5-(3,6-Dibromo-9H-carbazol-9-yl)penta-nenitrile.

Abstract

In the title compound, C(17)H(14)Br(2)N(2), the carbazole skeleton is nearly planar [maximum deviation = 0.055 (2) Å]. In the crystal, aromatic π-π stacking is observed between parallel carbazole ring systems of adjacent mol-ecules, the shortest centroid-centroid distance between benzene rings being 3.4769 (11) Å.

Full text

Page 1

5-(3,6-Dibromo-9H-carbazol-9-yl)-
pentanenitrile
Nesimi Uludag ˘,aMurat Ates ¸,aBarıs ¸ Tercanband Tuncer
Ho ¨kelekc*
aDepartment of Chemistry, Faculty of Arts and Sciences, Namık Kemal University,
59030 Deg ˘irmenaltı, Tekirdag ˘, Turkey,bDepartment of Physics, Karabu ¨k University,
78050, Karabu ¨k, Turkey, andcDepartment of Physics, Hacettepe University, 06800
Beytepe, Ankara, Turkey
Correspondence e-mail: merzifon@hacettepe.edu.tr
Received 9 February 2011; accepted 11 February 2011
Key indicators: single-crystal X-ray study; T = 100 K; mean ?(C–C) = 0.003 A ˚;
R factor = 0.023; wR factor = 0.054; data-to-parameter ratio = 20.6.
In the title compound, C17H14Br2N2, the carbazole skeleton is
nearly planar [maximum deviation = 0.055 (2) A˚]. In the
crystal, aromatic ?–? stacking is observed between parallel
carbazole ring systems of adjacent molecules, the shortest
centroid–centroid distance between benzene rings being
3.4769 (11) A˚.
Related literature
For tetrahydrocarbazole systems present in the framework of
a number of indole-type alkaloids of biological interest, see:
Saxton (1983). For related structures and background refer-
ences, see: Patır et al. (1997); Ho ¨kelek & Patır (1999). For
applications of carbazole derivatives, see: Cloutet et al. (1999);
Wei et al. (2006); Tirapattur et al. (2003); Taoudi et al. (2001);
Saraswathi et al. (1999); Sarac et al. (2000).
Experimental
Crystal data
C17H14Br2N2
Mr= 406.10
Monoclinic, P21=n
a = 10.5654 (2) A˚
b = 13.1471 (3) A˚
c = 11.6260 (2) A˚
? = 105.257 (2)?
V = 1557.99 (6) A˚3
Z = 4
Mo K? radiation
? = 5.20 mm?1
T = 100 K
0.34 ? 0.27 ? 0.24 mm
Data collection
Bruker Kappa APEXII CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
Tmin= 0.201, Tmax= 0.286
15409 measured reflections
3906 independent reflections
3344 reflections with I > 2?(I)
Rint= 0.022
Refinement
R[F2> 2?(F2)] = 0.023
wR(F2) = 0.054
S = 1.04
3906 reflections
190 parameters
H-atom parameters constrained
??max= 0.52 e A˚?3
??min= ?0.36 e A˚?3
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT
(Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick,
ORTEP-3 for Windows (Farrugia, 1997); software used to prepare
material for publication: WinGX (Farrugia, 1999) and PLATON
(Spek, 2009).
2008); molecular graphics:
The authors are indebted to Anadolu University and the
Medicinal Plants and Medicine Research Centre of Anadolu
University, Eskis ¸ehir, Turkey, for the use of X-ray diffract-
ometer. This work was supported financially by the Turkish
Scientific Research Council (grant No. TUBITAK-105 T516).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: XU5160).
References
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Cloutet, E., Yammine, P., Ades, D. & Siove, A. (1999). Synth. Met. 102, 1302–
1303.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Ho ¨kelek, T. & Patır, S. (1999). Acta Cryst. C55, 675–677.
Patır, S., Okay, G., Gu ¨lce, A., Salih, B. & Ho ¨kelek, T. (1997). J. Heterocycl.
Chem. 34, 1239–1242.
Sarac, A. S., Yavuz, O. & Sezer, E. (2000). Polymer, 41, 839–847.
Saraswathi, R., Gerard, M. & Malhotra, B. D. (1999). J. Appl. Polym. Sci. 74,
145–150.
Saxton, J. E. (1983). Editor. Heterocyclic Compounds, Vol. 25, The
Monoterpenoid Indole Alkaloids, ch. 8 and 11. New York: Wiley.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Taoudi, H., Bernede, J. C., Del Valle, M. A., Bonnet, A. & Morsli, M. (2001). J.
Mater. Sci. 36, 631–634.
Tirapattur, S., Belletete, M., Drolet, N., Leclerc, M. & Durocher, G. (2003).
Chem. Phys. Lett. 370, 799–804.
Wei, Z.-H., Xu, J.-K., Nie, G.-M., Du, Y.-K. & Pu, S.-Z. (2006). J. Electroanal.
Chem. 589, 112–119.
organic compounds
o642
Uludag ˘ et al.
doi:10.1107/S1600536811005162
Acta Cryst. (2011). E67, o642
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

Page 2

supplementary materials

Page 3

supplementary materials
sup-1
Acta Cryst. (2011). E67, o642 [ doi:10.1107/S1600536811005162 ]
5-(3,6-Dibromo-9H-carbazol-9-yl)pentanenitrile
N. Uludag, M. Ates, B. Tercan and T. Hökelek
Comment
Tetrahydrocarbazole systems are present in the framework of a number of indole-type alkaloids of biological interest (Saxton,
1983). The structures of tricyclic, tetracyclic and pentacyclic ring systems with dithiolane and other substituents of the
tetrahydrocarbazole core, have been reported previously (Patır et al., 1997; Hökelek & Patır, 1999). Substituted carbazole
based monomers exhibit good electroactive and photoactive properties which make them the most promising candidates for
hole transporting mobility of charge carriers (Cloutet et al., 1999) and photoluminescence efficiencies (Wei et al., 2006).
Carbazole based heterocyclic polymer systems can be chemically or electrochemically polymerized to yield materials with
interesting properties with a number of applications, such as electroluminescent (Tirapattur et al., 2003), photoactive devices
(Taoudi et al., 2001), sensors and rechargable batteries (Saraswathi et al., 1999) and electrochromic displays (Sarac et al.,
2000). The title compound, (I), may be considered as a synthetic precursor of tetracyclic indole alkaloids of biological
interests. The present study was undertaken to ascertain its crystal structure.
The title compound consists of a carbazole skeleton with a pentanenitrile group (Fig. 1), where the bond lengths and
angles are within normal ranges, and generally agree with those in the previously reported compounds. In all structures
atom N9 is substituted.
An examination of the deviations from the least-squares planes through individual rings shows that rings A (C1—C4/
C4a/C9a), B (C4a/C5a/C8a/N9/C9a) and C (C5a/C5—C8/C8a) are planar. The carbazole skeleton, containing the rings A,
B and C is also nearly coplanar [with a maximum deviation of 0.055 (2) Å for atom C2] with dihedral angles of A/B =
2.10 (6), A/C = 2.79 (5) and B/C = 0.69 (5) °. Atoms Br1, C10 and Br2 displaced by 0.0476 (2), 0.062 (2) and 0.0052 (2)
Å from the corresponding planes of the carbazole skeleton.
In the crystal structure, molecules are alongated along the b axis and stacked nearly parallel to (101) (Fig. 2). The π···π
contacts between the pyrrole and benzene rings and the benzene rings, Cg2—Cg3i and Cg3···Cg3i [symmetry code: (i)
-x, 1 - y, -z, where Cg1, Cg2 and Cg3 are centroids of the rings A (C1—C4/C4a/C9a), B (C4a/C5a/C8a/N9/C9a) and C
(C5a/C5—C8/C8a), respectively] may stabilize the structure, with centroid-centroid distances of 3.548 (1) and 3.4769 (11)
Å, respectively.
Experimental
For the preparation of the title compound, (I), sodium hydride (1.16 g, 30.76 mmol) was added to a solution of 3,6-dibromo-
carbazole (5.00 g, 15.38 mmol) in dry tetrahydrofuran (200 ml) in several portions, and stirred at 353 K for 2 h under argon
atmosphere. Then, chlorovaleronitrile (3.46 ml, 30.76 mmol) was added and stirred at 373 K for 6 d. The reaction mixture
was cooled in an ice bath, and hydrochloric acid (10%, 200 ml) was added. After the extraction with chloroform (300 ml),
the organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure. The
residue was purified by column chromatography using silica gel and chloroform, and the product was recrystallized from
diethyl ether (yield 4.50 g, 80.12%; m.p. 327 K).

Page 4

supplementary materials
sup-2
Refinement
H atoms were positioned geometrically with C—H = 0.95 and 0.99 Å for aromatic and methylene H atoms, respectively,
and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Figures
Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. The
displacement ellipsoids are drawn at the 50% probability level.
Fig. 2. A partial packing diagram. Hydrogen atoms have been omitted for clarity.
5-(3,6-Dibromo-9H-carbazol-9-yl)pentanenitrile
Crystal data
C17H14Br2N2
F(000) = 800
Dx = 1.731 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 6957 reflections
θ = 2.3–28.3°
µ = 5.20 mm−1
T = 100 K
Block, colorless
Mr = 406.10
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 10.5654 (2) Å
b = 13.1471 (3) Å
c = 11.6260 (2) Å
β = 105.257 (2)°
V = 1557.99 (6) Å3
Z = 4
0.34 × 0.27 × 0.24 mm
Data collection
Bruker Kappa APEXII CCD area-detector
diffractometer
3906 independent reflections

Page 5

supplementary materials
sup-3
Radiation source: fine-focus sealed tube
graphite
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
Tmin = 0.201, Tmax = 0.286
15409 measured reflections
3344 reflections with I > 2σ(I)
Rint = 0.022
θmax = 28.4°, θmin = 2.3°
h = −14→12
k = −17→16
l = −15→15
Refinement
Refinement on F2
Primary atom site location: structure-invariant direct
methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring
sites
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.023
wR(F2) = 0.054
H-atom parameters constrained
S = 1.04
w = 1/[σ2(Fo2) + (0.0246P)2 + 0.8394P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.52 e Å−3
Δρmin = −0.36 e Å−3
3906 reflections
190 parameters
0 restraints
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 mat-
rix. 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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-
factors(gt) etc. 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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
1.00971 (2)
0.636774 (19)
0.6131 (2)
0.5468
0.7401 (2)
0.7622
0.83635 (18)
0.81077 (18)
0.8771
0.68395 (18)
0.66897 (18)
y
0.746932 (15)
1.287581 (14)
0.78706 (15)
0.7526
0.75033 (15)
0.6904
0.80073 (14)
0.88872 (14)
0.9213
0.92805 (13)
1.09921 (13)
z
0.392293 (17)
0.589087 (17)
0.22924 (16)
0.1712
0.26348 (16)
0.2274
0.35103 (16)
0.40557 (15)
0.4655
0.36933 (15)
0.47909 (15)
Uiso*/Ueq
0.02544 (6)
0.02193 (6)
0.0211 (4)
0.025*
0.0210 (4)
0.025*
0.0190 (4)
0.0172 (4)
0.021*
0.0157 (3)
0.0160 (3)
Br1
Br2
C1
H1
C2
H2
C3
C4
H4
C4A
C5

Page 6

supplementary materials
sup-4
H5
C5A
C6
C7
H7
C8
H8
C8A
C9A
N9
N10
C10
H10A
H10B
C11
H11A
H11B
C12
H12A
H12B
C13
H13A
H13B
C14
0.7573
0.62282 (17)
0.58032 (18)
0.44886 (19)
0.3913
0.40232 (18)
0.3130
0.49060 (18)
0.58570 (18)
0.46917 (15)
−0.06092 (19)
0.34532 (18)
0.2718
0.3428
0.32683 (18)
0.3385
0.3944
0.19112 (18)
0.1235
0.1810
0.17058 (19)
0.1815
0.2388
0.0405 (2)
1.1017
1.01868 (14)
1.17500 (14)
1.17234 (15)
1.2259
1.09231 (15)
1.0893
1.01611 (14)
0.87634 (14)
0.92922 (12)
0.97527 (16)
0.90394 (15)
0.9203
0.8299
0.96151 (14)
1.0353
0.9395
0.94248 (15)
0.9614
0.8692
1.00466 (16)
1.0778
0.9857
0.98855 (16)
0.5261
0.40085 (14)
0.48494 (15)
0.41908 (16)
0.4268
0.34294 (16)
0.2984
0.33353 (15)
0.28268 (15)
0.26366 (13)
−0.28226 (17)
0.17760 (16)
0.2125
0.1615
0.06050 (16)
0.0771
0.0208
−0.02221 (15)
0.0189
−0.0421
−0.13739 (16)
−0.1169
−0.1778
−0.21986 (17)
0.019*
0.0152 (3)
0.0177 (4)
0.0196 (4)
0.024*
0.0193 (4)
0.023*
0.0168 (4)
0.0175 (4)
0.0185 (3)
0.0359 (4)
0.0208 (4)
0.025*
0.025*
0.0189 (4)
0.023*
0.023*
0.0193 (4)
0.023*
0.023*
0.0234 (4)
0.028*
0.028*
0.0247 (4)
Atomic displacement parameters (Å2)
U11
0.02541 (11)
0.02582 (11)
0.0282 (10)
0.0304 (11)
0.0194 (9)
0.0198 (9)
0.0202 (9)
0.0169 (9)
0.0165 (9)
0.0241 (10)
0.0205 (9)
0.0167 (9)
0.0195 (9)
0.0208 (9)
0.0186 (8)
0.0297 (11)
0.0199 (10)
0.0192 (9)
0.0186 (9)
0.0240 (10)
U22
0.02488 (11)
0.01562 (10)
0.0212 (10)
0.0171 (9)
0.0205 (10)
0.0190 (9)
0.0164 (9)
0.0167 (9)
0.0177 (9)
0.0140 (9)
0.0193 (9)
0.0233 (10)
0.0182 (9)
0.0195 (9)
0.0212 (8)
0.0438 (12)
0.0229 (10)
0.0196 (10)
0.0216 (10)
0.0257 (11)
U33
0.02659 (10)
0.02420 (10)
0.0139 (8)
0.0174 (9)
0.0184 (9)
0.0131 (8)
0.0111 (8)
0.0145 (8)
0.0123 (8)
0.0155 (8)
0.0204 (9)
0.0173 (9)
0.0124 (8)
0.0129 (8)
0.0138 (7)
0.0288 (10)
0.0177 (9)
0.0169 (8)
0.0166 (8)
0.0184 (9)
U12
0.00894 (8)
−0.00012 (7)
−0.0040 (8)
0.0008 (8)
0.0034 (7)
−0.0001 (7)
−0.0023 (7)
−0.0004 (7)
−0.0001 (7)
−0.0021 (7)
0.0054 (7)
0.0010 (7)
−0.0013 (7)
−0.0009 (7)
−0.0016 (6)
−0.0051 (9)
−0.0049 (7)
−0.0014 (7)
−0.0030 (7)
−0.0050 (8)
U13
0.00780 (8)
0.00630 (8)
0.0054 (7)
0.0096 (8)
0.0072 (7)
0.0050 (7)
0.0051 (7)
0.0046 (7)
0.0052 (7)
0.0059 (7)
0.0077 (7)
0.0033 (7)
0.0036 (7)
0.0054 (7)
0.0010 (6)
−0.0018 (8)
0.0015 (7)
0.0030 (7)
0.0029 (7)
0.0017 (7)
U23
−0.00022 (8)
−0.00316 (7)
−0.0019 (7)
−0.0014 (7)
0.0033 (7)
0.0014 (6)
0.0003 (6)
0.0019 (6)
0.0034 (6)
−0.0002 (6)
0.0052 (7)
0.0037 (7)
0.0030 (6)
0.0019 (6)
−0.0002 (6)
0.0102 (8)
0.0004 (7)
0.0022 (7)
0.0005 (7)
0.0035 (7)
Br1
Br2
C1
C2
C3
C4
C4A
C5
C5A
C6
C7
C8
C8A
C9A
N9
N10
C10
C11
C12
C13

Page 7

supplementary materials
sup-5
C14 0.0279 (11) 0.0258 (11) 0.0197 (9)−0.0012 (8)0.0048 (8)0.0053 (8)
Geometric parameters (Å, °)
Br1—C3
Br2—C6
C1—H1
C2—C1
C2—H2
C3—C2
C4—C3
C4—H4
C4A—C4
C4A—C5A
C5—C5A
C5—H5
C5A—C8A
C6—C5
C6—C7
C7—H7
C8—C7
C8—H8
C8A—C8
1.9033 (19)
1.9059 (18)
0.9500
1.382 (3)
0.9500
1.402 (3)
1.380 (3)
0.9500
1.394 (3)
1.448 (2)
1.397 (2)
0.9500
1.411 (3)
1.381 (3)
1.399 (3)
0.9500
1.380 (3)
0.9500
1.393 (3)
C9A—C1
C9A—C4A
N9—C8A
N9—C9A
N9—C10
N10—C14
C10—H10A
C10—H10B
C11—C10
C11—H11A
C11—H11B
C12—C11
C12—H12A
C12—H12B
C13—C12
C13—H13A
C13—H13B
C14—C13
1.394 (3)
1.416 (2)
1.385 (2)
1.380 (2)
1.461 (2)
1.138 (3)
0.9900
0.9900
1.525 (2)
0.9900
0.9900
1.522 (3)
0.9900
0.9900
1.535 (2)
0.9900
0.9900
1.470 (3)
C2—C1—C9A
C2—C1—H1
C9A—C1—H1
C1—C2—C3
C1—C2—H2
C3—C2—H2
C2—C3—Br1
C4—C3—Br1
C4—C3—C2
C3—C4—C4A
C3—C4—H4
C4A—C4—H4
C4—C4A—C5A
C4—C4A—C9A
C9A—C4A—C5A
C5A—C5—H5
C6—C5—C5A
C6—C5—H5
C5—C5A—C4A
C5—C5A—C8A
C8A—C5A—C4A
C5—C6—Br2
C5—C6—C7
C7—C6—Br2
C6—C7—H7
C8—C7—C6
117.75 (18)
121.1
121.1
120.53 (17)
119.7
119.7
118.28 (14)
119.19 (15)
122.51 (18)
117.46 (17)
121.3
121.3
133.33 (17)
120.22 (16)
106.44 (16)
121.5
116.97 (17)
121.5
133.30 (17)
120.28 (16)
106.41 (16)
119.25 (14)
122.91 (17)
117.83 (14)
119.8
120.35 (17)
N9—C8A—C8
C1—C9A—C4A
N9—C9A—C1
N9—C9A—C4A
C8A—N9—C10
C9A—N9—C8A
C9A—N9—C10
N9—C10—C11
N9—C10—H10A
N9—C10—H10B
C11—C10—H10A
C11—C10—H10B
H10A—C10—H10B
C10—C11—H11A
C10—C11—H11B
C12—C11—C10
C12—C11—H11A
C12—C11—H11B
H11A—C11—H11B
C11—C12—C13
C11—C12—H12A
C11—C12—H12B
C13—C12—H12A
C13—C12—H12B
H12A—C12—H12B
C12—C13—H13A
129.03 (17)
121.49 (17)
129.35 (18)
109.16 (16)
124.59 (16)
108.68 (15)
126.55 (16)
112.32 (15)
109.1
109.1
109.1
109.1
107.9
109.4
109.4
111.13 (15)
109.4
109.4
108.0
110.92 (15)
109.5
109.5
109.5
109.5
108.0
109.1

Page 8

supplementary materials
sup-6
C8—C7—H7
C7—C8—C8A
C7—C8—H8
C8A—C8—H8
C8—C8A—C5A
C1—C9A—C4A
N9—C8A—C5A
119.8
117.78 (17)
121.1
121.1
121.68 (17)
121.49 (17)
109.28 (16)
C12—C13—H13B
C14—C13—C12
C14—C13—H13A
C14—C13—H13B
H13A—C13—H13B
N10—C14—C13
109.1
112.69 (16)
109.1
109.1
107.8
178.9 (2)
C3—C2—C1—C9A
Br1—C3—C2—C1
C4—C3—C2—C1
C4A—C4—C3—Br1
C4A—C4—C3—C2
C5A—C4A—C4—C3
C9A—C4A—C4—C3
C4—C4A—C5A—C5
C4—C4A—C5A—C8A
C9A—C4A—C5A—C5
C9A—C4A—C5A—C8A
C6—C5—C5A—C4A
C6—C5—C5A—C8A
C4A—C5A—C8A—N9
C4A—C5A—C8A—C8
C5—C5A—C8A—N9
C5—C5A—C8A—C8
Br2—C6—C5—C5A
C7—C6—C5—C5A
Br2—C6—C7—C8
C5—C6—C7—C8
C8A—C8—C7—C6
1.4 (3)
−179.17 (14)
−0.9 (3)
177.36 (12)
−0.9 (3)
−176.78 (17)
2.1 (2)
−0.1 (3)
−179.90 (18)
−179.15 (17)
1.08 (18)
179.22 (17)
−1.0 (2)
0.02 (18)
179.44 (15)
−179.80 (14)
−0.4 (2)
−179.64 (12)
1.6 (2)
−179.52 (13)
−0.7 (3)
−0.7 (3)
N9—C8A—C8—C7
C5A—C8A—C8—C7
N9—C9A—C1—C2
C4A—C9A—C1—C2
N9—C9A—C4A—C4
N9—C9A—C4A—C5A
C1—C9A—C4A—C4
C1—C9A—C4A—C5A
C9A—N9—C8A—C5A
C9A—N9—C8A—C8
C10—N9—C8A—C5A
C10—N9—C8A—C8
C8A—N9—C9A—C1
C8A—N9—C9A—C4A
C10—N9—C9A—C1
C10—N9—C9A—C4A
C8A—N9—C10—C11
C9A—N9—C10—C11
C12—C11—C10—N9
C13—C12—C11—C10
C14—C13—C12—C11
−179.45 (16)
1.3 (2)
179.02 (17)
−0.1 (3)
179.02 (15)
−1.80 (18)
−1.7 (3)
177.48 (15)
−1.15 (19)
179.49 (17)
−176.60 (15)
4.0 (3)
−177.36 (17)
1.85 (19)
−2.0 (3)
177.18 (15)
79.5 (2)
−95.1 (2)
−173.89 (15)
177.23 (16)
−179.95 (17)

Page 9

supplementary materials
sup-7
Fig. 1

Page 10

supplementary materials
sup-8
Fig. 2