15,15-Diphenyl-2,3,4,5,6,8,9,11,12-octa­hydro­imidazo[2,1-h][1,4,12]trioxa[7]thia­[9]azacyclo­tetra­decin-14(15H)-one

The title mol­ecule, C₂₃H₂₆N₂O₄S, adopts a cup-shaped conformation. In the crystal, layers lying parallel to the ab plane are formed by C—H...O hydrogen bonds and C—H...π(ring) inter­actions. The layers stack along the c-axis direction through normal van der Waals inter­actions.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.083
• Data-to-parameter ratio = 19.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.75 Report

Alert level G
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         13 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         10 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
   2 ALERT level G = General information/check it is not something unexpected

   0 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

15,15-Diphenyl-2,3,4,5,6,8,9,11,12-octahydroimidazo[2,1-h][1,4,12]trioxa[7]thia[9]azacyclotetradecin-14(15H)-one

Crystal data

C23H26N2O4S	Dx = 1.335 Mg m^−3
Mr = 426.52	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 8169 reflections
a = 16.6007 (17) Å	θ = 2.5–28.1°
b = 9.2362 (10) Å	µ = 0.19 mm^−1
c = 13.8439 (14) Å	T = 150 K
V = 2122.6 (4) Å^3	Block, colourless
Z = 4	0.28 × 0.24 × 0.17 mm
F(000) = 904

Data collection

Bruker Smart APEX CCD diffractometer	5219 independent reflections
Radiation source: fine-focus sealed tube	4568 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 8.3333 pixels mm^-1	θmax = 28.3°, θmin = 2.5°
ω scans	h = −21→22
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −12→11
Tmin = 0.84, Tmax = 0.97	l = −18→18
19152 measured reflections

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0489P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
5219 reflections	Δρmax = 0.42 e Å^−3
272 parameters	Δρmin = −0.15 e Å^−3
1 restraint	Absolute structure: Refined as an inversion twin.
Primary atom site location: dual	Absolute structure parameter: 0.25 (7)

Special details

Experimental. The diffraction data were collected in three sets of 363 frames (0.5° width in ω) at φ = 0, 120 and 240°. A scan time of 30 sec/frame was used.

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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å). All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. Refinement in Pna2₁ with SHELXL resulted in a Flack parameter of ca 0.25 and the message `inversion twin or centrosymmetric space group'. As the intensity statistics and PLATON ADSYMM did not support a centrosymmetric space group, the refinement was finished in Pna2₁ treating the model as an inversion twin with the addition of the instructions TWIN and BASF 0.25. The refined value of BASF was 0.25 (7).

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

	x	y	z	Uiso*/Ueq
S1	0.22326 (3)	0.46089 (6)	0.63964 (4)	0.02584 (14)
O1	0.37107 (10)	0.15624 (16)	0.40483 (11)	0.0262 (3)
O2	0.26905 (9)	0.77584 (18)	0.59446 (13)	0.0305 (4)
O3	0.29439 (10)	0.71630 (18)	0.39376 (13)	0.0332 (4)
O4	0.26344 (11)	0.41717 (17)	0.31948 (13)	0.0311 (4)
N1	0.29066 (11)	0.2903 (2)	0.50682 (14)	0.0221 (4)
N2	0.37902 (11)	0.37283 (19)	0.61953 (13)	0.0220 (4)
C1	0.30600 (13)	0.3719 (2)	0.58992 (16)	0.0212 (4)
C2	0.36224 (13)	0.2330 (2)	0.47512 (15)	0.0209 (4)
C3	0.42545 (13)	0.2866 (2)	0.54857 (15)	0.0201 (4)
C4	0.27256 (15)	0.5931 (3)	0.71517 (17)	0.0293 (5)
H4A	0.231310	0.644885	0.753541	0.035*
H4B	0.308662	0.542256	0.760888	0.035*
C5	0.32084 (14)	0.7016 (3)	0.65901 (19)	0.0310 (6)
H5A	0.346442	0.771405	0.703764	0.037*
H5B	0.363887	0.651719	0.622371	0.037*
C6	0.31097 (16)	0.8699 (3)	0.5306 (2)	0.0346 (6)
H6A	0.351600	0.924720	0.568061	0.041*
H6B	0.272262	0.940579	0.503540	0.041*
C7	0.35286 (15)	0.7933 (3)	0.4482 (2)	0.0350 (6)
H7A	0.380465	0.864852	0.406480	0.042*
H7B	0.393736	0.725386	0.473819	0.042*
C8	0.32854 (16)	0.6518 (3)	0.30959 (19)	0.0326 (6)
H8A	0.378561	0.599576	0.327050	0.039*
H8B	0.342461	0.727969	0.262161	0.039*
C9	0.26965 (16)	0.5486 (3)	0.26582 (19)	0.0341 (6)
H9A	0.216034	0.595253	0.262729	0.041*
H9B	0.286596	0.525951	0.198937	0.041*
C10	0.20222 (15)	0.4167 (3)	0.39115 (18)	0.0302 (5)
H10A	0.148380	0.414019	0.360436	0.036*
H10B	0.205884	0.505135	0.431330	0.036*
C11	0.21474 (14)	0.2835 (3)	0.45276 (18)	0.0268 (5)
H11A	0.169351	0.273990	0.498704	0.032*
H11B	0.215005	0.196608	0.410870	0.032*
C12	0.48827 (13)	0.3867 (2)	0.50146 (16)	0.0205 (4)
C13	0.53956 (14)	0.4642 (2)	0.56242 (18)	0.0263 (5)
H13	0.535967	0.451446	0.630374	0.032*
C14	0.59561 (15)	0.5596 (2)	0.52449 (19)	0.0312 (6)
H14	0.630297	0.611768	0.566506	0.037*
C15	0.60130 (15)	0.5791 (3)	0.42553 (19)	0.0330 (6)
H15	0.639361	0.645390	0.399664	0.040*
C16	0.55158 (16)	0.5020 (3)	0.36486 (19)	0.0330 (6)
H16	0.555677	0.514677	0.296938	0.040*
C17	0.49500 (14)	0.4052 (3)	0.40275 (17)	0.0272 (5)
H17	0.461081	0.351902	0.360427	0.033*
C18	0.46593 (13)	0.1555 (2)	0.59558 (16)	0.0218 (5)
C19	0.46380 (15)	0.1332 (3)	0.69500 (18)	0.0285 (5)
H19	0.438323	0.201865	0.735956	0.034*
C20	0.49917 (17)	0.0100 (3)	0.7340 (2)	0.0377 (7)
H20	0.498233	−0.004434	0.801960	0.045*
C21	0.53572 (16)	−0.0920 (3)	0.6754 (2)	0.0374 (6)
H21	0.558427	−0.177220	0.702531	0.045*
C22	0.53873 (15)	−0.0684 (3)	0.5777 (2)	0.0334 (6)
H22	0.563913	−0.137691	0.536929	0.040*
C23	0.50554 (15)	0.0549 (3)	0.53801 (18)	0.0262 (5)
H23	0.509812	0.071219	0.470452	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0209 (2)	0.0282 (3)	0.0284 (3)	0.0015 (2)	0.0053 (2)	−0.0022 (3)
O1	0.0308 (9)	0.0251 (8)	0.0227 (8)	0.0017 (7)	−0.0012 (7)	−0.0063 (7)
O2	0.0252 (8)	0.0259 (9)	0.0403 (10)	0.0009 (7)	0.0014 (7)	−0.0011 (7)
O3	0.0290 (9)	0.0309 (9)	0.0398 (10)	−0.0008 (7)	0.0031 (8)	−0.0067 (8)
O4	0.0376 (10)	0.0279 (9)	0.0279 (9)	0.0030 (7)	0.0015 (8)	−0.0024 (7)
N1	0.0206 (9)	0.0232 (9)	0.0224 (9)	−0.0002 (7)	−0.0003 (7)	−0.0022 (8)
N2	0.0220 (9)	0.0237 (9)	0.0203 (10)	0.0015 (7)	0.0013 (7)	−0.0029 (7)
C1	0.0239 (11)	0.0186 (10)	0.0212 (11)	0.0000 (8)	0.0025 (9)	0.0006 (9)
C2	0.0230 (11)	0.0189 (10)	0.0207 (10)	−0.0004 (8)	−0.0002 (9)	0.0007 (8)
C3	0.0229 (11)	0.0191 (10)	0.0183 (10)	0.0010 (8)	−0.0003 (8)	−0.0027 (8)
C4	0.0288 (13)	0.0347 (13)	0.0243 (12)	0.0083 (10)	−0.0011 (10)	−0.0085 (10)
C5	0.0243 (12)	0.0293 (12)	0.0394 (15)	0.0043 (9)	−0.0049 (10)	−0.0108 (10)
C6	0.0313 (13)	0.0232 (12)	0.0493 (17)	−0.0033 (10)	0.0038 (12)	−0.0042 (11)
C7	0.0315 (13)	0.0313 (13)	0.0420 (15)	−0.0067 (11)	0.0035 (11)	−0.0012 (12)
C8	0.0366 (14)	0.0284 (13)	0.0328 (14)	0.0058 (11)	0.0051 (11)	0.0039 (11)
C9	0.0403 (15)	0.0377 (15)	0.0244 (13)	0.0057 (11)	−0.0031 (11)	0.0031 (10)
C10	0.0265 (12)	0.0375 (14)	0.0267 (12)	0.0032 (10)	−0.0035 (10)	−0.0027 (11)
C11	0.0214 (11)	0.0293 (12)	0.0298 (12)	−0.0037 (9)	−0.0046 (9)	−0.0051 (10)
C12	0.0202 (10)	0.0161 (10)	0.0251 (11)	0.0036 (8)	0.0018 (9)	−0.0001 (8)
C13	0.0254 (12)	0.0234 (11)	0.0301 (12)	0.0002 (9)	−0.0004 (10)	−0.0049 (10)
C14	0.0252 (12)	0.0228 (11)	0.0455 (15)	−0.0013 (9)	0.0007 (11)	−0.0050 (11)
C15	0.0233 (12)	0.0261 (12)	0.0495 (17)	0.0021 (10)	0.0071 (11)	0.0114 (11)
C16	0.0298 (13)	0.0373 (14)	0.0318 (13)	0.0056 (11)	0.0056 (10)	0.0116 (11)
C17	0.0253 (12)	0.0302 (13)	0.0262 (12)	0.0021 (9)	−0.0005 (10)	0.0024 (10)
C18	0.0182 (10)	0.0214 (10)	0.0259 (11)	−0.0023 (8)	−0.0016 (9)	0.0008 (9)
C19	0.0262 (13)	0.0341 (13)	0.0253 (12)	−0.0017 (10)	0.0012 (9)	0.0007 (10)
C20	0.0306 (14)	0.0514 (16)	0.0312 (14)	−0.0049 (12)	−0.0017 (11)	0.0191 (13)
C21	0.0243 (13)	0.0309 (13)	0.0569 (17)	0.0005 (11)	−0.0038 (11)	0.0162 (12)
C22	0.0246 (12)	0.0258 (12)	0.0497 (17)	0.0046 (10)	−0.0031 (12)	0.0004 (12)
C23	0.0252 (12)	0.0259 (12)	0.0274 (12)	0.0015 (9)	0.0003 (9)	−0.0007 (10)

Geometric parameters (Å, º)

S1—C1	1.742 (2)	C9—H9A	0.9900
S1—C4	1.804 (2)	C9—H9B	0.9900
O1—C2	1.213 (3)	C10—C11	1.512 (3)
O2—C5	1.417 (3)	C10—H10A	0.9900
O2—C6	1.421 (3)	C10—H10B	0.9900
O3—C7	1.420 (3)	C11—H11A	0.9900
O3—C8	1.426 (3)	C11—H11B	0.9900
O4—C10	1.420 (3)	C12—C17	1.382 (3)
O4—C9	1.427 (3)	C12—C13	1.396 (3)
N1—C2	1.373 (3)	C13—C14	1.385 (3)
N1—C1	1.399 (3)	C13—H13	0.9500
N1—C11	1.467 (3)	C14—C15	1.385 (4)
N2—C1	1.280 (3)	C14—H14	0.9500
N2—C3	1.481 (3)	C15—C16	1.376 (4)
C2—C3	1.543 (3)	C15—H15	0.9500
C3—C18	1.531 (3)	C16—C17	1.399 (4)
C3—C12	1.538 (3)	C16—H16	0.9500
C4—C5	1.501 (4)	C17—H17	0.9500
C4—H4A	0.9900	C18—C23	1.390 (3)
C4—H4B	0.9900	C18—C19	1.392 (3)
C5—H5A	0.9900	C19—C20	1.390 (4)
C5—H5B	0.9900	C19—H19	0.9500
C6—C7	1.512 (4)	C20—C21	1.383 (4)
C6—H6A	0.9900	C20—H20	0.9500
C6—H6B	0.9900	C21—C22	1.371 (4)
C7—H7A	0.9900	C21—H21	0.9500
C7—H7B	0.9900	C22—C23	1.379 (3)
C8—C9	1.494 (4)	C22—H22	0.9500
C8—H8A	0.9900	C23—H23	0.9500
C8—H8B	0.9900
C1—S1—C4	100.98 (11)	C8—C9—H9A	109.2
C5—O2—C6	113.00 (18)	O4—C9—H9B	109.2
C7—O3—C8	111.80 (19)	C8—C9—H9B	109.2
C10—O4—C9	114.71 (19)	H9A—C9—H9B	107.9
C2—N1—C1	108.25 (18)	O4—C10—C11	107.34 (19)
C2—N1—C11	124.32 (19)	O4—C10—H10A	110.2
C1—N1—C11	126.81 (19)	C11—C10—H10A	110.2
C1—N2—C3	106.09 (18)	O4—C10—H10B	110.2
N2—C1—N1	116.06 (19)	C11—C10—H10B	110.2
N2—C1—S1	128.12 (17)	H10A—C10—H10B	108.5
N1—C1—S1	115.82 (16)	N1—C11—C10	111.8 (2)
O1—C2—N1	125.9 (2)	N1—C11—H11A	109.3
O1—C2—C3	129.4 (2)	C10—C11—H11A	109.3
N1—C2—C3	104.72 (17)	N1—C11—H11B	109.3
N2—C3—C18	111.83 (18)	C10—C11—H11B	109.3
N2—C3—C12	108.13 (16)	H11A—C11—H11B	107.9
C18—C3—C12	110.98 (17)	C17—C12—C13	119.0 (2)
N2—C3—C2	104.83 (16)	C17—C12—C3	123.3 (2)
C18—C3—C2	108.94 (17)	C13—C12—C3	117.72 (19)
C12—C3—C2	112.00 (17)	C14—C13—C12	120.4 (2)
C5—C4—S1	113.21 (17)	C14—C13—H13	119.8
C5—C4—H4A	108.9	C12—C13—H13	119.8
S1—C4—H4A	108.9	C13—C14—C15	120.3 (2)
C5—C4—H4B	108.9	C13—C14—H14	119.9
S1—C4—H4B	108.9	C15—C14—H14	119.9
H4A—C4—H4B	107.7	C16—C15—C14	119.7 (2)
O2—C5—C4	109.02 (19)	C16—C15—H15	120.1
O2—C5—H5A	109.9	C14—C15—H15	120.1
C4—C5—H5A	109.9	C15—C16—C17	120.3 (2)
O2—C5—H5B	109.9	C15—C16—H16	119.8
C4—C5—H5B	109.9	C17—C16—H16	119.8
H5A—C5—H5B	108.3	C12—C17—C16	120.3 (2)
O2—C6—C7	114.1 (2)	C12—C17—H17	119.9
O2—C6—H6A	108.7	C16—C17—H17	119.9
C7—C6—H6A	108.7	C23—C18—C19	118.7 (2)
O2—C6—H6B	108.7	C23—C18—C3	119.5 (2)
C7—C6—H6B	108.7	C19—C18—C3	121.7 (2)
H6A—C6—H6B	107.6	C20—C19—C18	119.6 (2)
O3—C7—C6	108.7 (2)	C20—C19—H19	120.2
O3—C7—H7A	109.9	C18—C19—H19	120.2
C6—C7—H7A	109.9	C21—C20—C19	121.0 (2)
O3—C7—H7B	109.9	C21—C20—H20	119.5
C6—C7—H7B	109.9	C19—C20—H20	119.5
H7A—C7—H7B	108.3	C22—C21—C20	119.1 (3)
O3—C8—C9	109.7 (2)	C22—C21—H21	120.4
O3—C8—H8A	109.7	C20—C21—H21	120.4
C9—C8—H8A	109.7	C21—C22—C23	120.6 (3)
O3—C8—H8B	109.7	C21—C22—H22	119.7
C9—C8—H8B	109.7	C23—C22—H22	119.7
H8A—C8—H8B	108.2	C22—C23—C18	120.8 (2)
O4—C9—C8	112.3 (2)	C22—C23—H23	119.6
O4—C9—H9A	109.2	C18—C23—H23	119.6
C3—N2—C1—N1	2.5 (2)	C2—N1—C11—C10	−93.2 (3)
C3—N2—C1—S1	−176.97 (17)	C1—N1—C11—C10	76.6 (3)
C2—N1—C1—N2	−2.0 (3)	O4—C10—C11—N1	65.4 (2)
C11—N1—C1—N2	−173.2 (2)	N2—C3—C12—C17	−125.5 (2)
C2—N1—C1—S1	177.53 (15)	C18—C3—C12—C17	111.5 (2)
C11—N1—C1—S1	6.3 (3)	C2—C3—C12—C17	−10.5 (3)
C4—S1—C1—N2	17.3 (2)	N2—C3—C12—C13	53.2 (2)
C4—S1—C1—N1	−162.16 (17)	C18—C3—C12—C13	−69.8 (2)
C1—N1—C2—O1	179.9 (2)	C2—C3—C12—C13	168.20 (18)
C11—N1—C2—O1	−8.7 (4)	C17—C12—C13—C14	0.8 (3)
C1—N1—C2—C3	0.5 (2)	C3—C12—C13—C14	−177.91 (19)
C11—N1—C2—C3	172.0 (2)	C12—C13—C14—C15	0.1 (3)
C1—N2—C3—C18	−119.9 (2)	C13—C14—C15—C16	−0.7 (4)
C1—N2—C3—C12	117.66 (19)	C14—C15—C16—C17	0.5 (4)
C1—N2—C3—C2	−2.0 (2)	C13—C12—C17—C16	−1.0 (3)
O1—C2—C3—N2	−178.5 (2)	C3—C12—C17—C16	177.6 (2)
N1—C2—C3—N2	0.8 (2)	C15—C16—C17—C12	0.4 (4)
O1—C2—C3—C18	−58.6 (3)	N2—C3—C18—C23	173.82 (19)
N1—C2—C3—C18	120.68 (19)	C12—C3—C18—C23	−65.3 (3)
O1—C2—C3—C12	64.5 (3)	C2—C3—C18—C23	58.4 (3)
N1—C2—C3—C12	−116.16 (19)	N2—C3—C18—C19	−5.8 (3)
C1—S1—C4—C5	64.68 (19)	C12—C3—C18—C19	115.1 (2)
C6—O2—C5—C4	−173.52 (18)	C2—C3—C18—C19	−121.2 (2)
S1—C4—C5—O2	59.4 (2)	C23—C18—C19—C20	−1.7 (4)
C5—O2—C6—C7	77.0 (3)	C3—C18—C19—C20	177.9 (2)
C8—O3—C7—C6	174.8 (2)	C18—C19—C20—C21	−0.8 (4)
O2—C6—C7—O3	59.3 (3)	C19—C20—C21—C22	1.8 (4)
C7—O3—C8—C9	168.7 (2)	C20—C21—C22—C23	−0.3 (4)
C10—O4—C9—C8	91.9 (3)	C21—C22—C23—C18	−2.2 (4)
O3—C8—C9—O4	−74.9 (3)	C19—C18—C23—C22	3.2 (4)
C9—O4—C10—C11	−169.19 (19)	C3—C18—C23—C22	−176.4 (2)

Hydrogen-bond geometry (Å, º)

Cg3 is the centroid of the C18–C23 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···N2	0.99	2.59	3.233 (3)	123
C10—H10B···O3	0.99	2.50	3.162 (3)	124
C14—H14···O2^i	0.95	2.56	3.397 (3)	148
C6—H6A···Cg3^ii	0.99	2.84	3.792 (3)	162

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x, y+1, z.