(S)-trans-Cyclohexane-1,2-dicarboximide

The molecule of the title compound, C₈H₁₁NO₂, contains a strained bicyclic system with a significantly twisted imide chromophore. The five-membered ring fragment containing the imide function is strongly puckered and adopts a half-chair conformation. The six-membered ring has a slightly distorted chair conformation. The mol­ecules are joined by strong N—H...O and weak C—H...O hydrogen bonds into infinite chains.

S1. Comment

The title compound, (I), can be considered as an example of a strongly twisted succinimide moiety and imide chromophore arising from trans-fusion of the six- and five-membered rings. Compound (I) was synthesized, together with some optically active succinic anhydrides and imides of known absolute configuration, in order to study the chiroptical properties of five-membered ring compounds with C₂ and C_2v local symmetry of the chromophores (Połoński, 1988).

It has been shown that twisting of the chromophores profoundly influences the circular dichroism spectra of cyclic anhydrides and imides (Połoński, 1988; Połoński et al., 1993). Since the molecular geometry parameters of (I) were known only from semiempirical MNDO Please define calculations (Połoński et al., 1993), we decided to determine the structure of the S,S enantiomer of (I) by single-crystal X-ray analysis, and the results are presented here. \sch

A view of the molecule of (I) with the atom-labelling scheme is shown in Fig. 1 and torsion angles are given in Table 1. A search of the Cambridge Structural Database (CSD, Version?; Allen & Kennard, 1993) revealed that monocyclic as well as bicyclic succinimide and dithiosuccinimide derivatives exhibit various degrees of puckering of the five-membered ring, with the puckering amplitude (Cremer & Pople, 1975) being as high as 0.269 Å in tetramethyldithiosuccinimide (CSD refcode NINTAF; Ratajczak-Sitarz et al., 1996) or 0.285 Å in 1,6-dimethyl-8-hydroxy-8-azabicyclo[4.3.0]nonane-7,9-dione (CSD refcode DENVAT; Hengjin et al., 1985), and only 0.021 Å in succinimide (Fronczek, 1995). The puckering of the succinimide fragment of (I) is very similar to that of NINTAF and DENVAT, with a puckering amplitude of 0.289 (2) Å and a phase angle of 268.6 (4)° (266.8 and 272.5° for NINTAF and DENVAT, respectively), indicating a half-chair conformation of the five-membered ring. The six-membered ring has a slightly distorted chair conformation, with the absolute values of the endocyclic torsion angles in the range 53.0 (2)–65.4 (2)°.

Molecules of (I) are connected in the crystal via a strong N2—H2···O1(y - 1, x, -z) hydrogen bond and two weak C—H···O interactions (Table 2) into infinite polar chains. There is a striking similarity between the one-dimensional aggregate structure of this chiral imide and the one-dimensional networks formed by the achiral molecules of 3,6-dithia-3,4,5,6-tetrahydrophthalimide (DTTHP; Kirfel et al., 1975) and 3,4,5,6-tetrahydrophthalimide (THP; Kirfel, 1975) (Fig. 2). The latter two compounds are less strained than (I) but their bicyclic skeletons are significantly flattened, due to the C8═C9 double bond. Similar to (I), their polar one-dimensional networks are stabilized by an N—H···O hydrogen bond and C—H···O interactions. However, one of the short C—H.·O contacts in DTTHP is substituted by an S···O contact of 3.480 Å. Substantial differences in the packing modes of these one-dimensional aggregates are observed at the higher level of the structure organization, leading to different space-group symmetries in each case [P4₁2₁2 for (I), Pmca for THP and P2₁/c for DTTHP].

S2. Experimental

Optically active (I) was prepared as described previously by Połoński (1988). Crystals of (I) can be grown from various polar and nonpolar organic solvents as square plates with well developed {001} faces, but due to serious crystal defects they are not suitable for X-ray diffraction studies. However, after many crystallization attempts we were able to choose, with the help of a polarizing microscope, one good quality single-crystal which had the form of a {100} plate and gave a satisfactory diffraction pattern.

S3. Refinement

The enantiomorphous space group P4₁2₁2 was assigned based on the known absolute configuration of (I). H atoms were located in the difference Fourier map. Their positional and isotropic displacement parameters were included in the refinement, with C—H distances in the range 0.90 (3)–1.07 (3) Å.

Computing details

Data collection: KM-4 Sofware (Kuma Diffraction, 1991); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation (Siemens, 1989); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the structure of (I) with 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A comparision of the one-dimensional hydrogen-bonded networks in the crystal structures of hydrogenated phthalimide derivatives with approximately flat condensed ring systems, (a) (I) [symmetry codes: (i) x - 1, y - 1, z; (ii) y - 1, x, -z], (b) THP [symmetry codes: (iii) x, y, 1 + z; (iv) x, -1 - y, 1/2 + z], (c) DTTHP [symmetry codes: (v) x, y, 1 + z; (vi) x, -1/2 - y, 1/2 + z].

(S)-trans-cyclohexane-1,2-dicarboximide

Crystal data

C8H11NO2	Melting point: 204 K
Mr = 153.18	Cu Kα radiation, λ = 1.54178 Å
Tetragonal, P41212	Cell parameters from 46 reflections
a = 5.903 (1) Å	θ = 8–51°
c = 45.164 (4) Å	µ = 0.77 mm^−1
V = 1573.8 (3) Å^3	T = 293 K
Z = 8	Plate, colourless
F(000) = 656	0.5 × 0.5 × 0.2 mm
Dx = 1.292 Mg m^−3

Data collection

Kuma KM-4 four-circle diffractometer	Rint = 0.051
Radiation source: fine-focus sealed tube	θmax = 80.1°, θmin = 3.9°
Graphite monochromator	h = 0→7
ω/2θ scans	k = 0→7
1956 measured reflections	l = 0→57
1660 independent reflections	3 standard reflections every 100 reflections
1563 reflections with I > 2σ(I)	intensity decay: 1.5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	All H-atom parameters refined
wR(F^2) = 0.125	w = 1/[σ^2(Fo^2) + (0.0825P)^2 + 0.2028P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1660 reflections	Δρmax = 0.14 e Å^−3
145 parameters	Δρmin = −0.13 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (8)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.2199 (3)	0.6706 (3)	0.00123 (3)	0.0671 (4)
O2	0.0520 (3)	0.1146 (3)	−0.06514 (4)	0.0776 (5)
C1	0.2221 (3)	0.5674 (3)	−0.02201 (3)	0.0476 (4)
N2	0.0966 (3)	0.3754 (3)	−0.02770 (3)	0.0521 (4)
H2	−0.008 (5)	0.330 (4)	−0.0156 (5)	0.073 (7)*
C3	0.1516 (3)	0.2732 (3)	−0.05451 (4)	0.0510 (4)
C4	0.4049 (4)	0.4204 (3)	−0.09847 (4)	0.0556 (5)
H42	0.272 (4)	0.506 (4)	−0.1077 (4)	0.057 (5)*
H41	0.411 (4)	0.273 (5)	−0.1086 (5)	0.064 (6)*
C5	0.6283 (4)	0.5508 (4)	−0.10154 (4)	0.0618 (5)
H52	0.753 (5)	0.455 (5)	−0.0931 (5)	0.070 (7)*
H51	0.669 (4)	0.577 (4)	−0.1228 (5)	0.062 (6)*
C6	0.6321 (4)	0.7729 (4)	−0.08399 (4)	0.0625 (5)
H62	0.503 (5)	0.881 (5)	−0.0927 (6)	0.077 (7)*
H61	0.774 (5)	0.828 (5)	−0.0857 (6)	0.078 (7)*
C7	0.5717 (3)	0.7420 (3)	−0.05110 (4)	0.0542 (5)
H72	0.683 (5)	0.652 (4)	−0.0401 (5)	0.070 (7)*
H71	0.563 (5)	0.896 (5)	−0.0411 (6)	0.080 (7)*
C8	0.3461 (3)	0.6220 (2)	−0.05025 (3)	0.0414 (3)
H8	0.244 (4)	0.716 (4)	−0.0608 (5)	0.058 (6)*
C9	0.3594 (3)	0.3929 (3)	−0.06570 (3)	0.0424 (4)
H9	0.484 (4)	0.303 (4)	−0.0577 (4)	0.047 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0768 (9)	0.0723 (9)	0.0521 (6)	−0.0219 (7)	0.0129 (6)	−0.0180 (6)
O2	0.0892 (12)	0.0611 (9)	0.0826 (9)	−0.0357 (8)	−0.0015 (8)	−0.0158 (7)
C1	0.0490 (9)	0.0487 (9)	0.0451 (7)	−0.0072 (7)	0.0002 (6)	−0.0043 (6)
N2	0.0513 (8)	0.0531 (8)	0.0519 (7)	−0.0150 (7)	0.0029 (6)	−0.0014 (6)
C3	0.0578 (10)	0.0417 (8)	0.0534 (8)	−0.0107 (7)	−0.0055 (7)	−0.0004 (6)
C4	0.0737 (12)	0.0488 (9)	0.0441 (8)	−0.0080 (8)	−0.0013 (8)	−0.0087 (7)
C5	0.0711 (13)	0.0627 (11)	0.0516 (9)	−0.0084 (10)	0.0133 (9)	−0.0065 (8)
C6	0.0706 (13)	0.0609 (11)	0.0561 (9)	−0.0262 (10)	0.0094 (9)	−0.0036 (8)
C7	0.0604 (11)	0.0515 (9)	0.0508 (8)	−0.0176 (8)	−0.0003 (7)	−0.0067 (7)
C8	0.0471 (8)	0.0356 (7)	0.0415 (7)	−0.0034 (6)	−0.0022 (6)	−0.0018 (5)
C9	0.0496 (8)	0.0338 (7)	0.0440 (7)	−0.0028 (6)	−0.0038 (6)	−0.0025 (5)

Geometric parameters (Å, º)

O1—C1	1.214 (2)	C5—H52	1.00 (3)
O2—C3	1.206 (2)	C5—H51	1.00 (2)
C1—N2	1.378 (2)	C6—C7	1.539 (2)
C1—C8	1.506 (2)	C6—H62	1.07 (3)
N2—C3	1.392 (2)	C6—H61	0.90 (3)
N2—H2	0.87 (3)	C7—C8	1.509 (2)
C3—C9	1.503 (2)	C7—H72	0.98 (3)
C4—C9	1.513 (2)	C7—H71	1.02 (3)
C4—C5	1.534 (3)	C8—C9	1.524 (2)
C4—H42	1.02 (2)	C8—H8	0.95 (2)
C4—H41	0.98 (3)	C9—H9	0.98 (2)
C5—C6	1.532 (3)
O1—C1—N2	124.7 (2)	C7—C6—H62	105.1 (14)
O1—C1—C8	129.0 (2)	C5—C6—H61	106.1 (17)
N2—C1—C8	106.23 (13)	C7—C6—H61	110.0 (16)
C1—N2—C3	113.17 (14)	H62—C6—H61	115 (2)
C1—N2—H2	121.4 (17)	C8—C7—C6	106.56 (14)
C3—N2—H2	125.4 (17)	C8—C7—H72	109.0 (15)
O2—C3—N2	124.7 (2)	C6—C7—H72	113.4 (14)
O2—C3—C9	129.0 (2)	C8—C7—H71	111.4 (16)
N2—C3—C9	106.22 (13)	C6—C7—H71	109.6 (15)
C9—C4—C5	107.16 (14)	H72—C7—H71	107 (2)
C9—C4—H42	108.3 (11)	C1—C8—C7	123.46 (13)
C5—C4—H42	112.1 (13)	C1—C8—C9	102.87 (12)
C9—C4—H41	111.4 (13)	C7—C8—C9	111.09 (14)
C5—C4—H41	111.8 (14)	C1—C8—H8	103.9 (14)
H42—C4—H41	106.1 (19)	C7—C8—H8	106.0 (14)
C6—C5—C4	113.3 (2)	C9—C8—H8	108.8 (14)
C6—C5—H52	106.0 (14)	C3—C9—C4	121.63 (14)
C4—C5—H52	108.3 (15)	C3—C9—C8	102.80 (13)
C6—C5—H51	111.2 (13)	C4—C9—C8	111.21 (13)
C4—C5—H51	111.6 (14)	C3—C9—H9	103.5 (12)
H52—C5—H51	106.0 (19)	C4—C9—H9	106.6 (11)
C5—C6—C7	113.2 (2)	C8—C9—H9	110.7 (12)
C5—C6—H62	108.1 (14)
O1—C1—N2—C3	−172.1 (2)	C6—C7—C8—C9	59.7 (2)
C8—C1—N2—C3	10.5 (2)	O2—C3—C9—C4	33.8 (3)
C1—N2—C3—O2	−173.8 (2)	N2—C3—C9—C4	−148.9 (2)
C1—N2—C3—C9	8.8 (2)	O2—C3—C9—C8	159.0 (2)
C9—C4—C5—C6	−53.0 (2)	N2—C3—C9—C8	−23.7 (2)
C4—C5—C6—C7	53.5 (3)	C5—C4—C9—C3	179.6 (2)
C5—C6—C7—C8	−54.3 (2)	C5—C4—C9—C8	58.4 (2)
O1—C1—C8—C7	31.6 (3)	C1—C8—C9—C3	29.0 (2)
N2—C1—C8—C7	−151.2 (2)	C7—C8—C9—C3	162.93 (13)
O1—C1—C8—C9	158.0 (2)	C1—C8—C9—C4	160.64 (15)
N2—C1—C8—C9	−24.8 (2)	C7—C8—C9—C4	−65.4 (2)
C6—C7—C8—C1	−177.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.87 (3)	2.11 (3)	2.933 (2)	159 (2)
C7—H71···O1^ii	1.02 (3)	2.70 (3)	3.658 (2)	157 (2)
C6—H61···O2^iii	0.90 (3)	2.54 (3)	3.308 (2)	144 (2)

Symmetry codes: (i) y−1, x, −z; (ii) y, x+1, −z; (iii) x+1, y+1, z.