Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012743/jz1370sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012743/jz1370Isup2.hkl |
CCDC reference: 140976
Compound (I) was obtained as an unexpected product in 60% yield during the SeO2 oxidation of 4,4-diphenyl-2-cyclohexenone (Zimmerman & Schuster, 1962). Yellow crystals of (I) were obtained upon crystallization from ethyl acetate and hexane (m.p. 483 K).
All the H atoms have been generated at idealized geometries and refined isotropically using a riding model.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLUTON (Spek, 1992); software used to prepare material for publication: SHELXL97.
C36H26O2Se2 | Dx = 1.522 Mg m−3 |
Mr = 648.49 | Melting point: 483 K |
Orthorhombic, Pccn | Mo Kα radiation, λ = 0.71073 Å |
a = 17.4144 (16) Å | Cell parameters from 1650 reflections |
b = 10.6767 (10) Å | θ = 2.2–26.4° |
c = 15.2187 (14) Å | µ = 2.65 mm−1 |
V = 2829.6 (5) Å3 | T = 168 K |
Z = 4 | Plate, yellow |
F(000) = 1304 | 0.8 × 0.5 × 0.14 mm |
Siemens CCD area detector diffractometer | 2839 independent reflections |
Radiation source: fine-focus sealed tube | 2412 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 512 pixels mm-1 | θmax = 26.4°, θmin = 2.9° |
ϕ and ω scans | h = −21→10 |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | k = −13→13 |
Tmin = 0.218, Tmax = 0.690 | l = −18→18 |
29316 measured reflections |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.06 | Calculated w = 1/[σ2(Fo2) + (0.05P)2 + 1.9536P] where P = (Fo2 + 2Fc2)/3 |
2839 reflections | (Δ/σ)max = −0.002 |
181 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.73 e Å−3 |
C36H26O2Se2 | V = 2829.6 (5) Å3 |
Mr = 648.49 | Z = 4 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 17.4144 (16) Å | µ = 2.65 mm−1 |
b = 10.6767 (10) Å | T = 168 K |
c = 15.2187 (14) Å | 0.8 × 0.5 × 0.14 mm |
Siemens CCD area detector diffractometer | 2839 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 2412 reflections with I > 2σ(I) |
Tmin = 0.218, Tmax = 0.690 | Rint = 0.026 |
29316 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.55 e Å−3 |
2839 reflections | Δρmin = −0.73 e Å−3 |
181 parameters |
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 on F2 for ALL reflections. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor 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 | ||
Se1 | 0.690398 (14) | 0.29881 (2) | 0.005848 (14) | 0.03246 (11) | |
C2 | 0.64543 (12) | 0.20752 (18) | 0.10268 (13) | 0.0242 (4) | |
C17 | 0.51527 (14) | −0.1935 (2) | 0.06012 (15) | 0.0337 (5) | |
H17A | 0.4720 | −0.1866 | 0.0224 | 0.040* | |
C7 | 0.69311 (12) | −0.00199 (19) | 0.27886 (14) | 0.0244 (4) | |
C14 | 0.64115 (12) | −0.21193 (19) | 0.17006 (15) | 0.0281 (5) | |
H14A | 0.6846 | −0.2191 | 0.2075 | 0.034* | |
C3 | 0.66978 (12) | 0.09658 (19) | 0.13137 (13) | 0.0236 (4) | |
H3A | 0.7128 | 0.0602 | 0.1028 | 0.028* | |
O1 | 0.55606 (10) | 0.37295 (15) | 0.11616 (12) | 0.0404 (4) | |
C18 | 0.54083 (12) | −0.0895 (2) | 0.10593 (14) | 0.0276 (5) | |
H18A | 0.5148 | −0.0119 | 0.0993 | 0.033* | |
C6 | 0.54353 (13) | 0.2069 (2) | 0.21818 (16) | 0.0324 (5) | |
H6A | 0.5018 | 0.2462 | 0.2475 | 0.039* | |
C15 | 0.61504 (14) | −0.3167 (2) | 0.12408 (16) | 0.0344 (5) | |
H15A | 0.6406 | −0.3947 | 0.1308 | 0.041* | |
C16 | 0.55240 (14) | −0.3077 (2) | 0.06900 (15) | 0.0350 (5) | |
H16A | 0.5349 | −0.3790 | 0.0375 | 0.042* | |
C12 | 0.67207 (14) | −0.0728 (2) | 0.35236 (14) | 0.0304 (5) | |
H12A | 0.6210 | −0.1031 | 0.3577 | 0.036* | |
C1 | 0.57948 (13) | 0.27135 (19) | 0.14399 (14) | 0.0286 (5) | |
C10 | 0.79998 (16) | −0.0566 (3) | 0.41067 (17) | 0.0440 (6) | |
H10A | 0.8366 | −0.0771 | 0.4546 | 0.053* | |
C4 | 0.63378 (11) | 0.02471 (19) | 0.20601 (13) | 0.0224 (4) | |
C13 | 0.60417 (11) | −0.09720 (18) | 0.16161 (13) | 0.0217 (4) | |
C5 | 0.56725 (12) | 0.0948 (2) | 0.24623 (14) | 0.0277 (5) | |
H5A | 0.5408 | 0.0573 | 0.2941 | 0.033* | |
C11 | 0.72541 (15) | −0.0988 (2) | 0.41727 (15) | 0.0384 (6) | |
H11A | 0.7104 | −0.1466 | 0.4671 | 0.046* | |
C8 | 0.76782 (13) | 0.0434 (2) | 0.27405 (16) | 0.0345 (5) | |
H8A | 0.7827 | 0.0937 | 0.2255 | 0.041* | |
C9 | 0.82077 (14) | 0.0162 (3) | 0.33917 (18) | 0.0449 (6) | |
H9A | 0.8717 | 0.0476 | 0.3348 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Se1 | 0.03660 (18) | 0.03212 (17) | 0.02865 (15) | −0.01437 (9) | −0.00976 (9) | 0.00822 (8) |
C2 | 0.0255 (11) | 0.0233 (10) | 0.0238 (10) | −0.0074 (8) | −0.0048 (8) | −0.0006 (8) |
C17 | 0.0326 (12) | 0.0397 (13) | 0.0290 (11) | −0.0112 (10) | −0.0077 (9) | 0.0023 (9) |
C7 | 0.0275 (11) | 0.0219 (10) | 0.0239 (10) | 0.0005 (8) | −0.0010 (8) | −0.0041 (8) |
C14 | 0.0236 (11) | 0.0286 (11) | 0.0322 (11) | 0.0017 (8) | −0.0010 (9) | −0.0044 (8) |
C3 | 0.0211 (10) | 0.0257 (10) | 0.0239 (10) | −0.0044 (8) | 0.0000 (8) | −0.0011 (8) |
O1 | 0.0475 (10) | 0.0254 (8) | 0.0483 (10) | 0.0073 (7) | −0.0081 (8) | 0.0006 (7) |
C18 | 0.0247 (10) | 0.0289 (11) | 0.0292 (11) | −0.0036 (9) | −0.0016 (9) | 0.0056 (9) |
C6 | 0.0290 (12) | 0.0345 (12) | 0.0337 (12) | 0.0067 (9) | 0.0029 (10) | −0.0071 (9) |
C15 | 0.0381 (13) | 0.0275 (11) | 0.0376 (12) | 0.0041 (10) | 0.0024 (10) | −0.0066 (9) |
C16 | 0.0408 (13) | 0.0347 (13) | 0.0296 (11) | −0.0113 (10) | 0.0014 (10) | −0.0066 (9) |
C12 | 0.0373 (12) | 0.0273 (11) | 0.0265 (11) | 0.0012 (9) | 0.0015 (9) | −0.0009 (9) |
C1 | 0.0309 (11) | 0.0220 (10) | 0.0328 (11) | 0.0003 (9) | −0.0096 (9) | −0.0050 (8) |
C10 | 0.0507 (16) | 0.0467 (15) | 0.0345 (13) | 0.0149 (12) | −0.0170 (11) | −0.0101 (11) |
C4 | 0.0202 (9) | 0.0223 (9) | 0.0246 (9) | 0.0000 (8) | 0.0025 (8) | −0.0001 (8) |
C13 | 0.0190 (9) | 0.0248 (10) | 0.0214 (9) | −0.0033 (8) | 0.0046 (8) | −0.0006 (8) |
C5 | 0.0259 (11) | 0.0308 (11) | 0.0265 (10) | 0.0016 (9) | 0.0056 (9) | −0.0023 (8) |
C11 | 0.0558 (16) | 0.0344 (13) | 0.0250 (11) | 0.0108 (11) | −0.0027 (11) | −0.0021 (9) |
C8 | 0.0296 (12) | 0.0396 (13) | 0.0342 (12) | −0.0035 (10) | −0.0039 (9) | 0.0011 (10) |
C9 | 0.0319 (13) | 0.0568 (17) | 0.0462 (15) | −0.0042 (12) | −0.0115 (11) | −0.0048 (13) |
Se1—C2 | 1.932 (2) | C6—C5 | 1.336 (3) |
Se1—Se1i | 2.3229 (6) | C6—C1 | 1.463 (3) |
C2—C3 | 1.332 (3) | C6—H6A | 0.950 |
C2—C1 | 1.476 (3) | C15—C16 | 1.379 (3) |
C17—C18 | 1.384 (3) | C15—H15A | 0.950 |
C17—C16 | 1.386 (3) | C16—H16A | 0.950 |
C17—H17A | 0.950 | C12—C11 | 1.384 (3) |
C7—C8 | 1.390 (3) | C12—H12A | 0.950 |
C7—C12 | 1.399 (3) | C10—C11 | 1.379 (4) |
C7—C4 | 1.542 (3) | C10—C9 | 1.385 (4) |
C14—C13 | 1.390 (3) | C10—H10A | 0.950 |
C14—C15 | 1.395 (3) | C4—C5 | 1.509 (3) |
C14—H14A | 0.950 | C4—C13 | 1.555 (3) |
C3—C4 | 1.507 (3) | C5—H5A | 0.950 |
C3—H3A | 0.950 | C11—H11A | 0.950 |
O1—C1 | 1.234 (3) | C8—C9 | 1.385 (3) |
C18—C13 | 1.393 (3) | C8—H8A | 0.950 |
C18—H18A | 0.950 | C9—H9A | 0.950 |
C2—Se1—Se1i | 97.81 (6) | C11—C12—H12A | 119.9 |
C3—C2—C1 | 121.25 (19) | C7—C12—H12A | 119.9 |
C3—C2—Se1 | 124.72 (17) | O1—C1—C6 | 122.5 (2) |
C1—C2—Se1 | 114.03 (14) | O1—C1—C2 | 121.1 (2) |
C18—C17—C16 | 120.4 (2) | C6—C1—C2 | 116.39 (18) |
C18—C17—H17A | 119.8 | C11—C10—C9 | 119.2 (2) |
C16—C17—H17A | 119.8 | C11—C10—H10A | 120.4 |
C8—C7—C12 | 118.4 (2) | C9—C10—H10A | 120.4 |
C8—C7—C4 | 121.65 (19) | C3—C4—C5 | 111.86 (17) |
C12—C7—C4 | 119.95 (19) | C3—C4—C7 | 110.93 (16) |
C13—C14—C15 | 120.6 (2) | C5—C4—C7 | 108.32 (16) |
C13—C14—H14A | 119.7 | C3—C4—C13 | 103.69 (15) |
C15—C14—H14A | 119.7 | C5—C4—C13 | 109.70 (16) |
C2—C3—C4 | 124.57 (19) | C7—C4—C13 | 112.33 (16) |
C2—C3—H3A | 117.7 | C14—C13—C18 | 118.36 (19) |
C4—C3—H3A | 117.7 | C14—C13—C4 | 122.95 (18) |
C17—C18—C13 | 120.9 (2) | C18—C13—C4 | 118.53 (18) |
C17—C18—H18A | 119.6 | C6—C5—C4 | 123.5 (2) |
C13—C18—H18A | 119.5 | C6—C5—H5A | 118.2 |
C5—C6—C1 | 122.4 (2) | C4—C5—H5A | 118.2 |
C5—C6—H6A | 118.8 | C10—C11—C12 | 121.0 (2) |
C1—C6—H6A | 118.8 | C10—C11—H11A | 119.5 |
C16—C15—C14 | 120.5 (2) | C12—C11—H11A | 119.5 |
C16—C15—H15A | 119.7 | C9—C8—C7 | 120.8 (2) |
C14—C15—H15A | 119.8 | C9—C8—H8A | 119.5 |
C15—C16—C17 | 119.3 (2) | C7—C8—H8A | 119.6 |
C15—C16—H16A | 120.4 | C10—C9—C8 | 120.4 (2) |
C17—C16—H16A | 120.3 | C10—C9—H9A | 119.8 |
C11—C12—C7 | 120.2 (2) | C8—C9—H9A | 119.8 |
Symmetry code: (i) −x+3/2, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O1ii | 0.95 | 2.93 | 3.822 (3) | 157 |
C16—H16A···O1iii | 0.95 | 2.82 | 3.463 (3) | 125 |
C17—H17A···Se1iii | 0.95 | 3.10 | 3.886 (2) | 141 |
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C36H26O2Se2 |
Mr | 648.49 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 168 |
a, b, c (Å) | 17.4144 (16), 10.6767 (10), 15.2187 (14) |
V (Å3) | 2829.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.65 |
Crystal size (mm) | 0.8 × 0.5 × 0.14 |
Data collection | |
Diffractometer | Siemens CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.218, 0.690 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29316, 2839, 2412 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.086, 1.06 |
No. of reflections | 2839 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.73 |
Computer programs: SMART (Siemens, 1995), SMART, SHELXTL (Siemens, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLUTON (Spek, 1992), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O1i | 0.95 | 2.93 | 3.822 (3) | 157 |
C16—H16A···O1ii | 0.95 | 2.82 | 3.463 (3) | 125 |
C17—H17A···Se1ii | 0.95 | 3.10 | 3.886 (2) | 141 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y, −z. |
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The role of weak hydrogen bonds such as C—H···O, C—H···π, or in general C—H···X (X = heteroatom or metal) and X···X interactions in the stabilization of crystal structures is a theme of current interest (Desiraju & Steiner, 1999). In this context, the crystal structure of the title compound, (I), is pertinent because it has phenyl C—H donor groups, carbonyl acceptor atoms and a Se—Se bond.
The molecular geometry of (I) is shown in Fig. 1 (Johnson, 1976). The molecule lies on a twofold axis that bisects the Se1—Se1i bond [symmetry code: (i) 3/2 − x, 1/2 − y, z]; the asymmetric unit contains half a molecule of (I). The cyclohexa-2,5-dienone ring forms dihedral angles of 58.1 (1) and 89.85 (1)° with the two phenyl rings (C7—C12 and C13—C18). The diselenide geometry in (I) is normal, with a Se1—Se1i bond length of 2.3229 (6) Å and a C2—Se1—Se1i—C2i torsion angle of 79.35 (8)°. These values are comparable with those found in the crystal structure of dimesityl diselenide reported recently by Jeske et al. (1998) [Se—Se 2.3341 (6) Å and C—Se—Se—C 83.96 (12)°].
In the crystal structure of (I), space group Pccn, inversion related molecules are connected through C—H···O and C—H···Se interactions (Iwaoka & Tomoda, 1994; Narayanan et al., 1998) to produce a corrugated ribbon-like structure in (101) [C16—H16A···O1 2.82 Å, 125°; C17—H17A···Se1 3.10 Å, 141°] (Fig. 2). Such ribbons are connected by chains of C—H···O and C—H···π interactions along [001] through the C5 and C6 H-atoms of the cyclohexa-2,5-dienone as donors and the carbonyl group and phenyl ring as acceptors [C5—H5A···O1 2.93 Å, 157°; C6—H6A···πcentroid 2.57 Å, 153°]. The hydrogen bonds in this study have been considered with liberal distance and angle cut-off criteria of 2.0 < H···O < 3.0 Å and 120 < C—H···O < 180°, as advocated by Desiraju & Steiner (1999).
The approach of electrophilic and nucleophilic groups (X) to divalent Se (Y—Se—Z) has been discussed by Ramasubbu & Parthasarathy (1987) and categorized as type I or type II depending on whether the approaching atom is normal to the selenide plane and along the Se lone pair orbital (<θ> = 23°) or in the plane and along the C—Se σ* antibonding orbital (<θ> = 79°). In the spherical coordinate system, θ is the polar angle between the direction X···Se and the normal to the Y—Se—Z selenide plane. There are two interactions in (I) involving the Se-atom that deserve mention. In the C17—H17A···Se1 interaction, the C—H group approaches the Se acceptor along the direction for electrophilic donors with θ = 18.5°. Interestingly, the structure also has a C—Se···πcentroid contact of 3.59 Å (166.4°), which is shorter than the sum of the van der Waals radii (Se 2.0 and C 1.7 Å). The approach of the phenyl ring is in the C—Se—Se plane and from behind the C—Se bond, i.e. it is a type-II contact with θ = 83.9°. Based on this approach geometry, the interaction could be viewed as electrophile-nucleophile pairing, i.e. Se(δ+)···π(δ-). Thus, the stereochemical distribution of charge density at Se and its behaviour both as a donor and as an acceptor in the crystal structure of (I) is rationalized.