Crystal structure of 2α-(1,1-di­phenyl­eth­yl)-4-methyl-4α,5α-diphenyl-1,3-dioxolane: the result of a non-acid pinacol rearrangement

The title compound was produced unexpectedly from (±)-1,2-diphenyl-1,2-propane­diol by a sequential non-acid Pinacol rearrangement followed by acetal formation during recrystallization in 1-butanol. The tri-substituted dioxolane ring has a twist conformation and in the crystal, mol­ecules are linked by C—H...O hydrogen bonds, forming chains along [001].

Key indicators

• Single-crystal X-ray study
• T = 302 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.133
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H53    ..  O3      ..       2.61 Ang.
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -5.068 Report
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.452 Report

Alert level G
PLAT793_ALERT_4_G The Model has Chirality at C2      (Centro SPGR)          R Verify
PLAT793_ALERT_4_G The Model has Chirality at C4      (Centro SPGR)          S Verify
PLAT793_ALERT_4_G The Model has Chirality at C5      (Centro SPGR)          R Verify
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          6 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: ... Each of the eight authors has contributed significantly to this work. Kirchner: physical/inorganic professor, lead the student group that discovered the unexpected reaction, oversaw the project, and co-prepared the manuscript. Corfield: x-ray crystallographer, initiated the project, supervised the data collection,did the data reduction, prepared the ORTEP diagrams, did the database survey, co-prepared the manuscript. Annabi: undergraduate student,did recrystallizations, assisted in data collection, used SuperFilp to solve the structure, helped prepare the manuscript. Regan: organic professor who helped explain the unusual reation, assisted in characterizing the reaction, prepared chemical drawings. Speina: undergraduate student, experimented with a variety of solvents to be used in the recrystallizations, obtained good crystals. DiProperzio: undergraduate student, performed all the Spartan calculations. Ciaccio: organic professor, supplied initial starting material, did the NMR, contributed greatly to our understanding of the project. Capitani: theoretical professor, supervised the Spartan calculations, contributed to the analysis.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: Data reduction followed procedures in Corfield et al. (1973); Data were averaged with a local version of SORTAV (Blessing, 1989); program(s) used to solve structure: Superflip (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

2-(1,1-Diphenylethyl)-4-methyl-4,5-diphenyl-1,3-dioxolane

Crystal data

C30H28O2	F(000) = 896
Mr = 420.52	Dx = 1.200 Mg m^−3
Monoclinic, P21/c	Melting point = 436–443 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 16.720 (3) Å	Cell parameters from 25 reflections
b = 9.0056 (9) Å	θ = 4.5–10.1°
c = 16.6747 (12) Å	µ = 0.07 mm^−1
β = 112.040 (9)°	T = 302 K
V = 2327.3 (5) Å^3	Block, colourless
Z = 4	0.4 × 0.4 × 0.26 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.025
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 2.5°
Graphite monochromator	h = −20→19
θ/2θ scans	k = 0→11
6377 measured reflections	l = 0→20
4547 independent reflections	3 standard reflections every 180 min
2612 reflections with I > 2σ(I)	intensity decay: 3.1(8)

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.020P)^2 + 0.5P] where P = (Fo^2 + 2Fc^2)/3
4547 reflections	(Δ/σ)max < 0.001
291 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.18 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. In the monoclinic unit cell, the a and c axes are of very similar lengths, so that before data collection commenced, it was important to check that the Laue symmetry was indeed 2/m and not mmm. This was accomplished by temporarily transforming the cell to orthorhombic axes, and collecting all 8 forms of the (orthorhombic) 111 and 222 reflections. In each case, the 8 forms clearly split into two different sets of four, verifying the monoclinic symmetry.

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

	x	y	z	Uiso*/Ueq
O1	0.18420 (9)	0.57319 (14)	0.10104 (8)	0.0484 (4)
O3	0.19021 (8)	0.39714 (14)	0.00987 (8)	0.0419 (3)
C2	0.15272 (14)	0.5361 (2)	0.01270 (12)	0.0416 (5)
H2	0.0899	0.5249	−0.0083	0.042*
C4	0.19172 (13)	0.3148 (2)	0.08470 (12)	0.0419 (5)
C41	0.27953 (14)	0.2435 (2)	0.12749 (12)	0.0448 (5)
C42	0.29066 (18)	0.1231 (3)	0.18187 (15)	0.0669 (7)
H42	0.2430	0.0822	0.1897	0.080*
C43	0.3712 (2)	0.0626 (3)	0.22479 (17)	0.0879 (9)
H43	0.3775	−0.0186	0.2612	0.105*
C44	0.4421 (2)	0.1213 (4)	0.21416 (18)	0.0874 (9)
H44	0.4966	0.0810	0.2435	0.105*
C45	0.43208 (17)	0.2395 (3)	0.16012 (17)	0.0770 (8)
H45	0.4799	0.2790	0.1520	0.092*
C46	0.35148 (15)	0.3013 (3)	0.11716 (14)	0.0586 (6)
H46	0.3458	0.3826	0.0810	0.070*
C5	0.17302 (14)	0.4396 (2)	0.14164 (12)	0.0441 (5)
H5	0.1123	0.4325	0.1348	0.044*
C51	0.22718 (15)	0.4399 (2)	0.23635 (12)	0.0459 (5)
C52	0.19966 (18)	0.3615 (3)	0.29192 (14)	0.0636 (7)
H52	0.1466	0.3134	0.2707	0.076*
C53	0.2504 (2)	0.3536 (3)	0.37949 (16)	0.0801 (8)
H53	0.2321	0.2978	0.4164	0.096*
C54	0.3268 (2)	0.4272 (3)	0.41131 (16)	0.0814 (9)
H54	0.3605	0.4228	0.4701	0.098*
C55	0.35420 (18)	0.5080 (3)	0.35694 (16)	0.0758 (8)
H55	0.4063	0.5591	0.3790	0.091*
C56	0.30502 (16)	0.5139 (3)	0.26954 (14)	0.0588 (6)
H56	0.3244	0.5680	0.2329	0.071*
C6	0.17518 (13)	0.6541 (2)	−0.04152 (11)	0.0386 (5)
C7	0.13530 (15)	0.8014 (2)	−0.02620 (14)	0.0543 (6)
H7A	0.1514	0.8808	−0.0555	0.081*
H7B	0.1562	0.8222	0.0347	0.081*
H7C	0.0736	0.7926	−0.0483	0.081*
C81	0.13165 (12)	0.6192 (2)	−0.13860 (11)	0.0373 (5)
C82	0.07434 (14)	0.5033 (2)	−0.17192 (13)	0.0514 (6)
H82	0.0636	0.4371	−0.1344	0.062*
C83	0.03285 (15)	0.4846 (3)	−0.26028 (14)	0.0610 (6)
H83	−0.0060	0.4069	−0.2814	0.073*
C84	0.04836 (15)	0.5791 (3)	−0.31673 (14)	0.0560 (6)
H84	0.0199	0.5667	−0.3761	0.067*
C85	0.10630 (15)	0.6922 (2)	−0.28491 (13)	0.0554 (6)
H85	0.1182	0.7559	−0.3229	0.066*
C86	0.14699 (14)	0.7122 (2)	−0.19714 (12)	0.0478 (5)
H86	0.1858	0.7903	−0.1767	0.057*
C91	0.27312 (13)	0.6670 (2)	−0.01420 (12)	0.0417 (5)
C92	0.31673 (14)	0.5900 (2)	−0.05657 (14)	0.0518 (6)
H92	0.2862	0.5266	−0.1017	0.062*
C93	0.40453 (15)	0.6047 (3)	−0.03367 (16)	0.0679 (7)
H93	0.4322	0.5522	−0.0638	0.082*
C94	0.45124 (17)	0.6955 (3)	0.03284 (19)	0.0790 (8)
H94	0.5104	0.7064	0.0476	0.095*
C95	0.41022 (19)	0.7700 (3)	0.07731 (18)	0.0783 (8)
H95	0.4419	0.8300	0.1237	0.094*
C96	0.32217 (16)	0.7572 (3)	0.05420 (14)	0.0599 (6)
H96	0.2952	0.8099	0.0849	0.072*
C10	0.11855 (16)	0.2027 (3)	0.05553 (15)	0.0652 (7)
H10A	0.0660	0.2516	0.0205	0.098*
H10B	0.1118	0.1596	0.1053	0.098*
H10C	0.1316	0.1259	0.0223	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0752 (10)	0.0384 (8)	0.0376 (8)	0.0104 (7)	0.0280 (7)	0.0030 (6)
O3	0.0587 (9)	0.0362 (7)	0.0341 (7)	0.0042 (7)	0.0212 (6)	0.0009 (6)
C2	0.0501 (12)	0.0423 (11)	0.0353 (11)	0.0070 (10)	0.0192 (9)	0.0005 (9)
C4	0.0543 (13)	0.0391 (11)	0.0353 (10)	−0.0009 (10)	0.0201 (9)	0.0035 (9)
C41	0.0597 (14)	0.0408 (11)	0.0351 (10)	0.0052 (11)	0.0192 (10)	−0.0053 (9)
C42	0.0881 (19)	0.0587 (15)	0.0575 (14)	0.0193 (14)	0.0313 (14)	0.0118 (13)
C43	0.116 (3)	0.081 (2)	0.0603 (17)	0.043 (2)	0.0258 (18)	0.0202 (15)
C44	0.080 (2)	0.099 (2)	0.0642 (17)	0.041 (2)	0.0058 (16)	−0.0043 (17)
C45	0.0579 (17)	0.093 (2)	0.0720 (17)	0.0099 (16)	0.0146 (14)	−0.0103 (17)
C46	0.0570 (16)	0.0611 (15)	0.0532 (13)	0.0058 (13)	0.0156 (12)	−0.0017 (12)
C5	0.0502 (12)	0.0476 (12)	0.0418 (11)	0.0040 (10)	0.0256 (10)	0.0055 (10)
C51	0.0666 (15)	0.0406 (11)	0.0386 (11)	0.0077 (11)	0.0289 (11)	0.0003 (10)
C52	0.0938 (19)	0.0587 (15)	0.0499 (14)	−0.0016 (14)	0.0401 (13)	0.0036 (12)
C53	0.133 (3)	0.0688 (17)	0.0516 (15)	0.0109 (19)	0.0500 (17)	0.0131 (14)
C54	0.118 (3)	0.0799 (19)	0.0395 (14)	0.0189 (19)	0.0215 (16)	0.0017 (14)
C55	0.0838 (19)	0.0815 (19)	0.0527 (16)	0.0003 (16)	0.0148 (14)	−0.0081 (14)
C56	0.0742 (17)	0.0582 (14)	0.0469 (13)	0.0010 (13)	0.0261 (12)	0.0010 (11)
C6	0.0482 (12)	0.0341 (10)	0.0358 (10)	0.0042 (9)	0.0185 (9)	0.0009 (8)
C7	0.0690 (15)	0.0445 (12)	0.0512 (13)	0.0141 (11)	0.0246 (11)	0.0017 (10)
C81	0.0391 (11)	0.0370 (10)	0.0376 (10)	0.0061 (9)	0.0166 (9)	0.0044 (9)
C82	0.0552 (13)	0.0549 (13)	0.0423 (12)	−0.0080 (12)	0.0163 (10)	0.0081 (11)
C83	0.0616 (15)	0.0645 (15)	0.0467 (13)	−0.0164 (12)	0.0086 (11)	−0.0014 (12)
C84	0.0629 (15)	0.0630 (15)	0.0364 (11)	0.0050 (13)	0.0122 (11)	0.0030 (11)
C85	0.0750 (16)	0.0526 (14)	0.0432 (12)	0.0056 (13)	0.0275 (12)	0.0123 (11)
C86	0.0585 (14)	0.0432 (12)	0.0450 (12)	−0.0043 (11)	0.0231 (10)	0.0027 (10)
C91	0.0507 (13)	0.0354 (10)	0.0372 (10)	0.0011 (10)	0.0143 (9)	0.0040 (9)
C92	0.0471 (14)	0.0550 (13)	0.0491 (12)	0.0028 (11)	0.0131 (10)	−0.0005 (11)
C93	0.0479 (15)	0.0834 (18)	0.0709 (16)	0.0079 (14)	0.0205 (13)	0.0019 (15)
C94	0.0451 (15)	0.084 (2)	0.093 (2)	−0.0030 (15)	0.0084 (15)	0.0103 (17)
C95	0.070 (2)	0.0670 (17)	0.0729 (17)	−0.0140 (15)	−0.0023 (15)	−0.0068 (15)
C96	0.0648 (16)	0.0535 (14)	0.0530 (14)	−0.0017 (12)	0.0125 (12)	−0.0055 (11)
C10	0.0717 (17)	0.0556 (14)	0.0643 (15)	−0.0153 (13)	0.0210 (13)	0.0030 (12)

Geometric parameters (Å, º)

O1—C2	1.406 (2)	C56—H56	0.9300
O1—C5	1.427 (2)	C6—C91	1.531 (3)
O3—C2	1.408 (2)	C6—C81	1.538 (3)
O3—C4	1.444 (2)	C6—C7	1.549 (3)
C2—C6	1.531 (3)	C7—H7A	0.9600
C2—H2	0.9800	C7—H7B	0.9600
C4—C41	1.513 (3)	C7—H7C	0.9600
C4—C10	1.519 (3)	C81—C86	1.381 (3)
C4—C5	1.577 (3)	C81—C82	1.385 (3)
C41—C42	1.381 (3)	C82—C83	1.383 (3)
C41—C46	1.379 (3)	C82—H82	0.9300
C42—C43	1.379 (4)	C83—C84	1.364 (3)
C42—H42	0.9300	C83—H83	0.9300
C43—C44	1.369 (4)	C84—C85	1.368 (3)
C43—H43	0.9300	C84—H84	0.9300
C44—C45	1.364 (4)	C85—C86	1.375 (3)
C44—H44	0.9300	C85—H85	0.9300
C45—C46	1.384 (3)	C86—H86	0.9300
C45—H45	0.9300	C91—C92	1.378 (3)
C46—H46	0.9300	C91—C96	1.390 (3)
C5—C51	1.497 (3)	C92—C93	1.378 (3)
C5—H5	0.9800	C92—H92	0.9300
C51—C52	1.374 (3)	C93—C94	1.363 (4)
C51—C56	1.380 (3)	C93—H93	0.9300
C52—C53	1.388 (3)	C94—C95	1.361 (4)
C52—H52	0.9300	C94—H94	0.9300
C53—C54	1.358 (4)	C95—C96	1.379 (3)
C53—H53	0.9300	C95—H95	0.9300
C54—C55	1.368 (4)	C96—H96	0.9300
C54—H54	0.9300	C10—H10A	0.9600
C55—C56	1.380 (3)	C10—H10B	0.9600
C55—H55	0.9300	C10—H10C	0.9600
C2—O1—C5	103.44 (14)	C51—C56—H56	119.9
C2—O3—C4	106.93 (13)	C2—C6—C91	110.44 (15)
O1—C2—O3	104.48 (14)	C2—C6—C81	110.85 (15)
O1—C2—C6	112.05 (16)	C91—C6—C81	111.09 (15)
O3—C2—C6	112.72 (15)	C2—C6—C7	106.33 (15)
O1—C2—H2	109.2	C91—C6—C7	111.39 (16)
O3—C2—H2	109.2	C81—C6—C7	106.59 (15)
C6—C2—H2	109.2	C6—C7—H7A	109.5
O3—C4—C41	108.94 (15)	C6—C7—H7B	109.5
O3—C4—C10	108.30 (16)	H7A—C7—H7B	109.5
C41—C4—C10	113.07 (17)	C6—C7—H7C	109.5
O3—C4—C5	102.18 (14)	H7A—C7—H7C	109.5
C41—C4—C5	113.25 (16)	H7B—C7—H7C	109.5
C10—C4—C5	110.42 (17)	C86—C81—C82	117.24 (18)
C42—C41—C46	118.0 (2)	C86—C81—C6	118.70 (18)
C42—C41—C4	120.7 (2)	C82—C81—C6	124.00 (17)
C46—C41—C4	121.23 (19)	C83—C82—C81	120.9 (2)
C43—C42—C41	121.1 (3)	C83—C82—H82	119.5
C43—C42—H42	119.5	C81—C82—H82	119.5
C41—C42—H42	119.5	C84—C83—C82	120.7 (2)
C44—C43—C42	120.3 (3)	C84—C83—H83	119.7
C44—C43—H43	119.8	C82—C83—H83	119.7
C42—C43—H43	119.8	C83—C84—C85	119.1 (2)
C45—C44—C43	119.3 (3)	C83—C84—H84	120.4
C45—C44—H44	120.3	C85—C84—H84	120.4
C43—C44—H44	120.3	C84—C85—C86	120.4 (2)
C44—C45—C46	120.7 (3)	C84—C85—H85	119.8
C44—C45—H45	119.6	C86—C85—H85	119.8
C46—C45—H45	119.6	C85—C86—C81	121.6 (2)
C41—C46—C45	120.6 (2)	C85—C86—H86	119.2
C41—C46—H46	119.7	C81—C86—H86	119.2
C45—C46—H46	119.7	C92—C91—C96	116.9 (2)
O1—C5—C51	111.34 (17)	C92—C91—C6	121.47 (17)
O1—C5—C4	102.98 (14)	C96—C91—C6	121.64 (19)
C51—C5—C4	117.29 (17)	C91—C92—C93	121.6 (2)
O1—C5—H5	108.3	C91—C92—H92	119.2
C51—C5—H5	108.3	C93—C92—H92	119.2
C4—C5—H5	108.3	C94—C93—C92	120.6 (2)
C52—C51—C56	118.8 (2)	C94—C93—H93	119.7
C52—C51—C5	119.2 (2)	C92—C93—H93	119.7
C56—C51—C5	122.01 (18)	C95—C94—C93	119.1 (2)
C51—C52—C53	120.6 (3)	C95—C94—H94	120.4
C51—C52—H52	119.7	C93—C94—H94	120.4
C53—C52—H52	119.7	C94—C95—C96	120.7 (2)
C54—C53—C52	120.0 (2)	C94—C95—H95	119.7
C54—C53—H53	120.0	C96—C95—H95	119.7
C52—C53—H53	120.0	C95—C96—C91	121.1 (2)
C53—C54—C55	120.0 (2)	C95—C96—H96	119.4
C53—C54—H54	120.0	C91—C96—H96	119.4
C55—C54—H54	120.0	C4—C10—H10A	109.5
C54—C55—C56	120.4 (3)	C4—C10—H10B	109.5
C54—C55—H55	119.8	H10A—C10—H10B	109.5
C56—C55—H55	119.8	C4—C10—H10C	109.5
C55—C56—C51	120.2 (2)	H10A—C10—H10C	109.5
C55—C56—H56	119.9	H10B—C10—H10C	109.5
O1—C2—O3—C4	37.54 (19)	C4—C5—O1—C2	35.48 (18)
C2—O3—C4—C5	−14.20 (18)	C5—O1—C2—O3	−46.16 (18)
O3—C4—C5—O1	−13.06 (18)

Hydrogen-bond geometry (Å, º)

Cg3 and Cg5 are the centroids of the C51–C56 and C91–C96 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C53—H53···O3^i	0.93	2.61	3.533 (3)	170
C85—H85···O1^ii	0.93	2.50	3.411 (3)	167
C46—H46···Cg5	0.93	2.99	3.894 (3)	164
C86—H86···Cg3^ii	0.93	2.91	3.799 (2)	160

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+3/2, z−1/2.