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The X-ray structures of three new 1:1 pharmaceutical cocrystals of 11-aza­artemisinin (11-Aza; systematic name: 1,5,9-trimethyl-14,15,16-trioxa-11-aza­tetra­cyclo­[10.3.1.04,13.08,13]hexa­decan-10-one, C15H23NO4) with bromo-substituted salicylic acids [namely, 5-bromo- (5-BrSalA, C7H5BrO3), 4-bromo- (4-BrSalA, C7H5BrO3) and 3,5-di­bromo­salicylic acid (3,5-Br2SalA, C7H4Br2O3)] are reported. All the structures are related to the parent 11-Aza:SalA cocrystal (monoclinic P21) reported previously. The 5-BrSalA analogue is isostructural with the parent, with lattice expansion along the c axis. The 4-BrSalA and 3,5-Br2SalA cocrystals retain the highly preserved 21 stacks of the mol­ecular pairs, but these pack with a varying degree of slippage with respect to neighbouring stacks, altering the close contacts between them, and represent two potential alternative homostructural arrangements for the parent com­pound. Structure redeterminations of the bromo­salicylic acids 5-BrSalA, 4-BrSalA and 3,5-Br2SalA at 100 K show that the packing efficiency of the cocrystals need not be higher than the parent coformers, based on specific-volume calculations, attributable to the strong O—H...O=C hydrogen bonds of 2.54 Å in the cocrystals.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229621004460/dv3004sup1.cif
Contains datablocks mona16cult, mona22cult, mona23cult, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229621004460/dv3004mona16cultsup2.hkl
Contains datablock mona16cult

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229621004460/dv3004mona23cultsup3.hkl
Contains datablock mona23cult

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229621004460/dv3004mona22cultsup4.hkl
Contains datablock mona22cult

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229621004460/dv3004mona16cultsup5.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229621004460/dv3004mona23cultsup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229621004460/dv3004mona22cultsup7.cml
Supplementary material

txt

Text file https://doi.org/10.1107/S2053229621004460/dv3004sup8.txt
CIF data for a struture in Table 2

txt

Text file https://doi.org/10.1107/S2053229621004460/dv3004sup9.txt
CIF data for a struture in Table 2

txt

Text file https://doi.org/10.1107/S2053229621004460/dv3004sup10.txt
CIF data for a struture in Table 2

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229621004460/dv3004sup11.pdf
PXRD patterns

CCDC references: 2080188; 2080187; 2080186

Computing details top

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020). Program(s) used to solve structure: SHELXS (Sheldrick, 2008) for mona16cult; SHELXS1986 (Sheldrick, 2008) for mona22cult, mona23cult. For all structures, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

1,5,9-Trimethyl-14,15,16-trioxa-11-azatetracyclo[10.3.1.04,13.08,13]hexadecan-10-one; 5-bromosalicylic acid (mona16cult) top
Crystal data top
C15H23NO4·C7H5BrO3F(000) = 516
Mr = 498.36Dx = 1.494 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.54184 Å
a = 9.9325 (4) ÅCell parameters from 2387 reflections
b = 9.0196 (3) Åθ = 3.6–71.7°
c = 12.3942 (4) ŵ = 2.91 mm1
β = 93.844 (3)°T = 100 K
V = 1107.88 (6) Å3Needle, colourless
Z = 20.1 × 0.02 × 0.02 mm
Data collection top
Rigaku OD SuperNova Dual source
diffractometer with an Atlas detector
3193 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source2929 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.048
Detector resolution: 5.1788 pixels mm-1θmax = 72.5°, θmin = 3.6°
ω scansh = 1211
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2020)
k = 117
Tmin = 0.961, Tmax = 1.000l = 1515
6416 measured reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.034 w = 1/[σ2(Fo2) + (0.0101P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.061(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.24 e Å3
3193 reflectionsΔρmin = 0.39 e Å3
295 parametersAbsolute structure: Flack x determined using 735 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraintAbsolute structure parameter: 0.04 (2)
Primary atom site location: structure-invariant direct methods
Special details top

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) top
xyzUiso*/Ueq
O10.5532 (3)0.7034 (3)0.6656 (3)0.0225 (7)
C10.6030 (5)0.5514 (5)0.6640 (4)0.0207 (9)
O20.4123 (3)0.7154 (3)0.6221 (3)0.0251 (7)
C20.5065 (4)0.4579 (4)0.5911 (3)0.0220 (9)
H20.53680.35240.59790.026*
O30.3709 (3)0.4638 (3)0.6190 (2)0.0242 (7)
C30.3374 (5)0.6016 (5)0.6686 (4)0.0263 (10)
C40.3658 (5)0.5943 (5)0.7913 (4)0.0318 (11)
H4A0.28100.56920.82470.038*
H4B0.39460.69360.81780.038*
C50.4744 (5)0.4809 (5)0.8291 (4)0.0315 (11)
H5A0.48830.48790.90880.038*
H5B0.43890.38050.81190.038*
C60.6914 (6)0.3490 (5)0.7945 (4)0.0302 (12)
H60.63720.27110.75390.036*
C70.8260 (5)0.3602 (5)0.7435 (4)0.0374 (13)
H7A0.87090.26220.74740.045*
H7B0.88460.43110.78580.045*
C80.8120 (5)0.4107 (5)0.6261 (4)0.0322 (11)
H8A0.75970.33630.58210.039*
H8B0.90260.41880.59770.039*
C90.7269 (4)0.6305 (5)0.5031 (3)0.0230 (9)
H90.70320.73680.51440.028*
O100.6069 (3)0.5879 (3)0.3318 (3)0.0252 (7)
C100.6114 (4)0.5677 (4)0.4321 (4)0.0213 (9)
N110.5111 (4)0.5003 (4)0.4782 (3)0.0224 (8)
C110.6121 (5)0.4957 (5)0.7815 (4)0.0251 (10)
H11A0.66410.57180.82570.030*
C120.7402 (4)0.5617 (5)0.6168 (4)0.0248 (10)
H120.79540.63230.66370.030*
C130.1918 (4)0.6341 (7)0.6320 (4)0.0355 (11)
H13A0.16390.72710.66470.053*
H13B0.13430.55310.65470.053*
H13C0.18300.64310.55310.053*
C140.7080 (6)0.2995 (6)0.9124 (4)0.0448 (14)
H14A0.75210.37830.95620.067*
H14B0.76340.20960.91800.067*
H14C0.61910.27880.93880.067*
C150.8586 (4)0.6337 (7)0.4457 (4)0.0371 (12)
H15A0.88080.53310.42280.056*
H15B0.93150.67160.49540.056*
H15C0.84770.69840.38220.056*
Br50.22969 (5)0.15227 (6)0.14014 (4)0.03746 (12)
O200.4365 (3)0.4767 (3)0.1926 (3)0.0240 (7)
C200.3164 (5)0.4549 (5)0.2282 (4)0.0239 (11)
O210.2833 (3)0.4988 (3)0.3169 (2)0.0251 (7)
C210.2209 (4)0.3721 (5)0.1535 (3)0.0217 (9)
O220.0447 (3)0.3911 (4)0.2787 (3)0.0312 (8)
C220.0901 (5)0.3426 (5)0.1846 (4)0.0253 (9)
C230.0023 (5)0.2573 (5)0.1164 (4)0.0331 (12)
H230.08710.23880.13580.040*
C240.0445 (5)0.2005 (6)0.0221 (4)0.0341 (12)
H240.01460.14010.02240.041*
C250.1741 (5)0.2309 (5)0.0087 (4)0.0279 (10)
C260.2608 (5)0.3163 (5)0.0553 (3)0.0245 (9)
H260.34830.33770.03300.029*
H110.454 (6)0.466 (7)0.427 (5)0.06 (2)*
H220.107 (5)0.430 (5)0.314 (4)0.024 (14)*
H200.495 (7)0.516 (8)0.240 (6)0.09 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0228 (16)0.0180 (15)0.0268 (17)0.0030 (11)0.0017 (13)0.0012 (11)
C10.019 (2)0.016 (2)0.026 (2)0.0005 (17)0.0001 (18)0.0018 (16)
O20.0228 (16)0.0244 (15)0.0283 (17)0.0018 (13)0.0033 (13)0.0059 (12)
C20.022 (2)0.020 (2)0.023 (2)0.0036 (17)0.0007 (18)0.0014 (16)
O30.0230 (16)0.0231 (16)0.0265 (16)0.0041 (12)0.0020 (13)0.0034 (12)
C30.028 (2)0.025 (2)0.027 (2)0.0052 (17)0.009 (2)0.0037 (17)
C40.035 (3)0.035 (2)0.026 (2)0.000 (2)0.009 (2)0.0026 (18)
C50.040 (3)0.030 (3)0.024 (2)0.002 (2)0.001 (2)0.008 (2)
C60.036 (3)0.021 (2)0.032 (3)0.001 (2)0.007 (2)0.001 (2)
C70.031 (3)0.026 (2)0.053 (3)0.006 (2)0.014 (2)0.002 (2)
C80.020 (2)0.029 (2)0.047 (3)0.0039 (19)0.006 (2)0.008 (2)
C90.021 (2)0.025 (3)0.0229 (18)0.0023 (19)0.0010 (15)0.0085 (19)
O100.0250 (17)0.0283 (15)0.0220 (16)0.0060 (13)0.0004 (13)0.0024 (12)
C100.021 (2)0.015 (2)0.027 (2)0.0004 (17)0.0030 (19)0.0068 (17)
N110.023 (2)0.0190 (17)0.025 (2)0.0028 (15)0.0007 (16)0.0021 (15)
C110.031 (3)0.019 (2)0.024 (2)0.0005 (19)0.0068 (19)0.0006 (17)
C120.024 (2)0.021 (2)0.029 (3)0.0012 (18)0.0041 (19)0.0041 (17)
C130.023 (2)0.045 (3)0.039 (2)0.006 (3)0.0087 (19)0.013 (3)
C140.059 (4)0.033 (3)0.039 (3)0.002 (3)0.020 (3)0.009 (2)
C150.022 (2)0.056 (3)0.034 (2)0.009 (3)0.0030 (18)0.004 (3)
Br50.0368 (3)0.0506 (3)0.0255 (2)0.0097 (3)0.00600 (18)0.0104 (3)
O200.0220 (17)0.0262 (16)0.0239 (16)0.0061 (13)0.0030 (13)0.0032 (13)
C200.025 (3)0.018 (2)0.027 (3)0.0008 (19)0.004 (2)0.0069 (18)
O210.0244 (17)0.0279 (16)0.0230 (16)0.0007 (13)0.0025 (13)0.0025 (13)
C210.020 (2)0.024 (2)0.021 (2)0.0010 (17)0.0010 (17)0.0052 (16)
O220.0233 (19)0.043 (2)0.0277 (18)0.0010 (16)0.0033 (15)0.0028 (15)
C220.021 (2)0.031 (2)0.024 (2)0.0036 (18)0.0016 (18)0.0040 (18)
C230.022 (3)0.046 (3)0.032 (3)0.006 (2)0.006 (2)0.000 (2)
C240.023 (2)0.051 (3)0.027 (2)0.012 (2)0.002 (2)0.003 (2)
C250.030 (3)0.034 (2)0.020 (2)0.001 (2)0.001 (2)0.0020 (19)
C260.022 (2)0.029 (2)0.023 (2)0.0019 (18)0.0041 (18)0.0037 (18)
Geometric parameters (Å, º) top
O1—C11.458 (5)C8—C121.539 (6)
O1—O21.469 (4)C9—C101.509 (5)
C1—C21.526 (6)C9—C121.537 (6)
C1—C111.538 (6)C9—C151.530 (6)
C1—C121.522 (6)O10—C101.254 (5)
O2—C31.413 (5)C10—N111.329 (6)
C2—O31.413 (5)Br5—C251.892 (5)
C2—N111.454 (6)O20—C201.313 (6)
O3—C31.435 (5)C20—O211.233 (6)
C3—C41.530 (6)C20—C211.482 (6)
C3—C131.515 (6)C21—C221.405 (6)
C4—C51.536 (6)C21—C261.398 (6)
C5—C111.531 (7)O22—C221.351 (5)
C6—C71.521 (8)C22—C231.404 (7)
C6—C111.543 (6)C23—C241.367 (7)
C6—C141.526 (7)C24—C251.395 (6)
C7—C81.522 (7)C25—C261.369 (6)
C1—O1—O2112.3 (3)C15—C9—C12114.2 (4)
O1—C1—C2109.1 (3)O10—C10—C9119.9 (4)
O1—C1—C11107.0 (4)O10—C10—N11121.0 (4)
O1—C1—C12105.1 (4)N11—C10—C9118.9 (4)
C2—C1—C11112.0 (4)C10—N11—C2127.4 (4)
C12—C1—C2110.5 (4)C1—C11—C6112.1 (4)
C12—C1—C11112.8 (4)C5—C11—C1113.4 (4)
C3—O2—O1108.2 (3)C5—C11—C6110.4 (4)
O3—C2—C1113.9 (4)C1—C12—C8109.9 (4)
O3—C2—N11108.5 (3)C1—C12—C9110.7 (4)
N11—C2—C1111.4 (4)C9—C12—C8115.9 (4)
C2—O3—C3113.0 (3)O20—C20—C21115.0 (4)
O2—C3—O3108.1 (3)O21—C20—O20123.6 (5)
O2—C3—C4111.7 (4)O21—C20—C21121.4 (5)
O2—C3—C13104.8 (4)C22—C21—C20119.2 (4)
O3—C3—C4110.8 (3)C26—C21—C20121.2 (4)
O3—C3—C13106.5 (4)C26—C21—C22119.5 (4)
C13—C3—C4114.5 (4)O22—C22—C21123.0 (4)
C3—C4—C5114.3 (4)O22—C22—C23117.9 (4)
C11—C5—C4116.8 (4)C23—C22—C21119.1 (4)
C7—C6—C11110.9 (4)C24—C23—C22120.5 (4)
C7—C6—C14112.1 (5)C23—C24—C25120.2 (4)
C14—C6—C11111.9 (5)C24—C25—Br5119.4 (4)
C6—C7—C8113.0 (4)C26—C25—Br5120.1 (4)
C7—C8—C12110.4 (4)C26—C25—C24120.5 (4)
C10—C9—C12113.5 (4)C25—C26—C21120.3 (4)
C10—C9—C15112.1 (3)
O1—C1—C2—O354.5 (5)N11—C2—O3—C395.5 (4)
O1—C1—C2—N1168.6 (5)C11—C1—C2—O363.8 (5)
O1—C1—C11—C566.4 (5)C11—C1—C2—N11173.1 (3)
O1—C1—C11—C6167.9 (4)C11—C1—C12—C855.7 (5)
O1—C1—C12—C8171.9 (4)C11—C1—C12—C9175.1 (3)
O1—C1—C12—C958.9 (5)C11—C6—C7—C853.7 (6)
O1—O2—C3—O374.2 (4)C12—C1—C2—O3169.6 (3)
O1—O2—C3—C448.0 (4)C12—C1—C2—N1146.5 (5)
O1—O2—C3—C13172.5 (3)C12—C1—C11—C5178.5 (4)
C1—O1—O2—C346.3 (4)C12—C1—C11—C652.8 (5)
C1—C2—O3—C329.2 (5)C12—C9—C10—O10163.9 (4)
C1—C2—N11—C1023.4 (6)C12—C9—C10—N1120.7 (6)
O2—O1—C1—C214.6 (5)C13—C3—C4—C5145.8 (4)
O2—O1—C1—C11106.7 (4)C14—C6—C7—C8179.5 (4)
O2—O1—C1—C12133.1 (3)C14—C6—C11—C1176.3 (4)
O2—C3—C4—C595.3 (4)C14—C6—C11—C556.3 (6)
C2—C1—C11—C553.2 (5)C15—C9—C10—O1032.6 (6)
C2—C1—C11—C672.6 (5)C15—C9—C10—N11151.9 (4)
C2—C1—C12—C870.5 (5)C15—C9—C12—C1175.3 (4)
C2—C1—C12—C958.7 (5)C15—C9—C12—C849.4 (6)
C2—O3—C3—O233.5 (5)Br5—C25—C26—C21178.7 (3)
C2—O3—C3—C489.2 (4)O20—C20—C21—C22179.7 (4)
C2—O3—C3—C13145.7 (4)O20—C20—C21—C263.0 (6)
O3—C2—N11—C10149.5 (4)C20—C21—C22—O222.4 (6)
O3—C3—C4—C525.3 (6)C20—C21—C22—C23176.6 (4)
C3—C4—C5—C1155.3 (6)C20—C21—C26—C25175.2 (4)
C4—C5—C11—C133.8 (6)O21—C20—C21—C220.2 (6)
C4—C5—C11—C6160.5 (4)O21—C20—C21—C26176.8 (4)
C6—C7—C8—C1257.6 (5)C21—C22—C23—C241.6 (7)
C7—C6—C11—C150.4 (5)O22—C22—C23—C24177.4 (4)
C7—C6—C11—C5177.7 (4)C22—C21—C26—C251.5 (6)
C7—C8—C12—C157.2 (5)C22—C23—C24—C252.0 (8)
C7—C8—C12—C9176.4 (4)C23—C24—C25—Br5179.5 (4)
C9—C10—N11—C210.2 (6)C23—C24—C25—C260.7 (8)
O10—C10—N11—C2174.4 (4)C24—C25—C26—C211.0 (7)
C10—C9—C12—C145.1 (5)C26—C21—C22—O22179.1 (4)
C10—C9—C12—C880.8 (5)C26—C21—C22—C230.2 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O210.88 (6)2.12 (6)2.917 (5)150 (5)
O22—H22···O210.81 (5)1.85 (5)2.575 (4)147 (5)
O20—H20···O100.88 (7)1.66 (7)2.541 (4)179 (8)
1,5,9-Trimethyl-14,15,16-trioxa-11-azatetracyclo[10.3.1.04,13.08,13]hexadecan-10-one; 3,5-dibromosalicylic acid (mona22cult) top
Crystal data top
C15H23NO4·C7H4Br2O3F(000) = 584
Mr = 577.26Dx = 1.642 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.54184 Å
a = 9.52200 (19) ÅCell parameters from 3893 reflections
b = 9.3214 (2) Åθ = 3.3–72.4°
c = 13.3453 (3) ŵ = 4.78 mm1
β = 99.6446 (19)°T = 100 K
V = 1167.76 (4) Å3Block, colourless
Z = 20.05 × 0.05 × 0.04 mm
Data collection top
Rigaku OD SuperNova Dual source
diffractometer with an Atlas detector
4060 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source3811 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.028
Detector resolution: 5.1788 pixels mm-1θmax = 72.3°, θmin = 3.4°
ω scansh = 117
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2020)
k = 1110
Tmin = 0.977, Tmax = 1.000l = 1615
6899 measured reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030 w = 1/[σ2(Fo2) + (0.0219P)2 + 0.1825P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.067(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.27 e Å3
4060 reflectionsΔρmin = 0.44 e Å3
304 parametersAbsolute structure: Flack x determined using 1437 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
2 restraintsAbsolute structure parameter: 0.034 (19)
Primary atom site location: structure-invariant direct methods
Special details top

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) top
xyzUiso*/Ueq
O10.6727 (3)0.3538 (3)0.6057 (2)0.0174 (6)
C10.6336 (4)0.5012 (4)0.6270 (3)0.0157 (8)
O20.6895 (3)0.3363 (3)0.4986 (2)0.0183 (6)
C20.5850 (4)0.5833 (5)0.5291 (3)0.0161 (8)
H20.57500.68630.54770.019*
O30.6836 (3)0.5777 (3)0.4602 (2)0.0180 (6)
C30.7726 (4)0.4533 (5)0.4731 (3)0.0202 (8)
C40.9049 (4)0.4783 (5)0.5542 (3)0.0226 (9)
H4A0.92960.38740.59130.027*
H4B0.98570.50430.51980.027*
C50.8865 (4)0.5948 (5)0.6304 (4)0.0223 (9)
H5A0.86950.68690.59340.027*
H5B0.97710.60430.67860.027*
C60.7273 (5)0.7121 (5)0.7421 (3)0.0210 (9)
H60.70060.78450.68690.025*
C70.6002 (5)0.6935 (5)0.7974 (4)0.0223 (9)
H7A0.57340.78820.82180.027*
H7B0.62860.63130.85750.027*
C80.4707 (5)0.6274 (5)0.7296 (3)0.0210 (9)
H8A0.39310.61350.76960.025*
H8B0.43600.69370.67290.025*
C90.3858 (4)0.4046 (5)0.6214 (3)0.0173 (8)
H90.42280.30650.61040.021*
O100.2232 (3)0.4532 (4)0.4665 (2)0.0193 (6)
C100.3452 (4)0.4691 (5)0.5164 (3)0.0156 (7)
N110.4472 (4)0.5360 (4)0.4758 (3)0.0181 (7)
C110.7645 (4)0.5712 (5)0.6925 (3)0.0191 (8)
H11A0.80050.50270.74860.023*
H110.423 (8)0.567 (10)0.415 (7)0.08 (3)*
C120.5093 (4)0.4838 (4)0.6871 (3)0.0161 (8)
H120.54430.42050.74660.019*
C130.8082 (5)0.4155 (6)0.3693 (3)0.0258 (10)
H13A0.87060.33120.37550.039*
H13B0.85680.49670.34340.039*
H13C0.72020.39430.32220.039*
C140.8551 (5)0.7700 (6)0.8149 (4)0.0286 (11)
H14A0.89140.69570.86440.043*
H14B0.82610.85410.85050.043*
H14C0.93000.79760.77640.043*
C150.2569 (4)0.3815 (5)0.6734 (3)0.0233 (9)
H15A0.21390.47440.68450.035*
H15B0.28700.33390.73890.035*
H15C0.18700.32140.63030.035*
Br30.33108 (6)0.93495 (7)0.06310 (4)0.04324 (17)
Br50.20630 (5)0.96457 (6)0.06056 (4)0.03468 (14)
O200.1227 (3)0.5988 (4)0.3098 (2)0.0214 (6)
C200.2127 (5)0.6300 (5)0.2494 (3)0.0190 (9)
H200.157 (7)0.538 (8)0.357 (6)0.05 (2)*
O210.3362 (3)0.5814 (4)0.2614 (2)0.0217 (6)
C210.1605 (5)0.7287 (5)0.1647 (3)0.0192 (8)
O220.3880 (3)0.7220 (4)0.1071 (3)0.0274 (7)
C220.2539 (5)0.7720 (5)0.0994 (3)0.0216 (9)
H220.395 (10)0.661 (8)0.154 (5)0.09 (3)*
C230.2057 (5)0.8733 (6)0.0241 (3)0.0264 (10)
C240.0714 (5)0.9305 (5)0.0127 (3)0.0253 (10)
H240.04141.00000.03850.030*
C250.0206 (5)0.8849 (5)0.0778 (3)0.0232 (9)
C260.0220 (5)0.7856 (5)0.1532 (3)0.0207 (9)
H260.04160.75580.19690.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0197 (15)0.0152 (15)0.0177 (14)0.0032 (11)0.0042 (12)0.0010 (12)
C10.0155 (18)0.014 (2)0.017 (2)0.0015 (14)0.0008 (15)0.0002 (15)
O20.0189 (15)0.0195 (16)0.0177 (15)0.0005 (12)0.0062 (12)0.0017 (12)
C20.0123 (18)0.020 (2)0.017 (2)0.0000 (15)0.0028 (15)0.0014 (16)
O30.0163 (14)0.0213 (15)0.0173 (15)0.0000 (12)0.0056 (12)0.0012 (12)
C30.0189 (17)0.019 (2)0.025 (2)0.0010 (19)0.0098 (15)0.0005 (19)
C40.0125 (17)0.025 (2)0.031 (2)0.0003 (18)0.0045 (15)0.000 (2)
C50.0125 (19)0.024 (2)0.029 (2)0.0020 (17)0.0007 (17)0.0000 (18)
C60.023 (2)0.021 (2)0.017 (2)0.0006 (18)0.0027 (17)0.0010 (17)
C70.025 (2)0.024 (2)0.017 (2)0.0038 (18)0.0010 (17)0.0035 (17)
C80.023 (2)0.022 (2)0.018 (2)0.0044 (17)0.0053 (17)0.0009 (17)
C90.0156 (18)0.020 (2)0.017 (2)0.0012 (15)0.0055 (15)0.0022 (16)
O100.0120 (12)0.0259 (16)0.0195 (13)0.0010 (13)0.0006 (10)0.0018 (15)
C100.0129 (16)0.0166 (19)0.0175 (17)0.0038 (17)0.0035 (14)0.0008 (17)
N110.0142 (17)0.0228 (19)0.0170 (18)0.0013 (14)0.0021 (14)0.0015 (15)
C110.0140 (19)0.021 (2)0.021 (2)0.0014 (16)0.0020 (16)0.0006 (17)
C120.0155 (17)0.019 (2)0.0144 (17)0.0021 (16)0.0037 (14)0.0028 (16)
C130.022 (2)0.030 (3)0.029 (2)0.0010 (19)0.0130 (17)0.004 (2)
C140.031 (3)0.029 (3)0.023 (2)0.002 (2)0.004 (2)0.0003 (19)
C150.018 (2)0.036 (3)0.016 (2)0.0004 (18)0.0043 (16)0.0010 (18)
Br30.0427 (3)0.0631 (4)0.0272 (3)0.0045 (3)0.0155 (2)0.0110 (3)
Br50.0343 (2)0.0472 (3)0.0227 (2)0.0173 (2)0.00495 (17)0.0120 (2)
O200.0159 (14)0.0252 (17)0.0221 (16)0.0018 (12)0.0006 (12)0.0034 (13)
C200.019 (2)0.019 (2)0.017 (2)0.0039 (16)0.0008 (16)0.0063 (16)
O210.0185 (15)0.0252 (16)0.0203 (15)0.0025 (13)0.0004 (12)0.0030 (13)
C210.021 (2)0.020 (2)0.016 (2)0.0011 (17)0.0016 (16)0.0034 (17)
O220.0217 (15)0.036 (2)0.0248 (18)0.0004 (14)0.0058 (13)0.0025 (15)
C220.020 (2)0.026 (2)0.017 (2)0.0066 (18)0.0001 (17)0.0072 (17)
C230.028 (2)0.037 (3)0.015 (2)0.005 (2)0.0054 (17)0.0036 (18)
C240.034 (2)0.026 (3)0.015 (2)0.002 (2)0.0017 (16)0.002 (2)
C250.026 (2)0.025 (2)0.017 (2)0.0005 (18)0.0006 (17)0.0006 (17)
C260.022 (2)0.025 (2)0.014 (2)0.0004 (18)0.0001 (16)0.0009 (17)
Geometric parameters (Å, º) top
O1—C11.463 (5)C9—C101.514 (5)
O1—O21.474 (4)C9—C121.534 (5)
C1—C21.519 (6)C9—C151.523 (5)
C1—C111.542 (6)O10—C101.247 (4)
C1—C121.545 (5)C10—N111.342 (5)
O2—C31.421 (5)Br3—C231.891 (5)
C2—O31.421 (5)Br5—C251.896 (5)
C2—N111.452 (5)O20—C201.304 (6)
O3—C31.430 (6)C20—O211.245 (5)
C3—C41.534 (5)C20—C211.477 (6)
C3—C131.522 (6)C21—C221.405 (6)
C4—C51.518 (6)C21—C261.406 (6)
C5—C111.552 (6)O22—C221.347 (6)
C6—C71.529 (6)C22—C231.399 (7)
C6—C111.538 (6)C23—C241.370 (7)
C6—C141.523 (6)C24—C251.399 (6)
C7—C81.531 (6)C25—C261.378 (6)
C8—C121.523 (6)
C1—O1—O2111.4 (3)O10—C10—C9121.1 (4)
O1—C1—C2110.9 (3)O10—C10—N11120.8 (4)
O1—C1—C11107.4 (3)N11—C10—C9117.9 (3)
O1—C1—C12104.1 (3)C10—N11—C2126.8 (4)
C2—C1—C11112.0 (3)C1—C11—C5111.4 (4)
C2—C1—C12110.5 (3)C6—C11—C1112.5 (3)
C11—C1—C12111.5 (3)C6—C11—C5110.8 (4)
C3—O2—O1107.6 (3)C8—C12—C1110.8 (3)
O3—C2—C1113.5 (3)C8—C12—C9115.2 (3)
O3—C2—N11108.2 (3)C9—C12—C1109.5 (3)
N11—C2—C1112.9 (3)O20—C20—C21116.1 (4)
C2—O3—C3113.2 (3)O21—C20—O20122.9 (4)
O2—C3—O3108.0 (3)O21—C20—C21120.9 (4)
O2—C3—C4111.9 (4)C22—C21—C20119.2 (4)
O2—C3—C13105.0 (4)C22—C21—C26120.2 (4)
O3—C3—C4111.2 (4)C26—C21—C20120.5 (4)
O3—C3—C13107.2 (4)O22—C22—C21122.9 (4)
C13—C3—C4113.3 (3)O22—C22—C23118.8 (4)
C5—C4—C3114.1 (4)C23—C22—C21118.3 (4)
C4—C5—C11115.9 (4)C22—C23—Br3118.8 (4)
C7—C6—C11111.6 (4)C24—C23—Br3119.2 (4)
C14—C6—C7110.2 (4)C24—C23—C22122.0 (4)
C14—C6—C11111.1 (4)C23—C24—C25118.9 (4)
C6—C7—C8112.6 (4)C24—C25—Br5118.3 (3)
C12—C8—C7110.6 (3)C26—C25—Br5120.4 (4)
C10—C9—C12113.0 (3)C26—C25—C24121.2 (4)
C10—C9—C15112.2 (3)C25—C26—C21119.3 (4)
C15—C9—C12114.0 (3)
O1—C1—C2—O352.6 (4)C11—C1—C2—N11169.0 (3)
O1—C1—C2—N1171.0 (4)C11—C1—C12—C855.7 (4)
O1—C1—C11—C569.1 (4)C11—C1—C12—C9176.2 (3)
O1—C1—C11—C6165.8 (3)C11—C6—C7—C852.8 (5)
O1—C1—C12—C8171.2 (3)C12—C1—C2—O3167.6 (3)
O1—C1—C12—C960.6 (4)C12—C1—C2—N1143.9 (5)
O1—O2—C3—O375.7 (4)C12—C1—C11—C5177.4 (3)
O1—O2—C3—C447.0 (4)C12—C1—C11—C652.3 (5)
O1—O2—C3—C13170.2 (3)C12—C9—C10—O10155.5 (4)
C1—O1—O2—C346.2 (4)C12—C9—C10—N1128.7 (5)
C1—C2—O3—C325.7 (5)C13—C3—C4—C5144.5 (4)
C1—C2—N11—C1023.3 (6)C14—C6—C7—C8176.8 (4)
O2—O1—C1—C214.5 (4)C14—C6—C11—C1174.0 (4)
O2—O1—C1—C11108.2 (3)C14—C6—C11—C560.6 (5)
O2—O1—C1—C12133.3 (3)C15—C9—C10—O1025.0 (6)
O2—C3—C4—C597.1 (5)C15—C9—C10—N11159.3 (4)
C2—C1—C11—C553.0 (5)C15—C9—C12—C1180.0 (3)
C2—C1—C11—C672.2 (5)C15—C9—C12—C854.3 (5)
C2—C1—C12—C869.6 (4)Br3—C23—C24—C25179.7 (4)
C2—C1—C12—C958.5 (4)Br5—C25—C26—C21179.6 (3)
C2—O3—C3—O236.5 (4)O20—C20—C21—C22177.1 (4)
C2—O3—C3—C486.6 (4)O20—C20—C21—C261.0 (6)
C2—O3—C3—C13149.1 (3)C20—C21—C22—O223.4 (6)
O3—C2—N11—C10149.9 (4)C20—C21—C22—C23175.5 (4)
O3—C3—C4—C523.7 (5)C20—C21—C26—C25175.6 (4)
C3—C4—C5—C1159.0 (5)O21—C20—C21—C222.4 (6)
C4—C5—C11—C137.0 (5)O21—C20—C21—C26178.5 (4)
C4—C5—C11—C6163.1 (4)C21—C22—C23—Br3179.0 (3)
C6—C7—C8—C1256.6 (5)C21—C22—C23—C240.0 (7)
C7—C6—C11—C150.5 (5)O22—C22—C23—Br30.0 (6)
C7—C6—C11—C5175.9 (3)O22—C22—C23—C24179.0 (4)
C7—C8—C12—C157.4 (5)C22—C21—C26—C250.5 (7)
C7—C8—C12—C9177.6 (3)C22—C23—C24—C250.7 (7)
C9—C10—N11—C215.3 (6)C23—C24—C25—Br5179.7 (4)
O10—C10—N11—C2169.0 (4)C23—C24—C25—C260.8 (7)
C10—C9—C12—C150.3 (4)C24—C25—C26—C210.2 (7)
C10—C9—C12—C875.3 (4)C26—C21—C22—O22179.6 (4)
N11—C2—O3—C3100.4 (4)C26—C21—C22—C230.6 (6)
C11—C1—C2—O367.4 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O210.86 (9)2.08 (9)2.910 (5)163 (9)
O20—H20···O100.87 (8)1.68 (8)2.542 (4)167 (7)
O22—H22···O210.84 (3)1.79 (5)2.558 (5)152 (9)
1,5,9-Trimethyl-14,15,16-trioxa-11-azatetracyclo[10.3.1.04,13.08,13]hexadecan-10-one; 4-bromosalicylic acid (mona23cult) top
Crystal data top
C15H23NO4·C7H5BrO3F(000) = 516
Mr = 498.36Dx = 1.461 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.54184 Å
a = 11.0814 (2) ÅCell parameters from 3985 reflections
b = 9.28293 (18) Åθ = 4.0–72.3°
c = 11.1404 (2) ŵ = 2.84 mm1
β = 98.638 (2)°T = 100 K
V = 1132.99 (4) Å3Block, colourless
Z = 20.06 × 0.04 × 0.03 mm
Data collection top
Rigaku OD SuperNova Dual source
diffractometer with an Atlas detector
3833 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source3611 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.032
Detector resolution: 5.1788 pixels mm-1θmax = 72.5°, θmin = 4.0°
ω scansh = 1213
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2020)
k = 1110
Tmin = 0.889, Tmax = 1.000l = 1013
6749 measured reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.029 w = 1/[σ2(Fo2) + (0.0222P)2 + 0.0574P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.068(Δ/σ)max = 0.001
S = 1.04Δρmax = 0.32 e Å3
3833 reflectionsΔρmin = 0.57 e Å3
295 parametersAbsolute structure: Flack x determined using 1284 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraintAbsolute structure parameter: 0.020 (15)
Primary atom site location: structure-invariant direct methods
Special details top

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) top
xyzUiso*/Ueq
O10.5838 (2)0.3279 (3)0.3424 (2)0.0178 (5)
C10.6268 (3)0.4741 (3)0.3744 (3)0.0155 (7)
O20.4522 (2)0.3118 (3)0.3446 (2)0.0208 (5)
C20.5307 (3)0.5568 (4)0.4319 (3)0.0173 (7)
H20.55740.65960.44000.021*
O30.4133 (2)0.5542 (3)0.3608 (2)0.0191 (6)
C30.3931 (3)0.4310 (4)0.2818 (3)0.0209 (7)
C40.4383 (4)0.4588 (4)0.1612 (3)0.0228 (8)
H4A0.36810.48810.10050.027*
H4B0.47060.36750.13280.027*
C50.5375 (4)0.5742 (4)0.1662 (3)0.0219 (8)
H5A0.50230.66730.18680.026*
H5B0.56060.58390.08410.026*
C60.7283 (4)0.6861 (4)0.2824 (4)0.0235 (8)
H60.67490.75900.31480.028*
C70.8404 (4)0.6626 (5)0.3782 (4)0.0297 (9)
H7A0.88110.75630.39830.036*
H7B0.89870.59930.34420.036*
C80.8085 (4)0.5947 (5)0.4944 (4)0.0269 (8)
H8A0.88410.57850.55240.032*
H8B0.75570.66130.53270.032*
C90.7127 (3)0.3693 (4)0.5778 (3)0.0193 (7)
H90.68610.27100.54810.023*
O100.5944 (2)0.4163 (3)0.7382 (2)0.0229 (6)
C100.6058 (3)0.4341 (4)0.6289 (3)0.0175 (7)
N110.5211 (2)0.5039 (4)0.5528 (2)0.0176 (5)
C110.6542 (3)0.5467 (4)0.2570 (3)0.0183 (7)
H11A0.70560.47810.21740.022*
H110.460 (4)0.527 (5)0.579 (4)0.020 (11)*
C120.7425 (3)0.4519 (4)0.4665 (3)0.0192 (7)
H120.79810.38910.42650.023*
C130.2582 (4)0.3959 (5)0.2692 (4)0.0311 (9)
H13A0.23790.36640.34820.047*
H13B0.23920.31720.21080.047*
H13C0.21040.48120.24050.047*
C140.7670 (4)0.7477 (6)0.1660 (4)0.0326 (8)
H14A0.81980.83150.18640.049*
H14B0.69430.77680.11000.049*
H14C0.81160.67390.12750.049*
C150.8233 (4)0.3468 (5)0.6759 (4)0.0309 (9)
H15A0.84820.43940.71410.046*
H15B0.89090.30660.63900.046*
H15C0.80180.28000.73740.046*
Br40.00338 (4)0.99999 (6)1.00460 (4)0.02935 (11)
O200.4469 (3)0.5614 (3)0.8454 (2)0.0224 (6)
C200.3400 (3)0.5854 (4)0.7813 (3)0.0172 (7)
H200.489 (4)0.505 (8)0.807 (4)0.038 (12)*
O210.3082 (2)0.5340 (3)0.6785 (2)0.0202 (5)
C210.2576 (3)0.6798 (4)0.8389 (3)0.0172 (7)
O220.0968 (3)0.6524 (3)0.6671 (3)0.0268 (6)
C220.1403 (3)0.7102 (4)0.7765 (3)0.0195 (8)
H220.156 (5)0.605 (7)0.652 (5)0.050 (17)*
C230.0647 (3)0.8052 (4)0.8268 (4)0.0219 (8)
H230.01500.82590.78610.026*
C240.1077 (3)0.8693 (4)0.9377 (3)0.0211 (8)
C250.2221 (4)0.8425 (4)1.0010 (3)0.0209 (7)
H250.24920.88751.07680.025*
C260.2962 (3)0.7474 (5)0.9497 (3)0.0184 (6)
H260.37580.72770.99140.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0178 (12)0.0124 (12)0.0225 (12)0.0014 (10)0.0007 (10)0.0015 (9)
C10.0196 (16)0.0098 (18)0.0173 (15)0.0019 (12)0.0032 (12)0.0014 (12)
O20.0158 (12)0.0183 (12)0.0269 (14)0.0022 (10)0.0016 (10)0.0051 (10)
C20.0178 (17)0.0165 (16)0.0173 (16)0.0018 (13)0.0017 (13)0.0016 (12)
O30.0152 (13)0.0187 (13)0.0228 (13)0.0036 (9)0.0010 (10)0.0015 (10)
C30.0212 (19)0.0192 (18)0.0203 (18)0.0002 (15)0.0034 (14)0.0039 (14)
C40.0270 (19)0.022 (2)0.0176 (16)0.0000 (14)0.0015 (14)0.0002 (12)
C50.025 (2)0.0193 (18)0.0211 (18)0.0028 (15)0.0028 (14)0.0041 (14)
C60.0245 (19)0.0148 (16)0.034 (2)0.0015 (15)0.0133 (16)0.0013 (15)
C70.0218 (19)0.029 (2)0.040 (2)0.0082 (17)0.0110 (17)0.0032 (17)
C80.0211 (19)0.028 (2)0.031 (2)0.0051 (16)0.0015 (16)0.0065 (16)
C90.0192 (17)0.0215 (19)0.0175 (17)0.0060 (14)0.0031 (14)0.0016 (13)
O100.0243 (14)0.0263 (14)0.0184 (13)0.0081 (11)0.0041 (10)0.0020 (11)
C100.0183 (18)0.0170 (16)0.0165 (16)0.0006 (14)0.0003 (13)0.0044 (13)
N110.0169 (13)0.0176 (13)0.0193 (12)0.0048 (15)0.0063 (10)0.0007 (15)
C110.0197 (17)0.0156 (16)0.0211 (17)0.0021 (13)0.0076 (14)0.0003 (12)
C120.0153 (17)0.0191 (17)0.0232 (17)0.0029 (13)0.0032 (13)0.0029 (12)
C130.019 (2)0.034 (2)0.038 (2)0.0047 (16)0.0029 (16)0.0067 (17)
C140.040 (2)0.0242 (18)0.039 (2)0.000 (2)0.0229 (17)0.002 (2)
C150.023 (2)0.047 (3)0.0227 (19)0.0116 (19)0.0023 (15)0.0002 (18)
Br40.02513 (18)0.03240 (19)0.03221 (19)0.00913 (18)0.00980 (13)0.00367 (18)
O200.0232 (14)0.0245 (13)0.0200 (13)0.0088 (11)0.0046 (10)0.0016 (10)
C200.0197 (17)0.0124 (16)0.0199 (17)0.0001 (13)0.0039 (13)0.0043 (13)
O210.0213 (12)0.0172 (14)0.0230 (12)0.0018 (10)0.0065 (10)0.0013 (9)
C210.0171 (17)0.0150 (16)0.0198 (17)0.0001 (14)0.0038 (13)0.0030 (13)
O220.0193 (13)0.0320 (15)0.0281 (15)0.0009 (12)0.0007 (11)0.0092 (12)
C220.0158 (17)0.0215 (19)0.0211 (17)0.0043 (13)0.0027 (14)0.0006 (12)
C230.0140 (17)0.0239 (18)0.0270 (19)0.0002 (14)0.0005 (14)0.0013 (14)
C240.0188 (18)0.0199 (18)0.0269 (19)0.0025 (14)0.0110 (15)0.0021 (14)
C250.0243 (18)0.0224 (18)0.0166 (17)0.0021 (15)0.0049 (14)0.0022 (14)
C260.0187 (15)0.0176 (14)0.0192 (15)0.0009 (18)0.0037 (12)0.0024 (16)
Geometric parameters (Å, º) top
O1—C11.465 (4)C8—C121.524 (5)
O1—O21.470 (3)C9—C101.514 (5)
C1—C21.529 (5)C9—C121.535 (5)
C1—C111.542 (5)C9—C151.529 (5)
C1—C121.531 (5)O10—C101.254 (5)
O2—C31.416 (4)C10—N111.334 (5)
C2—O31.418 (4)Br4—C241.903 (4)
C2—N111.453 (5)O20—C201.307 (4)
O3—C31.440 (5)C20—O211.242 (4)
C3—C41.526 (5)C20—C211.479 (5)
C3—C131.515 (5)C21—C221.408 (5)
C4—C51.529 (5)C21—C261.394 (5)
C5—C111.538 (5)O22—C221.352 (5)
C6—C71.527 (6)C22—C231.391 (5)
C6—C111.536 (5)C23—C241.389 (6)
C6—C141.536 (5)C24—C251.378 (5)
C7—C81.528 (6)C25—C261.386 (5)
C1—O1—O2112.1 (2)C15—C9—C12113.5 (3)
O1—C1—C2110.2 (3)O10—C10—C9120.8 (3)
O1—C1—C11107.3 (3)O10—C10—N11121.1 (3)
O1—C1—C12104.3 (3)N11—C10—C9118.0 (3)
C2—C1—C11112.0 (3)C10—N11—C2127.7 (3)
C2—C1—C12110.7 (3)C5—C11—C1112.1 (3)
C12—C1—C11112.0 (3)C6—C11—C1112.3 (3)
C3—O2—O1107.4 (2)C6—C11—C5110.8 (3)
O3—C2—C1113.3 (3)C1—C12—C9110.4 (3)
O3—C2—N11108.9 (3)C8—C12—C1110.3 (3)
N11—C2—C1111.8 (3)C8—C12—C9115.1 (3)
C2—O3—C3113.6 (3)O20—C20—C21115.6 (3)
O2—C3—O3107.5 (3)O21—C20—O20123.1 (3)
O2—C3—C4112.2 (3)O21—C20—C21121.3 (3)
O2—C3—C13104.7 (3)C22—C21—C20119.3 (3)
O3—C3—C4111.3 (3)C26—C21—C20121.6 (3)
O3—C3—C13106.8 (3)C26—C21—C22119.0 (3)
C13—C3—C4113.9 (3)O22—C22—C21122.9 (3)
C3—C4—C5114.5 (3)O22—C22—C23117.4 (3)
C4—C5—C11115.9 (3)C23—C22—C21119.7 (3)
C7—C6—C11111.4 (3)C24—C23—C22118.9 (3)
C7—C6—C14110.0 (3)C23—C24—Br4118.3 (3)
C11—C6—C14111.5 (3)C25—C24—Br4118.7 (3)
C6—C7—C8112.5 (3)C25—C24—C23123.0 (3)
C12—C8—C7110.5 (3)C24—C25—C26117.4 (3)
C10—C9—C12112.4 (3)C25—C26—C21122.0 (3)
C10—C9—C15112.0 (3)
O1—C1—C2—O352.4 (4)N11—C2—O3—C399.5 (3)
O1—C1—C2—N1171.1 (4)C11—C1—C2—O366.9 (4)
O1—C1—C11—C568.2 (3)C11—C1—C2—N11169.6 (3)
O1—C1—C11—C6166.3 (3)C11—C1—C12—C855.9 (4)
O1—C1—C12—C8171.6 (3)C11—C1—C12—C9175.7 (3)
O1—C1—C12—C960.1 (3)C11—C6—C7—C853.1 (4)
O1—O2—C3—O375.8 (3)C12—C1—C2—O3167.3 (3)
O1—O2—C3—C446.9 (4)C12—C1—C2—N1143.7 (4)
O1—O2—C3—C13170.9 (3)C12—C1—C11—C5177.9 (3)
C1—O1—O2—C346.6 (3)C12—C1—C11—C652.4 (4)
C1—C2—O3—C325.6 (4)C12—C9—C10—O10155.1 (3)
C1—C2—N11—C1023.8 (6)C12—C9—C10—N1128.3 (5)
O2—O1—C1—C214.4 (3)C13—C3—C4—C5144.7 (4)
O2—O1—C1—C11107.7 (3)C14—C6—C7—C8177.3 (4)
O2—O1—C1—C12133.3 (3)C14—C6—C11—C1173.6 (3)
O2—C3—C4—C596.5 (4)C14—C6—C11—C560.2 (4)
C2—C1—C11—C552.9 (4)C15—C9—C10—O1025.9 (5)
C2—C1—C11—C672.7 (4)C15—C9—C10—N11157.5 (4)
C2—C1—C12—C869.9 (4)C15—C9—C12—C1178.2 (3)
C2—C1—C12—C958.5 (4)C15—C9—C12—C852.6 (4)
C2—O3—C3—O236.7 (4)Br4—C24—C25—C26179.7 (3)
C2—O3—C3—C486.5 (4)O20—C20—C21—C22179.5 (3)
C2—O3—C3—C13148.6 (3)O20—C20—C21—C265.0 (5)
O3—C2—N11—C10149.8 (4)C20—C21—C22—O222.5 (5)
O3—C3—C4—C524.0 (4)C20—C21—C22—C23176.5 (3)
C3—C4—C5—C1158.0 (4)C20—C21—C26—C25176.2 (3)
C4—C5—C11—C136.3 (4)O21—C20—C21—C221.0 (5)
C4—C5—C11—C6162.7 (3)O21—C20—C21—C26174.6 (3)
C6—C7—C8—C1257.3 (4)C21—C22—C23—C240.6 (5)
C7—C6—C11—C150.3 (4)O22—C22—C23—C24178.4 (3)
C7—C6—C11—C5176.5 (3)C22—C21—C26—C250.7 (6)
C7—C8—C12—C157.8 (4)C22—C23—C24—Br4179.6 (3)
C7—C8—C12—C9176.5 (3)C22—C23—C24—C250.4 (6)
C9—C10—N11—C216.0 (6)C23—C24—C25—C260.2 (6)
O10—C10—N11—C2167.4 (4)C24—C25—C26—C210.4 (6)
C10—C9—C12—C149.9 (4)C26—C21—C22—O22178.2 (3)
C10—C9—C12—C875.8 (4)C26—C21—C22—C230.8 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O210.81 (4)2.15 (4)2.931 (4)163 (4)
O20—H20···O100.86 (6)1.70 (6)2.550 (4)169 (6)
O22—H22···O210.83 (6)1.79 (6)2.574 (4)156 (6)
Unit cells for coformers and cocrystals 14 all at 100 K top
CompoundabcαβγVZMol. volumeReference
11-Aza11.71759 (15)11.71759 (15)9.48728 (13)90901201128.10 (3)3376.0Nisar et al. (2018a)
SalA4.8857 (5)11.2103 (7)11.2525 (11)9092.581 (9)90615.68 (9)4153.7Nisar et al. (2018a)
5-BrSalA6.9581 (7)7.1413 (8)8.0284 (9)81.959 (10)73.812 (10)71.352 (10)362.43 (8)2181.2This work
4-BrSalA3.8053 (2)14.6610 (8)12.9396 (7)9097.320 (6)90716.02 (7)4179.0This work
3,5-Br2SalA10.3703 (4)10.9444 (4)14.8108 (6)90103.350 (4)901635.55 (10)8204.4This work
1 11-Aza:SalA9.79451 (14)9.30687 (13)11.51291 (16)9092.3070 (12)901048.62 (3)2524.3Nisar et al. (2018a)
2 11-Aza: 5-BrSalA9.9325 (4)9.0196 (3)12.3942 (4)9093.844 (3)901107.88 (6)2554.0This work
3 11-Aza2: 4-BrSalA11.0814 (2)9.28293 (18)11.1404 (2)9098.638 (2)901132.99 (4)2566.5This work
4 11-Aza2: 35-Br2SalA9.52200 (19)9.3214 (2)13.3453 (3)9099.6446 (19)901167.76 (4)2583.9This work
Geometry (Å, °) of lactam–acid R22(8) heterosynthons in 14 top
CocrystalO10···O20N11···O21C10O10···O20—C20
12.549 (2)2.911 (2)41.6
22.541 (4)2.917 (5)31.7
32.550 (4)2.931 (4)40.8
42.542 (4)2.910 (5)37.6
Close contacts (Å) within and between 21 stacks for 14 top
1234Contact
Intra-stack
O1—H112.7802.6312.9872.82611Aza-11Aza
O2—H2/8a2.666/2.7773.066/3.1522.801/3.1742.856/2.74211Aza-11Aza
O3—H92.4322.7032.5742.47811Aza-11Aza
O10—H5a/62.808/2.9223.199/3.0652.731/3.2962.710/2.77311Aza-11Aza
O20—H4a2.9473.0633.1693.071SalA–11Aza
O21—H6/14b2.825/2.9002.742/3.4822.560/2.9082.885/2.885SalA–11Aza
O22—H122.9132.8832.7632.689SalA–11Aza
Inter-stack
O22—H24/2.8883.885/Br4 4.2234.536SalA–SalA
O20—H5a2.8203.5932.7745.62911Aza–SalA
O22—H13b2.6362.6774.4245.43711Aza–SalA
H5a—H262.4452.5352.5313.65311Aza–SalA
O10—H25/2.520/Br5 3.0222.500/H4b 2.527SalA–11Aza
O22—H8a3.9704.2942.5994.38411Aza–SalA
H8a—H15b2.8113.0454.1045.95511Aza-11Aza
O20—H13c8.5945.4592.81011Aza–SalA
O22—Br53.9113.530SalA–SalA
Hydrogen-bond comparison (Å) in coformers and cocrystals top
Cocrystal11-Aza N—H···OCocrystal N—H···OAcid O—H···.OCocrystal O—H···O
1 11-Aza:SalA3.033 (2)2.911 (2)2.651 (1)2.549 (2)
2 11-Aza:5-Br-SalA2.917 (5)2.645 (3)2.541 (4)
3 11-Aza2:4-Br-SalA2.931 (4)2.665 (5)2.550 (4)
4 11-Aza2:3,5-Br2-SalA2.910 (5)2.666 (3)2.542 (4)
Data for cocrystal 1 and 11-Aza are taken from Nisar et al. (2018a) and acids and cocrystals 24 are from this work.
Specific volumes (Å3) for cocrystals 14 at 100 K top
CocrystalAcid volumeaCombined volumebCocrystal volumecDifference in specific volume ΔV
1 11-Aza:SalA153.7529.7524.3-5.4 (-1.1%)
2 11-Aza:5-Br-SalA181.2557.2554.0-3.2 (-0.6%)
3 11-Aza2:4-Br-SalA179.0555.0566.5+11.5 (+2.1%)
4 11-Aza2:3,5-Br2-SalA204.4580.4583.9+3.5 (+0.6%)
Notes: (a) acid volumes from unit cells measured at 100 K (see Table 3); (b) specific volume of 376.0 Å for 11-azaartemisinin at 100 K (Nisar et al., 2018a); (c) corresponding combined volume from cocrystal structures 14.
 

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