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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 73| Part 9| September 2017| Pages 1357-1362
https://doi.org/10.1107/S2056989017011756

Crystal structures of two bi­cyclo­[5.1.0]octa­nes: potassium trans-bi­cyclo­[5.1.0]octane-4-carboxyl­ate monohydrate and cis-bi­cyclo­[5.1.0]octan-4-yl 4-bromo­benzene­sulfonate

CROSSMARK_Color_square_no_text.svg
Peter W. R. Corfielda* and Richard A. Kershawb

aDepartment of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA, and bDepartment of Chemistry, The Ohio State University, Columbus, Ohio 43210, USA
*Correspondence e-mail: pcorfield@fordham.edu

Edited by S. Parkin, University of Kentucky, USA (Received 8 July 2017; accepted 11 August 2017; online 21 August 2017)

The crystal structures of the trans-fused compound potassium trans-bi­cyclo­[5.1.0]octane-4-carboxyl­ate monohydrate, K+·C9H13O2−·H2O, (I), and of cis-bi­cyclo­[5.1.0]octan-4-yl 4-bromo­benzene­sulfonate, C14H17BrO3S, (II), have been determined. Compound (I) represents the smallest trans-fused cyclo­propane structure known to date, and features the expected shortening of the bridging C—C bond relative to the other cyclo­propane bond lengths, in contrast to the cis-fused system, (II), where all of the cyclo­propane bond lengths are the same. The bicyclic ring system of (I) is disordered across a crystallographic mirror plane. The geometries of the cis-fused and trans-fused ring systems are compared.

CCDC references: 1568784; 1568785

Similar articles

1. Chemical context

Extensive studies on the reactivities of the bridge bond in trans-fused bicyclic cyclo­propane derivatives (Gassman et al., 1968[Gassman, P. G., Williams, F. J. & Seter, J. (1968). J. Am. Chem. Soc. 90, 6893-6895.]) led to proposal of the `twist'-bent bond to describe the bonding in these [5.1.0] bicyclic systems (Gassman, 1967[Gassman, P. G. (1967). Chem. Commun. pp. 793-795.]). The [5.1.0]octa­nes are expected to be more highly strained than the corresponding trans-fused bi­cyclo­[4.2.0]octa­nes which had previously been prepared (Cava & Moroz, 1962[Cava, M. P. & Moroz, E. (1962). J. Am. Chem. Soc. 84, 115-116.]). Our studies were initiated in order to illuminate discussions of bonding by providing accurate geometric parameters for the most strained systems available. Several 4-substituted derivatives of trans-fused bicyclic [5.1.0]octa­nes were studied, but in most, disordering of the mol­ecules in the crystal precluded any refined structure that would give useful information. Even the trans-fused bicyclic [5.1.0]octane 4-carboxyl­ate structure presented here is disordered, but we were able to determine a reasonable geometry for the bicyclic system. The structure of a 4-substituted cis-fused bicyclic [5.1.0]octane was also determined, so that a comparison of the ring geometries could be made. These studies formed part of the MS and PhD theses of one of us (Kershaw, 1972[Kershaw, R. A. (1972). MS Thesis, The Ohio State University.], 1974[Kershaw, R. A. (1974). PhD Thesis, The Ohio State University.]), and were presented at the 1973 winter meeting of The American Crystallographic Association.

2. Structural commentary

Table 1[link] presents a comparison of the geometries of the trans-fused [5.1.0] (I)[link] and cis-fused [5.1.0] (II)[link] octane rings. Figs. 1[link] and 2[link] show the asymmetric units of the two mol­ecules, while Figs. 3[link] and 4[link] show the cis- and trans-fused rings superimposed upon one another. It can be seen that in the cis-fused system (II)[link], chemically equivalent bonds and angles are the same, and so are the torsional angles. Thus the cis-fused compound has an excellent, non-crystallographic mol­ecular mirror plane.

[Scheme 1]

Table 1
Selected bond lengths, angles, and conformational angles (Å, °), for (I)[link] and (II)

  (I) (trans) (II) (cis)   (I) (trans) (II) (cis)
C1—C2 1.513 (4) 1.485 (4) C7—C1—C2 112.9 (5) 119.5 (3)
C6—C7 1.514 (4) 1.502 (5) C6—C7—C1 112.8 (5) 119.6 (3)
           
C2—C3 1.543 (4) 1.534 (3) C1—C2—C3 107.1 (3) 112.9 (2)
C5—C6 1.543 (3) 1.542 (4) C5—C6—C7 107.1 (3) 113.3 (3)
           
C3—C4 1.538 (3) 1.510 (4) C2—C3—C4 117.8 (6) 113.1 (2)
C5—C4 1.538 (4) 1.500 (4) C6—C5—C4 117.2 (4) 112.2 (2)
      C3—C4—C5 118.0 (3) 118.5 (2)
           
      C2—C1—C8 130.5 (4) 121.6 (3)
      C6—C7—C8 130.4 (4) 120.9 (3)
C1—C8 1.500 (4) 1.499 (5) C7—C1—C8 60.82 (14) 59.7 (2)
C7—C8 1.500 (4) 1.489 (5) C1—C7—C8 60.80 (14) 60.3 (2)
C1—C7 1.463 (6) 1.493 (5) C1—C8—C7 58.4 (3) 60.0 (2)
           
      C1—C2—C3—C4 −28.1 (12) −81.7 (3)
      C7—C6—C5—C4 46.4 (12) 80.7 (4)
           
      C2—C3—C4—C5 82.2 (8) 64.4 (3)
      C6—C5—C4—C3 −66.4 (8) −63.4 (4)
           
      C3—C2—C1—C7 −53.6 (9) 66.1 (4)
      C5—C6—C7—C1 −75.1 (8) −67.2 (4)
           
      C2—C1—C7—C6 110.5 (5) 0.6 (5)
      C2—C1—C7—C8 −124.8 (3) 111.6 (4)
      C6—C7—C1—C8 −124.8 (3) −110.9 (4)
[Figure 1]
Figure 1
The asymmetric unit of compound (I)[link]. Displacement ellipsoids are at the 50% probability level. Sizes of the H atoms are arbitrary.
[Figure 2]
Figure 2
The asymmetric unit of compound (II)[link]. Displacement ellipsoids are at the 50% probability level. Sizes of the H atoms are arbitrary.
[Figure 3]
Figure 3
A superposition of the ring systems found for (I)[link] and (II)[link], viewed normal to the planes through C3, C4 and C5. The trans-fused structure is in black and the cis-fused structure in red.
[Figure 4]
Figure 4
A view of the superposition of (I)[link] and (II)[link] at 90° to that in Fig. 3[link].

In contrast, while the trans-fused derivative cannot have a mol­ecular mirror plane; the mol­ecule sits astride a crystallographic mirror plane, probably due to the packing requirements of the potassium cation and the carboxyl­ate part of the mol­ecule, and necessarily leading to a disordered structure. Treatment of the disorder is discussed in the Refinement section. One of the assumptions made in the refinements of (I)[link] was that chemically equivalent bonds and angles would be the same, so it was important to verify that this was the case in the cis-fused compound, (II)[link]. In both structures, the substituent on C4 is in the exo position. In (I)[link], the plane of the carboxyl­ate substituent on C4 is necessarily at 90° to the mol­ecular plane through C2, C3, C5 and C6, while in (II)[link] the roughly planar set C4, O1, S and C11 is tilted at 71.9 (2)° to the mol­ecular plane and at 49.6 (1)° to the plane through the phenyl group. In both structures, displacement ellipsoids for the cyclo­propane methyl­ene group indicate motion perpendicular to the cyclo­propane ring.

The two bicyclic systems are rather similar in the top view given in Fig. 3[link]. trans-Fusion changes the conformation angles around C2—C3 and C5—C6, as seen in Fig. 4[link] and in Table 1[link]. Fig. 3[link] shows that the trans-fusion is also accommodated by expansion of the angles at C3 and C5 from an average of 112.7 (2) to 117.5 (8)°, contraction of the angles at C2 and C6 from an average of 113.1 (3) to 107.1 (4)°, an increase in the external angles at C1 and C7 to 130.4 (8) from an average of 121.3 (3)°, and a lengthening of bonds C3—C4 and C5—C4 from 1.505 (4) to 1.538 (4) Å. The H1⋯H7 distance of 2.32 Å in (II)[link] is increased to 2.84 Å in the trans-fused (I)[link] structure. There is a significant shortening of the bridgehead bond C1—C7 in the trans-fused compound, from 1.493 (5) Å in (II)[link] to 1.463 (6) Å in (I)[link], which leads to a distortion of the cyclo­propane ring from equilateral triangular geometry, with reduction of the angle at C8 from 60.0 (2)° in (II)[link] to 58.4 (3)° in (I)[link]. Such shortening of the strained twist-bent bond, though counter-intuitive, was expected (Kershaw, 1974[Kershaw, R. A. (1974). PhD Thesis, The Ohio State University.], p2), because much of the electron density of the bond would lie outside the inter­nuclear line. We carried out geometry optimization of both trans- and cis-fused C8H14 systems using B3LYP density functional calculations (GAUSSIAN09; Frisch et al., 2013[Frisch, M. J., et al. (2013). GAUSSIAN09. Revision D.01. Gaussian Inc., Wallingford, CT, USA. https://www.gaussian.com.]), with results that also showed the trends noted above, including a calculated shortening of the bridgehead C1—C7 bond length by 0.014 Å.

3. Supra­molecular features

Fig. 5[link] gives a packing diagram for (I)[link]. There are alternating layers of hydro­phobic inter­actions between the cyclo­propane ends of the mol­ecules and of charge inter­actions between the carboxyl­ate ends of the mol­ecules and the potassium ions. In addition, the water mol­ecules in (I)[link] form strong hydrogen bonds (Table 2[link]) to carboxyl­ate oxygen atoms of two separate [5.1.0] octane mol­ecules, linking the anions into chains parallel to the b axis, as can be seen in Fig. 6[link]. The hydrogen-bond lengths are rather short, with O3—H⋯O1(x − [{1\over 2}], 1 − y, z) = 2.701 (3) Å and O3—H⋯O2(x − 1, y, z) = 2.757 (4) Å. The water O atoms may lie slightly off the mirror plane at y =1/4, as indicated by the displacement ellipsoid values, which would change the hydrogen-bond geometry a little. Strong hydrogen bonds are consistent with retention of the water of hydration even after recrystallization from a non-aqueous solvent, and also with the shifts in O—H stretching frequencies in the IR to 3060 and 3360 cm−1. The potassium ions lie in between two of the hydrogen-bonded chains, and have four carboxyl­ate and two water oxygen atoms as near neighbors, in a distorted flattened trigonal–prismatic array, with K—O distances ranging from 2.719 (3) to 2.879 (3) Å.

Table 2
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
OW—HWA⋯O1i 0.82 (1) 1.88 (1) 2.701 (3) 180 (4)
OW—HWB⋯O2ii 0.82 (1) 2.08 (3) 2.757 (4) 140 (3)
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, z]; (ii) x, y+1, z.
[Figure 5]
Figure 5
Projection of (I)[link] down the b axis. Disordered [5.1.0]octane moieties related by the mirror at z = 0.25 are not shown.
[Figure 6]
Figure 6
One of the two hydrogen-bonded chains parallel to the b axis in (I)[link].

The supra­molecular structure for (II)[link] features the presence of inter­molecular halogen bonds between Br and O2 (Fig. 7[link]), which link mol­ecules related by the screw axes at x = 0 into a helical arrangement. The Br ⋯ O2(2 − x, y − 1/2, −z − 1/2) distance is 3.230 (2) Å, which is 96% of the sum of the van der Waals radii, while the C14—Br ⋯ O2 and Br ⋯ O2—C9 angles are 170.06 (8) and 107.81 (9)°, respectively. These parameters are consistent with moderate halogen bonding according to a systematic study of such inter­molecular inter­actions in the CSD (Lommerse et al., 1996[Lommerse, J. P. M., Stone, A. J., Taylor, R. & Allen, F. H. (1996). J. Am. Chem. Soc. 118, 3108-3116.]). Also, a review of the role of halogen bonding in crystal engineering (Metrangolo et al., 2005[Metrangolo, P., Neukirch, H., Pilati, T. & Resnati, G. (2005). Acc. Chem. Res. 38, 386-395.]), stresses the importance in halogen bonding of the aromatically bound bromine seen in the present compound. There are no other inter­molecular contacts of note and the shortest H⋯H contact is H3A ⋯ H8B(x, [{1\over 2}] − y, z − [{1\over 2}]), at 2.47 Å.

[Figure 7]
Figure 7
Packing diagram for (II)[link], showing halogen bonds in red.

4. Database survey

Of 399 hits in the Cambridge Structure Database (CSD, Version 5.35; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) for the [5.1.0] ring system, 105 have 3D coordinates available, unsubstituted H atoms at the bridgehead positions, and conventional R factors of 0.05 or less, leading to 244 [5.1.0] geometries. All of the systems are cis-fused; no trans-fused [5.1.0] system was found. The average geometry of the CSD bicyclic ring systems displays the same near-perfect mirror symmetry found in the present cis-fused structure. The geometrical parameters of the cis-fused system described here do not differ significantly from the database geometries. In particular, the average bridgehead C—C bond length in the CSD set does not differ significantly from the other cyclo­propane bond lengths, just as in the present cis-fused structure, (II)[link], and in contrast to the trans-fused structure, (I)[link], where the bridgehead C—C bond length is shortened. Both the current cis-structure and the ensemble of [5.1.0] structures show the significant lengthening of bonds C2—C3 and C5—C6 relative to other bonds in the ring system noted in Table 1[link].

Searches for simple bicyclic [6.1.0] systems yielded only 14 hits. Two of these were trans-fused structures, (Szabo et al., 1973[Szabo, W. A., Betkouski, M. F., Deyrup, J. A., Mathew, M. & Palenik, G. J. (1973). J. Chem. Soc. Perkin Trans. 2, pp. 339-341.]; Hayes et al., 2005[Hayes, C. J., Herbert, N. N. A., Harrington-Frost, N. M. & Pattenden, G. (2005). Org. Biomol. Chem. 3, 316-327.]), with H1⋯H7 distances of 2.80 and 2.95 Å, respectively. In both structures, the bridgehead C—C bond length was longer by 0.03 Å than the other two cyclo­propane C—C bond lengths, in contrast to the shorter bridgehead C—C bond observed in (I)[link].

5. Synthesis and crystallization

Syntheses of these ring systems are described in Gassman et al. (1971[Gassman, P. G., Seter, J. & Williams, F. J. (1971). J. Am. Chem. Soc. 93, 1673-1681.]). Samples of trans-fused bi­cyclo [5.1.0] octane 4-carb­oxy­lic acid and crystals of the cis-bi­cyclo­[5.1.0]octan-4-yl 4-bromo­benzene­sulfonate were supplied by Dr Paul G. Gassman. The trans-fused acid was titrated with potassium hydroxide, and crystals of the potassium salt were obtained by evaporation to dryness and recrystallization from a benzene–methanol mixture. Analysis: C 50.89%, H 7.15%, in good agreement with calculated values of C 51.40% and H 7.19% for K[C9O2H13]·H2O.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. For the trans-fused structure (I)[link], only one octant of data was collected. Also in (I)[link], reflections with I<2σ were not saved when the data were processed. These weak reflections were later patched back into the structure factor file, with intensities set at σ(I), where σ(I) was the average value for reflections at a similar θ value for weak reflections in the data set with 2σ<I<3σ. It became apparent, however, that most of the missing reflections were higher order. We chose to use a cut-off value of 0.82 for the resolution of reflections used in final refinements, as about 50% of the intensities at this resolution were above 3σ, while only 11% of the reflections at resolutions above this value had I>2σ.

Table 3
Experimental details

  (I) (II)
Crystal data
Chemical formula K+·C9H13O2−·H2O C14H17BrO3S
Mr 210.31 345.24
Crystal system, space group Orthorhombic, Pbcm Monoclinic, P21/c
Temperature (K) 297 297
a, b, c (Å) 16.148 (13), 8.631 (9), 7.674 (10) 12.829 (1), 9.759 (1), 11.730 (2)
α, β, γ (°) 90, 90, 90 90, 95.74 (1), 90
V (Å3) 1070 (2) 1461.2 (3)
Z 4 4
Radiation type Mo Kα Cu Kα
μ (mm−1) 0.47 5.19
Crystal size (mm) 0.5 × 0.4 × 0.1 0.29 × 0.24 × 0.18
 
Data collection
Diffractometer Picker four-circle Picker four-circle
Absorption correction Gaussian (Busing & Levy, 1957[Busing, W. R. & Levy, H. A. (1957). Acta Cryst. 10, 180-182.]) Gaussian (Busing & Levy, 1957[Busing, W. R. & Levy, H. A. (1957). Acta Cryst. 10, 180-182.])
Tmin, Tmax 0.842, 0.954 0.267, 0.456
No. of measured, independent and observed [I > 2σ(I)] reflections 1926, 1104, 795 2447, 2381, 2154
Rint 0.02 0.02
(sin θ/λ)max (Å−1) 0.735 0.580
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.096, 1.00 0.027, 0.091, 1.08
No. of reflections 1104 2381
No. of parameters 98 173
No. of restraints 16 0
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.15, −0.17 0.34, −0.31
Data reduction followed procedures in Corfield et al. (1973[Corfield, P. W. R., Dabrowiak, J. C. & Gore, E. S. (1973). Inorg. Chem. 12, 1734-1740.]), with p = 0.05 for (I) and 0.06 for (II). Computer programs: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]) and local superposition program (Corfield, 1972[Corfield, P. W. R. (1972). Local versions of standard programs, written at Ohio State University.]).

After extensive efforts, it was concluded that the near-perfect mirror symmetry in (I)[link] apart from C1 and C7 hampered successful refinement in the non-centrosymmetric space group Pca21. Accordingly, all further refinements were carried out assuming a disordered structure in space group Pbcm. Initially, only atoms C1 and C7 were disordered, but it became apparent that bonded atoms C2 and C6 should be refined individually, and that C8 should also be allowed to move off the mirror plane at z = 0.25. Later, atoms C3 and C5 were also refined individually. It was necessary to impose tight restraints on the geometry to overcome the high correlation between parameters for C2 and C3 and the reflected images of C5 and C6. This was done by tightly restricting differences between chemically equivalent bond lengths and angles on either side of the octane ring.

No special measures were necessary in the refinement of (II)[link].

In both compounds, C-bound H atoms were constrained to idealized positions, with C—H distances of 0.97 Å for CH2 groups, 0.98 Å for methine CH groups and 0.93 Å for aromatic H atoms, and with Ueq values set at 1.3 times the Uiso of their bonded atoms for the CH2 H atoms, and 1.2 times for methine and aromatic H atoms. In (I)[link], H1 and H7 were initially refined independently, in case their positions could throw light on the twist-bent bond, but as they refined into positions indistinguishable from the constrained positions, they were constrained in the final refinements. The water H atoms in (I)[link] were found in a difference-Fourier map, and their positional coordinates were refined whilst their Ueq values set at 1.3 times the Uiso of the O atom. As a check, the Ueq values for these H atoms were allowed to vary, but as there was no appreciable change in these U values, they were constrained in the final refinement.

Supporting information

CCDC references: 1568784; 1568785

Crystal structure: contains datablocks I, II. DOI: https://doi.org/10.1107/S2056989017011756/pk2603sup1.cif

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989017011756/pk2603IIsup3.hkl

checkCIF report


Computing details top

For both structures, data collection: Corfield (1972); cell refinement: Corfield (1972). Data reduction: Data reduction followed procedures in Corfield et al. (1973), with p = 0.05 for (I); Data reduction followed procedures in Corfield et al. (1973), with P = 0.06 for (II). For both structures, program(s) used to solve structure: local superposition program (Corfield, 1972); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Potassium trans-bicyclo[5.1.0]octane-4-carboxylate monohydrate (I) top
Crystal data top
K+·C9H13O2−·H2OF(000) = 448
Mr = 210.31Dx = 1.306 Mg m−3
Dm = 1.345 (11) Mg m−3
Dm measured by Flotation in benzene–carbon tetrachloride mixtures
Orthorhombic, PbcmMo Kα radiation, λ = 0.7107 Å
a = 16.148 (13) ÅCell parameters from 19 reflections
b = 8.631 (9) ŵ = 0.47 mm−1
c = 7.674 (10) ÅT = 297 K
V = 1070 (2) Å3Plate, colorless
Z = 40.5 × 0.4 × 0.1 mm
Data collection top
Picker four-circle
diffractometer		795 reflections with I > 2σ(I)
Radiation source: sealed X-ray tubeRint = 0.02
Oriented graphite 200 reflection monochromatorθmax = 31.5°, θmin = 1.3°
θ/2θ scansh = 0→23
Absorption correction: gaussian
Busing & Levy (1957)		k = 0→12
Tmin = 0.842, Tmax = 0.954l = 0→11
1926 measured reflections9 standard reflections every 220 reflections
1104 independent reflections intensity decay: −3.0(8)
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: real-space vector search
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: mixed
wR(F2) = 0.096H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + 0.250P]
where P = (Fo2 + 2Fc2)/3
1104 reflections(Δ/σ)max = 0.002
98 parametersΔρmax = 0.15 e Å−3
16 restraintsΔρmin = −0.17 e Å−3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
K10.46108 (4)0.25000.50000.0513 (2)
OW0.42215 (13)0.4712 (2)0.75000.0625 (6)
HWA0.4717 (8)0.493 (4)0.75000.081*
HWB0.3937 (19)0.550 (3)0.75000.081*
O10.41518 (12)0.0440 (2)0.75000.0581 (6)
O20.40765 (12)−0.2105 (2)0.75000.0603 (6)
C10.1115 (2)−0.0466 (5)0.8279 (6)0.0760 (17)0.5
H10.1194−0.15510.79410.091*0.5
C20.1648 (4)0.0018 (15)0.9808 (6)0.0853 (9)0.5
H2A0.1645−0.07811.06970.111*0.5
H2B0.14390.09701.03150.111*0.5
C30.2534 (3)0.0263 (16)0.9108 (9)0.0640 (19)0.5
H3A0.25970.13530.88300.083*0.5
H3B0.29180.00321.00440.083*0.5
C40.28013 (16)−0.0677 (3)0.75000.0449 (7)
H40.2575−0.17250.76260.054*0.5
C50.2547 (3)−0.0071 (16)0.5693 (8)0.0640 (19)0.5
H5A0.2829−0.06910.48210.083*0.5
H5B0.27490.09820.55790.083*0.5
C60.1614 (4)−0.0070 (14)0.5256 (6)0.0853 (9)0.5
H6A0.15090.05490.42240.111*0.5
H6B0.1423−0.11180.50380.111*0.5
C70.1167 (2)0.0611 (5)0.6811 (6)0.0819 (19)0.5
H70.13690.16410.71400.098*0.5
C80.0335 (2)0.0232 (6)0.7568 (9)0.115 (2)0.5
H8A0.00600.10210.82580.149*0.5
H8B−0.0031−0.04300.68970.149*0.5
C90.37448 (16)−0.0812 (3)0.75000.0418 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K10.0584 (4)0.0468 (3)0.0486 (4)0.0000.0000.0004 (3)
OW0.0479 (13)0.0488 (12)0.0906 (17)0.0055 (10)0.0000.000
O10.0438 (11)0.0462 (11)0.0842 (16)−0.0067 (9)0.0000.000
O20.0428 (10)0.0413 (11)0.0967 (18)0.0057 (8)0.0000.000
C40.0361 (13)0.0468 (15)0.0517 (17)0.0021 (12)0.0000.000
C90.0377 (13)0.0462 (15)0.0416 (15)−0.0013 (13)0.0000.000
C10.037 (2)0.109 (4)0.081 (4)0.003 (3)0.003 (2)0.010 (4)
C20.0528 (13)0.139 (3)0.0644 (17)0.0065 (17)0.0150 (13)−0.0114 (17)
C30.0470 (11)0.096 (5)0.0494 (17)0.0065 (15)−0.0001 (11)−0.003 (3)
C50.0470 (11)0.096 (5)0.0494 (17)0.0065 (15)0.0001 (11)0.003 (3)
C60.0528 (13)0.139 (3)0.0644 (17)0.0065 (17)−0.0150 (13)0.0114 (17)
C70.043 (2)0.111 (4)0.092 (5)0.018 (3)−0.006 (2)0.026 (4)
C80.046 (2)0.169 (5)0.128 (5)0.020 (3)0.042 (6)0.002 (14)
Geometric parameters (Å, º) top
K1—O12.719 (3)C2—H2A0.9700
K1—O1i2.719 (3)C2—H2B0.9700
K1—OW2.779 (3)C3—C41.538 (3)
K1—OWi2.779 (3)C3—H3A0.9700
K1—O2ii2.879 (3)C3—H3B0.9700
K1—O2iii2.879 (3)C4—C91.528 (4)
K1—K1iv3.837 (5)C4—C51.538 (4)
K1—HWA2.85 (2)C4—H40.9800
OW—K1v2.779 (3)C5—C61.543 (3)
OW—HWA0.822 (10)C5—H5A0.9700
OW—HWB0.818 (10)C5—H5B0.9700
O1—C91.264 (3)C6—C71.513 (4)
O2—C91.238 (3)C6—H6A0.9700
C1—C71.463 (6)C6—H6B0.9700
C1—C81.500 (4)C7—C81.500 (4)
C1—C21.513 (4)C7—H70.9800
C1—H10.9800C8—H8A0.9700
C2—C31.543 (3)C8—H8B0.9700
O1—K1—O1i148.36 (9)C4—C3—H3A107.8
O1—K1—OW84.29 (10)C2—C3—H3A107.8
O1i—K1—OW88.63 (10)C4—C3—H3B107.8
O1—K1—OWi88.63 (10)C2—C3—H3B107.8
O1i—K1—OWi84.29 (10)H3A—C3—H3B107.2
OW—K1—OWi153.85 (9)C9—C4—C5107.00 (18)
O1—K1—O2ii78.92 (8)C9—C4—C3108.6 (2)
O1i—K1—O2ii126.41 (7)C5—C4—C3118.0 (3)
OW—K1—O2ii67.99 (7)C9—C4—H4107.6
OWi—K1—O2ii135.07 (7)C5—C4—H4107.6
O1—K1—O2iii126.41 (7)C3—C4—H4107.6
O1i—K1—O2iii78.92 (8)C4—C5—C6117.2 (4)
OW—K1—O2iii135.07 (7)C4—C5—H5A108.0
OWi—K1—O2iii67.99 (7)C6—C5—H5A108.0
O2ii—K1—O2iii85.18 (10)C4—C5—H5B108.0
K1—OW—K1v87.32 (11)C6—C5—H5B108.0
K1—OW—HWA86.3 (18)H5A—C5—H5B107.2
K1v—OW—HWA86.3 (18)C7—C6—C5107.1 (3)
K1—OW—HWB134.1 (7)C7—C6—H6A110.3
K1v—OW—HWB134.1 (7)C5—C6—H6A110.3
HWA—OW—HWB111 (4)C7—C6—H6B110.3
C9—O1—K1134.46 (6)C5—C6—H6B110.3
K1—O1—K1v89.76 (11)H6A—C6—H6B108.5
C9—O2—K1vi115.16 (11)C1—C7—C860.80 (14)
K1vi—O2—K1iii83.57 (10)C1—C7—C6112.8 (5)
C7—C1—C860.82 (14)C8—C7—C6130.4 (4)
C7—C1—C2112.9 (10)C1—C7—H7113.4
C8—C1—C2130.4 (4)C8—C7—H7113.4
C7—C1—H1113.3C6—C7—H7113.4
C8—C1—H1113.3C1—C8—C758.4 (3)
C2—C1—H1113.3C1—C8—H8A117.9
C1—C2—C3107.1 (3)C7—C8—H8A117.9
C1—C2—H2A110.3C1—C8—H8B117.9
C3—C2—H2A110.3C7—C8—H8B117.9
C1—C2—H2B110.3H8A—C8—H8B115.1
C3—C2—H2B110.3O2—C9—O1123.1 (2)
H2A—C2—H2B108.5O2—C9—C4120.0 (2)
C4—C3—C2117.8 (6)O1—C9—C4117.0 (2)
C1—C2—C3—C4−28.1 (12)C3—C2—C1—C7−53.6 (9)
C7—C6—C5—C446.4 (12)C2—C1—C7—C6110.5 (5)
C2—C3—C4—C582.2 (8)C2—C1—C7—C8−124.8 (3)
C6—C5—C4—C3−66.4 (8)C6—C7—C1—C8−124.8 (3)
C5—C6—C7—C1−75.1 (8)
Symmetry codes: (i) x, −y+1/2, −z+1; (ii) −x+1, y+1/2, z; (iii) −x+1, −y, −z+1; (iv) x, y, −z+1/2; (v) x, y, −z+3/2; (vi) −x+1, −y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW—HWA···O1ii0.82 (1)1.88 (1)2.701 (3)180 (4)
OW—HWB···O2vii0.82 (1)2.08 (3)2.757 (4)140 (3)
Symmetry codes: (ii) −x+1, y+1/2, z; (vii) x, y+1, z.
cis-Bicyclo[5.1.0]octan-4-yl 4-bromobenzenesulfonate (II) top
Crystal data top
C14H17BrO3SF(000) = 704
Mr = 345.24Dx = 1.569 Mg m−3
Dm = 1.566 Mg m−3
Dm measured by density gradient column made from potassium tartrate and iodide solutions
Monoclinic, P21/cCu Kα radiation, λ = 1.5418 Å
a = 12.829 (1) ÅCell parameters from 16 reflections
b = 9.759 (1) Åθ = 30.0°
c = 11.730 (2) ŵ = 5.19 mm−1
β = 95.74 (1)°T = 297 K
V = 1461.2 (3) Å3Block, colourless
Z = 40.29 × 0.24 × 0.18 mm
Data collection top
Picker four-circle
diffractometer		2154 reflections with I > 2σ(I)
Radiation source: sealed X-ray tubeRint = 0.02
Oriented graphite 200 reflection monochromatorθmax = 63.4°, θmin = 3.5°
θ/2θ scansh = 0→14
Absorption correction: gaussian
Busing & Levy (1957)		k = 0→11
Tmin = 0.267, Tmax = 0.456l = −13→13
2447 measured reflections3 standard reflections every 100 reflections
2381 independent reflections intensity decay: 2.4(8)
Refinement top
Refinement on F2Secondary atom site location: real-space vector search
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.091 w = 1/[σ2(Fo2) + 0.430P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.003
2381 reflectionsΔρmax = 0.34 e Å−3
173 parametersΔρmin = −0.31 e Å−3
0 restraintsExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: heavy-atom methodExtinction coefficient: 0.0062 (4)
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br1.00989 (3)0.32885 (3)−0.39343 (3)0.06640 (18)
S0.74088 (5)0.62673 (6)−0.03759 (5)0.04479 (19)
O10.69615 (16)0.50385 (19)0.02540 (14)0.0595 (5)
O20.81339 (16)0.70034 (19)0.03968 (16)0.0591 (5)
O30.65795 (18)0.7021 (2)−0.09750 (19)0.0727 (6)
C10.5504 (3)0.3765 (3)0.3453 (3)0.0671 (8)
H10.50060.30170.32690.081*
C20.5300 (2)0.5028 (3)0.2761 (2)0.0524 (6)
H2A0.56710.57880.31490.068*
H2B0.45570.52340.27080.068*
C30.5639 (2)0.4901 (3)0.1548 (2)0.0503 (6)
H3A0.54640.39910.12560.065*
H3B0.52480.55570.10520.065*
C40.6796 (2)0.5145 (3)0.15002 (19)0.0463 (6)
H40.69670.60780.17670.056*
C50.7557 (2)0.4164 (4)0.2114 (2)0.0646 (8)
H5A0.82620.44060.19580.084*
H5B0.74120.32460.18220.084*
C60.7495 (3)0.4170 (4)0.3420 (3)0.0730 (9)
H6A0.81490.38230.37970.095*
H6B0.74130.51070.36710.095*
C70.6607 (3)0.3324 (3)0.3782 (3)0.0782 (10)
H70.67220.23310.37770.094*
C80.5957 (4)0.3823 (4)0.4680 (3)0.0919 (12)
H8A0.61190.47180.50120.120*
H8B0.57150.31540.52050.120*
C110.80882 (18)0.5379 (2)−0.13726 (19)0.0399 (5)
C120.7890 (2)0.5658 (3)−0.2526 (2)0.0506 (6)
H120.73560.6259−0.27870.061*
C130.8491 (2)0.5039 (3)−0.3287 (2)0.0544 (7)
H130.83720.5233−0.40660.065*
C140.92621 (19)0.4138 (3)−0.2898 (2)0.0452 (5)
C150.9459 (2)0.3837 (3)−0.1741 (2)0.0540 (6)
H150.99850.3223−0.14850.065*
C160.8865 (2)0.4463 (3)−0.0981 (2)0.0504 (6)
H160.89840.4270−0.02020.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.0708 (3)0.0710 (3)0.0602 (2)0.00970 (14)0.02049 (16)−0.01377 (14)
S0.0477 (3)0.0424 (3)0.0456 (3)−0.0021 (2)0.0114 (3)−0.0016 (2)
O10.0852 (14)0.0547 (11)0.0426 (9)−0.0235 (10)0.0260 (9)−0.0096 (8)
O20.0678 (12)0.0560 (11)0.0553 (11)−0.0186 (9)0.0149 (9)−0.0152 (9)
O30.0680 (13)0.0787 (14)0.0725 (13)0.0296 (11)0.0124 (11)0.0048 (11)
C10.087 (2)0.0559 (16)0.0618 (17)−0.0115 (16)0.0251 (16)0.0041 (14)
C20.0514 (14)0.0613 (16)0.0462 (13)−0.0001 (12)0.0133 (11)−0.0045 (11)
C30.0543 (15)0.0546 (15)0.0423 (12)−0.0010 (11)0.0065 (11)−0.0022 (11)
C40.0563 (14)0.0484 (13)0.0359 (11)−0.0064 (11)0.0133 (10)−0.0054 (10)
C50.0561 (16)0.079 (2)0.0596 (16)0.0130 (15)0.0111 (13)−0.0017 (15)
C60.0702 (19)0.090 (2)0.0566 (17)0.0255 (18)−0.0044 (14)0.0041 (16)
C70.110 (3)0.064 (2)0.0631 (19)0.0213 (18)0.0215 (19)0.0184 (14)
C80.133 (3)0.091 (3)0.0566 (18)0.016 (2)0.032 (2)0.0242 (18)
C110.0412 (12)0.0409 (12)0.0380 (11)−0.0032 (9)0.0055 (9)0.0019 (9)
C120.0560 (14)0.0528 (14)0.0424 (12)0.0110 (12)0.0018 (11)0.0061 (11)
C130.0668 (17)0.0610 (16)0.0354 (12)0.0088 (13)0.0048 (12)0.0040 (11)
C140.0456 (13)0.0468 (13)0.0440 (12)−0.0005 (10)0.0074 (10)−0.0032 (10)
C150.0520 (14)0.0601 (16)0.0493 (14)0.0162 (12)0.0022 (11)0.0036 (12)
C160.0553 (15)0.0605 (15)0.0352 (11)0.0100 (12)0.0040 (10)0.0078 (11)
Geometric parameters (Å, º) top
Br—C141.892 (2)C5—C61.542 (4)
Br—O2i3.2301 (19)C5—H5A0.9700
S—O31.421 (2)C5—H5B0.9700
S—O21.426 (2)C6—C71.502 (5)
S—O11.5486 (18)C6—H6A0.9700
S—C111.755 (2)C6—H6B0.9700
O1—C41.502 (3)C7—C81.489 (5)
O2—Brii3.2301 (19)C7—H70.9800
C1—C21.485 (4)C8—H8A0.9700
C1—C81.499 (5)C8—H8B0.9700
C1—C71.493 (5)C11—C121.379 (3)
C1—H10.9800C11—C161.382 (3)
C2—C31.534 (3)C12—C131.376 (4)
C2—H2A0.9700C12—H120.9300
C2—H2B0.9700C13—C141.368 (4)
C3—C41.510 (4)C13—H130.9300
C3—H3A0.9700C14—C151.387 (4)
C3—H3B0.9700C15—C161.374 (4)
C4—C51.500 (4)C15—H150.9300
C4—H40.9800C16—H160.9300
C14—Br—O2i170.06 (8)H5A—C5—H5B107.9
O3—S—O2117.52 (14)C7—C6—C5113.3 (3)
O3—S—O1110.01 (14)C7—C6—H6A108.9
O2—S—O1109.64 (11)C5—C6—H6A108.9
O3—S—C11108.87 (12)C7—C6—H6B108.9
O2—S—C11109.64 (11)C5—C6—H6B108.9
O1—S—C1199.66 (10)H6A—C6—H6B107.7
C4—O1—S120.40 (15)C8—C7—C160.3 (2)
S—O2—Brii107.81 (9)C8—C7—C6120.9 (3)
C2—C1—C8121.6 (3)C1—C7—C6119.6 (3)
C2—C1—C7119.5 (3)C8—C7—H7115.0
C8—C1—C759.7 (2)C1—C7—H7115.0
C2—C1—H1115.0C6—C7—H7115.0
C8—C1—H1115.0C7—C8—C160.0 (2)
C7—C1—H1115.0C7—C8—H8A117.8
C1—C2—C3112.9 (2)C1—C8—H8A117.8
C1—C2—H2A109.0C7—C8—H8B117.8
C3—C2—H2A109.0C1—C8—H8B117.8
C1—C2—H2B109.0H8A—C8—H8B114.9
C3—C2—H2B109.0C12—C11—C16120.7 (2)
H2A—C2—H2B107.8C12—C11—S120.07 (19)
C4—C3—C2113.1 (2)C16—C11—S119.14 (17)
C4—C3—H3A109.0C13—C12—C11119.3 (2)
C2—C3—H3A109.0C13—C12—H12120.3
C4—C3—H3B109.0C11—C12—H12120.3
C2—C3—H3B109.0C12—C13—C14119.9 (2)
H3A—C3—H3B107.8C12—C13—H13120.0
O1—C4—C5105.9 (2)C14—C13—H13120.0
O1—C4—C3105.10 (19)C15—C14—C13121.2 (2)
C5—C4—C3118.5 (2)C15—C14—Br118.45 (19)
O1—C4—H4109.0C13—C14—Br120.35 (18)
C5—C4—H4109.0C14—C15—C16118.9 (2)
C3—C4—H4109.0C14—C15—H15120.6
C4—C5—C6112.2 (2)C16—C15—H15120.6
C4—C5—H5A109.2C11—C16—C15120.0 (2)
C6—C5—H5A109.2C11—C16—H16120.0
C4—C5—H5B109.2C15—C16—H16120.0
C6—C5—H5B109.2
C1—C2—C3—C4−81.7 (3)C5—C6—C7—C1−67.2 (4)
C7—C6—C5—C480.7 (4)C2—C1—C7—C60.6 (5)
C2—C3—C4—C564.4 (3)C2—C1—C7—C8111.6 (3)
C6—C5—C4—C3−63.4 (4)C6—C7—C1—C8−110.9 (4)
C3—C2—C1—C766.1 (4)
Symmetry codes: (i) −x+2, y−1/2, −z−1/2; (ii) −x+2, y+1/2, −z−1/2.
Selected bond lengths, angles, and conformational angles (Å, °), for (I) and (II) top
(I) (trans)(II) (cis)(I) (trans)(II) (cis)
C1—C21.513 (4)1.485 (4)C7—C1—C2112.9 (5)119.5 (3)
C6—C71.514 (4)1.502 (5)C6—C7—C1112.8 (5)119.6 (3)
C2—C31.543 (4)1.534 (3)C1—C2—C3107.1 (3)112.9 (2)
C5—C61.543 (3)1.542 (4)C5—C6—C7107.1 (3)113.3 (3)
C3—C41.538 (3)1.510 (4)C2—C3—C4117.8 (6)113.1 (2)
C5—C41.538 (4)1.500 (4)C6—C5—C4117.2 (4)112.2 (2)
C3—C4—C5118.0 (3)118.5 (2)
C2—C1—C8130.5 (4)121.6 (3)
C6—C7—C8130.4 (4)120.9 (3)
C1—C81.500 (4)1.499 (5)C7—C1—C860.82 (14)59.7 (2)
C7—C81.500 (4)1.489 (5)C1—C7—C860.80 (14)60.3 (2)
C1—C71.463 (6)1.493 (5)C1—C8—C758.4 (3)60.0 (2)
C1—C2—C3—C4-28.1 (12)-81.7 (3)
C7—C6—C5—C446.4 (12)80.7 (4)
C2—C3—C4—C582.2 (8)64.4 (3)
C6—C5—C4—C3-66.4 (8)-63.4 (4)
C3—C2—C1—C7-53.6 (9)66.1 (4)
C5—C6—C7—C1-75.1 (8)-67.2 (4)
C2—C1—C7—C6110.5 (5)0.6 (5)
C2—C1—C7—C8-124.8 (3)111.6 (4)
C6—C7—C1—C8-124.8 (3)-110.9 (4)
 

Acknowledgements

We are grateful for the provision of samples by Paul G. Gassman, as well as support from the National Science Foundation through equipment grant GP8534 awarded to the Ohio State University, where the experimental work was carried out. We gratefully acknowledge mentoring during the final months of the PhD project by Dr Gary G. Christoph, and assistance from Dr Paul Smith of Fordham University in the B3LYP geometry optimizations.

References

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ISSN: 2056-9890
Volume 73| Part 9| September 2017| Pages 1357-1362
https://doi.org/10.1107/S2056989017011756
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