4-[(4-Bromo-phenyl)amino]-2-methyl-idene-4-oxo-butanoic acid. - PDF Download Free (2024)

organic compounds = 5.04 mm1 T = 173 K

Acta Crystallographica Section E

Structure Reports Online

0.44 0.28 0.14 mm

Data collection

ISSN 1600-5368

4-[(4-Bromophenyl)amino]-2-methylidene-4-oxobutanoic acid

Agilent Eos Gemini diffractometer Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012) Tmin = 0.162, Tmax = 1.000

7163 measured reflections 4131 independent reflections 3490 reflections with I > 2(I) Rint = 0.033

Refinement

B. Narayana,a Prakash S. Nayak,a Balladka K. Sarojinib and Jerry P. Jasinskic* a

Department of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, bDepartment of Studies in Chemistry, Industrial Chemistry Section, Mangalore University, Mangalagangotri 574 199, India, and cDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA Correspondence e-mail: [emailprotected]

R[F 2 > 2(F 2)] = 0.076 wR(F 2) = 0.227 S = 1.03 4131 reflections

Table 1 ˚ , ). Hydrogen-bond geometry (A D—H A

Received 28 May 2014; accepted 3 June 2014

i

˚; Key indicators: single-crystal X-ray study; T = 173 K; mean (C–C) = 0.008 A R factor = 0.076; wR factor = 0.227; data-to-parameter ratio = 14.2.

In the title compound, C11H10BrNO3, two independent molecules (A and B) crystallize in the asymmetric unit. The dihedral angles between the mean planes of the 4-bromophenyl ring and amide group are 24.8 (7) in molecule A and 77.1 (6) in molecule B. The mean plane of the methylidene group is further inclined by 75.6 (4) in molecule A and 72.5 (6) in molecule B from that of the amide group. In the crystal, N—H O hydrogen bonds formed by amide groups and O—H O hydrogen bonds formed by carboxylic acid groups are observed and supported additionally by weak C— H O interactions between the methylidene and amide groups. Together, these link the molecules into chains of dimers along [110] and form R22(8) graph-set motifs.

Related literature For the pharmacological activity of amide derivatives, see: Galanakis et al. (2004); Kumar & Knaus (1993); Ban et al. (1998); Ukrainets et al. (2006), Lesyk & Zimenkovsky (2004); Gududuru et al. (2004). For related structures, see: Nayak et al. (2013a,b). For standard bond lengths, see: Allen et al. (1987).

Experimental Crystal data C11H10BrNO3 Mr = 284.11 Triclinic, P1 ˚ a = 6.2782 (4) A ˚ b = 8.3251 (5) A ˚ c = 21.3244 (12) A

Acta Cryst. (2014). E70, o779–o780

= 96.462 (5) = 92.026 (5) = 95.390 (5) ˚3 V = 1101.38 (11) A Z=4 Cu K radiation

291 parameters H-atom parameters constrained ˚ 3 max = 2.73 e A ˚ 3 min = 0.79 e A

O3A—H3A O2B N1A—H1A O1Bii O3B—H3B O2Aiii N1B—H1B O1Aiv C5B—H5BB O1Av

D—H

H A

D A

D—H A

0.84 0.88 0.84 0.88 0.95

1.85 2.06 1.82 2.04 2.54

2.685 (5) 2.933 (5) 2.654 (5) 2.848 (6) 3.464 (7)

174 170 170 152 164

Symmetry codes: (i) x; y; z 1; (ii) x þ 1; y þ 1; z þ 1; (iii) x; y; z þ 1; (iv) x þ 2; y þ 2; z þ 1; (v) x þ 1; y þ 2; z þ 1.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus et al., 2012); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2.

BN thanks the UGC for financial assistance through a BSR one-time grant for the purchase of chemicals. PSN thanks Mangalore University for research facilities and DST–PURSE financial assistance. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer. Supporting information for this paper is available from the IUCr electronic archives (Reference: BT6983).

References Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England. Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. Ban, M., Taguchi, H., Katushima, T., Takahashi, M., Shinoda, K., Watanabe, A. & Tominaga, T. (1998). Bioorg. Med. Chem. 6, 1069–1076. Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Galanakis, D., Kourounakis, A. P., Tsiakitzis, K. C., Doulgkeris, C., Rekka, E. A., Gavalas, A., Kravaritou, C., Christos, C. & Kourounakis, P. N. (2004). Bioorg. Med. Chem. Lett. 14, 3639–3643. Gududuru, V., Hurh, E., Dalton, J. T. & Miller, D. D. (2004). Bioorg. Med. Chem. Lett. 14, 5289–5293. Kumar, P. & Knaus, E. E. (1993). Eur. J. Med. Chem. 28, 881–885. Lesyk, R. & Zimenkovsky, B. (2004). Curr. Org. Chem. 8, 1547–1578. Nayak, P. S., Narayana, B., Jasinski, J. P., Yathirajan, H. S. & Kaur, M. (2013b). Acta Cryst. E69, o1752. Nayak, P. S., Narayana, B., Yathirajan, H. S., Gerber, T., van Brecht, B. & Betz, R. (2013a). Acta Cryst. E69, o83.

doi:10.1107/S1600536814012872

Narayana et al.

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organic compounds Palatinus, L., Prathapa, S. J. & van Smaalen, S. (2012). J. Appl. Cryst. 45, 575– 580. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

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C11H10BrNO3

Ukrainets, I. V., Sidorenko, L. V., Petrushovo, L. A. & Gorokhova, O. V. (2006). Chem. Heterocycl. Comput. 42, 64–69.

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supporting information

supporting information Acta Cryst. (2014). E70, o779–o780

[doi:10.1107/S1600536814012872]

4-[(4-Bromophenyl)amino]-2-methylidene-4-oxobutanoic acid B. Narayana, Prakash S. Nayak, Balladka K. Sarojini and Jerry P. Jasinski 1. Comment Amide bonds play a major role in the elaboration and composition of biological systems, which are the main chemical bonds that link amino acid building blocks together to give proteins. Amide bonds are not limited to biological systems and are indeed present in a huge array of molecules, including major marketed drugs. Amide derivatives possessing antiinflammatory (Galanakis et al., 2004; Kumar et al., 1993; Ban et al., 1998), antimicrobial (Ukrainets et al., 2006), antitubercular (Lesyk et al., 2004) and antiproliferative (Gududuru et al., 2004) activities are reported in the literature. Crystal structures of some related amide derivatives include, viz., 4-(4-iodoanilino)-2-methylene-4-oxobutanoic acid and 4-(3-fluoro-4-methylanilino)-2-methylidene-4-oxobutanoic acid (Nayak et al., 2013a,b). Hence in view of its pharmacological importance, the title compound 4-[(4-bromophenyl)amino]-2-methylidene-4-oxobutanoic acid (I), C11H10BrNO3, was synthesized from 3-methylidenedihydrofuran-2,5-dione with good yields and its crystal structure is reported here. In the title compound, two independent molecules (A & B) crystallize in the asymmetric unit (Fig. 1). The N–C(=O) bond lengths of 1.359 (6)A (A) and 1.346 (6)Å (B) are indicative of amide-type resonance. The bond lengths of the remaining atoms are in normal ranges (Allen et al., 1987). In the crystal, classical N—H···O and O—H···O hydrogen bonds are observed supported additionally by weak C—H···O intermolecular interactions between the 2-methylidene and amide groups (Table 1, Fig. 2) linking the molecules into chains of dimers along [1 1 0]. The N—H···O hydrogen bonds are supported by the carbonyl oxygen atom of the amide functionality as the acceptor. The carboxylic acid groups form a dimeric hydrogen bonding pattern commonly seen for many carbolylic acids into R22(8) graph-set motifs (Fig. 3). The dihedral angles between the mean planes of the 4-bromophenyl ring (C6A–C11A or C6B–C11B) and oxoamine group (N1A/C1A/O1A/C2A or N1B/C1B/O1B/C2B) are 24.8 (7)° (A) and 77.1 (6)° (B), respectively. The mean plane of the 2methylidene group (C2A–C5A or C2B–C5B) is further inclined by 75.6 (4)° (A) and 72.5 (6)° (B) from that of the oxoamine group (N1A/C1A/O1A/C2A or N1B/C1B/O1B/C2B). 2. Experimental 3-Methylidenedihydrofuran-2,5-dione (0.112 g, 1 mmol) was dissolved in 30 ml acetone and stirred at ambient temperature. 4-Bromoaniline (0.172 g, 1 mmol) in 20 mL acetone was added over 30 mins (Fig. 4). After sirring for 1.5 h the slurry was filtered. The solid was washed with acetone and dried to give title compound, C11H10BrNO3. Single crystals were grown from methanol by the slow evaporation method (yield 0.248 g, 87.32%; m.p.: 441–443 K). 3. Refinement All of the H atoms were placed in their calculated positions and then refined using the riding model with Atom—H lengths of 0.95Å (CH), 0.99Å (CH2), 0.88Å (NH) or 0.84Å (OH). Isotropic displacement parameters for these atoms were set to 1.2 (CH, CH2, NH) or 1.5 (OH) times Ueq of the parent atom. The idealised tetrahedral OH was refined as a

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supporting information rotating group: O3A(H3A), O3B(H3B). The highest four peaks in the residual density map are at approximately 1Å from the bromine atoms and have a height of about 2 e-/Å3.

Figure 1 ORTEP drawing of the title compound, C11H10BrNO3, showing the labeling scheme with 30% probability displacement ellipsoids.

Figure 2 Molecular packing for the title compound viewed along the a axis. Dashed lines indicate N—H···O, O—H···O hydrogen bonds and weak C—H···O intermolecular interactions linking the molecules into chains of dimers along [1 1 0]. H atoms not involved in hydrogen bonding or weak intermolecular interactions have been removed for clarity.

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supporting information

Figure 3 Molecular packing for the title compound viewed along the b axis. Dashed lines indicate O—H···O hydrogen bonds between the carboxylic groups forming R22(8) graph-set motifs linking the molecules into chains of dimers along [1 1 0]. H atoms not involved in hydrogen bonding have been removed for clarity.

Figure 4 Synthesis of C11H10BrNO3.

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supporting information 4-[(4-Bromophenyl)amino]-2-methylidene-4-oxobutanoic acid Crystal data V = 1101.38 (11) Å3 Z=4 F(000) = 568 Dx = 1.713 Mg m−3 Cu Kα radiation, λ = 1.54184 Å µ = 5.04 mm−1 T = 173 K Prism, colourless 0.44 × 0.28 × 0.14 mm

C11H10BrNO3 Mr = 284.11 Triclinic, P1 a = 6.2782 (4) Å b = 8.3251 (5) Å c = 21.3244 (12) Å α = 96.462 (5)° β = 92.026 (5)° γ = 95.390 (5)° Data collection Agilent Eos Gemini diffractometer Detector resolution: 16.0416 pixels mm-1 ω scans Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012) Tmin = 0.162, Tmax = 1.000

7163 measured reflections 4131 independent reflections 3490 reflections with I > 2σ(I) Rint = 0.033 θmax = 71.3°, θmin = 4.2° h = −7→6 k = −8→10 l = −26→25

Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.076 wR(F2) = 0.227 S = 1.03 4131 reflections 291 parameters 0 restraints

Primary atom site location: structure-invariant direct methods Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.1446P)2 + 3.2341P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 2.73 e Å−3 Δρmin = −0.79 e Å−3

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 (Å2)

Br1A O1A O2A O3A H3A N1A H1A C1A C2A

x

y

z

Uiso*/Ueq

0.19572 (14) 0.8488 (6) 0.6832 (6) 1.0137 (6) 0.9464 0.5872 (7) 0.5246 0.7571 (7) 0.8300 (8)

0.90862 (10) 0.7490 (4) 0.6335 (5) 0.7205 (5) 0.7607 0.5635 (5) 0.4649 0.6114 (6) 0.4766 (6)

0.46174 (4) 0.20741 (18) 0.05368 (18) 0.02870 (19) 0.0005 0.2341 (2) 0.2229 0.2006 (2) 0.1541 (2)

0.0619 (3) 0.0363 (9) 0.0338 (8) 0.0370 (9) 0.056* 0.0275 (9) 0.033* 0.0240 (9) 0.0266 (10)

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supporting information H2AA H2AB C3A C4A C5A H5AA H5AB C6A C7A H7A C8A H8A C9A C10A H10A C11A H11A Br1B O1B O2B O3B H3B N1B H1B C1B C2B H2BA H2BB C3B C4B C5B H5BA H5BB C6B C7B H7B C8B H8B C9B C10B H10B C11B H11B

0.9036 0.7033 0.9795 (8) 0.8780 (8) 1.1839 (9) 1.2692 1.2461 0.5009 (8) 0.6134 (10) 0.7542 0.5228 (11) 0.6006 0.3196 (10) 0.2019 (9) 0.0608 0.2942 (9) 0.2172 1.30729 (11) 0.6584 (6) 0.8098 (5) 0.4808 (6) 0.5499 0.8836 (7) 0.9272 0.7305 (7) 0.6529 (8) 0.7784 0.5740 0.5089 (8) 0.6144 (8) 0.3032 (8) 0.2219 0.2367 0.9792 (8) 1.1837 (9) 1.2567 1.2805 (8) 1.4207 1.1733 (9) 0.9703 (9) 0.8977 0.8740 (8) 0.7350

0.4004 0.4152 0.5448 (6) 0.6358 (6) 0.5217 (7) 0.5636 0.4633 0.6552 (6) 0.7860 (7) 0.8230 0.8617 (8) 0.9516 0.8086 (7) 0.6772 (8) 0.6415 0.6008 (7) 0.5099 0.53869 (9) 0.7564 (4) 0.8720 (5) 0.7820 (5) 0.7275 0.9562 (5) 1.0606 0.8992 (6) 1.0295 (6) 1.0939 1.1040 0.9580 (5) 0.8670 (6) 0.9786 (7) 0.9351 1.0368 0.8566 (6) 0.8118 (7) 0.8449 0.7188 (7) 0.6889 0.6699 (7) 0.7144 (8) 0.6808 0.8084 (7) 0.8398

0.1777 0.1307 0.1078 (2) 0.0606 (2) 0.1064 (3) 0.0749 0.1370 0.2849 (2) 0.3221 (3) 0.3118 0.3733 (3) 0.3981 0.3892 (3) 0.3529 (3) 0.3634 0.3017 (3) 0.2774 0.55597 (3) 0.79041 (17) 0.94320 (18) 0.96889 (19) 0.9919 0.7586 (2) 0.7645 0.7954 (2) 0.8428 (2) 0.8657 0.8198 0.8900 (2) 0.9365 (2) 0.8930 (2) 0.9250 0.8632 0.7107 (2) 0.7222 (3) 0.7620 0.6754 (3) 0.6830 0.6181 (2) 0.6061 (3) 0.5663 0.6526 (3) 0.6445

0.032* 0.032* 0.0274 (10) 0.0269 (10) 0.0354 (11) 0.042* 0.042* 0.0279 (10) 0.0375 (12) 0.045* 0.0448 (14) 0.054* 0.0400 (13) 0.0426 (13) 0.051* 0.0392 (12) 0.047* 0.0518 (3) 0.0313 (8) 0.0333 (8) 0.0365 (8) 0.055* 0.0310 (9) 0.037* 0.0237 (9) 0.0276 (10) 0.033* 0.033* 0.0252 (9) 0.0258 (9) 0.0331 (11) 0.040* 0.040* 0.0297 (10) 0.0334 (11) 0.040* 0.0343 (11) 0.041* 0.0336 (11) 0.0424 (13) 0.051* 0.0359 (12) 0.043*

Atomic displacement parameters (Å2)

Br1A

U11

U22

U33

U12

U13

U23

0.0789 (6)

0.0637 (5)

0.0493 (5)

0.0310 (4)

0.0312 (4)

0.0047 (3)

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supporting information O1A O2A O3A N1A C1A C2A C3A C4A C5A C6A C7A C8A C9A C10A C11A Br1B O1B O2B O3B N1B C1B C2B C3B C4B C5B C6B C7B C8B C9B C10B C11B

0.041 (2) 0.0245 (18) 0.0278 (18) 0.027 (2) 0.026 (2) 0.029 (2) 0.028 (2) 0.026 (2) 0.033 (3) 0.030 (2) 0.044 (3) 0.055 (4) 0.047 (3) 0.030 (3) 0.030 (3) 0.0503 (5) 0.0333 (19) 0.0243 (18) 0.0252 (17) 0.030 (2) 0.020 (2) 0.030 (2) 0.026 (2) 0.024 (2) 0.031 (3) 0.028 (2) 0.032 (3) 0.030 (3) 0.033 (3) 0.032 (3) 0.026 (2)

0.0251 (18) 0.039 (2) 0.047 (2) 0.0222 (19) 0.020 (2) 0.021 (2) 0.021 (2) 0.026 (2) 0.040 (3) 0.024 (2) 0.030 (3) 0.040 (3) 0.039 (3) 0.046 (3) 0.034 (3) 0.0635 (5) 0.0234 (17) 0.038 (2) 0.047 (2) 0.024 (2) 0.024 (2) 0.022 (2) 0.020 (2) 0.025 (2) 0.037 (3) 0.026 (2) 0.035 (3) 0.041 (3) 0.036 (3) 0.060 (4) 0.046 (3)

0.040 (2) 0.040 (2) 0.039 (2) 0.032 (2) 0.026 (2) 0.030 (2) 0.031 (2) 0.027 (2) 0.034 (3) 0.032 (2) 0.038 (3) 0.038 (3) 0.039 (3) 0.054 (4) 0.054 (3) 0.0428 (4) 0.0361 (19) 0.039 (2) 0.040 (2) 0.037 (2) 0.027 (2) 0.032 (2) 0.029 (2) 0.028 (2) 0.031 (3) 0.036 (3) 0.033 (3) 0.034 (3) 0.033 (3) 0.034 (3) 0.038 (3)

−0.0048 (16) 0.0063 (15) 0.0037 (16) −0.0017 (16) 0.0045 (18) 0.0065 (18) 0.0035 (18) 0.0023 (18) 0.011 (2) 0.0059 (19) 0.000 (2) 0.004 (3) 0.019 (3) 0.009 (2) 0.003 (2) 0.0220 (3) −0.0004 (14) 0.0041 (15) 0.0045 (16) 0.0008 (17) 0.0057 (18) 0.0050 (19) 0.0034 (18) 0.0052 (18) 0.008 (2) 0.0035 (19) 0.004 (2) 0.013 (2) 0.008 (2) 0.009 (3) 0.011 (2)

0.0117 (16) 0.0030 (14) 0.0037 (15) 0.0045 (16) 0.0000 (17) 0.0011 (18) 0.0017 (19) 0.0053 (18) 0.001 (2) 0.0064 (19) 0.007 (2) 0.007 (3) 0.021 (2) 0.016 (2) 0.011 (2) 0.0143 (3) 0.0089 (14) 0.0041 (14) 0.0022 (14) 0.0092 (17) −0.0015 (17) 0.0047 (19) 0.0031 (18) 0.0026 (17) 0.002 (2) 0.0087 (19) 0.002 (2) 0.005 (2) 0.009 (2) −0.002 (2) 0.002 (2)

−0.0027 (14) 0.0113 (15) 0.0125 (16) −0.0020 (15) 0.0010 (17) 0.0014 (17) −0.0039 (18) −0.0024 (18) 0.003 (2) 0.0058 (18) 0.001 (2) −0.001 (2) 0.008 (2) 0.008 (3) 0.002 (2) −0.0059 (3) −0.0006 (14) 0.0113 (15) 0.0143 (16) −0.0013 (16) 0.0004 (17) 0.0008 (18) −0.0034 (17) −0.0013 (17) −0.001 (2) 0.0030 (19) 0.002 (2) 0.004 (2) 0.000 (2) −0.001 (2) 0.006 (2)

Geometric parameters (Å, º) Br1A—C9A O1A—C1A O2A—C4A O3A—H3A O3A—C4A N1A—H1A N1A—C1A N1A—C6A C1A—C2A C2A—H2AA C2A—H2AB C2A—C3A C3A—C4A C3A—C5A

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1.899 (5) 1.223 (6) 1.225 (6) 0.8400 1.312 (6) 0.8800 1.359 (6) 1.408 (6) 1.527 (6) 0.9900 0.9900 1.506 (7) 1.487 (7) 1.316 (7)

Br1B—C9B O1B—C1B O2B—C4B O3B—H3B O3B—C4B N1B—H1B N1B—C1B N1B—C6B C1B—C2B C2B—H2BA C2B—H2BB C2B—C3B C3B—C4B C3B—C5B

1.893 (5) 1.224 (6) 1.226 (6) 0.8400 1.311 (6) 0.8800 1.346 (6) 1.428 (6) 1.525 (6) 0.9900 0.9900 1.511 (7) 1.488 (7) 1.321 (7)

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supporting information C5A—H5AA C5A—H5AB C6A—C7A C6A—C11A C7A—H7A C7A—C8A C8A—H8A C8A—C9A C9A—C10A C10A—H10A C10A—C11A C11A—H11A

0.9500 0.9500 1.391 (7) 1.406 (7) 0.9500 1.367 (8) 0.9500 1.377 (9) 1.400 (9) 0.9500 1.374 (8) 0.9500

C5B—H5BA C5B—H5BB C6B—C7B C6B—C11B C7B—H7B C7B—C8B C8B—H8B C8B—C9B C9B—C10B C10B—H10B C10B—C11B C11B—H11B

0.9500 0.9500 1.392 (7) 1.382 (8) 0.9500 1.385 (8) 0.9500 1.375 (8) 1.383 (8) 0.9500 1.384 (8) 0.9500

C4A—O3A—H3A C1A—N1A—H1A C1A—N1A—C6A C6A—N1A—H1A O1A—C1A—N1A O1A—C1A—C2A N1A—C1A—C2A C1A—C2A—H2AA C1A—C2A—H2AB H2AA—C2A—H2AB C3A—C2A—C1A C3A—C2A—H2AA C3A—C2A—H2AB C4A—C3A—C2A C5A—C3A—C2A C5A—C3A—C4A O2A—C4A—O3A O2A—C4A—C3A O3A—C4A—C3A C3A—C5A—H5AA C3A—C5A—H5AB H5AA—C5A—H5AB C7A—C6A—N1A C7A—C6A—C11A C11A—C6A—N1A C6A—C7A—H7A C8A—C7A—C6A C8A—C7A—H7A C7A—C8A—H8A C7A—C8A—C9A C9A—C8A—H8A C8A—C9A—Br1A C8A—C9A—C10A C10A—C9A—Br1A C9A—C10A—H10A

109.5 116.6 126.8 (4) 116.6 123.8 (4) 122.0 (4) 114.1 (4) 109.4 109.4 108.0 111.3 (4) 109.4 109.4 115.1 (4) 123.7 (5) 121.1 (5) 123.5 (5) 121.9 (5) 114.5 (4) 120.0 120.0 120.0 124.1 (5) 118.7 (5) 117.0 (5) 119.7 120.5 (6) 119.7 119.7 120.5 (6) 119.7 120.8 (5) 120.5 (5) 118.6 (4) 120.6

C4B—O3B—H3B C1B—N1B—H1B C1B—N1B—C6B C6B—N1B—H1B O1B—C1B—N1B O1B—C1B—C2B N1B—C1B—C2B C1B—C2B—H2BA C1B—C2B—H2BB H2BA—C2B—H2BB C3B—C2B—C1B C3B—C2B—H2BA C3B—C2B—H2BB C4B—C3B—C2B C5B—C3B—C2B C5B—C3B—C4B O2B—C4B—O3B O2B—C4B—C3B O3B—C4B—C3B C3B—C5B—H5BA C3B—C5B—H5BB H5BA—C5B—H5BB C7B—C6B—N1B C11B—C6B—N1B C11B—C6B—C7B C6B—C7B—H7B C8B—C7B—C6B C8B—C7B—H7B C7B—C8B—H8B C9B—C8B—C7B C9B—C8B—H8B C8B—C9B—Br1B C8B—C9B—C10B C10B—C9B—Br1B C9B—C10B—H10B

109.5 118.2 123.7 (4) 118.2 123.0 (4) 123.2 (4) 113.8 (4) 109.2 109.2 107.9 112.3 (4) 109.2 109.2 116.0 (4) 123.6 (5) 120.3 (5) 123.7 (4) 122.0 (5) 114.2 (4) 120.0 120.0 120.0 119.2 (5) 121.0 (5) 119.8 (5) 120.1 119.8 (5) 120.1 120.1 119.8 (5) 120.1 118.8 (4) 120.8 (5) 120.4 (4) 120.3

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supporting information C11A—C10A—C9A C11A—C10A—H10A C6A—C11A—H11A C10A—C11A—C6A C10A—C11A—H11A

118.7 (5) 120.6 119.5 121.1 (5) 119.5

C9B—C10B—C11B C11B—C10B—H10B C6B—C11B—C10B C6B—C11B—H11B C10B—C11B—H11B

119.4 (5) 120.3 120.3 (5) 119.8 119.8

Br1A—C9A—C10A—C11A O1A—C1A—C2A—C3A N1A—C1A—C2A—C3A N1A—C6A—C7A—C8A N1A—C6A—C11A—C10A C1A—N1A—C6A—C7A C1A—N1A—C6A—C11A C1A—C2A—C3A—C4A C1A—C2A—C3A—C5A C2A—C3A—C4A—O2A C2A—C3A—C4A—O3A C5A—C3A—C4A—O2A C5A—C3A—C4A—O3A C6A—N1A—C1A—O1A C6A—N1A—C1A—C2A C6A—C7A—C8A—C9A C7A—C6A—C11A—C10A C7A—C8A—C9A—Br1A C7A—C8A—C9A—C10A C8A—C9A—C10A—C11A C9A—C10A—C11A—C6A C11A—C6A—C7A—C8A

−177.6 (5) −15.6 (6) 166.0 (4) −175.5 (5) 176.3 (5) −22.1 (8) 163.5 (5) −70.4 (5) 112.3 (5) −10.9 (7) 167.5 (4) 166.4 (5) −15.1 (7) −6.1 (8) 172.3 (4) 0.7 (9) 1.6 (9) 178.0 (5) −0.6 (10) 1.0 (9) −1.5 (9) −1.1 (8)

Br1B—C9B—C10B—C11B O1B—C1B—C2B—C3B N1B—C1B—C2B—C3B N1B—C6B—C7B—C8B N1B—C6B—C11B—C10B C1B—N1B—C6B—C7B C1B—N1B—C6B—C11B C1B—C2B—C3B—C4B C1B—C2B—C3B—C5B C2B—C3B—C4B—O2B C2B—C3B—C4B—O3B C5B—C3B—C4B—O2B C5B—C3B—C4B—O3B C6B—N1B—C1B—O1B C6B—N1B—C1B—C2B C6B—C7B—C8B—C9B C7B—C6B—C11B—C10B C7B—C8B—C9B—Br1B C7B—C8B—C9B—C10B C8B—C9B—C10B—C11B C9B—C10B—C11B—C6B C11B—C6B—C7B—C8B

179.0 (5) 10.3 (6) −170.7 (4) −178.3 (5) 178.8 (5) −103.4 (6) 78.4 (7) 69.5 (5) −113.4 (5) 11.7 (7) −168.0 (4) −165.5 (5) 14.8 (7) −0.6 (8) −179.6 (4) −0.6 (8) 0.6 (9) −178.5 (4) 0.9 (9) −0.4 (10) −0.3 (9) −0.1 (8)

Hydrogen-bond geometry (Å, º) D—H···A i

O3A—H3A···O2B N1A—H1A···O1Bii O3B—H3B···O2Aiii N1B—H1B···O1Aiv C5B—H5BB···O1Av

D—H

H···A

D···A

D—H···A

0.84 0.88 0.84 0.88 0.95

1.85 2.06 1.82 2.04 2.54

2.685 (5) 2.933 (5) 2.654 (5) 2.848 (6) 3.464 (7)

174 170 170 152 164

Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1; (iii) x, y, z+1; (iv) −x+2, −y+2, −z+1; (v) −x+1, −y+2, −z+1.

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