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2015�©�The�Japan�Society�for�Analytical�Chemistry

Troponoids,� being� a� remarkable� class� of� the� non-benzenoid�p-conjugated� system,� have� been� used� as� building� blocks� of�liquid� crystals,� ionophores,� and� dyes.1� � Hinokitiol� is� a�representative� compound� of� troponoid.� � Although� the� crystal�structures� of� hinokitiol,2� 3,7-dibromohinokitiol3� and�5,7-dibromohinokitiol3�have�been�reported,�the�crystal�structure�of� 7-bromo-4-isopropyl-2-(tosyloxy)tropone� (1)� has� not� been�reported.��In�order�to�reveal�the�effect�upon�the�crystal�packing�of� substitutions� at� O2� and� C7� of� hinokitiol,� we� now� report� on�the� structure� of� 7-bromo-4-isopropyl-2-[[(4-methylphenyl)-sulfonyl]oxy]tropone�(1).

Compound� (1)� was� synthesized� by� the� reactions� of�7-bromohinokitiol�and�p-toluenesulfonyl�chloride�in�pyridine,�as�reported�in�a�previous�paper.4� �Single�crystals�of�1�were�grown�in� a� mixture� of� chloroform–ethyl� acetate� (1:1� v/v)� at� room�temperature.��The�data�collection�and�refinement�parameters�are�listed� in� Table� 1.� � The� H� atoms� were� positioned� with� the�idealized�geometry,�and�were�refined� to�be� isotropic� (Uiso(H)�=�1.2Ueq(C))�using�a�riding�model�with�C–H�=�0.95�Å�for�aromatic�H�atoms,�C–H�=�0.98�Å�for�methyl�H�atoms,�and�C–H�=�1.00�Å�for�methine�H�atoms.� �The�selected�bond�distances�and�torsion�angles�are�collected�in�Table�2.

An�ORTEP�drawing�of�the�molecule�of�1� is�shown�in�Fig.�2.��

The� tropone� and� benzene� rings� in� 1� adopt� a� syn� conformation�with� respect� to� each� other.� � The� dihedral� angle� between� the�tropone�plane�(defined�by�O1/C1/C2/C3/C4/C5/C6/C7)�and�the�benzene� plane� (defined� by� C11/C12/C13/C14/C15/C16)� is�54.6(1)˚,�which�is�smaller� than�that�(64.3(1)˚)5�of�2-(tosyloxy)-tropone.� � There� is� an� intramolecular� C–H·p� interaction�observed� in� the� molecular� structure� of� 1� (Table� 3� and� Fig.� 3),�with� some� distance� for� this� type� of� interaction� (2.8� –� 3.1� Å).6��The� tropone� ring� is� nearly� planar;� the� respective� deviations� of�each�atom�from� the� least-squares�plane,�defined�by�O1/C1/C2/

Crystal Structure of 7-Bromo-4-isopropyl-2-[[(4-methylphenyl)sulfonyl]oxy]-tropone

Kanji KUBO*† and Taisuke MATSUMOTO**

*�Department of Life Science and Technology, Faculty of Engineering, Hokkai-Gakuen University, Asahimachi, Toyohira-ku, Sapporo 062-8605, Japan

**�Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan

The� structure� of� 7-bromo-4-isopropyl-2-[[(4-methylphenyl)-sulfonyl]oxy]tropone� was� determined� by� X-ray�crystallography.��It�crystallizes�in�the�space�group�P21/c�(#14)�with�cell�parameters�a�=�9.4884(6)Å,�b�=�9.5235(6)Å,�c�=�18.1540(13)Å,�b�=�95.203(2)˚,�Z�=�4,�and�V�=�1633.7(2)Å3.��The�tropone�and�benzene�rings�in�1�adopt�a�syn�conformation�with� respect� to� each� other.� � Intramolecular� C–H·p� and� intermolecular� C–H·O,� C–H·Br,� and� p·p� interactions� were�observed�in�the�crystal�lattice.

(Received March 19, 2015; Accepted March 31, 2015; Published on web May 10, 2015)

OBrOS

O

OH3C

1

Table 1 Crystal and experimental data

Chemical formula: C17H17BrO4SFormula weight = 397.28T = 123 KCrystal system: Monoclinic Space group: P21/ca = 9.4884(6)Åb = 9.5235(6)Å b = 95.203(2)˚c = 18.1540(13)ÅV = 1633.7(2)Å3 Z = 4Dx = 1.615 g/cm3

Radiation: Mo Ka (l = 0.71075 Å)m(Mo Ka) = 26.682 cm–1 F(0 0 0) = 808Crystal size = 0.100 ¥ 0.060 ¥ 0.030 mm3

No. of re�ections collected = 15210No. of independent re�ections = 37492qmax = 61.5˚ with Mo Ka

Data/Restraints/Parameters = 3749/0/211R indices [I ≥ 2s(I)]: R1 = 0.0486R indices (all data): R1 = 0.0495, wR2 = 0.1211Goodness-of-�t on F2 = 1.395(D/s)max = 0.001(Dr)max = 0.78 eÅ–3 (Dr)min = –1.86 eÅ–3

Measurement: Rigaku Saturn 724 CCD diffractometerData collection & cell re�nement program: CrystalClearData reduction program: CrystalStructure 4.0Structure solving program: SIR2008Structure re�nement program: CRYSTALSCCDC 1054753

Fig. 1 Chemical�diagram�of�the�title�compound�(1).

�†�To�whom�correspondence�should�be�addressed.E-mail:�kubo@lst.hokkai-s-u.ac.jp

30 X-ray�Structure�Analysis�Online�2015,�VOL.�31

C3/C4/C5/C6/C7,� are� –0.002(2),� –0.0015(3),� –0.052(2),�0.041(2),� 0.036(2),� –0.060(2),� –0.008(2),� and� 0.059(2)Å.� � The�C–C�bond�lengths�(Table�2)�of�the�seven-membered�ring�of�1�are�similar� to� those� of� tropone.7� � The� angle� for� C1–C2–C3� of� the�tropone�ring�is�133.3(2)˚,�which�is�slightly�greater�than�those�of�tropone�(130˚,�131˚)7�and�2-(tosyloxy)tropone�(131.6˚).5

Intermolecular�C–H·O�and�C–H·Br�interactions�are�observed�in� the� crystal� structure� of� 1� (Table� 3� and� Fig.� 3).� � The� H·O�distances� are� those� for� this� type� of� interaction� (2.4� –� 2.7� Å).6��The�H·Br�distance�corresponds�quite�well�to�the�respective�sum�(3.05�Å)8�of�the�van�der�Waals�radii.

Intermolecular� p·p� interactions� between� the� tropone� planes�are� shown� in�Fig.� 3.� �The�distance�between� the� intermolecular�tropone�planes�is�3.617(4)Å�for�C5·C7i�(symmetry�code�(i)�–x,�–y,� 2–z),� which� is� within� the� range� associated� with� p·p�interactions� (3.3� –� 3.8� Å).6� � There� is� an� intermolecular� O·O�contact�in�1.��The�distance�is�2.782(2)Å�for�O2·O2iv�(symmetry�code�(iii)�–x,�1–y,�2–z).

These�C–H·O,�C–H·Br,�p·p,�and�C–H·p�interactions�help�to�stabilize�the�crystal�packing.

This� work� was� performed� under� the� Cooperative� Research�Program�of� “Network� Joint�Research�Center� for�Materials� and�Devices� (Institute� for� Materials� Chemistry� and� Engineering,�Kyushu�University)”.

References

� 1.� K.�Kubo,�Oleoscience,�2009,�9,�561.� 2.� K.� Tanaka,� R.� Nagahiro.� S.� Ohba,� and� M.� Eishima,�

Tetrahedron Lett.,�2001,�42,�925.� 3.� S.�Ito,�Y.�Fukazawa,�Tetrahedron Lett.,�1972,�13,�745.� 4.� H.�Takeshita,�B.�Z.�Yin,�K.�Kubo,�and�A.�Mori,�Bull. Chem.

Soc. Jpn.,�1993,�66,�3451.� 5.� P.�W.�Roesky�and�M.�R.�Burgstein,�Inorg. Chem.,�1999,�38,�

5629.� 6.� K.�Kubo�T.�Matsumoto,�and�H.�Takechi,�X-ray�Struc. Anal.

Online,�2014,�30,�23.� 7.� M.�J.�Barrow,�O.�S.�Mills,�and�G.�Filippini,�J. Chem. Soc.

Chem. Commum.,�197,�115.� 8.� A.�Bondi,�J. Phys. Chem.,�1964,�68,�441.

Table 2 Selected bond distances, angles and torsion angles (Å, ˚)

Br1-C7 1.900(3) S1-O2 1.6081(17)S1-O3 1.4240(19) S1-O4 1.4301(18)S1-C11 1.753(3) O1-C1 1.225(3)O2-C2 1.409(3) C1-C2 1.465(4)C1-C7 1.468(4) C2-C3 1.356(3)C3-C4 1.431(3) C4-C5 1.366(4)C5-C6 1.429(4) C6-C7 1.357(4)C4-C8 1.524(3) C8-C9 1.531(4)C8-C10 1.535(4) C11-C12 1.397(4)C11-C16 1.390(4) C12-C13 1.382(4)C13-C14 1.400(4) C14-C15 1.394(4)C14-C17 1.510(4) C15-C16 1.391(4)C2-C1-C7 118.8(2) C1-C2-C3 133.3(2)C2-C3-C4 130.9(3) C3-C4-C5 124.7(2)C4-C5-C6 129.3(3) C5-C6-C7 130.4(3)C1-C7-C6 131.5(3) S1-O2-C2-C1 –95.95(17)S1-O2-C2-C3 92.06(18) C11-S1-O2-C2 –82.30(14)O3-S1-O2-C2 163.65(13) O4-S1-O2-C2 33.69(16)C3-C4-C8-C9 –52.2(3) C3-C4-C8-C10 71.7(3)C5-C4-C8-C9 131.6(2) C5-C4-C8-C10 –104.5(3)

Table 3 Hydrogen bond geometry (Å, ˚) of 1

D-H·A D-H H·A D·A D-H·A

C9-H9A·Cg 0.98 3.096 3.915(3) 142C6-H6·O4i 0.95 2.492 3.318(3) 145C9-H9B·Br1i 0.98 3.005 3.902(3) 153C9-H9C·O1ii 0.98 2.480 3.350(3) 148C10-H10A·O1ii 0.98 2.522 3.387(3) 147C15-H15·O3iii 0.95 2.565 3.231(3) 127

Symmetry codes: (i) –x, –y, 2–z, (ii) 1+x, y, z, (iii) –x, y–1/2, 3/2–z. Cg is the centroid of C11/C12/C13/C14/C15/C16 ring.

Fig. 3 C–H·p,� C–H·O� and� CH·Br� interactions� and� O·O� contact�in�1.� �Symmetry�codes:� (i)�–x,�–y,�2–z,� (ii)�1+x,�y,�z,� (iii)�–x,�y–1/2,�3/2–z,� (iv)� –x,� 1–y,� 2–z.� � Cg� is� the� centroid� of� C11/C12/C13/C14/C15/C16�ring.

Fig. 2 ORTEP�structure�of�1,�showing�50%�probability�ellipsoids.