	1.362 (2)	C221—N2	1.467 (2)
C1—C2	1.395 (3)	C221—C222	1.503 (3)
C1—C6	1.396 (3)	C221—H22A	0.99
C2—C3	1.395 (3)	C221—H22B	0.99
C2—C20	1.507 (3)	C222—N221	1.332 (3)
C3—C4	1.386 (3)	C222—C223	1.375 (3)
C3—H3	0.95	C223—C224	1.376 (3)
C4—C5	1.393 (3)	C223—H223	0.95
C4—C7	1.528 (3)	C224—C225	1.362 (4)
C5—C6	1.386 (3)	C224—H224	0.95
C5—H5	0.95	C225—C226	1.367 (4)
C6—C60	1.511 (3)	C225—H225	0.95
C7—C8	1.520 (3)	C226—N221	1.338 (3)
C7—C9	1.522 (3)	C226—H226	0.95
C7—C10	1.537 (3)	C611—N6	1.459 (3)
C8—H8A	0.98	C611—C612	1.509 (3)
C8—H8B	0.98	C611—H61A	0.99
C8—H8C	0.98	C611—H61B	0.99
C9—H9A	0.98	C612—N611	1.343 (3)
C9—H9B	0.98	C612—C613	1.381 (3)
C9—H9C	0.98	C613—C614	1.376 (3)
C10—H10A	0.98	C613—H613	0.95
C10—H10B	0.98	C614—C615	1.378 (3)
C10—H10C	0.98	C614—H614	0.95
C20—N2	1.471 (2)	C615—C616	1.375 (3)
C20—H20A	0.99	C615—H615	0.95
C20—H20B	0.99	C616—N611	1.332 (3)
C60—N6	1.459 (2)	C616—H616	0.95
C60—H60A	0.99	C621—N6	1.460 (2)
C60—H60B	0.99	C621—C622	1.506 (3)
C211—N2	1.464 (3)	C621—H62A	0.99
C211—C212	1.499 (3)	C621—H62B	0.99
C211—H21A	0.99	C622—N621	1.338 (3)
C211—H21B	0.99	C622—C623	1.380 (3)
C212—N211	1.352 (3)	C623—C624	1.379 (3)
C212—C213	1.370 (4)	C623—H623	0.95
C213—C214	1.381 (4)	C624—C625	1.372 (3)
C213—H213	0.95	C624—H624	0.95
C214—C215	1.364 (5)	C625—C626	1.366 (3)
C214—H214	0.95	C625—H625	0.95
C215—C216	1.335 (6)	C626—N621	1.336 (3)
C215—H215	0.95	C626—H626	0.95
C216—N211	1.354 (4)	O1—H1	0.863 (19)
C216—H216	0.95
O1—C1—C2	122.73 (17)	N2—C221—C222	111.41 (16)
O1—C1—C6	116.91 (17)	N2—C221—H22A	109.3
C2—C1—C6	120.33 (17)	C222—C221—H22A	109.3
C3—C2—C1	118.73 (18)	N2—C221—H22B	109.3
C3—C2—C20	119.93 (18)	C222—C221—H22B	109.3
C1—C2—C20	121.20 (17)	H22A—C221—H22B	108
C4—C3—C2	122.48 (19)	N221—C222—C223	122.6 (2)
C4—C3—H3	118.8	N221—C222—C221	115.96 (19)
C2—C3—H3	118.8	C223—C222—C221	121.4 (2)
C3—C4—C5	116.96 (18)	C222—C223—C224	119.4 (2)
C3—C4—C7	122.68 (18)	C222—C223—H223	120.3
C5—C4—C7	120.33 (17)	C224—C223—H223	120.3
C6—C5—C4	122.64 (18)	C225—C224—C223	118.8 (2)
C6—C5—H5	118.7	C225—C224—H224	120.6
C4—C5—H5	118.7	C223—C224—H224	120.6
C5—C6—C1	118.79 (18)	C224—C225—C226	118.3 (3)
C5—C6—C60	123.23 (17)	C224—C225—H225	120.8
C1—C6—C60	117.98 (17)	C226—C225—H225	120.8
C8—C7—C9	109.27 (19)	N221—C226—C225	124.3 (3)
C8—C7—C4	112.48 (17)	N221—C226—H226	117.9
C9—C7—C4	110.49 (19)	C225—C226—H226	117.9
C8—C7—C10	107.3 (2)	N6—C611—C612	113.09 (16)
C9—C7—C10	108.77 (19)	N6—C611—H61A	109
C4—C7—C10	108.39 (17)	C612—C611—H61A	109
C7—C8—H8A	109.5	N6—C611—H61B	109
C7—C8—H8B	109.5	C612—C611—H61B	109
H8A—C8—H8B	109.5	H61A—C611—H61B	107.8
C7—C8—H8C	109.5	N611—C612—C613	122.02 (19)
H8A—C8—H8C	109.5	N611—C612—C611	114.49 (18)
H8B—C8—H8C	109.5	C613—C612—C611	123.49 (19)
C7—C9—H9A	109.5	C614—C613—C612	119.6 (2)
C7—C9—H9B	109.5	C614—C613—H613	120.2
H9A—C9—H9B	109.5	C612—C613—H613	120.2
C7—C9—H9C	109.5	C613—C614—C615	118.9 (2)
H9A—C9—H9C	109.5	C613—C614—H614	120.5
H9B—C9—H9C	109.5	C615—C614—H614	120.5
C7—C10—H10A	109.5	C616—C615—C614	117.8 (2)
C7—C10—H10B	109.5	C616—C615—H615	121.1
H10A—C10—H10B	109.5	C614—C615—H615	121.1
C7—C10—H10C	109.5	N611—C616—C615	124.4 (2)
H10A—C10—H10C	109.5	N611—C616—H616	117.8
H10B—C10—H10C	109.5	C615—C616—H616	117.8
N2—C20—C2	111.81 (16)	N6—C621—C622	113.81 (16)
N2—C20—H20A	109.3	N6—C621—H62A	108.8
C2—C20—H20A	109.3	C622—C621—H62A	108.8
N2—C20—H20B	109.3	N6—C621—H62B	108.8
C2—C20—H20B	109.3	C622—C621—H62B	108.8
H20A—C20—H20B	107.9	H62A—C621—H62B	107.7
N6—C60—C6	114.74 (16)	N621—C622—C623	122.7 (2)
N6—C60—H60A	108.6	N621—C622—C621	114.36 (18)
C6—C60—H60A	108.6	C623—C622—C621	122.90 (19)
N6—C60—H60B	108.6	C624—C623—C622	118.9 (2)
C6—C60—H60B	108.6	C624—C623—H623	120.6
H60A—C60—H60B	107.6	C622—C623—H623	120.6
N2—C211—C212	114.0 (2)	C625—C624—C623	118.8 (2)
N2—C211—H21A	108.8	C625—C624—H624	120.6
C212—C211—H21A	108.8	C623—C624—H624	120.6
N2—C211—H21B	108.8	C626—C625—C624	118.7 (2)
C212—C211—H21B	108.8	C626—C625—H625	120.7
H21A—C211—H21B	107.7	C624—C625—H625	120.7
N211—C212—C213	122.1 (3)	N621—C626—C625	123.8 (2)
N211—C212—C211	114.7 (3)	N621—C626—H626	118.1
C213—C212—C211	123.2 (2)	C625—C626—H626	118.1
C212—C213—C214	119.6 (3)	C211—N2—C221	111.48 (16)
C212—C213—H213	120.2	C211—N2—C20	110.24 (17)
C214—C213—H213	120.2	C221—N2—C20	110.91 (16)
C215—C214—C213	118.6 (4)	C611—N6—C60	111.80 (16)
C215—C214—H214	120.7	C611—N6—C621	109.89 (16)
C213—C214—H214	120.7	C60—N6—C621	109.32 (15)
C216—C215—C214	119.0 (4)	C212—N211—C216	116.0 (3)
C216—C215—H215	120.5	C222—N221—C226	116.7 (2)
C214—C215—H215	120.5	C616—N611—C612	117.20 (19)
C215—C216—N211	124.7 (4)	C626—N621—C622	117.15 (19)
C215—C216—H216	117.6	C1—O1—H1	111.1 (15)
N211—C216—H216	117.6
O1—C1—C2—C3	178.88 (18)	C224—C225—C226—N221	1.8 (4)
C6—C1—C2—C3	0.8 (3)	N6—C611—C612—N611	169.15 (17)
O1—C1—C2—C20	3.2 (3)	N6—C611—C612—C613	−10.6 (3)
C6—C1—C2—C20	−174.90 (18)	N611—C612—C613—C614	−0.9 (3)
C1—C2—C3—C4	−1.9 (3)	C611—C612—C613—C614	178.9 (2)
C20—C2—C3—C4	173.80 (18)	C612—C613—C614—C615	1.4 (3)
C2—C3—C4—C5	0.7 (3)	C613—C614—C615—C616	−0.6 (3)
C2—C3—C4—C7	178.71 (19)	C614—C615—C616—N611	−1.0 (3)
C3—C4—C5—C6	1.8 (3)	N6—C621—C622—N621	165.90 (16)
C7—C4—C5—C6	−176.29 (19)	N6—C621—C622—C623	−16.7 (3)
C4—C5—C6—C1	−2.9 (3)	N621—C622—C623—C624	0.4 (3)
C4—C5—C6—C60	177.30 (19)	C621—C622—C623—C624	−176.72 (19)
O1—C1—C6—C5	−176.67 (18)	C622—C623—C624—C625	0.3 (3)
C2—C1—C6—C5	1.5 (3)	C623—C624—C625—C626	−0.9 (3)
O1—C1—C6—C60	3.2 (3)	C624—C625—C626—N621	0.8 (3)
C2—C1—C6—C60	−178.65 (18)	C212—C211—N2—C221	−72.1 (2)
C3—C4—C7—C8	−0.7 (3)	C212—C211—N2—C20	164.25 (17)
C5—C4—C7—C8	177.3 (2)	C222—C221—N2—C211	173.69 (18)
C3—C4—C7—C9	121.7 (2)	C222—C221—N2—C20	−63.1 (2)
C5—C4—C7—C9	−60.3 (3)	C2—C20—N2—C211	−72.1 (2)
C3—C4—C7—C10	−119.2 (2)	C2—C20—N2—C221	163.96 (17)
C5—C4—C7—C10	58.8 (3)	C612—C611—N6—C60	162.33 (16)
C3—C2—C20—N2	136.68 (19)	C612—C611—N6—C621	−76.1 (2)
C1—C2—C20—N2	−47.7 (3)	C6—C60—N6—C611	−74.3 (2)
C5—C6—C60—N6	−5.7 (3)	C6—C60—N6—C621	163.80 (16)
C1—C6—C60—N6	174.48 (17)	C622—C621—N6—C611	160.51 (16)
N2—C211—C212—N211	152.76 (19)	C622—C621—N6—C60	−76.4 (2)
N2—C211—C212—C213	−30.5 (3)	C213—C212—N211—C216	−1.1 (4)
N211—C212—C213—C214	0.8 (4)	C211—C212—N211—C216	175.7 (2)
C211—C212—C213—C214	−175.8 (2)	C215—C216—N211—C212	0.8 (5)
C212—C213—C214—C215	0.1 (4)	C223—C222—N221—C226	−1.0 (3)
C213—C214—C215—C216	−0.4 (5)	C221—C222—N221—C226	177.4 (2)
C214—C215—C216—N211	0.0 (6)	C225—C226—N221—C222	−0.6 (4)
N2—C221—C222—N221	−46.8 (2)	C615—C616—N611—C612	1.5 (3)
N2—C221—C222—C223	131.5 (2)	C613—C612—N611—C616	−0.6 (3)
N221—C222—C223—C224	1.4 (3)	C611—C612—N611—C616	179.63 (18)
C221—C222—C223—C224	−176.9 (2)	C625—C626—N621—C622	−0.1 (3)
C222—C223—C224—C225	−0.2 (4)	C623—C622—N621—C626	−0.5 (3)
C223—C224—C225—C226	−1.3 (4)	C621—C622—N621—C626	176.88 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.86 (2)	2.11 (2)	2.807 (2)	138 (2)
O1—H1···N221	0.86 (2)	2.43 (2)	3.140 (2)	140 (2)