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organic compounds
cis-anti-cis-dicyclohexane-18-crown-6 acetonitrile disolvate
ofaChemistry Department, SUNY College at Buffalo, 1300 Elmwood Ave, Buffalo, New York 14222, USA
*Correspondence e-mail: nazareay@buffalostate.edu
The title compound (systematic name: cis-anti-cis-2,5,8,15,18,21-hexaoxatricyclo[20.4.0.09,14]hexacosane acetonitrile disolvate), C20H36O6·2CH3CN, crystallizes from an acetonitrile solution of dicyclohexane-18-crown-6 on evaporation. The molecule is arranged around a center of symmetry with half the crown ether molecule and one molecule of acetonitrile symmetry independent. All O—C—C—O torsion angles are gauche while all C—O—C—C angles are trans. The sequence of torsion angles is [(tg+t)(tg−t)]3; the geometry of oxygen atoms is close to pseudo-D3d with three atoms below and three atoms above the mean plane, with an average deviation of ±0.16 (1) Å from the mean plane. This geometry is identical to that observed in metal ion complexes of dicyclohexane-18-crown-6 but differs significantly from the conformation of a free unsolvated molecule. Each acetonitrile molecule connects to a crown ether molecule via two of its methyl group H atoms (C—H⋯O). Weaker interactions exist between the third H atom of the acetonitrile methyl group and an O atom of a neighbouring crown ether molecule (C—H⋯O); and between the N atom of the acetonitrile molecule and a H atom of another neighbouring crown ether molecule. All these intermolecular interactions create a three-dimensional network stabilizing the disolvate.
Keywords: crystal structure; dicyclohexane-18-crown-6; crown ether; acetonitrile; hydrogen bonding.
CCDC reference: 1405283
1. Related literature
The cis-anti-cis isomer of dicyclohexane-18-crown-6 was reported by Dalley et al. (1975) (no atomic coordinates given), and later re-investigated by Nazarenko (2002
). For the orthorhombic polymorph, see: Kravtsov et al. (2002
). Synthesis and crystal structures of solvates of dicyclohexane-18-crown-6 with dinitriles have been investigated; see: structures with malononitrile by Damewood et al. (1988
) and with succinonitrile by Dalley & Nazarenko (1999
). The importance of the different behavior of isomers of dicyclohexane-18-crown-6 was first stressed by Pedersen (1967
) and later studied in complexation, extraction, and transport reactions.
2. Experimental
2.1. Crystal data
|
2.3. Refinement
|
|
Data collection: APEX2 (Bruker, 2013); cell SAINT (Bruker, 2013
); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a
); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b
); molecular graphics: OLEX2 (Dolomanov et al., 2009
); software used to prepare material for publication: OLEX2.
Supporting information
CCDC reference: 1405283
10.1107/S2056989015011056/zl2627sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015011056/zl2627Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015011056/zl2627Isup3.cdx
Supporting information file. DOI: 10.1107/S2056989015011056/zl2627Isup4.cml
Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C20H36O6·2C2H3N | Z = 1 |
Mr = 454.59 | F(000) = 248 |
Triclinic, P1 | Dx = 1.193 Mg m−3 |
a = 6.9428 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.5286 (5) Å | Cell parameters from 9918 reflections |
c = 9.8927 (6) Å | θ = 3.0–33.2° |
α = 80.415 (2)° | µ = 0.09 mm−1 |
β = 81.697 (2)° | T = 173 K |
γ = 80.927 (2)° | Block, colourless |
V = 632.53 (6) Å3 | 0.49 × 0.34 × 0.28 mm |
Bruker PHOTON-100 CMOS diffractometer | 2476 reflections with I > 2σ(I) |
Detector resolution: 10 pixels mm-1 | Rint = 0.031 |
ϕ and ω scans | θmax = 28.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −9→9 |
Tmin = 0.956, Tmax = 1.000 | k = −12→12 |
20203 measured reflections | l = −13→13 |
3045 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | All H-atom parameters refined |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0454P)2 + 0.1761P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
3045 reflections | Δρmax = 0.29 e Å−3 |
229 parameters | Δρmin = −0.19 e Å−3 |
0 restraints |
C20H36O6·2C2H3N | γ = 80.927 (2)° |
Mr = 454.59 | V = 632.53 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.9428 (4) Å | Mo Kα radiation |
b = 9.5286 (5) Å | µ = 0.09 mm−1 |
c = 9.8927 (6) Å | T = 173 K |
α = 80.415 (2)° | 0.49 × 0.34 × 0.28 mm |
β = 81.697 (2)° |
Bruker PHOTON-100 CMOS diffractometer | 3045 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 2476 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 1.000 | Rint = 0.031 |
20203 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.104 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.29 e Å−3 |
3045 reflections | Δρmin = −0.19 e Å−3 |
229 parameters |
Experimental. SADABS-2014/5 (Bruker, 2014) was used for absorption correction. wR2(int) was 0.0615 before and 0.0513 after correction. The Ratio of minimum to maximum transmission is 0.9562. The λ/2 correction factor is 0.00150. |
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. |
x | y | z | Uiso*/Ueq | ||
O3 | 0.32768 (12) | 0.49496 (8) | 0.76820 (8) | 0.0246 (2) | |
O1 | 0.47462 (11) | 0.27282 (8) | 0.32574 (8) | 0.02307 (19) | |
O2 | 0.24108 (12) | 0.30700 (8) | 0.59392 (8) | 0.0258 (2) | |
C10 | 0.50905 (17) | 0.66821 (12) | 0.81733 (11) | 0.0222 (2) | |
C5 | 0.31527 (17) | 0.60704 (12) | 0.84980 (11) | 0.0217 (2) | |
C2 | 0.28223 (19) | 0.18001 (13) | 0.53071 (12) | 0.0265 (3) | |
C1 | 0.29308 (18) | 0.22030 (14) | 0.37680 (13) | 0.0275 (3) | |
C4 | 0.16935 (18) | 0.41295 (13) | 0.80064 (13) | 0.0259 (3) | |
C3 | 0.22641 (18) | 0.27499 (12) | 0.73991 (12) | 0.0244 (3) | |
C6 | 0.14216 (17) | 0.72519 (13) | 0.82817 (13) | 0.0245 (2) | |
C9 | 0.50976 (19) | 0.78031 (13) | 0.91167 (13) | 0.0278 (3) | |
C8 | 0.3383 (2) | 0.90062 (13) | 0.89292 (14) | 0.0312 (3) | |
C7 | 0.1431 (2) | 0.84186 (14) | 0.91736 (14) | 0.0319 (3) | |
C12 | 0.25068 (19) | 0.76690 (15) | 0.34942 (15) | 0.0356 (3) | |
N1 | 0.2335 (2) | 0.87640 (16) | 0.28169 (17) | 0.0589 (4) | |
C11 | 0.2721 (2) | 0.62716 (15) | 0.43442 (15) | 0.0346 (3) | |
H5 | 0.3067 (19) | 0.5644 (13) | 0.9475 (14) | 0.021 (3)* | |
H6A | 0.1510 (18) | 0.7665 (14) | 0.7324 (14) | 0.022 (3)* | |
H8A | 0.357 (2) | 0.9525 (15) | 0.7989 (16) | 0.032 (4)* | |
H1A | 0.183 (2) | 0.2961 (15) | 0.3529 (14) | 0.031 (4)* | |
H2A | 0.408 (2) | 0.1246 (15) | 0.5572 (15) | 0.032 (4)* | |
H10 | 0.618 (2) | 0.5904 (14) | 0.8319 (13) | 0.024 (3)* | |
H3A | 0.356 (2) | 0.2254 (14) | 0.7689 (13) | 0.023 (3)* | |
H9A | 0.499 (2) | 0.7318 (15) | 1.0061 (16) | 0.032 (4)* | |
H2B | 0.179 (2) | 0.1217 (15) | 0.5635 (14) | 0.029 (3)* | |
H4A | 0.140 (2) | 0.3869 (15) | 0.9035 (16) | 0.031 (4)* | |
H3B | 0.124 (2) | 0.2113 (14) | 0.7749 (14) | 0.026 (3)* | |
H6B | 0.015 (2) | 0.6841 (15) | 0.8527 (14) | 0.028 (3)* | |
H9B | 0.636 (2) | 0.8182 (15) | 0.8941 (15) | 0.032 (4)* | |
H7A | 0.121 (2) | 0.8002 (16) | 1.0119 (17) | 0.035 (4)* | |
H1B | 0.281 (2) | 0.1362 (17) | 0.3363 (15) | 0.036 (4)* | |
H8B | 0.337 (2) | 0.9694 (16) | 0.9556 (16) | 0.038 (4)* | |
H4B | 0.053 (2) | 0.4659 (16) | 0.7635 (15) | 0.033 (4)* | |
H7B | 0.034 (2) | 0.9160 (17) | 0.9006 (16) | 0.040 (4)* | |
H11A | 0.360 (3) | 0.5628 (19) | 0.3858 (19) | 0.055 (5)* | |
H11B | 0.147 (3) | 0.5936 (19) | 0.4572 (19) | 0.057 (5)* | |
H11C | 0.326 (3) | 0.635 (2) | 0.517 (2) | 0.069 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0272 (4) | 0.0223 (4) | 0.0253 (4) | −0.0080 (3) | 0.0043 (3) | −0.0085 (3) |
O1 | 0.0231 (4) | 0.0282 (4) | 0.0189 (4) | −0.0070 (3) | −0.0018 (3) | −0.0040 (3) |
O2 | 0.0344 (5) | 0.0210 (4) | 0.0222 (4) | −0.0053 (3) | 0.0006 (3) | −0.0055 (3) |
C10 | 0.0249 (6) | 0.0223 (5) | 0.0196 (5) | −0.0013 (4) | −0.0055 (4) | −0.0028 (4) |
C5 | 0.0283 (6) | 0.0208 (5) | 0.0163 (5) | −0.0032 (4) | −0.0013 (4) | −0.0047 (4) |
C2 | 0.0308 (6) | 0.0222 (6) | 0.0276 (6) | −0.0095 (5) | 0.0034 (5) | −0.0072 (5) |
C1 | 0.0263 (6) | 0.0324 (6) | 0.0273 (6) | −0.0117 (5) | −0.0003 (5) | −0.0099 (5) |
C4 | 0.0262 (6) | 0.0266 (6) | 0.0257 (6) | −0.0081 (5) | 0.0030 (5) | −0.0072 (5) |
C3 | 0.0286 (6) | 0.0229 (6) | 0.0222 (6) | −0.0086 (5) | 0.0009 (5) | −0.0034 (4) |
C6 | 0.0241 (6) | 0.0259 (6) | 0.0237 (6) | −0.0022 (4) | −0.0010 (4) | −0.0065 (5) |
C9 | 0.0335 (7) | 0.0308 (6) | 0.0221 (6) | −0.0079 (5) | −0.0054 (5) | −0.0078 (5) |
C8 | 0.0408 (7) | 0.0249 (6) | 0.0303 (7) | −0.0046 (5) | −0.0029 (5) | −0.0119 (5) |
C7 | 0.0329 (7) | 0.0292 (6) | 0.0335 (7) | 0.0011 (5) | 0.0009 (5) | −0.0137 (5) |
C12 | 0.0277 (7) | 0.0402 (8) | 0.0411 (8) | −0.0068 (5) | −0.0073 (5) | −0.0080 (6) |
N1 | 0.0539 (9) | 0.0474 (8) | 0.0755 (11) | −0.0121 (7) | −0.0197 (7) | 0.0062 (7) |
C11 | 0.0317 (7) | 0.0371 (7) | 0.0340 (7) | −0.0009 (6) | −0.0032 (6) | −0.0063 (6) |
O3—C5 | 1.4274 (13) | C4—H4B | 0.969 (15) |
O3—C4 | 1.4169 (14) | C3—H3A | 1.005 (13) |
O1—C10i | 1.4285 (13) | C3—H3B | 0.993 (14) |
O1—C1 | 1.4230 (14) | C6—C7 | 1.5313 (16) |
O2—C2 | 1.4241 (13) | C6—H6A | 0.961 (13) |
O2—C3 | 1.4177 (14) | C6—H6B | 1.006 (14) |
C10—O1i | 1.4285 (13) | C9—C8 | 1.5256 (18) |
C10—C5 | 1.5210 (16) | C9—H9A | 0.969 (15) |
C10—C9 | 1.5319 (16) | C9—H9B | 0.983 (15) |
C10—H10 | 0.982 (13) | C8—C7 | 1.5196 (19) |
C5—C6 | 1.5248 (16) | C8—H8A | 0.980 (15) |
C5—H5 | 0.981 (13) | C8—H8B | 0.972 (16) |
C2—C1 | 1.5009 (17) | C7—H7A | 0.953 (16) |
C2—H2A | 0.994 (15) | C7—H7B | 0.964 (16) |
C2—H2B | 0.964 (15) | C12—N1 | 1.1414 (19) |
C1—H1A | 0.992 (15) | C12—C11 | 1.450 (2) |
C1—H1B | 0.974 (16) | C11—H11A | 0.934 (19) |
C4—C3 | 1.5086 (16) | C11—H11B | 0.959 (19) |
C4—H4A | 1.005 (15) | C11—H11C | 0.97 (2) |
C4—O3—C5 | 114.40 (8) | O2—C3—H3B | 110.1 (8) |
C1—O1—C10i | 114.05 (8) | C4—C3—H3A | 109.8 (7) |
C3—O2—C2 | 111.74 (9) | C4—C3—H3B | 108.8 (8) |
O1i—C10—C5 | 106.49 (9) | H3A—C3—H3B | 109.1 (10) |
O1i—C10—C9 | 112.88 (9) | C5—C6—C7 | 110.51 (10) |
O1i—C10—H10 | 108.5 (8) | C5—C6—H6A | 109.1 (8) |
C5—C10—C9 | 109.33 (9) | C5—C6—H6B | 110.4 (8) |
C5—C10—H10 | 109.5 (8) | C7—C6—H6A | 109.7 (8) |
C9—C10—H10 | 110.0 (8) | C7—C6—H6B | 109.2 (8) |
O3—C5—C10 | 107.36 (9) | H6A—C6—H6B | 107.8 (11) |
O3—C5—C6 | 114.17 (9) | C10—C9—H9A | 107.7 (8) |
O3—C5—H5 | 108.6 (7) | C10—C9—H9B | 110.2 (8) |
C10—C5—C6 | 110.98 (9) | C8—C9—C10 | 110.82 (10) |
C10—C5—H5 | 106.1 (8) | C8—C9—H9A | 110.1 (9) |
C6—C5—H5 | 109.4 (7) | C8—C9—H9B | 111.4 (8) |
O2—C2—C1 | 109.38 (10) | H9A—C9—H9B | 106.6 (12) |
O2—C2—H2A | 109.3 (8) | C9—C8—H8A | 108.6 (8) |
O2—C2—H2B | 109.0 (8) | C9—C8—H8B | 110.4 (9) |
C1—C2—H2A | 110.7 (8) | C7—C8—C9 | 111.38 (11) |
C1—C2—H2B | 109.7 (8) | C7—C8—H8A | 109.9 (8) |
H2A—C2—H2B | 108.7 (11) | C7—C8—H8B | 109.5 (9) |
O1—C1—C2 | 109.04 (10) | H8A—C8—H8B | 107.0 (12) |
O1—C1—H1A | 109.4 (8) | C6—C7—H7A | 108.0 (9) |
O1—C1—H1B | 111.4 (9) | C6—C7—H7B | 108.9 (9) |
C2—C1—H1A | 110.0 (8) | C8—C7—C6 | 111.85 (10) |
C2—C1—H1B | 108.9 (9) | C8—C7—H7A | 108.5 (9) |
H1A—C1—H1B | 108.1 (12) | C8—C7—H7B | 112.3 (9) |
O3—C4—C3 | 109.11 (9) | H7A—C7—H7B | 106.9 (13) |
O3—C4—H4A | 110.3 (8) | N1—C12—C11 | 179.47 (16) |
O3—C4—H4B | 110.7 (9) | C12—C11—H11A | 109.2 (11) |
C3—C4—H4A | 107.7 (8) | C12—C11—H11B | 109.6 (11) |
C3—C4—H4B | 109.4 (9) | C12—C11—H11C | 108.9 (12) |
H4A—C4—H4B | 109.6 (12) | H11A—C11—H11B | 109.9 (15) |
O2—C3—C4 | 109.08 (9) | H11A—C11—H11C | 108.5 (17) |
O2—C3—H3A | 110.0 (7) | H11B—C11—H11C | 110.8 (16) |
O3—C5—C6—C7 | −178.84 (9) | C5—C10—C9—C8 | −58.39 (13) |
O3—C4—C3—O2 | −68.55 (12) | C5—C6—C7—C8 | 54.14 (14) |
O1i—C10—C5—O3 | 62.59 (10) | C2—O2—C3—C4 | −176.21 (10) |
O1i—C10—C5—C6 | −62.81 (11) | C4—O3—C5—C10 | 171.48 (9) |
O1i—C10—C9—C8 | 59.93 (13) | C4—O3—C5—C6 | −65.05 (12) |
O2—C2—C1—O1 | 75.52 (12) | C3—O2—C2—C1 | 179.16 (10) |
C10i—O1—C1—C2 | −172.39 (9) | C9—C10—C5—O3 | −175.17 (9) |
C10—C5—C6—C7 | −57.34 (13) | C9—C10—C5—C6 | 59.43 (12) |
C10—C9—C8—C7 | 55.90 (14) | C9—C8—C7—C6 | −53.72 (15) |
C5—O3—C4—C3 | −163.53 (9) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11A···O3i | 0.936 (19) | 2.51 (2) | 3.3528 (17) | 150.8 (16) |
C11—H11C···O1i | 0.97 (2) | 2.56 (2) | 3.4809 (16) | 159.1 (15) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11A···O3i | 0.936 (19) | 2.51 (2) | 3.3528 (17) | 150.8 (16) |
C11—H11C···O1i | 0.97 (2) | 2.56 (2) | 3.4809 (16) | 159.1 (15) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
Financial support from the State University of New York for acquisition of the X-ray diffractometer is gratefully acknowledged.
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