Synthesis and structure of push–pull merocyanines based on barbituric and thio­barbituric acid

The synthesis and crystal structures of 1,3-diethyl-5-{(2E,4E)-6-[(E)-1,3,3-tri­methyl­indolin-2-yl­idene]hexa-2,4-dien-1-yl­idene}pyrimidine-2,4,6(1H,3H,5H)-trione or TMI, C₂₅H₂₉N₃O₃, and 1,3-diethyl-2-sulfanyl­idene-5-[2-(1,3,3-tri­methyl­indolin-2-yl­idene)ethyl­idene]di­hydro­pyrimidine-4,6(1H,5H)-dione or DTB, C₂₁H₂₅N₃O₂S, are described. These compounds contain the same indole derivative donor group and differ in their acceptor groups (in TMI it contains oxygen in the para position, and in DTB sulfur) and the length of the π-bridge.

Key indicators

Structure: TMI

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.048
• wR factor = 0.117
• Data-to-parameter ratio = 24.7

Structure: DTB

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.046
• wR factor = 0.141
• Data-to-parameter ratio = 49.6

checkCIF/PLATON results

No syntax errors found



Datablock: TMI



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3       ..O2       .       2.61 Ang.

Alert level G
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         32 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         18 Info

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

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




Datablock: DTB



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H21A     ..S1       .       2.98 Ang.
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.962 Report

Alert level G
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         24 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         15 Info

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

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

---

Computing details

For both structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

1,3-Diethyl-5-{(2E,4E)-6-[(E)-1,3,3-trimethylindolin-2-ylidene]hexa-2,4-dien-1-ylidene}pyrimidine-2,4,6(1H,3H,5H)-trione (TMI)

Crystal data

C25H29N3O3	F(000) = 896
Mr = 419.51	Dx = 1.262 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.7624 (9) Å	Cell parameters from 8868 reflections
b = 22.9546 (19) Å	θ = 2.5–28.2°
c = 8.1934 (7) Å	µ = 0.08 mm^−1
β = 93.717 (2)°	T = 100 K
V = 2207.6 (3) Å^3	Plate, metallic light blue
Z = 4	0.3 × 0.25 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer	4810 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.085
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 31.1°, θmin = 1.7°
Tmin = 0.601, Tmax = 0.746	h = −16→17
69450 measured reflections	k = −33→33
7037 independent reflections	l = −11→11

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0433P)^2 + 0.7306P] where P = (Fo^2 + 2Fc^2)/3
7037 reflections	(Δ/σ)max < 0.001
285 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.28 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.57141 (8)	0.28544 (4)	0.06369 (11)	0.0250 (2)
C14	0.45141 (11)	0.39420 (5)	0.74941 (16)	0.0210 (3)
H14	0.486034	0.431317	0.765679	0.025*
O3	0.84399 (9)	0.40063 (4)	−0.13659 (12)	0.0300 (2)
O2	0.68018 (9)	0.46420 (4)	0.31743 (12)	0.0314 (2)
N1	0.28095 (9)	0.42110 (4)	1.26866 (12)	0.0195 (2)
N2	0.70066 (9)	0.34541 (5)	−0.04349 (13)	0.0203 (2)
N3	0.75975 (9)	0.43289 (4)	0.08893 (13)	0.0201 (2)
C7	0.29334 (10)	0.38885 (5)	1.13030 (15)	0.0172 (2)
C8	0.21355 (10)	0.33601 (5)	1.13327 (15)	0.0174 (2)
C5	0.15411 (11)	0.34692 (5)	1.28882 (15)	0.0187 (2)
C12	0.36413 (11)	0.40500 (5)	1.01155 (15)	0.0196 (2)
H12	0.404050	0.440701	1.028219	0.023*
C4	0.19733 (11)	0.39734 (5)	1.36456 (15)	0.0195 (2)
C13	0.38377 (11)	0.37410 (5)	0.86730 (15)	0.0201 (2)
H13	0.348086	0.337243	0.850912	0.024*
C20	0.62694 (11)	0.33057 (5)	0.07785 (15)	0.0195 (2)
C17	0.55933 (10)	0.35433 (5)	0.34446 (15)	0.0201 (2)
H17	0.523420	0.317338	0.333554	0.024*
C21	0.77321 (11)	0.39312 (6)	−0.03588 (15)	0.0212 (3)
C15	0.47303 (11)	0.36355 (6)	0.60582 (16)	0.0209 (3)
H15	0.439083	0.326297	0.589055	0.025*
C18	0.62303 (10)	0.37085 (5)	0.21547 (15)	0.0188 (2)
C19	0.68610 (11)	0.42537 (5)	0.21503 (15)	0.0206 (3)
C16	0.54072 (11)	0.38470 (6)	0.48855 (16)	0.0214 (3)
H16	0.576385	0.421508	0.506047	0.026*
C22	0.83708 (11)	0.48360 (5)	0.09856 (16)	0.0225 (3)
H22A	0.797739	0.517098	0.146023	0.027*
H22B	0.856797	0.494552	−0.013005	0.027*
C9	0.12617 (11)	0.33600 (6)	0.98519 (15)	0.0218 (3)
H9A	0.069422	0.305443	0.999149	0.033*
H9B	0.165282	0.328573	0.885221	0.033*
H9C	0.088140	0.373965	0.976858	0.033*
C6	0.06730 (11)	0.31656 (6)	1.35644 (16)	0.0229 (3)
H6	0.037084	0.282200	1.305626	0.028*
C3	0.15744 (12)	0.41847 (6)	1.50894 (16)	0.0243 (3)
H3	0.188713	0.452496	1.560313	0.029*
C10	0.28018 (11)	0.27818 (5)	1.14518 (17)	0.0230 (3)
H10A	0.226542	0.245599	1.148562	0.034*
H10B	0.330873	0.278119	1.244935	0.034*
H10C	0.325495	0.274050	1.049600	0.034*
C24	0.70962 (12)	0.30531 (6)	−0.18308 (15)	0.0235 (3)
H24A	0.730561	0.327686	−0.279980	0.028*
H24B	0.634697	0.286813	−0.209861	0.028*
C2	0.06930 (12)	0.38748 (6)	1.57531 (16)	0.0267 (3)
H2	0.039178	0.400960	1.673280	0.032*
C1	0.02468 (12)	0.33723 (6)	1.50078 (17)	0.0272 (3)
H1	−0.035165	0.316835	1.548404	0.033*
C11	0.34104 (12)	0.47513 (6)	1.30867 (17)	0.0255 (3)
H11A	0.331476	0.485237	1.423182	0.038*
H11B	0.309903	0.506406	1.237660	0.038*
H11C	0.422246	0.470163	1.292140	0.038*
C25	0.79828 (12)	0.25841 (6)	−0.14451 (18)	0.0289 (3)
H25A	0.805058	0.233709	−0.240946	0.043*
H25B	0.775041	0.234562	−0.053227	0.043*
H25C	0.871977	0.276688	−0.114467	0.043*
C23	0.94519 (12)	0.47040 (6)	0.20246 (19)	0.0297 (3)
H23A	0.994861	0.504712	0.206046	0.045*
H23B	0.984717	0.437534	0.154931	0.045*
H23C	0.925955	0.460408	0.313647	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0246 (5)	0.0215 (5)	0.0289 (5)	−0.0026 (4)	0.0012 (4)	−0.0021 (4)
C14	0.0197 (6)	0.0193 (6)	0.0243 (6)	−0.0012 (5)	0.0032 (5)	0.0022 (5)
O3	0.0326 (6)	0.0326 (5)	0.0261 (5)	−0.0046 (4)	0.0110 (4)	−0.0023 (4)
O2	0.0397 (6)	0.0235 (5)	0.0325 (5)	−0.0086 (4)	0.0153 (5)	−0.0079 (4)
N1	0.0213 (5)	0.0172 (5)	0.0200 (5)	−0.0035 (4)	0.0015 (4)	−0.0014 (4)
N2	0.0204 (5)	0.0212 (5)	0.0193 (5)	0.0011 (4)	0.0011 (4)	−0.0016 (4)
N3	0.0208 (5)	0.0184 (5)	0.0214 (5)	−0.0011 (4)	0.0047 (4)	0.0003 (4)
C7	0.0171 (6)	0.0148 (5)	0.0193 (5)	0.0003 (4)	−0.0010 (4)	0.0008 (4)
C8	0.0171 (6)	0.0151 (5)	0.0200 (5)	−0.0011 (4)	0.0018 (4)	−0.0005 (4)
C5	0.0190 (6)	0.0182 (5)	0.0186 (5)	0.0007 (5)	−0.0001 (4)	0.0017 (4)
C12	0.0184 (6)	0.0169 (5)	0.0234 (6)	−0.0015 (5)	0.0014 (5)	0.0013 (5)
C4	0.0197 (6)	0.0202 (6)	0.0183 (5)	−0.0003 (5)	−0.0006 (5)	0.0019 (4)
C13	0.0170 (6)	0.0184 (6)	0.0248 (6)	0.0005 (5)	0.0014 (5)	0.0023 (5)
C20	0.0170 (6)	0.0204 (6)	0.0210 (6)	0.0037 (5)	0.0001 (5)	0.0014 (5)
C17	0.0155 (6)	0.0197 (6)	0.0250 (6)	0.0000 (5)	0.0009 (5)	0.0006 (5)
C21	0.0210 (6)	0.0222 (6)	0.0203 (6)	0.0019 (5)	0.0012 (5)	0.0006 (5)
C15	0.0174 (6)	0.0199 (6)	0.0256 (6)	−0.0002 (5)	0.0025 (5)	0.0021 (5)
C18	0.0167 (6)	0.0185 (6)	0.0211 (6)	0.0008 (4)	0.0011 (4)	0.0001 (5)
C19	0.0202 (6)	0.0202 (6)	0.0217 (6)	0.0014 (5)	0.0033 (5)	0.0009 (5)
C16	0.0181 (6)	0.0212 (6)	0.0250 (6)	−0.0006 (5)	0.0024 (5)	0.0011 (5)
C22	0.0247 (7)	0.0182 (6)	0.0253 (6)	−0.0026 (5)	0.0060 (5)	0.0020 (5)
C9	0.0205 (6)	0.0243 (6)	0.0204 (6)	−0.0008 (5)	−0.0006 (5)	−0.0031 (5)
C6	0.0234 (7)	0.0216 (6)	0.0239 (6)	−0.0028 (5)	0.0025 (5)	0.0013 (5)
C3	0.0287 (7)	0.0246 (6)	0.0194 (6)	−0.0008 (5)	−0.0007 (5)	−0.0015 (5)
C10	0.0223 (6)	0.0166 (6)	0.0302 (7)	0.0004 (5)	0.0036 (5)	0.0015 (5)
C24	0.0254 (7)	0.0263 (6)	0.0187 (6)	0.0022 (5)	−0.0001 (5)	−0.0041 (5)
C2	0.0313 (7)	0.0303 (7)	0.0190 (6)	0.0013 (6)	0.0044 (5)	0.0014 (5)
C1	0.0269 (7)	0.0307 (7)	0.0245 (6)	−0.0037 (6)	0.0060 (5)	0.0041 (5)
C11	0.0294 (7)	0.0184 (6)	0.0283 (7)	−0.0063 (5)	−0.0013 (6)	−0.0032 (5)
C25	0.0254 (7)	0.0301 (7)	0.0308 (7)	0.0060 (6)	−0.0025 (6)	−0.0096 (6)
C23	0.0219 (7)	0.0270 (7)	0.0402 (8)	−0.0001 (5)	0.0020 (6)	−0.0045 (6)

Geometric parameters (Å, º)

O1—C20	1.2261 (15)	C15—C16	1.3756 (18)
C14—H14	0.9500	C18—C19	1.4550 (17)
C14—C13	1.3706 (18)	C16—H16	0.9500
C14—C15	1.4080 (18)	C22—H22A	0.9900
O3—C21	1.2218 (16)	C22—H22B	0.9900
O2—C19	1.2291 (15)	C22—C23	1.5144 (19)
N1—C7	1.3696 (15)	C9—H9A	0.9800
N1—C4	1.4080 (16)	C9—H9B	0.9800
N1—C11	1.4544 (16)	C9—H9C	0.9800
N2—C20	1.4029 (16)	C6—H6	0.9500
N2—C21	1.3873 (16)	C6—C1	1.3971 (19)
N2—C24	1.4772 (16)	C3—H3	0.9500
N3—C21	1.3876 (16)	C3—C2	1.3964 (19)
N3—C19	1.4014 (16)	C10—H10A	0.9800
N3—C22	1.4760 (16)	C10—H10B	0.9800
C7—C8	1.5347 (16)	C10—H10C	0.9800
C7—C12	1.3721 (17)	C24—H24A	0.9900
C8—C5	1.5137 (17)	C24—H24B	0.9900
C8—C9	1.5385 (17)	C24—C25	1.5177 (19)
C8—C10	1.5414 (17)	C2—H2	0.9500
C5—C4	1.3936 (17)	C2—C1	1.392 (2)
C5—C6	1.3816 (18)	C1—H1	0.9500
C12—H12	0.9500	C11—H11A	0.9800
C12—C13	1.4102 (18)	C11—H11B	0.9800
C4—C3	1.3881 (18)	C11—H11C	0.9800
C13—H13	0.9500	C25—H25A	0.9800
C20—C18	1.4614 (17)	C25—H25B	0.9800
C17—H17	0.9500	C25—H25C	0.9800
C17—C18	1.3874 (17)	C23—H23A	0.9800
C17—C16	1.4004 (18)	C23—H23B	0.9800
C15—H15	0.9500	C23—H23C	0.9800
C13—C14—H14	117.8	N3—C22—H22A	109.4
C13—C14—C15	124.41 (12)	N3—C22—H22B	109.4
C15—C14—H14	117.8	N3—C22—C23	111.37 (11)
C7—N1—C4	111.60 (10)	H22A—C22—H22B	108.0
C7—N1—C11	124.84 (11)	C23—C22—H22A	109.4
C4—N1—C11	123.46 (11)	C23—C22—H22B	109.4
C20—N2—C24	118.41 (10)	C8—C9—H9A	109.5
C21—N2—C20	124.51 (11)	C8—C9—H9B	109.5
C21—N2—C24	116.88 (11)	C8—C9—H9C	109.5
C21—N3—C19	124.60 (11)	H9A—C9—H9B	109.5
C21—N3—C22	117.31 (10)	H9A—C9—H9C	109.5
C19—N3—C22	117.77 (10)	H9B—C9—H9C	109.5
N1—C7—C8	108.43 (10)	C5—C6—H6	120.6
N1—C7—C12	122.88 (11)	C5—C6—C1	118.90 (12)
C12—C7—C8	128.65 (11)	C1—C6—H6	120.6
C7—C8—C9	111.44 (10)	C4—C3—H3	121.5
C7—C8—C10	111.88 (10)	C4—C3—C2	117.03 (12)
C5—C8—C7	101.47 (9)	C2—C3—H3	121.5
C5—C8—C9	110.04 (10)	C8—C10—H10A	109.5
C5—C8—C10	110.48 (10)	C8—C10—H10B	109.5
C9—C8—C10	111.14 (10)	C8—C10—H10C	109.5
C4—C5—C8	109.71 (11)	H10A—C10—H10B	109.5
C6—C5—C8	130.38 (11)	H10A—C10—H10C	109.5
C6—C5—C4	119.88 (12)	H10B—C10—H10C	109.5
C7—C12—H12	116.6	N2—C24—H24A	109.4
C7—C12—C13	126.75 (12)	N2—C24—H24B	109.4
C13—C12—H12	116.6	N2—C24—C25	111.31 (10)
C5—C4—N1	108.73 (11)	H24A—C24—H24B	108.0
C3—C4—N1	128.85 (12)	C25—C24—H24A	109.4
C3—C4—C5	122.41 (12)	C25—C24—H24B	109.4
C14—C13—C12	123.73 (12)	C3—C2—H2	119.3
C14—C13—H13	118.1	C1—C2—C3	121.31 (13)
C12—C13—H13	118.1	C1—C2—H2	119.3
O1—C20—N2	119.21 (11)	C6—C1—H1	119.8
O1—C20—C18	124.36 (12)	C2—C1—C6	120.47 (13)
N2—C20—C18	116.42 (11)	C2—C1—H1	119.8
C18—C17—H17	115.6	N1—C11—H11A	109.5
C18—C17—C16	128.88 (12)	N1—C11—H11B	109.5
C16—C17—H17	115.6	N1—C11—H11C	109.5
O3—C21—N2	121.68 (12)	H11A—C11—H11B	109.5
O3—C21—N3	121.35 (12)	H11A—C11—H11C	109.5
N2—C21—N3	116.95 (11)	H11B—C11—H11C	109.5
C14—C15—H15	118.3	C24—C25—H25A	109.5
C16—C15—C14	123.46 (12)	C24—C25—H25B	109.5
C16—C15—H15	118.3	C24—C25—H25C	109.5
C17—C18—C20	117.41 (11)	H25A—C25—H25B	109.5
C17—C18—C19	122.52 (11)	H25A—C25—H25C	109.5
C19—C18—C20	120.05 (11)	H25B—C25—H25C	109.5
O2—C19—N3	118.62 (12)	C22—C23—H23A	109.5
O2—C19—C18	124.79 (12)	C22—C23—H23B	109.5
N3—C19—C18	116.58 (11)	C22—C23—H23C	109.5
C17—C16—H16	118.6	H23A—C23—H23B	109.5
C15—C16—C17	122.84 (12)	H23A—C23—H23C	109.5
C15—C16—H16	118.6	H23B—C23—H23C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2^i	0.95	2.61	3.5458 (17)	167
C24—H24B···O1^ii	0.99	2.56	3.2939 (16)	131
C11—H11A···O2^i	0.98	2.43	3.3891 (17)	165

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

1,3-Diethyl-2-sulfanylidene-5-[2-(1,3,3-trimethylindolin-2-ylidene)ethylidene]dihydropyrimidine-4,6(1H,5H)-dione (DTB)

Crystal data

C21H25N3O2S	F(000) = 816
Mr = 383.50	Dx = 1.311 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.1504 (6) Å	Cell parameters from 9983 reflections
b = 8.1264 (3) Å	θ = 2.6–37.3°
c = 15.6487 (6) Å	µ = 0.19 mm^−1
β = 108.849 (1)°	T = 100 K
V = 1943.67 (13) Å^3	Block, clear light red
Z = 4	0.3 × 0.26 × 0.24 mm

Data collection

Bruker APEXII CCD diffractometer	8903 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.045
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 40.4°, θmin = 1.3°
Tmin = 0.678, Tmax = 0.748	h = −29→29
92854 measured reflections	k = −14→14
12354 independent reflections	l = −28→28

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0645P)^2 + 0.5305P] where P = (Fo^2 + 2Fc^2)/3
12354 reflections	(Δ/σ)max = 0.002
249 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −0.46 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.96141 (2)	0.35712 (4)	0.80259 (2)	0.03286 (7)
O1	0.66676 (4)	0.20400 (9)	0.60288 (4)	0.02461 (12)
N1	0.35986 (4)	0.35270 (9)	0.51788 (4)	0.01788 (11)
O2	0.69412 (5)	0.64835 (10)	0.80519 (6)	0.0389 (2)
N2	0.80016 (4)	0.28754 (10)	0.69633 (4)	0.02129 (12)
N3	0.81446 (5)	0.51652 (10)	0.79244 (5)	0.02353 (13)
C7	0.38323 (5)	0.56295 (9)	0.62627 (5)	0.01636 (11)
C5	0.27705 (5)	0.42249 (10)	0.50767 (5)	0.01701 (11)
C8	0.42390 (5)	0.42923 (10)	0.58292 (5)	0.01659 (11)
C4	0.28730 (5)	0.54688 (9)	0.57129 (5)	0.01715 (11)
C12	0.51201 (5)	0.38347 (10)	0.60429 (5)	0.01905 (12)
H12	0.526462	0.294068	0.572630	0.023*
C14	0.66935 (5)	0.43462 (10)	0.69647 (5)	0.01941 (12)
C13	0.57882 (5)	0.46339 (10)	0.66971 (5)	0.01924 (12)
H13	0.560884	0.549633	0.700776	0.023*
C16	0.70815 (5)	0.30405 (11)	0.66025 (5)	0.01949 (13)
C10	0.41564 (5)	0.73819 (10)	0.61661 (5)	0.01950 (12)
H10A	0.477565	0.747867	0.652692	0.029*
H10B	0.381410	0.818280	0.637982	0.029*
H10C	0.408539	0.759843	0.553031	0.029*
C3	0.21469 (5)	0.63327 (11)	0.57521 (6)	0.02240 (14)
H3	0.220551	0.718222	0.618475	0.027*
C6	0.19664 (5)	0.38216 (11)	0.44549 (5)	0.02134 (13)
H6	0.191296	0.298193	0.401796	0.026*
C11	0.39728 (5)	0.52071 (11)	0.72630 (5)	0.02033 (13)
H11A	0.377983	0.407614	0.730697	0.030*
H11B	0.363251	0.596715	0.750444	0.030*
H11C	0.459504	0.531035	0.761164	0.030*
C1	0.12383 (5)	0.47033 (12)	0.44987 (6)	0.02465 (15)
H1	0.067688	0.446104	0.408353	0.030*
C15	0.72309 (5)	0.54097 (11)	0.76693 (6)	0.02409 (15)
C9	0.37009 (6)	0.20956 (12)	0.46596 (6)	0.02593 (16)
H9A	0.345701	0.112329	0.486189	0.039*
H9B	0.432365	0.191579	0.475090	0.039*
H9C	0.339086	0.228611	0.401702	0.039*
C2	0.13236 (5)	0.59308 (12)	0.51416 (7)	0.02590 (16)
H2	0.081895	0.650225	0.516706	0.031*
C17	0.85370 (5)	0.38883 (12)	0.76148 (5)	0.02227 (14)
C18	0.83775 (5)	0.14263 (14)	0.66450 (6)	0.02812 (18)
H18B	0.898124	0.168077	0.665894	0.034*
H18A	0.802474	0.117384	0.601326	0.034*
C19	0.83898 (6)	−0.00613 (13)	0.72371 (7)	0.02925 (18)
H19B	0.865022	−0.099926	0.702348	0.044*
H19C	0.779012	−0.033514	0.720698	0.044*
H19A	0.873715	0.019095	0.786277	0.044*
C20	0.86824 (6)	0.62716 (12)	0.86467 (8)	0.0319 (2)
H20A	0.839194	0.735725	0.859387	0.038*
H20B	0.926070	0.643783	0.856798	0.038*
C21	0.88084 (7)	0.55668 (14)	0.95736 (7)	0.0341 (2)
H21A	0.909420	0.449030	0.962662	0.051*
H21B	0.823795	0.544084	0.966166	0.051*
H21C	0.917496	0.631204	1.003387	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01270 (8)	0.04879 (16)	0.03404 (12)	−0.00224 (8)	0.00332 (7)	−0.00092 (10)
O1	0.0176 (2)	0.0376 (4)	0.0168 (2)	0.0010 (2)	0.00299 (18)	−0.0047 (2)
N1	0.0150 (2)	0.0200 (3)	0.0174 (2)	−0.0009 (2)	0.00355 (18)	−0.00432 (19)
O2	0.0243 (3)	0.0270 (3)	0.0515 (5)	0.0064 (3)	−0.0069 (3)	−0.0139 (3)
N2	0.0135 (2)	0.0331 (4)	0.0167 (2)	−0.0002 (2)	0.00410 (18)	0.0020 (2)
N3	0.0161 (3)	0.0216 (3)	0.0269 (3)	−0.0032 (2)	−0.0013 (2)	0.0042 (2)
C7	0.0150 (2)	0.0183 (3)	0.0143 (2)	−0.0008 (2)	0.00274 (19)	−0.0018 (2)
C5	0.0142 (2)	0.0190 (3)	0.0167 (2)	−0.0017 (2)	0.00338 (19)	−0.0013 (2)
C8	0.0144 (2)	0.0196 (3)	0.0145 (2)	−0.0008 (2)	0.00288 (19)	−0.0009 (2)
C4	0.0147 (2)	0.0187 (3)	0.0169 (3)	−0.0005 (2)	0.00356 (19)	−0.0012 (2)
C12	0.0141 (3)	0.0240 (3)	0.0176 (3)	0.0006 (2)	0.0031 (2)	0.0000 (2)
C14	0.0143 (3)	0.0221 (3)	0.0186 (3)	−0.0005 (2)	0.0009 (2)	0.0033 (2)
C13	0.0152 (3)	0.0216 (3)	0.0185 (3)	0.0005 (2)	0.0020 (2)	0.0021 (2)
C16	0.0141 (2)	0.0290 (4)	0.0146 (2)	−0.0001 (2)	0.00368 (19)	0.0033 (2)
C10	0.0197 (3)	0.0189 (3)	0.0181 (3)	−0.0024 (2)	0.0035 (2)	−0.0010 (2)
C3	0.0179 (3)	0.0238 (3)	0.0248 (3)	0.0023 (3)	0.0059 (2)	−0.0021 (3)
C6	0.0165 (3)	0.0234 (3)	0.0209 (3)	−0.0043 (2)	0.0016 (2)	−0.0020 (2)
C11	0.0228 (3)	0.0225 (3)	0.0153 (3)	−0.0004 (3)	0.0056 (2)	−0.0004 (2)
C1	0.0149 (3)	0.0276 (4)	0.0277 (4)	−0.0029 (3)	0.0016 (2)	0.0017 (3)
C15	0.0176 (3)	0.0191 (3)	0.0286 (4)	0.0006 (2)	−0.0023 (2)	0.0022 (3)
C9	0.0231 (3)	0.0254 (4)	0.0280 (4)	−0.0003 (3)	0.0065 (3)	−0.0112 (3)
C2	0.0158 (3)	0.0275 (4)	0.0327 (4)	0.0022 (3)	0.0054 (3)	0.0008 (3)
C17	0.0144 (3)	0.0302 (4)	0.0207 (3)	−0.0028 (3)	0.0037 (2)	0.0056 (3)
C18	0.0166 (3)	0.0485 (6)	0.0202 (3)	0.0036 (3)	0.0072 (2)	−0.0065 (3)
C19	0.0206 (3)	0.0327 (4)	0.0337 (4)	0.0031 (3)	0.0078 (3)	−0.0107 (3)
C20	0.0221 (4)	0.0202 (4)	0.0415 (5)	−0.0045 (3)	−0.0061 (3)	−0.0001 (3)
C21	0.0306 (4)	0.0283 (4)	0.0324 (4)	0.0041 (3)	−0.0048 (3)	−0.0082 (3)

Geometric parameters (Å, º)

S1—C17	1.6683 (8)	C10—H10B	0.9800
O1—C16	1.2354 (10)	C10—H10C	0.9800
N1—C5	1.4135 (10)	C3—H3	0.9500
N1—C8	1.3462 (9)	C3—C2	1.4024 (12)
N1—C9	1.4585 (11)	C6—H6	0.9500
O2—C15	1.2329 (12)	C6—C1	1.3974 (12)
N2—C16	1.4152 (10)	C11—H11A	0.9800
N2—C17	1.3766 (11)	C11—H11B	0.9800
N2—C18	1.4829 (12)	C11—H11C	0.9800
N3—C15	1.4128 (11)	C1—H1	0.9500
N3—C17	1.3825 (13)	C1—C2	1.3915 (14)
N3—C20	1.4852 (12)	C9—H9A	0.9800
C7—C8	1.5362 (10)	C9—H9B	0.9800
C7—C4	1.5154 (10)	C9—H9C	0.9800
C7—C10	1.5414 (11)	C2—H2	0.9500
C7—C11	1.5460 (10)	C18—H18B	0.9900
C5—C4	1.3907 (10)	C18—H18A	0.9900
C5—C6	1.3871 (10)	C18—C19	1.5194 (16)
C8—C12	1.4027 (10)	C19—H19B	0.9800
C4—C3	1.3850 (11)	C19—H19C	0.9800
C12—H12	0.9500	C19—H19A	0.9800
C12—C13	1.3858 (11)	C20—H20A	0.9900
C14—C13	1.4043 (10)	C20—H20B	0.9900
C14—C16	1.4384 (12)	C20—C21	1.5109 (17)
C14—C15	1.4483 (12)	C21—H21A	0.9800
C13—H13	0.9500	C21—H21B	0.9800
C10—H10A	0.9800	C21—H21C	0.9800
C5—N1—C9	122.03 (6)	C7—C11—H11A	109.5
C8—N1—C5	111.58 (6)	C7—C11—H11B	109.5
C8—N1—C9	126.30 (7)	C7—C11—H11C	109.5
C16—N2—C18	115.62 (7)	H11A—C11—H11B	109.5
C17—N2—C16	124.48 (7)	H11A—C11—H11C	109.5
C17—N2—C18	119.75 (7)	H11B—C11—H11C	109.5
C15—N3—C20	115.50 (8)	C6—C1—H1	119.5
C17—N3—C15	124.17 (7)	C2—C1—C6	120.98 (7)
C17—N3—C20	119.97 (7)	C2—C1—H1	119.5
C8—C7—C10	113.77 (6)	O2—C15—N3	119.20 (8)
C8—C7—C11	110.25 (6)	O2—C15—C14	124.33 (8)
C4—C7—C8	101.13 (6)	N3—C15—C14	116.46 (8)
C4—C7—C10	109.95 (6)	N1—C9—H9A	109.5
C4—C7—C11	110.14 (6)	N1—C9—H9B	109.5
C10—C7—C11	111.16 (6)	N1—C9—H9C	109.5
C4—C5—N1	108.74 (6)	H9A—C9—H9B	109.5
C6—C5—N1	128.44 (7)	H9A—C9—H9C	109.5
C6—C5—C4	122.81 (7)	H9B—C9—H9C	109.5
N1—C8—C7	109.09 (6)	C3—C2—H2	119.7
N1—C8—C12	122.01 (7)	C1—C2—C3	120.67 (8)
C12—C8—C7	128.89 (6)	C1—C2—H2	119.7
C5—C4—C7	109.42 (6)	N2—C17—S1	121.36 (7)
C3—C4—C7	131.01 (7)	N2—C17—N3	117.32 (7)
C3—C4—C5	119.57 (7)	N3—C17—S1	121.31 (6)
C8—C12—H12	118.7	N2—C18—H18B	109.5
C13—C12—C8	122.66 (7)	N2—C18—H18A	109.5
C13—C12—H12	118.7	N2—C18—C19	110.68 (7)
C13—C14—C16	123.32 (7)	H18B—C18—H18A	108.1
C13—C14—C15	115.97 (8)	C19—C18—H18B	109.5
C16—C14—C15	120.66 (7)	C19—C18—H18A	109.5
C12—C13—C14	129.01 (8)	C18—C19—H19B	109.5
C12—C13—H13	115.5	C18—C19—H19C	109.5
C14—C13—H13	115.5	C18—C19—H19A	109.5
O1—C16—N2	118.64 (8)	H19B—C19—H19C	109.5
O1—C16—C14	124.72 (7)	H19B—C19—H19A	109.5
N2—C16—C14	116.59 (7)	H19C—C19—H19A	109.5
C7—C10—H10A	109.5	N3—C20—H20A	109.3
C7—C10—H10B	109.5	N3—C20—H20B	109.3
C7—C10—H10C	109.5	N3—C20—C21	111.43 (8)
H10A—C10—H10B	109.5	H20A—C20—H20B	108.0
H10A—C10—H10C	109.5	C21—C20—H20A	109.3
H10B—C10—H10C	109.5	C21—C20—H20B	109.3
C4—C3—H3	120.6	C20—C21—H21A	109.5
C4—C3—C2	118.80 (8)	C20—C21—H21B	109.5
C2—C3—H3	120.6	C20—C21—H21C	109.5
C5—C6—H6	121.4	H21A—C21—H21B	109.5
C5—C6—C1	117.15 (8)	H21A—C21—H21C	109.5
C1—C6—H6	121.4	H21B—C21—H21C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O1	0.95	2.28	2.9000 (10)	122
C19—H19B···S1^i	0.98	2.85	3.5573 (9)	130
C21—H21A···S1	0.98	2.98	3.4965 (12)	114

Symmetry code: (i) −x+2, y−1/2, −z+3/2.