The new chiral ligand 3-ethoxy-4-[(1R,2S)-(2-hydroxy-1,2-di­phenyl­ethyl)­amino]-3-cyclo­butene-1,2-dione

The asymmetric unit of C₂₀H₁₉NO₄ contains two mol­ecules with slightly different conformations. In the crystal, the mol­ecules are linked by O-H...O and N-H...O hydrogen bonds [O...O 2.764 (3) and 2.811 (3) Å; N...O 2.907 (3) and 2.968 (3) Å] to form a two-dimensional network.

S1. Comment

Squaric acid has long been known as an aromatic ring system having unique characteristics and its derivatives have wide ranging applications, but the report on the synthesis of chiral derivatives of squaric acid was few and the application in asymmetric catalytic reactions is totally unprecedented, none of the crystal structures of these compounds have been seen hitherto. The structure of the new chiral ligand reported here, (I), can provide an effective chiral environment for coordination of the substrate in the reactions, such as the enantioselective catalytic borane reduction of prochiral ketones and addition of dialkylzinc to aldehydes etc., ascribed to combining the aromatic squaric acid moiety of rigidity tetracarbon ring and flexible ethoxy group with (1S,2R)-(±)-2-amino-1,2-diphenylethanol. Promising results were obtained in the reactions mentioned when the new ligand was used.

S2. Experimental

The title compound was prepared by reaction of 3,4-diethoxy-3-cyclobutene-1,2-dione and (1S,2R)-(±)-2-amino-1,2-diphenylethanol in the presence of triethylamine (molar ratio 1.1:1:1) in ethanol and recrystallized from it.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

3-Ethoxy-4-[(1'R,2'S)-(2'-hydroxy-1',2'-diphenyl)ethylamino]-3-cyclobutene- 1,2-dione

Crystal data

C20H19NO4	Dx = 1.288 Mg m^−3
Mr = 337.36	Melting point = 481–483 K
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 10.758 (2) Å	Cell parameters from 25 reflections
b = 15.879 (3) Å	θ = 3.4–17.4°
c = 11.040 (2) Å	µ = 0.09 mm^−1
β = 112.74 (1)°	T = 296 K
V = 1739.3 (6) Å^3	Flake, colourless
Z = 4	0.48 × 0.38 × 0.36 mm
F(000) = 712

Data collection

Bruker P4 diffractometer	Rint = 0.016
Radiation source: normal-focus sealed tube	θmax = 28.5°, θmin = 2.0°
Graphite monochromator	h = −1→14
ω scans	k = −1→21
5817 measured reflections	l = −14→14
4871 independent reflections	3 standard reflections every 97 reflections
3018 reflections with I > 2σ(I)	intensity decay: 4.0%

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)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.0321P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.85	(Δ/σ)max = 0.001
4871 reflections	Δρmax = 0.16 e Å^−3
456 parameters	Δρmin = −0.14 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc^*=3DkFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0168 (8)

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.

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

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

	x	y	z	Uiso*/Ueq
O1	0.3818 (2)	0.06773 (12)	0.6832 (2)	0.0486 (5)
H1O	0.3916	0.0169	0.6962	0.058*
O2	0.32990 (19)	0.27491 (13)	0.32206 (16)	0.0507 (5)
O3	0.5318 (2)	0.40081 (12)	0.25040 (16)	0.0494 (5)
O4	0.77171 (18)	0.34608 (13)	0.53789 (16)	0.0474 (5)
N	0.5751 (2)	0.23305 (14)	0.60626 (18)	0.0370 (5)
H0	0.6560	0.2255	0.6625	0.044*
C1	0.6479 (3)	0.01575 (18)	0.5883 (3)	0.0474 (7)
H1	0.7156	0.0219	0.6714	0.057*
C2	0.6721 (3)	−0.0313 (2)	0.4944 (3)	0.0612 (9)
H2	0.7550	−0.0576	0.5151	0.073*
C3	0.5737 (4)	−0.0392 (2)	0.3703 (3)	0.0610 (9)
H3	0.5900	−0.0703	0.3066	0.073*
C4	0.4521 (4)	−0.0010 (2)	0.3416 (3)	0.0638 (9)
H4	0.3854	−0.0060	0.2578	0.077*
C5	0.4275 (3)	0.0449 (2)	0.4358 (2)	0.0504 (8)
H5	0.3440	0.0704	0.4150	0.061*
C6	0.5251 (2)	0.05343 (16)	0.5606 (2)	0.0347 (6)
C7	0.4963 (2)	0.10123 (16)	0.6653 (2)	0.0366 (6)
H7	0.5747	0.0967	0.7484	0.044*
C8	0.4650 (2)	0.19442 (15)	0.6333 (2)	0.0324 (5)
H8	0.3830	0.1982	0.5532	0.039*
C9	0.4399 (2)	0.24145 (15)	0.7424 (2)	0.0336 (6)
C10	0.3102 (3)	0.25466 (18)	0.7345 (2)	0.0467 (7)
H10	0.2377	0.2351	0.6618	0.056*
C11	0.2865 (3)	0.2964 (2)	0.8329 (3)	0.0574 (9)
H11	0.1986	0.3042	0.8266	0.069*
C12	0.3921 (3)	0.3265 (2)	0.9399 (3)	0.0563 (8)
H12	0.3762	0.3548	1.0063	0.068*
C13	0.5213 (3)	0.3146 (2)	0.9482 (3)	0.0551 (8)
H13	0.5933	0.3354	1.0202	0.066*
C14	0.5453 (3)	0.27216 (18)	0.8511 (2)	0.0464 (7)
H14	0.6336	0.2640	0.8585	0.056*
C15	0.5584 (2)	0.27859 (16)	0.5017 (2)	0.0315 (6)
C16	0.4473 (3)	0.29696 (17)	0.3756 (2)	0.0363 (6)
C17	0.5413 (3)	0.35431 (16)	0.3423 (2)	0.0362 (6)
C18	0.6450 (3)	0.33035 (16)	0.4681 (2)	0.0338 (6)
C19	0.8392 (3)	0.4036 (2)	0.4807 (3)	0.0526 (8)
H19A	0.8149	0.4613	0.4900	0.063*
H19B	0.8133	0.3916	0.3880	0.063*
C20	0.9872 (3)	0.3908 (2)	0.5528 (3)	0.0756 (11)
H20A	1.0117	0.4043	0.6439	0.091*
H20B	1.0354	0.4267	0.5162	0.091*
H20C	1.0094	0.3331	0.5448	0.091*
O1'	−0.12148 (19)	0.38791 (12)	0.1911 (2)	0.0507 (5)
H1'O	−0.0871	0.4343	0.2143	0.061*
O2'	−0.16835 (19)	0.19230 (14)	−0.18421 (17)	0.0558 (6)
O3'	0.0141 (2)	0.04816 (12)	−0.24695 (17)	0.0556 (6)
O4'	0.26944 (17)	0.11000 (12)	0.02442 (16)	0.0441 (5)
N'	0.0825 (2)	0.24079 (13)	0.08601 (18)	0.0358 (5)
H'	0.1540	0.2364	0.1565	0.043*
C1'	0.0554 (3)	0.20636 (18)	0.3724 (2)	0.0445 (7)
H1'	0.1442	0.2195	0.3868	0.053*
C2'	0.0295 (3)	0.1424 (2)	0.4433 (3)	0.0552 (9)
H2'	0.1007	0.1128	0.5046	0.066*
C3'	−0.1003 (4)	0.1220 (2)	0.4241 (3)	0.0607 (9)
H3'	−0.1177	0.0798	0.4738	0.073*
C4'	−0.2050 (3)	0.1646 (2)	0.3307 (3)	0.0614 (9)
H4'	−0.2936	0.1501	0.3153	0.074*
C5'	−0.1788 (3)	0.22893 (19)	0.2595 (3)	0.0503 (7)
H5'	−0.2504	0.2574	0.1968	0.060*
C6'	−0.0478 (2)	0.25167 (16)	0.2801 (2)	0.0364 (6)
C7'	−0.0186 (2)	0.32683 (16)	0.2115 (2)	0.0372 (6)
H7'	0.0685	0.3511	0.2676	0.045*
C8'	−0.0169 (2)	0.30707 (16)	0.0763 (2)	0.0352 (6)
H8'	−0.1063	0.2860	0.0201	0.042*
C9'	0.0120 (3)	0.38485 (15)	0.0112 (2)	0.0347 (6)
C10'	−0.0860 (3)	0.4190 (2)	−0.1005 (3)	0.0514 (8)
H10'	−0.1708	0.3942	−0.1364	0.062*
C11'	−0.0585 (4)	0.4891 (2)	−0.1587 (3)	0.0618 (9)
H11'	−0.1259	0.5118	−0.2327	0.074*
C12'	0.0660 (4)	0.5265 (2)	−0.1100 (3)	0.0591 (9)
H12'	0.0841	0.5732	−0.1514	0.071*
C13'	0.1627 (3)	0.4936 (2)	0.0006 (3)	0.0554 (8)
H13'	0.2473	0.5188	0.0356	0.066*
C14'	0.1371 (3)	0.42341 (18)	0.0614 (3)	0.0461 (7)
H14'	0.2044	0.4019	0.1366	0.055*
C15'	0.0633 (2)	0.18835 (16)	−0.0116 (2)	0.0315 (6)
C16'	−0.0529 (3)	0.16716 (17)	−0.1328 (3)	0.0376 (6)
C17'	0.0330 (3)	0.10166 (17)	−0.1615 (2)	0.0383 (6)
C18'	0.1416 (3)	0.12883 (16)	−0.0418 (2)	0.0335 (6)
C19'	0.3314 (3)	0.0519 (2)	−0.0384 (3)	0.0544 (8)
H19C	0.2973	0.0626	−0.1321	0.065*
H19D	0.3097	−0.0057	−0.0250	0.065*
C20'	0.4790 (3)	0.0644 (2)	0.0201 (3)	0.0657 (9)
H20D	0.5002	0.1201	0.0000	0.079*
H20E	0.5217	0.0236	−0.0153	0.079*
H20F	0.5110	0.0576	0.1137	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0624 (14)	0.0358 (11)	0.0616 (12)	−0.0064 (11)	0.0391 (11)	−0.0014 (11)
O2	0.0331 (11)	0.0647 (14)	0.0441 (10)	−0.0087 (10)	0.0036 (9)	0.0040 (10)
O3	0.0676 (13)	0.0447 (11)	0.0352 (9)	−0.0033 (11)	0.0191 (9)	0.0067 (9)
O4	0.0344 (11)	0.0594 (13)	0.0448 (10)	−0.0109 (10)	0.0114 (8)	0.0041 (10)
N	0.0245 (11)	0.0487 (13)	0.0304 (10)	−0.0016 (11)	0.0025 (9)	0.0082 (10)
C1	0.0414 (16)	0.0514 (18)	0.0519 (16)	0.0042 (15)	0.0207 (13)	0.0054 (15)
C2	0.064 (2)	0.054 (2)	0.082 (2)	0.0116 (18)	0.047 (2)	0.0060 (19)
C3	0.089 (3)	0.0481 (19)	0.069 (2)	−0.0051 (19)	0.055 (2)	−0.0104 (17)
C4	0.072 (2)	0.075 (2)	0.0468 (18)	−0.009 (2)	0.0248 (16)	−0.0136 (17)
C5	0.0466 (18)	0.062 (2)	0.0416 (15)	0.0029 (16)	0.0161 (14)	−0.0070 (15)
C6	0.0382 (15)	0.0333 (14)	0.0367 (12)	−0.0055 (12)	0.0188 (12)	0.0008 (11)
C7	0.0348 (14)	0.0392 (15)	0.0335 (12)	−0.0006 (12)	0.0106 (11)	0.0004 (11)
C8	0.0270 (12)	0.0373 (14)	0.0296 (11)	−0.0049 (11)	0.0072 (10)	0.0019 (11)
C9	0.0367 (14)	0.0276 (13)	0.0336 (12)	−0.0008 (12)	0.0106 (11)	0.0046 (11)
C10	0.0405 (16)	0.0516 (18)	0.0464 (14)	−0.0039 (15)	0.0150 (12)	−0.0028 (14)
C11	0.058 (2)	0.062 (2)	0.0619 (18)	0.0059 (18)	0.0338 (17)	−0.0062 (18)
C12	0.073 (2)	0.0517 (19)	0.0445 (15)	0.0154 (18)	0.0232 (16)	−0.0043 (15)
C13	0.062 (2)	0.0523 (19)	0.0399 (15)	0.0071 (18)	0.0070 (14)	−0.0076 (15)
C14	0.0424 (16)	0.0468 (17)	0.0425 (14)	0.0039 (14)	0.0081 (13)	−0.0055 (13)
C15	0.0277 (13)	0.0336 (14)	0.0307 (12)	−0.0008 (11)	0.0086 (10)	−0.0033 (11)
C16	0.0356 (16)	0.0396 (15)	0.0316 (12)	−0.0009 (14)	0.0108 (11)	−0.0023 (12)
C17	0.0466 (17)	0.0318 (14)	0.0308 (13)	0.0016 (13)	0.0157 (12)	−0.0037 (12)
C18	0.0326 (15)	0.0357 (14)	0.0323 (12)	0.0000 (13)	0.0118 (11)	−0.0027 (12)
C19	0.0468 (19)	0.0526 (18)	0.0672 (18)	−0.0105 (16)	0.0317 (16)	−0.0011 (17)
C20	0.0472 (19)	0.086 (3)	0.104 (3)	−0.014 (2)	0.0407 (19)	−0.029 (2)
O1'	0.0600 (14)	0.0360 (11)	0.0675 (13)	0.0087 (11)	0.0373 (11)	0.0045 (11)
O2'	0.0351 (12)	0.0644 (14)	0.0525 (11)	0.0074 (11)	−0.0002 (9)	−0.0066 (11)
O3'	0.0629 (14)	0.0490 (12)	0.0447 (10)	0.0041 (11)	0.0094 (10)	−0.0123 (10)
O4'	0.0351 (11)	0.0540 (12)	0.0408 (9)	0.0130 (10)	0.0120 (8)	−0.0052 (9)
N'	0.0315 (12)	0.0382 (12)	0.0303 (10)	0.0083 (10)	0.0039 (9)	−0.0029 (10)
C1'	0.0411 (16)	0.0423 (16)	0.0473 (14)	0.0002 (14)	0.0139 (13)	0.0008 (13)
C2'	0.060 (2)	0.0472 (18)	0.0484 (17)	0.0053 (17)	0.0105 (15)	0.0091 (16)
C3'	0.079 (3)	0.0433 (18)	0.067 (2)	−0.0036 (18)	0.0367 (18)	0.0083 (17)
C4'	0.051 (2)	0.053 (2)	0.086 (2)	−0.0125 (18)	0.0333 (18)	0.003 (2)
C5'	0.0438 (17)	0.0481 (17)	0.0558 (16)	−0.0005 (15)	0.0155 (13)	0.0056 (15)
C6'	0.0401 (15)	0.0338 (14)	0.0371 (13)	0.0002 (13)	0.0168 (12)	−0.0038 (11)
C7'	0.0360 (14)	0.0369 (15)	0.0380 (13)	0.0030 (12)	0.0134 (11)	0.0012 (12)
C8'	0.0291 (13)	0.0383 (14)	0.0333 (12)	0.0050 (12)	0.0068 (10)	−0.0024 (11)
C9'	0.0389 (14)	0.0348 (15)	0.0327 (12)	0.0056 (13)	0.0162 (11)	−0.0029 (11)
C10'	0.0495 (19)	0.0546 (19)	0.0428 (15)	0.0051 (16)	0.0100 (14)	0.0051 (15)
C11'	0.074 (2)	0.059 (2)	0.0468 (17)	0.0112 (19)	0.0180 (16)	0.0192 (16)
C12'	0.088 (3)	0.0454 (19)	0.0613 (19)	0.0021 (19)	0.0487 (19)	0.0081 (16)
C13'	0.054 (2)	0.0554 (19)	0.065 (2)	−0.0053 (17)	0.0322 (17)	0.0021 (18)
C14'	0.0436 (17)	0.0484 (17)	0.0459 (15)	0.0035 (14)	0.0168 (13)	0.0064 (14)
C15'	0.0328 (14)	0.0324 (14)	0.0286 (12)	−0.0005 (12)	0.0113 (11)	0.0016 (11)
C16'	0.0334 (17)	0.0389 (16)	0.0373 (13)	−0.0008 (13)	0.0101 (12)	0.0003 (12)
C17'	0.0422 (17)	0.0374 (15)	0.0319 (12)	0.0003 (14)	0.0107 (12)	−0.0014 (13)
C18'	0.0323 (15)	0.0357 (15)	0.0324 (12)	0.0043 (13)	0.0125 (11)	0.0028 (12)
C19'	0.0486 (19)	0.0586 (19)	0.0619 (17)	0.0151 (17)	0.0280 (15)	−0.0040 (17)
C20'	0.0481 (19)	0.078 (2)	0.078 (2)	0.0199 (19)	0.0313 (16)	0.014 (2)

Geometric parameters (Å, º)

O1—C7	1.423 (3)	O2'—C16'	1.216 (3)
O2—C16	1.221 (3)	O3'—C17'	1.227 (3)
O3—C17	1.226 (3)	O4'—C18'	1.319 (3)
O4—C18	1.305 (3)	O4'—C19'	1.461 (3)
O4—C19	1.453 (3)	N'—C15'	1.314 (3)
N—C15	1.315 (3)	N'—C8'	1.475 (3)
N—C8	1.463 (3)	C1'—C2'	1.375 (4)
C1—C6	1.372 (3)	C1'—C6'	1.383 (3)
C1—C2	1.382 (4)	C2'—C3'	1.368 (4)
C2—C3	1.376 (4)	C3'—C4'	1.376 (4)
C3—C4	1.363 (5)	C4'—C5'	1.382 (4)
C4—C5	1.377 (4)	C5'—C6'	1.387 (4)
C5—C6	1.379 (3)	C6'—C7'	1.510 (3)
C6—C7	1.512 (3)	C7'—C8'	1.532 (3)
C7—C8	1.528 (3)	C8'—C9'	1.521 (3)
C8—C9	1.527 (3)	C9'—C14'	1.384 (4)
C9—C10	1.381 (4)	C9'—C10'	1.386 (3)
C9—C14	1.383 (3)	C10'—C11'	1.374 (4)
C10—C11	1.378 (4)	C11'—C12'	1.370 (4)
C11—C12	1.370 (4)	C12'—C13'	1.366 (4)
C12—C13	1.371 (4)	C13'—C14'	1.383 (4)
C13—C14	1.373 (4)	C15'—C18'	1.390 (3)
C15—C18	1.396 (3)	C15'—C16'	1.474 (4)
C15—C16	1.471 (3)	C16'—C17'	1.505 (4)
C16—C17	1.508 (4)	C16'—C18'	2.033 (4)
C17—C18	1.456 (3)	C17'—C18'	1.450 (3)
C19—C20	1.493 (4)	C19'—C20'	1.478 (4)
O1'—C7'	1.423 (3)
C18—O4—C19	116.5 (2)	C3'—C2'—C1'	120.4 (3)
C15—N—C8	124.3 (2)	C2'—C3'—C4'	119.4 (3)
C6—C1—C2	120.8 (3)	C3'—C4'—C5'	120.1 (3)
C3—C2—C1	120.1 (3)	C4'—C5'—C6'	121.1 (3)
C4—C3—C2	119.4 (3)	C1'—C6'—C5'	117.4 (3)
C3—C4—C5	120.5 (3)	C1'—C6'—C7'	121.2 (2)
C4—C5—C6	120.8 (3)	C5'—C6'—C7'	121.3 (2)
C1—C6—C5	118.4 (2)	O1'—C7'—C6'	108.58 (19)
C1—C6—C7	120.8 (2)	O1'—C7'—C8'	106.67 (18)
C5—C6—C7	120.7 (2)	C6'—C7'—C8'	114.2 (2)
O1—C7—C6	111.3 (2)	N'—C8'—C9'	109.79 (19)
O1—C7—C8	105.63 (19)	N'—C8'—C7'	110.92 (18)
C6—C7—C8	113.6 (2)	C9'—C8'—C7'	112.1 (2)
N—C8—C9	111.07 (19)	C14'—C9'—C10'	118.1 (3)
N—C8—C7	109.3 (2)	C14'—C9'—C8'	121.0 (2)
C9—C8—C7	112.38 (19)	C10'—C9'—C8'	120.9 (2)
C10—C9—C14	118.1 (2)	C11'—C10'—C9'	120.4 (3)
C10—C9—C8	120.5 (2)	C12'—C11'—C10'	121.5 (3)
C14—C9—C8	121.4 (2)	C13'—C12'—C11'	118.5 (3)
C11—C10—C9	120.9 (3)	C12'—C13'—C14'	121.1 (3)
C12—C11—C10	120.3 (3)	C13'—C14'—C9'	120.5 (3)
C11—C12—C13	119.4 (3)	N'—C15'—C18'	135.2 (2)
C12—C13—C14	120.5 (3)	N'—C15'—C16'	134.3 (2)
C13—C14—C9	120.8 (3)	C18'—C15'—C16'	90.4 (2)
N—C15—C18	132.8 (2)	O2'—C16'—C15'	134.7 (3)
N—C15—C16	136.5 (2)	O2'—C16'—C17'	136.7 (3)
C18—C15—C16	90.8 (2)	C15'—C16'—C17'	88.5 (2)
O2—C16—C15	135.3 (2)	O2'—C16'—C18'	177.8 (2)
O2—C16—C17	136.1 (2)	C15'—C16'—C18'	43.13 (14)
C15—C16—C17	88.6 (2)	C17'—C16'—C18'	45.41 (15)
O3—C17—C18	137.3 (3)	O3'—C17'—C18'	138.0 (3)
O3—C17—C16	135.7 (2)	O3'—C17'—C16'	135.0 (3)
C18—C17—C16	87.02 (19)	C18'—C17'—C16'	86.9 (2)
O4—C18—C15	127.4 (2)	O4'—C18'—C15'	128.3 (2)
O4—C18—C17	138.9 (2)	O4'—C18'—C17'	137.6 (2)
C15—C18—C17	93.6 (2)	C15'—C18'—C17'	94.1 (2)
O4—C19—C20	106.9 (2)	O4'—C18'—C16'	174.7 (2)
C18'—O4'—C19'	116.72 (19)	C15'—C18'—C16'	46.46 (15)
C15'—N'—C8'	120.86 (19)	C17'—C18'—C16'	47.66 (15)
C2'—C1'—C6'	121.5 (3)	O4'—C19'—C20'	108.5 (3)
C6—C1—C2—C3	1.5 (5)	C4'—C5'—C6'—C1'	1.4 (4)
C1—C2—C3—C4	−0.6 (5)	C4'—C5'—C6'—C7'	−174.4 (2)
C2—C3—C4—C5	−0.2 (5)	C1'—C6'—C7'—O1'	−144.5 (2)
C3—C4—C5—C6	0.3 (5)	C5'—C6'—C7'—O1'	31.2 (3)
C2—C1—C6—C5	−1.5 (4)	C1'—C6'—C7'—C8'	96.7 (3)
C2—C1—C6—C7	176.9 (3)	C5'—C6'—C7'—C8'	−87.7 (3)
C4—C5—C6—C1	0.6 (4)	C15'—N'—C8'—C9'	−86.4 (3)
C4—C5—C6—C7	−177.8 (3)	C15'—N'—C8'—C7'	149.2 (2)
C1—C6—C7—O1	−122.5 (3)	O1'—C7'—C8'—N'	−177.2 (2)
C5—C6—C7—O1	55.9 (3)	C6'—C7'—C8'—N'	−57.2 (3)
C1—C6—C7—C8	118.5 (3)	O1'—C7'—C8'—C9'	59.7 (2)
C5—C6—C7—C8	−63.2 (3)	C6'—C7'—C8'—C9'	179.7 (2)
C15—N—C8—C9	−106.2 (3)	N'—C8'—C9'—C14'	−55.8 (3)
C15—N—C8—C7	129.2 (2)	C7'—C8'—C9'—C14'	67.9 (3)
O1—C7—C8—N	−176.97 (19)	N'—C8'—C9'—C10'	123.9 (2)
C6—C7—C8—N	−54.7 (2)	C7'—C8'—C9'—C10'	−112.4 (2)
O1—C7—C8—C9	59.3 (2)	C14'—C9'—C10'—C11'	−0.1 (4)
C6—C7—C8—C9	−178.5 (2)	C8'—C9'—C10'—C11'	−179.8 (3)
N—C8—C9—C10	140.4 (2)	C9'—C10'—C11'—C12'	1.1 (5)
C7—C8—C9—C10	−96.8 (3)	C10'—C11'—C12'—C13'	−1.6 (5)
N—C8—C9—C14	−39.4 (3)	C11'—C12'—C13'—C14'	1.0 (4)
C7—C8—C9—C14	83.4 (3)	C12'—C13'—C14'—C9'	−0.1 (4)
C14—C9—C10—C11	−0.7 (4)	C10'—C9'—C14'—C13'	−0.4 (4)
C8—C9—C10—C11	179.5 (2)	C8'—C9'—C14'—C13'	179.3 (2)
C9—C10—C11—C12	0.8 (5)	C8'—N'—C15'—C18'	169.2 (3)
C10—C11—C12—C13	−0.1 (5)	C8'—N'—C15'—C16'	−13.0 (4)
C11—C12—C13—C14	−0.7 (5)	N'—C15'—C16'—O2'	2.1 (5)
C12—C13—C14—C9	0.7 (5)	C18'—C15'—C16'—O2'	−179.5 (3)
C10—C9—C14—C13	0.0 (4)	N'—C15'—C16'—C17'	−177.2 (3)
C8—C9—C14—C13	179.8 (3)	C18'—C15'—C16'—C17'	1.3 (2)
C8—N—C15—C18	168.6 (3)	N'—C15'—C16'—C18'	−178.5 (4)
C8—N—C15—C16	−11.3 (5)	O2'—C16'—C17'—O3'	−2.7 (6)
N—C15—C16—O2	−1.4 (6)	C15'—C16'—C17'—O3'	176.5 (3)
C18—C15—C16—O2	178.7 (3)	C18'—C16'—C17'—O3'	177.7 (4)
N—C15—C16—C17	178.6 (3)	O2'—C16'—C17'—C18'	179.6 (3)
C18—C15—C16—C17	−1.3 (2)	C15'—C16'—C17'—C18'	−1.2 (2)
O2—C16—C17—O3	2.2 (6)	C19'—O4'—C18'—C15'	−172.6 (3)
C15—C16—C17—O3	−177.8 (3)	C19'—O4'—C18'—C17'	7.5 (4)
O2—C16—C17—C18	−178.8 (3)	C19'—O4'—C18'—C16'	−162 (2)
C15—C16—C17—C18	1.2 (2)	N'—C15'—C18'—O4'	−2.8 (5)
C19—O4—C18—C15	−179.2 (2)	C16'—C15'—C18'—O4'	178.7 (3)
C19—O4—C18—C17	−0.8 (5)	N'—C15'—C18'—C17'	177.1 (3)
N—C15—C18—O4	0.4 (5)	C16'—C15'—C18'—C17'	−1.4 (2)
C16—C15—C18—O4	−179.7 (3)	N'—C15'—C18'—C16'	178.5 (4)
N—C15—C18—C17	−178.5 (3)	O3'—C17'—C18'—O4'	3.7 (6)
C16—C15—C18—C17	1.3 (2)	C16'—C17'—C18'—O4'	−178.7 (3)
O3—C17—C18—O4	−1.0 (6)	O3'—C17'—C18'—C15'	−176.3 (3)
C16—C17—C18—O4	180.0 (3)	C16'—C17'—C18'—C15'	1.3 (2)
O3—C17—C18—C15	177.7 (3)	O3'—C17'—C18'—C16'	−177.6 (4)
C16—C17—C18—C15	−1.3 (2)	O2'—C16'—C18'—O4'	−1 (8)
C18—O4—C19—C20	−162.0 (2)	C15'—C16'—C18'—O4'	−11 (2)
C6'—C1'—C2'—C3'	−0.2 (4)	C17'—C16'—C18'—O4'	171 (2)
C1'—C2'—C3'—C4'	1.8 (5)	O2'—C16'—C18'—C15'	10 (6)
C2'—C3'—C4'—C5'	−1.8 (5)	C17'—C16'—C18'—C15'	−178.2 (3)
C3'—C4'—C5'—C6'	0.2 (5)	O2'—C16'—C18'—C17'	−172 (6)
C2'—C1'—C6'—C5'	−1.4 (4)	C15'—C16'—C18'—C17'	178.2 (3)
C2'—C1'—C6'—C7'	174.4 (2)	C18'—O4'—C19'—C20'	157.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O3^i	0.82	2.01	2.811 (3)	165
O1′—H1′O···O3′^ii	0.82	1.95	2.764 (3)	173
N—H···O2′^iii	0.86	2.06	2.907 (3)	169
N′—H′···O2	0.86	2.15	2.968 (3)	159

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