Related literature   {#sec1}
====================

For background to the use of indoles as scaffolds in the synthesis of HIV-agents, see: Hassam *et al.* (2012[@bb5]) and for a recent review on stages of non-nucleoside reverse trans­criptase inhibitors, see: Reynolds *et al.* (2012[@bb7]). For the crystal structures of closely related compounds, see: Beddoes *et al.* (1986[@bb3]), Hassam & Smith (2012[@bb6]).

Experimental   {#sec2}
==============

 {#sec2.1}

### Crystal data   {#sec2.1.1}

C~21~H~20~BrNO~5~S*M* *~r~* = 478.35Monoclinic,*a* = 16.220 (3) Å*b* = 15.361 (3) Å*c* = 18.224 (4) Åβ = 113.792 (2)°*V* = 4154.7 (15) Å^3^*Z* = 8Mo *K*α radiationμ = 2.11 mm^−1^*T* = 100 K0.34 × 0.21 × 0.17 mm

### Data collection   {#sec2.1.2}

Bruker APEXII CCD diffractometerAbsorption correction: multi-scan \[symmetry-related measurements (*SADABS*; Bruker, 2009[@bb4])\] *T* ~min~ = 0.537, *T* ~max~ = 0.72123562 measured reflections4855 independent reflections4101 reflections with *I* \> 2σ(*I*)*R* ~int~ = 0.039

### Refinement   {#sec2.1.3}

*R*\[*F* ^2^ \> 2σ(*F* ^2^)\] = 0.029*wR*(*F* ^2^) = 0.066*S* = 1.054855 reflections279 parameters13 restraintsH-atom parameters constrainedΔρ~max~ = 0.38 e Å^−3^Δρ~min~ = −0.38 e Å^−3^

 {#d5e406}

Data collection: *APEX2* (Bruker, 2009[@bb4]); cell refinement: *SAINT* (Bruker, 2009[@bb4]); data reduction: *SAINT*; program(s) used to solve structure: *SHELXS97* (Sheldrick, 2008[@bb8]); program(s) used to refine structure: *SHELXL97* (Sheldrick, 2008[@bb8]); molecular graphics: *X-SEED* (Barbour, 2001[@bb2]; Atwood & Barbour, 2003[@bb1]); software used to prepare material for publication: *X-SEED*.

Supplementary Material
======================

###### 

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: [10.1107/S1600536813000809/jj2160sup1.cif](http://dx.doi.org/10.1107/S1600536813000809/jj2160sup1.cif)

###### 

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: [10.1107/S1600536813000809/jj2160Isup2.hkl](http://dx.doi.org/10.1107/S1600536813000809/jj2160Isup2.hkl)

###### 

Click here for additional data file.

Supplementary material file. DOI: [10.1107/S1600536813000809/jj2160Isup3.cml](http://dx.doi.org/10.1107/S1600536813000809/jj2160Isup3.cml)

Additional supplementary materials: [crystallographic information](http://scripts.iucr.org/cgi-bin/sendsupfiles?jj2160&file=jj2160sup0.html&mime=text/html); [3D view](http://scripts.iucr.org/cgi-bin/sendcif?jj2160sup1&Qmime=cif); [checkCIF report](http://scripts.iucr.org/cgi-bin/paper?jj2160&checkcif=yes)

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: [JJ2160](http://scripts.iucr.org/cgi-bin/sendsup?jj2160)).

MH thanks Professor Willem A. L. van Otterlo and Dr S. C. Pelly for their valuable input and research oversight. Stellenbosch University's Science Faculty is also acknowledged for providing laboratory space and financial research support (Subcommittee B). The South African National Research Foundation (NRF), Pretoria, is also acknowledged for providing research funds.

Comment
=======

Ethyl-5-bromo-1*H*-indole-2-carboxylate has been employed as a building block in the synthesis of various anti-HIV active molecules, particularly in the search for novel non-nucleoside reverse transcriptase inhibitors (Hassam *et al.* 2012). Protection on the indole NH of ethyl 5-bromo-3-(2- thiophenoyl)-1*H*-indole-2-carboxylate was carried out with di-*tert* -butyl-dicarbonate using 4-dimethylaminopyridine as a catalytic base.

The title compound, C~21~H~20~BrNO~5~S, crystallizes with one molecule in the asymmetric unit (Fig. 1). The thiophene moiety is disordered over two positions with major (A) and minor (B) components in a 0.9021 (19):0.0979 (19)(2) ratio. The dihedral angles between the mean planes of the 5-bromo indole ring (Br1/N1/C1-C8) and the disordered thiophene rings (S1A/C10/C11A/C13A and S1B/C10/C11B/C13B) are 59.67 (9)° and 60.20 (76)°, respectively. The angles between the mean planes of the indole ring and the *N*-*tert*- butyloxy, ethyl ester and the ketone groups are 31.72 (7)°, 45.08 (6)° and 47.88 (7)°, respectively. The torsion angles of O5/C9/C10/S1A and O5/C9/C10/S1B are -20.67 (24)° and 159.92 (34)°, respectively, thereby describing the major component in a *cis* conformation and the minor component in a *trans* conformation. Molecular packing shows the molecules forming centrosymmetric dimers linked *via* weak C12A---H12A···O3 intermolecular interactions (Fig. 2, Table 1).

Experimental {#experimental}
============

4-dimethylaminopyridine (0.0100 g, 0.0818 mmol) was added to a solution of ethyl 5-bromo-3-(2-thiophenoyl)-1*H*-indole-2-carboxylate (1.10 g, 2.91 mmol) in THF (20 ml), followed by the addition of di-*tert*-butyl dicarbonate (1.16 g, 5.32 mmol). The reaction mixture was stirred at 298.15 K for 2 h. Colourless crystals were obtained from a hexane/dichloromethane solvent mixture (4:1) (1.15 g, 83%).

Refinement {#refinement}
==========

All non-hydrogen atoms were refined anisotropically. H atoms were placed geometrically \[C---H = 0.95 - 0.99 Å; with *U*~iso~(H) = 1.2 - 1.5*U*~eq~(C)\] and constrained to ride on their parent atoms. The site-occupancy factors of the disordered thiophene moieties were initially set to 0.5 and then refined, leading to an occupancy of 0.9021 (19) and 0.0979 (19)(2) for the major and minor components, respectively. Bond lengths for the thiophene and phenyl moieties were restrained using the *SHELXL* SADI command (s.u. = 0.002 Å). Atom displacement parameters for overlaping atoms of the disordered models were constrained using EADP.

Figures
=======

![Molecular structure of the title compound with atom displacement ellipsoidsdrawn at the 50% probability level. Disordered components (0.9021 (19) = blue) and (0.0979 (19) = purple).](e-69-0o237-fig1){#Fap1}

![Molecular Packing of the title compound viewed along the b axis. Centrosymmetric dimers are linked via weak C---H···O intermolecular interactions (dashed lines).](e-69-0o237-fig2){#Fap2}

Crystal data {#tablewrapcrystaldatalong}
============

  ------------------------ ---------------------------------------
  C~21~H~20~BrNO~5~S       *F*(000) = 1952
  *M~r~* = 478.35          *D*~x~ = 1.530 Mg m^−3^
  Monoclinic, *C*2/*c*     Melting point: 370.13 K
  Hall symbol: -C 2yc      Mo *K*α radiation, λ = 0.71073 Å
  *a* = 16.220 (3) Å       Cell parameters from 6586 reflections
  *b* = 15.361 (3) Å       θ = 2.4--27.6°
  *c* = 18.224 (4) Å       µ = 2.11 mm^−1^
  β = 113.792 (2)°         *T* = 100 K
  *V* = 4154.7 (15) Å^3^   Rectangular prisms, colourless
  *Z* = 8                  0.34 × 0.21 × 0.17 mm
  ------------------------ ---------------------------------------

Data collection {#tablewrapdatacollectionlong}
===============

  ---------------------------------------------------------------------------------------------- --------------------------------------
  Bruker APEXII CCD diffractometer                                                               4855 independent reflections
  Radiation source: fine-focus sealed tube, Bruker SMART Apex                                    4101 reflections with *I* \> 2σ(*I*)
  Graphite monochromator                                                                         *R*~int~ = 0.039
  φ and ω scans                                                                                  θ~max~ = 28.2°, θ~min~ = 1.9°
  Absorption correction: multi-scan \[symmetry-related measurements (*SADABS*; Bruker, 2009)\]   *h* = −20→20
  *T*~min~ = 0.537, *T*~max~ = 0.721                                                             *k* = −19→19
  23562 measured reflections                                                                     *l* = −24→24
  ---------------------------------------------------------------------------------------------- --------------------------------------

Refinement {#tablewraprefinementdatalong}
==========

  ------------------------------------- -------------------------------------------------------------------------------------------------
  Refinement on *F*^2^                  Primary atom site location: structure-invariant direct methods
  Least-squares matrix: full            Secondary atom site location: difference Fourier map
  *R*\[*F*^2^ \> 2σ(*F*^2^)\] = 0.029   Hydrogen site location: inferred from neighbouring sites
  *wR*(*F*^2^) = 0.066                  H-atom parameters constrained
  *S* = 1.05                            *w* = 1/\[σ^2^(*F*~o~^2^) + (0.0296*P*)^2^ + 2.6317*P*\] where *P* = (*F*~o~^2^ + 2*F*~c~^2^)/3
  4855 reflections                      (Δ/σ)~max~ = 0.001
  279 parameters                        Δρ~max~ = 0.38 e Å^−3^
  13 restraints                         Δρ~min~ = −0.38 e Å^−3^
  ------------------------------------- -------------------------------------------------------------------------------------------------

Special details {#specialdetails}
===============

  -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
  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. Refinement of *F*^2^ against ALL reflections. The weighted *R*-factor *wR* and goodness of fit *S* are based on *F*^2^, conventional *R*-factors *R* are based on *F*, with *F* set to zero for negative *F*^2^. The threshold expression of *F*^2^ \> σ(*F*^2^) is used only for calculating *R*-factors(gt) *etc*. and is not relevant to the choice of reflections for refinement. *R*-factors based on *F*^2^ 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 (Å^2^) {#tablewrapcoords}
==================================================================================================

  ------ ---------------- ---------------- ---------------- -------------------- -------------
         *x*              *y*              *z*              *U*~iso~\*/*U*~eq~   Occ. (\<1)
  Br1    −0.187401 (12)   −0.022969 (12)   −0.284234 (11)   0.02154 (6)          
  O1     0.21832 (9)      0.04217 (8)      0.06003 (8)      0.0220 (3)           
  N1     0.09114 (9)      0.12572 (9)      0.02039 (8)      0.0140 (3)           
  C1     0.04334 (12)     0.19832 (11)     0.02894 (10)     0.0143 (4)           
  O2     0.22623 (8)      0.18743 (8)      0.08505 (7)      0.0168 (3)           
  C2     0.03540 (10)     0.08118 (9)      −0.04949 (10)    0.0143 (3)           
  O3     0.11295 (9)      0.22588 (8)      0.16936 (7)      0.0223 (3)           
  C3     0.05264 (11)     0.00587 (10)     −0.08360 (9)     0.0165 (4)           
  H3     0.1083           −0.0243          −0.0598          0.020\*              
  O4     0.06607 (8)      0.33759 (8)      0.08185 (7)      0.0167 (3)           
  C4     −0.01584 (11)    −0.02275 (11)    −0.15432 (10)    0.0173 (4)           
  H4     −0.0072          −0.0740          −0.1795          0.021\*              
  O5     −0.14693 (9)     0.30149 (9)      −0.11372 (7)     0.0229 (3)           
  C5     −0.09682 (11)    0.02238 (10)     −0.18879 (10)    0.0167 (4)           
  C6     −0.11345 (11)    0.09814 (10)     −0.15555 (9)     0.0159 (4)           
  H6     −0.1687          0.1289           −0.1802          0.019\*              
  C7     −0.04550 (10)    0.12713 (11)     −0.08437 (9)     0.0143 (3)           
  C8     −0.03952 (12)    0.20088 (11)     −0.03284 (10)    0.0147 (4)           
  C9     −0.11022 (12)    0.26847 (12)     −0.04742 (11)    0.0165 (4)           
  C10    −0.13346 (11)    0.29232 (11)     0.01992 (10)     0.0147 (4)           
  C14    0.07984 (11)     0.25376 (11)     0.10226 (11)     0.0158 (4)           
  C15    0.08485 (13)     0.39806 (12)     0.14842 (11)     0.0217 (4)           
  H15A   0.1485           0.3932           0.1869           0.026\*              
  H15B   0.0457           0.3853           0.1771           0.026\*              
  C16    0.06589 (15)     0.48791 (13)     0.11250 (13)     0.0294 (5)           
  H16C   0.0026           0.4918           0.0748           0.044\*              
  H16A   0.1047           0.4994           0.0840           0.044\*              
  H16B   0.0780           0.5310           0.1553           0.044\*              
  C17    0.18541 (12)     0.11267 (11)     0.05822 (10)     0.0159 (4)           
  C18    0.32643 (12)     0.19106 (12)     0.13180 (11)     0.0190 (4)           
  C19    0.37308 (13)     0.16063 (14)     0.07930 (12)     0.0249 (4)           
  H19C   0.3471           0.1907           0.0275           0.037\*              
  H19A   0.3648           0.0977           0.0708           0.037\*              
  H19B   0.4376           0.1738           0.1056           0.037\*              
  C20    0.34088 (14)     0.28765 (13)     0.14976 (13)     0.0293 (5)           
  H20A   0.3061           0.3063           0.1802           0.044\*              
  H20B   0.3209           0.3202           0.0993           0.044\*              
  H20C   0.4050           0.2988           0.1814           0.044\*              
  C21    0.35137 (14)     0.13828 (14)     0.20765 (11)     0.0278 (5)           
  H21A   0.3417           0.0763           0.1940           0.042\*              
  H21C   0.3137           0.1561           0.2357           0.042\*              
  H21B   0.4149           0.1481           0.2425           0.042\*              
  S1A    −0.18632 (4)     0.39061 (3)      0.01797 (3)      0.01650 (16)         0.9021 (19)
  C11A   −0.12031 (18)    0.24830 (18)     0.08752 (18)     0.0212 (5)           0.902 (2)
  H11A   −0.0924          0.1927           0.0987           0.025\*              0.9021 (19)
  C12A   −0.1506 (2)      0.2902 (3)       0.1402 (3)       0.0196 (4)           0.9021 (19)
  H12A   −0.1462          0.2667           0.1899           0.024\*              0.9021 (19)
  C13A   −0.1874 (3)      0.3695 (3)       0.11084 (15)     0.0161 (6)           0.9021 (19)
  H13A   −0.2108          0.4084           0.1382           0.019\*              0.9021 (19)
  S1B    −0.1088 (5)      0.2256 (4)       0.1026 (3)       0.01650 (16)         0.0979 (19)
  C11B   −0.1782 (13)     0.3643 (9)       0.0245 (15)      0.0212 (5)           0.0979 (19)
  H11B   −0.1971          0.4082           −0.0157          0.025\*              0.0979 (19)
  C12B   −0.194 (3)       0.368 (3)        0.0944 (18)      0.0161 (6)           0.0979 (19)
  H12B   −0.2251          0.4149           0.1065           0.019\*              0.0979 (19)
  C13B   −0.161 (2)       0.298 (2)        0.143 (3)        0.0196 (4)           0.0979 (19)
  H13B   −0.1655          0.2895           0.1930           0.024\*              0.0979 (19)
  ------ ---------------- ---------------- ---------------- -------------------- -------------

Atomic displacement parameters (Å^2^) {#tablewrapadps}
=====================================

  ------ -------------- -------------- -------------- -------------- ------------- --------------
         *U*^11^        *U*^22^        *U*^33^        *U*^12^        *U*^13^       *U*^23^
  Br1    0.01920 (10)   0.02324 (11)   0.01899 (10)   −0.00231 (8)   0.00438 (7)   −0.00483 (7)
  O1     0.0186 (7)     0.0174 (7)     0.0266 (7)     0.0045 (5)     0.0056 (6)    −0.0011 (5)
  N1     0.0133 (7)     0.0144 (7)     0.0138 (7)     0.0008 (6)     0.0051 (6)    −0.0017 (6)
  C1     0.0166 (9)     0.0130 (8)     0.0164 (9)     0.0025 (7)     0.0099 (7)    0.0014 (7)
  O2     0.0136 (6)     0.0167 (6)     0.0178 (6)     −0.0006 (5)    0.0040 (5)    −0.0017 (5)
  C2     0.0147 (8)     0.0139 (8)     0.0145 (8)     −0.0028 (7)    0.0061 (7)    0.0000 (7)
  O3     0.0296 (7)     0.0216 (7)     0.0148 (7)     0.0044 (6)     0.0078 (6)    0.0005 (5)
  C3     0.0165 (9)     0.0145 (9)     0.0199 (9)     0.0022 (7)     0.0087 (7)    0.0006 (7)
  O4     0.0196 (6)     0.0139 (6)     0.0158 (6)     −0.0004 (5)    0.0062 (5)    −0.0028 (5)
  C4     0.0213 (9)     0.0141 (8)     0.0189 (9)     −0.0002 (7)    0.0106 (8)    −0.0022 (7)
  O5     0.0266 (7)     0.0251 (7)     0.0167 (7)     0.0076 (6)     0.0084 (6)    0.0043 (5)
  C5     0.0176 (9)     0.0186 (9)     0.0138 (8)     −0.0040 (7)    0.0065 (7)    −0.0013 (7)
  C6     0.0152 (9)     0.0179 (9)     0.0158 (9)     0.0003 (7)     0.0075 (7)    0.0019 (7)
  C7     0.0158 (9)     0.0143 (8)     0.0158 (9)     0.0009 (7)     0.0093 (7)    0.0016 (7)
  C8     0.0185 (9)     0.0143 (8)     0.0146 (9)     0.0008 (7)     0.0103 (7)    0.0010 (7)
  C9     0.0154 (9)     0.0165 (9)     0.0183 (9)     −0.0005 (7)    0.0074 (7)    −0.0011 (7)
  C10    0.0116 (8)     0.0154 (8)     0.0172 (9)     0.0019 (7)     0.0059 (7)    −0.0003 (7)
  C14    0.0131 (8)     0.0175 (9)     0.0193 (9)     0.0013 (7)     0.0091 (7)    −0.0015 (7)
  C15    0.0258 (10)    0.0202 (10)    0.0167 (9)     −0.0030 (8)    0.0060 (8)    −0.0082 (7)
  C16    0.0334 (12)    0.0202 (10)    0.0264 (11)    0.0014 (9)     0.0034 (9)    −0.0064 (8)
  C17    0.0172 (9)     0.0186 (9)     0.0124 (8)     0.0006 (7)     0.0068 (7)    0.0005 (7)
  C18    0.0128 (8)     0.0260 (10)    0.0161 (9)     −0.0030 (7)    0.0036 (7)    −0.0009 (7)
  C19    0.0187 (10)    0.0322 (11)    0.0250 (10)    0.0017 (8)     0.0100 (8)    0.0047 (9)
  C20    0.0249 (11)    0.0277 (11)    0.0309 (11)    −0.0083 (9)    0.0068 (9)    −0.0066 (9)
  C21    0.0235 (10)    0.0381 (12)    0.0178 (10)    −0.0044 (9)    0.0043 (8)    0.0046 (9)
  S1A    0.0180 (3)     0.0143 (3)     0.0192 (3)     0.0051 (2)     0.0095 (2)    0.0010 (2)
  C11A   0.0184 (13)    0.0143 (13)    0.0291 (14)    0.0058 (10)    0.0080 (11)   0.0014 (10)
  C12A   0.0206 (13)    0.0209 (13)    0.0189 (10)    0.0016 (10)    0.0096 (10)   0.0000 (8)
  C13A   0.0188 (12)    0.0188 (9)     0.0142 (15)    0.0031 (9)     0.0102 (14)   −0.0018 (14)
  S1B    0.0180 (3)     0.0143 (3)     0.0192 (3)     0.0051 (2)     0.0095 (2)    0.0010 (2)
  C11B   0.0184 (13)    0.0143 (13)    0.0291 (14)    0.0058 (10)    0.0080 (11)   0.0014 (10)
  C12B   0.0188 (12)    0.0188 (9)     0.0142 (15)    0.0031 (9)     0.0102 (14)   −0.0018 (14)
  C13B   0.0206 (13)    0.0209 (13)    0.0189 (10)    0.0016 (10)    0.0096 (10)   0.0000 (8)
  ------ -------------- -------------- -------------- -------------- ------------- --------------

Geometric parameters (Å, º) {#tablewrapgeomlong}
===========================

  ---------------------- -------------- -------------------------- --------------
  Br1---C5               1.8993 (17)    C15---H15A                 0.9900
  O1---C17               1.202 (2)      C15---H15B                 0.9900
  N1---C1                1.402 (2)      C16---H16C                 0.9800
  N1---C2                1.406 (2)      C16---H16A                 0.9800
  N1---C17               1.415 (2)      C16---H16B                 0.9800
  C1---C8                1.362 (2)      C18---C21                  1.510 (3)
  C1---C14               1.491 (2)      C18---C19                  1.514 (3)
  O2---C17               1.317 (2)      C18---C20                  1.517 (3)
  O2---C18               1.501 (2)      C19---H19C                 0.9800
  C2---C3                1.3940 (15)    C19---H19A                 0.9800
  C2---C7                1.3968 (15)    C19---H19B                 0.9800
  O3---C14               1.199 (2)      C20---H20A                 0.9800
  C3---C4                1.3903 (16)    C20---H20B                 0.9800
  C3---H3                0.9500         C20---H20C                 0.9800
  O4---C14               1.334 (2)      C21---H21A                 0.9800
  O4---C15               1.459 (2)      C21---H21C                 0.9800
  C4---C5                1.3909 (16)    C21---H21B                 0.9800
  C4---H4                0.9500         S1A---C13A                 1.730 (3)
  O5---C9                1.221 (2)      C11A---C12A                1.400 (3)
  C5---C6                1.3878 (15)    C11A---H11A                0.9500
  C6---C7                1.3935 (16)    C12A---C13A                1.367 (3)
  C6---H6                0.9500         C12A---H12A                0.9500
  C7---C8                1.450 (2)      C13A---H13A                0.9500
  C8---C9                1.489 (2)      S1B---C13B                 1.730 (3)
  C9---C10               1.468 (2)      C11B---C12B                1.400 (4)
  C10---C11B             1.344 (4)      C11B---H11B                0.9500
  C10---C11A             1.345 (3)      C12B---C13B                1.367 (3)
  C10---S1A              1.7297 (17)    C12B---H12B                0.9500
  C10---S1B              1.730 (2)      C13B---H13B                0.9500
  C15---C16              1.505 (3)                                 
                                                                   
  C1---N1---C2           107.77 (13)    H16C---C16---H16A          109.5
  C1---N1---C17          126.56 (15)    C15---C16---H16B           109.5
  C2---N1---C17          123.07 (13)    H16C---C16---H16B          109.5
  C8---C1---N1           109.67 (15)    H16A---C16---H16B          109.5
  C8---C1---C14          128.83 (16)    O1---C17---O2              128.62 (17)
  N1---C1---C14          121.09 (15)    O1---C17---N1              121.44 (16)
  C17---O2---C18         120.67 (14)    O2---C17---N1              109.86 (15)
  C3---C2---C7           122.48 (14)    O2---C18---C21             109.18 (15)
  C3---C2---N1           129.51 (13)    O2---C18---C19             109.43 (14)
  C7---C2---N1           108.00 (12)    C21---C18---C19            113.28 (17)
  C4---C3---C2           116.55 (15)    O2---C18---C20             101.33 (14)
  C4---C3---H3           121.7          C21---C18---C20            111.51 (16)
  C2---C3---H3           121.7          C19---C18---C20            111.42 (16)
  C14---O4---C15         115.31 (14)    C18---C19---H19C           109.5
  C3---C4---C5           121.11 (15)    C18---C19---H19A           109.5
  C3---C4---H4           119.4          H19C---C19---H19A          109.5
  C5---C4---H4           119.4          C18---C19---H19B           109.5
  C6---C5---C4           122.36 (15)    H19C---C19---H19B          109.5
  C6---C5---Br1          119.51 (11)    H19A---C19---H19B          109.5
  C4---C5---Br1          118.13 (11)    C18---C20---H20A           109.5
  C5---C6---C7           117.02 (15)    C18---C20---H20B           109.5
  C5---C6---H6           121.5          H20A---C20---H20B          109.5
  C7---C6---H6           121.5          C18---C20---H20C           109.5
  C6---C7---C2           120.47 (14)    H20A---C20---H20C          109.5
  C6---C7---C8           132.37 (15)    H20B---C20---H20C          109.5
  C2---C7---C8           107.16 (14)    C18---C21---H21A           109.5
  C1---C8---C7           107.38 (15)    C18---C21---H21C           109.5
  C1---C8---C9           126.85 (16)    H21A---C21---H21C          109.5
  C7---C8---C9           125.72 (15)    C18---C21---H21B           109.5
  O5---C9---C10          122.43 (16)    H21A---C21---H21B          109.5
  O5---C9---C8           119.94 (16)    H21C---C21---H21B          109.5
  C10---C9---C8          117.62 (15)    C10---S1A---C13A           90.96 (18)
  C11B---C10---C11A      104.3 (12)     C10---C11A---C12A          115.3 (3)
  C11B---C10---C9        125.8 (12)     C10---C11A---H11A          122.3
  C11A---C10---C9        129.86 (16)    C12A---C11A---H11A         122.3
  C11A---C10---S1A       110.60 (15)    C13A---C12A---C11A         111.1 (4)
  C9---C10---S1A         119.53 (12)    C13A---C12A---H12A         124.5
  C11B---C10---S1B       112.0 (12)     C11A---C12A---H12A         124.5
  C9---C10---S1B         122.2 (3)      C12A---C13A---S1A          112.1 (4)
  S1A---C10---S1B        118.3 (3)      C12A---C13A---H13A         124.0
  O3---C14---O4          125.80 (16)    S1A---C13A---H13A          124.0
  O3---C14---C1          124.23 (16)    C13B---S1B---C10           90.7 (19)
  O4---C14---C1          109.90 (15)    C10---C11B---C12B          113 (3)
  O4---C15---C16         106.54 (15)    C10---C11B---H11B          123.4
  O4---C15---H15A        110.4          C12B---C11B---H11B         123.4
  C16---C15---H15A       110.4          C13B---C12B---C11B         113 (4)
  O4---C15---H15B        110.4          C13B---C12B---H12B         123.6
  C16---C15---H15B       110.4          C11B---C12B---H12B         123.6
  H15A---C15---H15B      108.6          C12B---C13B---S1B          111 (4)
  C15---C16---H16C       109.5          C12B---C13B---H13B         124.4
  C15---C16---H16A       109.5          S1B---C13B---H13B          124.4
                                                                   
  C2---N1---C1---C8      −0.25 (19)     C8---C9---C10---S1B        −19.6 (4)
  C17---N1---C1---C8     161.74 (16)    C15---O4---C14---O3        −6.9 (2)
  C2---N1---C1---C14     173.05 (15)    C15---O4---C14---C1        170.13 (14)
  C17---N1---C1---C14    −25.0 (3)      C8---C1---C14---O3         127.0 (2)
  C1---N1---C2---C3      179.52 (17)    N1---C1---C14---O3         −44.9 (3)
  C17---N1---C2---C3     16.8 (3)       C8---C1---C14---O4         −50.1 (2)
  C1---N1---C2---C7      1.06 (19)      N1---C1---C14---O4         138.06 (16)
  C17---N1---C2---C7     −161.70 (15)   C14---O4---C15---C16       179.51 (15)
  C7---C2---C3---C4      −1.0 (3)       C18---O2---C17---O1        −6.5 (3)
  N1---C2---C3---C4      −179.25 (17)   C18---O2---C17---N1        176.60 (14)
  C2---C3---C4---C5      0.3 (3)        C1---N1---C17---O1         165.06 (17)
  C3---C4---C5---C6      0.7 (3)        C2---N1---C17---O1         −35.5 (3)
  C3---C4---C5---Br1     −178.72 (14)   C1---N1---C17---O2         −17.8 (2)
  C4---C5---C6---C7      −1.1 (3)       C2---N1---C17---O2         141.64 (15)
  Br1---C5---C6---C7     178.34 (12)    C17---O2---C18---C21       −61.6 (2)
  C5---C6---C7---C2      0.4 (2)        C17---O2---C18---C19       62.9 (2)
  C5---C6---C7---C8      −178.75 (17)   C17---O2---C18---C20       −179.30 (15)
  C3---C2---C7---C6      0.6 (3)        C11B---C10---S1A---C13A    24 (8)
  N1---C2---C7---C6      179.21 (15)    C11A---C10---S1A---C13A    0.89 (19)
  C3---C2---C7---C8      179.98 (16)    C9---C10---S1A---C13A      −179.27 (18)
  N1---C2---C7---C8      −1.43 (19)     S1B---C10---S1A---C13A     0.2 (3)
  N1---C1---C8---C7      −0.63 (19)     C11B---C10---C11A---C12A   −3.2 (11)
  C14---C1---C8---C7     −173.26 (16)   C9---C10---C11A---C12A     179.8 (2)
  N1---C1---C8---C9      −178.36 (16)   S1A---C10---C11A---C12A    −0.4 (3)
  C14---C1---C8---C9     9.0 (3)        S1B---C10---C11A---C12A    175 (3)
  C6---C7---C8---C1      −179.46 (18)   C10---C11A---C12A---C13A   −0.5 (3)
  C2---C7---C8---C1      1.28 (19)      C11A---C12A---C13A---S1A   1.2 (2)
  C6---C7---C8---C9      −1.7 (3)       C10---S1A---C13A---C12A    −1.20 (17)
  C2---C7---C8---C9      179.04 (16)    C11B---C10---S1B---C13B    0.0 (4)
  C1---C8---C9---O5      131.0 (2)      C11A---C10---S1B---C13B    −2 (3)
  C7---C8---C9---O5      −46.3 (3)      C9---C10---S1B---C13B      −177.5 (11)
  C1---C8---C9---C10     −49.4 (3)      S1A---C10---S1B---C13B     3.1 (10)
  C7---C8---C9---C10     133.27 (18)    C11A---C10---C11B---C12B   0.3 (6)
  O5---C9---C10---C11B   −17.3 (12)     C9---C10---C11B---C12B     177.4 (11)
  C8---C9---C10---C11B   163.2 (11)     S1A---C10---C11B---C12B    −157 (8)
  O5---C9---C10---C11A   159.1 (2)      S1B---C10---C11B---C12B    0.0 (5)
  C8---C9---C10---C11A   −20.4 (3)      C10---C11B---C12B---C13B   0.0 (3)
  O5---C9---C10---S1A    −20.7 (2)      C11B---C12B---C13B---S1B   0.0 (2)
  C8---C9---C10---S1A    159.78 (13)    C10---S1B---C13B---C12B    0.0 (3)
  O5---C9---C10---S1B    159.9 (3)                                 
  ---------------------- -------------- -------------------------- --------------

Hydrogen-bond geometry (Å, º) {#tablewraphbondslong}
=============================

  ------------------------- --------- --------- ----------- ---------------
  *D*---H···*A*             *D*---H   H···*A*   *D*···*A*   *D*---H···*A*
  C12*A*---H12*A*···O3^i^   0.95      2.48      3.418 (5)   169
  ------------------------- --------- --------- ----------- ---------------

Symmetry code: (i) −*x*, *y*, −*z*+1/2.

###### Hydrogen-bond geometry (Å, °)

  *D*---H⋯*A*             *D*---H   H⋯*A*   *D*⋯*A*     *D*---H⋯*A*
  ----------------------- --------- ------- ----------- -------------
  C12*A*---H12*A*⋯O3^i^   0.95      2.48    3.418 (5)   169

Symmetry code: (i) .
