Crystal structure of (−)-(5R,7R,8S,9R,10S)-8-methyl-7-[(5R)-3-methyl-2-oxooxolan-3-en-5-yl]-1-aza-6-oxatri­cyclo­[8.3.0.0^5,9]tridecan-13-one monohydrate

The title compound is an epimer of natural tetra­cyclic isosaxorumamide. The di­hydro­furan­one, oxolane, azepane and pyrrolidine rings adopt planar, twist, twist-chair and envelope forms, respectively. In the crystal, O—H...O hydrogen bonds connect the water and main mol­ecules into a tape structure, which is further expanded into a three-dimensional network by C—H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.033
• wR factor = 0.069
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.595          5 Report

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT398_ALERT_2_G Deviating  C-O-C    Angle From 120 for O17            108.9 Degree
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT791_ALERT_4_G Model has Chirality at C5          (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G Model has Chirality at C7          (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G Model has Chirality at C8          (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G Model has Chirality at C9          (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G Model has Chirality at C10         (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G Model has Chirality at C16         (Chiral SPGR)          R Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          3 Note
PLAT909_ALERT_3_G Percentage of I>2sig(I) Data at Theta(Max) Still        89% Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          9 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  15 ALERT level G = General information/check it is not something unexpected

   1 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
   5 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

(-)-(5R,7R,8S,9R,10S)-8-Methyl-7-[(5R)-3-methyl-2-oxooxolan-3-en-5-yl]-1-aza-6-oxatricyclo[8.3.0.0^5,9]tridecan-13-one monohydrate

Crystal data

C17H23NO4·H2O	Dx = 1.312 Mg m^−3
Mr = 323.38	Melting point = 466–467 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 6.6180 (3) Å	Cell parameters from 9946 reflections
b = 7.1197 (3) Å	θ = 2.4–25.1°
c = 34.7351 (15) Å	µ = 0.10 mm^−1
V = 1636.65 (12) Å^3	T = 90 K
Z = 4	Prism, pale yellow
F(000) = 696	0.23 × 0.20 × 0.18 mm

Data collection

Bruker D8 Venture diffractometer	2879 independent reflections
Radiation source: fine-focus sealed tube	2759 reflections with I > 2σ(I)
Multilayered confocal mirror monochromator	Rint = 0.047
Detector resolution: 7.4074 pixels mm^-1	θmax = 25.0°, θmin = 2.4°
φ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −8→8
Tmin = 0.98, Tmax = 0.98	l = −41→41
29644 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: mixed
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + 1.385P] where P = (Fo^2 + 2Fc^2)/3
2879 reflections	(Δ/σ)max < 0.001
216 parameters	Δρmax = 0.21 e Å^−3
3 restraints	Δρmin = −0.19 e Å^−3

Special details

Experimental. IR (film): 2925, 2855, 1756, 1667, 1455, 1261, 1083, 802 cm^-1; ¹H NMR (500 MHz, CDCl₃): δ (p.p.m.) 6.97 (dq, J = 1.7, 1.4 Hz, 1H; H20), 4.89–4.86 (m, 1H; H16), 4.22 (dd, J = 8.3, 0.9 Hz, 1H; H7), 4.07–4.01 (m, 1H; H2B), 3.92 (ddd, J = 10.9, 6.9, 6.3 Hz, 1H; H10), 3.73 (ddd, J = 10.2, 9.7, 2.9 Hz, 1H; H5), 2.72–2.65 (m, 1H; H2A), 2.59–2.51 (m, 1H; H8), 2.47 (ddd, J = 12.0, 9.7, 6.9 Hz, 1H; H9), 2.42–2.31 (m, 2H; H12AB), 2.00–1.92 (m, 2H; H4A & H11A), 1.95 (dd, J = 1.7, 1.4 Hz, 3H; H22ABC), 1.74–1.59 (m, 2H; H3B & H11B), 1.45–1.28 (m, 2H; H3A & H4B), 1.24 (d, J = 6.6 Hz, 3H; H15ABC) ¹³C NMR (125 MHz, CDCl₃): δ (p.p.m.) 174.7 (C; C18), 174.1 (C; C13), 146.7 (CH; C19), 131.1 (C; C20), 80.6, 80.3, 80.0 (CH x3; C16, C7 & C5), 56.3 (CH; C10), 51.3 (CH; C9), 40.5 (CH₂; C2), 38.5 (CH; C8), 35.1 (CH₂; C12), 31.0 (CH₂; C11), 25.9 (CH₂; C4), 22.1 (CH₂; C3), 13.1 (CH₃; C22), 10.9 (CH₃; C15)

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.

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 > 2σ(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
N1	1.0068 (3)	0.5967 (3)	0.18662 (5)	0.0148 (4)
C2	1.0057 (4)	0.4003 (3)	0.17441 (6)	0.0163 (5)
H2A	0.8647	0.3539	0.1739	0.02*
H2B	1.0817	0.3241	0.1933	0.02*
C3	1.0999 (4)	0.3752 (4)	0.13469 (7)	0.0174 (5)
H3A	1.2346	0.4357	0.1346	0.021*
H3B	1.1204	0.2393	0.13	0.021*
C4	0.9764 (4)	0.4558 (3)	0.10156 (7)	0.0160 (5)
H4A	1.0537	0.4403	0.0774	0.019*
H4B	0.8499	0.3825	0.099	0.019*
C5	0.9231 (4)	0.6613 (3)	0.10638 (6)	0.0138 (5)
H5	1.0485	0.7338	0.1126	0.017*
O6	0.8410 (3)	0.7277 (2)	0.07027 (4)	0.0169 (4)
C7	0.6625 (4)	0.8368 (3)	0.07655 (7)	0.0165 (5)
H7	0.678	0.9594	0.0628	0.02*
C8	0.6556 (4)	0.8755 (3)	0.11996 (7)	0.0156 (5)
H8	0.7432	0.9872	0.1251	0.019*
C9	0.7626 (4)	0.7031 (3)	0.13668 (6)	0.0129 (5)
H9	0.6641	0.5966	0.1368	0.015*
C10	0.8418 (4)	0.7289 (3)	0.17783 (6)	0.0144 (5)
H10	0.7283	0.7068	0.1963	0.017*
C11	0.9401 (4)	0.9177 (3)	0.18706 (7)	0.0171 (5)
H11A	0.8389	1.0086	0.1967	0.021*
H11B	1.0069	0.9711	0.164	0.021*
C12	1.0951 (4)	0.8701 (4)	0.21821 (7)	0.0186 (6)
H12A	1.2148	0.9531	0.2164	0.022*
H12B	1.0354	0.8817	0.2442	0.022*
C13	1.1500 (4)	0.6692 (3)	0.20942 (7)	0.0165 (5)
O14	1.2991 (3)	0.5844 (3)	0.22177 (5)	0.0233 (4)
C15	0.4482 (4)	0.9164 (4)	0.13680 (7)	0.0218 (6)
H15A	0.382	1.0147	0.1216	0.033*
H15B	0.4629	0.9589	0.1635	0.033*
H15C	0.366	0.802	0.1362	0.033*
C16	0.4817 (4)	0.7338 (3)	0.05958 (6)	0.0180 (5)
H16	0.3564	0.8095	0.0639	0.022*
O17	0.4601 (3)	0.5530 (2)	0.07769 (5)	0.0184 (4)
C18	0.4827 (4)	0.4170 (4)	0.05060 (7)	0.0196 (5)
C19	0.5050 (4)	0.5060 (4)	0.01261 (7)	0.0207 (6)
C20	0.5018 (4)	0.6892 (4)	0.01778 (7)	0.0203 (6)
H20	0.5109	0.7799	−0.0022	0.024*
O21	0.4813 (3)	0.2530 (3)	0.05902 (5)	0.0289 (5)
C22	0.5281 (4)	0.3907 (4)	−0.02303 (7)	0.0292 (7)
H22A	0.5321	0.4736	−0.0455	0.044*
H22B	0.4134	0.3044	−0.0253	0.044*
H22C	0.654	0.3185	−0.0216	0.044*
O1W	0.5010 (4)	0.2300 (3)	0.21248 (6)	0.0424 (6)
H1WA	0.440 (5)	0.334 (4)	0.2174 (10)	0.064*
H1WB	0.549 (6)	0.198 (5)	0.2345 (7)	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0184 (10)	0.0129 (10)	0.0131 (9)	0.0011 (10)	−0.0012 (9)	0.0001 (8)
C2	0.0202 (12)	0.0116 (11)	0.0170 (11)	−0.0013 (12)	−0.0012 (11)	0.0025 (9)
C3	0.0188 (13)	0.0137 (12)	0.0197 (13)	0.0027 (11)	−0.0005 (11)	−0.0013 (10)
C4	0.0149 (13)	0.0179 (13)	0.0152 (11)	0.0027 (11)	0.0027 (11)	−0.0030 (10)
C5	0.0147 (12)	0.0168 (12)	0.0098 (11)	−0.0005 (10)	−0.0003 (10)	0.0009 (9)
O6	0.0151 (9)	0.0225 (9)	0.0133 (8)	0.0052 (8)	0.0010 (7)	0.0030 (7)
C7	0.0147 (12)	0.0161 (12)	0.0186 (12)	0.0030 (11)	0.0018 (10)	0.0049 (10)
C8	0.0164 (12)	0.0120 (12)	0.0184 (12)	0.0001 (11)	−0.0021 (10)	0.0000 (10)
C9	0.0123 (11)	0.0130 (12)	0.0134 (11)	0.0000 (10)	0.0018 (10)	−0.0001 (10)
C10	0.0157 (12)	0.0146 (12)	0.0130 (11)	0.0009 (11)	0.0038 (10)	0.0002 (10)
C11	0.0204 (13)	0.0133 (12)	0.0177 (12)	0.0015 (11)	0.0027 (10)	−0.0031 (10)
C12	0.0230 (13)	0.0186 (13)	0.0141 (12)	−0.0010 (11)	0.0010 (11)	−0.0045 (10)
C13	0.0220 (14)	0.0183 (13)	0.0092 (11)	−0.0005 (12)	0.0011 (10)	0.0023 (10)
O14	0.0257 (10)	0.0215 (9)	0.0227 (9)	0.0035 (9)	−0.0099 (8)	−0.0002 (8)
C15	0.0203 (13)	0.0235 (13)	0.0217 (13)	0.0057 (12)	−0.0004 (11)	−0.0050 (11)
C16	0.0171 (13)	0.0193 (12)	0.0177 (11)	0.0038 (11)	0.0002 (11)	0.0030 (10)
O17	0.0194 (9)	0.0202 (9)	0.0157 (8)	−0.0035 (8)	−0.0002 (7)	0.0015 (7)
C18	0.0139 (12)	0.0230 (14)	0.0220 (13)	0.0017 (12)	−0.0053 (11)	−0.0009 (11)
C19	0.0133 (12)	0.0297 (14)	0.0190 (12)	0.0060 (13)	−0.0038 (11)	−0.0020 (11)
C20	0.0143 (13)	0.0297 (14)	0.0169 (12)	0.0007 (13)	−0.0022 (11)	0.0058 (10)
O21	0.0334 (11)	0.0210 (10)	0.0324 (10)	0.0006 (10)	−0.0099 (10)	0.0010 (8)
C22	0.0267 (15)	0.0374 (16)	0.0234 (14)	0.0100 (15)	−0.0053 (12)	−0.0085 (12)
O1W	0.0562 (15)	0.0365 (12)	0.0345 (11)	0.0201 (13)	−0.0228 (12)	−0.0136 (10)

Geometric parameters (Å, º)

N1—C13	1.338 (3)	C10—H10	1.0
N1—C2	1.461 (3)	C11—C12	1.529 (3)
N1—C10	1.474 (3)	C11—H11A	0.99
C2—C3	1.525 (3)	C11—H11B	0.99
C2—H2A	0.99	C12—C13	1.507 (3)
C2—H2B	0.99	C12—H12A	0.99
C3—C4	1.524 (3)	C12—H12B	0.99
C3—H3A	0.99	C13—O14	1.234 (3)
C3—H3B	0.99	C15—H15A	0.98
C4—C5	1.515 (3)	C15—H15B	0.98
C4—H4A	0.99	C15—H15C	0.98
C4—H4B	0.99	C16—O17	1.440 (3)
C5—O6	1.446 (3)	C16—C20	1.492 (3)
C5—C9	1.525 (3)	C16—H16	1.0
C5—H5	1.0	O17—C18	1.359 (3)
O6—C7	1.431 (3)	C18—O21	1.204 (3)
C7—C16	1.522 (4)	C18—C19	1.471 (3)
C7—C8	1.534 (3)	C19—C20	1.317 (4)
C7—H7	1.0	C19—C22	1.493 (3)
C8—C15	1.521 (3)	C20—H20	0.95
C8—C9	1.531 (3)	C22—H22A	0.98
C8—H8	1.0	C22—H22B	0.98
C9—C10	1.533 (3)	C22—H22C	0.98
C9—H9	1.0	O1W—H1WA	0.86 (2)
C10—C11	1.528 (3)	O1W—H1WB	0.86 (2)
C13—N1—C2	123.0 (2)	C11—C10—C9	116.5 (2)
C13—N1—C10	113.62 (19)	N1—C10—H10	108.9
C2—N1—C10	123.2 (2)	C11—C10—H10	108.9
N1—C2—C3	111.90 (19)	C9—C10—H10	108.9
N1—C2—H2A	109.2	C10—C11—C12	103.9 (2)
C3—C2—H2A	109.2	C10—C11—H11A	111.0
N1—C2—H2B	109.2	C12—C11—H11A	111.0
C3—C2—H2B	109.2	C10—C11—H11B	111.0
H2A—C2—H2B	107.9	C12—C11—H11B	111.0
C4—C3—C2	114.8 (2)	H11A—C11—H11B	109.0
C4—C3—H3A	108.6	C13—C12—C11	103.2 (2)
C2—C3—H3A	108.6	C13—C12—H12A	111.1
C4—C3—H3B	108.6	C11—C12—H12A	111.1
C2—C3—H3B	108.6	C13—C12—H12B	111.1
H3A—C3—H3B	107.5	C11—C12—H12B	111.1
C5—C4—C3	113.9 (2)	H12A—C12—H12B	109.1
C5—C4—H4A	108.8	O14—C13—N1	125.7 (2)
C3—C4—H4A	108.8	O14—C13—C12	125.9 (2)
C5—C4—H4B	108.8	N1—C13—C12	108.4 (2)
C3—C4—H4B	108.8	C8—C15—H15A	109.5
H4A—C4—H4B	107.7	C8—C15—H15B	109.5
O6—C5—C4	107.90 (18)	H15A—C15—H15B	109.5
O6—C5—C9	105.84 (19)	C8—C15—H15C	109.5
C4—C5—C9	115.3 (2)	H15A—C15—H15C	109.5
O6—C5—H5	109.2	H15B—C15—H15C	109.5
C4—C5—H5	109.2	O17—C16—C20	104.1 (2)
C9—C5—H5	109.2	O17—C16—C7	109.86 (19)
C7—O6—C5	110.83 (17)	C20—C16—C7	114.2 (2)
O6—C7—C16	109.18 (19)	O17—C16—H16	109.5
O6—C7—C8	105.77 (19)	C20—C16—H16	109.5
C16—C7—C8	116.4 (2)	C7—C16—H16	109.5
O6—C7—H7	108.4	C18—O17—C16	108.90 (17)
C16—C7—H7	108.4	O21—C18—O17	121.5 (2)
C8—C7—H7	108.4	O21—C18—C19	129.5 (2)
C15—C8—C9	115.1 (2)	O17—C18—C19	109.0 (2)
C15—C8—C7	116.1 (2)	C20—C19—C18	107.6 (2)
C9—C8—C7	102.43 (19)	C20—C19—C22	131.2 (2)
C15—C8—H8	107.6	C18—C19—C22	121.2 (2)
C9—C8—H8	107.6	C19—C20—C16	110.2 (2)
C7—C8—H8	107.6	C19—C20—H20	124.9
C5—C9—C8	102.52 (19)	C16—C20—H20	124.9
C5—C9—C10	115.4 (2)	C19—C22—H22A	109.5
C8—C9—C10	114.6 (2)	C19—C22—H22B	109.5
C5—C9—H9	108.0	H22A—C22—H22B	109.5
C8—C9—H9	108.0	C19—C22—H22C	109.5
C10—C9—H9	108.0	H22A—C22—H22C	109.5
N1—C10—C11	101.69 (19)	H22B—C22—H22C	109.5
N1—C10—C9	111.73 (18)	H1WA—O1W—H1WB	103 (3)
C13—N1—C2—C3	−96.5 (3)	C5—C9—C10—C11	77.7 (3)
C10—N1—C2—C3	89.0 (3)	C8—C9—C10—C11	−41.0 (3)
N1—C2—C3—C4	−69.5 (3)	N1—C10—C11—C12	−28.7 (2)
C2—C3—C4—C5	54.7 (3)	C9—C10—C11—C12	−150.4 (2)
C3—C4—C5—O6	169.37 (19)	C10—C11—C12—C13	28.6 (2)
C3—C4—C5—C9	−72.6 (3)	C2—N1—C13—O14	2.5 (4)
C4—C5—O6—C7	134.6 (2)	C10—N1—C13—O14	177.4 (2)
C9—C5—O6—C7	10.7 (3)	C2—N1—C13—C12	−176.1 (2)
C5—O6—C7—C16	−113.8 (2)	C10—N1—C13—C12	−1.1 (3)
C5—O6—C7—C8	12.1 (3)	C11—C12—C13—O14	163.8 (2)
O6—C7—C8—C15	−155.9 (2)	C11—C12—C13—N1	−17.7 (2)
C16—C7—C8—C15	−34.4 (3)	O6—C7—C16—O17	59.7 (2)
O6—C7—C8—C9	−29.6 (2)	C8—C7—C16—O17	−59.9 (3)
C16—C7—C8—C9	91.8 (2)	O6—C7—C16—C20	−56.8 (3)
O6—C5—C9—C8	−28.7 (2)	C8—C7—C16—C20	−176.4 (2)
C4—C5—C9—C8	−147.9 (2)	C20—C16—O17—C18	4.8 (3)
O6—C5—C9—C10	−153.92 (19)	C7—C16—O17—C18	−117.8 (2)
C4—C5—C9—C10	86.9 (3)	C16—O17—C18—O21	176.1 (3)
C15—C8—C9—C5	161.9 (2)	C16—O17—C18—C19	−4.3 (3)
C7—C8—C9—C5	35.0 (2)	O21—C18—C19—C20	−178.6 (3)
C15—C8—C9—C10	−72.4 (3)	O17—C18—C19—C20	1.9 (3)
C7—C8—C9—C10	160.7 (2)	O21—C18—C19—C22	0.8 (4)
C13—N1—C10—C11	19.3 (2)	O17—C18—C19—C22	−178.7 (2)
C2—N1—C10—C11	−165.7 (2)	C18—C19—C20—C16	1.2 (3)
C13—N1—C10—C9	144.3 (2)	C22—C19—C20—C16	−178.1 (3)
C2—N1—C10—C9	−40.7 (3)	O17—C16—C20—C19	−3.7 (3)
C5—C9—C10—N1	−38.5 (3)	C7—C16—C20—C19	116.1 (3)
C8—C9—C10—N1	−157.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O14^i	0.86 (2)	2.02 (2)	2.874 (3)	173 (3)
O1W—H1WB···O14^ii	0.86 (2)	1.99 (2)	2.835 (3)	167 (3)
C7—H7···O21^iii	1.00	2.47	3.254 (3)	135
C22—H22C···O21^iv	0.98	2.58	3.407 (3)	142

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