Invariom-model refinement and Hirshfeld surface analysis of well-ordered solvent-free dibenzo-21-crown-7

Crown ethers and their supra­molecular derivatives are well-known chelators and scavengers for a variety of cations, most notably heavier alkali and alkaline-earth ions. Although they are widely used in synthetic chemistry, available crystal structures of uncoordinated and solvent-free crown ethers regularly suffer from disorder. In this study, we present the X-ray crystal structure analysis of well-ordered solvent-free crystals of dibenzo-21-crown-7 (systematic name: dibenzo[b,k]-1,4,7,10,13,16,19-hepta­oxa­cyclo­heneicosa-2,11-diene, C₂₂H₂₈O₇). Because of the quality of the crystal and diffraction data, we have chosen invarioms, in addition to standard independent spherical atoms, for modelling and briefly discuss the different refinement results. The electrostatic potential, which is directly deducible from the invariom model, and the Hirshfeld surface are analysed and complemented with inter­action-energy computations to characterize inter­molecular contacts. The boat-like mol­ecules stack along the a axis and are arranged as dimers of chains, which assemble as rows to form a three-dimensional structure. Dispersive C—H...H—C and C—H...π inter­actions dominate, but nonclassical hydrogen bonds are present and reflect the overall rather weak electrostatic influence. A fingerprint plot of the Hirshfeld surface summarizes and visualizes the inter­molecular inter­actions. The insight gained into the crystal structure of dibenzo-21-crown-7 not only demonstrates the power of invariom refinement, Hirshfeld surface analysis and inter­action-energy computation, but also hints at favourable conditions for crystallizing solvent-free crown ethers.

Computing details

For both structures, data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a). Program(s) used to refine structure: XD2016 (Volkov et al., 2016) for Invariom; SHELXL2016 (Sheldrick, 2015b) for IAM. For both structures, molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008). Software used to prepare material for publication: WinXD (Volkov et al., 2016) for Invariom; OLEX2 (Dolomanov et al., 2009) for IAM.

Dibenzo[b,k][1,4,7,10,13,16,19]heptaoxacyclohenicosa-2,11-diene (Invariom)

Crystal data

C22H28O7	Dx = 1.34 Mg m^−3
Mr = 404.44	Melting point: 388 K
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 4.9801 (1) Å	Cell parameters from 7438 reflections
b = 17.4771 (2) Å	θ = 2.5–73.5°
c = 23.1000 (2) Å	µ = 0.82 mm^−1
β = 94.124 (1)°	T = 150 K
V = 2005.37 (5) Å^3	Shard, colourless
Z = 4	0.74 × 0.14 × 0.08 mm
F(000) = 864

Data collection

Agilent SuperNova (single source) diffractometer	3925 independent reflections
Radiation source: micro-focus sealed tube, Agilent Nova	3559 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.018
Detector resolution: 10.5435 pixels mm^-1	θmax = 73.7°, θmin = 3.2°
ω scans	h = −5→6
Absorption correction: gaussian (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −21→21
Tmin = 0.598, Tmax = 1.000	l = −27→28
13236 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Only H-atom displacement parameters refined
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0497P)^2 + 0.1P] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
3664 reflections	Δρmax = 0.41 e Å^−3
290 parameters	Δρmin = −0.24 e Å^−3
0 restraints

Special details

Refinement. After conventional IAM refinement, invarioms were assigned and set up using MoleCoolQt Revision 558 (Hübschle & Dittrich, 2011).

All hydrogen atoms were reset to neutron-diffraction–derived distances to their carrier atoms after every refinement cycle (d = 1.0962 Å for methylene groups, d = 1.0823 Å for aromatics).

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

	x	y	z	Uiso*/Ueq
C2	1.0446 (2)	0.65479 (6)	0.55315 (5)	0.027
H2A	1.15515	0.70408	0.537643	0.056 (5)*
H2B	0.921845	0.673982	0.587914	0.051 (4)*
C3	0.8678 (2)	0.61989 (6)	0.50382 (5)	0.026
H3A	0.99184	0.597868	0.470203	0.040 (4)*
H3B	0.749237	0.572587	0.519914	0.042 (4)*
C5	0.5121 (2)	0.66085 (6)	0.43710 (4)	0.024
C6	0.4908 (2)	0.58977 (6)	0.41032 (5)	0.027
H6	0.628561	0.544207	0.423852	0.043 (4)*
C7	0.2899 (2)	0.57697 (7)	0.36562 (5)	0.03
H7	0.275295	0.52187	0.344238	0.053 (4)*
C8	0.1099 (2)	0.63436 (7)	0.34872 (5)	0.031
H8	−0.046729	0.623725	0.314726	0.057 (5)*
C9	0.1296 (2)	0.70607 (6)	0.37537 (5)	0.028
H9	−0.011815	0.750858	0.362114	0.051 (4)*
C10	0.3311 (2)	0.71984 (6)	0.41890 (4)	0.024
C12	0.1553 (2)	0.84115 (7)	0.44408 (5)	0.033
H12A	−0.023216	0.814777	0.460837	0.061 (5)*
H12B	0.104154	0.859291	0.399212	0.060 (5)*
C13	0.2414 (3)	0.90954 (7)	0.48096 (5)	0.037
H13A	0.424768	0.933229	0.46439	0.064 (5)*
H13B	0.08429	0.953382	0.475337	0.064 (5)*
C15	0.5459 (3)	0.85914 (8)	0.55510 (6)	0.041
H15A	0.69461	0.880486	0.526282	0.075 (6)*
H15B	0.528137	0.797078	0.549115	0.081 (6)*
C16	0.6417 (3)	0.87561 (8)	0.61654 (6)	0.04
H16A	0.854031	0.859333	0.623821	0.092 (7)*
H16B	0.624433	0.937083	0.624937	0.075 (6)*
C18	0.5696 (3)	0.84899 (7)	0.71319 (6)	0.039
H18A	0.450759	0.896087	0.729498	0.069 (6)*
H18B	0.781893	0.866109	0.716492	0.066 (5)*
C19	0.5354 (2)	0.77896 (6)	0.74960 (5)	0.032
H19A	0.561502	0.793497	0.795824	0.054 (4)*
H19B	0.33372	0.754776	0.740426	0.057 (5)*
C21	0.7616 (2)	0.66022 (6)	0.76552 (5)	0.026
C22	0.6192 (2)	0.64273 (6)	0.81330 (5)	0.03
H22	0.476384	0.683409	0.828543	0.054 (4)*
C23	0.6593 (2)	0.57272 (7)	0.84169 (5)	0.034
H23	0.547514	0.559374	0.87888	0.059 (5)*
C24	0.8413 (2)	0.52029 (7)	0.82286 (5)	0.034
H24	0.871798	0.466227	0.845215	0.050 (4)*
C25	0.9859 (2)	0.53724 (6)	0.77468 (5)	0.03
H25	1.129405	0.496312	0.760065	0.055 (4)*
C26	0.9465 (2)	0.60623 (6)	0.74558 (5)	0.026
C28	1.2705 (2)	0.57778 (6)	0.67776 (5)	0.026
H28A	1.182808	0.521846	0.666116	0.045 (4)*
H28B	1.432227	0.569403	0.711938	0.043 (4)*
C29	1.3829 (2)	0.61374 (7)	0.62490 (5)	0.029
H29A	1.391005	0.675946	0.630839	0.051 (4)*
H29B	1.589078	0.59329	0.621268	0.054 (5)*
O1	1.22374 (18)	0.59660 (5)	0.57328 (4)	0.037
O4	0.69566 (15)	0.67931 (4)	0.48120 (3)	0.028
O11	0.37270 (15)	0.78813 (4)	0.44647 (3)	0.03
O14	0.29216 (18)	0.89459 (5)	0.54075 (4)	0.04
O17	0.48593 (19)	0.83406 (5)	0.65485 (4)	0.041
O20	0.73637 (16)	0.72575 (4)	0.73461 (4)	0.033
O27	1.06943 (15)	0.62756 (5)	0.69748 (3)	0.031

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0249 (5)	0.0283 (5)	0.0278 (5)	0.0033 (4)	−0.0007 (4)	−0.0021 (4)
C3	0.0234 (5)	0.0272 (5)	0.0270 (5)	0.0028 (4)	−0.0005 (4)	−0.0013 (4)
C5	0.0203 (5)	0.0241 (5)	0.0262 (5)	0.0025 (4)	0.0008 (4)	−0.0020 (4)
C6	0.0228 (5)	0.0246 (5)	0.0330 (6)	0.0032 (4)	−0.0010 (4)	−0.0055 (4)
C7	0.0264 (6)	0.0293 (6)	0.0342 (6)	0.0012 (4)	−0.0033 (4)	−0.0068 (4)
C8	0.0272 (6)	0.0326 (6)	0.0313 (6)	0.0014 (4)	−0.0051 (4)	−0.0021 (5)
C9	0.0264 (5)	0.0289 (6)	0.0294 (5)	0.0031 (4)	−0.0027 (4)	0.0018 (4)
C10	0.0237 (5)	0.0234 (5)	0.0259 (5)	0.0038 (4)	0.0013 (4)	0.0006 (4)
C12	0.0358 (6)	0.0281 (6)	0.0340 (6)	0.0106 (5)	0.0025 (5)	−0.0001 (5)
C13	0.0508 (8)	0.0278 (6)	0.0342 (6)	0.0113 (5)	0.0060 (5)	−0.0023 (5)
C15	0.0394 (7)	0.0482 (8)	0.0350 (7)	0.0064 (6)	0.0050 (5)	−0.0052 (6)
C16	0.0397 (7)	0.0396 (7)	0.0394 (7)	−0.0005 (5)	0.0035 (5)	−0.0083 (5)
C18	0.0516 (8)	0.0280 (6)	0.0361 (6)	0.0036 (5)	−0.0010 (5)	−0.0021 (5)
C19	0.0353 (6)	0.0281 (6)	0.0319 (6)	0.0056 (5)	0.0031 (5)	−0.0034 (4)
C21	0.0246 (5)	0.0245 (5)	0.0282 (5)	−0.0006 (4)	0.0025 (4)	−0.0054 (4)
C22	0.0311 (6)	0.0280 (5)	0.0315 (6)	−0.0019 (4)	0.0058 (4)	−0.0041 (4)
C23	0.0366 (6)	0.0314 (6)	0.0339 (6)	−0.0043 (5)	0.0063 (5)	−0.0006 (5)
C24	0.0345 (6)	0.0286 (6)	0.0384 (6)	−0.0022 (5)	0.0023 (5)	0.0029 (5)
C25	0.0272 (6)	0.0269 (6)	0.0362 (6)	0.0006 (4)	0.0005 (4)	−0.0007 (5)
C26	0.0216 (5)	0.0255 (5)	0.0300 (5)	0.0006 (4)	0.0001 (4)	−0.0042 (4)
C28	0.0200 (5)	0.0287 (5)	0.0303 (5)	0.0027 (4)	−0.0011 (4)	−0.0049 (4)
C29	0.0244 (5)	0.0330 (6)	0.0293 (5)	0.0034 (4)	−0.0004 (4)	−0.0023 (4)
O1	0.0432 (5)	0.0342 (4)	0.0319 (4)	0.0131 (4)	−0.0102 (4)	−0.0083 (3)
O4	0.0251 (4)	0.0261 (4)	0.0311 (4)	0.0045 (3)	−0.0034 (3)	−0.0041 (3)
O11	0.0291 (4)	0.0252 (4)	0.0343 (4)	0.0055 (3)	−0.0003 (3)	−0.0034 (3)
O14	0.0411 (5)	0.0465 (5)	0.0322 (4)	0.0101 (4)	0.0081 (4)	−0.0028 (4)
O17	0.0489 (5)	0.0393 (5)	0.0349 (5)	−0.0029 (4)	−0.0011 (4)	0.0011 (4)
O20	0.0358 (4)	0.0283 (4)	0.0353 (4)	0.0053 (3)	0.0093 (3)	−0.0001 (3)
O27	0.0284 (4)	0.0310 (4)	0.0332 (4)	0.0059 (3)	0.0055 (3)	−0.0004 (3)

Geometric parameters (Å, º)

C2—H2A	1.0962	C16—H16A	1.0962
C2—H2B	1.0962	C16—H16B	1.0963
C2—C3	1.5171 (15)	C16—O17	1.4181 (16)
C2—O1	1.4095 (13)	C18—H18A	1.0962
C3—H3A	1.0963	C18—H18B	1.0962
C3—H3B	1.0963	C18—C19	1.5015 (17)
C3—O4	1.4221 (12)	C18—O17	1.4060 (15)
C5—C6	1.3885 (15)	C19—H19A	1.0962
C5—C10	1.4135 (14)	C19—H19B	1.0962
C5—O4	1.3577 (12)	C19—O20	1.4270 (13)
C6—H6	1.0822	C21—C22	1.3882 (15)
C6—C7	1.4033 (15)	C21—C26	1.4184 (14)
C7—H7	1.0822	C21—O20	1.3507 (13)
C7—C8	1.3827 (16)	C22—H22	1.0822
C8—H8	1.0823	C22—C23	1.3957 (17)
C8—C9	1.3966 (16)	C23—H23	1.0823
C9—H9	1.0822	C23—C24	1.3810 (17)
C9—C10	1.3896 (15)	C24—H24	1.0823
C10—O11	1.3618 (13)	C24—C25	1.3999 (17)
C12—H12A	1.0963	C25—H25	1.0823
C12—H12B	1.0962	C25—C26	1.3875 (16)
C12—C13	1.5120 (17)	C26—O27	1.3589 (13)
C12—O11	1.4232 (13)	C28—H28A	1.0963
C13—H13A	1.0962	C28—H28B	1.0962
C13—H13B	1.0962	C28—C29	1.5157 (16)
C13—O14	1.4105 (15)	C28—O27	1.4258 (12)
C15—H15A	1.0963	C29—H29A	1.0963
C15—H15B	1.0962	C29—H29B	1.0962
C15—C16	1.4924 (18)	C29—O1	1.4155 (13)
C15—O14	1.4248 (16)
H2A—C2—H2B	108.58	H16A—C16—O17	109.65
H2A—C2—C3	110.40	H16B—C16—O17	109.76
H2A—C2—O1	110.73	H18A—C18—H18B	108.23
H2B—C2—C3	110.43	H18A—C18—C19	109.50
H2B—C2—O1	110.62	H18A—C18—O17	109.79
C3—C2—O1	106.08 (8)	H18B—C18—C19	109.34
C2—C3—H3A	110.31	H18B—C18—O17	109.58
C2—C3—H3B	110.26	C19—C18—O17	110.36 (10)
C2—C3—O4	106.52 (8)	C18—C19—H19A	110.27
H3A—C3—H3B	108.67	C18—C19—H19B	110.20
H3A—C3—O4	110.58	C18—C19—O20	106.59 (9)
H3B—C3—O4	110.49	H19A—C19—H19B	108.69
C6—C5—C10	119.56 (10)	H19A—C19—O20	110.56
C6—C5—O4	124.93 (9)	H19B—C19—O20	110.53
C10—C5—O4	115.50 (9)	C22—C21—C26	119.50 (10)
C5—C6—H6	120.20	C22—C21—O20	125.01 (10)
C5—C6—C7	119.87 (10)	C26—C21—O20	115.49 (9)
H6—C6—C7	119.93	C21—C22—H22	119.95
C6—C7—H7	119.90	C21—C22—C23	120.17 (10)
C6—C7—C8	120.38 (10)	H22—C22—C23	119.88
H7—C7—C8	119.72	C22—C23—H23	119.83
C7—C8—H8	119.93	C22—C23—C24	120.58 (11)
C7—C8—C9	120.20 (10)	H23—C23—C24	119.59
H8—C8—C9	119.87	C23—C24—H24	120.11
C8—C9—H9	120.05	C23—C24—C25	119.78 (11)
C8—C9—C10	119.90 (10)	H24—C24—C25	120.10
H9—C9—C10	120.05	C24—C25—H25	119.81
C5—C10—C9	120.06 (10)	C24—C25—C26	120.41 (11)
C5—C10—O11	115.32 (9)	H25—C25—C26	119.78
C9—C10—O11	124.61 (9)	C21—C26—C25	119.56 (10)
H12A—C12—H12B	108.44	C21—C26—O27	115.11 (9)
H12A—C12—C13	109.75	C25—C26—O27	125.33 (10)
H12A—C12—O11	110.28	H28A—C28—H28B	108.47
H12B—C12—C13	109.95	H28A—C28—C29	109.61
H12B—C12—O11	110.44	H28A—C28—O27	110.23
C13—C12—O11	107.97 (10)	H28B—C28—C29	109.93
C12—C13—H13A	108.15	H28B—C28—O27	110.36
C12—C13—H13B	108.33	C29—C28—O27	108.23 (9)
C12—C13—O14	115.39 (10)	C28—C29—H29A	108.84
H13A—C13—H13B	107.46	C28—C29—H29B	109.19
H13A—C13—O14	108.47	C28—C29—O1	111.98 (9)
H13B—C13—O14	108.76	H29A—C29—H29B	107.85
H15A—C15—H15B	108.18	H29A—C29—O1	109.19
H15A—C15—C16	109.15	H29B—C29—O1	109.72
H15A—C15—O14	109.71	C2—O1—C29	115.34 (8)
H15B—C15—C16	109.15	C3—O4—C5	117.24 (8)
H15B—C15—O14	109.80	C10—O11—C12	117.56 (8)
C16—C15—O14	110.79 (10)	C13—O14—C15	113.69 (9)
C15—C16—H16A	109.56	C16—O17—C18	111.43 (10)
C15—C16—H16B	109.48	C19—O20—C21	117.68 (9)
C15—C16—O17	110.05 (11)	C26—O27—C28	117.51 (9)
H16A—C16—H16B	108.31
H2A—C2—C3—H3A	63.05	C16—C15—O14—C13	154.91 (14)
H2A—C2—C3—H3B	−176.92	O14—C15—C16—H16A	−167.24
H2A—C2—C3—O4	−57.00	O14—C15—C16—H16B	−48.60
H2A—C2—O1—C29	68.75	O14—C15—C16—O17	72.12 (12)
H2B—C2—C3—H3A	−176.87	C15—C16—O17—C18	−179.38 (14)
H2B—C2—C3—H3B	−56.83	H16A—C16—O17—C18	60.04 (11)
H2B—C2—C3—O4	63.08	H16B—C16—O17—C18	−58.83
H2B—C2—O1—C29	−51.67	H18A—C18—C19—H19A	−47.69
O1—C2—C3—H3A	−56.97	H18A—C18—C19—H19B	72.30
O1—C2—C3—H3B	63.07	H18A—C18—C19—O20	−167.74
C3—C2—O1—C29	−171.45 (12)	H18A—C18—O17—C16	92.57
O1—C2—C3—O4	−177.02 (11)	H18B—C18—C19—H19A	70.74
C2—C3—O4—C5	−178.27 (12)	H18B—C18—C19—H19B	−169.27
H3A—C3—O4—C5	61.85	H18B—C18—C19—O20	−49.31
H3B—C3—O4—C5	−58.50	H18B—C18—O17—C16	−26.18
C10—C5—C6—H6	179.91 (16)	C19—C18—O17—C16	−146.64 (14)
C10—C5—C6—C7	−0.19 (10)	O17—C18—C19—H19A	−168.66
C6—C5—C10—C9	1.44 (10)	O17—C18—C19—H19B	−48.67
C6—C5—C10—O11	−178.08 (14)	O17—C18—C19—O20	71.29 (11)
C6—C5—O4—C3	−4.01 (10)	C18—C19—O20—C21	174.35 (13)
O4—C5—C6—H6	−0.88	H19A—C19—O20—C21	54.49
O4—C5—C6—C7	179.03 (16)	H19B—C19—O20—C21	−65.90
C10—C5—O4—C3	175.23 (13)	C26—C21—C22—H22	−179.44
O4—C5—C10—C9	−177.85 (14)	C26—C21—C22—C23	0.42 (10)
O4—C5—C10—O11	2.63 (8)	C22—C21—C26—C25	−1.08 (10)
C5—C6—C7—H7	178.98	C22—C21—C26—O27	177.96 (15)
C5—C6—C7—C8	−1.08 (10)	C22—C21—O20—C19	−4.50 (10)
H6—C6—C7—H7	−1.12	O20—C21—C22—H22	−0.55
H6—C6—C7—C8	178.82	O20—C21—C22—C23	179.31 (17)
C6—C7—C8—H8	−178.94	C26—C21—O20—C19	174.42 (14)
C6—C7—C8—C9	1.11 (11)	O20—C21—C26—C25	179.93 (15)
H7—C7—C8—H8	1.00	O20—C21—C26—O27	−1.03 (9)
H7—C7—C8—C9	−178.95	C21—C22—C23—H23	−179.90 (18)
C7—C8—C9—H9	−179.89 (17)	C21—C22—C23—C24	0.29 (11)
C7—C8—C9—C10	0.15 (11)	H22—C22—C23—H23	−0.04 (10)
H8—C8—C9—H9	0.15 (10)	H22—C22—C23—C24	−179.85 (18)
H8—C8—C9—C10	−179.80 (17)	C22—C23—C24—H24	179.75 (18)
C8—C9—C10—C5	−1.42 (10)	C22—C23—C24—C25	−0.35 (11)
C8—C9—C10—O11	178.05 (17)	H23—C23—C24—H24	−0.05 (10)
H9—C9—C10—C5	178.62	H23—C23—C24—C25	179.84 (18)
H9—C9—C10—O11	−1.91	C23—C24—C25—H25	179.62 (18)
C5—C10—O11—C12	−160.57 (13)	C23—C24—C25—C26	−0.32 (11)
C9—C10—O11—C12	19.94 (10)	H24—C24—C25—H25	−0.48 (10)
H12A—C12—C13—H13A	177.62	H24—C24—C25—C26	179.58 (18)
H12A—C12—C13—H13B	−66.19	C24—C25—C26—C21	1.03 (10)
H12A—C12—C13—O14	55.97	C24—C25—C26—O27	−177.91 (17)
H12A—C12—O11—C10	56.09	H25—C25—C26—C21	−178.92
H12B—C12—C13—H13A	−63.17	H25—C25—C26—O27	2.15
H12B—C12—C13—H13B	53.01	C21—C26—O27—C28	175.91 (13)
H12B—C12—C13—O14	175.18	C25—C26—O27—C28	−5.11 (10)
H12B—C12—O11—C10	−63.75	H28A—C28—C29—H29A	156.43
C13—C12—O11—C10	176.00 (13)	H28A—C28—C29—H29B	−86.08
O11—C12—C13—H13A	57.38	H28A—C28—C29—O1	35.63
O11—C12—C13—H13B	173.57	H28A—C28—O27—C26	61.37
O11—C12—C13—O14	−64.27 (11)	H28B—C28—C29—H29A	−84.43
C12—C13—O14—C15	77.86 (12)	H28B—C28—C29—H29B	33.06
H13A—C13—O14—C15	−43.62	H28B—C28—C29—O1	154.77
H13B—C13—O14—C15	−160.21	H28B—C28—O27—C26	−58.42
H15A—C15—C16—H16A	−46.32	C29—C28—O27—C26	−178.76 (12)
H15A—C15—C16—H16B	72.32	O27—C28—C29—H29A	36.17
H15A—C15—C16—O17	−166.96	O27—C28—C29—H29B	153.66
H15A—C15—O14—C13	34.32	O27—C28—C29—O1	−84.63 (10)
H15B—C15—C16—H16A	71.73	C28—C29—O1—C2	99.84 (11)
H15B—C15—C16—H16B	−169.63	H29A—C29—O1—C2	−20.76
H15B—C15—C16—O17	−48.91	H29B—C29—O1—C2	−138.75
H15B—C15—O14—C13	−84.44

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O11^i	1.10	2.85	3.8410 (14)	151
C6—H6···O1^ii	1.08	2.57	3.5631 (13)	153
C7—H7···O27^iii	1.08	3.23	4.2104 (14)	151
C13—H13B···O14^iv	1.10	3.26	4.3405 (15)	170
C16—H16A···O17^i	1.10	3.21	4.2956 (16)	172
C19—H19B···O20^v	1.10	3.01	4.0769 (14)	164
C29—H29A···O17^i	1.10	2.85	3.9393 (15)	172
C29—H29B···O1^i	1.10	3.42	4.4459 (14)	156

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

Dibenzo[b,k][1,4,7,10,13,16,19]heptaoxacyclohenicosa-2,11-diene (IAM)

Crystal data

C22H28O7	Dx = 1.340 Mg m^−3
Mr = 404.44	Melting point: 388 K
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 4.9801 (1) Å	Cell parameters from 7438 reflections
b = 17.4771 (2) Å	θ = 2.5–73.5°
c = 23.1000 (2) Å	µ = 0.82 mm^−1
β = 94.124 (1)°	T = 150 K
V = 2005.37 (5) Å^3	Shard, colourless
Z = 4	0.74 × 0.14 × 0.08 mm
F(000) = 864

Data collection

Agilent SuperNova (Single Source) diffractometer	3925 independent reflections
Radiation source: micro-focus sealed tube, Agilent Nova	3559 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.018
Detector resolution: 10.5435 pixels mm^-1	θmax = 73.7°, θmin = 3.2°
ω scans	h = −5→6
Absorption correction: gaussian (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −21→21
Tmin = 0.598, Tmax = 1.000	l = −27→28
13236 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0497P)^2 + 0.7337P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3925 reflections	Δρmax = 0.39 e Å^−3
262 parameters	Δρmin = −0.28 e Å^−3
0 restraints

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.

Refinement. All hydrogen atoms were refined with standard riding models (d = 0.99 Å for methylene groups, d = 0.95 Å for aromatics) and U_iso(H) = 1.2 × U_eq(C).

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

	x	y	z	Uiso*/Ueq
C2	1.0441 (3)	0.65491 (8)	0.55310 (6)	0.0297 (3)
H2A	1.144473	0.699349	0.539126	0.036*
H2B	0.933591	0.672147	0.584572	0.036*
C3	0.8681 (3)	0.61985 (7)	0.50392 (6)	0.0284 (3)
H3A	0.979783	0.600009	0.473489	0.034*
H3B	0.760709	0.577146	0.518369	0.034*
C5	0.5116 (2)	0.66076 (7)	0.43693 (5)	0.0263 (3)
C6	0.4900 (3)	0.58992 (8)	0.41022 (6)	0.0296 (3)
H6	0.611055	0.549979	0.422126	0.036*
C7	0.2897 (3)	0.57723 (8)	0.36571 (6)	0.0330 (3)
H7	0.277119	0.528863	0.346947	0.040*
C8	0.1107 (3)	0.63442 (8)	0.34888 (6)	0.0333 (3)
H8	−0.026797	0.625078	0.319046	0.040*
C9	0.1303 (3)	0.70585 (8)	0.37543 (6)	0.0312 (3)
H9	0.006182	0.745160	0.363804	0.037*
C10	0.3313 (3)	0.71958 (7)	0.41884 (5)	0.0272 (3)
C12	0.1548 (3)	0.84138 (8)	0.44420 (6)	0.0354 (3)
H12A	−0.006134	0.817332	0.459237	0.042*
H12B	0.109109	0.857535	0.403608	0.042*
C13	0.2412 (3)	0.90949 (8)	0.48085 (6)	0.0400 (3)
H13A	0.406919	0.930919	0.465993	0.048*
H13B	0.099447	0.949141	0.475868	0.048*
C15	0.5467 (3)	0.85913 (10)	0.55533 (7)	0.0431 (4)
H15A	0.680158	0.878400	0.529116	0.052*
H15B	0.529938	0.803124	0.549722	0.052*
C16	0.6416 (3)	0.87554 (9)	0.61641 (7)	0.0418 (4)
H16A	0.833382	0.860914	0.623103	0.050*
H16B	0.626119	0.931038	0.624099	0.050*
C18	0.5696 (3)	0.84884 (9)	0.71328 (7)	0.0413 (3)
H18A	0.462399	0.891458	0.727912	0.050*
H18B	0.761253	0.864425	0.716177	0.050*
C19	0.5352 (3)	0.77915 (8)	0.74954 (6)	0.0343 (3)
H19A	0.558938	0.792103	0.791319	0.041*
H19B	0.353259	0.757138	0.741314	0.041*
C21	0.7615 (3)	0.66002 (7)	0.76567 (6)	0.0284 (3)
C22	0.6198 (3)	0.64255 (8)	0.81321 (6)	0.0326 (3)
H22	0.494445	0.678260	0.826614	0.039*
C23	0.6602 (3)	0.57274 (8)	0.84152 (6)	0.0362 (3)
H23	0.561808	0.561065	0.874138	0.043*
C24	0.8411 (3)	0.52054 (8)	0.82273 (6)	0.0363 (3)
H24	0.867921	0.473103	0.842373	0.044*
C25	0.9854 (3)	0.53739 (8)	0.77473 (6)	0.0329 (3)
H25	1.111404	0.501449	0.761901	0.039*
C26	0.9459 (2)	0.60618 (7)	0.74572 (6)	0.0283 (3)
C28	1.2710 (2)	0.57773 (8)	0.67757 (6)	0.0290 (3)
H28A	1.191303	0.527226	0.667225	0.035*
H28B	1.416418	0.570221	0.708571	0.035*
C29	1.3829 (3)	0.61383 (8)	0.62507 (6)	0.0316 (3)
H29A	1.390228	0.670029	0.630294	0.038*
H29B	1.568907	0.595295	0.621641	0.038*
O1	1.2240 (2)	0.59634 (6)	0.57316 (4)	0.0395 (3)
O4	0.69569 (18)	0.67957 (5)	0.48126 (4)	0.0302 (2)
O11	0.37362 (19)	0.78814 (5)	0.44656 (4)	0.0323 (2)
O14	0.2914 (2)	0.89471 (6)	0.54092 (4)	0.0422 (3)
O17	0.4851 (2)	0.83391 (6)	0.65474 (5)	0.0439 (3)
O20	0.7371 (2)	0.72584 (5)	0.73445 (4)	0.0354 (2)
O27	1.06917 (19)	0.62778 (5)	0.69739 (4)	0.0331 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0276 (6)	0.0300 (7)	0.0313 (7)	0.0043 (5)	0.0006 (5)	−0.0009 (5)
C3	0.0262 (6)	0.0282 (6)	0.0304 (6)	0.0042 (5)	0.0004 (5)	−0.0001 (5)
C5	0.0219 (6)	0.0304 (6)	0.0266 (6)	0.0000 (5)	0.0025 (5)	−0.0008 (5)
C6	0.0249 (6)	0.0283 (6)	0.0357 (7)	0.0041 (5)	0.0018 (5)	−0.0027 (5)
C7	0.0302 (7)	0.0320 (7)	0.0365 (7)	−0.0008 (5)	0.0008 (5)	−0.0068 (6)
C8	0.0286 (7)	0.0388 (8)	0.0317 (7)	−0.0012 (5)	−0.0030 (5)	−0.0013 (6)
C9	0.0282 (7)	0.0329 (7)	0.0321 (7)	0.0039 (5)	0.0001 (5)	0.0042 (5)
C10	0.0281 (6)	0.0262 (6)	0.0278 (6)	0.0012 (5)	0.0054 (5)	−0.0002 (5)
C12	0.0371 (7)	0.0312 (7)	0.0378 (7)	0.0121 (6)	0.0031 (6)	0.0015 (6)
C13	0.0529 (9)	0.0323 (7)	0.0353 (7)	0.0120 (7)	0.0066 (6)	−0.0001 (6)
C15	0.0406 (8)	0.0492 (9)	0.0399 (8)	0.0075 (7)	0.0060 (6)	−0.0043 (7)
C16	0.0408 (8)	0.0411 (8)	0.0440 (8)	−0.0008 (6)	0.0056 (6)	−0.0073 (6)
C18	0.0532 (9)	0.0323 (7)	0.0377 (8)	0.0043 (7)	−0.0015 (7)	−0.0036 (6)
C19	0.0366 (7)	0.0316 (7)	0.0349 (7)	0.0064 (6)	0.0038 (6)	−0.0052 (6)
C21	0.0273 (6)	0.0262 (6)	0.0313 (6)	−0.0026 (5)	−0.0014 (5)	−0.0049 (5)
C22	0.0318 (7)	0.0317 (7)	0.0345 (7)	−0.0029 (5)	0.0041 (5)	−0.0071 (5)
C23	0.0376 (8)	0.0368 (8)	0.0344 (7)	−0.0071 (6)	0.0046 (6)	−0.0021 (6)
C24	0.0367 (7)	0.0310 (7)	0.0406 (8)	−0.0044 (6)	−0.0015 (6)	0.0026 (6)
C25	0.0278 (7)	0.0304 (7)	0.0400 (7)	0.0003 (5)	−0.0013 (5)	−0.0034 (6)
C26	0.0236 (6)	0.0303 (7)	0.0305 (6)	−0.0028 (5)	−0.0014 (5)	−0.0048 (5)
C28	0.0218 (6)	0.0309 (7)	0.0338 (7)	0.0037 (5)	−0.0015 (5)	−0.0061 (5)
C29	0.0270 (7)	0.0353 (7)	0.0320 (7)	0.0037 (5)	−0.0017 (5)	−0.0038 (5)
O1	0.0458 (6)	0.0367 (5)	0.0338 (5)	0.0139 (4)	−0.0116 (4)	−0.0084 (4)
O4	0.0272 (5)	0.0287 (5)	0.0338 (5)	0.0050 (4)	−0.0042 (4)	−0.0042 (4)
O11	0.0319 (5)	0.0267 (5)	0.0378 (5)	0.0061 (4)	−0.0005 (4)	−0.0043 (4)
O14	0.0436 (6)	0.0504 (6)	0.0335 (5)	0.0113 (5)	0.0078 (4)	−0.0021 (5)
O17	0.0525 (6)	0.0431 (6)	0.0355 (5)	−0.0040 (5)	−0.0007 (5)	0.0012 (4)
O20	0.0387 (5)	0.0302 (5)	0.0383 (5)	0.0064 (4)	0.0099 (4)	0.0006 (4)
O27	0.0310 (5)	0.0335 (5)	0.0353 (5)	0.0063 (4)	0.0068 (4)	−0.0003 (4)

Geometric parameters (Å, º)

C2—H2A	0.9900	C16—H16A	0.9900
C2—H2B	0.9900	C16—H16B	0.9900
C2—C3	1.5138 (18)	C16—O17	1.4214 (19)
C2—O1	1.4160 (16)	C18—H18A	0.9900
C3—H3A	0.9900	C18—H18B	0.9900
C3—H3B	0.9900	C18—C19	1.495 (2)
C3—O4	1.4267 (15)	C18—O17	1.4114 (18)
C5—C6	1.3841 (18)	C19—H19A	0.9900
C5—C10	1.4085 (18)	C19—H19B	0.9900
C5—O4	1.3646 (15)	C19—O20	1.4321 (16)
C6—H6	0.9500	C21—C22	1.3817 (19)
C6—C7	1.3977 (19)	C21—C26	1.4151 (18)
C7—H7	0.9500	C21—O20	1.3585 (16)
C7—C8	1.377 (2)	C22—H22	0.9500
C8—H8	0.9500	C22—C23	1.392 (2)
C8—C9	1.391 (2)	C23—H23	0.9500
C9—H9	0.9500	C23—C24	1.374 (2)
C9—C10	1.3858 (19)	C24—H24	0.9500
C10—O11	1.3678 (16)	C24—C25	1.395 (2)
C12—H12A	0.9900	C25—H25	0.9500
C12—H12B	0.9900	C25—C26	1.3834 (19)
C12—C13	1.505 (2)	C26—O27	1.3654 (16)
C12—O11	1.4308 (15)	C28—H28A	0.9900
C13—H13A	0.9900	C28—H28B	0.9900
C13—H13B	0.9900	C28—C29	1.5087 (19)
C13—O14	1.4159 (18)	C28—O27	1.4321 (15)
C15—H15A	0.9900	C29—H29A	0.9900
C15—H15B	0.9900	C29—H29B	0.9900
C15—C16	1.483 (2)	C29—O1	1.4216 (16)
C15—O14	1.4328 (19)
H2A—C2—H2B	108.7	O17—C16—H16A	109.7
C3—C2—H2A	110.6	O17—C16—H16B	109.7
C3—C2—H2B	110.6	H18A—C18—H18B	108.1
O1—C2—H2A	110.6	C19—C18—H18A	109.6
O1—C2—H2B	110.6	C19—C18—H18B	109.6
O1—C2—C3	105.76 (10)	O17—C18—H18A	109.6
C2—C3—H3A	110.5	O17—C18—H18B	109.6
C2—C3—H3B	110.5	O17—C18—C19	110.35 (12)
H3A—C3—H3B	108.7	C18—C19—H19A	110.4
O4—C3—C2	106.26 (10)	C18—C19—H19B	110.4
O4—C3—H3A	110.5	H19A—C19—H19B	108.6
O4—C3—H3B	110.5	O20—C19—C18	106.42 (12)
C6—C5—C10	119.54 (12)	O20—C19—H19A	110.4
O4—C5—C6	125.21 (12)	O20—C19—H19B	110.4
O4—C5—C10	115.24 (11)	C22—C21—C26	119.51 (12)
C5—C6—H6	120.1	O20—C21—C22	125.29 (12)
C5—C6—C7	119.89 (12)	O20—C21—C26	115.20 (12)
C7—C6—H6	120.1	C21—C22—H22	119.9
C6—C7—H7	119.8	C21—C22—C23	120.14 (13)
C8—C7—C6	120.39 (13)	C23—C22—H22	119.9
C8—C7—H7	119.8	C22—C23—H23	119.7
C7—C8—H8	119.9	C24—C23—C22	120.62 (13)
C7—C8—C9	120.23 (12)	C24—C23—H23	119.7
C9—C8—H8	119.9	C23—C24—H24	120.1
C8—C9—H9	120.0	C23—C24—C25	119.86 (13)
C10—C9—C8	119.91 (12)	C25—C24—H24	120.1
C10—C9—H9	120.0	C24—C25—H25	119.8
C9—C10—C5	120.01 (12)	C26—C25—C24	120.31 (13)
O11—C10—C5	115.27 (11)	C26—C25—H25	119.8
O11—C10—C9	124.71 (12)	C25—C26—C21	119.55 (13)
H12A—C12—H12B	108.4	O27—C26—C21	115.01 (12)
C13—C12—H12A	110.1	O27—C26—C25	125.43 (12)
C13—C12—H12B	110.1	H28A—C28—H28B	108.4
O11—C12—H12A	110.1	C29—C28—H28A	110.1
O11—C12—H12B	110.1	C29—C28—H28B	110.1
O11—C12—C13	107.87 (12)	O27—C28—H28A	110.1
C12—C13—H13A	108.4	O27—C28—H28B	110.1
C12—C13—H13B	108.4	O27—C28—C29	108.05 (11)
H13A—C13—H13B	107.5	C28—C29—H29A	109.2
O14—C13—C12	115.47 (12)	C28—C29—H29B	109.2
O14—C13—H13A	108.4	H29A—C29—H29B	107.9
O14—C13—H13B	108.4	O1—C29—C28	111.89 (11)
H15A—C15—H15B	108.1	O1—C29—H29A	109.2
C16—C15—H15A	109.5	O1—C29—H29B	109.2
C16—C15—H15B	109.5	C2—O1—C29	114.92 (10)
O14—C15—H15A	109.5	C5—O4—C3	116.94 (10)
O14—C15—H15B	109.5	C10—O11—C12	117.42 (10)
O14—C15—C16	110.73 (12)	C13—O14—C15	113.46 (11)
C15—C16—H16A	109.7	C18—O17—C16	111.29 (12)
C15—C16—H16B	109.7	C21—O20—C19	117.34 (11)
H16A—C16—H16B	108.2	C26—O27—C28	117.35 (10)
O17—C16—C15	109.99 (13)
C2—C3—O4—C5	−178.30 (10)	C22—C21—C26—O27	177.94 (11)
C3—C2—O1—C29	−171.31 (11)	C22—C21—O20—C19	−4.54 (19)
C5—C6—C7—C8	−1.1 (2)	C22—C23—C24—C25	−0.2 (2)
C5—C10—O11—C12	−160.54 (11)	C23—C24—C25—C26	−0.4 (2)
C6—C5—C10—C9	1.36 (19)	C24—C25—C26—C21	1.10 (19)
C6—C5—C10—O11	−178.08 (11)	C24—C25—C26—O27	−177.90 (12)
C6—C5—O4—C3	−3.98 (18)	C25—C26—O27—C28	−5.00 (18)
C6—C7—C8—C9	1.1 (2)	C26—C21—C22—C23	0.55 (19)
C7—C8—C9—C10	0.2 (2)	C26—C21—O20—C19	174.39 (11)
C8—C9—C10—C5	−1.4 (2)	C28—C29—O1—C2	100.04 (14)
C8—C9—C10—O11	177.99 (12)	C29—C28—O27—C26	−178.62 (10)
C9—C10—O11—C12	20.06 (18)	O1—C2—C3—O4	−176.91 (10)
C10—C5—C6—C7	−0.11 (19)	O4—C5—C6—C7	179.02 (12)
C10—C5—O4—C3	175.18 (11)	O4—C5—C10—C9	−177.86 (11)
C12—C13—O14—C15	78.08 (17)	O4—C5—C10—O11	2.71 (16)
C13—C12—O11—C10	176.07 (11)	O11—C12—C13—O14	−64.62 (16)
C15—C16—O17—C18	−179.56 (12)	O14—C15—C16—O17	72.03 (17)
C16—C15—O14—C13	155.01 (14)	O17—C18—C19—O20	71.48 (15)
C18—C19—O20—C21	174.35 (11)	O20—C21—C22—C23	179.43 (12)
C19—C18—O17—C16	−146.68 (13)	O20—C21—C26—C25	179.85 (11)
C21—C22—C23—C24	0.1 (2)	O20—C21—C26—O27	−1.05 (16)
C21—C26—O27—C28	175.96 (11)	O27—C28—C29—O1	−85.10 (13)
C22—C21—C26—C25	−1.16 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O11^i	0.99	2.94	3.8408 (17)	152
C6—H6···O1^ii	0.95	2.69	3.5630 (16)	154
C7—H7···O27^iii	0.95	3.36	4.2170 (17)	152
C13—H13B···O14^iv	0.99	3.36	4.3366 (18)	170
C16—H16A···O17^i	0.99	3.31	4.292 (2)	172
C19—H19B···O20^v	0.99	3.11	4.0729 (18)	165
C29—H29A···O17^i	0.99	2.95	3.9337 (18)	172
C29—H29B···O1^i	0.99	3.52	4.4497 (17)	156

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