Different forms of antiparallel stacking of hydrogen-bonded antidromic rings in the solid state: polymorphism with virtually the same unit cell and two-dimensional isostructurality with alternating layers

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.

Computing details

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).

Figures

trans-2-hydroxy-cycloheptanecarboxamide

Crystal data

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) Å^3	Prism, colourless
Z = 8	0.55 × 0.50 × 0.20 mm
F(000) = 688

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	Riding
S = 0.85	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
2969 reflections	(Δ/σ)max < 0.001
101 parameters	Δρmax = 0.30 e Å^−3
139 restraints	Δρmin = −0.20 e Å^−3

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.98	2.7875 (12)	168
N3—H3A···O1^ii	0.86	2.13	2.9883 (14)	177
N3—H3B···O2^iii	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.