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As a continuation of a systematic structural analysis of 2-hydroxycycloalkanecarboxylic acids and their carboxamide analogs, the effects of antidromic rings [Jeffrey & Saenger (1991). Hydrogen Bonding in Biological Structures. Berlin, Heidelberg: Springer Verlag] upon the layer stacking of cyclopentane and cycloheptane derivatives are compared. Determination of the structure of trans-2-hydroxycycloheptanecarboxylic acid (2) led to the discovery of two polymorphs with virtually the same unit cell [Kálmán et al. (2003). J. Am. Chem. Soc. 125, 34-35]. (i) The layer stacking of the antidromic rings for the whole single crystal is antiparallel (2b). (ii) The antidromic rings and the 21 axis are parallel (2a), consequently the domains of the single crystal must be antiparallel. While their polymorphism is solvent-controlled, they illustrate a novel form of two-dimensional isostructurality. Antiparallel layer stacking is again demonstrated by trans-2-hydroxycycloheptanecarboxamide (3) (space group Pbca). It is built up from layers isostructural with those in the homologous trans-2-hydroxycyclopentanecarboxamide (4) [Kálmán et al. (2001). Acta Cryst. B57, 539-550], but in this structure (space group Pca21) the layers are stacked in parallel mode. Similar to (2a) and (2b), the antiparallel layer stacking in (3) versus their parallel array in (4) illustrates the two-dimensional isostructurality with alternating layer orientations. Although (3) and (4) display isostructurality, they are not isomorphous.
Supporting information
CCDC reference: 257804
Data collection: CAD-4 EXPRESS; cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
trans-2-hydroxy-cycloheptanecarboxamide
top
Crystal data top
C8H15NO2 | Dx = 1.216 Mg m−3 |
Mr = 157.21 | Mo Kα radiation, λ = 0.710730 Å |
Orthorhombic, Pbca | Cell parameters from 25 reflections |
a = 8.248 (1) Å | θ = 15.4–17.2° |
b = 19.679 (3) Å | µ = 0.09 mm−1 |
c = 10.581 (1) Å | T = 293 K |
V = 1717.4 (4) Å3 | Prism, colourless |
Z = 8 | 0.55 × 0.50 × 0.20 mm |
F(000) = 688 | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 1666 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 32.0°, θmin = 2.8° |
ω–2θ scans | h = −12→12 |
Absorption correction: ψ scan DATCOR (Reibenspies, 1989) | k = −29→29 |
Tmin = 0.876, Tmax = 0.980 | l = −15→15 |
6109 measured reflections | 3 standard reflections every 60 min |
2969 independent reflections | intensity decay: 5% |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.145 | Riding |
S = 0.85 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
2969 reflections | (Δ/σ)max < 0.001 |
101 parameters | Δρmax = 0.30 e Å−3 |
139 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C8H15NO2 | V = 1717.4 (4) Å3 |
Mr = 157.21 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.248 (1) Å | µ = 0.09 mm−1 |
b = 19.679 (3) Å | T = 293 K |
c = 10.581 (1) Å | 0.55 × 0.50 × 0.20 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | 1666 reflections with I > 2σ(I) |
Absorption correction: ψ scan DATCOR (Reibenspies, 1989) | Rint = 0.022 |
Tmin = 0.876, Tmax = 0.980 | 3 standard reflections every 60 min |
6109 measured reflections | intensity decay: 5% |
2969 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 139 restraints |
wR(F2) = 0.145 | Riding |
S = 0.85 | Δρmax = 0.30 e Å−3 |
2969 reflections | Δρmin = −0.20 e Å−3 |
101 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.15925 (11) | 0.23346 (5) | 0.56171 (9) | 0.0428 (2) | |
H1 | 0.1393 | 0.2663 | 0.5167 | 0.056* | |
O2 | 0.56510 (9) | 0.16858 (5) | 0.61384 (8) | 0.0392 (2) | |
N3 | 0.39337 (12) | 0.17709 (6) | 0.77762 (9) | 0.0403 (3) | |
H3A | 0.4673 | 0.1941 | 0.8253 | 0.052* | |
H3B | 0.2972 | 0.1709 | 0.8067 | 0.052* | |
C1 | 0.29351 (12) | 0.12841 (6) | 0.58154 (9) | 0.0291 (2) | |
H1A | 0.2045 | 0.1163 | 0.6386 | 0.038* | |
C2 | 0.22993 (14) | 0.18064 (6) | 0.48698 (10) | 0.0344 (3) | |
H2 | 0.3223 | 0.1996 | 0.4406 | 0.045* | |
C3 | 0.10694 (18) | 0.15365 (9) | 0.39157 (13) | 0.0530 (4) | |
H3C | 0.0224 | 0.1294 | 0.4367 | 0.069* | |
H3D | 0.0568 | 0.1918 | 0.3487 | 0.069* | |
C4 | 0.1808 (2) | 0.10624 (11) | 0.29291 (13) | 0.0669 (5) | |
H4A | 0.2900 | 0.1217 | 0.2747 | 0.087* | |
H4B | 0.1184 | 0.1103 | 0.2156 | 0.087* | |
C5 | 0.1883 (2) | 0.03162 (10) | 0.32952 (16) | 0.0675 (5) | |
H5A | 0.0842 | 0.0111 | 0.3106 | 0.088* | |
H5B | 0.2687 | 0.0095 | 0.2767 | 0.088* | |
C6 | 0.22912 (18) | 0.01696 (7) | 0.46668 (15) | 0.0530 (4) | |
H6A | 0.2648 | −0.0299 | 0.4735 | 0.069* | |
H6B | 0.1311 | 0.0216 | 0.5166 | 0.069* | |
C7 | 0.35954 (13) | 0.06279 (6) | 0.52316 (12) | 0.0372 (3) | |
H7A | 0.4366 | 0.0745 | 0.4574 | 0.048* | |
H7B | 0.4175 | 0.0376 | 0.5877 | 0.048* | |
C8 | 0.42747 (11) | 0.16047 (5) | 0.65990 (10) | 0.0288 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0404 (5) | 0.0465 (5) | 0.0415 (5) | 0.0109 (4) | −0.0009 (4) | 0.0079 (4) |
O2 | 0.0218 (4) | 0.0575 (5) | 0.0382 (4) | −0.0076 (3) | 0.0014 (3) | 0.0049 (4) |
N3 | 0.0247 (4) | 0.0613 (7) | 0.0348 (5) | −0.0014 (4) | −0.0016 (4) | −0.0073 (4) |
C1 | 0.0188 (4) | 0.0389 (5) | 0.0296 (5) | −0.0018 (4) | 0.0012 (4) | 0.0025 (4) |
C2 | 0.0267 (5) | 0.0466 (6) | 0.0301 (5) | 0.0014 (4) | −0.0018 (4) | 0.0039 (4) |
C3 | 0.0391 (7) | 0.0733 (9) | 0.0466 (7) | 0.0032 (6) | −0.0160 (6) | −0.0013 (7) |
C4 | 0.0595 (10) | 0.1043 (14) | 0.0368 (7) | −0.0021 (9) | −0.0123 (7) | −0.0143 (8) |
C5 | 0.0489 (8) | 0.0894 (13) | 0.0642 (9) | −0.0099 (8) | −0.0037 (7) | −0.0351 (9) |
C6 | 0.0409 (7) | 0.0527 (8) | 0.0655 (9) | −0.0101 (6) | 0.0028 (7) | −0.0164 (7) |
C7 | 0.0282 (5) | 0.0402 (6) | 0.0433 (6) | −0.0012 (4) | 0.0028 (5) | −0.0033 (5) |
C8 | 0.0198 (4) | 0.0346 (5) | 0.0319 (5) | −0.0003 (4) | −0.0020 (4) | 0.0054 (4) |
Geometric parameters (Å, º) top
O1—C2 | 1.4302 (15) | C3—H3C | 0.9700 |
O1—H1 | 0.8200 | C3—H3D | 0.9700 |
O2—C8 | 1.2456 (12) | C4—C5 | 1.520 (3) |
N3—C8 | 1.3181 (15) | C4—H4A | 0.9700 |
N3—H3A | 0.8600 | C4—H4B | 0.9700 |
N3—H3B | 0.8600 | C5—C6 | 1.517 (2) |
C1—C2 | 1.5272 (15) | C5—H5A | 0.9700 |
C1—C8 | 1.5186 (14) | C5—H5B | 0.9700 |
C1—C7 | 1.5316 (16) | C6—C7 | 1.5256 (17) |
C1—H1A | 0.9800 | C6—H6A | 0.9700 |
C2—C3 | 1.5265 (18) | C6—H6B | 0.9700 |
C2—H2 | 0.9800 | C7—H7A | 0.9700 |
C3—C4 | 1.527 (2) | C7—H7B | 0.9700 |
| | | |
C2—O1—H1 | 109.5 | C3—C4—H4B | 108.4 |
C8—N3—H3A | 120.0 | C5—C4—H4B | 108.4 |
C8—N3—H3B | 120.0 | H4A—C4—H4B | 107.4 |
H3A—N3—H3B | 120.0 | C6—C5—C4 | 115.88 (13) |
C2—C1—C8 | 109.15 (9) | C6—C5—H5A | 108.3 |
C2—C1—C7 | 115.16 (9) | C4—C5—H5A | 108.3 |
C8—C1—C7 | 108.17 (9) | C6—C5—H5B | 108.3 |
C2—C1—H1A | 108.1 | C4—C5—H5B | 108.3 |
C8—C1—H1A | 108.1 | H5A—C5—H5B | 107.4 |
C7—C1—H1A | 108.1 | C5—C6—C7 | 114.75 (13) |
O1—C2—C1 | 105.47 (8) | C5—C6—H6A | 108.6 |
O1—C2—C3 | 110.34 (10) | C7—C6—H6A | 108.6 |
C1—C2—C3 | 115.30 (11) | C5—C6—H6B | 108.6 |
O1—C2—H2 | 108.5 | C7—C6—H6B | 108.6 |
C1—C2—H2 | 108.5 | H6A—C6—H6B | 107.6 |
C3—C2—H2 | 108.5 | C6—C7—C1 | 113.94 (10) |
C4—C3—C2 | 113.55 (12) | C6—C7—H7A | 108.8 |
C4—C3—H3C | 108.9 | C1—C7—H7A | 108.8 |
C2—C3—H3C | 108.9 | C6—C7—H7B | 108.8 |
C4—C3—H3D | 108.9 | C1—C7—H7B | 108.8 |
C2—C3—H3D | 108.9 | H7A—C7—H7B | 107.7 |
H3C—C3—H3D | 107.7 | O2—C8—N3 | 122.17 (10) |
C3—C4—C5 | 115.62 (14) | O2—C8—C1 | 120.18 (10) |
C3—C4—H4A | 108.4 | N3—C8—C1 | 117.63 (9) |
C5—C4—H4A | 108.4 | | |
| | | |
C8—C1—C2—O1 | −64.31 (11) | C4—C5—C6—C7 | −40.1 (2) |
C7—C1—C2—O1 | 173.84 (9) | C5—C6—C7—C1 | 88.39 (15) |
C8—C1—C2—C3 | 173.70 (10) | C2—C1—C7—C6 | −70.69 (13) |
C7—C1—C2—C3 | 51.85 (13) | C8—C1—C7—C6 | 166.93 (10) |
O1—C2—C3—C4 | 169.75 (12) | C2—C1—C8—O2 | −76.23 (12) |
C1—C2—C3—C4 | −70.91 (16) | C7—C1—C8—O2 | 49.76 (13) |
C2—C3—C4—C5 | 87.76 (18) | C2—C1—C8—N3 | 105.73 (11) |
C3—C4—C5—C6 | −38.2 (2) | C7—C1—C8—N3 | −128.28 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 1.98 | 2.7875 (12) | 168 |
N3—H3A···O1ii | 0.86 | 2.13 | 2.9883 (14) | 177 |
N3—H3B···O2iii | 0.86 | 2.09 | 2.9459 (13) | 173 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, y, −z+3/2; (iii) x−1/2, y, −z+3/2. |
Experimental details
Crystal data |
Chemical formula | C8H15NO2 |
Mr | 157.21 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 8.248 (1), 19.679 (3), 10.581 (1) |
V (Å3) | 1717.4 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.55 × 0.50 × 0.20 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | ψ scan DATCOR (Reibenspies, 1989) |
Tmin, Tmax | 0.876, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6109, 2969, 1666 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.745 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.145, 0.85 |
No. of reflections | 2969 |
No. of parameters | 101 |
No. of restraints | 139 |
H-atom treatment | Riding |
Δρmax, Δρmin (e Å−3) | 0.30, −0.20 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 1.98 | 2.7875 (12) | 167.8 |
N3—H3A···O1ii | 0.86 | 2.13 | 2.9883 (14) | 177.1 |
N3—H3B···O2iii | 0.86 | 2.09 | 2.9459 (13) | 172.6 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, y, −z+3/2; (iii) x−1/2, y, −z+3/2. |
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