5-(4-Meth­oxy­phen­yl)-1-[4-(4-meth­oxy­phen­yl)thia­zol-2-yl]-3-[4-(prop-2-yn­yloxy)phen­yl]-4,5-di­hydro-1H-pyrazole

The title compound, C₂₉H₂₅N₃O₃S, crystallizes in the monoclinic space group P2₁/n. The mol­ecule contains a central four-ring system in which all of the rings are almost coplanar. Both the 4-meth­oxy­phenyl ring and the prop-2-yn­yloxy substituent are disordered over two equivalent conformations with occupancy ratios of 0.903 (2):0.097 (2) and 0.776 (5):0.224 (5), respectively. In the crystal, π–π inter­actions [centroid–centroid distance = 3.7327 (11) Å] between the di­hydro­pyrazole ring and the 4-meth­oxy­phenyl ring link the mol­ecules into centrosymmetric dimers. In addition, there are weak C—H...S, C—H...N and C—H...O inter­actions, which link the mol­ecules into a complex three-dimensional array.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.051
• wR factor = 0.153
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT936_ALERT_2_B The Embedded .res File Includes a DAMP Command .       50.0 Report

Author Response: This structure contained disordered residues where the minor component was only 10% and thus needed a DAMP 50 instruction in order to converge.

Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          8 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          6 Note

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         22 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...         22 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT175_ALERT_4_G The CIF-Embedded .res File Contains SAME Records          2 Report
PLAT177_ALERT_4_G The CIF-Embedded .res File Contains DELU Records          2 Report
PLAT178_ALERT_4_G The CIF-Embedded .res File Contains SIMU Records          2 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        31% Note
PLAT367_ALERT_2_G Long?  C(sp?)-C(sp?) Bond  C1       - C2       .       1.54 Ang.
PLAT410_ALERT_2_G Short Intra H...H Contact  H1A      ..H19B     .       1.88 Ang.
                                                      x,y,z  =      1_555 Check
PLAT410_ALERT_2_G Short Intra H...H Contact  H23A     ..H27D     .       2.04 Ang.
                                                      x,y,z  =      1_555 Check
PLAT432_ALERT_2_G Short Inter X...Y Contact  O1       ..C20A     .       2.87 Ang.
                                          3/2-x,1/2+y,3/2-z  =      2_656 Check
PLAT480_ALERT_4_G Long H...A H-Bond Reported H20A     ..S1       .       2.96 Ang.
PLAT793_ALERT_4_G Model has Chirality at C1          (Centro SPGR)          S Verify
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............        373 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         10 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          9 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  18 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXT (Sheldrick 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick 2008); software used to prepare material for publication: SHELXTL (Sheldrick 2008).

5-(4-Methoxyphenyl)-1-[4-(4-methoxyphenyl)thiazol-2-yl]-3-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydro-1H-pyrazole

Crystal data

C29H25N3O3S	F(000) = 1040
Mr = 495.58	Dx = 1.308 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.9677 (11) Å	Cell parameters from 8545 reflections
b = 9.7997 (5) Å	θ = 2.2–27.5°
c = 18.4125 (14) Å	µ = 0.17 mm^−1
β = 92.980 (3)°	T = 100 K
V = 2516.9 (3) Å^3	Prism, yellow-orange
Z = 4	0.37 × 0.28 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer	4412 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.057
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 28.3°, θmin = 2.4°
Tmin = 0.687, Tmax = 0.743	h = −18→18
38138 measured reflections	k = −10→13
6228 independent reflections	l = −24→24

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0685P)^2 + 0.8521P] where P = (Fo^2 + 2Fc^2)/3
6228 reflections	(Δ/σ)max = 0.001
405 parameters	Δρmax = 0.41 e Å^−3
373 restraints	Δρmin = −0.35 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.

Refinement. All hydrogen atoms were placed geometrically and refined as riding atoms with their U_iso values 1.2 times that of their attached atoms (1.5 times for CH₃ groups).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.48897 (4)	0.77965 (6)	0.35477 (3)	0.05560 (16)
O1	0.48046 (12)	0.71860 (17)	0.79512 (8)	0.0688 (4)
O3	0.71638 (11)	0.50421 (15)	−0.05972 (7)	0.0580 (4)
N1	0.64253 (11)	0.61143 (15)	0.34811 (8)	0.0419 (3)
N2	0.63262 (11)	0.62808 (14)	0.27352 (8)	0.0418 (3)
N3	0.57829 (10)	0.65183 (14)	0.46069 (8)	0.0394 (3)
C1	0.70011 (13)	0.48893 (17)	0.37091 (9)	0.0408 (4)
H1A	0.656212	0.415582	0.387049	0.049*
C2	0.74028 (14)	0.44839 (19)	0.29771 (9)	0.0445 (4)
H2A	0.810217	0.464927	0.297907	0.053*
H2B	0.727491	0.351023	0.286636	0.053*
C3	0.68676 (13)	0.54007 (17)	0.24351 (9)	0.0406 (4)
C4	0.57693 (12)	0.66946 (17)	0.39064 (9)	0.0391 (4)
C5	0.45341 (15)	0.8047 (2)	0.44223 (11)	0.0550 (5)
H5A	0.402316	0.862735	0.454685	0.066*
C6	0.50804 (13)	0.73061 (17)	0.49073 (10)	0.0420 (4)
C7	0.50199 (12)	0.72744 (17)	0.57007 (10)	0.0412 (4)
C8	0.55106 (13)	0.62850 (18)	0.61154 (10)	0.0449 (4)
H8A	0.588689	0.563153	0.587729	0.054*
C9	0.54668 (14)	0.62246 (19)	0.68636 (10)	0.0486 (4)
H9A	0.581093	0.554079	0.713367	0.058*
C10	0.49168 (14)	0.7170 (2)	0.72161 (10)	0.0501 (4)
C11	0.44338 (15)	0.8183 (2)	0.68139 (11)	0.0533 (5)
H11A	0.406665	0.884324	0.705488	0.064*
C12	0.44837 (14)	0.82349 (19)	0.60720 (11)	0.0486 (4)
H12A	0.414977	0.893304	0.580556	0.058*
C13	0.5360 (2)	0.6235 (3)	0.83832 (12)	0.0809 (8)
H13A	0.520380	0.632679	0.889376	0.121*
H13B	0.604304	0.641978	0.833629	0.121*
H13C	0.521258	0.530507	0.821611	0.121*
O2	0.96938 (12)	0.63122 (18)	0.60184 (9)	0.0653 (5)	0.9031 (18)
C14	0.77537 (9)	0.52104 (14)	0.43282 (6)	0.0390 (4)	0.9031 (18)
C15	0.84871 (10)	0.61382 (15)	0.42253 (6)	0.0475 (5)	0.9031 (18)
H15A	0.854884	0.654687	0.376226	0.057*	0.9031 (18)
C16	0.91302 (9)	0.64680 (15)	0.48000 (7)	0.0531 (5)	0.9031 (18)
H16A	0.963144	0.710213	0.472969	0.064*	0.9031 (18)
C17	0.90399 (10)	0.58700 (15)	0.54776 (6)	0.0490 (5)	0.9031 (18)
C18	0.83065 (11)	0.49422 (15)	0.55805 (5)	0.0501 (5)	0.9031 (18)
H18A	0.824483	0.453354	0.604357	0.060*	0.9031 (18)
C19	0.76634 (9)	0.46124 (13)	0.50058 (7)	0.0463 (4)	0.9031 (18)
H19A	0.716222	0.397826	0.507615	0.056*	0.9031 (18)
C20	0.9610 (2)	0.5818 (3)	0.67135 (12)	0.0777 (8)	0.9031 (18)
H20A	1.010049	0.623856	0.704115	0.117*	0.9031 (18)
H20B	0.969662	0.482600	0.671442	0.117*	0.9031 (18)
H20C	0.897241	0.603953	0.687890	0.117*	0.9031 (18)
O2A	0.9164 (9)	0.5416 (13)	0.6245 (4)	0.0582 (13)	0.0969 (18)
C14A	0.7577 (9)	0.4962 (15)	0.4289 (4)	0.0432 (12)	0.0969 (18)
C15A	0.8359 (10)	0.5840 (14)	0.4354 (5)	0.0453 (11)	0.0969 (18)
H15B	0.852659	0.637862	0.395113	0.054*	0.0969 (18)
C16A	0.8895 (9)	0.5930 (14)	0.5010 (5)	0.0489 (11)	0.0969 (18)
H16B	0.942930	0.652944	0.505490	0.059*	0.0969 (18)
C17A	0.8650 (9)	0.5142 (14)	0.5600 (4)	0.0505 (11)	0.0969 (18)
C18A	0.7868 (9)	0.4264 (13)	0.5534 (5)	0.0479 (13)	0.0969 (18)
H18B	0.770080	0.372543	0.593724	0.057*	0.0969 (18)
C19A	0.7332 (8)	0.4174 (14)	0.4878 (6)	0.0459 (12)	0.0969 (18)
H19B	0.679808	0.357460	0.483347	0.055*	0.0969 (18)
C20A	0.9051 (19)	0.460 (2)	0.6841 (6)	0.082 (3)	0.0969 (18)
H20D	0.962533	0.403490	0.692864	0.123*	0.0969 (18)
H20E	0.849170	0.400739	0.675099	0.123*	0.0969 (18)
H20F	0.895649	0.517020	0.726775	0.123*	0.0969 (18)
C21	0.69613 (13)	0.53308 (17)	0.16510 (9)	0.0402 (4)
C22	0.74989 (14)	0.42971 (18)	0.13576 (10)	0.0442 (4)
H22A	0.781885	0.366216	0.167561	0.053*
C23	0.75834 (14)	0.41626 (18)	0.06136 (10)	0.0467 (4)
H23A	0.795108	0.343945	0.042691	0.056*
C24	0.71301 (14)	0.50857 (19)	0.01473 (10)	0.0450 (4)
C25	0.66104 (16)	0.6156 (2)	0.04303 (11)	0.0541 (5)
H25A	0.631401	0.680960	0.011091	0.065*
C26	0.65219 (16)	0.6276 (2)	0.11689 (10)	0.0524 (5)
H26A	0.615940	0.700623	0.135363	0.063*
C27A	0.7636 (6)	0.3881 (8)	−0.08931 (18)	0.0595 (7)	0.776 (5)
H27A	0.739898	0.303503	−0.066937	0.071*	0.776 (5)
H27B	0.833461	0.394482	−0.077831	0.071*	0.776 (5)
C28A	0.7450 (3)	0.3823 (4)	−0.16871 (16)	0.0668 (8)	0.776 (5)
C29A	0.7342 (3)	0.3741 (5)	−0.23140 (18)	0.0949 (13)	0.776 (5)
H29A	0.725292	0.367315	−0.282778	0.114*	0.776 (5)
C27B	0.760 (2)	0.389 (3)	−0.0900 (5)	0.0633 (15)	0.224 (5)
H27C	0.717276	0.307691	−0.089321	0.076*	0.224 (5)
H27D	0.821888	0.366756	−0.064344	0.076*	0.224 (5)
C28B	0.7724 (10)	0.4367 (14)	−0.1646 (4)	0.0670 (15)	0.224 (5)
C29B	0.7878 (11)	0.4729 (16)	−0.2228 (5)	0.089 (2)	0.224 (5)
H29B	0.800357	0.502657	−0.270433	0.107*	0.224 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0604 (3)	0.0595 (3)	0.0466 (3)	0.0194 (2)	0.0006 (2)	0.0083 (2)
O1	0.0788 (11)	0.0863 (11)	0.0411 (8)	0.0198 (9)	0.0030 (7)	−0.0116 (7)
O3	0.0703 (9)	0.0672 (9)	0.0365 (7)	0.0163 (7)	0.0031 (6)	0.0021 (6)
N1	0.0473 (8)	0.0432 (8)	0.0348 (7)	0.0073 (6)	−0.0008 (6)	0.0003 (6)
N2	0.0480 (8)	0.0412 (7)	0.0357 (7)	0.0014 (6)	−0.0023 (6)	0.0000 (6)
N3	0.0393 (8)	0.0382 (7)	0.0406 (8)	0.0018 (6)	0.0017 (6)	−0.0013 (6)
C1	0.0434 (9)	0.0384 (8)	0.0406 (9)	0.0035 (7)	0.0015 (7)	0.0013 (7)
C2	0.0512 (10)	0.0452 (9)	0.0370 (9)	0.0064 (8)	0.0000 (8)	−0.0012 (7)
C3	0.0447 (9)	0.0370 (8)	0.0396 (9)	−0.0032 (7)	−0.0032 (7)	0.0001 (7)
C4	0.0385 (9)	0.0355 (8)	0.0430 (9)	−0.0006 (7)	−0.0002 (7)	−0.0007 (7)
C5	0.0560 (12)	0.0572 (11)	0.0523 (11)	0.0203 (9)	0.0065 (9)	0.0052 (9)
C6	0.0398 (9)	0.0375 (8)	0.0488 (10)	0.0031 (7)	0.0038 (7)	−0.0007 (7)
C7	0.0375 (9)	0.0381 (8)	0.0480 (10)	0.0000 (7)	0.0033 (7)	−0.0020 (7)
C8	0.0433 (10)	0.0440 (9)	0.0478 (10)	0.0074 (7)	0.0066 (8)	−0.0033 (7)
C9	0.0491 (10)	0.0495 (10)	0.0468 (10)	0.0083 (8)	−0.0009 (8)	−0.0011 (8)
C10	0.0504 (11)	0.0570 (11)	0.0430 (10)	0.0005 (9)	0.0022 (8)	−0.0091 (8)
C11	0.0538 (11)	0.0518 (10)	0.0545 (11)	0.0112 (9)	0.0051 (9)	−0.0133 (9)
C12	0.0495 (10)	0.0423 (9)	0.0540 (11)	0.0085 (8)	0.0026 (9)	−0.0045 (8)
C13	0.0922 (19)	0.107 (2)	0.0423 (12)	0.0244 (16)	−0.0058 (12)	−0.0021 (12)
O2	0.0609 (10)	0.0750 (11)	0.0582 (9)	−0.0034 (8)	−0.0138 (8)	−0.0081 (8)
C14	0.0414 (10)	0.0405 (9)	0.0350 (8)	0.0054 (8)	0.0014 (7)	−0.0004 (7)
C15	0.0459 (10)	0.0530 (11)	0.0433 (10)	−0.0013 (8)	−0.0003 (8)	0.0058 (8)
C16	0.0470 (11)	0.0566 (12)	0.0550 (11)	−0.0064 (9)	−0.0034 (9)	0.0027 (9)
C17	0.0489 (10)	0.0543 (10)	0.0427 (9)	0.0053 (8)	−0.0084 (8)	−0.0067 (8)
C18	0.0567 (11)	0.0570 (11)	0.0363 (9)	0.0042 (9)	−0.0013 (8)	0.0020 (8)
C19	0.0500 (10)	0.0489 (10)	0.0397 (9)	−0.0011 (8)	0.0010 (8)	0.0031 (8)
C20	0.0746 (17)	0.103 (2)	0.0528 (13)	0.0058 (15)	−0.0228 (12)	−0.0144 (13)
O2A	0.057 (2)	0.071 (2)	0.045 (2)	0.003 (2)	−0.011 (2)	−0.006 (2)
C14A	0.043 (2)	0.048 (2)	0.038 (2)	0.001 (2)	−0.001 (2)	0.001 (2)
C15A	0.046 (2)	0.049 (2)	0.041 (2)	−0.0004 (19)	−0.002 (2)	0.004 (2)
C16A	0.048 (2)	0.055 (2)	0.0433 (19)	−0.001 (2)	−0.0039 (19)	0.001 (2)
C17A	0.050 (2)	0.058 (2)	0.0418 (18)	0.0006 (19)	−0.0055 (19)	−0.0013 (19)
C18A	0.051 (3)	0.054 (3)	0.039 (2)	0.000 (2)	−0.003 (2)	0.002 (2)
C19A	0.049 (2)	0.050 (2)	0.038 (2)	0.000 (2)	−0.002 (2)	0.001 (2)
C20A	0.086 (7)	0.105 (7)	0.055 (5)	0.005 (7)	−0.012 (6)	0.006 (5)
C21	0.0445 (9)	0.0376 (8)	0.0381 (9)	−0.0030 (7)	−0.0015 (7)	0.0001 (7)
C22	0.0526 (10)	0.0396 (9)	0.0400 (9)	0.0040 (8)	−0.0007 (8)	0.0041 (7)
C23	0.0557 (11)	0.0413 (9)	0.0432 (10)	0.0044 (8)	0.0031 (8)	−0.0004 (7)
C24	0.0484 (10)	0.0483 (10)	0.0382 (9)	−0.0008 (8)	0.0004 (8)	0.0007 (7)
C25	0.0663 (13)	0.0536 (11)	0.0416 (10)	0.0142 (9)	−0.0037 (9)	0.0057 (8)
C26	0.0662 (13)	0.0485 (10)	0.0421 (10)	0.0138 (9)	−0.0009 (9)	−0.0003 (8)
C27A	0.0708 (17)	0.0651 (14)	0.0433 (12)	0.0111 (13)	0.0087 (12)	−0.0033 (12)
C28A	0.0751 (19)	0.0782 (19)	0.0477 (13)	0.0140 (15)	0.0078 (13)	−0.0069 (13)
C29A	0.105 (3)	0.130 (3)	0.0498 (16)	0.037 (2)	0.0049 (17)	−0.0135 (19)
C27B	0.074 (3)	0.072 (3)	0.045 (2)	0.013 (3)	0.008 (3)	−0.006 (3)
C28B	0.077 (3)	0.079 (3)	0.045 (2)	0.017 (3)	0.011 (2)	−0.007 (2)
C29B	0.102 (5)	0.117 (5)	0.050 (4)	0.019 (5)	0.016 (4)	0.004 (4)

Geometric parameters (Å, º)

S1—C5	1.727 (2)	C16—H16A	0.9500
S1—C4	1.7399 (18)	C17—C18	1.3900
O1—C10	1.371 (2)	C18—C19	1.3900
O1—C13	1.428 (3)	C18—H18A	0.9500
O3—C24	1.375 (2)	C19—H19A	0.9500
O3—C27B	1.41 (3)	C20—H20A	0.9800
O3—C27A	1.437 (8)	C20—H20B	0.9800
N1—C4	1.360 (2)	C20—H20C	0.9800
N1—N2	1.3829 (19)	O2A—C20A	1.374 (6)
N1—C1	1.493 (2)	O2A—C17A	1.382 (4)
N2—C3	1.290 (2)	C14A—C15A	1.3900
N3—C4	1.300 (2)	C14A—C19A	1.3900
N3—C6	1.386 (2)	C15A—C16A	1.3900
C1—C14A	1.305 (7)	C15A—H15B	0.9500
C1—C2	1.539 (2)	C16A—C17A	1.3900
C1—C14	1.5424 (19)	C16A—H16B	0.9500
C1—H1A	1.0000	C17A—C18A	1.3900
C2—C3	1.511 (2)	C18A—C19A	1.3900
C2—H2A	0.9900	C18A—H18B	0.9500
C2—H2B	0.9900	C19A—H19B	0.9500
C3—C21	1.458 (2)	C20A—H20D	0.9800
C5—C6	1.355 (3)	C20A—H20E	0.9800
C5—H5A	0.9500	C20A—H20F	0.9800
C6—C7	1.468 (3)	C21—C22	1.387 (2)
C7—C8	1.392 (2)	C21—C26	1.402 (2)
C7—C12	1.403 (2)	C22—C23	1.387 (2)
C8—C9	1.384 (3)	C22—H22A	0.9500
C8—H8A	0.9500	C23—C24	1.378 (3)
C9—C10	1.386 (3)	C23—H23A	0.9500
C9—H9A	0.9500	C24—C25	1.392 (3)
C10—C11	1.392 (3)	C25—C26	1.377 (3)
C11—C12	1.372 (3)	C25—H25A	0.9500
C11—H11A	0.9500	C26—H26A	0.9500
C12—H12A	0.9500	C27A—C28A	1.472 (4)
C13—H13A	0.9800	C27A—H27A	0.9900
C13—H13B	0.9800	C27A—H27B	0.9900
C13—H13C	0.9800	C28A—C29A	1.159 (4)
O2—C20	1.379 (3)	C29A—H29A	0.9500
O2—C17	1.3852 (17)	C27B—C28B	1.473 (6)
C14—C15	1.3900	C27B—H27C	0.9900
C14—C19	1.3900	C27B—H27D	0.9900
C15—C16	1.3900	C28B—C29B	1.159 (5)
C15—H15A	0.9500	C29B—H29B	0.9500
C16—C17	1.3900
C5—S1—C4	88.05 (9)	C17—C18—C19	120.0
C10—O1—C13	117.13 (17)	C17—C18—H18A	120.0
C24—O3—C27B	117.1 (5)	C19—C18—H18A	120.0
C24—O3—C27A	116.29 (19)	C18—C19—C14	120.0
C4—N1—N2	119.12 (14)	C18—C19—H19A	120.0
C4—N1—C1	122.91 (14)	C14—C19—H19A	120.0
N2—N1—C1	113.50 (13)	O2—C20—H20A	109.5
C3—N2—N1	108.41 (14)	O2—C20—H20B	109.5
C4—N3—C6	110.35 (15)	H20A—C20—H20B	109.5
C14A—C1—N1	119.1 (7)	O2—C20—H20C	109.5
C14A—C1—C2	119.5 (6)	H20A—C20—H20C	109.5
N1—C1—C2	100.19 (13)	H20B—C20—H20C	109.5
N1—C1—C14	112.35 (13)	C20A—O2A—C17A	119.8 (8)
C2—C1—C14	115.75 (14)	C1—C14A—C15A	123.6 (8)
N1—C1—H1A	109.4	C1—C14A—C19A	116.2 (8)
C2—C1—H1A	109.4	C15A—C14A—C19A	120.0
C14—C1—H1A	109.4	C16A—C15A—C14A	120.0
C3—C2—C1	103.56 (14)	C16A—C15A—H15B	120.0
C3—C2—H2A	111.0	C14A—C15A—H15B	120.0
C1—C2—H2A	111.0	C15A—C16A—C17A	120.0
C3—C2—H2B	111.0	C15A—C16A—H16B	120.0
C1—C2—H2B	111.0	C17A—C16A—H16B	120.0
H2A—C2—H2B	109.0	O2A—C17A—C16A	115.2 (5)
N2—C3—C21	122.71 (15)	O2A—C17A—C18A	124.5 (5)
N2—C3—C2	113.29 (15)	C16A—C17A—C18A	120.0
C21—C3—C2	123.99 (15)	C19A—C18A—C17A	120.0
N3—C4—N1	122.67 (16)	C19A—C18A—H18B	120.0
N3—C4—S1	115.63 (13)	C17A—C18A—H18B	120.0
N1—C4—S1	121.63 (13)	C18A—C19A—C14A	120.0
C6—C5—S1	111.04 (15)	C18A—C19A—H19B	120.0
C6—C5—H5A	124.5	C14A—C19A—H19B	120.0
S1—C5—H5A	124.5	O2A—C20A—H20D	109.5
C5—C6—N3	114.93 (17)	O2A—C20A—H20E	109.5
C5—C6—C7	127.42 (17)	H20D—C20A—H20E	109.5
N3—C6—C7	117.64 (15)	O2A—C20A—H20F	109.5
C8—C7—C12	117.40 (17)	H20D—C20A—H20F	109.5
C8—C7—C6	120.55 (16)	H20E—C20A—H20F	109.5
C12—C7—C6	122.05 (16)	C22—C21—C26	117.63 (17)
C9—C8—C7	122.00 (16)	C22—C21—C3	119.89 (15)
C9—C8—H8A	119.0	C26—C21—C3	122.48 (16)
C7—C8—H8A	119.0	C23—C22—C21	121.97 (16)
C8—C9—C10	119.47 (17)	C23—C22—H22A	119.0
C8—C9—H9A	120.3	C21—C22—H22A	119.0
C10—C9—H9A	120.3	C24—C23—C22	119.53 (17)
O1—C10—C9	124.39 (18)	C24—C23—H23A	120.2
O1—C10—C11	116.10 (17)	C22—C23—H23A	120.2
C9—C10—C11	119.51 (18)	O3—C24—C23	124.22 (17)
C12—C11—C10	120.53 (17)	O3—C24—C25	116.25 (16)
C12—C11—H11A	119.7	C23—C24—C25	119.52 (17)
C10—C11—H11A	119.7	C26—C25—C24	120.63 (17)
C11—C12—C7	121.07 (18)	C26—C25—H25A	119.7
C11—C12—H12A	119.5	C24—C25—H25A	119.7
C7—C12—H12A	119.5	C25—C26—C21	120.67 (18)
O1—C13—H13A	109.5	C25—C26—H26A	119.7
O1—C13—H13B	109.5	C21—C26—H26A	119.7
H13A—C13—H13B	109.5	O3—C27A—C28A	110.3 (5)
O1—C13—H13C	109.5	O3—C27A—H27A	109.6
H13A—C13—H13C	109.5	C28A—C27A—H27A	109.6
H13B—C13—H13C	109.5	O3—C27A—H27B	109.6
C20—O2—C17	118.21 (19)	C28A—C27A—H27B	109.6
C15—C14—C19	120.0	H27A—C27A—H27B	108.1
C15—C14—C1	120.76 (10)	C29A—C28A—C27A	176.8 (5)
C19—C14—C1	119.16 (10)	C28A—C29A—H29A	180.0
C16—C15—C14	120.0	O3—C27B—C28B	100.7 (15)
C16—C15—H15A	120.0	O3—C27B—H27C	111.6
C14—C15—H15A	120.0	C28B—C27B—H27C	111.6
C17—C16—C15	120.0	O3—C27B—H27D	111.6
C17—C16—H16A	120.0	C28B—C27B—H27D	111.6
C15—C16—H16A	120.0	H27C—C27B—H27D	109.4
O2—C17—C16	115.22 (12)	C29B—C28B—C27B	176.2 (19)
O2—C17—C18	124.73 (12)	C28B—C29B—H29B	180.0
C16—C17—C18	120.0
C4—N1—N2—C3	−164.73 (16)	C19—C14—C15—C16	0.0
C1—N1—N2—C3	−7.73 (19)	C1—C14—C15—C16	176.71 (14)
C4—N1—C1—C14A	−61.3 (7)	C14—C15—C16—C17	0.0
N2—N1—C1—C14A	142.7 (7)	C20—O2—C17—C16	176.35 (18)
C4—N1—C1—C2	166.41 (16)	C20—O2—C17—C18	−1.0 (3)
N2—N1—C1—C2	10.40 (18)	C15—C16—C17—O2	−177.48 (14)
C4—N1—C1—C14	−70.1 (2)	C15—C16—C17—C18	0.0
N2—N1—C1—C14	133.85 (14)	O2—C17—C18—C19	177.23 (16)
C14A—C1—C2—C3	−140.7 (7)	C16—C17—C18—C19	0.0
N1—C1—C2—C3	−8.68 (17)	C17—C18—C19—C14	0.0
C14—C1—C2—C3	−129.73 (15)	C15—C14—C19—C18	0.0
N1—N2—C3—C21	−177.66 (15)	C1—C14—C19—C18	−176.76 (13)
N1—N2—C3—C2	1.1 (2)	N1—C1—C14A—C15A	−62.8 (10)
C1—C2—C3—N2	5.4 (2)	C2—C1—C14A—C15A	60.5 (11)
C1—C2—C3—C21	−175.90 (16)	N1—C1—C14A—C19A	112.5 (7)
C6—N3—C4—N1	175.47 (16)	C2—C1—C14A—C19A	−124.2 (7)
C6—N3—C4—S1	−1.41 (19)	C1—C14A—C15A—C16A	175.1 (13)
N2—N1—C4—N3	175.93 (15)	C19A—C14A—C15A—C16A	0.0
C1—N1—C4—N3	21.2 (3)	C14A—C15A—C16A—C17A	0.0
N2—N1—C4—S1	−7.4 (2)	C20A—O2A—C17A—C16A	−173.0 (16)
C1—N1—C4—S1	−162.11 (13)	C20A—O2A—C17A—C18A	14 (2)
C5—S1—C4—N3	0.97 (15)	C15A—C16A—C17A—O2A	−173.4 (13)
C5—S1—C4—N1	−175.95 (16)	C15A—C16A—C17A—C18A	0.0
C4—S1—C5—C6	−0.22 (16)	O2A—C17A—C18A—C19A	172.7 (14)
S1—C5—C6—N3	−0.5 (2)	C16A—C17A—C18A—C19A	0.0
S1—C5—C6—C7	178.12 (15)	C17A—C18A—C19A—C14A	0.0
C4—N3—C6—C5	1.2 (2)	C1—C14A—C19A—C18A	−175.5 (12)
C4—N3—C6—C7	−177.54 (15)	C15A—C14A—C19A—C18A	0.0
C5—C6—C7—C8	168.4 (2)	N2—C3—C21—C22	−175.21 (17)
N3—C6—C7—C8	−13.0 (2)	C2—C3—C21—C22	6.2 (3)
C5—C6—C7—C12	−12.4 (3)	N2—C3—C21—C26	4.6 (3)
N3—C6—C7—C12	166.16 (17)	C2—C3—C21—C26	−174.07 (18)
C12—C7—C8—C9	1.0 (3)	C26—C21—C22—C23	−1.9 (3)
C6—C7—C8—C9	−179.83 (17)	C3—C21—C22—C23	177.88 (17)
C7—C8—C9—C10	0.3 (3)	C21—C22—C23—C24	0.6 (3)
C13—O1—C10—C9	5.6 (3)	C27B—O3—C24—C23	7.7 (14)
C13—O1—C10—C11	−174.6 (2)	C27A—O3—C24—C23	5.7 (4)
C8—C9—C10—O1	178.44 (18)	C27B—O3—C24—C25	−173.3 (13)
C8—C9—C10—C11	−1.4 (3)	C27A—O3—C24—C25	−175.3 (4)
O1—C10—C11—C12	−178.57 (19)	C22—C23—C24—O3	−179.70 (18)
C9—C10—C11—C12	1.3 (3)	C22—C23—C24—C25	1.3 (3)
C10—C11—C12—C7	0.0 (3)	O3—C24—C25—C26	178.99 (19)
C8—C7—C12—C11	−1.1 (3)	C23—C24—C25—C26	−2.0 (3)
C6—C7—C12—C11	179.72 (18)	C24—C25—C26—C21	0.7 (3)
N1—C1—C14—C15	−62.36 (16)	C22—C21—C26—C25	1.2 (3)
C2—C1—C14—C15	51.90 (17)	C3—C21—C26—C25	−178.52 (18)
N1—C1—C14—C19	114.38 (13)	C24—O3—C27A—C28A	168.6 (4)
C2—C1—C14—C19	−131.37 (13)	C24—O3—C27B—C28B	−165.9 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20A···S1^i	0.98	2.96	3.642 (2)	128
C20A—H20D···O1^ii	0.98	1.99	2.87 (2)	148
C23—H23A···N3^iii	0.95	2.59	3.490 (2)	159

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+1/2.