Unusual structure of a biphenyl fragment: the important role of weak inter­actions

1,5-Bis([1,1′-biphen­yl]-4-yl)-5-hy­droxy-3-methyl­heptane-1,6-dione, C₃₂H₃₀O₃, was investigated by X-ray analysis, quantum chemical calculations and AIM (atoms in mol­ecules) analysis. It was shown that four intra­molecular C—H...π forces are established between the two biphenyl fragments. C—H...π inter­actions lead to a bending of the biphenyl part. The energy of the intra­molecular inter­actions was estimated and the exclusive role of the moment of force was established.

Computing details

Data collection: SAINT (Bruker, 2017); cell refinement: APEX3 (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008).

(I)

Crystal data

C32H30O3	Z = 2
Mr = 462.56	F(000) = 492
Triclinic, P1	Dx = 1.248 Mg m^−3
a = 5.954 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.88 (2) Å	Cell parameters from 539 reflections
c = 26.30 (7) Å	θ = 2.5–25.1°
α = 89.56 (7)°	µ = 0.08 mm^−1
β = 86.85 (6)°	T = 100 K
γ = 87.68 (6)°	Prism, clear light colourless
V = 1231 (6) Å^3	0.38 × 0.12 × 0.08 mm

Data collection

Bruker D8 Venture Photon 100 CMOS diffractometer	5226 independent reflections
Radiation source: IuS	4335 reflections with I > 2σ(I)
No monochromator	Rint = 0.065
Detector resolution: 0.79 pixels mm^-1	θmax = 26.8°, θmin = 2.3°
ω and φ scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −9→9
Tmin = 0.702, Tmax = 0.745	l = −33→33
54736 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0595P)^2 + 0.6514P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.004
5226 reflections	Δρmax = 0.31 e Å^−3
321 parameters	Δρmin = −0.37 e Å^−3
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.11500 (17)	0.59036 (15)	0.08376 (5)	0.0340 (3)
O2	0.89890 (18)	0.12003 (15)	0.13185 (4)	0.0308 (3)
O3	0.45100 (16)	0.67774 (12)	0.05605 (4)	0.0195 (2)
H3	0.582 (3)	0.637 (2)	0.0638 (7)	0.029*
C1	0.4885 (4)	0.7109 (3)	0.40948 (7)	0.0457 (5)
H1	0.519064	0.713965	0.444531	0.055*
C2	0.3032 (4)	0.6288 (3)	0.39392 (7)	0.0517 (5)
H2	0.207458	0.573579	0.418337	0.062*
C3	0.2562 (3)	0.6269 (3)	0.34244 (6)	0.0417 (4)
H3A	0.126980	0.571509	0.332440	0.050*
C4	0.3952 (3)	0.70461 (18)	0.30538 (6)	0.0246 (3)
C5	0.3504 (2)	0.69506 (17)	0.24985 (5)	0.0210 (3)
C6	0.1686 (2)	0.6067 (2)	0.23274 (6)	0.0263 (3)
H6	0.062221	0.562051	0.257013	0.032*
C7	0.1407 (2)	0.58299 (19)	0.18109 (5)	0.0239 (3)
H7	0.015440	0.523160	0.170875	0.029*
C8	0.2937 (2)	0.64567 (16)	0.14392 (5)	0.0167 (3)
C9	0.2845 (2)	0.59661 (16)	0.08728 (5)	0.0161 (3)
C10	0.2943 (2)	0.40066 (17)	0.07844 (5)	0.0178 (3)
H10A	0.168629	0.352800	0.099419	0.021*
H10B	0.263033	0.381764	0.042380	0.021*
C11	0.5107 (2)	0.29412 (17)	0.08956 (5)	0.0179 (3)
H11	0.642503	0.345815	0.071028	0.021*
C12	0.5520 (2)	0.28629 (18)	0.14674 (5)	0.0227 (3)
H12A	0.556194	0.404252	0.159275	0.027*
H12B	0.421071	0.233764	0.164498	0.027*
C13	0.7637 (2)	0.19030 (17)	0.16233 (5)	0.0203 (3)
C14	0.8094 (2)	0.19095 (17)	0.21833 (5)	0.0205 (3)
C15	1.0030 (3)	0.1047 (2)	0.23466 (6)	0.0277 (3)
H15	1.099133	0.042518	0.210840	0.033*
C16	1.0557 (3)	0.1095 (2)	0.28562 (6)	0.0317 (4)
H16	1.188292	0.050601	0.295840	0.038*
C17	0.9184 (3)	0.19882 (19)	0.32221 (6)	0.0260 (3)
C18	0.9749 (3)	0.2060 (2)	0.37702 (6)	0.0312 (4)
C19	1.1674 (5)	0.1275 (3)	0.39442 (8)	0.0677 (8)
H19	1.267952	0.066923	0.371133	0.081*
C20	1.2177 (5)	0.1354 (4)	0.44565 (9)	0.0771 (9)
H20	1.352458	0.081302	0.456481	0.092*
C21	1.0763 (4)	0.2194 (3)	0.48023 (8)	0.0583 (6)
H21	1.107629	0.219650	0.515264	0.070*
C22	0.6286 (4)	0.7882 (3)	0.37356 (7)	0.0482 (5)
H22	0.757280	0.843554	0.383877	0.058*
C23	0.5821 (3)	0.7855 (3)	0.32210 (7)	0.0401 (4)
H23	0.679745	0.839961	0.297900	0.048*
C24	0.0542 (2)	0.66209 (17)	0.06869 (5)	0.0183 (3)
C25	0.0441 (2)	0.8097 (2)	0.03301 (6)	0.0284 (3)
H25A	−0.112203	0.833463	0.024411	0.043*
H25B	0.136554	0.783205	0.001889	0.043*
H25C	0.101259	0.909638	0.049253	0.043*
C26	0.4818 (3)	0.11474 (18)	0.06834 (6)	0.0250 (3)
H26A	0.618396	0.044272	0.073303	0.038*
H26B	0.455857	0.122803	0.031916	0.038*
H26C	0.352878	0.063197	0.086331	0.038*
C27	0.8375 (4)	0.2960 (4)	0.41242 (8)	0.0761 (9)
H27	0.705391	0.354151	0.401649	0.091*
C28	0.8882 (5)	0.3034 (5)	0.46354 (9)	0.0871 (10)
H28	0.791574	0.367121	0.486885	0.104*
C29	0.7243 (3)	0.2826 (2)	0.30556 (6)	0.0375 (4)
H29	0.627046	0.343714	0.329411	0.045*
C30	0.6705 (3)	0.2785 (2)	0.25466 (6)	0.0342 (4)
H30	0.536951	0.336240	0.244515	0.041*
C31	0.4657 (2)	0.74429 (18)	0.16047 (5)	0.0220 (3)
H31	0.564737	0.796467	0.136072	0.026*
C32	0.4939 (3)	0.76713 (19)	0.21236 (6)	0.0257 (3)
H32	0.613537	0.833283	0.222460	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0122 (5)	0.0412 (7)	0.0490 (7)	−0.0047 (4)	−0.0060 (5)	0.0163 (5)
O2	0.0241 (5)	0.0410 (6)	0.0262 (5)	0.0097 (5)	0.0001 (4)	0.0006 (5)
O3	0.0101 (4)	0.0255 (5)	0.0228 (5)	−0.0014 (4)	−0.0014 (4)	0.0070 (4)
C1	0.0565 (12)	0.0588 (12)	0.0227 (8)	0.0011 (10)	−0.0114 (8)	−0.0046 (8)
C2	0.0602 (13)	0.0718 (14)	0.0241 (9)	−0.0169 (11)	−0.0019 (8)	0.0031 (9)
C3	0.0452 (10)	0.0569 (12)	0.0244 (8)	−0.0168 (9)	−0.0029 (7)	−0.0001 (8)
C4	0.0279 (8)	0.0221 (7)	0.0235 (7)	0.0042 (6)	−0.0029 (6)	−0.0031 (6)
C5	0.0225 (7)	0.0187 (7)	0.0218 (7)	0.0028 (5)	−0.0016 (5)	−0.0024 (5)
C6	0.0204 (7)	0.0348 (8)	0.0235 (7)	−0.0055 (6)	0.0035 (6)	0.0005 (6)
C7	0.0162 (6)	0.0308 (8)	0.0252 (7)	−0.0063 (6)	−0.0008 (5)	−0.0007 (6)
C8	0.0134 (6)	0.0153 (6)	0.0213 (7)	0.0023 (5)	−0.0028 (5)	0.0008 (5)
C9	0.0106 (6)	0.0185 (6)	0.0193 (6)	−0.0013 (5)	−0.0018 (5)	0.0033 (5)
C10	0.0149 (6)	0.0198 (7)	0.0191 (6)	−0.0025 (5)	−0.0044 (5)	0.0006 (5)
C11	0.0161 (6)	0.0173 (6)	0.0205 (6)	−0.0005 (5)	−0.0019 (5)	0.0004 (5)
C12	0.0228 (7)	0.0233 (7)	0.0219 (7)	0.0056 (6)	−0.0049 (5)	−0.0025 (5)
C13	0.0187 (7)	0.0174 (6)	0.0248 (7)	−0.0009 (5)	−0.0020 (5)	0.0021 (5)
C14	0.0203 (7)	0.0180 (6)	0.0234 (7)	−0.0009 (5)	−0.0031 (5)	0.0030 (5)
C15	0.0225 (7)	0.0324 (8)	0.0274 (8)	0.0069 (6)	−0.0011 (6)	0.0030 (6)
C16	0.0237 (8)	0.0414 (9)	0.0297 (8)	0.0083 (7)	−0.0066 (6)	0.0049 (7)
C17	0.0283 (8)	0.0245 (7)	0.0257 (7)	−0.0021 (6)	−0.0064 (6)	0.0025 (6)
C18	0.0358 (9)	0.0333 (8)	0.0256 (8)	−0.0061 (7)	−0.0081 (7)	0.0036 (6)
C19	0.0842 (17)	0.0793 (16)	0.0392 (11)	0.0431 (14)	−0.0310 (11)	−0.0160 (11)
C20	0.100 (2)	0.0869 (18)	0.0451 (13)	0.0391 (16)	−0.0419 (13)	−0.0106 (12)
C21	0.0713 (15)	0.0796 (16)	0.0265 (9)	−0.0125 (12)	−0.0183 (10)	0.0046 (10)
C22	0.0480 (11)	0.0655 (13)	0.0333 (10)	−0.0129 (10)	−0.0152 (8)	−0.0039 (9)
C23	0.0396 (10)	0.0530 (11)	0.0292 (9)	−0.0122 (8)	−0.0074 (7)	0.0004 (8)
C24	0.0135 (6)	0.0212 (7)	0.0207 (6)	0.0005 (5)	−0.0043 (5)	−0.0026 (5)
C25	0.0192 (7)	0.0295 (8)	0.0371 (8)	0.0002 (6)	−0.0099 (6)	0.0097 (6)
C26	0.0278 (8)	0.0194 (7)	0.0280 (7)	−0.0006 (6)	−0.0036 (6)	−0.0036 (6)
C27	0.0483 (13)	0.149 (3)	0.0291 (10)	0.0287 (15)	−0.0095 (9)	−0.0165 (13)
C28	0.0602 (15)	0.171 (3)	0.0293 (11)	0.0173 (18)	−0.0052 (10)	−0.0208 (15)
C29	0.0417 (10)	0.0431 (10)	0.0266 (8)	0.0186 (8)	−0.0052 (7)	−0.0056 (7)
C30	0.0313 (8)	0.0418 (9)	0.0287 (8)	0.0187 (7)	−0.0077 (7)	−0.0023 (7)
C31	0.0222 (7)	0.0206 (7)	0.0236 (7)	−0.0063 (5)	−0.0009 (5)	0.0017 (5)
C32	0.0279 (8)	0.0238 (7)	0.0265 (7)	−0.0087 (6)	−0.0054 (6)	−0.0020 (6)

Geometric parameters (Å, º)

O1—C24	1.221 (3)	C14—C30	1.396 (3)
O2—C13	1.223 (3)	C15—H15	0.9500
O3—H3	0.86 (2)	C15—C16	1.394 (4)
O3—C9	1.421 (3)	C16—H16	0.9500
C1—H1	0.9500	C16—C17	1.403 (3)
C1—C2	1.383 (4)	C17—C18	1.500 (4)
C1—C22	1.380 (4)	C17—C29	1.397 (4)
C2—H2	0.9500	C18—C19	1.379 (4)
C2—C3	1.398 (4)	C18—C27	1.385 (4)
C3—H3A	0.9500	C19—H19	0.9500
C3—C4	1.398 (3)	C19—C20	1.399 (4)
C4—C5	1.502 (4)	C20—H20	0.9500
C4—C23	1.397 (4)	C20—C21	1.361 (4)
C5—C6	1.407 (3)	C21—H21	0.9500
C5—C32	1.401 (3)	C21—C28	1.370 (5)
C6—H6	0.9500	C22—H22	0.9500
C6—C7	1.392 (4)	C22—C23	1.397 (4)
C7—H7	0.9500	C23—H23	0.9500
C7—C8	1.400 (3)	C24—C25	1.490 (4)
C8—C9	1.547 (4)	C25—H25A	0.9800
C8—C31	1.400 (3)	C25—H25B	0.9800
C9—C10	1.561 (5)	C25—H25C	0.9800
C9—C24	1.548 (4)	C26—H26A	0.9800
C10—H10A	0.9900	C26—H26B	0.9800
C10—H10B	0.9900	C26—H26C	0.9800
C10—C11	1.549 (4)	C27—H27	0.9500
C11—H11	1.0000	C27—C28	1.396 (4)
C11—C12	1.537 (4)	C28—H28	0.9500
C11—C26	1.543 (4)	C29—H29	0.9500
C12—H12A	0.9900	C29—C30	1.395 (4)
C12—H12B	0.9900	C30—H30	0.9500
C12—C13	1.518 (4)	C31—H31	0.9500
C13—C14	1.513 (4)	C31—C32	1.398 (4)
C14—C15	1.400 (3)	C32—H32	0.9500
C9—O3—H3	108.4 (12)	C15—C16—H16	119.1
C2—C1—H1	120.3	C15—C16—C17	121.83 (19)
C22—C1—H1	120.3	C17—C16—H16	119.1
C22—C1—C2	119.3 (2)	C16—C17—C18	122.18 (19)
C1—C2—H2	119.8	C29—C17—C16	117.2 (2)
C1—C2—C3	120.32 (19)	C29—C17—C18	120.66 (16)
C3—C2—H2	119.8	C19—C18—C17	122.04 (18)
C2—C3—H3A	119.3	C19—C18—C27	116.8 (2)
C4—C3—C2	121.4 (2)	C27—C18—C17	121.2 (2)
C4—C3—H3A	119.3	C18—C19—H19	119.3
C3—C4—C5	121.27 (19)	C18—C19—C20	121.3 (2)
C3—C4—C23	117.1 (2)	C20—C19—H19	119.3
C23—C4—C5	121.62 (15)	C19—C20—H20	119.5
C6—C5—C4	121.72 (14)	C21—C20—C19	121.0 (3)
C32—C5—C4	121.56 (19)	C21—C20—H20	119.5
C32—C5—C6	116.7 (2)	C20—C21—H21	120.6
C5—C6—H6	119.2	C20—C21—C28	118.7 (2)
C7—C6—C5	121.62 (14)	C28—C21—H21	120.6
C7—C6—H6	119.2	C1—C22—H22	119.8
C6—C7—H7	119.4	C1—C22—C23	120.3 (2)
C6—C7—C8	121.24 (19)	C23—C22—H22	119.8
C8—C7—H7	119.4	C4—C23—H23	119.2
C7—C8—C9	121.34 (17)	C22—C23—C4	121.55 (18)
C7—C8—C31	117.4 (2)	C22—C23—H23	119.2
C31—C8—C9	121.08 (13)	O1—C24—C9	118.7 (2)
O3—C9—C8	111.96 (16)	O1—C24—C25	121.71 (16)
O3—C9—C10	111.28 (15)	C25—C24—C9	119.60 (14)
O3—C9—C24	106.2 (2)	C24—C25—H25A	109.5
C8—C9—C10	113.34 (12)	C24—C25—H25B	109.5
C8—C9—C24	107.83 (13)	C24—C25—H25C	109.5
C24—C9—C10	105.72 (13)	H25A—C25—H25B	109.5
C9—C10—H10A	107.4	H25A—C25—H25C	109.5
C9—C10—H10B	107.4	H25B—C25—H25C	109.5
H10A—C10—H10B	106.9	C11—C26—H26A	109.5
C11—C10—C9	119.81 (15)	C11—C26—H26B	109.5
C11—C10—H10A	107.4	C11—C26—H26C	109.5
C11—C10—H10B	107.4	H26A—C26—H26B	109.5
C10—C11—H11	109.0	H26A—C26—H26C	109.5
C12—C11—C10	112.14 (12)	H26B—C26—H26C	109.5
C12—C11—H11	109.0	C18—C27—H27	119.2
C12—C11—C26	110.89 (15)	C18—C27—C28	121.7 (3)
C26—C11—C10	106.81 (18)	C28—C27—H27	119.2
C26—C11—H11	109.0	C21—C28—C27	120.4 (2)
C11—C12—H12A	108.0	C21—C28—H28	119.8
C11—C12—H12B	108.0	C27—C28—H28	119.8
H12A—C12—H12B	107.3	C17—C29—H29	119.3
C13—C12—C11	117.11 (13)	C30—C29—C17	121.35 (16)
C13—C12—H12A	108.0	C30—C29—H29	119.3
C13—C12—H12B	108.0	C14—C30—H30	119.4
O2—C13—C12	123.22 (19)	C29—C30—C14	121.2 (2)
O2—C13—C14	119.93 (18)	C29—C30—H30	119.4
C14—C13—C12	116.79 (13)	C8—C31—H31	119.5
C15—C14—C13	119.02 (14)	C32—C31—C8	121.00 (14)
C30—C14—C13	122.92 (18)	C32—C31—H31	119.5
C30—C14—C15	118.0 (2)	C5—C32—H32	119.1
C14—C15—H15	119.8	C31—C32—C5	121.75 (19)
C16—C15—C14	120.47 (15)	C31—C32—H32	119.1
C16—C15—H15	119.8
O2—C13—C14—C15	−2.5 (2)	C11—C12—C13—C14	176.89 (11)
O2—C13—C14—C30	175.47 (15)	C12—C13—C14—C15	−179.79 (13)
O3—C9—C10—C11	61.0 (2)	C12—C13—C14—C30	−1.8 (2)
O3—C9—C24—O1	167.99 (13)	C13—C14—C15—C16	176.96 (14)
O3—C9—C24—C25	−11.86 (17)	C13—C14—C30—C29	−176.88 (16)
C1—C2—C3—C4	1.0 (3)	C14—C15—C16—C17	0.3 (3)
C1—C22—C23—C4	−0.4 (3)	C15—C14—C30—C29	1.1 (3)
C2—C1—C22—C23	0.8 (3)	C15—C16—C17—C18	−179.41 (15)
C2—C3—C4—C5	177.02 (17)	C15—C16—C17—C29	0.4 (3)
C2—C3—C4—C23	−0.5 (3)	C16—C17—C18—C19	1.2 (3)
C3—C4—C5—C6	−0.5 (2)	C16—C17—C18—C27	179.6 (2)
C3—C4—C5—C32	−177.54 (15)	C16—C17—C29—C30	−0.4 (3)
C3—C4—C23—C22	0.2 (3)	C17—C18—C19—C20	−180.0 (2)
C4—C5—C6—C7	−173.26 (14)	C17—C18—C27—C28	179.9 (3)
C4—C5—C32—C31	173.58 (13)	C17—C29—C30—C14	−0.3 (3)
C5—C4—C23—C22	−177.31 (17)	C18—C17—C29—C30	179.40 (16)
C5—C6—C7—C8	0.3 (2)	C18—C19—C20—C21	0.8 (5)
C6—C5—C32—C31	−3.6 (2)	C18—C27—C28—C21	−0.7 (5)
C6—C7—C8—C9	170.52 (13)	C19—C18—C27—C28	−1.6 (4)
C6—C7—C8—C31	−4.8 (2)	C19—C20—C21—C28	−3.1 (5)
C7—C8—C9—O3	178.49 (12)	C20—C21—C28—C27	3.0 (5)
C7—C8—C9—C10	−54.6 (2)	C22—C1—C2—C3	−1.1 (3)
C7—C8—C9—C24	62.0 (2)	C23—C4—C5—C6	176.89 (15)
C7—C8—C31—C32	5.2 (2)	C23—C4—C5—C32	−0.1 (2)
C8—C9—C10—C11	−66.22 (17)	C24—C9—C10—C11	175.88 (11)
C8—C9—C24—O1	−71.8 (2)	C26—C11—C12—C13	62.7 (2)
C8—C9—C24—C25	108.3 (2)	C27—C18—C19—C20	1.5 (4)
C8—C31—C32—C5	−1.0 (2)	C29—C17—C18—C19	−178.7 (2)
C9—C8—C31—C32	−170.23 (13)	C29—C17—C18—C27	−0.3 (3)
C9—C10—C11—C12	68.05 (17)	C30—C14—C15—C16	−1.1 (2)
C9—C10—C11—C26	−170.27 (12)	C31—C8—C9—O3	−6.32 (17)
C10—C9—C24—O1	49.7 (2)	C31—C8—C9—C10	120.56 (17)
C10—C9—C24—C25	−130.17 (19)	C31—C8—C9—C24	−122.8 (2)
C10—C11—C12—C13	−177.99 (11)	C32—C5—C6—C7	3.9 (2)
C11—C12—C13—O2	−0.3 (2)