Design of peptides with [alpha],[beta]-de­hydro residues: a dipeptide with a branched [beta]-carbon de­hydro residue at the (i+1) position, methyl N-(benzyloxycarbonyl)-[alpha],[beta]-dide­hydro­valyl-L-tryptophanate

The structure of the title peptide, C₂₅H₂₇N₃O₅, has been determined and its conformation analysed. Values of the standard peptide torsion angles are [varphi]₁ = -44.2 (3)°, [psi]₁ = 135.9 (2)°, [varphi]₂ = -141.6 (2)° and [psi]₂^T = 168.0 (2)°. The crystal structure is stabilized by an intermolecular hydrogen bond, with an N...O distance of 2.919 (3) Å, which is formed between screw-axis-related NH and CO groups of de­hydro­valine residues.

S1. Comment

α,β-Dehydroamino acids are strong inducers of folded conformations in peptides. A set of design rules have been developed with dehydrophenylalanine (ΔPhe), dehydroleucine (ΔLeu), dehydro-α-aminobutyric acid (ΔAbu) and dehydroalanine (ΔAla) (Singh & Kaur, 1996). However, the branched β-carbon residues such as valine and isoleucine have not been used so far as dehydro residues though the conformational preferences of valine and isoleucine are known to be different than other residues. In order to develop new design rules with dehydrovaline (ΔVal) and dehydroisoleucine (ΔIle), the structure of a dipeptide, (II), with ΔVal has been determined.

The structure (Fig. 1) shows that the C1A—C1B distance of 1.339 (3) Å in ΔVal corresponds to a standard C═C double-bond distance of 1.32 Å (Rose et al., 1985). Due to unfavourable interactions between the atoms of the backbone and those of the side chain, the closing of the angle N1—C1A—C1P to 114.2 (2)° occurs. The other two angles N1—C1A—C1B and C1P—C1A—C1B are 121.3 (2) and 123.5 (2)°, respectively.

The peptide adopts a conformation characterized by torsion angles, ϕ₁ (CP–N1–C1A–C1P) = -44.2 (3)°, ψ₁ (N1–C1A–C1P–N2) = 135.9 (2)°, ϕ₂ (C1P–N2–C2A–C2P) = -141.6 (2)° and ψ₂^T (N2–C2A–C2P–O3T) = 168.0 (2)°. It may be noted that the values of torsion angles of ΔVal correspond to the ϕ,ψ values of an (i+1)t h residue in a β-turn II conformation. It indicates that the ΔVal residue at (i+1) position may promote a β-turn II conformation. The values of torsion angles χ₁^1,1 (N1–C1A–C1B–C1G1) and χ₁^1,2 (N1–C1A–C1B–C1G2) of dehydrovaline are -6.6 (4) and 170.1 (3)°, respectively, and indicate that the side chain of ΔVal is essentially planar.

The crystal packing is stabilized by a hydrophobic region formed by the aromatic rings of tryptophans and benzene rings of carbobenzoxy (Cbz) groups. The packing is further stabilized by an intermolecular hydrogen bond formed between the screw axis related NH and CO groups of ΔVal residue [N1—H1···O1Pⁱ, with N1···OPⁱ = 2.919 (3) Å, H1···O1Pⁱ = 2.16 Å and N1–H1···O1Pⁱ = 147°; symmetry code: (i) -x, y - 1/2, -z + 1/2].

S2. Experimental

The synthesis of Cbz-ΔVal-OH, (I), was carried out by condensation of 2-oxo-3-methylbutanoic acid (1 g, 7.2 mmol) with benzyl carbamate (1.98 g, 10.8 mmol) and p-toluenesulfonic acid (0.47 g, 2.1 mmol) in dry benzene. The reaction mixture was refluxed at 373 K using a Dean–Stark water remover for 8 h. The solution was the extracted with saturated sodium bicarbonate. The extracts were neutralized by adding concentrated HCl dropwise to yield a white solid, which was filtered and recrystallized from benzene. The solid product of Cbz-ΔVal-OH was obtained at a yield of 67%. For the synthesis of Cbz-ΔVal-L-Trp-OCH₃, (II), N-methylmorpholine (0.29 ml, 2.69 mmol) was added to a chilled (263 K) solution of (1) (0.67 g, 2.69 mmol) in tetrahydrofuran. This was followed by the addition of isobutyl chloroformate (0.36 ml, 2.69 mmol) and the resulting solution was stirred for 20 min. A precooled solution of L-Trp-OCH₃·HCl (0.82 g, 3.2 mmol) was added (Trp is L-tryptophan) to the reaction mixture. This was stirred for 2 h at 273 K and then overnight at room temperature. After completion of the reaction (monitored by thin-layer chromatography), the solvent was removed under vacuum; the resulting residual material was dissolved in ethyl acetate and was washed successively with water, 10% sodium bicarbonate, 5% citric acid and water. The organic layer was dried over anhydrous sodium sulfate and then evaporated to yield 72% of compound (2) (m.p. 438 K). The peptide was crystallized from a solution in acetone–water (4:1) by slow evaporation.

S3. Refinement

All H atoms were visible in difference maps and were allowed for as riding atoms (with C—H distances of 0.93–0.98 Å and an N—H distance of 0.86 Å). In this light-atom structure, it was not possible to establish the absolute configuration from the Flack parameter [0.1 (3)]; the configuration chosen and shown in both the Scheme and Fig. 1 was determined by the configuration of the starting material in the synthesis (L-tryptophan).

Computing details

Data collection: SDP (Enraf-Nonius, 1979); cell refinement: SDP; 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.

Figures

Fig. 1. The molecular structure of the designed peptide with the atom-numbering scheme and 30% probability displacement ellipsoids.

Methyl N-(carbobenzoxy)-α,β-didehydrovalyl-L-tryptophanate

Crystal data

C25H27N3O5	F(000) = 952
Mr = 449.50	Dx = 1.315 Mg m^−3
Monoclinic, A2	Cu Kα radiation, λ = 1.54180 Å
a = 17.1524 (9) Å	Cell parameters from 25 reflections
b = 6.1439 (9) Å	θ = 0–25°
c = 22.6183 (11) Å	µ = 0.76 mm^−1
β = 107.791 (12)°	T = 293 K
V = 2269.6 (4) Å^3	Prism, colourless
Z = 4	0.3 × 0.2 × 0.1 mm

Data collection

Enraf Nonius CAD-4 diffractometer	2434 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 75.6°, θmin = 2.7°
ω–2θ scans	h = 0→21
Absorption correction: empirical (using intensity measurements) (SDP; Enraf-Nonius, 1979)	k = 0→7
Tmin = 0.835, Tmax = 0.928	l = −28→26
2576 measured reflections	3 standard reflections every 60 min
2576 independent reflections	intensity decay: none

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)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.146	w = 1/[σ^2(Fo^2) + (0.1137P)^2 + 0.5403P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2576 reflections	Δρmax = 0.24 e Å^−3
302 parameters	Δρmin = −0.25 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (4)

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
C1	0.25344 (16)	−0.1196 (5)	0.42144 (11)	0.0412 (6)
C2	0.32078 (19)	−0.0895 (7)	0.47407 (13)	0.0520 (7)
H2	0.3237	0.0346	0.4982	0.062*
C3	0.38262 (19)	−0.2397 (8)	0.49081 (15)	0.0614 (9)
H3	0.4270	−0.2171	0.5261	0.074*
C4	0.37927 (19)	−0.4229 (8)	0.45567 (16)	0.0605 (9)
H4	0.4210	−0.5256	0.4673	0.073*
C5	0.31380 (19)	−0.4548 (7)	0.40293 (15)	0.0550 (8)
H5	0.3119	−0.5780	0.3786	0.066*
C6	0.25112 (17)	−0.3042 (6)	0.38619 (13)	0.0467 (7)
H6	0.2069	−0.3274	0.3508	0.056*
C	0.18659 (18)	0.0482 (6)	0.40716 (11)	0.0488 (7)
HA	0.1613	0.0466	0.4401	0.059*
HB	0.2109	0.1907	0.4072	0.059*
O	0.12362 (11)	0.0172 (4)	0.34845 (8)	0.0448 (5)
CP	0.14020 (15)	0.1042 (5)	0.29894 (11)	0.0378 (5)
OP	0.20673 (11)	0.1712 (5)	0.29888 (9)	0.0502 (5)
N1	0.07163 (12)	0.1100 (4)	0.24917 (10)	0.0368 (5)
H1	0.0282	0.0436	0.2509	0.044*
C1A	0.07046 (13)	0.2234 (4)	0.19467 (11)	0.0326 (5)
C1B	0.02481 (16)	0.1545 (5)	0.13862 (12)	0.0401 (6)
C1G1	−0.0201 (2)	−0.0575 (6)	0.13009 (15)	0.0550 (8)
H1G1	0.0027	−0.1478	0.1658	0.082*
H1G2	−0.0150	−0.1295	0.0938	0.082*
H1G3	−0.0769	−0.0312	0.1252	0.082*
C1G2	0.0107 (2)	0.2848 (8)	0.08027 (13)	0.0588 (9)
H1G4	0.0237	0.4347	0.0907	0.088*
H1G5	−0.0457	0.2728	0.0556	0.088*
H1G6	0.0450	0.2303	0.0571	0.088*
C1P	0.10973 (13)	0.4429 (4)	0.20610 (10)	0.0331 (5)
O1P	0.09455 (11)	0.5705 (4)	0.24300 (9)	0.0420 (4)
N2	0.15980 (13)	0.4943 (4)	0.17228 (10)	0.0377 (5)
H2A	0.1713	0.3961	0.1492	0.045*
C2A	0.19466 (15)	0.7091 (5)	0.17368 (12)	0.0386 (6)
H2A1	0.1589	0.8129	0.1857	0.046*
C2B	0.28064 (15)	0.7260 (5)	0.22117 (13)	0.0436 (6)
H2B1	0.3020	0.8708	0.2187	0.052*
H2B2	0.2758	0.7084	0.2625	0.052*
C2G	0.34043 (15)	0.5637 (5)	0.21234 (12)	0.0396 (6)
C2D1	0.35385 (17)	0.3602 (6)	0.23859 (14)	0.0476 (7)
H2D1	0.3251	0.3009	0.2636	0.057*
N2E1	0.41537 (15)	0.2569 (5)	0.22285 (13)	0.0530 (6)
H2E1	0.4328	0.1275	0.2340	0.064*
C2E2	0.44480 (16)	0.3926 (6)	0.18640 (13)	0.0449 (6)
C2D2	0.39879 (15)	0.5870 (5)	0.17815 (12)	0.0390 (5)
C2Z2	0.50991 (18)	0.3654 (7)	0.16256 (15)	0.0543 (8)
H2Z2	0.5406	0.2378	0.1692	0.065*
C2H2	0.5271 (2)	0.5339 (8)	0.12881 (16)	0.0627 (10)
H2H2	0.5702	0.5196	0.1122	0.075*
C2Z3	0.4814 (2)	0.7276 (8)	0.11871 (16)	0.0609 (9)
H2Z3	0.4945	0.8390	0.0956	0.073*
C2E3	0.41698 (18)	0.7539 (6)	0.14292 (14)	0.0488 (7)
H2E3	0.3863	0.8814	0.1357	0.059*
C2P	0.19505 (18)	0.7658 (6)	0.10838 (15)	0.0460 (7)
O2P	0.18347 (19)	0.6408 (6)	0.06631 (11)	0.0758 (8)
O3T	0.21165 (17)	0.9766 (5)	0.10509 (13)	0.0645 (7)
C3T	0.2174 (3)	1.0508 (10)	0.0458 (2)	0.0917 (16)
H3T1	0.2645	0.9864	0.0383	0.137*
H3T2	0.2226	1.2064	0.0463	0.137*
H3T3	0.1690	1.0088	0.0134	0.137*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0401 (12)	0.0487 (15)	0.0352 (11)	−0.0046 (13)	0.0122 (10)	0.0028 (12)
C2	0.0498 (15)	0.0600 (19)	0.0421 (13)	−0.0093 (16)	0.0081 (11)	−0.0052 (14)
C3	0.0416 (15)	0.086 (3)	0.0485 (15)	−0.0040 (18)	0.0021 (11)	0.0019 (18)
C4	0.0424 (14)	0.078 (2)	0.0601 (16)	0.0105 (17)	0.0146 (13)	0.0085 (19)
C5	0.0533 (16)	0.0576 (19)	0.0559 (15)	−0.0002 (16)	0.0193 (12)	−0.0053 (16)
C6	0.0419 (13)	0.0532 (17)	0.0419 (12)	−0.0074 (14)	0.0080 (10)	−0.0017 (13)
C	0.0528 (15)	0.0554 (18)	0.0365 (11)	0.0038 (15)	0.0110 (10)	0.0044 (13)
O	0.0418 (9)	0.0535 (12)	0.0392 (8)	0.0018 (9)	0.0124 (7)	0.0120 (9)
CP	0.0349 (11)	0.0405 (14)	0.0392 (11)	0.0038 (11)	0.0131 (9)	0.0061 (10)
OP	0.0330 (9)	0.0658 (14)	0.0498 (10)	−0.0062 (10)	0.0096 (7)	0.0124 (11)
N1	0.0296 (9)	0.0423 (12)	0.0390 (10)	−0.0033 (9)	0.0113 (8)	0.0032 (9)
C1A	0.0261 (9)	0.0348 (13)	0.0379 (11)	0.0018 (9)	0.0114 (8)	0.0008 (10)
C1B	0.0348 (11)	0.0445 (15)	0.0405 (12)	−0.0017 (11)	0.0109 (9)	−0.0017 (12)
C1G1	0.0498 (16)	0.0515 (18)	0.0573 (15)	−0.0133 (15)	0.0069 (13)	−0.0080 (15)
C1G2	0.0563 (17)	0.078 (2)	0.0357 (12)	−0.0079 (18)	0.0050 (11)	0.0038 (15)
C1P	0.0273 (10)	0.0367 (13)	0.0346 (10)	0.0031 (10)	0.0084 (8)	0.0027 (10)
O1P	0.0410 (9)	0.0409 (10)	0.0486 (9)	−0.0014 (9)	0.0205 (7)	−0.0040 (9)
N2	0.0350 (10)	0.0375 (12)	0.0457 (10)	−0.0034 (9)	0.0198 (8)	−0.0001 (9)
C2A	0.0341 (11)	0.0354 (13)	0.0509 (13)	−0.0023 (10)	0.0199 (10)	0.0028 (11)
C2B	0.0372 (12)	0.0448 (16)	0.0512 (14)	−0.0054 (12)	0.0172 (10)	−0.0069 (12)
C2G	0.0336 (11)	0.0383 (13)	0.0450 (12)	−0.0036 (11)	0.0091 (9)	−0.0002 (11)
C2D1	0.0395 (13)	0.0467 (15)	0.0552 (15)	−0.0026 (13)	0.0126 (11)	0.0095 (14)
N2E1	0.0446 (12)	0.0420 (13)	0.0677 (15)	0.0045 (12)	0.0105 (11)	0.0077 (13)
C2E2	0.0354 (12)	0.0451 (16)	0.0499 (13)	−0.0040 (12)	0.0065 (10)	−0.0057 (13)
C2D2	0.0324 (11)	0.0402 (13)	0.0421 (12)	−0.0038 (11)	0.0081 (9)	−0.0032 (11)
C2Z2	0.0390 (13)	0.061 (2)	0.0604 (17)	0.0062 (15)	0.0118 (12)	−0.0130 (17)
C2H2	0.0469 (15)	0.085 (3)	0.0636 (17)	−0.0051 (19)	0.0275 (14)	−0.019 (2)
C2Z3	0.0548 (17)	0.078 (3)	0.0573 (17)	−0.0141 (19)	0.0281 (14)	0.0033 (19)
C2E3	0.0439 (14)	0.0493 (17)	0.0546 (15)	−0.0054 (14)	0.0169 (11)	0.0040 (14)
C2P	0.0399 (13)	0.0473 (15)	0.0540 (15)	0.0007 (13)	0.0188 (11)	0.0119 (14)
O2P	0.097 (2)	0.080 (2)	0.0558 (13)	−0.0109 (18)	0.0316 (13)	0.0013 (15)
O3T	0.0718 (15)	0.0503 (14)	0.0840 (16)	0.0009 (13)	0.0425 (13)	0.0228 (13)
C3T	0.102 (3)	0.088 (4)	0.106 (3)	0.023 (3)	0.063 (3)	0.053 (3)

Geometric parameters (Å, º)

C1—C6	1.380 (5)	C1P—N2	1.351 (3)
C1—C2	1.395 (4)	N2—C2A	1.445 (4)
C1—C	1.502 (4)	N2—H2A	0.86
C2—C3	1.369 (5)	C2A—C2P	1.520 (4)
C2—H2	0.93	C2A—C2B	1.540 (4)
C3—C4	1.369 (6)	C2A—H2A1	0.98
C3—H3	0.93	C2B—C2G	1.487 (4)
C4—C5	1.380 (5)	C2B—H2B1	0.97
C4—H4	0.93	C2B—H2B2	0.97
C5—C6	1.381 (5)	C2G—C2D1	1.373 (5)
C5—H5	0.93	C2G—C2D2	1.447 (4)
C6—H6	0.93	C2D1—N2E1	1.368 (4)
C—O	1.446 (3)	C2D1—H2D1	0.93
C—HA	0.97	N2E1—C2E2	1.373 (4)
C—HB	0.97	N2E1—H2E1	0.86
O—CP	1.347 (3)	C2E2—C2Z2	1.391 (4)
CP—OP	1.214 (3)	C2E2—C2D2	1.412 (4)
CP—N1	1.357 (3)	C2D2—C2E3	1.391 (4)
N1—C1A	1.411 (3)	C2Z2—C2H2	1.371 (6)
N1—H1	0.86	C2Z2—H2Z2	0.93
C1A—C1B	1.339 (3)	C2H2—C2Z3	1.405 (6)
C1A—C1P	1.494 (3)	C2H2—H2H2	0.93
C1B—C1G1	1.495 (4)	C2Z3—C2E3	1.384 (4)
C1B—C1G2	1.499 (4)	C2Z3—H2Z3	0.93
C1G1—H1G1	0.96	C2E3—H2E3	0.93
C1G1—H1G2	0.96	C2P—O2P	1.191 (5)
C1G1—H1G3	0.96	C2P—O3T	1.333 (4)
C1G2—H1G4	0.96	O3T—C3T	1.449 (4)
C1G2—H1G5	0.96	C3T—H3T1	0.96
C1G2—H1G6	0.96	C3T—H3T2	0.96
C1P—O1P	1.229 (3)	C3T—H3T3	0.96
C6—C1—C2	118.2 (3)	C1P—N2—C2A	122.1 (2)
C6—C1—C	123.7 (2)	C1P—N2—H2A	118.9
C2—C1—C	118.1 (3)	C2A—N2—H2A	118.9
C3—C2—C1	121.1 (3)	N2—C2A—C2P	108.2 (2)
C3—C2—H2	119.5	N2—C2A—C2B	112.3 (2)
C1—C2—H2	119.5	C2P—C2A—C2B	112.0 (2)
C2—C3—C4	120.1 (3)	N2—C2A—H2A1	108.1
C2—C3—H3	119.9	C2P—C2A—H2A1	108.1
C4—C3—H3	119.9	C2B—C2A—H2A1	108.1
C3—C4—C5	119.8 (4)	C2G—C2B—C2A	114.4 (2)
C3—C4—H4	120.1	C2G—C2B—H2B1	108.6
C5—C4—H4	120.1	C2A—C2B—H2B1	108.6
C4—C5—C6	120.1 (4)	C2G—C2B—H2B2	108.6
C4—C5—H5	119.9	C2A—C2B—H2B2	108.6
C6—C5—H5	119.9	H2B1—C2B—H2B2	107.6
C1—C6—C5	120.7 (3)	C2D1—C2G—C2D2	105.6 (3)
C1—C6—H6	119.7	C2D1—C2G—C2B	125.7 (3)
C5—C6—H6	119.7	C2D2—C2G—C2B	128.6 (3)
O—C—C1	114.5 (3)	N2E1—C2D1—C2G	110.5 (3)
O—C—HA	108.6	N2E1—C2D1—H2D1	124.7
C1—C—HA	108.6	C2G—C2D1—H2D1	124.7
O—C—HB	108.6	C2D1—N2E1—C2E2	109.2 (3)
C1—C—HB	108.6	C2D1—N2E1—H2E1	125.4
HA—C—HB	107.6	C2E2—N2E1—H2E1	125.4
CP—O—C	115.0 (2)	N2E1—C2E2—C2Z2	130.2 (3)
OP—CP—O	125.0 (2)	N2E1—C2E2—C2D2	107.4 (3)
OP—CP—N1	124.5 (2)	C2Z2—C2E2—C2D2	122.2 (3)
O—CP—N1	110.5 (2)	C2E3—C2D2—C2E2	119.0 (3)
CP—N1—C1A	121.0 (2)	C2E3—C2D2—C2G	133.8 (3)
CP—N1—H1	119.5	C2E2—C2D2—C2G	107.2 (3)
C1A—N1—H1	119.5	C2H2—C2Z2—C2E2	117.4 (3)
C1B—C1A—N1	121.3 (2)	C2H2—C2Z2—H2Z2	121.3
C1B—C1A—C1P	123.5 (2)	C2E2—C2Z2—H2Z2	121.3
N1—C1A—C1P	114.2 (2)	C2Z2—C2H2—C2Z3	121.7 (3)
C1A—C1B—C1G1	121.8 (3)	C2Z2—C2H2—H2H2	119.1
C1A—C1B—C1G2	123.7 (3)	C2Z3—C2H2—H2H2	119.1
C1G1—C1B—C1G2	114.4 (3)	C2E3—C2Z3—C2H2	120.5 (4)
C1B—C1G1—H1G1	109.5	C2E3—C2Z3—H2Z3	119.7
C1B—C1G1—H1G2	109.5	C2H2—C2Z3—H2Z3	119.7
H1G1—C1G1—H1G2	109.5	C2Z3—C2E3—C2D2	119.1 (3)
C1B—C1G1—H1G3	109.5	C2Z3—C2E3—H2E3	120.4
H1G1—C1G1—H1G3	109.5	C2D2—C2E3—H2E3	120.4
H1G2—C1G1—H1G3	109.5	O2P—C2P—O3T	124.6 (3)
C1B—C1G2—H1G4	109.5	O2P—C2P—C2A	125.4 (3)
C1B—C1G2—H1G5	109.5	O3T—C2P—C2A	110.0 (3)
H1G4—C1G2—H1G5	109.5	C2P—O3T—C3T	115.7 (4)
C1B—C1G2—H1G6	109.5	O3T—C3T—H3T1	109.5
H1G4—C1G2—H1G6	109.5	O3T—C3T—H3T2	109.5
H1G5—C1G2—H1G6	109.5	H3T1—C3T—H3T2	109.5
O1P—C1P—N2	122.6 (3)	O3T—C3T—H3T3	109.5
O1P—C1P—C1A	121.0 (2)	H3T1—C3T—H3T3	109.5
N2—C1P—C1A	116.4 (2)	H3T2—C3T—H3T3	109.5
C6—C1—C2—C3	−0.6 (5)	C2P—C2A—C2B—C2G	−66.3 (3)
C—C1—C2—C3	178.0 (3)	C2A—C2B—C2G—C2D1	−89.7 (3)
C1—C2—C3—C4	0.2 (5)	C2A—C2B—C2G—C2D2	93.8 (3)
C2—C3—C4—C5	0.7 (6)	C2D2—C2G—C2D1—N2E1	−0.4 (3)
C3—C4—C5—C6	−1.1 (5)	C2B—C2G—C2D1—N2E1	−177.5 (3)
C2—C1—C6—C5	0.2 (4)	C2G—C2D1—N2E1—C2E2	0.9 (3)
C—C1—C6—C5	−178.3 (3)	C2D1—N2E1—C2E2—C2Z2	175.6 (3)
C4—C5—C6—C1	0.6 (5)	C2D1—N2E1—C2E2—C2D2	−1.1 (3)
C6—C1—C—O	−7.9 (4)	N2E1—C2E2—C2D2—C2E3	179.6 (2)
C2—C1—C—O	173.6 (2)	C2Z2—C2E2—C2D2—C2E3	2.6 (4)
C1—C—O—CP	−85.5 (3)	N2E1—C2E2—C2D2—C2G	0.8 (3)
C—O—CP—OP	12.5 (4)	C2Z2—C2E2—C2D2—C2G	−176.1 (3)
C—O—CP—N1	−166.4 (2)	C2D1—C2G—C2D2—C2E3	−178.8 (3)
OP—CP—N1—C1A	−8.6 (4)	C2B—C2G—C2D2—C2E3	−1.8 (5)
O—CP—N1—C1A	170.4 (2)	C2D1—C2G—C2D2—C2E2	−0.3 (3)
CP—N1—C1A—C1B	147.4 (3)	C2B—C2G—C2D2—C2E2	176.7 (3)
CP—N1—C1A—C1P	−44.2 (3)	N2E1—C2E2—C2Z2—C2H2	−177.9 (3)
N1—C1A—C1B—C1G1	−6.6 (4)	C2D2—C2E2—C2Z2—C2H2	−1.7 (4)
C1P—C1A—C1B—C1G1	−173.9 (2)	C2E2—C2Z2—C2H2—C2Z3	0.3 (5)
N1—C1A—C1B—C1G2	170.1 (3)	C2Z2—C2H2—C2Z3—C2E3	0.1 (5)
C1P—C1A—C1B—C1G2	2.8 (4)	C2H2—C2Z3—C2E3—C2D2	0.9 (5)
C1B—C1A—C1P—O1P	121.8 (3)	C2E2—C2D2—C2E3—C2Z3	−2.1 (4)
N1—C1A—C1P—O1P	−46.4 (3)	C2G—C2D2—C2E3—C2Z3	176.2 (3)
C1B—C1A—C1P—N2	−56.0 (3)	N2—C2A—C2P—O2P	−13.0 (4)
N1—C1A—C1P—N2	135.9 (2)	C2B—C2A—C2P—O2P	111.3 (4)
O1P—C1P—N2—C2A	−4.5 (4)	N2—C2A—C2P—O3T	168.0 (2)
C1A—C1P—N2—C2A	173.1 (2)	C2B—C2A—C2P—O3T	−67.8 (3)
C1P—N2—C2A—C2P	−141.6 (2)	O2P—C2P—O3T—C3T	−1.6 (5)
C1P—N2—C2A—C2B	94.3 (3)	C2A—C2P—O3T—C3T	177.4 (3)
N2—C2A—C2B—C2G	55.7 (3)