organic compounds
5,7,8,10,11,13,14,16-Octahydro-6,15-(ethanoxyethanoxyethano)-1,4:17,20-dietheno[9,12,6,15]benzodioxadiazacyclodocosine†
aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
*Correspondence e-mail: ffroncz@lsu.edu
The title compound, C32H40N2O4, is a 1,10-diaza-18-crown-6 with an o-terphenyl bridge. In the polyether ring, two adjacent –CH2– groups are disordered with very nearly equal populations of two conformers. The ordered bond lengths are normal, with average C—C = 1.511 (3) Å, C—O = 1.421 (3) Å, and C—N = 1.466 (4) Å. The r.m.s. deviations of the three rings of the terphenyl bridge vary from 0.007 to 0.009 Å and the two rings ortho to one another are twisted by 50.75 (5) and 47.76 (4)° with respect to the third ring. The N⋯N distance is 5.408 (1) Å.
Related literature
For the synthesis of the title compound, see: Rossa & Vögtle (1981). For the structure of the NaSCN complex, see: Weber (1981). For a related structure, see: Vögtle et al. (1983). For the synthesis of cryptands, see: Dietrich et al. (1969a,b). For a background to guest–host interactions, see: Dunitz et al. (1974); Cram & Trueblood (1981); Cram (1988).
Experimental
Crystal data
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Data collection: COLLECT (Nonius, 2000); cell DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536812044017/bv2212sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044017/bv2212Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812044017/bv2212Isup3.cml
The title compound was prepared as decribed by Rossa & Vögtle (1981), and the sample was kindly provided by Professor Vögtle. Crystals were grown from chloroform.
All H atoms were placed in calculated positions, guided by difference maps. The C—H bond distances were restrained to the range 0.95 to 0.99 Å, with Uiso=1.2Ueq and thereafter refined as riding.
Two carbon atoms, C5 and C6, and their attached hydrogen atoms, are disordered and were treated as separately attached groups (A and B) using the PART command in SHELXL97 (Sheldrick, 2008). Their occupation factors were refined as parameter x and 1 - x, with x = 0.490 (3).
Data collection: COLLECT (Nonius, 2000); cell
DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).C32H40N2O4 | Z = 2 |
Mr = 516.66 | F(000) = 556 |
Triclinic, P1 | Dx = 1.201 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6757 (3) Å | Cell parameters from 10814 reflections |
b = 12.1582 (4) Å | θ = 2.6–33.1° |
c = 12.5129 (5) Å | µ = 0.08 mm−1 |
α = 88.178 (2)° | T = 100 K |
β = 82.616 (2)° | Fragment, colorless |
γ = 78.072 (2)° | 0.33 × 0.32 × 0.22 mm |
V = 1428.26 (9) Å3 |
Nonius KappaCCD diffractometer | 10763 independent reflections |
Radiation source: sealed tube | 5346 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0 |
Detector resolution: 9 pixels mm-1 | θmax = 33.1°, θmin = 2.6° |
ω and ϕ scans | h = −14→14 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −18→18 |
Tmin = 0.975, Tmax = 0.983 | l = 0→19 |
10763 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0599P)2 + 0.0637P] where P = (Fo2 + 2Fc2)/3 |
S = 0.81 | (Δ/σ)max = 0.001 |
10763 reflections | Δρmax = 0.30 e Å−3 |
351 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0078 (12) |
Primary atom site location: structure-invariant direct methods |
C32H40N2O4 | γ = 78.072 (2)° |
Mr = 516.66 | V = 1428.26 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.6757 (3) Å | Mo Kα radiation |
b = 12.1582 (4) Å | µ = 0.08 mm−1 |
c = 12.5129 (5) Å | T = 100 K |
α = 88.178 (2)° | 0.33 × 0.32 × 0.22 mm |
β = 82.616 (2)° |
Nonius KappaCCD diffractometer | 10763 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 5346 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.983 | Rint = 0 |
10763 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.81 | Δρmax = 0.30 e Å−3 |
10763 reflections | Δρmin = −0.22 e Å−3 |
351 parameters |
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 | Occ. (<1) | |
N1 | −0.23215 (9) | 0.53384 (7) | 0.19296 (7) | 0.0211 (2) | |
C2 | −0.37788 (11) | 0.58008 (10) | 0.24093 (9) | 0.0247 (2) | |
H2A | −0.4347 | 0.5208 | 0.2433 | 0.03* | |
H2B | −0.421 | 0.642 | 0.1947 | 0.03* | |
C3 | −0.38478 (11) | 0.62427 (10) | 0.35394 (9) | 0.0270 (3) | |
H3A | −0.3355 | 0.5654 | 0.4003 | 0.032* | |
H3B | −0.3393 | 0.6902 | 0.3524 | 0.032* | |
O4 | −0.53150 (8) | 0.65506 (7) | 0.39325 (6) | 0.02816 (19) | |
C5A | −0.5774 (2) | 0.7325 (2) | 0.47940 (19) | 0.0250 (7) | 0.490 (3) |
H5A1 | −0.6827 | 0.7488 | 0.4907 | 0.03* | 0.490 (3) |
H5A2 | −0.5473 | 0.8037 | 0.4569 | 0.03* | 0.490 (3) |
C6A | −0.5257 (3) | 0.6977 (4) | 0.5841 (3) | 0.0393 (7) | 0.490 (3) |
H6AA | −0.5853 | 0.7448 | 0.6426 | 0.047* | 0.490 (3) |
H6AB | −0.5312 | 0.6182 | 0.5996 | 0.047* | 0.490 (3) |
C5B | −0.5732 (2) | 0.6471 (2) | 0.50314 (18) | 0.0268 (7) | 0.510 (3) |
H5B1 | −0.5277 | 0.5718 | 0.528 | 0.032* | 0.510 (3) |
H5B2 | −0.6774 | 0.6517 | 0.5144 | 0.032* | 0.510 (3) |
C6B | −0.54004 (7) | 0.73216 (6) | 0.57237 (5) | 0.0393 (7) | 0.510 (3) |
H6BA | −0.5715 | 0.8083 | 0.5424 | 0.047* | 0.510 (3) |
H6BB | −0.5917 | 0.7289 | 0.6456 | 0.047* | 0.510 (3) |
O7 | −0.38556 (7) | 0.71046 (6) | 0.57801 (5) | 0.0337 (2) | |
C8 | −0.35602 (7) | 0.80673 (6) | 0.62382 (5) | 0.0246 (2) | |
H8A | −0.3743 | 0.803 | 0.7034 | 0.03* | |
H8B | −0.418 | 0.8755 | 0.5989 | 0.03* | |
C9 | −0.20174 (11) | 0.80985 (9) | 0.58898 (8) | 0.0224 (2) | |
H9A | −0.172 | 0.8631 | 0.6352 | 0.027* | |
H9B | −0.1426 | 0.7344 | 0.5992 | 0.027* | |
N10 | −0.17621 (9) | 0.84405 (7) | 0.47596 (7) | 0.02067 (19) | |
C11 | −0.02881 (11) | 0.80186 (9) | 0.42935 (9) | 0.0227 (2) | |
H11A | 0.0359 | 0.8144 | 0.4809 | 0.027* | |
H11B | −0.0079 | 0.8449 | 0.3628 | 0.027* | |
C12 | 0.00009 (11) | 0.67766 (9) | 0.40272 (9) | 0.0239 (2) | |
H12A | −0.0193 | 0.6329 | 0.4683 | 0.029* | |
H12B | −0.0607 | 0.6636 | 0.3489 | 0.029* | |
O13 | 0.14635 (8) | 0.64881 (6) | 0.36029 (7) | 0.02792 (19) | |
C14 | 0.20675 (12) | 0.53217 (9) | 0.35947 (10) | 0.0274 (3) | |
H14A | 0.1765 | 0.4994 | 0.4299 | 0.033* | |
H14B | 0.3117 | 0.5222 | 0.3515 | 0.033* | |
C15 | 0.16638 (11) | 0.46794 (9) | 0.27126 (9) | 0.0259 (2) | |
H15A | 0.1703 | 0.5114 | 0.2031 | 0.031* | |
H15B | 0.2344 | 0.3952 | 0.2598 | 0.031* | |
O16 | 0.02643 (7) | 0.44884 (6) | 0.30085 (6) | 0.02359 (18) | |
C17 | −0.02009 (12) | 0.38896 (10) | 0.22075 (9) | 0.0268 (3) | |
H17A | 0.0121 | 0.307 | 0.2309 | 0.032* | |
H17B | 0.0205 | 0.4097 | 0.148 | 0.032* | |
C18 | −0.18012 (12) | 0.41909 (9) | 0.23150 (9) | 0.0235 (2) | |
H18A | −0.2153 | 0.3652 | 0.1896 | 0.028* | |
H18B | −0.2188 | 0.4126 | 0.3081 | 0.028* | |
C19 | −0.22206 (12) | 0.53917 (9) | 0.07518 (9) | 0.0237 (2) | |
H19A | −0.3009 | 0.5094 | 0.0513 | 0.028* | |
H19B | −0.1312 | 0.4913 | 0.0438 | 0.028* | |
C20 | −0.22940 (11) | 0.65830 (9) | 0.03457 (8) | 0.0217 (2) | |
C21 | −0.33622 (11) | 0.71247 (9) | −0.02373 (9) | 0.0240 (2) | |
H21 | −0.4051 | 0.673 | −0.0418 | 0.029* | |
C22 | −0.34428 (11) | 0.82403 (9) | −0.05634 (8) | 0.0237 (2) | |
H22 | −0.4183 | 0.8595 | −0.0965 | 0.028* | |
C23 | −0.24558 (11) | 0.88407 (9) | −0.03088 (8) | 0.0216 (2) | |
C24 | −0.13529 (11) | 0.82843 (9) | 0.02581 (9) | 0.0224 (2) | |
H24 | −0.0648 | 0.8671 | 0.0421 | 0.027* | |
C25 | −0.12808 (11) | 0.71798 (9) | 0.05823 (8) | 0.0225 (2) | |
H25 | −0.0531 | 0.6819 | 0.0972 | 0.027* | |
C26 | −0.25954 (11) | 1.00549 (9) | −0.06088 (9) | 0.0224 (2) | |
C27 | −0.27508 (12) | 1.03916 (10) | −0.16710 (9) | 0.0293 (3) | |
H27 | −0.2808 | 0.9846 | −0.2182 | 0.035* | |
C28 | −0.28245 (13) | 1.15045 (11) | −0.20031 (10) | 0.0329 (3) | |
H28 | −0.293 | 1.1714 | −0.2731 | 0.039* | |
C29 | −0.27428 (12) | 1.23011 (10) | −0.12599 (10) | 0.0321 (3) | |
H29 | −0.277 | 1.306 | −0.1478 | 0.039* | |
C30 | −0.26221 (12) | 1.19882 (10) | −0.01984 (10) | 0.0279 (3) | |
H30 | −0.2581 | 1.2544 | 0.0306 | 0.033* | |
C31 | −0.25585 (11) | 1.08767 (9) | 0.01550 (9) | 0.0221 (2) | |
C32 | −0.24813 (11) | 1.06006 (9) | 0.13170 (9) | 0.0213 (2) | |
C33 | −0.15041 (11) | 1.09725 (9) | 0.18699 (9) | 0.0241 (2) | |
H33 | −0.0899 | 1.1427 | 0.1508 | 0.029* | |
C34 | −0.14044 (12) | 1.06865 (9) | 0.29445 (9) | 0.0244 (2) | |
H34 | −0.0729 | 1.0948 | 0.3306 | 0.029* | |
C35 | −0.22686 (11) | 1.00284 (9) | 0.34998 (9) | 0.0222 (2) | |
C36 | −0.32687 (11) | 0.96731 (9) | 0.29568 (9) | 0.0229 (2) | |
H36 | −0.3883 | 0.923 | 0.3326 | 0.027* | |
C37 | −0.33787 (11) | 0.99569 (9) | 0.18866 (9) | 0.0216 (2) | |
H37 | −0.4073 | 0.9712 | 0.1534 | 0.026* | |
C38 | −0.21402 (12) | 0.96682 (9) | 0.46525 (9) | 0.0244 (2) | |
H38A | −0.1403 | 1.0004 | 0.4921 | 0.029* | |
H38B | −0.3057 | 0.9953 | 0.5102 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0243 (5) | 0.0195 (5) | 0.0185 (5) | −0.0034 (4) | −0.0008 (4) | 0.0012 (4) |
C2 | 0.0226 (5) | 0.0265 (6) | 0.0246 (6) | −0.0044 (5) | −0.0022 (4) | −0.0001 (5) |
C3 | 0.0194 (5) | 0.0364 (7) | 0.0251 (6) | −0.0069 (5) | 0.0009 (4) | −0.0047 (5) |
O4 | 0.0193 (4) | 0.0385 (5) | 0.0254 (4) | −0.0042 (3) | 0.0005 (3) | −0.0042 (4) |
C5A | 0.0188 (11) | 0.0283 (16) | 0.0270 (13) | −0.0040 (10) | 0.0011 (9) | −0.0065 (11) |
C6A | 0.0244 (8) | 0.063 (2) | 0.0326 (9) | −0.0174 (10) | 0.0067 (6) | −0.0113 (11) |
C5B | 0.0221 (11) | 0.0331 (16) | 0.0250 (12) | −0.0092 (10) | 0.0027 (9) | 0.0036 (10) |
C6B | 0.0244 (8) | 0.063 (2) | 0.0326 (9) | −0.0174 (10) | 0.0067 (6) | −0.0113 (11) |
O7 | 0.0271 (4) | 0.0398 (5) | 0.0357 (5) | −0.0136 (4) | 0.0049 (4) | −0.0161 (4) |
C8 | 0.0291 (6) | 0.0230 (6) | 0.0196 (6) | −0.0025 (5) | 0.0010 (4) | −0.0034 (4) |
C9 | 0.0272 (6) | 0.0219 (6) | 0.0184 (5) | −0.0043 (4) | −0.0045 (4) | −0.0006 (4) |
N10 | 0.0240 (5) | 0.0177 (4) | 0.0193 (5) | −0.0026 (4) | −0.0017 (4) | −0.0001 (4) |
C11 | 0.0226 (5) | 0.0200 (5) | 0.0257 (6) | −0.0059 (4) | −0.0016 (4) | 0.0000 (4) |
C12 | 0.0200 (5) | 0.0216 (6) | 0.0297 (6) | −0.0051 (4) | 0.0002 (4) | −0.0023 (5) |
O13 | 0.0200 (4) | 0.0189 (4) | 0.0424 (5) | −0.0028 (3) | 0.0030 (3) | 0.0011 (3) |
C14 | 0.0196 (5) | 0.0204 (6) | 0.0411 (7) | −0.0020 (5) | −0.0033 (5) | −0.0007 (5) |
C15 | 0.0222 (5) | 0.0235 (6) | 0.0298 (6) | −0.0029 (5) | 0.0022 (5) | 0.0013 (5) |
O16 | 0.0230 (4) | 0.0249 (4) | 0.0235 (4) | −0.0064 (3) | −0.0016 (3) | −0.0037 (3) |
C17 | 0.0315 (6) | 0.0226 (6) | 0.0253 (6) | −0.0008 (5) | −0.0065 (5) | −0.0045 (5) |
C18 | 0.0298 (6) | 0.0196 (5) | 0.0227 (6) | −0.0077 (5) | −0.0051 (5) | 0.0000 (4) |
C19 | 0.0274 (6) | 0.0214 (6) | 0.0215 (6) | −0.0037 (5) | −0.0018 (4) | −0.0012 (4) |
C20 | 0.0249 (5) | 0.0220 (6) | 0.0156 (5) | −0.0018 (4) | 0.0021 (4) | −0.0019 (4) |
C21 | 0.0252 (6) | 0.0254 (6) | 0.0216 (6) | −0.0059 (5) | −0.0022 (4) | −0.0020 (5) |
C22 | 0.0249 (6) | 0.0252 (6) | 0.0196 (6) | −0.0013 (5) | −0.0048 (4) | 0.0013 (4) |
C23 | 0.0227 (5) | 0.0221 (6) | 0.0180 (5) | −0.0022 (4) | 0.0015 (4) | 0.0000 (4) |
C24 | 0.0203 (5) | 0.0245 (6) | 0.0214 (6) | −0.0038 (4) | 0.0006 (4) | −0.0014 (4) |
C25 | 0.0210 (5) | 0.0241 (6) | 0.0204 (6) | 0.0001 (4) | −0.0018 (4) | −0.0011 (4) |
C26 | 0.0202 (5) | 0.0232 (6) | 0.0224 (6) | −0.0033 (4) | −0.0004 (4) | 0.0035 (4) |
C27 | 0.0316 (6) | 0.0320 (7) | 0.0230 (6) | −0.0050 (5) | −0.0021 (5) | 0.0023 (5) |
C28 | 0.0367 (7) | 0.0373 (7) | 0.0244 (6) | −0.0082 (6) | −0.0041 (5) | 0.0114 (5) |
C29 | 0.0341 (7) | 0.0266 (6) | 0.0365 (7) | −0.0093 (5) | −0.0054 (5) | 0.0127 (5) |
C30 | 0.0286 (6) | 0.0253 (6) | 0.0310 (7) | −0.0090 (5) | −0.0040 (5) | 0.0047 (5) |
C31 | 0.0188 (5) | 0.0231 (6) | 0.0237 (6) | −0.0042 (4) | −0.0012 (4) | 0.0039 (4) |
C32 | 0.0215 (5) | 0.0171 (5) | 0.0231 (6) | −0.0009 (4) | 0.0003 (4) | 0.0005 (4) |
C33 | 0.0263 (6) | 0.0193 (5) | 0.0275 (6) | −0.0080 (5) | −0.0010 (5) | 0.0013 (4) |
C34 | 0.0265 (6) | 0.0217 (6) | 0.0260 (6) | −0.0062 (5) | −0.0048 (5) | −0.0022 (5) |
C35 | 0.0266 (6) | 0.0163 (5) | 0.0214 (6) | −0.0006 (4) | −0.0005 (4) | −0.0017 (4) |
C36 | 0.0238 (5) | 0.0186 (5) | 0.0245 (6) | −0.0036 (4) | 0.0022 (4) | 0.0005 (4) |
C37 | 0.0198 (5) | 0.0204 (5) | 0.0239 (6) | −0.0033 (4) | −0.0015 (4) | −0.0014 (4) |
C38 | 0.0307 (6) | 0.0183 (5) | 0.0235 (6) | −0.0033 (5) | −0.0035 (5) | −0.0016 (4) |
N1—C2 | 1.4632 (14) | O16—C17 | 1.4265 (13) |
N1—C19 | 1.4647 (15) | C17—C18 | 1.5050 (16) |
N1—C18 | 1.4703 (14) | C17—H17A | 0.99 |
C2—C3 | 1.5173 (16) | C17—H17B | 0.99 |
C2—H2A | 0.99 | C18—H18A | 0.99 |
C2—H2B | 0.99 | C18—H18B | 0.99 |
C3—O4 | 1.4178 (13) | C19—C20 | 1.5104 (16) |
C3—H3A | 0.99 | C19—H19A | 0.99 |
C3—H3B | 0.99 | C19—H19B | 0.99 |
O4—C5B | 1.389 (2) | C20—C21 | 1.3842 (16) |
O4—C5A | 1.419 (2) | C20—C25 | 1.3992 (15) |
C5A—C6A | 1.480 (5) | C21—C22 | 1.3934 (16) |
C5A—H5A1 | 0.99 | C21—H21 | 0.95 |
C5A—H5A2 | 0.99 | C22—C23 | 1.3884 (16) |
C6A—O7 | 1.389 (3) | C22—H22 | 0.95 |
C6A—H6AA | 0.99 | C23—C24 | 1.4018 (15) |
C6A—H6AB | 0.99 | C23—C26 | 1.4945 (16) |
C5B—C6B | 1.479 (2) | C24—C25 | 1.3808 (16) |
C5B—H5B1 | 0.99 | C24—H24 | 0.95 |
C5B—H5B2 | 0.99 | C25—H25 | 0.95 |
C6B—O7 | 1.4737 | C26—C27 | 1.3957 (16) |
C6B—H6BA | 0.99 | C26—C31 | 1.4133 (15) |
C6B—H6BB | 0.99 | C27—C28 | 1.3930 (17) |
O7—C8 | 1.4153 | C27—H27 | 0.95 |
C8—C9 | 1.5084 (13) | C28—C29 | 1.3845 (17) |
C8—H8A | 0.99 | C28—H28 | 0.95 |
C8—H8B | 0.99 | C29—C30 | 1.3827 (17) |
C9—N10 | 1.4660 (15) | C29—H29 | 0.95 |
C9—H9A | 0.99 | C30—C31 | 1.4001 (16) |
C9—H9B | 0.99 | C30—H30 | 0.95 |
N10—C11 | 1.4630 (14) | C31—C32 | 1.4896 (16) |
N10—C38 | 1.4677 (14) | C32—C33 | 1.3935 (15) |
C11—C12 | 1.5175 (15) | C32—C37 | 1.4003 (15) |
C11—H11A | 0.99 | C33—C34 | 1.3885 (16) |
C11—H11B | 0.99 | C33—H33 | 0.95 |
C12—O13 | 1.4217 (13) | C34—C35 | 1.3836 (16) |
C12—H12A | 0.99 | C34—H34 | 0.95 |
C12—H12B | 0.99 | C35—C36 | 1.3947 (15) |
O13—C14 | 1.4176 (14) | C35—C38 | 1.5069 (16) |
C14—C15 | 1.5074 (16) | C36—C37 | 1.3842 (16) |
C14—H14A | 0.99 | C36—H36 | 0.95 |
C14—H14B | 0.99 | C37—H37 | 0.95 |
C15—O16 | 1.4215 (13) | C38—H38A | 0.99 |
C15—H15A | 0.99 | C38—H38B | 0.99 |
C15—H15B | 0.99 | ||
C2—N1—C19 | 110.31 (8) | C14—C15—H15B | 109.8 |
C2—N1—C18 | 112.01 (9) | H15A—C15—H15B | 108.2 |
C19—N1—C18 | 111.70 (8) | C15—O16—C17 | 112.76 (9) |
N1—C2—C3 | 112.64 (9) | O16—C17—C18 | 108.22 (9) |
N1—C2—H2A | 109.1 | O16—C17—H17A | 110.1 |
C3—C2—H2A | 109.1 | C18—C17—H17A | 110.1 |
N1—C2—H2B | 109.1 | O16—C17—H17B | 110.1 |
C3—C2—H2B | 109.1 | C18—C17—H17B | 110.1 |
H2A—C2—H2B | 107.8 | H17A—C17—H17B | 108.4 |
O4—C3—C2 | 105.97 (9) | N1—C18—C17 | 111.99 (9) |
O4—C3—H3A | 110.5 | N1—C18—H18A | 109.2 |
C2—C3—H3A | 110.5 | C17—C18—H18A | 109.2 |
O4—C3—H3B | 110.5 | N1—C18—H18B | 109.2 |
C2—C3—H3B | 110.5 | C17—C18—H18B | 109.2 |
H3A—C3—H3B | 108.7 | H18A—C18—H18B | 107.9 |
C5B—O4—C3 | 118.81 (12) | N1—C19—C20 | 111.27 (8) |
C3—O4—C5A | 119.96 (11) | N1—C19—H19A | 109.4 |
O4—C5A—C6A | 116.8 (3) | C20—C19—H19A | 109.4 |
O4—C5A—H5A1 | 108.1 | N1—C19—H19B | 109.4 |
C6A—C5A—H5A1 | 108.1 | C20—C19—H19B | 109.4 |
O4—C5A—H5A2 | 108.1 | H19A—C19—H19B | 108 |
C6A—C5A—H5A2 | 108.1 | C21—C20—C25 | 118.19 (10) |
H5A1—C5A—H5A2 | 107.3 | C21—C20—C19 | 122.03 (10) |
O7—C6A—C5A | 108.2 (3) | C25—C20—C19 | 119.76 (10) |
O7—C6A—H6AA | 110.1 | C20—C21—C22 | 120.98 (10) |
C5A—C6A—H6AA | 110.1 | C20—C21—H21 | 119.5 |
O7—C6A—H6AB | 110.1 | C22—C21—H21 | 119.5 |
C5A—C6A—H6AB | 110.1 | C23—C22—C21 | 120.87 (10) |
H6AA—C6A—H6AB | 108.4 | C23—C22—H22 | 119.6 |
O4—C5B—C6B | 116.73 (18) | C21—C22—H22 | 119.6 |
O4—C5B—H5B1 | 108.1 | C22—C23—C24 | 118.18 (10) |
C6B—C5B—H5B1 | 108.1 | C22—C23—C26 | 120.55 (10) |
O4—C5B—H5B2 | 108.1 | C24—C23—C26 | 121.25 (10) |
C6B—C5B—H5B2 | 108.1 | C25—C24—C23 | 120.68 (10) |
H5B1—C5B—H5B2 | 107.3 | C25—C24—H24 | 119.7 |
O7—C6B—C5B | 109.69 (9) | C23—C24—H24 | 119.7 |
O7—C6B—H6BA | 109.7 | C24—C25—C20 | 121.07 (10) |
C5B—C6B—H6BA | 109.7 | C24—C25—H25 | 119.5 |
O7—C6B—H6BB | 109.7 | C20—C25—H25 | 119.5 |
C5B—C6B—H6BB | 109.7 | C27—C26—C31 | 118.76 (10) |
H6BA—C6B—H6BB | 108.2 | C27—C26—C23 | 119.57 (10) |
C6A—O7—C8 | 119.25 (18) | C31—C26—C23 | 121.67 (10) |
C8—O7—C6B | 107.2 | C28—C27—C26 | 121.87 (11) |
O7—C8—C9 | 108.1 | C28—C27—H27 | 119.1 |
O7—C8—H8A | 110.1 | C26—C27—H27 | 119.1 |
C9—C8—H8A | 110.1 | C29—C28—C27 | 119.19 (11) |
O7—C8—H8B | 110.1 | C29—C28—H28 | 120.4 |
C9—C8—H8B | 110.1 | C27—C28—H28 | 120.4 |
H8A—C8—H8B | 108.4 | C30—C29—C28 | 119.76 (12) |
N10—C9—C8 | 112.30 (8) | C30—C29—H29 | 120.1 |
N10—C9—H9A | 109.1 | C28—C29—H29 | 120.1 |
C8—C9—H9A | 109.1 | C29—C30—C31 | 122.00 (11) |
N10—C9—H9B | 109.1 | C29—C30—H30 | 119 |
C8—C9—H9B | 109.1 | C31—C30—H30 | 119 |
H9A—C9—H9B | 107.9 | C30—C31—C26 | 118.36 (10) |
C11—N10—C9 | 111.85 (8) | C30—C31—C32 | 119.43 (10) |
C11—N10—C38 | 110.53 (9) | C26—C31—C32 | 122.19 (10) |
C9—N10—C38 | 110.63 (8) | C33—C32—C37 | 117.92 (10) |
N10—C11—C12 | 112.35 (9) | C33—C32—C31 | 120.80 (10) |
N10—C11—H11A | 109.1 | C37—C32—C31 | 121.29 (10) |
C12—C11—H11A | 109.1 | C34—C33—C32 | 120.74 (11) |
N10—C11—H11B | 109.1 | C34—C33—H33 | 119.6 |
C12—C11—H11B | 109.1 | C32—C33—H33 | 119.6 |
H11A—C11—H11B | 107.9 | C35—C34—C33 | 121.31 (10) |
O13—C12—C11 | 105.86 (9) | C35—C34—H34 | 119.3 |
O13—C12—H12A | 110.6 | C33—C34—H34 | 119.3 |
C11—C12—H12A | 110.6 | C34—C35—C36 | 118.20 (11) |
O13—C12—H12B | 110.6 | C34—C35—C38 | 122.29 (10) |
C11—C12—H12B | 110.6 | C36—C35—C38 | 119.50 (10) |
H12A—C12—H12B | 108.7 | C37—C36—C35 | 120.89 (11) |
C14—O13—C12 | 115.10 (9) | C37—C36—H36 | 119.6 |
O13—C14—C15 | 114.27 (10) | C35—C36—H36 | 119.6 |
O13—C14—H14A | 108.7 | C36—C37—C32 | 120.92 (10) |
C15—C14—H14A | 108.7 | C36—C37—H37 | 119.5 |
O13—C14—H14B | 108.7 | C32—C37—H37 | 119.5 |
C15—C14—H14B | 108.7 | N10—C38—C35 | 111.78 (8) |
H14A—C14—H14B | 107.6 | N10—C38—H38A | 109.3 |
O16—C15—C14 | 109.39 (9) | C35—C38—H38A | 109.3 |
O16—C15—H15A | 109.8 | N10—C38—H38B | 109.3 |
C14—C15—H15A | 109.8 | C35—C38—H38B | 109.3 |
O16—C15—H15B | 109.8 | H38A—C38—H38B | 107.9 |
C19—N1—C2—C3 | −154.83 (10) | C21—C22—C23—C26 | −176.63 (10) |
C18—N1—C2—C3 | 80.09 (12) | C22—C23—C24—C25 | −2.00 (15) |
N1—C2—C3—O4 | −174.14 (9) | C26—C23—C24—C25 | 176.41 (9) |
C2—C3—O4—C5B | 149.61 (15) | C23—C24—C25—C20 | 0.65 (16) |
C2—C3—O4—C5A | −158.83 (15) | C21—C20—C25—C24 | 0.93 (15) |
C5B—O4—C5A—C6A | 38.8 (2) | C19—C20—C25—C24 | −177.45 (9) |
C3—O4—C5A—C6A | −63.2 (3) | C22—C23—C26—C27 | −52.09 (14) |
O4—C5A—C6A—O7 | 77.2 (4) | C24—C23—C26—C27 | 129.53 (11) |
C3—O4—C5B—C6B | 72.7 (2) | C22—C23—C26—C31 | 128.64 (11) |
C5A—O4—C5B—C6B | −31.95 (16) | C24—C23—C26—C31 | −49.74 (15) |
O4—C5B—C6B—O7 | −71.37 (18) | C31—C26—C27—C28 | 2.06 (16) |
C5A—C6A—O7—C8 | 100.0 (2) | C23—C26—C27—C28 | −177.23 (10) |
C5A—C6A—O7—C6B | 51.1 (4) | C26—C27—C28—C29 | −0.05 (18) |
C5B—C6B—O7—C6A | −56.4 (4) | C27—C28—C29—C30 | −1.45 (18) |
C5B—C6B—O7—C8 | 167.06 (11) | C28—C29—C30—C31 | 0.92 (18) |
C6A—O7—C8—C9 | −170.1 (2) | C29—C30—C31—C26 | 1.10 (16) |
C6B—O7—C8—C9 | −156.45 (5) | C29—C30—C31—C32 | −177.80 (10) |
O7—C8—C9—N10 | 74.35 (8) | C27—C26—C31—C30 | −2.53 (15) |
C8—C9—N10—C11 | −155.18 (8) | C23—C26—C31—C30 | 176.75 (10) |
C8—C9—N10—C38 | 81.14 (10) | C27—C26—C31—C32 | 176.33 (10) |
C9—N10—C11—C12 | 76.27 (11) | C23—C26—C31—C32 | −4.39 (15) |
C38—N10—C11—C12 | −159.99 (9) | C30—C31—C32—C33 | −48.86 (14) |
N10—C11—C12—O13 | −179.07 (8) | C26—C31—C32—C33 | 132.28 (11) |
C11—C12—O13—C14 | 162.24 (9) | C30—C31—C32—C37 | 131.47 (11) |
C12—O13—C14—C15 | 76.42 (13) | C26—C31—C32—C37 | −47.38 (14) |
O13—C14—C15—O16 | −78.05 (12) | C37—C32—C33—C34 | 1.60 (15) |
C14—C15—O16—C17 | 179.56 (9) | C31—C32—C33—C34 | −178.07 (10) |
C15—O16—C17—C18 | −153.77 (9) | C32—C33—C34—C35 | −0.13 (16) |
C2—N1—C18—C17 | −156.80 (9) | C33—C34—C35—C36 | −1.17 (16) |
C19—N1—C18—C17 | 78.88 (11) | C33—C34—C35—C38 | 177.48 (10) |
O16—C17—C18—N1 | 72.81 (12) | C34—C35—C36—C37 | 0.97 (15) |
C2—N1—C19—C20 | 73.08 (11) | C38—C35—C36—C37 | −177.73 (9) |
C18—N1—C19—C20 | −161.66 (9) | C35—C36—C37—C32 | 0.53 (15) |
N1—C19—C20—C21 | −119.16 (11) | C33—C32—C37—C36 | −1.80 (15) |
N1—C19—C20—C25 | 59.15 (13) | C31—C32—C37—C36 | 177.87 (9) |
C25—C20—C21—C22 | −1.15 (15) | C11—N10—C38—C35 | 70.84 (11) |
C19—C20—C21—C22 | 177.19 (10) | C9—N10—C38—C35 | −164.72 (9) |
C20—C21—C22—C23 | −0.23 (16) | C34—C35—C38—N10 | −118.41 (11) |
C21—C22—C23—C24 | 1.79 (15) | C36—C35—C38—N10 | 60.23 (13) |
Experimental details
Crystal data | |
Chemical formula | C32H40N2O4 |
Mr | 516.66 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 9.6757 (3), 12.1582 (4), 12.5129 (5) |
α, β, γ (°) | 88.178 (2), 82.616 (2), 78.072 (2) |
V (Å3) | 1428.26 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.33 × 0.32 × 0.22 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.975, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10763, 10763, 5346 |
Rint | 0 |
(sin θ/λ)max (Å−1) | 0.768 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.115, 0.81 |
No. of reflections | 10763 |
No. of parameters | 351 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.22 |
Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Footnotes
†CAS 77968–08–2.
Acknowledgements
The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.
References
Cram, D. J. (1988). J. Inclusion Phenom. 6, 397–413. CrossRef CAS Web of Science Google Scholar
Cram, D. J. & Trueblood, K. N. (1981). Top. Curr. Chem. 98, 43–106. CrossRef CAS Google Scholar
Dietrich, B., Lehn, J. M. & Sauvage, J. P. (1969a). Tetrahedron Lett. 34, 2885–2888. CrossRef Google Scholar
Dietrich, B., Lehn, J. M. & Sauvage, J. P. (1969b). Tetrahedron Lett. 34, 2889–2892. CrossRef Google Scholar
Dunitz, J. D., Dobler, M., Seiler, P. & Phizackerley, R. P. (1974). Acta Cryst. B30, 2733–2738. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Rossa, L. & Vögtle, F. (1981). Liebigs Ann. Chem. pp. 459–466. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vögtle, F., Muller, W. M., Puff, H. & Friedrichs, E. (1983). Chem. Ber. 116, 2344–2354. Google Scholar
Weber, G. (1981). Acta Cryst. B37, 1832–1835. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Cryptands, first synthesized in Lehn's laboratories (Dietrich et al. 1969a,b) have been designed for many years as supramolecular hosts for complexation of metal ions and other guests (Cram, 1988). Dunitz et al. (1974) and Cram & Trueblood (1981) emphasized the cavity size of the host matching the size of the guest, both by construction of the host and by its organization by the guest. In the title compound, C32H40N2O4, an o-terphenyl bridge was inserted into the macrobicyclic framework by Rossa & Vögtle (1981) to control the cavity size of cryptand-[2.2.2]. We report here the structure of the altered cryptand.
The molecule has approximate C2 symmetry, with the central ring of the terphenyl group forming dihedral angles of 50.75 (5) and 47.76 (4)° with the other two benzene rings. The three rings of the terphenyl bridge are essentially planar, with r.m.s. deviations ranging from 0.007 to 0.009 Å. In the diaza-18-crown-6 ring, one –(CH2)2– group (C5 and C6) is disordered with very nearly equal populations of the two conformers [0.490 (3) and 0.510 (3)]. The bond lengths in the ordered part of the molecule are normal, with average C—C = 1.511 (3) Å, C—O = 1.421 (3) Å, and C—N = 1.466 (4) Å.
The Na+ complex of the title cryptand has been reported (Weber, 1981) as the thiocyanate salt, methanol solvate. In that structure, the conformation of the terphenyl subunit is quite similar to that in the title cryptand, with the central phenyl group forming dihedral angles of 49.2 and 54.9° with the other two. The N···N distance in the Na+ complex, 5.341 (1) Å, is also not much different from that in the uncomplexed cryptand, 5.408 (1) Å.