N-{N-[N-(1,1-Dimethyl-ethoxy-carbon-yl)-l-leuc-yl]-N-methyl-l-leuc-yl}-N-methyl-l-leucine benzyl ester.

The tripeptide title compound, C(32)H(53)N(3)O(6), synthesized in 80% yield by coupling of N-methyl-l-leucine benzyl ester with tert-butoxy-carbonyl-l-leucyl-N-methyl-l-leucine at 273 K, conjugates through two amide linkages and includes two protecting groups: a tert-butyl-oxycarbonyl group at the C-tip and a benzyl group at the N-tip. A classical inter-molecular N-H⋯O hydrogen bond and a weak non-conventional inter-molecular C-H⋯O contact connect the mol-ecules, forming layers parallel to (001).

Related literature

For the structure of a related dipeptide, see: Liao et al. (2007 ▶). For the synthesis of linear peptide fragments of cyclic penta­peptide, see: Xu et al. (2008 ▶).

Experimental

Crystal data

C32H53N3O6

M = 575.77

Trigonal,

a = 13.9784 (3) Å

c = 30.4763 (15) Å

V = 5157.1 (3) Å3

Z = 6

Mo Kα radiation

μ = 0.08 mm−1

T = 173 (2) K

0.47 × 0.42 × 0.26 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.965, T max = 0.981

27507 measured reflections

4232 independent reflections

3541 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.138

S = 1.05

4232 reflections

381 parameters

18 restraints

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034247/si2119sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034247/si2119Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C32H53N3O6	Dx = 1.112 Mg m−3
Mr = 575.77	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3121	Cell parameters from 5764 reflections
Hall symbol: P 31 2"	θ = 2.2–26.7°
a = 13.9784 (3) Å	µ = 0.08 mm−1
c = 30.4763 (15) Å	T = 173 K
V = 5157.1 (3) Å3	Block, colorless
Z = 6	0.47 × 0.42 × 0.26 mm
F(000) = 1884

Bruker SMART 1000 CCD diffractometer	4232 independent reflections
Radiation source: fine-focus sealed tube	3541 reflections with I > 2σ(I)
graphite	Rint = 0.032
ω scans	θmax = 27.1°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→13
Tmin = 0.965, Tmax = 0.981	k = −17→17
27507 measured reflections	l = −39→23

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.076P)2 + 1.5629P] where P = (Fo2 + 2Fc2)/3
4232 reflections	(Δ/σ)max < 0.001
381 parameters	Δρmax = 0.43 e Å−3
18 restraints	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.2754 (3)	0.1859 (3)	0.23021 (11)	0.0520 (8)
H1	0.3538	0.2238	0.2318	0.062*
C2	0.2238 (4)	0.2413 (3)	0.21488 (13)	0.0598 (10)
H2	0.2666	0.3165	0.2064	0.072*
C3	0.1141 (4)	0.1899 (4)	0.2119 (2)	0.0928 (17)
H3	0.0784	0.2276	0.2010	0.111*
C4	0.0541 (4)	0.0827 (5)	0.2248 (3)	0.130 (3)
H4	−0.0242	0.0461	0.2234	0.156*
C5	0.1050 (4)	0.0259 (4)	0.2399 (2)	0.1001 (19)
H5	0.0617	−0.0496	0.2480	0.120*
C6	0.2170 (3)	0.0782 (3)	0.24319 (12)	0.0505 (8)
C7	0.2703 (3)	0.0129 (3)	0.25971 (12)	0.0519 (8)
H7A	0.2490	−0.0099	0.2906	0.062*
H7B	0.2463	−0.0542	0.2416	0.062*
C8	0.4532 (3)	0.0463 (3)	0.26799 (10)	0.0437 (7)
C9	0.5736 (3)	0.1334 (2)	0.26120 (9)	0.0360 (6)
H9	0.5924	0.1264	0.2301	0.043*
C10	0.6515 (3)	0.1151 (3)	0.29028 (10)	0.0457 (8)
H10A	0.6264	0.0352	0.2910	0.055*
H10B	0.6474	0.1384	0.3206	0.055*
C11	0.7710 (3)	0.1778 (3)	0.27493 (11)	0.0511 (8)
H11	0.7880	0.2533	0.2656	0.061*
C12	0.8493 (4)	0.1908 (5)	0.31243 (15)	0.0809 (14)
H12A	0.8332	0.1177	0.3225	0.121*
H12B	0.8392	0.2308	0.3367	0.121*
H12C	0.9259	0.2323	0.3020	0.121*
C13	0.7895 (4)	0.1226 (5)	0.23608 (13)	0.0694 (12)
H13A	0.7761	0.0493	0.2447	0.104*
H13B	0.8658	0.1675	0.2258	0.104*
H13C	0.7385	0.1149	0.2124	0.104*
C14	0.5605 (3)	0.2723 (3)	0.30884 (9)	0.0432 (7)
H14A	0.6278	0.3280	0.3236	0.065*
H14B	0.5241	0.2056	0.3270	0.065*
H14C	0.5104	0.3015	0.3045	0.065*
C15	0.6162 (2)	0.3192 (2)	0.23346 (9)	0.0321 (6)
C16	0.6491 (2)	0.2951 (2)	0.18839 (8)	0.0298 (5)
H16	0.6844	0.2488	0.1929	0.036*
C17	0.7328 (2)	0.4028 (2)	0.16595 (9)	0.0379 (6)
H17A	0.6977	0.4481	0.1603	0.045*
H17B	0.7961	0.4449	0.1859	0.045*
C18	0.7752 (3)	0.3829 (3)	0.12259 (10)	0.0412 (7)
H18	0.7100	0.3250	0.1061	0.049*
C19	0.8540 (4)	0.3405 (4)	0.12951 (13)	0.0650 (10)
H19A	0.8768	0.3262	0.1010	0.097*
H19B	0.8174	0.2719	0.1465	0.097*
H19C	0.9191	0.3958	0.1455	0.097*
C20	0.8274 (4)	0.4870 (4)	0.09480 (13)	0.0723 (13)
H20A	0.8921	0.5452	0.1100	0.108*
H20B	0.7736	0.5114	0.0899	0.108*
H20C	0.8502	0.4716	0.0665	0.108*
C21	0.4911 (3)	0.2895 (3)	0.14652 (9)	0.0365 (6)
H21A	0.5140	0.3169	0.1166	0.055*
H21B	0.5089	0.3517	0.1662	0.055*
H21C	0.4113	0.2378	0.1471	0.055*
C22	0.5311 (2)	0.1349 (2)	0.14422 (8)	0.0296 (5)
C23	0.4365 (2)	0.0770 (2)	0.11090 (8)	0.0294 (5)
H23	0.4220	0.1331	0.0968	0.035*
C24	0.3335 (2)	−0.0066 (2)	0.13576 (9)	0.0317 (6)
H24A	0.3193	0.0325	0.1597	0.038*
H24B	0.3488	−0.0618	0.1494	0.038*
C25	0.2289 (2)	−0.0677 (3)	0.10791 (9)	0.0378 (6)
H25	0.2416	−0.1116	0.0851	0.045*
C26	0.1327 (3)	−0.1472 (3)	0.13673 (11)	0.0447 (7)
H26A	0.1177	−0.1054	0.1587	0.067*
H26B	0.1517	−0.1978	0.1515	0.067*
H26C	0.0670	−0.1897	0.1185	0.067*
C27	0.2013 (3)	0.0120 (4)	0.08478 (14)	0.0685 (12)
H27A	0.1348	−0.0299	0.0669	0.103*
H27B	0.2632	0.0616	0.0659	0.103*
H27C	0.1882	0.0555	0.1067	0.103*
C28	0.5515 (2)	0.0915 (2)	0.05042 (8)	0.0335 (6)
C29	0.6809 (3)	0.0907 (3)	−0.00321 (9)	0.0383 (6)
C30	0.7820 (3)	0.1894 (3)	0.01674 (10)	0.0512 (8)
H30A	0.7653	0.2483	0.0229	0.077*
H30B	0.8439	0.2164	−0.0039	0.077*
H30C	0.8020	0.1668	0.0441	0.077*
C31	0.7080 (3)	0.0009 (3)	−0.01504 (10)	0.0463 (8)
H31A	0.7347	−0.0194	0.0111	0.069*
H31B	0.7653	0.0285	−0.0377	0.069*
H31C	0.6414	−0.0641	−0.0261	0.069*
C32	0.6356 (3)	0.1225 (3)	−0.04226 (10)	0.0460 (7)
H32A	0.5678	0.0576	−0.0526	0.069*
H32B	0.6905	0.1501	−0.0659	0.069*
H32C	0.6192	0.1803	−0.0336	0.069*
N1	0.5894 (2)	0.24496 (19)	0.26592 (7)	0.0338 (5)
N2	0.54989 (18)	0.23237 (18)	0.16121 (7)	0.0288 (5)
N3	0.46804 (19)	0.02448 (19)	0.07749 (7)	0.0302 (5)
H3A	0.4344	−0.0479	0.0749	0.036*
O1	0.38691 (19)	0.08380 (19)	0.25637 (8)	0.0500 (6)
O2	0.4211 (3)	−0.0461 (2)	0.27986 (13)	0.0891 (11)
O3	0.61650 (19)	0.40624 (17)	0.23920 (6)	0.0398 (5)
O4	0.58401 (17)	0.09059 (17)	0.15495 (7)	0.0391 (5)
O5	0.5840 (2)	0.18927 (17)	0.04605 (7)	0.0438 (5)
O6	0.59298 (17)	0.03485 (17)	0.02975 (6)	0.0362 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0459 (19)	0.056 (2)	0.0467 (17)	0.0203 (18)	0.0047 (15)	0.0046 (15)
C2	0.059 (2)	0.052 (2)	0.067 (2)	0.0271 (19)	−0.0005 (19)	−0.0033 (18)
C3	0.054 (3)	0.055 (3)	0.167 (5)	0.027 (2)	−0.005 (3)	0.003 (3)
C4	0.048 (3)	0.078 (4)	0.262 (8)	0.029 (3)	0.006 (4)	0.030 (4)
C5	0.042 (2)	0.051 (3)	0.198 (6)	0.016 (2)	0.014 (3)	0.022 (3)
C6	0.0374 (17)	0.0439 (19)	0.0607 (19)	0.0131 (15)	0.0018 (15)	−0.0149 (15)
C7	0.0398 (18)	0.0465 (19)	0.0574 (19)	0.0124 (16)	0.0059 (15)	0.0048 (16)
C8	0.0471 (18)	0.0354 (16)	0.0453 (16)	0.0181 (14)	−0.0030 (14)	0.0052 (13)
C9	0.0430 (16)	0.0338 (15)	0.0351 (14)	0.0221 (13)	0.0023 (12)	0.0029 (11)
C10	0.0532 (19)	0.0512 (19)	0.0404 (15)	0.0319 (16)	−0.0035 (14)	0.0060 (14)
C11	0.049 (2)	0.058 (2)	0.0544 (18)	0.0330 (18)	−0.0101 (15)	−0.0005 (16)
C12	0.069 (3)	0.102 (4)	0.082 (3)	0.051 (3)	−0.031 (2)	−0.016 (3)
C13	0.064 (3)	0.108 (4)	0.061 (2)	0.061 (3)	−0.001 (2)	−0.001 (2)
C14	0.0485 (18)	0.0439 (17)	0.0366 (14)	0.0227 (15)	0.0067 (13)	−0.0019 (13)
C15	0.0271 (13)	0.0327 (14)	0.0364 (13)	0.0149 (11)	−0.0039 (11)	−0.0024 (11)
C16	0.0283 (13)	0.0271 (13)	0.0323 (12)	0.0124 (11)	−0.0015 (10)	−0.0013 (10)
C17	0.0357 (15)	0.0317 (15)	0.0385 (14)	0.0110 (13)	0.0037 (12)	−0.0009 (11)
C18	0.0357 (16)	0.0377 (16)	0.0386 (14)	0.0097 (13)	0.0046 (12)	−0.0005 (12)
C19	0.057 (2)	0.085 (3)	0.061 (2)	0.042 (2)	0.0086 (18)	−0.004 (2)
C20	0.082 (3)	0.062 (3)	0.063 (2)	0.028 (2)	0.032 (2)	0.018 (2)
C21	0.0406 (16)	0.0354 (15)	0.0416 (14)	0.0251 (13)	−0.0056 (12)	−0.0046 (12)
C22	0.0279 (13)	0.0303 (13)	0.0304 (12)	0.0144 (11)	0.0036 (10)	0.0015 (10)
C23	0.0293 (13)	0.0294 (13)	0.0310 (12)	0.0157 (11)	0.0008 (10)	−0.0012 (10)
C24	0.0293 (13)	0.0333 (14)	0.0311 (12)	0.0146 (12)	0.0032 (10)	−0.0004 (11)
C25	0.0286 (14)	0.0444 (17)	0.0366 (14)	0.0154 (13)	0.0020 (11)	−0.0058 (12)
C26	0.0306 (15)	0.0423 (17)	0.0557 (17)	0.0141 (14)	0.0047 (13)	0.0026 (14)
C27	0.0367 (18)	0.080 (3)	0.075 (2)	0.0188 (19)	−0.0063 (18)	0.031 (2)
C28	0.0342 (14)	0.0344 (15)	0.0306 (12)	0.0162 (12)	0.0005 (11)	−0.0011 (11)
C29	0.0335 (15)	0.0444 (17)	0.0325 (13)	0.0161 (13)	0.0068 (11)	0.0034 (12)
C30	0.0382 (17)	0.058 (2)	0.0446 (16)	0.0149 (16)	0.0044 (14)	−0.0013 (15)
C31	0.0451 (18)	0.063 (2)	0.0389 (15)	0.0335 (17)	0.0094 (14)	0.0024 (15)
C32	0.0512 (19)	0.053 (2)	0.0362 (15)	0.0282 (17)	0.0038 (14)	0.0045 (14)
N1	0.0375 (13)	0.0324 (12)	0.0321 (11)	0.0179 (11)	0.0019 (10)	0.0012 (9)
N2	0.0291 (11)	0.0259 (11)	0.0325 (10)	0.0146 (9)	−0.0017 (9)	−0.0004 (9)
N3	0.0294 (11)	0.0267 (11)	0.0313 (10)	0.0115 (10)	0.0029 (9)	−0.0022 (9)
O1	0.0342 (12)	0.0387 (13)	0.0714 (15)	0.0139 (10)	0.0029 (11)	0.0066 (11)
O2	0.0613 (19)	0.0446 (16)	0.145 (3)	0.0144 (14)	−0.0121 (19)	0.0392 (18)
O3	0.0495 (13)	0.0329 (10)	0.0424 (10)	0.0247 (10)	0.0024 (9)	−0.0012 (8)
O4	0.0400 (12)	0.0364 (11)	0.0479 (11)	0.0242 (10)	−0.0094 (9)	−0.0083 (9)
O5	0.0502 (13)	0.0315 (11)	0.0461 (11)	0.0176 (10)	0.0135 (10)	0.0055 (9)
O6	0.0374 (11)	0.0361 (11)	0.0362 (9)	0.0191 (9)	0.0109 (8)	0.0039 (8)

C1—C6	1.364 (5)	C18—C20	1.518 (5)
C1—C2	1.377 (6)	C18—H18	1.0000
C1—H1	0.9500	C19—H19A	0.9800
C2—C3	1.331 (6)	C19—H19B	0.9800
C2—H2	0.9500	C19—H19C	0.9800
C3—C4	1.359 (8)	C20—H20A	0.9800
C3—H3	0.9500	C20—H20B	0.9800
C4—C5	1.382 (8)	C20—H20C	0.9800
C4—H4	0.9500	C21—N2	1.473 (3)
C5—C6	1.362 (6)	C21—H21A	0.9800
C5—H5	0.9500	C21—H21B	0.9800
C6—C7	1.524 (5)	C21—H21C	0.9800
C7—O1	1.426 (4)	C22—O4	1.223 (3)
C7—H7A	0.9900	C22—N2	1.355 (3)
C7—H7B	0.9900	C22—C23	1.537 (4)
C8—O2	1.193 (4)	C23—N3	1.447 (3)
C8—O1	1.320 (4)	C23—C24	1.526 (4)
C8—C9	1.520 (5)	C23—H23	1.0000
C9—N1	1.468 (4)	C24—C25	1.530 (4)
C9—C10	1.522 (4)	C24—H24A	0.9900
C9—H9	1.0000	C24—H24B	0.9900
C10—C11	1.522 (5)	C25—C27	1.521 (5)
C10—H10A	0.9900	C25—C26	1.523 (4)
C10—H10B	0.9900	C25—H25	1.0000
C11—C13	1.505 (5)	C26—H26A	0.9800
C11—C12	1.529 (5)	C26—H26B	0.9800
C11—H11	1.0000	C26—H26C	0.9800
C12—H12A	0.9800	C27—H27A	0.9800
C12—H12B	0.9800	C27—H27B	0.9800
C12—H12C	0.9800	C27—H27C	0.9800
C13—H13A	0.9800	C28—O5	1.213 (4)
C13—H13B	0.9800	C28—O6	1.349 (3)
C13—H13C	0.9800	C28—N3	1.351 (4)
C14—N1	1.475 (4)	C29—O6	1.473 (3)
C14—H14A	0.9800	C29—C32	1.516 (4)
C14—H14B	0.9800	C29—C30	1.523 (5)
C14—H14C	0.9800	C29—C31	1.525 (5)
C15—O3	1.227 (3)	C30—H30A	0.9800
C15—N1	1.344 (4)	C30—H30B	0.9800
C15—C16	1.538 (4)	C30—H30C	0.9800
C16—N2	1.470 (3)	C31—H31A	0.9800
C16—C17	1.530 (4)	C31—H31B	0.9800
C16—H16	1.0000	C31—H31C	0.9800
C17—C18	1.529 (4)	C32—H32A	0.9800
C17—H17A	0.9900	C32—H32B	0.9800
C17—H17B	0.9900	C32—H32C	0.9800
C18—C19	1.504 (5)	N3—H3A	0.8800
C6—C1—C2	121.7 (4)	C18—C19—H19C	109.5
C6—C1—H1	119.1	H19A—C19—H19C	109.5
C2—C1—H1	119.1	H19B—C19—H19C	109.5
C3—C2—C1	120.4 (4)	C18—C20—H20A	109.5
C3—C2—H2	119.8	C18—C20—H20B	109.5
C1—C2—H2	119.8	H20A—C20—H20B	109.5
C2—C3—C4	119.0 (5)	C18—C20—H20C	109.5
C2—C3—H3	120.5	H20A—C20—H20C	109.5
C4—C3—H3	120.5	H20B—C20—H20C	109.5
C3—C4—C5	121.2 (5)	N2—C21—H21A	109.5
C3—C4—H4	119.4	N2—C21—H21B	109.5
C5—C4—H4	119.4	H21A—C21—H21B	109.5
C6—C5—C4	120.0 (4)	N2—C21—H21C	109.5
C6—C5—H5	120.0	H21A—C21—H21C	109.5
C4—C5—H5	120.0	H21B—C21—H21C	109.5
C5—C6—C1	117.7 (4)	O4—C22—N2	123.0 (2)
C5—C6—C7	118.6 (4)	O4—C22—C23	119.2 (2)
C1—C6—C7	123.7 (3)	N2—C22—C23	117.7 (2)
O1—C7—C6	106.9 (3)	N3—C23—C24	111.8 (2)
O1—C7—H7A	110.3	N3—C23—C22	109.4 (2)
C6—C7—H7A	110.3	C24—C23—C22	108.0 (2)
O1—C7—H7B	110.3	N3—C23—H23	109.2
C6—C7—H7B	110.3	C24—C23—H23	109.2
H7A—C7—H7B	108.6	C22—C23—H23	109.2
O2—C8—O1	123.6 (3)	C23—C24—C25	115.1 (2)
O2—C8—C9	125.1 (3)	C23—C24—H24A	108.5
O1—C8—C9	111.2 (3)	C25—C24—H24A	108.5
N1—C9—C8	110.8 (3)	C23—C24—H24B	108.5
N1—C9—C10	112.4 (3)	C25—C24—H24B	108.5
C8—C9—C10	112.6 (2)	H24A—C24—H24B	107.5
N1—C9—H9	106.9	C27—C25—C26	110.4 (3)
C8—C9—H9	106.9	C27—C25—C24	111.7 (3)
C10—C9—H9	106.9	C26—C25—C24	109.6 (2)
C9—C10—C11	113.3 (3)	C27—C25—H25	108.3
C9—C10—H10A	108.9	C26—C25—H25	108.3
C11—C10—H10A	108.9	C24—C25—H25	108.3
C9—C10—H10B	108.9	C25—C26—H26A	109.5
C11—C10—H10B	108.9	C25—C26—H26B	109.5
H10A—C10—H10B	107.7	H26A—C26—H26B	109.5
C13—C11—C10	111.5 (3)	C25—C26—H26C	109.5
C13—C11—C12	110.7 (3)	H26A—C26—H26C	109.5
C10—C11—C12	110.7 (3)	H26B—C26—H26C	109.5
C13—C11—H11	107.9	C25—C27—H27A	109.5
C10—C11—H11	107.9	C25—C27—H27B	109.5
C12—C11—H11	107.9	H27A—C27—H27B	109.5
C11—C12—H12A	109.5	C25—C27—H27C	109.5
C11—C12—H12B	109.5	H27A—C27—H27C	109.5
H12A—C12—H12B	109.5	H27B—C27—H27C	109.5
C11—C12—H12C	109.5	O5—C28—O6	125.5 (3)
H12A—C12—H12C	109.5	O5—C28—N3	123.8 (3)
H12B—C12—H12C	109.5	O6—C28—N3	110.7 (2)
C11—C13—H13A	109.5	O6—C29—C32	109.3 (2)
C11—C13—H13B	109.5	O6—C29—C30	111.0 (2)
H13A—C13—H13B	109.5	C32—C29—C30	112.5 (3)
C11—C13—H13C	109.5	O6—C29—C31	102.1 (2)
H13A—C13—H13C	109.5	C32—C29—C31	111.6 (3)
H13B—C13—H13C	109.5	C30—C29—C31	109.9 (3)
N1—C14—H14A	109.5	C29—C30—H30A	109.5
N1—C14—H14B	109.5	C29—C30—H30B	109.5
H14A—C14—H14B	109.5	H30A—C30—H30B	109.5
N1—C14—H14C	109.5	C29—C30—H30C	109.5
H14A—C14—H14C	109.5	H30A—C30—H30C	109.5
H14B—C14—H14C	109.5	H30B—C30—H30C	109.5
O3—C15—N1	121.4 (3)	C29—C31—H31A	109.5
O3—C15—C16	119.4 (2)	C29—C31—H31B	109.5
N1—C15—C16	119.1 (2)	H31A—C31—H31B	109.5
N2—C16—C17	111.3 (2)	C29—C31—H31C	109.5
N2—C16—C15	109.7 (2)	H31A—C31—H31C	109.5
C17—C16—C15	110.4 (2)	H31B—C31—H31C	109.5
N2—C16—H16	108.4	C29—C32—H32A	109.5
C17—C16—H16	108.4	C29—C32—H32B	109.5
C15—C16—H16	108.4	H32A—C32—H32B	109.5
C18—C17—C16	112.5 (2)	C29—C32—H32C	109.5
C18—C17—H17A	109.1	H32A—C32—H32C	109.5
C16—C17—H17A	109.1	H32B—C32—H32C	109.5
C18—C17—H17B	109.1	C15—N1—C9	125.7 (2)
C16—C17—H17B	109.1	C15—N1—C14	117.4 (2)
H17A—C17—H17B	107.8	C9—N1—C14	116.5 (2)
C19—C18—C20	111.1 (3)	C22—N2—C16	117.8 (2)
C19—C18—C17	112.1 (3)	C22—N2—C21	123.3 (2)
C20—C18—C17	110.6 (3)	C16—N2—C21	117.6 (2)
C19—C18—H18	107.6	C28—N3—C23	117.0 (2)
C20—C18—H18	107.6	C28—N3—H3A	121.5
C17—C18—H18	107.6	C23—N3—H3A	121.5
C18—C19—H19A	109.5	C8—O1—C7	119.3 (3)
C18—C19—H19B	109.5	C28—O6—C29	119.8 (2)
H19A—C19—H19B	109.5
C6—C1—C2—C3	−0.7 (7)	C22—C23—C24—C25	176.7 (2)
C1—C2—C3—C4	0.8 (9)	C23—C24—C25—C27	−56.8 (4)
C2—C3—C4—C5	−1.4 (12)	C23—C24—C25—C26	−179.5 (2)
C3—C4—C5—C6	1.7 (13)	O3—C15—N1—C9	172.2 (3)
C4—C5—C6—C1	−1.5 (9)	C16—C15—N1—C9	−8.8 (4)
C4—C5—C6—C7	−179.6 (6)	O3—C15—N1—C14	−0.1 (4)
C2—C1—C6—C5	1.0 (6)	C16—C15—N1—C14	178.8 (2)
C2—C1—C6—C7	179.0 (3)	C8—C9—N1—C15	−111.7 (3)
C5—C6—C7—O1	175.1 (4)	C10—C9—N1—C15	121.2 (3)
C1—C6—C7—O1	−2.9 (5)	C8—C9—N1—C14	60.7 (3)
O2—C8—C9—N1	−154.8 (4)	C10—C9—N1—C14	−66.3 (3)
O1—C8—C9—N1	29.2 (4)	O4—C22—N2—C16	9.8 (4)
O2—C8—C9—C10	−27.9 (5)	C23—C22—N2—C16	−172.0 (2)
O1—C8—C9—C10	156.1 (3)	O4—C22—N2—C21	176.2 (3)
N1—C9—C10—C11	−71.4 (3)	C23—C22—N2—C21	−5.5 (4)
C8—C9—C10—C11	162.6 (3)	C17—C16—N2—C22	112.7 (3)
C9—C10—C11—C13	−76.7 (4)	C15—C16—N2—C22	−124.8 (2)
C9—C10—C11—C12	159.6 (3)	C17—C16—N2—C21	−54.5 (3)
O3—C15—C16—N2	−92.8 (3)	C15—C16—N2—C21	68.0 (3)
N1—C15—C16—N2	88.2 (3)	O5—C28—N3—C23	−16.8 (4)
O3—C15—C16—C17	30.3 (4)	O6—C28—N3—C23	162.6 (2)
N1—C15—C16—C17	−148.7 (3)	C24—C23—N3—C28	173.5 (2)
N2—C16—C17—C18	−62.4 (3)	C22—C23—N3—C28	−66.9 (3)
C15—C16—C17—C18	175.5 (2)	O2—C8—O1—C7	2.9 (5)
C16—C17—C18—C19	−73.4 (4)	C9—C8—O1—C7	178.9 (3)
C16—C17—C18—C20	161.9 (3)	C6—C7—O1—C8	−178.8 (3)
O4—C22—C23—N3	−38.3 (3)	O5—C28—O6—C29	−3.9 (4)
N2—C22—C23—N3	143.3 (2)	N3—C28—O6—C29	176.7 (2)
O4—C22—C23—C24	83.5 (3)	C32—C29—O6—C28	−65.8 (3)
N2—C22—C23—C24	−94.8 (3)	C30—C29—O6—C28	58.8 (4)
N3—C23—C24—C25	−62.9 (3)	C31—C29—O6—C28	175.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O3i	0.88	2.09	2.923 (3)	157
C2—H2···O4ii	0.95	2.57	3.499 (5)	166
C18—H18···O5	1.00	2.57	3.560 (4)	163
C9—H9···O4	0.99	2.33	3.309 (4)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O3i	0.88	2.09	2.923 (3)	157
C2—H2⋯O4ii	0.95	2.57	3.499 (5)	166
C18—H18⋯O5	1.00	2.57	3.560 (4)	163
C9—H9⋯O4	0.99	2.33	3.309 (4)	164

Symmetry codes: (i) ; (ii) .