Synthesis, crystallization, X-ray structural characterization and solid-state assembly of a cyclic hexapeptoid with propargyl and methoxyethyl side chains

The synthesis and the structural characterization of a cyclic hexapeptoid with four meth­oxy­ethyl and two propargyl side chains have disclosed the presence of a hydrate crystal form [form (I)] and an anhydrous crystal form [form (II)]. The relative amounts of form (I) and form (II) in the as-purified product were determined by Rietveld refinement and depend on the purification procedures. In crystal form (I), peptoid molecules assemble in a columnar arrangement by means of side-chain-to-backbone C=CH...OC hydrogen bonds. In the anhydrous crystal form (II), cyclopeptoid molecules form ribbons by means of backbone-to-backbone CH₂...OC hydrogen bonds, thus mimicking β-sheet secondary structures in proteins. In both crystal forms side chains act as joints among the columns or the ribbons and contribute to the stability of the whole solid-state assembly. Water molecules in the hydrate crystal form (I) bridge columns of cyclic peptoid molecules, providing a more efficient packing.

Computing details

Data collection: CrystalClear (Rigaku Inc., 2007) for form_II. Cell refinement: CrystalClear (Rigaku Inc., 2007) for form_II. Data reduction: CrystalClear (Rigaku Inc., 2007) for form_II. Program(s) used to solve structure: SIR2014/14.10 for form_II. For both compounds, program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015).

(form_I_prime)

Crystal data

C30H46N6O10·H2O	Z = 2
Mr = 668.74	F(000) = 716
Triclinic, P1	Dx = 1.342 Mg m^−3
a = 8.363 (4) Å	Synchrotron radiation, λ = 0.2952 Å
b = 9.394 (4) Å	Cell parameters from 8341 reflections
c = 21.648 (10) Å	θ = 0.8–12.3°
α = 78.362 (5)°	µ = 0.03 mm^−1
β = 88.664 (7)°	T = 100 K
γ = 83.547 (5)°	Needle, colorless
V = 1655.1 (13) Å^3	0.35 × 0.03 × 0.01 mm

Data collection

ID11 ESRF beamline goniometer diffractometer	θmax = 12.3°, θmin = 0.8°
32391 measured reflections	h = −11→11
8341 independent reflections	k = −12→11
7288 reflections with I > 2σ(I)	l = −30→30
Rint = 0.039

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.073	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.195	w = 1/[σ^2(Fo^2) + (0.1031P)^2 + 1.1901P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max = 0.001
8341 reflections	Δρmax = 0.71 e Å^−3
430 parameters	Δρmin = −0.38 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
O1A	0.74225 (17)	0.92177 (16)	1.02791 (7)	0.0252 (3)
N1A	0.74524 (18)	0.81106 (17)	0.94374 (8)	0.0178 (3)
C1A	0.9907 (2)	0.7823 (2)	1.00927 (9)	0.0185 (3)
H1A1	1.0249	0.7091	0.9831	0.022*
H1A2	1.0590	0.8633	0.9980	0.022*
O2A	0.87603 (16)	0.53295 (15)	1.05882 (7)	0.0209 (3)
N2A	1.01386 (18)	0.71441 (17)	1.07611 (8)	0.0185 (3)
C2A	0.8142 (2)	0.84198 (19)	0.99489 (9)	0.0179 (3)
O3A	1.00499 (17)	0.12331 (15)	1.13677 (7)	0.0232 (3)
N3A	0.97028 (18)	0.34172 (17)	1.16749 (8)	0.0181 (3)
C3A	0.5785 (2)	0.8740 (2)	0.92715 (10)	0.0198 (4)
H3A1	0.5469	0.9533	0.9504	0.024*
H3A2	0.5721	0.9168	0.8815	0.024*
O4A	1.34183 (16)	0.62653 (16)	1.12899 (8)	0.0254 (3)
C4A	0.4666 (2)	0.7620 (2)	0.94270 (10)	0.0236 (4)
O5A	0.9467 (2)	0.25030 (18)	1.30553 (8)	0.0310 (3)
C5A	0.3817 (3)	0.6672 (3)	0.95528 (13)	0.0325 (5)
H5A	0.3137	0.5912	0.9654	0.039*
C6A	1.0091 (2)	0.4919 (2)	1.15991 (9)	0.0193 (4)
H6A1	1.1265	0.4914	1.1651	0.023*
H6A2	0.9539	0.5377	1.1931	0.023*
C7A	0.9573 (2)	0.58310 (19)	1.09454 (9)	0.0175 (3)
C8A	1.0958 (2)	0.7886 (2)	1.11771 (10)	0.0204 (4)
H8A1	1.0690	0.7474	1.1620	0.024*
H8A2	1.0541	0.8936	1.1089	0.024*
C9A	1.2776 (2)	0.7753 (2)	1.11053 (10)	0.0228 (4)
H9A1	1.3065	0.8129	1.0661	0.027*
H9A2	1.3240	0.8346	1.1371	0.027*
C10A	1.5140 (3)	0.6127 (3)	1.12554 (12)	0.0309 (5)
H10A	1.5562	0.5095	1.1384	0.046*
H10B	1.5475	0.6498	1.0821	0.046*
H10C	1.5560	0.6692	1.1537	0.046*
C11A	1.1839 (2)	0.2998 (2)	1.09022 (9)	0.0187 (3)
H11A	1.1431	0.3887	1.0594	0.022*
H11B	1.2681	0.3263	1.1159	0.022*
C12A	1.0452 (2)	0.2471 (2)	1.13357 (9)	0.0186 (3)
C14A	0.8652 (2)	0.1851 (2)	1.26333 (10)	0.0240 (4)
H14A	0.7650	0.1505	1.2831	0.029*
H14B	0.9344	0.1000	1.2533	0.029*
C15A	1.0130 (3)	0.1411 (3)	1.35706 (12)	0.0400 (6)
H15A	1.0687	0.1875	1.3857	0.060*
H15B	0.9263	0.0906	1.3798	0.060*
H15C	1.0895	0.0703	1.3410	0.060*
O1B	0.68448 (19)	0.88806 (17)	0.40395 (8)	0.0284 (3)
N1B	0.7209 (2)	0.69122 (18)	0.35604 (8)	0.0218 (3)
C1B	0.5631 (3)	0.6705 (2)	0.45226 (10)	0.0287 (4)
H1B1	0.4716	0.6418	0.4311	0.034*
H1B2	0.6306	0.5798	0.4716	0.034*
O2B	0.64804 (18)	0.57381 (18)	0.57418 (8)	0.0290 (3)
N2B	0.4995 (2)	0.7449 (2)	0.50258 (9)	0.0276 (4)
C2B	0.6626 (2)	0.7611 (2)	0.40253 (10)	0.0224 (4)
O3B	0.50204 (18)	0.37605 (16)	0.72072 (8)	0.0273 (3)
N3B	0.4831 (2)	0.62066 (18)	0.67600 (8)	0.0217 (3)
C3B	0.8003 (2)	0.7757 (2)	0.30153 (10)	0.0240 (4)
H3B1	0.7789	0.8811	0.3023	0.029*
H3B2	0.7536	0.7597	0.2622	0.029*
O4B	0.1552 (2)	0.7213 (2)	0.51828 (9)	0.0359 (4)
C4B	0.9758 (3)	0.7345 (2)	0.30111 (11)	0.0273 (4)
O5B	0.59209 (19)	0.89820 (17)	0.70119 (8)	0.0292 (3)
C5B	1.1172 (3)	0.7014 (3)	0.29982 (13)	0.0365 (5)
H5B	1.2301	0.6749	0.2988	0.044*
C6B	0.4449 (2)	0.7278 (2)	0.61745 (10)	0.0216 (4)
H6B1	0.4734	0.8248	0.6218	0.026*
H6B2	0.3281	0.7368	0.6087	0.026*
C7B	0.5411 (2)	0.6768 (2)	0.56247 (10)	0.0239 (4)
C8B	0.3725 (3)	0.8673 (2)	0.48626 (11)	0.0299 (4)
H8B1	0.4106	0.9400	0.4509	0.036*
H8B2	0.3534	0.9153	0.5229	0.036*
C9B	0.2141 (3)	0.8231 (3)	0.46754 (12)	0.0374 (5)
H9B1	0.1346	0.9106	0.4568	0.045*
H9B2	0.2304	0.7783	0.4299	0.045*
C10B	−0.0021 (4)	0.6887 (4)	0.50510 (18)	0.0538 (8)
H10D	−0.0394	0.6184	0.5409	0.081*
H10E	−0.0766	0.7787	0.4983	0.081*
H10F	0.0018	0.6466	0.4671	0.081*
C11B	0.2922 (2)	0.4623 (2)	0.64413 (10)	0.0211 (4)
H11C	0.1924	0.5052	0.6620	0.025*
H11D	0.3029	0.5159	0.6002	0.025*
C12B	0.4384 (2)	0.4822 (2)	0.68309 (10)	0.0211 (4)
C13B	0.6309 (2)	0.6366 (2)	0.70932 (11)	0.0251 (4)
H13A	0.7191	0.6508	0.6782	0.030*
H13B	0.6617	0.5445	0.7399	0.030*
C13A	0.8258 (2)	0.2977 (2)	1.20353 (10)	0.0204 (4)
H13C	0.7565	0.2571	1.1765	0.024*
H13D	0.7642	0.3853	1.2146	0.024*
C14B	0.6151 (3)	0.7616 (2)	0.74407 (11)	0.0266 (4)
H14C	0.5226	0.7522	0.7734	0.032*
H14D	0.7135	0.7572	0.7692	0.032*
C15B	0.5930 (3)	1.0176 (3)	0.73273 (13)	0.0343 (5)
H15D	0.5769	1.1099	0.7019	0.052*
H15E	0.5061	1.0141	0.7640	0.052*
H15F	0.6966	1.0107	0.7540	0.052*
O1W	0.2646 (2)	0.0544 (2)	0.84233 (8)	0.0323 (4)
H1W	0.186 (5)	−0.005 (4)	0.8422 (19)	0.060*
H2W	0.258 (5)	0.076 (4)	0.883 (2)	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0187 (7)	0.0252 (7)	0.0322 (8)	0.0056 (5)	−0.0047 (6)	−0.0111 (6)
N1A	0.0081 (7)	0.0178 (7)	0.0286 (8)	−0.0007 (5)	−0.0003 (6)	−0.0075 (6)
C1A	0.0110 (8)	0.0158 (8)	0.0281 (10)	−0.0026 (6)	−0.0017 (6)	−0.0026 (6)
O2A	0.0133 (6)	0.0188 (6)	0.0315 (7)	−0.0049 (5)	−0.0020 (5)	−0.0055 (5)
N2A	0.0119 (7)	0.0163 (7)	0.0276 (8)	−0.0027 (5)	−0.0027 (6)	−0.0043 (6)
C2A	0.0119 (8)	0.0130 (8)	0.0289 (9)	−0.0022 (6)	−0.0013 (7)	−0.0039 (6)
O3A	0.0188 (7)	0.0177 (7)	0.0348 (8)	−0.0057 (5)	0.0039 (6)	−0.0079 (5)
N3A	0.0121 (7)	0.0154 (7)	0.0267 (8)	−0.0028 (5)	0.0031 (6)	−0.0036 (5)
C3A	0.0097 (8)	0.0192 (8)	0.0303 (10)	−0.0010 (6)	−0.0024 (7)	−0.0046 (7)
O4A	0.0121 (7)	0.0215 (7)	0.0414 (9)	−0.0019 (5)	−0.0035 (6)	−0.0035 (6)
C4A	0.0115 (8)	0.0253 (10)	0.0357 (11)	−0.0009 (6)	−0.0012 (7)	−0.0106 (8)
O5A	0.0317 (9)	0.0312 (8)	0.0295 (8)	−0.0040 (6)	−0.0036 (6)	−0.0041 (6)
C5A	0.0155 (9)	0.0309 (11)	0.0550 (15)	−0.0066 (8)	0.0037 (9)	−0.0157 (10)
C6A	0.0152 (8)	0.0162 (8)	0.0274 (9)	−0.0028 (6)	0.0003 (7)	−0.0062 (6)
C7A	0.0086 (7)	0.0153 (8)	0.0289 (9)	−0.0016 (6)	0.0014 (6)	−0.0056 (6)
C8A	0.0167 (9)	0.0137 (8)	0.0327 (10)	−0.0031 (6)	−0.0020 (7)	−0.0084 (6)
C9A	0.0160 (9)	0.0204 (9)	0.0333 (11)	−0.0045 (6)	−0.0035 (7)	−0.0065 (7)
C10A	0.0142 (10)	0.0348 (12)	0.0434 (13)	−0.0010 (8)	−0.0040 (8)	−0.0074 (9)
C11A	0.0114 (8)	0.0178 (8)	0.0286 (10)	−0.0036 (6)	0.0015 (7)	−0.0072 (6)
C12A	0.0105 (8)	0.0189 (8)	0.0265 (9)	−0.0014 (6)	−0.0011 (6)	−0.0051 (6)
C14A	0.0215 (9)	0.0178 (9)	0.0320 (11)	−0.0029 (7)	0.0043 (8)	−0.0034 (7)
C15A	0.0305 (12)	0.0514 (15)	0.0322 (13)	0.0030 (10)	−0.0022 (10)	0.0018 (10)
O1B	0.0284 (8)	0.0243 (8)	0.0351 (8)	−0.0092 (6)	0.0025 (6)	−0.0091 (6)
N1B	0.0170 (8)	0.0207 (8)	0.0285 (9)	−0.0054 (6)	0.0018 (6)	−0.0054 (6)
C1B	0.0345 (12)	0.0257 (10)	0.0285 (11)	−0.0103 (8)	0.0063 (8)	−0.0081 (8)
O2B	0.0200 (7)	0.0290 (8)	0.0399 (9)	−0.0018 (6)	0.0029 (6)	−0.0123 (6)
N2B	0.0297 (10)	0.0249 (9)	0.0296 (9)	−0.0062 (7)	0.0053 (7)	−0.0075 (7)
C2B	0.0187 (9)	0.0221 (9)	0.0277 (10)	−0.0058 (7)	−0.0004 (7)	−0.0063 (7)
O3B	0.0203 (7)	0.0225 (7)	0.0382 (9)	−0.0028 (5)	−0.0056 (6)	−0.0031 (6)
N3B	0.0150 (7)	0.0210 (8)	0.0298 (9)	−0.0039 (6)	−0.0026 (6)	−0.0053 (6)
C3B	0.0185 (9)	0.0234 (9)	0.0299 (10)	−0.0058 (7)	0.0026 (7)	−0.0032 (7)
O4B	0.0274 (8)	0.0390 (10)	0.0415 (10)	−0.0093 (7)	−0.0086 (7)	−0.0047 (7)
C4B	0.0213 (10)	0.0274 (10)	0.0350 (11)	−0.0079 (7)	0.0021 (8)	−0.0079 (8)
O5B	0.0281 (8)	0.0232 (8)	0.0377 (9)	−0.0032 (6)	−0.0048 (6)	−0.0085 (6)
C5B	0.0208 (11)	0.0373 (13)	0.0543 (15)	−0.0047 (9)	0.0014 (10)	−0.0156 (11)
C6B	0.0168 (9)	0.0202 (9)	0.0284 (10)	−0.0024 (6)	0.0003 (7)	−0.0063 (7)
C7B	0.0198 (9)	0.0230 (9)	0.0321 (11)	−0.0102 (7)	0.0046 (7)	−0.0093 (7)
C8B	0.0352 (12)	0.0234 (10)	0.0304 (11)	−0.0027 (8)	0.0014 (9)	−0.0042 (8)
C9B	0.0385 (13)	0.0383 (13)	0.0333 (12)	−0.0014 (10)	−0.0080 (10)	−0.0030 (9)
C10B	0.0338 (15)	0.0611 (19)	0.071 (2)	−0.0146 (13)	−0.0180 (14)	−0.0179 (15)
C11B	0.0146 (8)	0.0195 (9)	0.0301 (10)	−0.0036 (6)	−0.0010 (7)	−0.0058 (7)
C12B	0.0135 (8)	0.0209 (9)	0.0299 (10)	−0.0019 (6)	0.0011 (7)	−0.0073 (7)
C13B	0.0155 (9)	0.0235 (10)	0.0377 (11)	−0.0037 (7)	−0.0063 (8)	−0.0075 (8)
C13A	0.0122 (8)	0.0197 (9)	0.0291 (10)	−0.0020 (6)	0.0040 (7)	−0.0045 (7)
C14B	0.0196 (9)	0.0273 (10)	0.0342 (11)	−0.0046 (7)	−0.0046 (8)	−0.0075 (8)
C15B	0.0292 (11)	0.0282 (11)	0.0487 (14)	−0.0008 (8)	−0.0057 (10)	−0.0155 (9)
O1W	0.0234 (8)	0.0411 (10)	0.0333 (9)	−0.0107 (7)	0.0017 (6)	−0.0058 (7)

Geometric parameters (Å, º)

O1A—C2A	1.237 (2)	N1B—C3B	1.472 (3)
N1A—C2A	1.356 (2)	C1B—N2B	1.468 (3)
N1A—C11A^i	1.458 (2)	C1B—C2B	1.524 (3)
N1A—C3A	1.475 (2)	C1B—H1B1	0.9900
C1A—N2A	1.467 (3)	C1B—H1B2	0.9900
C1A—C2A	1.535 (2)	O2B—C7B	1.232 (3)
C1A—H1A1	0.9900	N2B—C7B	1.359 (3)
C1A—H1A2	0.9900	N2B—C8B	1.468 (3)
O2A—C7A	1.235 (2)	O3B—C12B	1.230 (3)
N2A—C7A	1.352 (2)	N3B—C12B	1.372 (3)
N2A—C8A	1.469 (2)	N3B—C6B	1.468 (3)
O3A—C12A	1.235 (2)	N3B—C13B	1.482 (2)
N3A—C12A	1.356 (2)	C3B—C4B	1.475 (3)
N3A—C6A	1.459 (2)	C3B—H3B1	0.9900
N3A—C13A	1.476 (2)	C3B—H3B2	0.9900
C3A—C4A	1.469 (3)	O4B—C9B	1.421 (3)
C3A—H3A1	0.9900	O4B—C10B	1.432 (3)
C3A—H3A2	0.9900	C4B—C5B	1.189 (3)
O4A—C9A	1.421 (2)	O5B—C14B	1.421 (3)
O4A—C10A	1.432 (3)	O5B—C15B	1.426 (3)
C4A—C5A	1.187 (3)	C5B—H5B	0.9500
O5A—C14A	1.422 (3)	C6B—C7B	1.547 (3)
O5A—C15A	1.429 (3)	C6B—H6B1	0.9900
C5A—H5A	0.9500	C6B—H6B2	0.9900
C6A—C7A	1.543 (3)	C8B—C9B	1.519 (4)
C6A—H6A1	0.9900	C8B—H8B1	0.9900
C6A—H6A2	0.9900	C8B—H8B2	0.9900
C8A—C9A	1.518 (3)	C9B—H9B1	0.9900
C8A—H8A1	0.9900	C9B—H9B2	0.9900
C8A—H8A2	0.9900	C10B—H10D	0.9800
C9A—H9A1	0.9900	C10B—H10E	0.9800
C9A—H9A2	0.9900	C10B—H10F	0.9800
C10A—H10A	0.9800	C11B—N1B^ii	1.460 (2)
C10A—H10B	0.9800	C11B—C12B	1.551 (3)
C10A—H10C	0.9800	C11B—H11C	0.9900
C11A—N1A^i	1.458 (2)	C11B—H11D	0.9900
C11A—C12A	1.536 (3)	C13B—C14B	1.510 (3)
C11A—H11A	0.9900	C13B—H13A	0.9900
C11A—H11B	0.9900	C13B—H13B	0.9900
C14A—C13A	1.514 (3)	C13A—H13C	0.9900
C14A—H14A	0.9900	C13A—H13D	0.9900
C14A—H14B	0.9900	C14B—H14C	0.9900
C15A—H15A	0.9800	C14B—H14D	0.9900
C15A—H15B	0.9800	C15B—H15D	0.9800
C15A—H15C	0.9800	C15B—H15E	0.9800
O1B—C2B	1.233 (3)	C15B—H15F	0.9800
N1B—C2B	1.362 (3)	O1W—H1W	0.91 (4)
N1B—C11B^ii	1.460 (2)	O1W—H2W	0.94 (4)
C2A—N1A—C11A^i	123.55 (15)	C2B—C1B—H1B2	108.6
C2A—N1A—C3A	118.89 (15)	H1B1—C1B—H1B2	107.6
C11A^i—N1A—C3A	116.79 (15)	C7B—N2B—C8B	124.50 (18)
N2A—C1A—C2A	111.46 (15)	C7B—N2B—C1B	116.21 (18)
N2A—C1A—H1A1	109.3	C8B—N2B—C1B	118.00 (19)
C2A—C1A—H1A1	109.3	O1B—C2B—N1B	123.33 (19)
N2A—C1A—H1A2	109.3	O1B—C2B—C1B	122.36 (19)
C2A—C1A—H1A2	109.3	N1B—C2B—C1B	114.29 (17)
H1A1—C1A—H1A2	108.0	C12B—N3B—C6B	119.98 (17)
C7A—N2A—C1A	115.52 (15)	C12B—N3B—C13B	116.88 (17)
C7A—N2A—C8A	124.63 (17)	C6B—N3B—C13B	116.13 (16)
C1A—N2A—C8A	119.84 (15)	N1B—C3B—C4B	112.50 (18)
O1A—C2A—N1A	122.24 (17)	N1B—C3B—H3B1	109.1
O1A—C2A—C1A	119.56 (17)	C4B—C3B—H3B1	109.1
N1A—C2A—C1A	118.09 (16)	N1B—C3B—H3B2	109.1
C12A—N3A—C6A	122.06 (16)	C4B—C3B—H3B2	109.1
C12A—N3A—C13A	117.28 (15)	H3B1—C3B—H3B2	107.8
C6A—N3A—C13A	119.62 (15)	C9B—O4B—C10B	111.4 (2)
C4A—C3A—N1A	111.02 (16)	C5B—C4B—C3B	179.0 (3)
C4A—C3A—H3A1	109.4	C14B—O5B—C15B	111.55 (18)
N1A—C3A—H3A1	109.4	C4B—C5B—H5B	180.0
C4A—C3A—H3A2	109.4	N3B—C6B—C7B	109.12 (16)
N1A—C3A—H3A2	109.4	N3B—C6B—H6B1	109.9
H3A1—C3A—H3A2	108.0	C7B—C6B—H6B1	109.9
C9A—O4A—C10A	110.55 (16)	N3B—C6B—H6B2	109.9
C5A—C4A—C3A	177.2 (2)	C7B—C6B—H6B2	109.9
C14A—O5A—C15A	110.36 (19)	H6B1—C6B—H6B2	108.3
C4A—C5A—H5A	180.0	O2B—C7B—N2B	122.50 (19)
N3A—C6A—C7A	111.44 (15)	O2B—C7B—C6B	119.34 (19)
N3A—C6A—H6A1	109.3	N2B—C7B—C6B	118.12 (18)
C7A—C6A—H6A1	109.3	N2B—C8B—C9B	114.0 (2)
N3A—C6A—H6A2	109.3	N2B—C8B—H8B1	108.7
C7A—C6A—H6A2	109.3	C9B—C8B—H8B1	108.7
H6A1—C6A—H6A2	108.0	N2B—C8B—H8B2	108.7
O2A—C7A—N2A	121.39 (18)	C9B—C8B—H8B2	108.7
O2A—C7A—C6A	120.73 (16)	H8B1—C8B—H8B2	107.6
N2A—C7A—C6A	117.70 (16)	O4B—C9B—C8B	109.67 (19)
N2A—C8A—C9A	114.07 (16)	O4B—C9B—H9B1	109.7
N2A—C8A—H8A1	108.7	C8B—C9B—H9B1	109.7
C9A—C8A—H8A1	108.7	O4B—C9B—H9B2	109.7
N2A—C8A—H8A2	108.7	C8B—C9B—H9B2	109.7
C9A—C8A—H8A2	108.7	H9B1—C9B—H9B2	108.2
H8A1—C8A—H8A2	107.6	O4B—C10B—H10D	109.5
O4A—C9A—C8A	109.74 (15)	O4B—C10B—H10E	109.5
O4A—C9A—H9A1	109.7	H10D—C10B—H10E	109.5
C8A—C9A—H9A1	109.7	O4B—C10B—H10F	109.5
O4A—C9A—H9A2	109.7	H10D—C10B—H10F	109.5
C8A—C9A—H9A2	109.7	H10E—C10B—H10F	109.5
H9A1—C9A—H9A2	108.2	N1B^ii—C11B—C12B	112.21 (16)
O4A—C10A—H10A	109.5	N1B^ii—C11B—H11C	109.2
O4A—C10A—H10B	109.5	C12B—C11B—H11C	109.2
H10A—C10A—H10B	109.5	N1B^ii—C11B—H11D	109.2
O4A—C10A—H10C	109.5	C12B—C11B—H11D	109.2
H10A—C10A—H10C	109.5	H11C—C11B—H11D	107.9
H10B—C10A—H10C	109.5	O3B—C12B—N3B	123.74 (18)
N1A^i—C11A—C12A	112.30 (15)	O3B—C12B—C11B	118.84 (18)
N1A^i—C11A—H11A	109.1	N3B—C12B—C11B	117.30 (17)
C12A—C11A—H11A	109.1	N3B—C13B—C14B	114.55 (17)
N1A^i—C11A—H11B	109.1	N3B—C13B—H13A	108.6
C12A—C11A—H11B	109.1	C14B—C13B—H13A	108.6
H11A—C11A—H11B	107.9	N3B—C13B—H13B	108.6
O3A—C12A—N3A	122.11 (17)	C14B—C13B—H13B	108.6
O3A—C12A—C11A	120.57 (17)	H13A—C13B—H13B	107.6
N3A—C12A—C11A	117.32 (16)	N3A—C13A—C14A	113.00 (16)
O5A—C14A—C13A	108.82 (16)	N3A—C13A—H13C	109.0
O5A—C14A—H14A	109.9	C14A—C13A—H13C	109.0
C13A—C14A—H14A	109.9	N3A—C13A—H13D	109.0
O5A—C14A—H14B	109.9	C14A—C13A—H13D	109.0
C13A—C14A—H14B	109.9	H13C—C13A—H13D	107.8
H14A—C14A—H14B	108.3	O5B—C14B—C13B	110.87 (18)
O5A—C15A—H15A	109.5	O5B—C14B—H14C	109.5
O5A—C15A—H15B	109.5	C13B—C14B—H14C	109.5
H15A—C15A—H15B	109.5	O5B—C14B—H14D	109.5
O5A—C15A—H15C	109.5	C13B—C14B—H14D	109.5
H15A—C15A—H15C	109.5	H14C—C14B—H14D	108.1
H15B—C15A—H15C	109.5	O5B—C15B—H15D	109.5
C2B—N1B—C11B^ii	124.37 (17)	O5B—C15B—H15E	109.5
C2B—N1B—C3B	118.35 (17)	H15D—C15B—H15E	109.5
C11B^ii—N1B—C3B	117.27 (17)	O5B—C15B—H15F	109.5
N2B—C1B—C2B	114.71 (18)	H15D—C15B—H15F	109.5
N2B—C1B—H1B1	108.6	H15E—C15B—H15F	109.5
C2B—C1B—H1B1	108.6	H1W—O1W—H2W	104 (3)
N2B—C1B—H1B2	108.6
C2A—C1A—N2A—C7A	73.4 (2)	C2B—C1B—N2B—C7B	−122.9 (2)
C2A—C1A—N2A—C8A	−107.33 (18)	C2B—C1B—N2B—C8B	69.5 (3)
C11A^i—N1A—C2A—O1A	−170.00 (18)	C11B^ii—N1B—C2B—O1B	174.88 (19)
C3A—N1A—C2A—O1A	−0.4 (3)	C3B—N1B—C2B—O1B	−6.3 (3)
C11A^i—N1A—C2A—C1A	13.6 (3)	C11B^ii—N1B—C2B—C1B	−6.7 (3)
C3A—N1A—C2A—C1A	−176.73 (15)	C3B—N1B—C2B—C1B	172.14 (18)
N2A—C1A—C2A—O1A	50.4 (2)	N2B—C1B—C2B—O1B	−1.6 (3)
N2A—C1A—C2A—N1A	−133.17 (17)	N2B—C1B—C2B—N1B	−179.98 (18)
C2A—N1A—C3A—C4A	−106.4 (2)	C2B—N1B—C3B—C4B	108.9 (2)
C11A^i—N1A—C3A—C4A	63.9 (2)	C11B^ii—N1B—C3B—C4B	−72.1 (2)
C12A—N3A—C6A—C7A	67.6 (2)	C12B—N3B—C6B—C7B	−66.2 (2)
C13A—N3A—C6A—C7A	−100.49 (19)	C13B—N3B—C6B—C7B	83.6 (2)
C1A—N2A—C7A—O2A	−7.8 (3)	C8B—N2B—C7B—O2B	179.6 (2)
C8A—N2A—C7A—O2A	172.99 (17)	C1B—N2B—C7B—O2B	12.9 (3)
C1A—N2A—C7A—C6A	167.36 (15)	C8B—N2B—C7B—C6B	2.1 (3)
C8A—N2A—C7A—C6A	−11.8 (3)	C1B—N2B—C7B—C6B	−164.67 (17)
N3A—C6A—C7A—O2A	8.2 (2)	N3B—C6B—C7B—O2B	−10.4 (2)
N3A—C6A—C7A—N2A	−167.05 (16)	N3B—C6B—C7B—N2B	167.25 (17)
C7A—N2A—C8A—C9A	101.6 (2)	C7B—N2B—C8B—C9B	−99.8 (2)
C1A—N2A—C8A—C9A	−77.6 (2)	C1B—N2B—C8B—C9B	66.7 (3)
C10A—O4A—C9A—C8A	−177.11 (17)	C10B—O4B—C9B—C8B	173.8 (2)
N2A—C8A—C9A—O4A	−64.2 (2)	N2B—C8B—C9B—O4B	59.9 (3)
C6A—N3A—C12A—O3A	−174.94 (17)	C6B—N3B—C12B—O3B	158.53 (19)
C13A—N3A—C12A—O3A	−6.6 (3)	C13B—N3B—C12B—O3B	8.9 (3)
C6A—N3A—C12A—C11A	4.9 (3)	C6B—N3B—C12B—C11B	−25.5 (3)
C13A—N3A—C12A—C11A	173.28 (16)	C13B—N3B—C12B—C11B	−175.11 (17)
N1A^i—C11A—C12A—O3A	−0.1 (3)	N1B^ii—C11B—C12B—O3B	−17.2 (3)
N1A^i—C11A—C12A—N3A	−179.97 (16)	N1B^ii—C11B—C12B—N3B	166.63 (17)
C15A—O5A—C14A—C13A	−168.86 (18)	C12B—N3B—C13B—C14B	−134.2 (2)
C12A—N3A—C13A—C14A	76.4 (2)	C6B—N3B—C13B—C14B	75.0 (2)
C6A—N3A—C13A—C14A	−114.92 (19)	C15B—O5B—C14B—C13B	−174.20 (17)
O5A—C14A—C13A—N3A	66.3 (2)	N3B—C13B—C14B—O5B	−66.2 (2)

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

(form_II)

Crystal data

C30H46N6O10	F(000) = 696
Mr = 650.73	Dx = 1.280 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0367 (17) Å	Cell parameters from 5055 reflections
b = 10.6221 (18) Å	θ = 2.2–28.9°
c = 18.022 (3) Å	µ = 0.10 mm^−1
β = 102.661 (4)°	T = 100 K
V = 1687.9 (5) Å^3	Plate, colorless
Z = 2	0.4 × 0.3 × 0.2 mm

Data collection

AFC7S Rigaku diffractometer	4342 independent reflections
Radiation source: Sealed Tube	2516 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.055
Detector resolution: 13.6612 pixels mm^-1	θmax = 29.0°, θmin = 2.2°
dtprofit.ref scans	h = −7→12
Absorption correction: multi-scan Blessing, 1995	k = −14→10
Tmin = 0.766, Tmax = 1.000	l = −24→23
14363 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.061	w = 1/[σ^2(Fo^2) + (0.0853P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.173	(Δ/σ)max < 0.001
S = 0.92	Δρmax = 0.36 e Å^−3
4342 reflections	Δρmin = −0.31 e Å^−3
209 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2014), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0064 (17)

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.

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

	x	y	z	Uiso*/Ueq
O1	0.06954 (17)	0.06173 (12)	−0.17281 (8)	0.0358 (4)
O2	0.47174 (15)	−0.02091 (11)	−0.09270 (7)	0.0267 (3)
O3	0.87960 (15)	−0.17924 (12)	−0.05125 (8)	0.0302 (4)
O4	0.31564 (17)	−0.38143 (12)	−0.01185 (9)	0.0358 (4)
O5	0.7970 (2)	−0.24785 (12)	−0.29492 (9)	0.0457 (5)
N1	0.19920 (19)	0.19463 (13)	−0.08366 (9)	0.0260 (4)
N2	0.26354 (17)	−0.13750 (13)	−0.09465 (9)	0.0250 (4)
N3	0.64527 (18)	−0.21513 (13)	−0.12366 (9)	0.0245 (4)
C1	0.2025 (2)	−0.03279 (16)	−0.05714 (12)	0.0269 (4)
H1A	0.2807	−0.0044	−0.0128	0.032*
H1B	0.1141	−0.0630	−0.0381	0.032*
C2	0.1543 (2)	0.07796 (17)	−0.11014 (12)	0.0269 (4)
C3	0.1213 (2)	0.30404 (17)	−0.12311 (12)	0.0313 (5)
H3A	0.0995	0.3644	−0.0850	0.038*
H3B	0.0231	0.2768	−0.1552	0.038*
C4	0.2096 (3)	0.36767 (18)	−0.17088 (12)	0.0358 (5)
C5	0.2832 (3)	0.4190 (2)	−0.20880 (14)	0.0462 (6)
H5	0.3422	0.4601	−0.2392	0.055*
C6	0.4850 (2)	−0.23825 (17)	−0.12908 (12)	0.0260 (4)
H6A	0.4729	−0.3102	−0.0960	0.031*
H6B	0.4365	−0.2610	−0.1821	0.031*
C7	0.4051 (2)	−0.12224 (16)	−0.10520 (11)	0.0241 (4)
C8	0.1723 (2)	−0.25234 (16)	−0.11115 (12)	0.0280 (5)
H8A	0.2134	−0.3044	−0.1475	0.034*
H8B	0.0671	−0.2289	−0.1359	0.034*
C9	0.1696 (2)	−0.33025 (17)	−0.04121 (13)	0.0316 (5)
H9A	0.1388	−0.2769	−0.0021	0.038*
H9B	0.0947	−0.3992	−0.0545	0.038*
C10	0.3211 (3)	−0.44937 (19)	0.05695 (13)	0.0417 (6)
H10A	0.2909	−0.3938	0.0945	0.063*
H10B	0.4246	−0.4798	0.0769	0.063*
H10C	0.2515	−0.5212	0.0468	0.063*
C11	0.6839 (2)	−0.21781 (17)	0.01622 (11)	0.0251 (4)
H11A	0.5992	−0.1581	0.0147	0.030*
H11B	0.6439	−0.3042	0.0183	0.030*
C12	0.7451 (2)	−0.20279 (16)	−0.05599 (11)	0.0235 (4)
C13	0.6958 (2)	−0.18054 (16)	−0.19275 (11)	0.0253 (4)
H13A	0.7793	−0.1186	−0.1798	0.030*
H13B	0.6109	−0.1400	−0.2290	0.030*
C14	0.7501 (2)	−0.29427 (16)	−0.23049 (11)	0.0274 (4)
H14A	0.8356	−0.3358	−0.1953	0.033*
H14B	0.6669	−0.3560	−0.2457	0.033*
C15	0.8611 (4)	−0.3446 (2)	−0.33318 (15)	0.0556 (8)
H15A	0.9451	−0.3849	−0.2974	0.083*
H15B	0.8989	−0.3078	−0.3753	0.083*
H15C	0.7833	−0.4076	−0.3531	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0334 (9)	0.0393 (8)	0.0301 (9)	0.0090 (6)	−0.0029 (7)	−0.0082 (6)
O2	0.0243 (8)	0.0279 (7)	0.0295 (8)	−0.0013 (5)	0.0093 (6)	−0.0002 (5)
O3	0.0211 (8)	0.0394 (8)	0.0309 (9)	−0.0001 (5)	0.0071 (6)	−0.0016 (6)
O4	0.0342 (9)	0.0361 (7)	0.0387 (9)	0.0084 (6)	0.0117 (7)	0.0057 (6)
O5	0.0761 (13)	0.0301 (8)	0.0450 (10)	0.0074 (7)	0.0436 (9)	0.0027 (6)
N1	0.0249 (9)	0.0275 (8)	0.0245 (9)	0.0029 (6)	0.0029 (7)	0.0014 (6)
N2	0.0187 (9)	0.0262 (8)	0.0309 (10)	−0.0013 (6)	0.0074 (7)	−0.0032 (6)
N3	0.0192 (9)	0.0331 (8)	0.0217 (9)	0.0018 (6)	0.0060 (7)	−0.0013 (6)
C1	0.0208 (10)	0.0289 (10)	0.0325 (12)	0.0014 (7)	0.0093 (9)	−0.0016 (7)
C2	0.0214 (10)	0.0334 (10)	0.0265 (11)	0.0043 (7)	0.0063 (9)	−0.0019 (8)
C3	0.0345 (12)	0.0297 (10)	0.0281 (12)	0.0060 (8)	0.0035 (10)	0.0008 (7)
C4	0.0441 (14)	0.0312 (10)	0.0282 (12)	−0.0004 (9)	−0.0002 (10)	0.0020 (8)
C5	0.0582 (17)	0.0448 (13)	0.0325 (13)	−0.0124 (11)	0.0031 (12)	0.0037 (9)
C6	0.0190 (10)	0.0319 (10)	0.0280 (11)	0.0007 (7)	0.0070 (8)	−0.0034 (7)
C7	0.0199 (10)	0.0285 (10)	0.0228 (10)	0.0012 (7)	0.0025 (8)	0.0021 (7)
C8	0.0198 (10)	0.0300 (10)	0.0343 (12)	−0.0007 (7)	0.0066 (9)	−0.0026 (8)
C9	0.0250 (11)	0.0311 (10)	0.0397 (13)	−0.0003 (8)	0.0095 (10)	0.0002 (8)
C10	0.0546 (16)	0.0347 (11)	0.0374 (14)	0.0041 (10)	0.0138 (12)	0.0031 (9)
C11	0.0220 (11)	0.0302 (9)	0.0233 (10)	0.0008 (7)	0.0055 (8)	−0.0007 (7)
C12	0.0202 (10)	0.0244 (9)	0.0277 (11)	0.0012 (7)	0.0091 (8)	−0.0024 (7)
C13	0.0236 (10)	0.0303 (10)	0.0227 (10)	0.0037 (7)	0.0067 (8)	0.0009 (7)
C14	0.0296 (12)	0.0309 (10)	0.0241 (11)	−0.0002 (8)	0.0109 (9)	−0.0013 (7)
C15	0.091 (2)	0.0384 (12)	0.0541 (17)	0.0130 (12)	0.0522 (16)	0.0002 (10)

Geometric parameters (Å, º)

O1—C2	1.230 (2)	C6—C7	1.536 (3)
O2—C7	1.230 (2)	C6—H6A	0.9900
O3—C12	1.225 (2)	C6—H6B	0.9900
O4—C9	1.419 (2)	C8—C9	1.513 (3)
O4—C10	1.426 (2)	C8—H8A	0.9900
O5—C14	1.410 (2)	C8—H8B	0.9900
O5—C15	1.429 (3)	C9—H9A	0.9900
N1—C2	1.358 (2)	C9—H9B	0.9900
N1—C11^i	1.446 (2)	C10—H10A	0.9800
N1—C3	1.460 (2)	C10—H10B	0.9800
N2—C7	1.344 (2)	C10—H10C	0.9800
N2—C8	1.466 (2)	C11—N1^i	1.446 (2)
N2—C1	1.470 (2)	C11—C12	1.530 (3)
N3—C12	1.355 (2)	C11—H11A	0.9900
N3—C6	1.451 (2)	C11—H11B	0.9900
N3—C13	1.464 (2)	C13—C14	1.520 (2)
C1—C2	1.518 (3)	C13—H13A	0.9900
C1—H1A	0.9900	C13—H13B	0.9900
C1—H1B	0.9900	C14—H14A	0.9900
C3—C4	1.461 (3)	C14—H14B	0.9900
C3—H3A	0.9900	C15—H15A	0.9800
C3—H3B	0.9900	C15—H15B	0.9800
C4—C5	1.186 (3)	C15—H15C	0.9800
C5—H5	0.9500
C9—O4—C10	111.72 (16)	C9—C8—H8B	108.9
C14—O5—C15	111.87 (15)	H8A—C8—H8B	107.7
C2—N1—C11^i	123.90 (15)	O4—C9—C8	109.65 (17)
C2—N1—C3	118.71 (16)	O4—C9—H9A	109.7
C11^i—N1—C3	117.33 (14)	C8—C9—H9A	109.7
C7—N2—C8	125.60 (15)	O4—C9—H9B	109.7
C7—N2—C1	116.01 (14)	C8—C9—H9B	109.7
C8—N2—C1	118.17 (15)	H9A—C9—H9B	108.2
C12—N3—C6	122.33 (16)	O4—C10—H10A	109.5
C12—N3—C13	118.10 (16)	O4—C10—H10B	109.5
C6—N3—C13	118.55 (16)	H10A—C10—H10B	109.5
N2—C1—C2	112.44 (16)	O4—C10—H10C	109.5
N2—C1—H1A	109.1	H10A—C10—H10C	109.5
C2—C1—H1A	109.1	H10B—C10—H10C	109.5
N2—C1—H1B	109.1	N1^i—C11—C12	111.30 (16)
C2—C1—H1B	109.1	N1^i—C11—H11A	109.4
H1A—C1—H1B	107.8	C12—C11—H11A	109.4
O1—C2—N1	121.92 (17)	N1^i—C11—H11B	109.4
O1—C2—C1	120.28 (16)	C12—C11—H11B	109.4
N1—C2—C1	117.64 (17)	H11A—C11—H11B	108.0
N1—C3—C4	112.80 (17)	O3—C12—N3	122.48 (17)
N1—C3—H3A	109.0	O3—C12—C11	120.01 (18)
C4—C3—H3A	109.0	N3—C12—C11	117.51 (16)
N1—C3—H3B	109.0	N3—C13—C14	111.88 (14)
C4—C3—H3B	109.0	N3—C13—H13A	109.2
H3A—C3—H3B	107.8	C14—C13—H13A	109.2
C5—C4—C3	179.0 (3)	N3—C13—H13B	109.2
C4—C5—H5	180.0	C14—C13—H13B	109.2
N3—C6—C7	111.63 (15)	H13A—C13—H13B	107.9
N3—C6—H6A	109.3	O5—C14—C13	106.00 (14)
C7—C6—H6A	109.3	O5—C14—H14A	110.5
N3—C6—H6B	109.3	C13—C14—H14A	110.5
C7—C6—H6B	109.3	O5—C14—H14B	110.5
H6A—C6—H6B	108.0	C13—C14—H14B	110.5
O2—C7—N2	121.50 (16)	H14A—C14—H14B	108.7
O2—C7—C6	120.82 (17)	O5—C15—H15A	109.5
N2—C7—C6	117.59 (15)	O5—C15—H15B	109.5
N2—C8—C9	113.43 (17)	H15A—C15—H15B	109.5
N2—C8—H8A	108.9	O5—C15—H15C	109.5
C9—C8—H8A	108.9	H15A—C15—H15C	109.5
N2—C8—H8B	108.9	H15B—C15—H15C	109.5
C7—N2—C1—C2	76.1 (2)	N3—C6—C7—N2	−168.51 (16)
C8—N2—C1—C2	−109.07 (19)	C7—N2—C8—C9	101.0 (2)
C11^i—N1—C2—O1	−170.09 (19)	C1—N2—C8—C9	−73.2 (2)
C3—N1—C2—O1	12.7 (3)	C10—O4—C9—C8	176.38 (16)
C11^i—N1—C2—C1	14.5 (3)	N2—C8—C9—O4	−67.8 (2)
C3—N1—C2—C1	−162.64 (17)	C6—N3—C12—O3	−177.58 (16)
N2—C1—C2—O1	51.2 (3)	C13—N3—C12—O3	−9.3 (2)
N2—C1—C2—N1	−133.33 (18)	C6—N3—C12—C11	1.7 (2)
C2—N1—C3—C4	−103.5 (2)	C13—N3—C12—C11	169.97 (14)
C11^i—N1—C3—C4	79.1 (2)	N1^i—C11—C12—O3	2.8 (2)
C12—N3—C6—C7	70.2 (2)	N1^i—C11—C12—N3	−176.48 (14)
C13—N3—C6—C7	−98.02 (18)	C12—N3—C13—C14	96.14 (19)
C8—N2—C7—O2	177.07 (17)	C6—N3—C13—C14	−95.13 (19)
C1—N2—C7—O2	−8.6 (3)	C15—O5—C14—C13	176.0 (2)
C8—N2—C7—C6	−6.4 (3)	N3—C13—C14—O5	−179.14 (16)
C1—N2—C7—C6	167.95 (16)	C2—N1—C11^i—C12^i	−80.0 (2)
N3—C6—C7—O2	8.0 (3)

Symmetry code: (i) −x+1, −y, −z.