Bis{5-[(2-propyn-1-yl-oxy)meth-yl]-1,3-phenyl-ene}-32-crown-10.

The mol-ecule of the title compound {systematic name: 17,35-bis-[(2-propyn-1-yl-oxy)meth-yl]-2,5,8,11,14,20,23,26,29,32-deca-oxatricyclo-[31.3.1.1(15,19)]octa-triaconta-1(37),15,17,19 (38),33,35-hex-a--ene}, C(36)H(48)O(12), has crystallographic inversion symmetry and adopts a chair-like conformation. The polyether bridges of the macrocycle adopt gauche conformations and the cavity of the macrocycle is collapsed. In the crystal structure, there are weak inter-molecular C-H⋯O hydrogen bonds driven in part by the elevated acidity of acetylenyl H atoms.

Related literature

For applications of crown ethers, see: Gokel et al. (2004 ▶); Raymo et al. (1999 ▶) and of bis­phenyl­ene crown erthers, see: Loeb (2007 ▶); Fang et al. (2010 ▶); Kay et al. (2007 ▶). For cryptands, see: Zhang et al. (2010 ▶). For supra­molecular inter­locked structures, see: Xu et al. (2011 ▶) For the synthesis of bis­(5-hy­droxy­methyl-1,3-phenyl­ene)-32-crown-10, see: Gibson & Nagvekar (1997 ▶) and for the synthesis of the title compound, see: Xu et al. (2010 ▶).

Experimental

Crystal data

C36H48O12

M = 672.74

Triclinic,

a = 9.2256 (13) Å

b = 9.8561 (14) Å

c = 10.0808 (14) Å

α = 97.213 (2)°

β = 98.658 (2)°

γ = 99.226 (2)°

V = 883.9 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.09 mm−1

T = 298 K

0.64 × 0.32 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.965, T max = 0.991

4551 measured reflections

3108 independent reflections

2350 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.113

S = 1.05

3108 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811046435/ld2029sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046435/ld2029Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811046435/ld2029Isup3.cml

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

C36H48O12	V = 883.9 (2) Å3
Mr = 672.74	Z = 1
Triclinic, P1	F(000) = 360
Hall symbol: -P 1	Dx = 1.264 Mg m−3
a = 9.2256 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8561 (14) Å	µ = 0.09 mm−1
c = 10.0808 (14) Å	T = 298 K
α = 97.213 (2)°	Block, colourless
β = 98.658 (2)°	0.64 × 0.32 × 0.10 mm
γ = 99.226 (2)°

Bruker APEXII CCD diffractometer	3108 independent reflections
Radiation source: fine-focus sealed tube	2350 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 25.2°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→10
Tmin = 0.965, Tmax = 0.991	k = −7→11
4551 measured reflections	l = −12→10

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0506P)2 + 0.1259P] where P = (Fo2 + 2Fc2)/3
3108 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.21 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	0.19258 (19)	0.18786 (18)	0.55393 (17)	0.0405 (4)
H1	0.0968	0.1897	0.5717	0.049*
C2	0.21585 (18)	0.15530 (18)	0.42298 (16)	0.0393 (4)
C3	0.35977 (19)	0.15509 (19)	0.39575 (17)	0.0428 (4)
H3	0.3744	0.1335	0.3068	0.051*
C5	0.45832 (19)	0.21882 (18)	0.63403 (17)	0.0427 (4)
H5	0.5393	0.2404	0.7049	0.051*
C6	0.31507 (19)	0.21810 (18)	0.65978 (16)	0.0392 (4)
C8	−0.13388 (19)	0.0898 (2)	0.18269 (18)	0.0472 (5)
H8A	−0.1242	−0.0054	0.1536	0.057*
H8B	−0.2380	0.0914	0.1867	0.057*
C7	−0.04096 (18)	0.1423 (2)	0.32005 (17)	0.0456 (4)
H7A	−0.0407	0.2406	0.3455	0.055*
H7B	−0.0801	0.0923	0.3878	0.055*
C9	−0.1580 (2)	0.1224 (2)	−0.04624 (17)	0.0513 (5)
H9A	−0.2653	0.1062	−0.0510	0.062*
H9B	−0.1291	0.0348	−0.0762	0.062*
C10	0.4014 (2)	0.2810 (2)	0.89901 (17)	0.0519 (5)
H10A	0.4619	0.3688	0.8916	0.062*
H10B	0.4639	0.2107	0.8987	0.062*
C11	0.3400 (2)	0.2938 (2)	1.02859 (17)	0.0520 (5)
H11A	0.2712	0.2091	1.0311	0.062*
H11B	0.4206	0.3065	1.1054	0.062*
C12	0.2334 (2)	0.4423 (2)	1.17067 (16)	0.0492 (5)
H12A	0.3250	0.4829	1.2333	0.059*
H12B	0.1886	0.3588	1.2018	0.059*
C13	0.1296 (2)	0.5426 (2)	1.16786 (17)	0.0513 (5)
H13A	0.0356	0.4998	1.1098	0.062*
H13B	0.1102	0.5687	1.2587	0.062*
C14	0.1140 (2)	0.7742 (2)	1.13577 (19)	0.0553 (5)
H14A	0.1367	0.8184	1.2299	0.066*
H14B	0.0076	0.7388	1.1128	0.066*
C4	0.47982 (19)	0.18667 (18)	0.49997 (17)	0.0408 (4)
C15	0.63517 (19)	0.1857 (2)	0.46986 (19)	0.0492 (5)
H15A	0.6738	0.1108	0.5088	0.059*
H15B	0.6298	0.1666	0.3723	0.059*
C16	0.6984 (3)	0.4263 (2)	0.4602 (2)	0.0663 (6)
H16A	0.7603	0.5112	0.5111	0.080*
H16B	0.5954	0.4319	0.4656	0.080*
C18	0.7341 (2)	0.4114 (2)	0.2047 (2)	0.0671 (6)
H18	0.7476	0.4066	0.1147	0.081*
C17	0.7173 (2)	0.4175 (2)	0.3175 (2)	0.0567 (5)
O6	0.73584 (14)	0.31229 (15)	0.52126 (12)	0.0566 (4)
O1	0.10633 (13)	0.11960 (14)	0.31046 (11)	0.0512 (4)
O3	0.28037 (13)	0.24304 (13)	0.78669 (11)	0.0463 (3)
O4	0.26536 (15)	0.40777 (14)	1.03810 (11)	0.0512 (3)
O5	0.19356 (13)	0.66270 (14)	1.11802 (12)	0.0506 (3)
O2	−0.08593 (13)	0.17487 (13)	0.08915 (11)	0.0490 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0395 (9)	0.0443 (10)	0.0403 (10)	0.0095 (8)	0.0102 (7)	0.0095 (8)
C2	0.0433 (9)	0.0424 (10)	0.0335 (9)	0.0107 (8)	0.0051 (7)	0.0089 (7)
C3	0.0487 (10)	0.0493 (11)	0.0342 (9)	0.0136 (8)	0.0121 (8)	0.0088 (8)
C5	0.0413 (9)	0.0467 (11)	0.0391 (10)	0.0050 (8)	0.0047 (7)	0.0095 (8)
C6	0.0464 (10)	0.0416 (10)	0.0313 (9)	0.0067 (8)	0.0113 (7)	0.0076 (7)
C8	0.0416 (9)	0.0574 (12)	0.0425 (10)	0.0079 (9)	0.0061 (8)	0.0098 (9)
C7	0.0414 (10)	0.0587 (12)	0.0398 (10)	0.0125 (9)	0.0097 (8)	0.0122 (9)
C9	0.0546 (11)	0.0577 (12)	0.0383 (10)	0.0145 (9)	−0.0011 (8)	0.0002 (9)
C10	0.0512 (11)	0.0671 (13)	0.0349 (10)	0.0101 (10)	0.0029 (8)	0.0043 (9)
C11	0.0608 (12)	0.0579 (12)	0.0353 (10)	0.0090 (10)	0.0023 (8)	0.0089 (9)
C12	0.0623 (11)	0.0568 (12)	0.0271 (9)	0.0020 (9)	0.0092 (8)	0.0103 (8)
C13	0.0495 (10)	0.0712 (14)	0.0298 (9)	0.0012 (10)	0.0071 (8)	0.0074 (9)
C14	0.0589 (11)	0.0735 (14)	0.0369 (10)	0.0245 (11)	0.0067 (8)	0.0070 (9)
C4	0.0443 (10)	0.0416 (10)	0.0399 (10)	0.0101 (8)	0.0118 (8)	0.0106 (8)
C15	0.0441 (10)	0.0566 (12)	0.0510 (11)	0.0109 (9)	0.0140 (8)	0.0148 (9)
C16	0.0830 (15)	0.0566 (13)	0.0629 (14)	0.0066 (12)	0.0300 (12)	0.0094 (11)
C18	0.0694 (14)	0.0862 (17)	0.0565 (14)	0.0202 (12)	0.0215 (11)	0.0315 (12)
C17	0.0597 (12)	0.0608 (13)	0.0564 (13)	0.0135 (10)	0.0199 (10)	0.0201 (10)
O6	0.0530 (8)	0.0709 (10)	0.0438 (8)	−0.0001 (7)	0.0092 (6)	0.0150 (7)
O1	0.0435 (7)	0.0752 (9)	0.0350 (7)	0.0193 (6)	0.0034 (5)	0.0017 (6)
O3	0.0456 (7)	0.0607 (8)	0.0307 (6)	0.0048 (6)	0.0077 (5)	0.0051 (6)
O4	0.0700 (8)	0.0582 (8)	0.0279 (6)	0.0123 (7)	0.0118 (6)	0.0114 (6)
O5	0.0489 (7)	0.0630 (9)	0.0454 (7)	0.0154 (6)	0.0136 (6)	0.0163 (6)
O2	0.0529 (7)	0.0567 (8)	0.0336 (7)	0.0045 (6)	0.0002 (5)	0.0078 (6)

C1—C2	1.376 (2)	C10—H10B	0.9700
C1—C6	1.398 (2)	C11—O4	1.409 (2)
C1—H1	0.9300	C11—H11A	0.9700
C2—O1	1.3682 (19)	C11—H11B	0.9700
C2—C3	1.396 (2)	C12—O4	1.423 (2)
C3—C4	1.373 (2)	C12—C13	1.482 (3)
C3—H3	0.9300	C12—H12A	0.9700
C5—C6	1.384 (2)	C12—H12B	0.9700
C5—C4	1.400 (2)	C13—O5	1.420 (2)
C5—H5	0.9300	C13—H13A	0.9700
C6—O3	1.3672 (19)	C13—H13B	0.9700
C8—O2	1.412 (2)	C14—O5	1.423 (2)
C8—C7	1.497 (2)	C14—C9i	1.492 (3)
C8—H8A	0.9700	C14—H14A	0.9700
C8—H8B	0.9700	C14—H14B	0.9700
C7—O1	1.428 (2)	C4—C15	1.510 (2)
C7—H7A	0.9700	C15—O6	1.418 (2)
C7—H7B	0.9700	C15—H15A	0.9700
C9—O2	1.418 (2)	C15—H15B	0.9700
C9—C14i	1.492 (3)	C16—O6	1.412 (3)
C9—H9A	0.9700	C16—C17	1.468 (3)
C9—H9B	0.9700	C16—H16A	0.9700
C10—O3	1.431 (2)	C16—H16B	0.9700
C10—C11	1.499 (2)	C18—C17	1.167 (3)
C10—H10A	0.9700	C18—H18	0.9300
C2—C1—C6	118.97 (15)	C10—C11—H11B	109.6
C2—C1—H1	120.5	H11A—C11—H11B	108.1
C6—C1—H1	120.5	O4—C12—C13	109.57 (14)
O1—C2—C1	125.21 (15)	O4—C12—H12A	109.8
O1—C2—C3	114.18 (14)	C13—C12—H12A	109.8
C1—C2—C3	120.60 (15)	O4—C12—H12B	109.8
C4—C3—C2	120.15 (15)	C13—C12—H12B	109.8
C4—C3—H3	119.9	H12A—C12—H12B	108.2
C2—C3—H3	119.9	O5—C13—C12	109.56 (15)
C6—C5—C4	119.21 (15)	O5—C13—H13A	109.8
C6—C5—H5	120.4	C12—C13—H13A	109.8
C4—C5—H5	120.4	O5—C13—H13B	109.8
O3—C6—C5	124.27 (15)	C12—C13—H13B	109.8
O3—C6—C1	114.76 (14)	H13A—C13—H13B	108.2
C5—C6—C1	120.95 (15)	O5—C14—C9i	109.25 (15)
O2—C8—C7	109.34 (15)	O5—C14—H14A	109.8
O2—C8—H8A	109.8	C9i—C14—H14A	109.8
C7—C8—H8A	109.8	O5—C14—H14B	109.8
O2—C8—H8B	109.8	C9i—C14—H14B	109.8
C7—C8—H8B	109.8	H14A—C14—H14B	108.3
H8A—C8—H8B	108.3	C3—C4—C5	120.11 (15)
O1—C7—C8	106.52 (14)	C3—C4—C15	119.87 (15)
O1—C7—H7A	110.4	C5—C4—C15	120.02 (16)
C8—C7—H7A	110.4	O6—C15—C4	113.54 (15)
O1—C7—H7B	110.4	O6—C15—H15A	108.9
C8—C7—H7B	110.4	C4—C15—H15A	108.9
H7A—C7—H7B	108.6	O6—C15—H15B	108.9
O2—C9—C14i	108.95 (16)	C4—C15—H15B	108.9
O2—C9—H9A	109.9	H15A—C15—H15B	107.7
C14i—C9—H9A	109.9	O6—C16—C17	113.58 (17)
O2—C9—H9B	109.9	O6—C16—H16A	108.8
C14i—C9—H9B	109.9	C17—C16—H16A	108.8
H9A—C9—H9B	108.3	O6—C16—H16B	108.8
O3—C10—C11	109.13 (15)	C17—C16—H16B	108.8
O3—C10—H10A	109.9	H16A—C16—H16B	107.7
C11—C10—H10A	109.9	C17—C18—H18	180.0
O3—C10—H10B	109.9	C18—C17—C16	179.1 (2)
C11—C10—H10B	109.9	C16—O6—C15	113.57 (15)
H10A—C10—H10B	108.3	C2—O1—C7	119.54 (13)
O4—C11—C10	110.25 (15)	C6—O3—C10	117.49 (13)
O4—C11—H11A	109.6	C11—O4—C12	112.09 (13)
C10—C11—H11A	109.6	C13—O5—C14	112.83 (14)
O4—C11—H11B	109.6	C8—O2—C9	112.47 (14)
C6—C1—C2—O1	177.94 (16)	C5—C4—C15—O6	−55.4 (2)
C6—C1—C2—C3	−1.3 (3)	O6—C16—C17—C18	−90 (17)
O1—C2—C3—C4	−178.87 (15)	C17—C16—O6—C15	−69.0 (2)
C1—C2—C3—C4	0.4 (3)	C4—C15—O6—C16	−64.9 (2)
C4—C5—C6—O3	177.64 (16)	C1—C2—O1—C7	13.2 (3)
C4—C5—C6—C1	−1.0 (3)	C3—C2—O1—C7	−167.59 (15)
C2—C1—C6—O3	−177.18 (15)	C8—C7—O1—C2	−178.61 (15)
C2—C1—C6—C5	1.5 (3)	C5—C6—O3—C10	4.2 (2)
O2—C8—C7—O1	−67.06 (18)	C1—C6—O3—C10	−177.17 (16)
O3—C10—C11—O4	−67.2 (2)	C11—C10—O3—C6	−176.06 (15)
O4—C12—C13—O5	−57.51 (19)	C10—C11—O4—C12	−167.39 (15)
C2—C3—C4—C5	0.2 (3)	C13—C12—O4—C11	−168.70 (16)
C2—C3—C4—C15	179.74 (16)	C12—C13—O5—C14	−169.02 (14)
C6—C5—C4—C3	0.1 (3)	C9i—C14—O5—C13	−163.09 (15)
C6—C5—C4—C15	−179.47 (16)	C7—C8—O2—C9	173.50 (14)
C3—C4—C15—O6	125.04 (18)	C14i—C9—O2—C8	173.71 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···O6ii	0.97	2.49	3.247 (2)	135.
C18—H18···O4iii	0.93	2.54	3.203 (2)	128.
C18—H18···O5iii	0.93	2.52	3.431 (3)	166.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13B⋯O6i	0.97	2.49	3.247 (2)	135
C18—H18⋯O4ii	0.93	2.54	3.203 (2)	128
C18—H18⋯O5ii	0.93	2.52	3.431 (3)	166

Symmetry codes: (i) ; (ii) .