Z. Kristallogr. NCS 228 (2013) 23-24 / DOI 10.1524/ncrs.2013.0078
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© by Oldenbourg Wissenschaftsverlag, München
Redetermination of the structure of 9,10-dibromoanthracene, C14H8Br2 Arun M. IsloorI, A. M. VijeshII, Thomas GerberIII, Eric HostenIII and Richard Betz*, III I
National Institute of Technology-Karnataka, Department of Chemistry, Medicinal Chemistry Laboratory, Surathkal, Mangalore 575 025, India GITAM University, Department of Engineering Chemistry, GIT, Rushikonda, Visakhapatnam, A.P. 530 045, India III Nelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa II
Received October 11, 2012, accepted December 03, 2012, available online March 01, 2013, CCDC no. 1267/3933
Abstract C14H8Br2, triclinic, P1 (no. 2), a = 4.0107(1) Å, b = 8.8373(3) Å, c = 16.1148(5) Å, ' = 78.658(2)°, & = 83.321(1)°, # = 80.259(1)°, V = 549.9 Å3, Z = 2, Rgt(F) = 0.0211, wRref(F2) = 0.0526, T = 200 K. Table 1. Data collection and handling. Crystal: Wavelength: *: Diffractometer, scan mode: 2(max: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs:
green needles, size 0.09#0.10#0.48 mm Mo K! radiation (0.71073 Å) 73.34 cm"1 Bruker APEX-II CCD, ! and " 56.5° 9398, 2678 Iobs > 2 %(Iobs), 2418 145 SHELX [7], ORTEP-3 [8], MERCURY [9], PLATON [10]
Source of material Bromine (5.67 g, 0.035 mol) was added dropwise to a pre-cooled solution of anthracene (3.0 g, 0.017 mol) in carbon tetrachloride (30 mL). When the bromine has been added, the mixture was gently warmed on a steam bath with continuous stirring for one hour. The mixture is then allowed to cool for some hours, without stirring, and the crude dibromoanthracene is filtered off, washed with a little cold carbon tetrachloride, and dried [6]. The crude product was recrystallized from ethanol, yield: 4.25 g (75 %). Experimental details Carbon-bound H atoms were placed in calculated positions (C–H 0.95 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2 Ueq(C). Discussion Anthracene is a tricyclic aromatic hydrocarbon derived from coal tar and is a basic substance for the production of anthraquinone, dyes, pigments, insecticides, wood preservatives and coating ma-
terials. Anthracene is also used for the preparation of conjugated polymers [1]. It forms reversible photodimers through the 9-,10positions in response to light and provides photochromic applications. Due to )-electron cloud overlaps, anthracene exhibits semiconductor properties. Derivatives of anthracene have been investigated as organic electroluminescence materials for applications in organic solar cells, biosensitizers and display devices such as OLEDs (Organic Light Emiting Diode) [2]. Although the literature mentions three reports about the structure of the title compound, these either do not provide atomic coordinates at all [3], do not take into account hydrogen atom positions [4] or were just conducted at room temperature [5], the latter finding being valid for all previous studies. At the beginning of a comprehensive study about structural features of 9,10disubstituted anthracene derivatives this situation was found to be unsatisfactory with regards to comparisons of metrical features among the different compounds to be researched. Keeping in view the importance of the title compound in synthetic chemistry as well as its OLED applications, we hereby report its crystal structure, determined at 200 K. The asymmetric unit contains two half molecules. Both completed molecules are essentially planar, the discrete least-squares planes defined by the respective carbon atoms of the "outer" phenyl moieties in both molecules intersect at angles of 0.57(11)° and 0.88(10)°. The two molecules are orientated neither parallel nor perpendicular to each other, the least-squares planes defined by the carbon atoms of each of the two completed molecules intersect at an angle of 44.92(5)°. The bromine atoms are displaced by 0.063(1) Å and -0.064(1) Å, respectively, from the latter least-squares planes. These nearly identical values differ significantly from the values reported in the literature where a markedly higher as well as a markedly lower value for the displacement of the two halogen atoms is given [5]. The crystal structure does not show any intermolecular contacts whose range is marked by a shortening of sum of vander-Waals radii of atoms. The shortest intercentroid distance between two aromatic systems was found at 3.5712(12) Å and is apparent between one of the "outer" and the "inner" aromatic system in one of the two molecules. A comparable situation is at hand for the second molecule in the asymmetric unit with the shortest inter centroid di stance located between th e corresponding aromatic systems as in the first molecule, however, the shortest distance here was measured at 3.7476(11) Å. The closest interaction between two intercentroid distances located on the two different molecules was measured at 5.9635(12) Å and is found between two of the "outer" phenyl moieties.
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* Correspondence author (e-mail:
[email protected])
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C14H8Br2
Table 2. Atomic coordinates and displacement parameters (in Å2).
Table 2. continued.
Atom
Site
Uiso
Atom
Site
x
y
z
Uiso
H(11) H(12) H(16) H(17)
2i 2i 2i 2i
0.045 0.038 0.038 0.045
H(21) H(22) H(23) H(24)
2i 2i 2i 2i
0.2515 0.5809 0.6970 0.4759
0.1169 0.1221 0.3602 0.5930
0.4782 0.3519 0.2683 0.3115
0.030 0.036 0.036 0.030
x
y
"0.2065 "0.0388 0.6528 "0.0120
z
0.4604 0.3298 "0.1267 0.3598
"0.0911 0.0382 0.2096 "0.2152
Table 3. Atomic coordinates and displacement parameters (in Å2). Atom
Site
Br(1) C(11) C(12) C(13) C(14) C(15) C(16) C(17) Br(2) C(21) C(22) C(23) C(24) C(25) C(26) C(27)
2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i 2i
x 0.24494(6) "0.0561(6) 0.0443(5) 0.2731(5) 0.3892(5) 0.6099(5) 0.7262(5) 0.0599(6) 0.14411(5) 0.2919(5) 0.4885(5) 0.5574(5) 0.4249(5) 0.2111(4) 0.0629(5) "0.1441(4)
y 0.14632(3) 0.3645(3) 0.2875(2) 0.1435(2) 0.0607(2) "0.0805(2) "0.1664(3) 0.3040(3) 0.83255(2) 0.2144(2) 0.2173(2) 0.3600(3) 0.4978(2) 0.5013(2) 0.6403(2) 0.6445(2)
z 0.17297(1) "0.0878(2) "0.0114(1) "0.0040(1) 0.0730(1) 0.0800(1) 0.1588(1) "0.1621(2) 0.37979(1) 0.4449(1) 0.3705(1) 0.3202(1) 0.3456(1) 0.4226(1) 0.4499(1) 0.5258(1)
U11
U22
U33
0.0455(1) 0.031(1) 0.030(1) 0.0236(9) 0.0260(9) 0.0246(9) 0.032(1) 0.035(1) 0.0347(1) 0.0291(9) 0.032(1) 0.028(1) 0.0242(9) 0.0197(8) 0.0231(8) 0.0207(8)
0.0465(1) 0.026(1) 0.026(1) 0.0230(9) 0.0289(9) 0.0256(9) 0.038(1) 0.039(1) 0.0176(1) 0.0170(8) 0.026(1) 0.037(1) 0.0264(9) 0.0202(8) 0.0153(8) 0.0163(8)
0.0289(1) 0.054(1) 0.041(1) 0.028(1) 0.0219(9) 0.0229(9) 0.025(1) 0.036(1) 0.0345(1) 0.031(1) 0.035(1) 0.027(1) 0.0233(9) 0.0201(8) 0.0230(9) 0.0234(9)
Acknowledgments. A. M. I. is thankful to the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India for a 'Young scientist' award.
References 1. Egbe, D. A. M.; Türk, S.; Rathgeber, S.; Kühnlenz, F.; Jadhav, R.; Wild, A.; Birckner, E.; Adam, G.; Pivrikas, A.; Cimrova, V.; Knör, G.; Sariciftci, N. S.; Hoppe, H.: Anthracene Based Conjugated Polymers: Correlation between )$)-Stacking Ability, Photophysical Properties, Charge Carrier Mobility, and Photovoltaic Performance. Macromolecules 43 (2010) 1261-1269. 2. Park, H.; Lee, J.; Kang, I.; Chu, H. Y.; Lee, J.-I.; Kwon, S.-K.; Kim, Y.-H.: Highly rigid and twisted anthracene derivatives: a strategy for deep blue OLED materials with theoretical limit efficiency. J. Mater. Chem. 22 (2012) 2695-2700. 3. Kitaigorodskij, A. I.: CSD-Ref Code: DBANTH. Acta Physicochim. (USSR) 21 767.
U12 "0.0048(1) "0.0055(9) "0.0060(8) "0.0096(7) "0.0104(8) "0.0119(7) "0.0121(9) "0.0133(9) "0.00545(7) "0.0003(7) 0.0051(8) "0.0005(8) "0.0032(7) "0.0027(7) "0.0031(6) "0.0015(6)
U13 0.00120(9) "0.010(1) "0.0027(9) "0.0007(7) 0.0014(7) "0.0014(7) "0.0043(8) "0.0118(9) "0.00236(8) "0.0091(8) "0.0075(8) "0.0018(8) "0.0046(7) "0.0080(7) "0.0079(7) "0.0080(7)
U23 "0.0158(1) 0.0016(9) "0.0068(8) "0.0029(7) "0.0068(7) "0.0004(7) 0.0007(8) 0.0111(9) 0.00392(7) "0.0061(7) "0.0139(8) "0.0108(8) "0.0019(7) "0.0024(6) 0.0003(6) "0.0044(7)
4. Trotter, J.: The crystal structures of some anthracene derivatives. II. 9:10Dibromoanthracene. Acta Crystallogr. (1958) 803-807 5. Trotter, J.: Refinements of the structures of 9,10-dibromo- and 9,10dichloroanthracene Acta Crystallogr. C42 (1986) 862-864. 6. Heilbron, M; Heaton, J. S.: 9,10-Dibromoanthracene. Organic Synthesis Coll. 1 (1941) 207-208. 7. Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112-122. 8. Farrugia, L. J.: ORTEP-3 for Windows - a version of ORTEP-III with a Graphical User Interface (GUI) J. Appl. Crystallogr. 30 (1997) 565. 9. Macrae, C. F.; Bruno, I. J.; Chisholm, J. A.; Edgington, P. R.; McCabe, P.; Pidcock, E.; Rodriguez-Monge, L.; Taylor, R.; van de Streek, J.; Wood, P.A.: MERCURY CSD 2.0— new features for the visualization and investigation of crystal structures. J. Appl. Crystallogr. 41 (2008) 466-470. 10. Spek, A. L.: Single-crystal structure validation with the program PLATON. J. Appl. Crystallogr. 36 (2003) 7-13.
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