Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102011526/fr1380sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102011526/fr1380Isup2.hkl |
CCDC reference: 193434
The title compound has not been previously reported. The pyrrolidine enamine of cyclohexanone was treated with methyl vinyl ketone to generate the expected mixture of octalone enamines, which was isolated and purified by distillation (Stork et al., 1963; House et al., 1965). This was alkylated with ethyl bromoacetate, and the resulting product was isolated by distillation and saponified. Material suitable for X-ray was obtained from cyclohexane/benzene or /ethyl acetate (m.p. ca 368 K), with loss of water. Attempts to obtain usable crystals of the anhydrous form were unsuccessful.
All H atoms for molecules I and I' were found in electron-density difference maps but were placed in calculated positions (0.98 Å for the methine and 0.97 Å for the methylene H atoms) and allowed to refine as riding models on their respective C atoms. The displacement parameters were fixed at 120% of those of their respective C atoms. The positional parameters of the carboxyl H atom and the water H atoms for both molecules I and I' were allowed to refine, but their displacement parameters were fixed at 0.08 Å2.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 in SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 in SHELXTL; molecular graphics: SHELXP97 in SHELXTL; software used to prepare material for publication: SHELXL97 in SHELXTL.
C12H16O3·H2O | Dx = 1.237 Mg m−3 |
Mr = 226.26 | Melting point: 368 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.153 (6) Å | Cell parameters from 37 reflections |
b = 9.386 (3) Å | θ = 2.0–10.0° |
c = 17.122 (6) Å | µ = 0.09 mm−1 |
β = 93.629 (14)° | T = 293 K |
V = 2430.2 (15) Å3 | Pyramid frustum, colourless |
Z = 8 | 0.44 × 0.30 × 0.24 mm |
F(000) = 976 |
Siemens P4 diffractometer | 2276 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 25.0°, θmin = 2.4° |
2θ/θ scans | h = −18→1 |
Absorption correction: numerical (SHELXTL; Sheldrick, 1997) | k = −1→11 |
Tmin = 0.94, Tmax = 0.96 | l = −20→20 |
5434 measured reflections | 3 standard reflections every 97 reflections |
4273 independent reflections | intensity decay: variation < 1.9% |
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)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0463P)2 + 0.773P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
4273 reflections | Δρmax = 0.20 e Å−3 |
308 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97 in SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0011 (3) |
C12H16O3·H2O | V = 2430.2 (15) Å3 |
Mr = 226.26 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.153 (6) Å | µ = 0.09 mm−1 |
b = 9.386 (3) Å | T = 293 K |
c = 17.122 (6) Å | 0.44 × 0.30 × 0.24 mm |
β = 93.629 (14)° |
Siemens P4 diffractometer | 2276 reflections with I > 2σ(I) |
Absorption correction: numerical (SHELXTL; Sheldrick, 1997) | Rint = 0.031 |
Tmin = 0.94, Tmax = 0.96 | 3 standard reflections every 97 reflections |
5434 measured reflections | intensity decay: variation < 1.9% |
4273 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.20 e Å−3 |
4273 reflections | Δρmin = −0.16 e Å−3 |
308 parameters |
Experimental. crystal mounted on glass fiber using cyanoacrylate cement |
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 | ||
O1 | 0.26215 (15) | 0.9816 (2) | 0.37815 (13) | 0.0713 (7) | |
O2 | 0.03598 (13) | 0.9225 (2) | 0.29939 (11) | 0.0602 (6) | |
O3 | −0.00080 (15) | 1.0538 (2) | 0.40079 (12) | 0.0598 (6) | |
O4 | −0.10169 (15) | 1.2220 (2) | 0.30984 (13) | 0.0619 (6) | |
O1' | 0.76558 (16) | 1.1173 (2) | 0.87722 (14) | 0.0761 (7) | |
O2' | 0.53650 (13) | 1.0622 (2) | 0.79772 (11) | 0.0589 (6) | |
O3' | 0.49506 (14) | 1.1832 (2) | 0.90148 (12) | 0.0577 (6) | |
O4' | 0.39593 (15) | 1.3572 (2) | 0.81181 (13) | 0.0606 (6) | |
C1 | 0.17217 (17) | 0.7789 (3) | 0.39256 (14) | 0.0405 (7) | |
C2 | 0.25204 (19) | 0.8522 (3) | 0.36719 (16) | 0.0491 (8) | |
C3 | 0.3156 (2) | 0.7674 (3) | 0.3217 (2) | 0.0658 (9) | |
C4 | 0.32025 (19) | 0.6149 (4) | 0.3469 (2) | 0.0647 (9) | |
C4A | 0.22998 (18) | 0.5433 (3) | 0.34476 (17) | 0.0497 (8) | |
C5 | 0.2357 (2) | 0.4001 (3) | 0.38760 (19) | 0.0671 (9) | |
C6 | 0.1472 (2) | 0.3253 (3) | 0.3924 (2) | 0.0713 (10) | |
C7 | 0.0815 (2) | 0.4229 (3) | 0.4297 (2) | 0.0695 (10) | |
C8 | 0.07255 (19) | 0.5638 (3) | 0.38615 (18) | 0.0551 (8) | |
C8A | 0.15972 (17) | 0.6384 (3) | 0.37723 (15) | 0.0420 (7) | |
C9 | 0.10520 (18) | 0.8751 (3) | 0.42767 (15) | 0.0470 (7) | |
C10 | 0.04437 (17) | 0.9512 (3) | 0.36851 (17) | 0.0413 (7) | |
C1' | 0.67417 (17) | 0.9178 (3) | 0.89103 (14) | 0.0398 (7) | |
C2' | 0.75437 (18) | 0.9886 (3) | 0.86581 (16) | 0.0476 (7) | |
C3' | 0.81756 (19) | 0.9020 (3) | 0.82110 (19) | 0.0600 (9) | |
C4' | 0.82305 (18) | 0.7501 (3) | 0.85118 (18) | 0.0581 (8) | |
C4'A | 0.73266 (18) | 0.6793 (3) | 0.84857 (17) | 0.0494 (8) | |
C5' | 0.7370 (2) | 0.5382 (3) | 0.8940 (2) | 0.0738 (10) | |
C6' | 0.6485 (3) | 0.4644 (4) | 0.8966 (2) | 0.0901 (13) | |
C7' | 0.5815 (3) | 0.5629 (4) | 0.9315 (2) | 0.0825 (12) | |
C8' | 0.5736 (2) | 0.7027 (3) | 0.88656 (19) | 0.0628 (9) | |
C8'A | 0.66143 (17) | 0.7765 (3) | 0.87760 (15) | 0.0430 (7) | |
C9' | 0.60735 (18) | 1.0151 (3) | 0.92552 (15) | 0.0485 (7) | |
C10' | 0.54332 (17) | 1.0873 (3) | 0.86724 (16) | 0.0409 (7) | |
H3 | −0.029 (2) | 1.095 (4) | 0.3671 (19) | 0.080* | |
H4A | −0.141 (2) | 1.271 (4) | 0.3316 (19) | 0.080* | |
H4B | −0.083 (2) | 1.277 (4) | 0.2745 (19) | 0.080* | |
H3' | 0.459 (2) | 1.231 (4) | 0.8688 (18) | 0.080* | |
H4'A | 0.356 (2) | 1.412 (4) | 0.8335 (19) | 0.080* | |
H4'B | 0.416 (2) | 1.411 (4) | 0.7806 (19) | 0.080* | |
H3A | 0.2972 | 0.7719 | 0.2665 | 0.079* | |
H3B | 0.3740 | 0.8096 | 0.3288 | 0.079* | |
H4C | 0.3472 | 0.6099 | 0.3998 | 0.078* | |
H4D | 0.3579 | 0.5632 | 0.3130 | 0.078* | |
H4AA | 0.2120 | 0.5240 | 0.2898 | 0.060* | |
H5A | 0.2752 | 0.3379 | 0.3610 | 0.081* | |
H5B | 0.2613 | 0.4155 | 0.4403 | 0.081* | |
H6A | 0.1551 | 0.2390 | 0.4233 | 0.086* | |
H6B | 0.1242 | 0.2986 | 0.3403 | 0.086* | |
H7A | 0.0243 | 0.3765 | 0.4290 | 0.083* | |
H7B | 0.1012 | 0.4404 | 0.4838 | 0.083* | |
H8A | 0.0443 | 0.5468 | 0.3346 | 0.066* | |
H8B | 0.0343 | 0.6263 | 0.4140 | 0.066* | |
H9A | 0.0697 | 0.8185 | 0.4613 | 0.056* | |
H9B | 0.1365 | 0.9456 | 0.4602 | 0.056* | |
H3'A | 0.8758 | 0.9452 | 0.8262 | 0.072* | |
H3'B | 0.7980 | 0.9015 | 0.7660 | 0.072* | |
H4'C | 0.8484 | 0.7502 | 0.9047 | 0.070* | |
H4'D | 0.8619 | 0.6955 | 0.8196 | 0.070* | |
H4'E | 0.7161 | 0.6567 | 0.7937 | 0.059* | |
H5'A | 0.7779 | 0.4747 | 0.8700 | 0.089* | |
H5'B | 0.7601 | 0.5566 | 0.9471 | 0.089* | |
H6'A | 0.6551 | 0.3786 | 0.9280 | 0.108* | |
H6'B | 0.6273 | 0.4370 | 0.8441 | 0.108* | |
H7'A | 0.5242 | 0.5164 | 0.9299 | 0.099* | |
H7'B | 0.5997 | 0.5821 | 0.9858 | 0.099* | |
H8'A | 0.5459 | 0.6842 | 0.8350 | 0.075* | |
H8'B | 0.5352 | 0.7664 | 0.9134 | 0.075* | |
H9'A | 0.5737 | 0.9600 | 0.9612 | 0.058* | |
H9'B | 0.6391 | 1.0881 | 0.9560 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0737 (16) | 0.0518 (14) | 0.0901 (17) | −0.0175 (12) | 0.0172 (13) | −0.0058 (13) |
O2 | 0.0639 (14) | 0.0685 (15) | 0.0480 (13) | 0.0183 (12) | 0.0016 (10) | −0.0083 (11) |
O3 | 0.0682 (15) | 0.0556 (14) | 0.0561 (14) | 0.0205 (12) | 0.0093 (11) | −0.0036 (11) |
O4 | 0.0658 (15) | 0.0541 (15) | 0.0670 (15) | 0.0148 (12) | 0.0144 (11) | 0.0120 (11) |
O1' | 0.0830 (17) | 0.0484 (14) | 0.0987 (18) | −0.0128 (13) | 0.0215 (14) | −0.0007 (13) |
O2' | 0.0598 (13) | 0.0687 (14) | 0.0479 (13) | 0.0208 (11) | 0.0018 (10) | −0.0040 (11) |
O3' | 0.0587 (14) | 0.0562 (14) | 0.0582 (13) | 0.0220 (11) | 0.0050 (10) | −0.0045 (11) |
O4' | 0.0624 (15) | 0.0547 (15) | 0.0659 (15) | 0.0148 (12) | 0.0143 (11) | 0.0099 (11) |
C1 | 0.0386 (16) | 0.0455 (17) | 0.0375 (14) | 0.0031 (14) | 0.0019 (12) | 0.0028 (13) |
C2 | 0.0409 (17) | 0.050 (2) | 0.0553 (18) | −0.0051 (15) | −0.0023 (14) | 0.0049 (16) |
C3 | 0.0452 (18) | 0.068 (2) | 0.086 (2) | 0.0032 (17) | 0.0205 (17) | 0.014 (2) |
C4 | 0.0444 (18) | 0.072 (2) | 0.078 (2) | 0.0119 (17) | 0.0126 (16) | 0.0056 (19) |
C4A | 0.0488 (17) | 0.0521 (19) | 0.0487 (17) | 0.0100 (15) | 0.0058 (14) | −0.0024 (14) |
C5 | 0.076 (2) | 0.053 (2) | 0.073 (2) | 0.0191 (19) | 0.0089 (18) | 0.0006 (18) |
C6 | 0.090 (3) | 0.047 (2) | 0.078 (2) | −0.006 (2) | 0.010 (2) | 0.0002 (18) |
C7 | 0.075 (2) | 0.058 (2) | 0.078 (2) | −0.0167 (19) | 0.0191 (19) | 0.0005 (19) |
C8 | 0.0447 (17) | 0.054 (2) | 0.067 (2) | −0.0030 (15) | 0.0066 (15) | −0.0002 (16) |
C8A | 0.0391 (16) | 0.0427 (17) | 0.0440 (15) | 0.0031 (14) | 0.0016 (12) | 0.0051 (13) |
C9 | 0.0486 (17) | 0.0454 (17) | 0.0475 (16) | −0.0001 (14) | 0.0074 (14) | −0.0015 (14) |
C10 | 0.0365 (15) | 0.0388 (16) | 0.0494 (17) | −0.0012 (14) | 0.0098 (13) | −0.0036 (14) |
C1' | 0.0382 (15) | 0.0421 (17) | 0.0390 (15) | 0.0072 (13) | 0.0010 (12) | 0.0045 (13) |
C2' | 0.0450 (17) | 0.0472 (19) | 0.0504 (17) | 0.0015 (15) | 0.0002 (14) | 0.0062 (15) |
C3' | 0.0387 (17) | 0.066 (2) | 0.077 (2) | −0.0031 (16) | 0.0132 (15) | 0.0034 (19) |
C4' | 0.0417 (17) | 0.063 (2) | 0.071 (2) | 0.0118 (16) | 0.0089 (15) | 0.0019 (18) |
C4'A | 0.0520 (18) | 0.0456 (18) | 0.0509 (17) | 0.0063 (15) | 0.0053 (14) | −0.0016 (15) |
C5' | 0.087 (3) | 0.047 (2) | 0.088 (3) | 0.0116 (19) | 0.008 (2) | 0.0102 (18) |
C6' | 0.119 (3) | 0.051 (2) | 0.103 (3) | −0.016 (2) | 0.028 (3) | 0.010 (2) |
C7' | 0.089 (3) | 0.083 (3) | 0.077 (2) | −0.039 (2) | 0.020 (2) | 0.004 (2) |
C8' | 0.0500 (19) | 0.071 (2) | 0.068 (2) | −0.0134 (17) | 0.0115 (16) | −0.0073 (19) |
C8'A | 0.0376 (15) | 0.0500 (18) | 0.0413 (15) | 0.0005 (14) | 0.0016 (12) | 0.0030 (13) |
C9' | 0.0495 (17) | 0.0520 (18) | 0.0444 (16) | 0.0070 (15) | 0.0053 (14) | −0.0026 (15) |
C10' | 0.0360 (15) | 0.0408 (16) | 0.0470 (17) | 0.0002 (13) | 0.0107 (13) | 0.0005 (14) |
O1—C2 | 1.237 (3) | O4—H4B | 0.86 (3) |
O2—C10 | 1.213 (3) | O3'—H3' | 0.89 (3) |
O3—C10 | 1.322 (3) | O4'—H4'A | 0.89 (3) |
O1'—C2' | 1.234 (3) | O4'—H4'B | 0.81 (3) |
O2'—C10' | 1.211 (3) | C3—H3A | 0.9700 |
O3'—C10' | 1.320 (3) | C3—H3B | 0.9700 |
C1—C8A | 1.355 (4) | C4—H4C | 0.9700 |
C1—C2 | 1.481 (4) | C4—H4D | 0.9700 |
C1—C9 | 1.511 (4) | C4A—H4AA | 0.9800 |
C2—C3 | 1.503 (4) | C5—H5A | 0.9700 |
C3—C4 | 1.495 (4) | C5—H5B | 0.9700 |
C4—C4A | 1.522 (4) | C6—H6A | 0.9700 |
C4A—C8A | 1.521 (4) | C6—H6B | 0.9700 |
C4A—C5 | 1.532 (4) | C7—H7A | 0.9700 |
C5—C6 | 1.520 (4) | C7—H7B | 0.9700 |
C6—C7 | 1.522 (4) | C8—H8A | 0.9700 |
C7—C8 | 1.520 (4) | C8—H8B | 0.9700 |
C8—C8A | 1.511 (4) | C9—H9A | 0.9700 |
C9—C10 | 1.506 (4) | C9—H9B | 0.9700 |
C1'—C8'A | 1.358 (4) | C3'—H3'A | 0.9700 |
C1'—C2' | 1.473 (4) | C3'—H3'B | 0.9700 |
C1'—C9' | 1.511 (4) | C4'—H4'C | 0.9700 |
C2'—C3' | 1.502 (4) | C4'—H4'D | 0.9700 |
C3'—C4' | 1.516 (4) | C4'A—H4'E | 0.9800 |
C4'—C4'A | 1.520 (4) | C5'—H5'A | 0.9700 |
C4'A—C8'A | 1.521 (4) | C5'—H5'B | 0.9700 |
C4'A—C5' | 1.535 (4) | C6'—H6'A | 0.9700 |
C5'—C6' | 1.513 (5) | C6'—H6'B | 0.9700 |
C6'—C7' | 1.523 (5) | C7'—H7'A | 0.9700 |
C7'—C8' | 1.522 (4) | C7'—H7'B | 0.9700 |
C8'—C8'A | 1.517 (4) | C8'—H8'A | 0.9700 |
C9'—C10' | 1.508 (4) | C8'—H8'B | 0.9700 |
O3—H3 | 0.80 (3) | C9'—H9'A | 0.9700 |
O4—H4A | 0.86 (3) | C9'—H9'B | 0.9700 |
C8A—C1—C2 | 120.1 (3) | C4A—C5—H5A | 108.7 |
C8A—C1—C9 | 124.7 (3) | C6—C5—H5B | 108.7 |
C2—C1—C9 | 114.9 (2) | C4A—C5—H5B | 108.7 |
O1—C2—C1 | 120.5 (3) | H5A—C5—H5B | 107.6 |
O1—C2—C3 | 121.4 (3) | C5—C6—H6A | 109.6 |
C1—C2—C3 | 117.9 (3) | C7—C6—H6A | 109.6 |
C4—C3—C2 | 112.2 (3) | C5—C6—H6B | 109.6 |
C3—C4—C4A | 112.9 (3) | C7—C6—H6B | 109.6 |
C8A—C4A—C4 | 112.4 (3) | H6A—C6—H6B | 108.1 |
C8A—C4A—C5 | 111.1 (2) | C8—C7—H7A | 109.4 |
C4—C4A—C5 | 110.7 (3) | C6—C7—H7A | 109.4 |
C6—C5—C4A | 114.1 (3) | C8—C7—H7B | 109.4 |
C5—C6—C7 | 110.3 (3) | C6—C7—H7B | 109.4 |
C8—C7—C6 | 111.0 (3) | H7A—C7—H7B | 108.0 |
C8A—C8—C7 | 113.7 (3) | C8A—C8—H8A | 108.8 |
C1—C8A—C8 | 122.9 (3) | C7—C8—H8A | 108.8 |
C1—C8A—C4A | 123.3 (3) | C8A—C8—H8B | 108.8 |
C8—C8A—C4A | 113.7 (2) | C7—C8—H8B | 108.8 |
C10—C9—C1 | 114.4 (2) | H8A—C8—H8B | 107.7 |
O2—C10—O3 | 123.0 (3) | C10—C9—H9A | 108.7 |
O2—C10—C9 | 125.0 (3) | C1—C9—H9A | 108.7 |
O3—C10—C9 | 112.0 (2) | C10—C9—H9B | 108.7 |
C8'A—C1'—C2' | 120.1 (3) | C1—C9—H9B | 108.7 |
C8'A—C1'—C9' | 124.4 (3) | H9A—C9—H9B | 107.6 |
C2'—C1'—C9' | 115.3 (2) | C2'—C3'—H3'A | 109.4 |
O1'—C2'—C1' | 120.2 (3) | C4'—C3'—H3'A | 109.4 |
O1'—C2'—C3' | 121.7 (3) | C2'—C3'—H3'B | 109.4 |
C1'—C2'—C3' | 118.0 (3) | C4'—C3'—H3'B | 109.4 |
C2'—C3'—C4' | 111.0 (2) | H3'A—C3'—H3'B | 108.0 |
C3'—C4'—C4'A | 111.8 (2) | C3'—C4'—H4'C | 109.3 |
C4'—C4'A—C8'A | 112.6 (2) | C4'A—C4'—H4'C | 109.3 |
C4'—C4'A—C5' | 110.7 (3) | C3'—C4'—H4'D | 109.3 |
C8'A—C4'A—C5' | 111.1 (2) | C4'A—C4'—H4'D | 109.3 |
C6'—C5'—C4'A | 113.6 (3) | H4'C—C4'—H4'D | 107.9 |
C5'—C6'—C7' | 110.3 (3) | C4'—C4'A—H4'E | 107.4 |
C8'—C7'—C6' | 111.0 (3) | C8'A—C4'A—H4'E | 107.4 |
C8'A—C8'—C7' | 113.8 (3) | C5'—C4'A—H4'E | 107.4 |
C1'—C8'A—C8' | 123.1 (3) | C6'—C5'—H5'A | 108.8 |
C1'—C8'A—C4'A | 123.1 (3) | C4'A—C5'—H5'A | 108.8 |
C8'—C8'A—C4'A | 113.8 (3) | C6'—C5'—H5'B | 108.8 |
C10'—C9'—C1' | 115.6 (2) | C4'A—C5'—H5'B | 108.8 |
O2'—C10'—O3' | 123.6 (3) | H5'A—C5'—H5'B | 107.7 |
O2'—C10'—C9' | 125.0 (3) | C5'—C6'—H6'A | 109.6 |
O3'—C10'—C9' | 111.3 (2) | C7'—C6'—H6'A | 109.6 |
C10—O3—H3 | 109 (3) | C5'—C6'—H6'B | 109.6 |
H4A—O4—H4B | 105 (3) | C7'—C6'—H6'B | 109.6 |
C10'—O3'—H3' | 114 (2) | H6'A—C6'—H6'B | 108.1 |
H4'A—O4'—H4'B | 102 (3) | C8'—C7'—H7'A | 109.4 |
C4—C3—H3A | 109.2 | C6'—C7'—H7'A | 109.4 |
C2—C3—H3A | 109.2 | C8'—C7'—H7'B | 109.4 |
C4—C3—H3B | 109.2 | C6'—C7'—H7'B | 109.4 |
C2—C3—H3B | 109.2 | H7'A—C7'—H7'B | 108.0 |
H3A—C3—H3B | 107.9 | C8'A—C8'—H8'A | 108.8 |
C3—C4—H4C | 109.0 | C7'—C8'—H8'A | 108.8 |
C4A—C4—H4C | 109.0 | C8'A—C8'—H8'B | 108.8 |
C3—C4—H4D | 109.0 | C7'—C8'—H8'B | 108.8 |
C4A—C4—H4D | 109.0 | H8'A—C8'—H8'B | 107.7 |
H4C—C4—H4D | 107.8 | C10'—C9'—H9'A | 108.4 |
C8A—C4A—H4AA | 107.5 | C1'—C9'—H9'A | 108.4 |
C4—C4A—H4AA | 107.5 | C10'—C9'—H9'B | 108.4 |
C5—C4A—H4AA | 107.5 | C1'—C9'—H9'B | 108.4 |
C6—C5—H5A | 108.7 | H9'A—C9'—H9'B | 107.4 |
C8A—C1—C2—O1 | 177.1 (3) | C8'A—C1'—C2'—O1' | 179.2 (3) |
C9—C1—C2—O1 | 2.9 (4) | C9'—C1'—C2'—O1' | 3.8 (4) |
C8A—C1—C2—C3 | 2.4 (4) | C8'A—C1'—C2'—C3' | 3.6 (4) |
C9—C1—C2—C3 | −171.7 (2) | C9'—C1'—C2'—C3' | −171.8 (2) |
O1—C2—C3—C4 | 151.8 (3) | O1'—C2'—C3'—C4' | 148.1 (3) |
C1—C2—C3—C4 | −33.7 (4) | C1'—C2'—C3'—C4' | −36.4 (4) |
C2—C3—C4—C4A | 53.7 (4) | C2'—C3'—C4'—C4'A | 56.1 (3) |
C3—C4—C4A—C8A | −42.7 (4) | C3'—C4'—C4'A—C8'A | −43.6 (3) |
C3—C4—C4A—C5 | −167.5 (3) | C3'—C4'—C4'A—C5' | −168.7 (3) |
C8A—C4A—C5—C6 | 51.0 (4) | C4'—C4'A—C5'—C6' | 177.7 (3) |
C4—C4A—C5—C6 | 176.6 (3) | C8'A—C4'A—C5'—C6' | 51.8 (4) |
C4A—C5—C6—C7 | −55.3 (4) | C4'A—C5'—C6'—C7' | −56.6 (4) |
C5—C6—C7—C8 | 55.1 (4) | C5'—C6'—C7'—C8' | 55.7 (4) |
C6—C7—C8—C8A | −53.7 (4) | C6'—C7'—C8'—C8'A | −52.7 (4) |
C2—C1—C8A—C8 | −167.2 (2) | C2'—C1'—C8'A—C8' | −167.3 (3) |
C9—C1—C8A—C8 | 6.4 (4) | C9'—C1'—C8'A—C8' | 7.7 (4) |
C2—C1—C8A—C4A | 8.9 (4) | C2'—C1'—C8'A—C4'A | 9.8 (4) |
C9—C1—C8A—C4A | −177.5 (2) | C9'—C1'—C8'A—C4'A | −175.2 (2) |
C7—C8—C8A—C1 | −133.2 (3) | C7'—C8'—C8'A—C1' | −133.8 (3) |
C7—C8—C8A—C4A | 50.3 (3) | C7'—C8'—C8'A—C4'A | 48.9 (4) |
C4—C4A—C8A—C1 | 11.4 (4) | C4'—C4'A—C8'A—C1' | 10.9 (4) |
C5—C4A—C8A—C1 | 136.0 (3) | C5'—C4'A—C8'A—C1' | 135.7 (3) |
C4—C4A—C8A—C8 | −172.1 (2) | C4'—C4'A—C8'A—C8' | −171.8 (2) |
C5—C4A—C8A—C8 | −47.6 (3) | C5'—C4'A—C8'A—C8' | −47.0 (3) |
C8A—C1—C9—C10 | −91.8 (3) | C8'A—C1'—C9'—C10' | −90.3 (3) |
C2—C1—C9—C10 | 82.0 (3) | C2'—C1'—C9'—C10' | 84.9 (3) |
C1—C9—C10—O2 | 13.2 (4) | C1'—C9'—C10'—O2' | 7.6 (4) |
C1—C9—C10—O3 | −167.7 (2) | C1'—C9'—C10'—O3' | −172.1 (2) |
Experimental details
Crystal data | |
Chemical formula | C12H16O3·H2O |
Mr | 226.26 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 15.153 (6), 9.386 (3), 17.122 (6) |
β (°) | 93.629 (14) |
V (Å3) | 2430.2 (15) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.44 × 0.30 × 0.24 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Numerical (SHELXTL; Sheldrick, 1997) |
Tmin, Tmax | 0.94, 0.96 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5434, 4273, 2276 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.140, 1.01 |
No. of reflections | 4273 |
No. of parameters | 308 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.16 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 in SHELXTL (Sheldrick, 1997), SHELXL97 in SHELXTL, SHELXP97 in SHELXTL.
O2—C10 | 1.213 (3) | O2'—C10' | 1.211 (3) |
O3—C10 | 1.322 (3) | O3'—C10' | 1.320 (3) |
O2—C10—C9 | 125.0 (3) | O2'—C10'—C9' | 125.0 (3) |
O3—C10—C9 | 112.0 (2) | O3'—C10'—C9' | 111.3 (2) |
Five hydrogen-bonding modes are known for keto carboxylic acids, whose crystal structures are the basis of our continuing study. Besides the common dimeric and rare chain arrangements typical of simpler acids, the five also include two intermolecular acid-to-ketone patterns and an intramolecular hydrogen-bonding mode. Several examples of hydrated arrangements also exist, and we report here the structure and hydrogen-bonding pattern of (±)-2,3,4,4a,5,6,7,8-octahydro-2-oxonaphthalene-1-acetic acid monohydrate, (I).
The asymmetric unit of (I) contains two hydrated molecules, I and I', which are nearly identical. Fig. 1 shows one of these, half of the asymmetric unit, with the atom-numbering. The molecule has little conformational flexibility and the only available rotations involve the bonds to atom C9 and the carboxyl group. The former is turned so that the C10—C9—C1—C8a torsion angle is -91.8 (3)° for molecule I and -90.3 (3)° for molecule I', and the carboxyl group is turned so that its carbonyl is aimed back `under' the conjugated ketone system, with an O2—C10—C9—C1 torsion angle which is 13.2 (4) and 7.6 (4)° for molecules I and I', respectively. The resulting dihedral angle between the ketone and carboxyl planes is 88.0 (2)° for molecule I and 88.8 (2)° for molecule I'. Each carboxyl group donates a hydrogen bond to a water of hydration, which, in turn, donates hydrogen bonds to two different C═O groups in separate neighboring molecules (see below), and Fig. 1 shows this water, arbitrarily, in its hydrogen-bonding relationship to the carboxyl OH group.
The two nearly identical halves of the asymmetric unit have a non-crystallographic translational relationship. They are found at positions which differ by essentially half a cell each in a and c, but whose difference in b is non-crystallographic, amounting to between one-seventh and one-eighth of the b cell dimension [Δxave = 0.5010 (3), Δyave = 0.1370 (4), Δzave = 0.5009 (2)]. No additional symmetry beyond P21/c (Z = 8) could be found.
Averaging of the C—O bond lengths and C—C—O angles by disorder is common in carboxyl dimers (Leiserowitz, 1976) but is not seen in hydrated hydrogen-bonding arrangements, whose geometries exclude the averaging mechanisms. Here, these C—O bond lengths are 1.213 (3)/1.322 (3) Å for molecule I and 1.211 (3)/1.320 (3) Å for molecule I', with angles of 125.0 (3)/112.0 (2) and 125.0 (3)/111.3 (2)° for molecules I and I', respectively. Our own survey of 56 keto acid structures which are not acid dimers gives average values of 1.200 (10)/1.32 (2) Å and 124.5 (14)/112.7 (17)° for these lengths and angles, in accord with typical values of 1.21/1.31 Å and 123/112° cited for highly ordered dimeric carboxyls (Borthwick, 1980).
Fig. 2 illustrates the packing arrangement with its hydrogen bonding, which adheres to a recurrent pattern among hydrated keto acids (Thompson & Lalancette, 2001). In virtually identical arrangements for each half of the asymmetric unit, the carboxyl donates its hydrogen bond to a water molecule, which, in turn, donates hydrogen bonds to the carbonyl groups of a carboxyl in a glide-related molecule and a ketone in a molecule of opposite type (I versus I'). Thus, each water molecule participates in hydrogen bonds to three separate molecules, while each molecule participates in hydrogen bonds to three separate water molecules, producing a complex three-dimensional network.
We characterize the geometry of hydrogen bonding to carbonyls using a combination of the H···O═C angle and the H···O═C—X torsion angle. These describe the approach of the H atom to the O atom in terms of its deviation from, respectively, C═O axiality (ideal = 120°) and planarity with the carbonyl (ideal = 0°). Here, these criteria are applicable to two of the three hydrogen bonds present. Approach angles for the water-to-acid hydrogen bond are 138.0 (10) and 2.6 (15)° for molecule I and 138.0 (10) and 9.0 (15)° for molecule I'. The analogous values for the water-to-ketone hydrogen bond are 123.9 (10) and -5.9 (12)° for molecule I, and 122.3 (10) and -3.5 (12)° for molecule I'. No C—H···O close contacts were found within the 2.7 Å range we usually employ for such non-bonded packing interactions (Steiner, 1997).
The solid-state (KBr) IR spectrum of (I) displays C═O absorptions at 1709 and 1637 cm-1 for hydrogen-bonded carboxyl and ketone groups, respectively, with an alkene peak at 1611 cm-1. In CHCl3 solution, bands appear at 1711, 1660 and 1629 cm-1; a band at 1749 cm-1 is presumably due to monomeric acid.