Buy article online - an online subscription or single-article purchase is required to access this article.
Three related compounds containing a pyrazole moiety with vicinal phenyl rings featuring a methylsulfonyl substituent are described, namely 3-methyl-1-[4-(methylsulfonyl)phenyl]-5-phenyl-1H-pyrazole, C17H16N2O2S, ethyl 1-[4-(methylsulfonyl)phenyl]-5-phenyl-1H-pyrazole-3-carboxylate, C19H18N2O4S, and 1-[4-(methylsulfonyl)phenyl]-3-[3-(morpholino)phenoxymethyl]-5-phenyl-1H-pyrazole, C27H27N3O4S. The design of these compounds was based on celecoxib, a selective cyclooxygenase-2 (COX-2) inhibitor, in order to study the influence of various substituents on COX-2 and 5-lipoxygenase (5-LOX) inhibition.
Supporting information
CCDC references: 251314; 251315; 251316
Crystals of (I), (II) and (III) were obtained by slow evaporation from a diethyl ether, methanol and isooctane solution, respectively.
For the three compounds, all H atoms were fixed at idealized positions, with C—H distances in the range 0.93–0.97 Å. Compound (II) crystallized in a non-centrosymmetric space group; however, owing to the absence of Friedel pairs, the absolute structure could not be determined unambiguously. In (III), the morpholine moiety of one of the molecules in the asymmetric unit is disordered. This group was refined with a split model over two positions for all atoms of the group, except N33. On the basis of CSD statistics for morpholine bond geometry, distances restraints were applied on C—C, C—N and C—O distances involving disordered atoms. Constrained refinement of the site-occupation factors led to a value of 0.620 for the major conformation.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994) for (I), (III); CAD-4 EXPRESS (Enraf–Nonius 1994) for (II). Cell refinement: CAD-4 EXPRES for (I); CAD-4 EXPRESS for (II), (III). For all compounds, data reduction: PLATON (Spek, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: PLATON for (I), (III); PLATON (Spek, 2003) for (II). Software used to prepare material for publication: reference? for (I), (II).
(I) 3-methyl-1-[4-(methylsulfonyl)phenyl]-5-phenyl-1
H-pyrazole
top
Crystal data top
C17H16N2O2S | F(000) = 1312 |
Mr = 312.39 | Dx = 1.287 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 11.007 (1) Å | θ = 30–40° |
b = 13.061 (1) Å | µ = 1.85 mm−1 |
c = 24.298 (1) Å | T = 293 K |
β = 112.652 (5)° | Needle, colorless |
V = 3223.7 (4) Å3 | 0.35 × 0.30 × 0.20 mm |
Z = 8 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 5480 reflections with I > 2σ(I) |
Radiation source: long fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 71.9°, θmin = 3.9° |
θ/2θ scans | h = −13→11 |
Absorption correction: analytical (Alcock, 1970) | k = 0→16 |
Tmin = 0.563, Tmax = 0.708 | l = −27→29 |
11113 measured reflections | 3 standard reflections every 200 reflections |
6323 independent reflections | intensity decay: 4.2% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0652P)2 + 0.6922P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.003 |
6323 reflections | Δρmax = 0.33 e Å−3 |
402 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0048 (2) |
Crystal data top
C17H16N2O2S | V = 3223.7 (4) Å3 |
Mr = 312.39 | Z = 8 |
Monoclinic, P21/c | Cu Kα radiation |
a = 11.007 (1) Å | µ = 1.85 mm−1 |
b = 13.061 (1) Å | T = 293 K |
c = 24.298 (1) Å | 0.35 × 0.30 × 0.20 mm |
β = 112.652 (5)° | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 5480 reflections with I > 2σ(I) |
Absorption correction: analytical (Alcock, 1970) | Rint = 0.028 |
Tmin = 0.563, Tmax = 0.708 | 3 standard reflections every 200 reflections |
11113 measured reflections | intensity decay: 4.2% |
6323 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.33 e Å−3 |
6323 reflections | Δρmin = −0.30 e Å−3 |
402 parameters | |
Special details top
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 F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.6078 (2) | 0.27103 (15) | 0.46200 (9) | 0.0674 (5) | |
C10 | 0.16734 (18) | 0.05058 (14) | 0.09649 (8) | 0.0640 (5) | |
C11 | 0.29134 (16) | 0.05367 (12) | 0.14019 (7) | 0.0522 (4) | |
C12 | 0.41719 (16) | 0.02082 (12) | 0.13783 (7) | 0.0521 (4) | |
C13 | 0.49882 (18) | −0.04831 (14) | 0.17920 (8) | 0.0595 (4) | |
C14 | 0.6128 (2) | −0.08314 (17) | 0.17443 (10) | 0.0744 (5) | |
C15 | 0.6468 (2) | −0.0497 (2) | 0.12895 (12) | 0.0869 (7) | |
C16 | 0.5670 (3) | 0.01799 (19) | 0.08743 (12) | 0.0867 (7) | |
C17 | 0.4515 (2) | 0.05256 (15) | 0.09121 (9) | 0.0674 (5) | |
C2 | 0.55376 (15) | 0.15000 (12) | 0.36078 (7) | 0.0465 (3) | |
C21 | 1.1107 (2) | 0.10766 (16) | 0.45929 (8) | 0.0716 (5) | |
C22 | 1.07084 (14) | 0.25844 (12) | 0.37443 (6) | 0.0457 (3) | |
C23 | 0.95724 (16) | 0.31045 (12) | 0.36815 (7) | 0.0494 (3) | |
C24 | 0.86933 (15) | 0.33608 (12) | 0.31176 (7) | 0.0483 (3) | |
C25 | 0.89562 (14) | 0.30840 (11) | 0.26241 (6) | 0.0427 (3) | |
C26 | 1.01007 (15) | 0.25654 (12) | 0.26882 (7) | 0.0489 (3) | |
C27 | 1.09837 (15) | 0.23204 (13) | 0.32532 (7) | 0.0505 (4) | |
C28 | 0.61091 (16) | 0.34014 (13) | 0.13540 (7) | 0.0541 (4) | |
C29 | 0.46360 (17) | 0.33466 (16) | 0.10588 (10) | 0.0739 (6) | |
C3 | 0.43866 (16) | 0.09914 (13) | 0.35421 (7) | 0.0520 (4) | |
C30 | 0.69991 (17) | 0.37261 (13) | 0.11094 (7) | 0.0543 (4) | |
C31 | 0.82223 (16) | 0.36780 (12) | 0.15610 (7) | 0.0475 (3) | |
C32 | 0.95216 (16) | 0.40003 (12) | 0.15793 (7) | 0.0503 (4) | |
C33 | 1.02515 (17) | 0.47421 (14) | 0.19799 (8) | 0.0595 (4) | |
C34 | 1.1451 (2) | 0.50591 (17) | 0.19806 (10) | 0.0776 (6) | |
C35 | 1.1943 (2) | 0.4626 (2) | 0.15974 (12) | 0.0899 (7) | |
C36 | 1.1245 (2) | 0.3891 (2) | 0.12012 (11) | 0.0890 (7) | |
C37 | 1.0017 (2) | 0.35844 (17) | 0.11817 (9) | 0.0688 (5) | |
C4 | 0.34770 (16) | 0.07811 (13) | 0.29791 (7) | 0.0519 (4) | |
C5 | 0.37174 (15) | 0.10785 (11) | 0.24827 (7) | 0.0463 (3) | |
C6 | 0.48606 (16) | 0.15999 (12) | 0.25478 (7) | 0.0507 (4) | |
C7 | 0.57805 (16) | 0.18075 (13) | 0.31128 (7) | 0.0507 (4) | |
C8 | 0.08157 (18) | 0.07832 (15) | 0.12345 (9) | 0.0674 (5) | |
C9 | −0.0667 (2) | 0.0821 (2) | 0.09590 (13) | 0.1001 (8) | |
N1 | 0.27573 (13) | 0.08458 (10) | 0.19073 (6) | 0.0513 (3) | |
N2 | 0.14523 (14) | 0.09971 (12) | 0.18081 (7) | 0.0630 (4) | |
N21 | 0.80202 (12) | 0.33318 (10) | 0.20478 (6) | 0.0474 (3) | |
N22 | 0.67111 (12) | 0.31599 (11) | 0.19264 (6) | 0.0535 (3) | |
O1 | 0.79096 (14) | 0.20599 (17) | 0.42922 (7) | 0.0983 (6) | |
O2 | 0.67735 (17) | 0.08180 (11) | 0.46806 (6) | 0.0834 (4) | |
O21 | 1.17705 (18) | 0.29454 (13) | 0.48832 (7) | 0.1012 (6) | |
O22 | 1.30384 (13) | 0.19570 (17) | 0.44295 (7) | 0.0997 (6) | |
S1 | 0.67233 (4) | 0.17145 (3) | 0.433574 (18) | 0.05509 (14) | |
S21 | 1.18032 (4) | 0.22062 (4) | 0.446317 (17) | 0.05724 (14) | |
H10 | 0.1450 | 0.0333 | 0.0567 | 0.077* | |
H13 | 0.4764 | −0.0712 | 0.2103 | 0.071* | |
H14 | 0.6666 | −0.1295 | 0.2022 | 0.089* | |
H15 | 0.7240 | −0.0728 | 0.1261 | 0.104* | |
H16 | 0.5907 | 0.0407 | 0.0567 | 0.104* | |
H17 | 0.3969 | 0.0971 | 0.0625 | 0.081* | |
H1A | 0.6638 | 0.2829 | 0.5030 | 0.101* | |
H1B | 0.5212 | 0.2528 | 0.4594 | 0.101* | |
H1C | 0.6028 | 0.3321 | 0.4393 | 0.101* | |
H21A | 1.1672 | 0.0788 | 0.4968 | 0.107* | |
H21B | 1.1003 | 0.0597 | 0.4279 | 0.107* | |
H21C | 1.0262 | 0.1224 | 0.4604 | 0.107* | |
H23 | 0.9401 | 0.3281 | 0.4015 | 0.059* | |
H24 | 0.7928 | 0.3718 | 0.3069 | 0.058* | |
H26 | 1.0272 | 0.2385 | 0.2355 | 0.059* | |
H27 | 1.1761 | 0.1979 | 0.3304 | 0.061* | |
H29A | 0.4293 | 0.3015 | 0.1321 | 0.111* | |
H29B | 0.4391 | 0.2963 | 0.0695 | 0.111* | |
H29C | 0.4282 | 0.4026 | 0.0971 | 0.111* | |
H3 | 0.4229 | 0.0793 | 0.3876 | 0.062* | |
H30 | 0.6803 | 0.3934 | 0.0718 | 0.065* | |
H33 | 0.9932 | 0.5027 | 0.2249 | 0.071* | |
H34 | 1.1925 | 0.5569 | 0.2243 | 0.093* | |
H35 | 1.2759 | 0.4833 | 0.1606 | 0.108* | |
H36 | 1.1590 | 0.3595 | 0.0945 | 0.107* | |
H37 | 0.9528 | 0.3102 | 0.0903 | 0.083* | |
H4 | 0.2702 | 0.0440 | 0.2932 | 0.062* | |
H6 | 0.5009 | 0.1809 | 0.2213 | 0.061* | |
H7 | 0.6555 | 0.2150 | 0.3161 | 0.061* | |
H9A | −0.0990 | 0.1132 | 0.1234 | 0.150* | |
H9B | −0.1009 | 0.0138 | 0.0869 | 0.150* | |
H9C | −0.0945 | 0.1217 | 0.0599 | 0.150* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0699 (12) | 0.0599 (11) | 0.0619 (11) | 0.0053 (9) | 0.0135 (9) | −0.0098 (8) |
C10 | 0.0639 (10) | 0.0605 (10) | 0.0545 (10) | −0.0009 (8) | 0.0083 (8) | 0.0047 (8) |
C11 | 0.0578 (9) | 0.0463 (8) | 0.0485 (8) | −0.0012 (7) | 0.0160 (7) | 0.0043 (6) |
C12 | 0.0579 (9) | 0.0473 (8) | 0.0495 (8) | −0.0067 (7) | 0.0191 (7) | −0.0066 (7) |
C13 | 0.0619 (10) | 0.0578 (10) | 0.0552 (9) | 0.0012 (8) | 0.0186 (8) | −0.0037 (8) |
C14 | 0.0649 (11) | 0.0694 (12) | 0.0815 (13) | 0.0053 (9) | 0.0200 (10) | −0.0114 (10) |
C15 | 0.0732 (13) | 0.0822 (15) | 0.117 (2) | −0.0076 (11) | 0.0498 (14) | −0.0243 (14) |
C16 | 0.1077 (18) | 0.0798 (14) | 0.1000 (17) | −0.0199 (14) | 0.0704 (15) | −0.0141 (13) |
C17 | 0.0874 (13) | 0.0570 (10) | 0.0644 (11) | −0.0064 (9) | 0.0365 (10) | −0.0011 (8) |
C2 | 0.0462 (8) | 0.0461 (8) | 0.0476 (8) | 0.0041 (6) | 0.0187 (6) | 0.0005 (6) |
C21 | 0.0795 (13) | 0.0708 (12) | 0.0526 (10) | 0.0055 (10) | 0.0124 (9) | 0.0149 (9) |
C22 | 0.0433 (7) | 0.0467 (8) | 0.0409 (7) | −0.0011 (6) | 0.0094 (6) | 0.0028 (6) |
C23 | 0.0526 (8) | 0.0520 (8) | 0.0457 (8) | 0.0014 (7) | 0.0213 (7) | 0.0002 (6) |
C24 | 0.0433 (7) | 0.0512 (8) | 0.0516 (8) | 0.0072 (6) | 0.0197 (6) | 0.0064 (7) |
C25 | 0.0405 (7) | 0.0425 (7) | 0.0427 (7) | −0.0005 (6) | 0.0133 (6) | 0.0064 (6) |
C26 | 0.0515 (8) | 0.0519 (8) | 0.0445 (8) | 0.0067 (7) | 0.0198 (7) | 0.0028 (6) |
C27 | 0.0439 (8) | 0.0554 (9) | 0.0503 (8) | 0.0097 (7) | 0.0162 (6) | 0.0048 (7) |
C28 | 0.0493 (8) | 0.0485 (8) | 0.0518 (9) | −0.0017 (7) | 0.0056 (7) | 0.0007 (7) |
C29 | 0.0497 (10) | 0.0715 (12) | 0.0773 (13) | −0.0062 (8) | −0.0013 (9) | 0.0063 (10) |
C3 | 0.0582 (9) | 0.0527 (9) | 0.0526 (8) | −0.0008 (7) | 0.0295 (7) | 0.0025 (7) |
C30 | 0.0601 (9) | 0.0547 (9) | 0.0400 (8) | 0.0030 (7) | 0.0103 (7) | 0.0002 (7) |
C31 | 0.0543 (8) | 0.0455 (8) | 0.0419 (7) | 0.0025 (6) | 0.0176 (6) | 0.0020 (6) |
C32 | 0.0540 (9) | 0.0513 (8) | 0.0461 (8) | 0.0048 (7) | 0.0198 (7) | 0.0119 (7) |
C33 | 0.0579 (9) | 0.0575 (10) | 0.0609 (10) | 0.0003 (8) | 0.0205 (8) | 0.0070 (8) |
C34 | 0.0661 (12) | 0.0735 (13) | 0.0859 (14) | −0.0113 (10) | 0.0213 (11) | 0.0113 (11) |
C35 | 0.0703 (13) | 0.1008 (18) | 0.1108 (19) | −0.0066 (12) | 0.0482 (14) | 0.0229 (15) |
C36 | 0.0897 (16) | 0.1096 (19) | 0.0911 (16) | 0.0073 (14) | 0.0609 (14) | 0.0133 (14) |
C37 | 0.0781 (12) | 0.0753 (12) | 0.0632 (11) | −0.0004 (10) | 0.0382 (10) | 0.0031 (9) |
C4 | 0.0491 (8) | 0.0510 (9) | 0.0609 (9) | −0.0054 (7) | 0.0272 (7) | −0.0021 (7) |
C5 | 0.0475 (8) | 0.0415 (7) | 0.0502 (8) | 0.0029 (6) | 0.0192 (6) | −0.0010 (6) |
C6 | 0.0571 (9) | 0.0495 (8) | 0.0503 (8) | −0.0046 (7) | 0.0260 (7) | 0.0022 (6) |
C7 | 0.0478 (8) | 0.0526 (9) | 0.0544 (9) | −0.0055 (7) | 0.0228 (7) | 0.0000 (7) |
C8 | 0.0527 (10) | 0.0564 (10) | 0.0772 (12) | 0.0023 (8) | 0.0076 (9) | 0.0035 (9) |
C9 | 0.0540 (12) | 0.0888 (16) | 0.128 (2) | 0.0053 (11) | 0.0021 (12) | −0.0068 (15) |
N1 | 0.0461 (7) | 0.0509 (7) | 0.0543 (7) | 0.0009 (6) | 0.0164 (6) | −0.0020 (6) |
N2 | 0.0475 (7) | 0.0590 (8) | 0.0789 (10) | 0.0034 (6) | 0.0204 (7) | −0.0036 (7) |
N21 | 0.0411 (6) | 0.0523 (7) | 0.0449 (7) | 0.0004 (5) | 0.0122 (5) | 0.0087 (5) |
N22 | 0.0409 (7) | 0.0571 (8) | 0.0570 (8) | −0.0024 (6) | 0.0127 (6) | 0.0095 (6) |
O1 | 0.0474 (7) | 0.1736 (18) | 0.0709 (9) | −0.0130 (9) | 0.0196 (6) | −0.0074 (10) |
O2 | 0.1132 (12) | 0.0641 (8) | 0.0565 (7) | 0.0205 (8) | 0.0145 (7) | 0.0113 (6) |
O21 | 0.1223 (14) | 0.0875 (11) | 0.0567 (8) | 0.0080 (10) | −0.0065 (8) | −0.0261 (8) |
O22 | 0.0436 (7) | 0.1725 (17) | 0.0718 (9) | 0.0156 (9) | 0.0099 (6) | 0.0315 (10) |
S1 | 0.0473 (2) | 0.0662 (3) | 0.0482 (2) | 0.00759 (17) | 0.01444 (17) | 0.00225 (17) |
S21 | 0.0477 (2) | 0.0696 (3) | 0.0414 (2) | 0.00038 (18) | 0.00290 (16) | −0.00097 (17) |
Geometric parameters (Å, º) top
S1—O1 | 1.4234 (15) | S21—O21 | 1.4155 (16) |
S1—O2 | 1.4284 (15) | S21—O22 | 1.4307 (15) |
S1—C1 | 1.7471 (19) | S21—C21 | 1.746 (2) |
S1—C2 | 1.7697 (16) | S21—C22 | 1.7679 (15) |
N1—C11 | 1.365 (2) | N21—C31 | 1.3623 (19) |
N1—N2 | 1.3761 (19) | N21—N22 | 1.3734 (17) |
N1—C5 | 1.423 (2) | N21—C25 | 1.4197 (18) |
N2—C8 | 1.326 (3) | N22—C28 | 1.328 (2) |
C7—C6 | 1.383 (2) | C25—C26 | 1.385 (2) |
C7—C2 | 1.388 (2) | C25—C24 | 1.386 (2) |
C7—H7 | 0.9300 | C22—C23 | 1.379 (2) |
C2—C3 | 1.384 (2) | C22—C27 | 1.383 (2) |
C5—C6 | 1.385 (2) | C27—C26 | 1.380 (2) |
C5—C4 | 1.386 (2) | C27—H27 | 0.9300 |
C12—C17 | 1.388 (2) | C30—C31 | 1.372 (2) |
C12—C13 | 1.392 (2) | C30—C28 | 1.393 (2) |
C12—C11 | 1.472 (2) | C30—H30 | 0.9300 |
C3—C4 | 1.376 (2) | C28—C29 | 1.501 (2) |
C3—H3 | 0.9300 | C23—C24 | 1.380 (2) |
C4—H4 | 0.9300 | C23—H23 | 0.9300 |
C11—C10 | 1.370 (2) | C24—H24 | 0.9300 |
C8—C10 | 1.389 (3) | C32—C33 | 1.389 (2) |
C8—C9 | 1.507 (3) | C32—C37 | 1.390 (2) |
C13—C14 | 1.381 (3) | C32—C31 | 1.475 (2) |
C13—H13 | 0.9300 | C33—C34 | 1.383 (3) |
C1—H1A | 0.9600 | C33—H33 | 0.9300 |
C1—H1B | 0.9600 | C26—H26 | 0.9300 |
C1—H1C | 0.9600 | C21—H21A | 0.9600 |
C10—H10 | 0.9300 | C21—H21B | 0.9600 |
C6—H6 | 0.9300 | C21—H21C | 0.9600 |
C17—C16 | 1.385 (3) | C37—C36 | 1.393 (3) |
C17—H17 | 0.9300 | C37—H37 | 0.9300 |
C14—C15 | 1.368 (3) | C34—C35 | 1.367 (3) |
C14—H14 | 0.9300 | C34—H34 | 0.9300 |
C15—C16 | 1.374 (4) | C29—H29A | 0.9600 |
C15—H15 | 0.9300 | C29—H29B | 0.9600 |
C16—H16 | 0.9300 | C29—H29C | 0.9600 |
C9—H9A | 0.9600 | C36—C35 | 1.367 (4) |
C9—H9B | 0.9600 | C36—H36 | 0.9300 |
C9—H9C | 0.9600 | C35—H35 | 0.9300 |
| | | |
O1—S1—O2 | 118.30 (11) | O21—S21—O22 | 119.01 (12) |
O1—S1—C1 | 108.54 (11) | O21—S21—C21 | 108.14 (11) |
O2—S1—C1 | 107.94 (10) | O22—S21—C21 | 108.12 (11) |
O1—S1—C2 | 108.69 (8) | O21—S21—C22 | 108.96 (9) |
O2—S1—C2 | 107.67 (8) | O22—S21—C22 | 107.95 (8) |
C1—S1—C2 | 104.90 (8) | C21—S21—C22 | 103.58 (8) |
C11—N1—N2 | 111.68 (13) | C31—N21—N22 | 112.10 (12) |
C11—N1—C5 | 130.08 (13) | C31—N21—C25 | 129.27 (13) |
N2—N1—C5 | 118.13 (13) | N22—N21—C25 | 118.52 (12) |
C8—N2—N1 | 104.31 (15) | C28—N22—N21 | 104.21 (13) |
C6—C7—C2 | 119.45 (14) | C26—C25—C24 | 120.95 (13) |
C6—C7—H7 | 120.3 | C26—C25—N21 | 120.36 (13) |
C2—C7—H7 | 120.3 | C24—C25—N21 | 118.68 (13) |
C3—C2—C7 | 120.80 (15) | C23—C22—C27 | 121.20 (14) |
C3—C2—S1 | 118.76 (12) | C23—C22—S21 | 119.41 (12) |
C7—C2—S1 | 120.40 (12) | C27—C22—S21 | 119.35 (12) |
C6—C5—C4 | 120.51 (15) | C26—C27—C22 | 119.74 (14) |
C6—C5—N1 | 121.03 (14) | C26—C27—H27 | 120.1 |
C4—C5—N1 | 118.46 (14) | C22—C27—H27 | 120.1 |
C17—C12—C13 | 118.69 (17) | C31—C30—C28 | 106.22 (14) |
C17—C12—C11 | 120.04 (16) | C31—C30—H30 | 126.9 |
C13—C12—C11 | 121.08 (15) | C28—C30—H30 | 126.9 |
C4—C3—C2 | 119.57 (14) | N22—C28—C30 | 111.71 (14) |
C4—C3—H3 | 120.2 | N22—C28—C29 | 120.06 (17) |
C2—C3—H3 | 120.2 | C30—C28—C29 | 128.18 (16) |
C3—C4—C5 | 119.96 (15) | C22—C23—C24 | 119.25 (14) |
C3—C4—H4 | 120.0 | C22—C23—H23 | 120.4 |
C5—C4—H4 | 120.0 | C24—C23—H23 | 120.4 |
N1—C11—C10 | 105.85 (16) | C23—C24—C25 | 119.72 (14) |
N1—C11—C12 | 124.58 (14) | C23—C24—H24 | 120.1 |
C10—C11—C12 | 129.26 (16) | C25—C24—H24 | 120.1 |
N2—C8—C10 | 111.76 (16) | C33—C32—C37 | 118.95 (17) |
N2—C8—C9 | 120.2 (2) | C33—C32—C31 | 120.84 (15) |
C10—C8—C9 | 128.0 (2) | C37—C32—C31 | 120.18 (16) |
C14—C13—C12 | 120.52 (18) | N21—C31—C30 | 105.76 (14) |
C14—C13—H13 | 119.7 | N21—C31—C32 | 123.31 (13) |
C12—C13—H13 | 119.7 | C30—C31—C32 | 130.72 (14) |
S1—C1—H1A | 109.5 | C34—C33—C32 | 120.27 (19) |
S1—C1—H1B | 109.5 | C34—C33—H33 | 119.9 |
H1A—C1—H1B | 109.5 | C32—C33—H33 | 119.9 |
S1—C1—H1C | 109.5 | C27—C26—C25 | 119.13 (14) |
H1A—C1—H1C | 109.5 | C27—C26—H26 | 120.4 |
H1B—C1—H1C | 109.5 | C25—C26—H26 | 120.4 |
C11—C10—C8 | 106.38 (17) | S21—C21—H21A | 109.5 |
C11—C10—H10 | 126.8 | S21—C21—H21B | 109.5 |
C8—C10—H10 | 126.8 | H21A—C21—H21B | 109.5 |
C7—C6—C5 | 119.70 (14) | S21—C21—H21C | 109.5 |
C7—C6—H6 | 120.2 | H21A—C21—H21C | 109.5 |
C5—C6—H6 | 120.2 | H21B—C21—H21C | 109.5 |
C16—C17—C12 | 120.1 (2) | C32—C37—C36 | 120.0 (2) |
C16—C17—H17 | 119.9 | C32—C37—H37 | 120.0 |
C12—C17—H17 | 119.9 | C36—C37—H37 | 120.0 |
C15—C14—C13 | 120.2 (2) | C35—C34—C33 | 120.2 (2) |
C15—C14—H14 | 119.9 | C35—C34—H34 | 119.9 |
C13—C14—H14 | 119.9 | C33—C34—H34 | 119.9 |
C14—C15—C16 | 120.2 (2) | C28—C29—H29A | 109.5 |
C14—C15—H15 | 119.9 | C28—C29—H29B | 109.5 |
C16—C15—H15 | 119.9 | H29A—C29—H29B | 109.5 |
C15—C16—C17 | 120.3 (2) | C28—C29—H29C | 109.5 |
C15—C16—H16 | 119.9 | H29A—C29—H29C | 109.5 |
C17—C16—H16 | 119.9 | H29B—C29—H29C | 109.5 |
C8—C9—H9A | 109.5 | C35—C36—C37 | 120.1 (2) |
C8—C9—H9B | 109.5 | C35—C36—H36 | 120.0 |
H9A—C9—H9B | 109.5 | C37—C36—H36 | 120.0 |
C8—C9—H9C | 109.5 | C34—C35—C36 | 120.5 (2) |
H9A—C9—H9C | 109.5 | C34—C35—H35 | 119.8 |
H9B—C9—H9C | 109.5 | C36—C35—H35 | 119.8 |
| | | |
C11—N1—N2—C8 | −0.43 (19) | C31—N21—N22—C28 | 0.33 (18) |
C5—N1—N2—C8 | 176.07 (15) | C25—N21—N22—C28 | −176.21 (14) |
C6—C7—C2—C3 | −0.1 (2) | C31—N21—C25—C26 | −40.8 (2) |
C6—C7—C2—S1 | 177.71 (12) | N22—N21—C25—C26 | 135.02 (15) |
O1—S1—C2—C3 | 168.73 (15) | C31—N21—C25—C24 | 139.89 (16) |
O2—S1—C2—C3 | 39.46 (15) | N22—N21—C25—C24 | −44.3 (2) |
C1—S1—C2—C3 | −75.33 (15) | O21—S21—C22—C23 | −33.18 (17) |
O1—S1—C2—C7 | −9.17 (17) | O22—S21—C22—C23 | −163.75 (15) |
O2—S1—C2—C7 | −138.44 (14) | C21—S21—C22—C23 | 81.75 (15) |
C1—S1—C2—C7 | 106.77 (15) | O21—S21—C22—C27 | 149.15 (15) |
C11—N1—C5—C6 | 39.3 (2) | O22—S21—C22—C27 | 18.58 (17) |
N2—N1—C5—C6 | −136.42 (16) | C21—S21—C22—C27 | −95.91 (15) |
C11—N1—C5—C4 | −141.37 (17) | C23—C22—C27—C26 | −1.0 (2) |
N2—N1—C5—C4 | 42.9 (2) | S21—C22—C27—C26 | 176.60 (12) |
C7—C2—C3—C4 | 0.5 (2) | N21—N22—C28—C30 | −0.26 (19) |
S1—C2—C3—C4 | −177.38 (12) | N21—N22—C28—C29 | −177.81 (15) |
C2—C3—C4—C5 | 0.0 (2) | C31—C30—C28—N22 | 0.1 (2) |
C6—C5—C4—C3 | −0.9 (2) | C31—C30—C28—C29 | 177.41 (18) |
N1—C5—C4—C3 | 179.81 (14) | C27—C22—C23—C24 | 0.3 (2) |
N2—N1—C11—C10 | 0.98 (18) | S21—C22—C23—C24 | −177.30 (12) |
C5—N1—C11—C10 | −174.98 (16) | C22—C23—C24—C25 | 0.7 (2) |
N2—N1—C11—C12 | −173.18 (15) | C26—C25—C24—C23 | −1.0 (2) |
C5—N1—C11—C12 | 10.9 (3) | N21—C25—C24—C23 | 178.31 (14) |
C17—C12—C11—N1 | −138.01 (17) | N22—N21—C31—C30 | −0.27 (18) |
C13—C12—C11—N1 | 47.0 (2) | C25—N21—C31—C30 | 175.80 (15) |
C17—C12—C11—C10 | 49.2 (3) | N22—N21—C31—C32 | 175.01 (14) |
C13—C12—C11—C10 | −125.8 (2) | C25—N21—C31—C32 | −8.9 (2) |
N1—N2—C8—C10 | −0.3 (2) | C28—C30—C31—N21 | 0.09 (18) |
N1—N2—C8—C9 | 177.55 (18) | C28—C30—C31—C32 | −174.70 (16) |
C17—C12—C13—C14 | 1.1 (3) | C33—C32—C31—N21 | −54.7 (2) |
C11—C12—C13—C14 | 176.16 (16) | C37—C32—C31—N21 | 127.20 (18) |
N1—C11—C10—C8 | −1.10 (19) | C33—C32—C31—C30 | 119.3 (2) |
C12—C11—C10—C8 | 172.69 (17) | C37—C32—C31—C30 | −58.8 (3) |
N2—C8—C10—C11 | 0.9 (2) | C37—C32—C33—C34 | 0.0 (3) |
C9—C8—C10—C11 | −176.7 (2) | C31—C32—C33—C34 | −178.10 (16) |
C2—C7—C6—C5 | −0.7 (2) | C22—C27—C26—C25 | 0.7 (2) |
C4—C5—C6—C7 | 1.3 (2) | C24—C25—C26—C27 | 0.3 (2) |
N1—C5—C6—C7 | −179.46 (14) | N21—C25—C26—C27 | −179.00 (14) |
C13—C12—C17—C16 | −1.9 (3) | C33—C32—C37—C36 | 1.9 (3) |
C11—C12—C17—C16 | −177.04 (18) | C31—C32—C37—C36 | −179.94 (18) |
C12—C13—C14—C15 | 0.2 (3) | C32—C33—C34—C35 | −1.7 (3) |
C13—C14—C15—C16 | −0.6 (3) | C32—C37—C36—C35 | −2.3 (3) |
C14—C15—C16—C17 | −0.2 (4) | C33—C34—C35—C36 | 1.3 (4) |
C12—C17—C16—C15 | 1.5 (3) | C37—C36—C35—C34 | 0.6 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O22i | 0.96 | 2.39 | 3.344 (3) | 173 |
C7—H7···O1 | 0.93 | 2.58 | 2.939 (2) | 104 |
C23—H23···O1 | 0.93 | 2.56 | 3.083 (3) | 116 |
C27—H27···O22 | 0.93 | 2.55 | 2.921 (2) | 104 |
C30—H30···O2ii | 0.93 | 2.53 | 3.436 (2) | 165 |
Symmetry codes: (i) x−1, y, z; (ii) x, −y+1/2, z−1/2. |
(II) ethyl 1-[4-(methylsulfonyl)phenyl]-5-phenyl-1
H-pyrazole-3-carboxylate
top
Crystal data top
C19H18N2O4S | F(000) = 1552 |
Mr = 370.41 | Dx = 1.341 Mg m−3 |
Orthorhombic, Pca21 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2c -2ac | Cell parameters from 24 reflections |
a = 19.479 (1) Å | θ = 40–45° |
b = 5.610 (1) Å | µ = 1.80 mm−1 |
c = 33.586 (3) Å | T = 293 K |
V = 3670.2 (8) Å3 | Needle, colorless |
Z = 8 | 0.42 × 0.05 × 0.04 mm |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 2391 reflections with I > 2σ(I) |
Radiation source: long fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 72.0°, θmin = 2.6° |
θ/2θ scans | h = −20→24 |
Absorption correction: analytical (Alcock, 1970) | k = −6→0 |
Tmin = 0.519, Tmax = 0.932 | l = 0→41 |
6078 measured reflections | 3 standard reflections every 200 reflections |
3651 independent reflections | intensity decay: 3% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.049P)2 + 0.121P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.012 |
3651 reflections | Δρmax = 0.18 e Å−3 |
475 parameters | Δρmin = −0.18 e Å−3 |
1 restraint | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00046 (7) |
Crystal data top
C19H18N2O4S | V = 3670.2 (8) Å3 |
Mr = 370.41 | Z = 8 |
Orthorhombic, Pca21 | Cu Kα radiation |
a = 19.479 (1) Å | µ = 1.80 mm−1 |
b = 5.610 (1) Å | T = 293 K |
c = 33.586 (3) Å | 0.42 × 0.05 × 0.04 mm |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 2391 reflections with I > 2σ(I) |
Absorption correction: analytical (Alcock, 1970) | Rint = 0.028 |
Tmin = 0.519, Tmax = 0.932 | 3 standard reflections every 200 reflections |
6078 measured reflections | intensity decay: 3% |
3651 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.18 e Å−3 |
3651 reflections | Δρmin = −0.18 e Å−3 |
475 parameters | |
Special details top
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 F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.1008 (3) | 0.4671 (13) | 0.23797 (15) | 0.097 (2) | |
C10 | −0.0189 (2) | 0.4595 (8) | 0.45582 (12) | 0.0426 (10) | |
C11 | 0.0310 (2) | 0.6411 (8) | 0.46895 (12) | 0.0422 (10) | |
C12 | 0.0990 (2) | 0.6349 (9) | 0.45690 (14) | 0.0543 (12) | |
C13 | 0.1452 (3) | 0.8049 (10) | 0.47048 (15) | 0.0603 (13) | |
C14 | 0.1233 (3) | 0.9820 (9) | 0.49586 (16) | 0.0635 (13) | |
C15 | 0.0566 (3) | 0.9875 (10) | 0.50848 (15) | 0.0632 (14) | |
C16 | 0.0104 (2) | 0.8166 (8) | 0.49505 (13) | 0.0502 (11) | |
C17 | −0.1556 (2) | 0.0180 (9) | 0.45707 (14) | 0.0490 (11) | |
C18 | −0.2241 (3) | −0.2933 (10) | 0.43027 (18) | 0.0768 (17) | |
C19 | −0.2257 (3) | −0.4389 (12) | 0.3937 (2) | 0.089 (2) | |
C2 | 0.0980 (2) | 0.5326 (8) | 0.31869 (13) | 0.0461 (11) | |
C21 | 0.3555 (4) | 0.8161 (14) | 0.31983 (16) | 0.101 (2) | |
C22 | 0.3447 (2) | 0.9209 (8) | 0.23979 (13) | 0.0456 (11) | |
C23 | 0.2964 (2) | 1.0886 (9) | 0.22976 (13) | 0.0524 (12) | |
C24 | 0.2555 (2) | 1.0507 (8) | 0.19670 (13) | 0.0497 (11) | |
C25 | 0.2632 (2) | 0.8458 (7) | 0.17505 (11) | 0.0399 (10) | |
C26 | 0.3103 (2) | 0.6751 (8) | 0.18573 (13) | 0.0530 (12) | |
C27 | 0.3521 (2) | 0.7111 (9) | 0.21838 (14) | 0.0534 (12) | |
C28 | 0.1326 (2) | 0.6550 (8) | 0.11237 (12) | 0.0437 (10) | |
C29 | 0.1572 (2) | 0.8360 (8) | 0.08773 (12) | 0.0451 (11) | |
C3 | 0.1094 (3) | 0.3163 (9) | 0.33729 (15) | 0.0569 (12) | |
C30 | 0.2131 (2) | 0.9300 (8) | 0.10672 (12) | 0.0405 (10) | |
C31 | 0.2617 (2) | 1.1155 (7) | 0.09382 (12) | 0.0408 (10) | |
C32 | 0.3303 (2) | 1.1198 (8) | 0.10533 (13) | 0.0474 (11) | |
C33 | 0.3737 (2) | 1.2941 (9) | 0.09230 (14) | 0.0582 (13) | |
C34 | 0.3508 (3) | 1.4710 (9) | 0.06714 (15) | 0.0624 (13) | |
C35 | 0.2838 (3) | 1.4680 (9) | 0.05466 (15) | 0.0597 (13) | |
C36 | 0.2393 (2) | 1.2923 (8) | 0.06779 (12) | 0.0491 (11) | |
C37 | 0.0747 (2) | 0.4947 (10) | 0.10531 (15) | 0.0528 (12) | |
C38 | 0.0077 (3) | 0.1781 (10) | 0.13123 (16) | 0.0727 (16) | |
C39 | 0.0074 (3) | 0.0250 (10) | 0.16705 (17) | 0.0761 (16) | |
C4 | 0.0723 (2) | 0.2565 (8) | 0.37115 (14) | 0.0538 (12) | |
C5 | 0.0237 (2) | 0.4136 (8) | 0.38466 (12) | 0.0423 (10) | |
C6 | 0.0104 (2) | 0.6272 (8) | 0.36632 (14) | 0.0504 (11) | |
C7 | 0.0487 (2) | 0.6865 (9) | 0.33249 (14) | 0.0510 (11) | |
C8 | −0.0989 (2) | 0.1818 (8) | 0.44939 (13) | 0.0447 (10) | |
C9 | −0.0728 (2) | 0.3558 (8) | 0.47539 (12) | 0.0454 (11) | |
N1 | −0.01658 (17) | 0.3505 (7) | 0.41944 (9) | 0.0430 (9) | |
N2 | −0.06500 (18) | 0.1800 (7) | 0.41477 (10) | 0.0463 (9) | |
N21 | 0.21930 (17) | 0.8049 (6) | 0.14157 (10) | 0.0418 (8) | |
N22 | 0.17038 (17) | 0.6346 (6) | 0.14556 (10) | 0.0458 (9) | |
O1 | 0.21163 (18) | 0.5010 (7) | 0.27923 (14) | 0.0943 (13) | |
O2 | 0.1420 (2) | 0.8608 (7) | 0.27151 (14) | 0.1093 (16) | |
O21 | 0.46217 (16) | 0.8620 (8) | 0.27527 (13) | 0.0934 (13) | |
O22 | 0.3948 (2) | 1.2197 (7) | 0.29103 (14) | 0.1099 (16) | |
O23 | 0.04019 (17) | 0.5020 (7) | 0.07566 (11) | 0.0774 (11) | |
O24 | 0.06306 (16) | 0.3475 (6) | 0.13552 (10) | 0.0617 (9) | |
O3 | −0.18626 (18) | 0.0095 (8) | 0.48787 (11) | 0.0794 (12) | |
O4 | −0.16947 (17) | −0.1189 (6) | 0.42581 (10) | 0.0651 (9) | |
S1 | 0.14544 (7) | 0.6086 (2) | 0.27617 (6) | 0.0640 (4) | |
S21 | 0.39735 (6) | 0.9702 (2) | 0.28211 (6) | 0.0635 (4) | |
H12 | 0.1138 | 0.5160 | 0.4396 | 0.065* | |
H13 | 0.1909 | 0.7991 | 0.4624 | 0.072* | |
H14 | 0.1540 | 1.0981 | 0.5044 | 0.076* | |
H15 | 0.0422 | 1.1055 | 0.5260 | 0.076* | |
H16 | −0.0349 | 0.8208 | 0.5038 | 0.060* | |
H18A | −0.2678 | −0.2135 | 0.4340 | 0.092* | |
H18B | −0.2155 | −0.3936 | 0.4533 | 0.092* | |
H19A | −0.2369 | −0.3395 | 0.3714 | 0.133* | |
H19B | −0.2596 | −0.5618 | 0.3964 | 0.133* | |
H19C | −0.1814 | −0.5102 | 0.3896 | 0.133* | |
H1A | 0.0562 | 0.5377 | 0.2353 | 0.145* | |
H1B | 0.0960 | 0.3008 | 0.2441 | 0.145* | |
H1C | 0.1256 | 0.4847 | 0.2135 | 0.145* | |
H21A | 0.3795 | 0.8392 | 0.3445 | 0.151* | |
H21B | 0.3545 | 0.6492 | 0.3135 | 0.151* | |
H21C | 0.3094 | 0.8745 | 0.3224 | 0.151* | |
H23 | 0.2913 | 1.2259 | 0.2450 | 0.063* | |
H24 | 0.2229 | 1.1635 | 0.1893 | 0.060* | |
H26 | 0.3141 | 0.5354 | 0.1710 | 0.064* | |
H27 | 0.3844 | 0.5974 | 0.2258 | 0.064* | |
H29 | 0.1392 | 0.8832 | 0.0633 | 0.054* | |
H3 | 0.1419 | 0.2110 | 0.3271 | 0.068* | |
H32 | 0.3469 | 1.0016 | 0.1222 | 0.057* | |
H33 | 0.4193 | 1.2935 | 0.1005 | 0.070* | |
H34 | 0.3804 | 1.5908 | 0.0587 | 0.075* | |
H35 | 0.2682 | 1.5849 | 0.0373 | 0.072* | |
H36 | 0.1940 | 1.2924 | 0.0591 | 0.059* | |
H38A | 0.0146 | 0.0820 | 0.1076 | 0.087* | |
H38B | −0.0357 | 0.2611 | 0.1287 | 0.087* | |
H39A | 0.0506 | −0.0566 | 0.1692 | 0.114* | |
H39B | −0.0290 | −0.0895 | 0.1650 | 0.114* | |
H39C | 0.0005 | 0.1218 | 0.1903 | 0.114* | |
H4 | 0.0801 | 0.1133 | 0.3843 | 0.065* | |
H6 | −0.0231 | 0.7297 | 0.3761 | 0.060* | |
H7 | 0.0407 | 0.8299 | 0.3194 | 0.061* | |
H9 | −0.0888 | 0.3929 | 0.5007 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.131 (6) | 0.116 (6) | 0.042 (3) | −0.040 (5) | 0.014 (3) | −0.005 (3) |
C10 | 0.051 (2) | 0.044 (3) | 0.033 (2) | 0.003 (2) | −0.0008 (19) | −0.0023 (19) |
C11 | 0.051 (3) | 0.041 (3) | 0.034 (2) | 0.003 (2) | −0.0045 (18) | 0.003 (2) |
C12 | 0.055 (3) | 0.055 (3) | 0.053 (3) | −0.003 (2) | −0.005 (2) | −0.005 (2) |
C13 | 0.057 (3) | 0.065 (4) | 0.059 (3) | −0.009 (3) | −0.007 (2) | −0.001 (3) |
C14 | 0.084 (4) | 0.045 (3) | 0.062 (3) | −0.017 (3) | −0.021 (3) | −0.001 (3) |
C15 | 0.078 (3) | 0.053 (3) | 0.059 (3) | 0.004 (3) | −0.017 (3) | −0.013 (3) |
C16 | 0.057 (3) | 0.047 (3) | 0.046 (2) | 0.003 (2) | −0.005 (2) | −0.002 (2) |
C17 | 0.051 (2) | 0.052 (3) | 0.044 (2) | −0.005 (2) | 0.000 (2) | −0.003 (2) |
C18 | 0.065 (3) | 0.075 (4) | 0.090 (4) | −0.025 (3) | 0.008 (3) | −0.009 (3) |
C19 | 0.088 (4) | 0.090 (5) | 0.089 (4) | −0.024 (4) | −0.005 (3) | −0.021 (4) |
C2 | 0.049 (2) | 0.046 (3) | 0.043 (2) | −0.009 (2) | 0.0048 (18) | −0.004 (2) |
C21 | 0.126 (6) | 0.130 (6) | 0.045 (3) | −0.031 (5) | −0.014 (3) | 0.002 (4) |
C22 | 0.049 (2) | 0.047 (3) | 0.041 (2) | −0.009 (2) | −0.0031 (19) | 0.002 (2) |
C23 | 0.059 (3) | 0.049 (3) | 0.050 (3) | −0.001 (2) | −0.004 (2) | −0.008 (2) |
C24 | 0.052 (3) | 0.047 (3) | 0.049 (3) | 0.008 (2) | −0.003 (2) | −0.001 (2) |
C25 | 0.048 (2) | 0.041 (2) | 0.031 (2) | −0.005 (2) | 0.0011 (17) | 0.0060 (19) |
C26 | 0.068 (3) | 0.042 (3) | 0.049 (3) | 0.002 (2) | −0.006 (2) | −0.007 (2) |
C27 | 0.055 (3) | 0.048 (3) | 0.057 (3) | 0.007 (2) | −0.010 (2) | 0.005 (2) |
C28 | 0.043 (2) | 0.053 (3) | 0.035 (2) | −0.001 (2) | 0.0005 (17) | −0.004 (2) |
C29 | 0.047 (2) | 0.052 (3) | 0.036 (2) | 0.007 (2) | 0.0027 (18) | −0.001 (2) |
C3 | 0.063 (3) | 0.047 (3) | 0.060 (3) | 0.004 (3) | 0.019 (2) | −0.011 (2) |
C30 | 0.045 (2) | 0.042 (3) | 0.034 (2) | 0.0034 (19) | 0.0041 (17) | 0.0002 (18) |
C31 | 0.047 (2) | 0.034 (2) | 0.042 (2) | −0.0001 (19) | 0.0064 (18) | −0.0002 (19) |
C32 | 0.058 (3) | 0.041 (3) | 0.043 (2) | 0.002 (2) | 0.009 (2) | 0.007 (2) |
C33 | 0.058 (3) | 0.061 (3) | 0.056 (3) | −0.006 (3) | 0.010 (2) | −0.006 (3) |
C34 | 0.083 (4) | 0.046 (3) | 0.058 (3) | −0.007 (3) | 0.021 (3) | 0.001 (3) |
C35 | 0.085 (4) | 0.041 (3) | 0.053 (3) | 0.007 (3) | 0.019 (3) | 0.005 (2) |
C36 | 0.051 (3) | 0.048 (3) | 0.048 (3) | 0.008 (2) | 0.011 (2) | 0.007 (2) |
C37 | 0.047 (2) | 0.064 (3) | 0.047 (3) | −0.004 (2) | 0.004 (2) | −0.010 (3) |
C38 | 0.056 (3) | 0.079 (4) | 0.083 (4) | −0.028 (3) | 0.002 (3) | −0.011 (3) |
C39 | 0.081 (4) | 0.066 (4) | 0.082 (4) | −0.018 (3) | 0.012 (3) | −0.004 (3) |
C4 | 0.069 (3) | 0.039 (3) | 0.053 (3) | 0.008 (2) | 0.006 (2) | 0.000 (2) |
C5 | 0.045 (2) | 0.045 (3) | 0.037 (2) | −0.003 (2) | 0.0030 (18) | −0.002 (2) |
C6 | 0.049 (2) | 0.053 (3) | 0.049 (2) | 0.013 (2) | 0.010 (2) | 0.004 (2) |
C7 | 0.056 (3) | 0.048 (3) | 0.049 (3) | 0.002 (2) | 0.005 (2) | 0.005 (2) |
C8 | 0.040 (2) | 0.052 (3) | 0.042 (2) | 0.000 (2) | −0.0003 (18) | 0.005 (2) |
C9 | 0.048 (2) | 0.052 (3) | 0.036 (2) | −0.002 (2) | 0.0018 (18) | −0.003 (2) |
N1 | 0.051 (2) | 0.044 (2) | 0.0341 (18) | −0.0036 (18) | 0.0007 (15) | −0.0003 (16) |
N2 | 0.051 (2) | 0.048 (2) | 0.0406 (19) | −0.0050 (19) | 0.0000 (16) | 0.0006 (17) |
N21 | 0.0459 (19) | 0.045 (2) | 0.0341 (18) | −0.0078 (17) | −0.0025 (15) | 0.0047 (17) |
N22 | 0.0477 (19) | 0.049 (2) | 0.0403 (19) | −0.0090 (18) | 0.0063 (16) | −0.0049 (18) |
O1 | 0.069 (2) | 0.105 (3) | 0.109 (3) | 0.000 (2) | 0.042 (2) | −0.013 (3) |
O2 | 0.154 (4) | 0.047 (2) | 0.127 (4) | −0.017 (2) | 0.083 (3) | 0.003 (2) |
O21 | 0.0564 (19) | 0.131 (4) | 0.093 (3) | 0.005 (2) | −0.020 (2) | −0.002 (3) |
O22 | 0.149 (4) | 0.056 (3) | 0.124 (4) | −0.015 (3) | −0.077 (3) | −0.017 (2) |
O23 | 0.071 (2) | 0.102 (3) | 0.060 (2) | −0.026 (2) | −0.0172 (18) | 0.007 (2) |
O24 | 0.0587 (19) | 0.066 (2) | 0.061 (2) | −0.0222 (18) | −0.0060 (16) | 0.0048 (18) |
O3 | 0.078 (2) | 0.106 (3) | 0.054 (2) | −0.034 (2) | 0.0238 (18) | −0.013 (2) |
O4 | 0.070 (2) | 0.067 (2) | 0.058 (2) | −0.0243 (19) | 0.0091 (16) | −0.0134 (18) |
S1 | 0.0715 (8) | 0.0568 (8) | 0.0637 (8) | −0.0147 (6) | 0.0288 (7) | −0.0067 (7) |
S21 | 0.0687 (8) | 0.0629 (9) | 0.0588 (7) | −0.0133 (6) | −0.0195 (6) | −0.0022 (7) |
Geometric parameters (Å, º) top
S1—O2 | 1.425 (4) | S21—O21 | 1.420 (4) |
S1—O1 | 1.428 (4) | S21—O22 | 1.433 (4) |
S1—C1 | 1.741 (6) | S21—C21 | 1.736 (6) |
S1—C2 | 1.754 (5) | S21—C22 | 1.774 (5) |
O4—C17 | 1.329 (5) | O24—C37 | 1.328 (6) |
O4—C18 | 1.454 (6) | O24—C38 | 1.444 (5) |
O3—C17 | 1.196 (5) | O23—C37 | 1.202 (6) |
N2—C8 | 1.337 (5) | N21—N22 | 1.356 (4) |
N2—N1 | 1.352 (5) | N21—C30 | 1.370 (5) |
N1—C10 | 1.367 (5) | N21—C25 | 1.431 (5) |
N1—C5 | 1.451 (5) | N22—C28 | 1.340 (5) |
C10—C9 | 1.368 (6) | C25—C24 | 1.369 (6) |
C10—C11 | 1.475 (6) | C25—C26 | 1.375 (6) |
C11—C16 | 1.378 (6) | C28—C29 | 1.395 (6) |
C11—C12 | 1.385 (6) | C28—C37 | 1.463 (6) |
C2—C7 | 1.372 (6) | C31—C36 | 1.392 (6) |
C2—C3 | 1.383 (7) | C31—C32 | 1.392 (6) |
C6—C5 | 1.372 (6) | C31—C30 | 1.471 (6) |
C6—C7 | 1.399 (6) | C30—C29 | 1.367 (6) |
C6—H6 | 0.9300 | C24—C23 | 1.384 (6) |
C8—C9 | 1.405 (6) | C24—H24 | 0.9300 |
C8—C17 | 1.459 (6) | C22—C23 | 1.373 (6) |
C12—C13 | 1.388 (7) | C22—C27 | 1.387 (6) |
C12—H12 | 0.9300 | C32—C33 | 1.365 (6) |
C9—H9 | 0.9300 | C32—H32 | 0.9300 |
C16—C15 | 1.391 (6) | C27—C26 | 1.380 (6) |
C16—H16 | 0.9300 | C27—H27 | 0.9300 |
C5—C4 | 1.370 (6) | C29—H29 | 0.9300 |
C7—H7 | 0.9300 | C35—C34 | 1.371 (7) |
C15—C14 | 1.367 (7) | C35—C36 | 1.385 (6) |
C15—H15 | 0.9300 | C35—H35 | 0.9300 |
C4—C3 | 1.389 (6) | C26—H26 | 0.9300 |
C4—H4 | 0.9300 | C23—H23 | 0.9300 |
C3—H3 | 0.9300 | C34—C33 | 1.377 (7) |
C13—C14 | 1.377 (7) | C34—H34 | 0.9300 |
C13—H13 | 0.9300 | C33—H33 | 0.9300 |
C14—H14 | 0.9300 | C36—H36 | 0.9300 |
C18—C19 | 1.475 (8) | C39—C38 | 1.478 (8) |
C18—H18A | 0.9700 | C39—H39A | 0.9600 |
C18—H18B | 0.9700 | C39—H39B | 0.9600 |
C19—H19A | 0.9600 | C39—H39C | 0.9600 |
C19—H19B | 0.9600 | C38—H38A | 0.9700 |
C19—H19C | 0.9600 | C38—H38B | 0.9700 |
C1—H1A | 0.9600 | C21—H21A | 0.9600 |
C1—H1B | 0.9600 | C21—H21B | 0.9600 |
C1—H1C | 0.9600 | C21—H21C | 0.9600 |
| | | |
O2—S1—O1 | 118.1 (3) | O21—S21—O22 | 118.9 (3) |
O2—S1—C1 | 110.4 (4) | O21—S21—C21 | 108.8 (3) |
O1—S1—C1 | 108.1 (3) | O22—S21—C21 | 108.5 (4) |
O2—S1—C2 | 107.8 (2) | O21—S21—C22 | 108.5 (3) |
O1—S1—C2 | 108.3 (3) | O22—S21—C22 | 107.4 (2) |
C1—S1—C2 | 103.1 (2) | C21—S21—C22 | 103.7 (2) |
C17—O4—C18 | 117.2 (4) | C37—O24—C38 | 117.4 (4) |
C8—N2—N1 | 103.8 (3) | N22—N21—C30 | 112.5 (3) |
N2—N1—C10 | 113.4 (3) | N22—N21—C25 | 117.0 (3) |
N2—N1—C5 | 117.1 (3) | C30—N21—C25 | 130.0 (3) |
C10—N1—C5 | 128.9 (4) | C28—N22—N21 | 104.1 (3) |
N1—C10—C9 | 105.3 (4) | C24—C25—C26 | 121.3 (4) |
N1—C10—C11 | 123.7 (4) | C24—C25—N21 | 119.1 (4) |
C9—C10—C11 | 130.9 (4) | C26—C25—N21 | 119.5 (4) |
C16—C11—C12 | 118.8 (4) | N22—C28—C29 | 111.6 (4) |
C16—C11—C10 | 119.4 (4) | N22—C28—C37 | 120.4 (4) |
C12—C11—C10 | 121.7 (4) | C29—C28—C37 | 128.1 (4) |
C7—C2—C3 | 120.8 (4) | C36—C31—C32 | 117.6 (4) |
C7—C2—S1 | 119.4 (4) | C36—C31—C30 | 119.2 (4) |
C3—C2—S1 | 119.8 (4) | C32—C31—C30 | 123.2 (4) |
C5—C6—C7 | 118.1 (4) | C29—C30—N21 | 105.7 (4) |
C5—C6—H6 | 120.9 | C29—C30—C31 | 130.3 (4) |
C7—C6—H6 | 120.9 | N21—C30—C31 | 123.8 (4) |
N2—C8—C9 | 111.5 (4) | C25—C24—C23 | 119.5 (4) |
N2—C8—C17 | 121.5 (4) | C25—C24—H24 | 120.3 |
C9—C8—C17 | 127.0 (4) | C23—C24—H24 | 120.3 |
C11—C12—C13 | 120.4 (5) | C23—C22—C27 | 121.7 (4) |
C11—C12—H12 | 119.8 | C23—C22—S21 | 119.1 (4) |
C13—C12—H12 | 119.8 | C27—C22—S21 | 119.2 (4) |
C10—C9—C8 | 105.9 (4) | C33—C32—C31 | 121.2 (4) |
C10—C9—H9 | 127.0 | C33—C32—H32 | 119.4 |
C8—C9—H9 | 127.0 | C31—C32—H32 | 119.4 |
O3—C17—O4 | 124.0 (4) | C26—C27—C22 | 118.4 (4) |
O3—C17—C8 | 123.8 (4) | C26—C27—H27 | 120.8 |
O4—C17—C8 | 112.2 (4) | C22—C27—H27 | 120.8 |
C11—C16—C15 | 120.7 (4) | C30—C29—C28 | 106.1 (4) |
C11—C16—H16 | 119.7 | C30—C29—H29 | 126.9 |
C15—C16—H16 | 119.7 | C28—C29—H29 | 126.9 |
C4—C5—C6 | 122.9 (4) | C34—C35—C36 | 120.5 (5) |
C4—C5—N1 | 118.9 (4) | C34—C35—H35 | 119.7 |
C6—C5—N1 | 118.2 (4) | C36—C35—H35 | 119.7 |
C2—C7—C6 | 119.8 (4) | C25—C26—C27 | 120.0 (4) |
C2—C7—H7 | 120.1 | C25—C26—H26 | 120.0 |
C6—C7—H7 | 120.1 | C27—C26—H26 | 120.0 |
C14—C15—C16 | 120.0 (5) | C22—C23—C24 | 119.1 (4) |
C14—C15—H15 | 120.0 | C22—C23—H23 | 120.4 |
C16—C15—H15 | 120.0 | C24—C23—H23 | 120.4 |
C5—C4—C3 | 118.4 (4) | C35—C34—C33 | 119.1 (5) |
C5—C4—H4 | 120.8 | C35—C34—H34 | 120.4 |
C3—C4—H4 | 120.8 | C33—C34—H34 | 120.4 |
C2—C3—C4 | 119.9 (4) | C32—C33—C34 | 120.8 (5) |
C2—C3—H3 | 120.1 | C32—C33—H33 | 119.6 |
C4—C3—H3 | 120.1 | C34—C33—H33 | 119.6 |
C14—C13—C12 | 119.9 (5) | O23—C37—O24 | 124.0 (4) |
C14—C13—H13 | 120.0 | O23—C37—C28 | 123.0 (5) |
C12—C13—H13 | 120.0 | O24—C37—C28 | 113.0 (4) |
C15—C14—C13 | 120.2 (5) | C35—C36—C31 | 120.7 (4) |
C15—C14—H14 | 119.9 | C35—C36—H36 | 119.6 |
C13—C14—H14 | 119.9 | C31—C36—H36 | 119.6 |
O4—C18—C19 | 107.6 (5) | C38—C39—H39A | 109.5 |
O4—C18—H18A | 110.2 | C38—C39—H39B | 109.5 |
C19—C18—H18A | 110.2 | H39A—C39—H39B | 109.5 |
O4—C18—H18B | 110.2 | C38—C39—H39C | 109.5 |
C19—C18—H18B | 110.2 | H39A—C39—H39C | 109.5 |
H18A—C18—H18B | 108.5 | H39B—C39—H39C | 109.5 |
C18—C19—H19A | 109.5 | O24—C38—C39 | 107.7 (4) |
C18—C19—H19B | 109.5 | O24—C38—H38A | 110.2 |
H19A—C19—H19B | 109.5 | C39—C38—H38A | 110.2 |
C18—C19—H19C | 109.5 | O24—C38—H38B | 110.2 |
H19A—C19—H19C | 109.5 | C39—C38—H38B | 110.2 |
H19B—C19—H19C | 109.5 | H38A—C38—H38B | 108.5 |
S1—C1—H1A | 109.5 | S21—C21—H21A | 109.5 |
S1—C1—H1B | 109.5 | S21—C21—H21B | 109.5 |
H1A—C1—H1B | 109.5 | H21A—C21—H21B | 109.5 |
S1—C1—H1C | 109.5 | S21—C21—H21C | 109.5 |
H1A—C1—H1C | 109.5 | H21A—C21—H21C | 109.5 |
H1B—C1—H1C | 109.5 | H21B—C21—H21C | 109.5 |
| | | |
C8—N2—N1—C10 | 0.0 (5) | C30—N21—N22—C28 | −0.2 (4) |
C8—N2—N1—C5 | −172.4 (3) | C25—N21—N22—C28 | 172.8 (4) |
N2—N1—C10—C9 | −1.1 (5) | N22—N21—C25—C24 | −108.0 (4) |
C5—N1—C10—C9 | 170.1 (4) | C30—N21—C25—C24 | 63.5 (6) |
N2—N1—C10—C11 | 176.3 (4) | N22—N21—C25—C26 | 69.5 (5) |
C5—N1—C10—C11 | −12.5 (7) | C30—N21—C25—C26 | −118.9 (5) |
N1—C10—C11—C16 | 149.6 (4) | N21—N22—C28—C29 | −0.1 (4) |
C9—C10—C11—C16 | −33.7 (7) | N21—N22—C28—C37 | 178.7 (4) |
N1—C10—C11—C12 | −32.9 (6) | N22—N21—C30—C29 | 0.5 (5) |
C9—C10—C11—C12 | 143.8 (5) | C25—N21—C30—C29 | −171.4 (4) |
O2—S1—C2—C7 | 21.7 (5) | N22—N21—C30—C31 | −176.4 (4) |
O1—S1—C2—C7 | 150.5 (4) | C25—N21—C30—C31 | 11.7 (7) |
C1—S1—C2—C7 | −95.1 (4) | C36—C31—C30—C29 | 28.9 (7) |
O2—S1—C2—C3 | −160.0 (4) | C32—C31—C30—C29 | −148.9 (5) |
O1—S1—C2—C3 | −31.2 (5) | C36—C31—C30—N21 | −155.1 (4) |
C1—S1—C2—C3 | 83.2 (5) | C32—C31—C30—N21 | 27.1 (6) |
N1—N2—C8—C9 | 1.2 (5) | C26—C25—C24—C23 | 0.8 (7) |
N1—N2—C8—C17 | −178.9 (4) | N21—C25—C24—C23 | 178.3 (4) |
C16—C11—C12—C13 | −0.9 (7) | O21—S21—C22—C23 | −148.8 (4) |
C10—C11—C12—C13 | −178.5 (4) | O22—S21—C22—C23 | −19.1 (5) |
N1—C10—C9—C8 | 1.7 (5) | C21—S21—C22—C23 | 95.7 (5) |
C11—C10—C9—C8 | −175.4 (4) | O21—S21—C22—C27 | 33.1 (5) |
N2—C8—C9—C10 | −1.9 (5) | O22—S21—C22—C27 | 162.8 (4) |
C17—C8—C9—C10 | 178.2 (4) | C21—S21—C22—C27 | −82.5 (5) |
C18—O4—C17—O3 | −1.8 (7) | C36—C31—C32—C33 | 1.5 (6) |
C18—O4—C17—C8 | 178.6 (4) | C30—C31—C32—C33 | 179.3 (4) |
N2—C8—C17—O3 | 178.2 (5) | C23—C22—C27—C26 | 1.4 (7) |
C9—C8—C17—O3 | −1.9 (8) | S21—C22—C27—C26 | 179.5 (4) |
N2—C8—C17—O4 | −2.3 (6) | N21—C30—C29—C28 | −0.5 (5) |
C9—C8—C17—O4 | 177.6 (4) | C31—C30—C29—C28 | 176.1 (4) |
C12—C11—C16—C15 | 1.3 (7) | N22—C28—C29—C30 | 0.4 (5) |
C10—C11—C16—C15 | 178.8 (4) | C37—C28—C29—C30 | −178.3 (4) |
C7—C6—C5—C4 | −0.5 (7) | C24—C25—C26—C27 | −1.4 (7) |
C7—C6—C5—N1 | −179.2 (4) | N21—C25—C26—C27 | −178.9 (4) |
N2—N1—C5—C4 | −72.7 (5) | C22—C27—C26—C25 | 0.3 (7) |
C10—N1—C5—C4 | 116.4 (5) | C27—C22—C23—C24 | −2.0 (7) |
N2—N1—C5—C6 | 106.1 (5) | S21—C22—C23—C24 | 179.9 (4) |
C10—N1—C5—C6 | −64.8 (6) | C25—C24—C23—C22 | 0.9 (7) |
C3—C2—C7—C6 | 1.5 (7) | C36—C35—C34—C33 | 1.3 (7) |
S1—C2—C7—C6 | 179.8 (4) | C31—C32—C33—C34 | −0.3 (7) |
C5—C6—C7—C2 | −0.1 (7) | C35—C34—C33—C32 | −1.1 (7) |
C11—C16—C15—C14 | −0.2 (7) | C38—O24—C37—O23 | 3.4 (7) |
C6—C5—C4—C3 | −0.2 (7) | C38—O24—C37—C28 | −178.7 (4) |
N1—C5—C4—C3 | 178.5 (4) | N22—C28—C37—O23 | −178.3 (5) |
C7—C2—C3—C4 | −2.2 (7) | C29—C28—C37—O23 | 0.3 (8) |
S1—C2—C3—C4 | 179.5 (4) | N22—C28—C37—O24 | 3.8 (6) |
C5—C4—C3—C2 | 1.5 (7) | C29—C28—C37—O24 | −177.6 (4) |
C11—C12—C13—C14 | −0.5 (7) | C34—C35—C36—C31 | 0.0 (7) |
C16—C15—C14—C13 | −1.3 (8) | C32—C31—C36—C35 | −1.3 (6) |
C12—C13—C14—C15 | 1.6 (8) | C30—C31—C36—C35 | −179.2 (4) |
C17—O4—C18—C19 | −174.5 (5) | C37—O24—C38—C39 | 176.5 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1C···N22 | 0.96 | 2.58 | 3.515 (6) | 164 |
C7—H7···O2 | 0.93 | 2.55 | 2.908 (6) | 103 |
C21—H21A···N2i | 0.96 | 2.60 | 3.545 (7) | 169 |
C23—H23···O1ii | 0.93 | 2.47 | 3.292 (6) | 147 |
C23—H23···O22 | 0.93 | 2.54 | 2.907 (6) | 104 |
Symmetry codes: (i) x+1/2, −y+1, z; (ii) x, y+1, z. |
(III) 1-[4-(methylsulfonyl)phenyl]-3-[3-(morpholino)phenoxymethyl]-5-phenyl-1
H- pyrazole
top
Crystal data top
C27H27N3O4S | Z = 4 |
Mr = 489.59 | F(000) = 1032 |
Triclinic, P1 | Dx = 1.325 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 10.325 (2) Å | Cell parameters from 25 reflections |
b = 13.874 (2) Å | θ = 38–42° |
c = 18.094 (2) Å | µ = 1.49 mm−1 |
α = 100.823 (9)° | T = 293 K |
β = 104.704 (8)° | Needle, colorless |
γ = 91.888 (11)° | 0.40 × 0.28 × 0.24 mm |
V = 2453.6 (7) Å3 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 8261 reflections with I > 2σ(I) |
Radiation source: long fine-focus sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 74.3°, θmin = 2.6° |
θ/2θ scans | h = −12→10 |
Absorption correction: analytical (Alcock, 1970) | k = −17→17 |
Tmin = 0.587, Tmax = 0.716 | l = −21→22 |
15978 measured reflections | 3 standard reflections every 200 reflections |
9997 independent reflections | intensity decay: 5% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.085P)2 + 0.8675P] where P = (Fo2 + 2Fc2)/3 |
9997 reflections | (Δ/σ)max = 0.001 |
646 parameters | Δρmax = 0.47 e Å−3 |
766 restraints | Δρmin = −0.39 e Å−3 |
Crystal data top
C27H27N3O4S | γ = 91.888 (11)° |
Mr = 489.59 | V = 2453.6 (7) Å3 |
Triclinic, P1 | Z = 4 |
a = 10.325 (2) Å | Cu Kα radiation |
b = 13.874 (2) Å | µ = 1.49 mm−1 |
c = 18.094 (2) Å | T = 293 K |
α = 100.823 (9)° | 0.40 × 0.28 × 0.24 mm |
β = 104.704 (8)° | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 8261 reflections with I > 2σ(I) |
Absorption correction: analytical (Alcock, 1970) | Rint = 0.018 |
Tmin = 0.587, Tmax = 0.716 | 3 standard reflections every 200 reflections |
15978 measured reflections | intensity decay: 5% |
9997 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 766 restraints |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.47 e Å−3 |
9997 reflections | Δρmin = −0.39 e Å−3 |
646 parameters | |
Special details top
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 F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.4313 (3) | 0.25596 (18) | −0.24064 (14) | 0.0639 (6) | |
H1A | 0.3818 | 0.2024 | −0.2806 | 0.096* | |
H1B | 0.3698 | 0.2999 | −0.2237 | 0.096* | |
H1C | 0.4820 | 0.2306 | −0.1972 | 0.096* | |
S1 | 0.54094 (6) | 0.31973 (4) | −0.27781 (3) | 0.05244 (15) | |
O1 | 0.63071 (19) | 0.25199 (13) | −0.30209 (11) | 0.0776 (5) | |
O2 | 0.4635 (2) | 0.37016 (13) | −0.33385 (10) | 0.0779 (5) | |
C2 | 0.6361 (2) | 0.40977 (14) | −0.19805 (11) | 0.0466 (4) | |
C3 | 0.7091 (2) | 0.38190 (15) | −0.13051 (12) | 0.0507 (4) | |
H3 | 0.7074 | 0.3160 | −0.1267 | 0.061* | |
C4 | 0.7839 (2) | 0.45327 (14) | −0.06922 (12) | 0.0492 (4) | |
H4 | 0.8325 | 0.4356 | −0.0237 | 0.059* | |
C5 | 0.78641 (19) | 0.55119 (14) | −0.07576 (11) | 0.0446 (4) | |
C6 | 0.7164 (2) | 0.57815 (15) | −0.14410 (12) | 0.0506 (4) | |
H6 | 0.7205 | 0.6438 | −0.1486 | 0.061* | |
C7 | 0.6407 (2) | 0.50724 (15) | −0.20542 (12) | 0.0509 (4) | |
H7 | 0.5933 | 0.5249 | −0.2512 | 0.061* | |
N1 | 0.86316 (16) | 0.62534 (12) | −0.01359 (9) | 0.0468 (4) | |
N2 | 0.92993 (17) | 0.70156 (12) | −0.03156 (10) | 0.0504 (4) | |
C8 | 0.99508 (19) | 0.75569 (14) | 0.03688 (12) | 0.0471 (4) | |
C9 | 0.9728 (2) | 0.71614 (15) | 0.09895 (12) | 0.0500 (4) | |
H9 | 1.0085 | 0.7413 | 0.1520 | 0.060* | |
C10 | 0.88785 (19) | 0.63297 (14) | 0.06521 (11) | 0.0465 (4) | |
C11 | 0.8250 (2) | 0.56538 (14) | 0.10258 (11) | 0.0476 (4) | |
C12 | 0.9043 (3) | 0.51776 (17) | 0.15553 (13) | 0.0618 (5) | |
H12 | 0.9974 | 0.5271 | 0.1668 | 0.074* | |
C13 | 0.8453 (3) | 0.4559 (2) | 0.19202 (16) | 0.0800 (8) | |
H13 | 0.8988 | 0.4236 | 0.2276 | 0.096* | |
C14 | 0.7074 (4) | 0.4426 (2) | 0.17527 (17) | 0.0842 (9) | |
H14 | 0.6677 | 0.4018 | 0.2002 | 0.101* | |
C15 | 0.6287 (3) | 0.4889 (2) | 0.12225 (18) | 0.0751 (7) | |
H15 | 0.5356 | 0.4786 | 0.1106 | 0.090* | |
C16 | 0.6861 (2) | 0.55099 (17) | 0.08565 (15) | 0.0612 (5) | |
H16 | 0.6320 | 0.5829 | 0.0500 | 0.073* | |
C17 | 1.0808 (2) | 0.84681 (15) | 0.04117 (12) | 0.0531 (5) | |
H17A | 1.1301 | 0.8360 | 0.0017 | 0.064* | |
H17B | 1.0259 | 0.9013 | 0.0333 | 0.064* | |
O3 | 1.17033 (18) | 0.86680 (12) | 0.11680 (9) | 0.0715 (5) | |
C18 | 1.2717 (2) | 0.93993 (14) | 0.13405 (12) | 0.0525 (5) | |
C19 | 1.3584 (3) | 0.95075 (17) | 0.20796 (13) | 0.0620 (6) | |
H19 | 1.3436 | 0.9130 | 0.2429 | 0.074* | |
C20 | 1.4670 (3) | 1.01936 (18) | 0.22779 (15) | 0.0714 (7) | |
H20 | 1.5265 | 1.0276 | 0.2771 | 0.086* | |
C21 | 1.4907 (2) | 1.07623 (18) | 0.17714 (15) | 0.0673 (6) | |
H21 | 1.5654 | 1.1218 | 0.1927 | 0.081* | |
C22 | 1.4035 (2) | 1.06602 (14) | 0.10258 (12) | 0.0503 (4) | |
C23 | 1.2909 (2) | 0.99671 (14) | 0.08225 (12) | 0.0498 (4) | |
H23 | 1.2293 | 0.9893 | 0.0337 | 0.060* | |
N3 | 1.42877 (18) | 1.11837 (13) | 0.04857 (12) | 0.0596 (5) | |
C24 | 1.5332 (3) | 1.1972 (2) | 0.07319 (18) | 0.0838 (8) | |
H24A | 1.6126 | 1.1751 | 0.1051 | 0.101* | |
H24B | 1.5047 | 1.2517 | 0.1058 | 0.101* | |
C25 | 1.5698 (3) | 1.2330 (2) | 0.00947 (19) | 0.0826 (8) | |
H25A | 1.6226 | 1.2958 | 0.0312 | 0.099* | |
H25B | 1.6276 | 1.1874 | −0.0109 | 0.099* | |
O4 | 1.4663 (2) | 1.24537 (17) | −0.05218 (14) | 0.0989 (7) | |
C26 | 1.3704 (3) | 1.1663 (2) | −0.07796 (18) | 0.0812 (8) | |
H26A | 1.4055 | 1.1137 | −0.1087 | 0.097* | |
H26B | 1.2922 | 1.1860 | −0.1126 | 0.097* | |
C27 | 1.3254 (3) | 1.1259 (3) | −0.01786 (18) | 0.0863 (9) | |
H27A | 1.2602 | 1.1673 | −0.0010 | 0.104* | |
H27B | 1.2800 | 1.0609 | −0.0415 | 0.104* | |
C31 | −0.1115 (3) | −0.1793 (2) | 0.78731 (17) | 0.0779 (7) | |
H31A | −0.1230 | −0.2346 | 0.7448 | 0.117* | |
H31B | −0.1612 | −0.1271 | 0.7694 | 0.117* | |
H31C | −0.1438 | −0.1986 | 0.8281 | 0.117* | |
S31 | 0.05876 (5) | −0.13839 (4) | 0.82311 (3) | 0.05404 (15) | |
O31 | 0.1324 (2) | −0.21904 (15) | 0.84274 (12) | 0.0848 (6) | |
O32 | 0.0705 (2) | −0.05167 (13) | 0.88235 (9) | 0.0745 (5) | |
C32 | 0.10664 (19) | −0.10369 (15) | 0.74394 (11) | 0.0466 (4) | |
C33 | 0.1065 (2) | −0.00605 (15) | 0.73708 (11) | 0.0510 (4) | |
H33 | 0.0789 | 0.0405 | 0.7728 | 0.061* | |
C34 | 0.1479 (2) | 0.02166 (14) | 0.67640 (12) | 0.0507 (4) | |
H34 | 0.1482 | 0.0870 | 0.6711 | 0.061* | |
C35 | 0.18858 (19) | −0.04863 (14) | 0.62388 (11) | 0.0447 (4) | |
C36 | 0.1901 (2) | −0.14649 (15) | 0.63101 (12) | 0.0505 (4) | |
H36 | 0.2191 | −0.1928 | 0.5958 | 0.061* | |
C37 | 0.1478 (2) | −0.17406 (15) | 0.69137 (12) | 0.0513 (5) | |
H37 | 0.1471 | −0.2395 | 0.6966 | 0.062* | |
N31 | 0.23178 (16) | −0.01802 (12) | 0.56227 (9) | 0.0465 (4) | |
N32 | 0.32112 (18) | 0.06340 (12) | 0.58138 (10) | 0.0519 (4) | |
C38 | 0.3429 (2) | 0.07394 (15) | 0.51443 (12) | 0.0511 (5) | |
C39 | 0.2686 (2) | 0.00116 (16) | 0.45204 (12) | 0.0523 (5) | |
H39 | 0.2677 | −0.0060 | 0.3998 | 0.063* | |
C40 | 0.19758 (19) | −0.05749 (14) | 0.48397 (11) | 0.0456 (4) | |
C41 | 0.0994 (2) | −0.14261 (14) | 0.44341 (11) | 0.0465 (4) | |
C42 | −0.0179 (2) | −0.16250 (15) | 0.46418 (13) | 0.0515 (5) | |
H42 | −0.0360 | −0.1227 | 0.5072 | 0.062* | |
C43 | −0.1078 (2) | −0.24159 (17) | 0.42090 (16) | 0.0646 (6) | |
H43 | −0.1854 | −0.2553 | 0.4356 | 0.078* | |
C44 | −0.0833 (3) | −0.29996 (18) | 0.35645 (17) | 0.0749 (7) | |
H44 | −0.1440 | −0.3530 | 0.3277 | 0.090* | |
C45 | 0.0311 (3) | −0.27961 (19) | 0.33477 (16) | 0.0776 (7) | |
H45 | 0.0471 | −0.3185 | 0.2907 | 0.093* | |
C46 | 0.1225 (3) | −0.20186 (17) | 0.37783 (14) | 0.0634 (6) | |
H46 | 0.2001 | −0.1891 | 0.3629 | 0.076* | |
C47 | 0.4388 (2) | 0.15764 (18) | 0.51406 (13) | 0.0596 (5) | |
H47A | 0.4257 | 0.2168 | 0.5486 | 0.071* | |
H47B | 0.5308 | 0.1417 | 0.5321 | 0.071* | |
O33 | 0.4139 (2) | 0.17282 (14) | 0.43770 (10) | 0.0787 (6) | |
C48 | 0.4891 (2) | 0.24647 (16) | 0.42323 (12) | 0.0555 (5) | |
C49 | 0.4718 (2) | 0.24821 (17) | 0.34530 (13) | 0.0594 (5) | |
H49 | 0.4131 | 0.2015 | 0.3066 | 0.071* | |
C50 | 0.5434 (3) | 0.32059 (18) | 0.32631 (13) | 0.0628 (6) | |
H50 | 0.5334 | 0.3216 | 0.2739 | 0.075* | |
C51 | 0.6298 (3) | 0.39188 (17) | 0.38213 (13) | 0.0600 (5) | |
H51 | 0.6761 | 0.4403 | 0.3672 | 0.072* | |
C52 | 0.6473 (2) | 0.39100 (15) | 0.46114 (12) | 0.0529 (5) | |
C53 | 0.5766 (2) | 0.31620 (16) | 0.48109 (12) | 0.0560 (5) | |
H53 | 0.5884 | 0.3132 | 0.5333 | 0.067* | |
N33 | 0.7361 (2) | 0.46071 (14) | 0.51869 (10) | 0.0680 (5) | |
C54 | 0.8085 (6) | 0.5400 (4) | 0.4979 (3) | 0.101 (2) | 0.62 |
H54A | 0.7452 | 0.5855 | 0.4787 | 0.121* | 0.62 |
H54B | 0.8476 | 0.5121 | 0.4561 | 0.121* | 0.62 |
C55 | 0.9184 (6) | 0.5958 (6) | 0.5660 (3) | 0.118 (3) | 0.62 |
H55A | 0.9936 | 0.5558 | 0.5760 | 0.141* | 0.62 |
H55B | 0.9495 | 0.6554 | 0.5527 | 0.141* | 0.62 |
O34 | 0.8735 (6) | 0.6212 (6) | 0.6346 (4) | 0.0985 (11) | 0.62 |
C56 | 0.8526 (6) | 0.5303 (5) | 0.6567 (4) | 0.090 (2) | 0.62 |
H56A | 0.8440 | 0.5405 | 0.7097 | 0.108* | 0.62 |
H56B | 0.9254 | 0.4890 | 0.6523 | 0.108* | 0.62 |
C57 | 0.7232 (6) | 0.4861 (5) | 0.59881 (15) | 0.104 (2) | 0.62 |
H57A | 0.6930 | 0.4271 | 0.6134 | 0.125* | 0.62 |
H57B | 0.6553 | 0.5325 | 0.6008 | 0.125* | 0.62 |
C54' | 0.7348 (9) | 0.5619 (3) | 0.5052 (5) | 0.101 (2) | 0.38 |
H54C | 0.6474 | 0.5853 | 0.5055 | 0.121* | 0.38 |
H54D | 0.7484 | 0.5619 | 0.4541 | 0.121* | 0.38 |
C55' | 0.8420 (11) | 0.6313 (10) | 0.5660 (6) | 0.118 (3) | 0.38 |
H55C | 0.9146 | 0.6399 | 0.5421 | 0.141* | 0.38 |
H55D | 0.8043 | 0.6944 | 0.5734 | 0.141* | 0.38 |
O34' | 0.9036 (11) | 0.6157 (10) | 0.6420 (7) | 0.0985 (11) | 0.38 |
C56' | 0.7957 (11) | 0.5561 (8) | 0.6502 (8) | 0.090 (2) | 0.38 |
H56C | 0.7210 | 0.5971 | 0.6477 | 0.108* | 0.38 |
H56D | 0.8223 | 0.5453 | 0.7031 | 0.108* | 0.38 |
C57' | 0.7378 (16) | 0.4579 (9) | 0.5996 (3) | 0.104 (2) | 0.38 |
H57C | 0.7919 | 0.4065 | 0.6170 | 0.125* | 0.38 |
H57D | 0.6472 | 0.4438 | 0.6032 | 0.125* | 0.38 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0657 (13) | 0.0639 (13) | 0.0578 (12) | −0.0207 (11) | 0.0171 (11) | 0.0049 (10) |
S1 | 0.0643 (3) | 0.0506 (3) | 0.0396 (2) | −0.0116 (2) | 0.0150 (2) | 0.00304 (19) |
O1 | 0.0845 (12) | 0.0720 (11) | 0.0728 (11) | −0.0052 (9) | 0.0371 (10) | −0.0141 (9) |
O2 | 0.1034 (14) | 0.0671 (10) | 0.0494 (9) | −0.0193 (9) | −0.0033 (9) | 0.0147 (7) |
C2 | 0.0499 (10) | 0.0465 (10) | 0.0423 (9) | −0.0066 (8) | 0.0151 (8) | 0.0044 (8) |
C3 | 0.0582 (11) | 0.0416 (9) | 0.0507 (10) | −0.0009 (8) | 0.0133 (9) | 0.0072 (8) |
C4 | 0.0512 (10) | 0.0477 (10) | 0.0459 (10) | −0.0009 (8) | 0.0092 (8) | 0.0086 (8) |
C5 | 0.0436 (9) | 0.0470 (10) | 0.0433 (9) | −0.0065 (7) | 0.0160 (8) | 0.0049 (7) |
C6 | 0.0592 (11) | 0.0434 (10) | 0.0499 (10) | −0.0094 (8) | 0.0166 (9) | 0.0111 (8) |
C7 | 0.0579 (11) | 0.0508 (10) | 0.0437 (10) | −0.0072 (9) | 0.0124 (9) | 0.0122 (8) |
N1 | 0.0496 (9) | 0.0452 (8) | 0.0446 (8) | −0.0130 (7) | 0.0146 (7) | 0.0062 (7) |
N2 | 0.0533 (9) | 0.0481 (9) | 0.0494 (9) | −0.0145 (7) | 0.0156 (7) | 0.0093 (7) |
C8 | 0.0448 (10) | 0.0469 (10) | 0.0482 (10) | −0.0070 (8) | 0.0101 (8) | 0.0110 (8) |
C9 | 0.0516 (10) | 0.0496 (10) | 0.0458 (10) | −0.0105 (8) | 0.0109 (8) | 0.0073 (8) |
C10 | 0.0470 (10) | 0.0474 (10) | 0.0456 (10) | −0.0049 (8) | 0.0146 (8) | 0.0091 (8) |
C11 | 0.0580 (11) | 0.0411 (9) | 0.0449 (10) | −0.0085 (8) | 0.0218 (8) | 0.0029 (7) |
C12 | 0.0697 (14) | 0.0566 (12) | 0.0555 (12) | −0.0141 (10) | 0.0112 (10) | 0.0134 (10) |
C13 | 0.111 (2) | 0.0636 (15) | 0.0633 (15) | −0.0196 (14) | 0.0147 (14) | 0.0224 (12) |
C14 | 0.118 (2) | 0.0683 (16) | 0.0726 (16) | −0.0352 (15) | 0.0450 (17) | 0.0100 (13) |
C15 | 0.0756 (16) | 0.0694 (15) | 0.0882 (18) | −0.0171 (12) | 0.0466 (14) | 0.0052 (13) |
C16 | 0.0598 (12) | 0.0579 (12) | 0.0726 (14) | −0.0022 (10) | 0.0315 (11) | 0.0117 (11) |
C17 | 0.0552 (11) | 0.0531 (11) | 0.0455 (10) | −0.0183 (9) | 0.0049 (9) | 0.0121 (8) |
O3 | 0.0823 (11) | 0.0694 (10) | 0.0502 (8) | −0.0366 (9) | −0.0046 (8) | 0.0188 (7) |
C18 | 0.0592 (12) | 0.0425 (10) | 0.0475 (10) | −0.0111 (8) | 0.0041 (9) | 0.0050 (8) |
C19 | 0.0753 (15) | 0.0524 (12) | 0.0484 (11) | −0.0060 (10) | −0.0002 (10) | 0.0106 (9) |
C20 | 0.0727 (15) | 0.0640 (14) | 0.0565 (13) | −0.0098 (12) | −0.0147 (11) | 0.0070 (11) |
C21 | 0.0584 (13) | 0.0566 (12) | 0.0681 (14) | −0.0153 (10) | −0.0098 (11) | 0.0061 (11) |
C22 | 0.0468 (10) | 0.0391 (9) | 0.0565 (11) | −0.0060 (8) | 0.0044 (8) | 0.0033 (8) |
C23 | 0.0500 (10) | 0.0438 (10) | 0.0466 (10) | −0.0099 (8) | 0.0006 (8) | 0.0062 (8) |
N3 | 0.0523 (10) | 0.0519 (10) | 0.0669 (11) | −0.0169 (8) | 0.0035 (8) | 0.0136 (8) |
C24 | 0.0698 (16) | 0.0873 (18) | 0.0837 (18) | −0.0391 (14) | 0.0096 (14) | 0.0139 (15) |
C25 | 0.0751 (17) | 0.0707 (16) | 0.100 (2) | −0.0258 (13) | 0.0255 (15) | 0.0135 (15) |
O4 | 0.1021 (16) | 0.0948 (15) | 0.1017 (16) | −0.0336 (12) | 0.0215 (13) | 0.0391 (13) |
C26 | 0.0862 (18) | 0.0763 (17) | 0.0790 (17) | −0.0217 (14) | 0.0116 (14) | 0.0296 (14) |
C27 | 0.0633 (15) | 0.107 (2) | 0.0839 (18) | −0.0318 (15) | −0.0026 (13) | 0.0440 (17) |
C31 | 0.0654 (14) | 0.0859 (18) | 0.0758 (16) | −0.0270 (13) | 0.0225 (13) | 0.0008 (14) |
S31 | 0.0591 (3) | 0.0593 (3) | 0.0432 (3) | −0.0112 (2) | 0.0110 (2) | 0.0154 (2) |
O31 | 0.0991 (14) | 0.0927 (13) | 0.0813 (12) | 0.0170 (11) | 0.0302 (11) | 0.0536 (11) |
O32 | 0.0975 (13) | 0.0763 (11) | 0.0427 (8) | −0.0274 (9) | 0.0182 (8) | 0.0010 (7) |
C32 | 0.0473 (10) | 0.0508 (10) | 0.0397 (9) | −0.0078 (8) | 0.0066 (8) | 0.0132 (8) |
C33 | 0.0632 (12) | 0.0475 (10) | 0.0420 (10) | −0.0021 (9) | 0.0152 (9) | 0.0075 (8) |
C34 | 0.0647 (12) | 0.0408 (9) | 0.0462 (10) | −0.0054 (8) | 0.0140 (9) | 0.0100 (8) |
C35 | 0.0453 (9) | 0.0473 (10) | 0.0396 (9) | −0.0071 (8) | 0.0078 (7) | 0.0109 (7) |
C36 | 0.0564 (11) | 0.0455 (10) | 0.0493 (10) | −0.0004 (8) | 0.0148 (9) | 0.0088 (8) |
C37 | 0.0605 (12) | 0.0424 (10) | 0.0512 (11) | −0.0028 (8) | 0.0121 (9) | 0.0146 (8) |
N31 | 0.0487 (8) | 0.0463 (8) | 0.0432 (8) | −0.0099 (7) | 0.0120 (7) | 0.0084 (6) |
N32 | 0.0554 (9) | 0.0495 (9) | 0.0475 (9) | −0.0143 (7) | 0.0106 (7) | 0.0092 (7) |
C38 | 0.0488 (10) | 0.0539 (11) | 0.0493 (10) | −0.0104 (8) | 0.0126 (8) | 0.0107 (9) |
C39 | 0.0548 (11) | 0.0577 (11) | 0.0450 (10) | −0.0099 (9) | 0.0175 (9) | 0.0082 (9) |
C40 | 0.0461 (10) | 0.0464 (10) | 0.0434 (9) | −0.0034 (8) | 0.0130 (8) | 0.0067 (8) |
C41 | 0.0480 (10) | 0.0440 (9) | 0.0443 (10) | −0.0039 (8) | 0.0086 (8) | 0.0075 (8) |
C42 | 0.0486 (10) | 0.0513 (11) | 0.0542 (11) | −0.0042 (8) | 0.0108 (9) | 0.0146 (9) |
C43 | 0.0535 (12) | 0.0578 (12) | 0.0796 (16) | −0.0123 (10) | 0.0050 (11) | 0.0270 (12) |
C44 | 0.0787 (17) | 0.0497 (12) | 0.0763 (16) | −0.0163 (12) | −0.0061 (13) | 0.0041 (11) |
C45 | 0.097 (2) | 0.0586 (14) | 0.0622 (14) | −0.0067 (13) | 0.0112 (14) | −0.0095 (11) |
C46 | 0.0697 (14) | 0.0607 (13) | 0.0560 (12) | −0.0057 (11) | 0.0206 (11) | −0.0009 (10) |
C47 | 0.0589 (12) | 0.0649 (13) | 0.0528 (11) | −0.0193 (10) | 0.0128 (10) | 0.0136 (10) |
O33 | 0.0955 (13) | 0.0803 (11) | 0.0513 (9) | −0.0460 (10) | 0.0102 (9) | 0.0133 (8) |
C48 | 0.0617 (12) | 0.0531 (11) | 0.0504 (11) | −0.0127 (9) | 0.0145 (9) | 0.0111 (9) |
C49 | 0.0658 (13) | 0.0602 (12) | 0.0461 (11) | −0.0116 (10) | 0.0078 (10) | 0.0083 (9) |
C50 | 0.0768 (15) | 0.0663 (13) | 0.0466 (11) | −0.0041 (11) | 0.0154 (10) | 0.0179 (10) |
C51 | 0.0735 (14) | 0.0560 (12) | 0.0535 (12) | −0.0098 (10) | 0.0189 (10) | 0.0181 (10) |
C52 | 0.0572 (11) | 0.0497 (11) | 0.0523 (11) | −0.0065 (9) | 0.0152 (9) | 0.0121 (9) |
C53 | 0.0662 (13) | 0.0559 (12) | 0.0444 (10) | −0.0153 (10) | 0.0143 (9) | 0.0106 (9) |
N33 | 0.0851 (14) | 0.0610 (11) | 0.0548 (10) | −0.0273 (10) | 0.0181 (10) | 0.0102 (9) |
C54 | 0.115 (5) | 0.108 (3) | 0.069 (2) | −0.070 (3) | 0.012 (3) | 0.021 (2) |
C55 | 0.133 (6) | 0.124 (5) | 0.078 (2) | −0.087 (5) | 0.016 (3) | 0.009 (3) |
O34 | 0.115 (3) | 0.0828 (15) | 0.0746 (17) | −0.045 (2) | −0.003 (2) | 0.0069 (12) |
C56 | 0.096 (5) | 0.096 (4) | 0.061 (2) | −0.042 (3) | −0.002 (4) | 0.015 (2) |
C57 | 0.135 (3) | 0.099 (4) | 0.0637 (16) | −0.070 (3) | 0.0256 (19) | −0.0040 (18) |
C54' | 0.115 (5) | 0.108 (3) | 0.069 (2) | −0.070 (3) | 0.012 (3) | 0.021 (2) |
C55' | 0.133 (6) | 0.124 (5) | 0.078 (2) | −0.087 (5) | 0.016 (3) | 0.009 (3) |
O34' | 0.115 (3) | 0.0828 (15) | 0.0746 (17) | −0.045 (2) | −0.003 (2) | 0.0069 (12) |
C56' | 0.096 (5) | 0.096 (4) | 0.061 (2) | −0.042 (3) | −0.002 (4) | 0.015 (2) |
C57' | 0.135 (3) | 0.099 (4) | 0.0637 (16) | −0.070 (3) | 0.0256 (19) | −0.0040 (18) |
Geometric parameters (Å, º) top
C1—S1 | 1.750 (2) | C32—C33 | 1.383 (3) |
C1—H1A | 0.9600 | C32—C37 | 1.387 (3) |
C1—H1B | 0.9600 | C33—C34 | 1.386 (3) |
C1—H1C | 0.9600 | C33—H33 | 0.9300 |
S1—O1 | 1.4299 (19) | C34—C35 | 1.383 (3) |
S1—O2 | 1.4313 (19) | C34—H34 | 0.9300 |
S1—C2 | 1.770 (2) | C35—C36 | 1.388 (3) |
C2—C7 | 1.384 (3) | C35—N31 | 1.428 (2) |
C2—C3 | 1.393 (3) | C36—C37 | 1.385 (3) |
C3—C4 | 1.382 (3) | C36—H36 | 0.9300 |
C3—H3 | 0.9300 | C37—H37 | 0.9300 |
C4—C5 | 1.386 (3) | N31—N32 | 1.367 (2) |
C4—H4 | 0.9300 | N31—C40 | 1.369 (2) |
C5—C6 | 1.389 (3) | N32—C38 | 1.320 (3) |
C5—N1 | 1.418 (2) | C38—C39 | 1.401 (3) |
C6—C7 | 1.382 (3) | C38—C47 | 1.504 (3) |
C6—H6 | 0.9300 | C39—C40 | 1.373 (3) |
C7—H7 | 0.9300 | C39—H39 | 0.9300 |
N1—C10 | 1.366 (2) | C40—C41 | 1.476 (3) |
N1—N2 | 1.376 (2) | C41—C42 | 1.389 (3) |
N2—C8 | 1.321 (3) | C41—C46 | 1.390 (3) |
C8—C9 | 1.403 (3) | C42—C43 | 1.386 (3) |
C8—C17 | 1.497 (3) | C42—H42 | 0.9300 |
C9—C10 | 1.368 (3) | C43—C44 | 1.374 (4) |
C9—H9 | 0.9300 | C43—H43 | 0.9300 |
C10—C11 | 1.476 (3) | C44—C45 | 1.373 (4) |
C11—C12 | 1.378 (3) | C44—H44 | 0.9300 |
C11—C16 | 1.388 (3) | C45—C46 | 1.381 (3) |
C12—C13 | 1.387 (3) | C45—H45 | 0.9300 |
C12—H12 | 0.9300 | C46—H46 | 0.9300 |
C13—C14 | 1.378 (5) | C47—O33 | 1.397 (3) |
C13—H13 | 0.9300 | C47—H47A | 0.9700 |
C14—C15 | 1.366 (5) | C47—H47B | 0.9700 |
C14—H14 | 0.9300 | O33—C48 | 1.366 (2) |
C15—C16 | 1.382 (3) | C48—C49 | 1.381 (3) |
C15—H15 | 0.9300 | C48—C53 | 1.389 (3) |
C16—H16 | 0.9300 | C49—C50 | 1.372 (3) |
C17—O3 | 1.415 (2) | C49—H49 | 0.9300 |
C17—H17A | 0.9700 | C50—C51 | 1.380 (3) |
C17—H17B | 0.9700 | C50—H50 | 0.9300 |
O3—C18 | 1.366 (2) | C51—C52 | 1.397 (3) |
C18—C23 | 1.378 (3) | C51—H51 | 0.9300 |
C18—C19 | 1.386 (3) | C52—N33 | 1.392 (3) |
C19—C20 | 1.375 (3) | C52—C53 | 1.402 (3) |
C19—H19 | 0.9300 | C53—H53 | 0.9300 |
C20—C21 | 1.376 (4) | N33—C57 | 1.4673 (10) |
C20—H20 | 0.9300 | N33—C54 | 1.4677 (10) |
C21—C22 | 1.398 (3) | N33—C57' | 1.4685 (10) |
C21—H21 | 0.9300 | N33—C54' | 1.4690 (10) |
C22—N3 | 1.391 (3) | C54—C55 | 1.5091 (10) |
C22—C23 | 1.411 (3) | C54—H54A | 0.9700 |
C23—H23 | 0.9300 | C54—H54B | 0.9700 |
N3—C27 | 1.413 (3) | C55—O34 | 1.4206 (10) |
N3—C24 | 1.433 (3) | C55—H55A | 0.9700 |
C24—C25 | 1.464 (4) | C55—H55B | 0.9700 |
C24—H24A | 0.9700 | O34—C56 | 1.4192 (10) |
C24—H24B | 0.9700 | C56—C57 | 1.5009 (10) |
C25—O4 | 1.376 (4) | C56—H56A | 0.9700 |
C25—H25A | 0.9700 | C56—H56B | 0.9700 |
C25—H25B | 0.9700 | C57—H57A | 0.9700 |
O4—C26 | 1.380 (3) | C57—H57B | 0.9700 |
C26—C27 | 1.477 (4) | C54'—C55' | 1.5094 (10) |
C26—H26A | 0.9700 | C54'—H54C | 0.9700 |
C26—H26B | 0.9700 | C54'—H54D | 0.9700 |
C27—H27A | 0.9700 | C55'—O34' | 1.4203 (10) |
C27—H27B | 0.9700 | C55'—H55C | 0.9700 |
C31—S31 | 1.746 (3) | C55'—H55D | 0.9700 |
C31—H31A | 0.9600 | O34'—C56' | 1.4195 (10) |
C31—H31B | 0.9600 | C56'—C57' | 1.5006 (10) |
C31—H31C | 0.9600 | C56'—H56C | 0.9700 |
S31—O31 | 1.423 (2) | C56'—H56D | 0.9700 |
S31—O32 | 1.4323 (18) | C57'—H57C | 0.9700 |
S31—C32 | 1.7693 (19) | C57'—H57D | 0.9700 |
| | | |
S1—C1—H1A | 109.5 | C32—C33—C34 | 119.30 (19) |
S1—C1—H1B | 109.5 | C32—C33—H33 | 120.3 |
H1A—C1—H1B | 109.5 | C34—C33—H33 | 120.3 |
S1—C1—H1C | 109.5 | C35—C34—C33 | 119.51 (18) |
H1A—C1—H1C | 109.5 | C35—C34—H34 | 120.2 |
H1B—C1—H1C | 109.5 | C33—C34—H34 | 120.2 |
O1—S1—O2 | 118.34 (12) | C34—C35—C36 | 121.35 (18) |
O1—S1—C1 | 107.69 (12) | C34—C35—N31 | 118.40 (17) |
O2—S1—C1 | 108.73 (13) | C36—C35—N31 | 120.24 (18) |
O1—S1—C2 | 107.89 (11) | C37—C36—C35 | 119.00 (19) |
O2—S1—C2 | 107.72 (10) | C37—C36—H36 | 120.5 |
C1—S1—C2 | 105.80 (10) | C35—C36—H36 | 120.5 |
C7—C2—C3 | 120.99 (18) | C36—C37—C32 | 119.70 (18) |
C7—C2—S1 | 118.76 (16) | C36—C37—H37 | 120.2 |
C3—C2—S1 | 120.20 (15) | C32—C37—H37 | 120.2 |
C4—C3—C2 | 119.27 (18) | N32—N31—C40 | 112.14 (15) |
C4—C3—H3 | 120.4 | N32—N31—C35 | 117.68 (15) |
C2—C3—H3 | 120.4 | C40—N31—C35 | 130.18 (16) |
C3—C4—C5 | 119.87 (19) | C38—N32—N31 | 104.52 (16) |
C3—C4—H4 | 120.1 | N32—C38—C39 | 111.87 (17) |
C5—C4—H4 | 120.1 | N32—C38—C47 | 118.82 (18) |
C4—C5—C6 | 120.55 (18) | C39—C38—C47 | 129.31 (19) |
C4—C5—N1 | 120.62 (18) | C40—C39—C38 | 105.86 (17) |
C6—C5—N1 | 118.81 (17) | C40—C39—H39 | 127.1 |
C7—C6—C5 | 119.87 (18) | C38—C39—H39 | 127.1 |
C7—C6—H6 | 120.1 | N31—C40—C39 | 105.61 (17) |
C5—C6—H6 | 120.1 | N31—C40—C41 | 126.16 (17) |
C6—C7—C2 | 119.41 (19) | C39—C40—C41 | 128.17 (18) |
C6—C7—H7 | 120.3 | C42—C41—C46 | 118.80 (19) |
C2—C7—H7 | 120.3 | C42—C41—C40 | 123.69 (18) |
C10—N1—N2 | 111.61 (15) | C46—C41—C40 | 117.38 (18) |
C10—N1—C5 | 130.04 (16) | C43—C42—C41 | 120.1 (2) |
N2—N1—C5 | 118.30 (15) | C43—C42—H42 | 119.9 |
C8—N2—N1 | 104.44 (15) | C41—C42—H42 | 119.9 |
N2—C8—C9 | 111.92 (17) | C44—C43—C42 | 120.5 (2) |
N2—C8—C17 | 120.19 (17) | C44—C43—H43 | 119.8 |
C9—C8—C17 | 127.89 (18) | C42—C43—H43 | 119.8 |
C10—C9—C8 | 105.69 (17) | C45—C44—C43 | 119.7 (2) |
C10—C9—H9 | 127.2 | C45—C44—H44 | 120.2 |
C8—C9—H9 | 127.2 | C43—C44—H44 | 120.2 |
N1—C10—C9 | 106.34 (16) | C44—C45—C46 | 120.5 (2) |
N1—C10—C11 | 124.37 (17) | C44—C45—H45 | 119.7 |
C9—C10—C11 | 129.19 (18) | C46—C45—H45 | 119.7 |
C12—C11—C16 | 119.80 (19) | C45—C46—C41 | 120.4 (2) |
C12—C11—C10 | 120.02 (19) | C45—C46—H46 | 119.8 |
C16—C11—C10 | 120.2 (2) | C41—C46—H46 | 119.8 |
C11—C12—C13 | 120.1 (2) | O33—C47—C38 | 108.03 (17) |
C11—C12—H12 | 120.0 | O33—C47—H47A | 110.1 |
C13—C12—H12 | 120.0 | C38—C47—H47A | 110.1 |
C14—C13—C12 | 119.7 (3) | O33—C47—H47B | 110.1 |
C14—C13—H13 | 120.1 | C38—C47—H47B | 110.1 |
C12—C13—H13 | 120.1 | H47A—C47—H47B | 108.4 |
C15—C14—C13 | 120.3 (2) | C48—O33—C47 | 118.50 (17) |
C15—C14—H14 | 119.9 | O33—C48—C49 | 115.04 (19) |
C13—C14—H14 | 119.9 | O33—C48—C53 | 123.99 (19) |
C14—C15—C16 | 120.6 (3) | C49—C48—C53 | 120.96 (19) |
C14—C15—H15 | 119.7 | C50—C49—C48 | 118.3 (2) |
C16—C15—H15 | 119.7 | C50—C49—H49 | 120.8 |
C15—C16—C11 | 119.5 (2) | C48—C49—H49 | 120.8 |
C15—C16—H16 | 120.2 | C49—C50—C51 | 122.4 (2) |
C11—C16—H16 | 120.2 | C49—C50—H50 | 118.8 |
O3—C17—C8 | 105.72 (16) | C51—C50—H50 | 118.8 |
O3—C17—H17A | 110.6 | C50—C51—C52 | 119.7 (2) |
C8—C17—H17A | 110.6 | C50—C51—H51 | 120.2 |
O3—C17—H17B | 110.6 | C52—C51—H51 | 120.2 |
C8—C17—H17B | 110.6 | N33—C52—C51 | 120.93 (18) |
H17A—C17—H17B | 108.7 | N33—C52—C53 | 120.69 (19) |
C18—O3—C17 | 118.46 (16) | C51—C52—C53 | 118.4 (2) |
O3—C18—C23 | 123.74 (18) | C48—C53—C52 | 120.29 (19) |
O3—C18—C19 | 114.38 (19) | C48—C53—H53 | 119.9 |
C23—C18—C19 | 121.84 (19) | C52—C53—H53 | 119.9 |
C20—C19—C18 | 117.6 (2) | C52—N33—C57 | 122.1 (3) |
C20—C19—H19 | 121.2 | C52—N33—C54 | 120.7 (2) |
C18—C19—H19 | 121.2 | C57—N33—C54 | 112.5 (4) |
C19—C20—C21 | 122.2 (2) | C52—N33—C57' | 116.1 (5) |
C19—C20—H20 | 118.9 | C54—N33—C57' | 122.6 (5) |
C21—C20—H20 | 118.9 | C52—N33—C54' | 115.5 (4) |
C20—C21—C22 | 120.6 (2) | C57'—N33—C54' | 111.6 (6) |
C20—C21—H21 | 119.7 | N33—C54—C55 | 112.6 (4) |
C22—C21—H21 | 119.7 | N33—C54—H54A | 109.1 |
N3—C22—C21 | 121.93 (19) | C55—C54—H54A | 109.1 |
N3—C22—C23 | 120.53 (18) | N33—C54—H54B | 109.1 |
C21—C22—C23 | 117.5 (2) | C55—C54—H54B | 109.1 |
C18—C23—C22 | 120.27 (19) | H54A—C54—H54B | 107.8 |
C18—C23—H23 | 119.9 | O34—C55—C54 | 111.9 (6) |
C22—C23—H23 | 119.9 | O34—C55—H55A | 109.2 |
C22—N3—C27 | 120.42 (18) | C54—C55—H55A | 109.2 |
C22—N3—C24 | 119.6 (2) | O34—C55—H55B | 109.2 |
C27—N3—C24 | 114.8 (2) | C54—C55—H55B | 109.2 |
N3—C24—C25 | 114.6 (2) | H55A—C55—H55B | 107.9 |
N3—C24—H24A | 108.6 | C56—O34—C55 | 104.9 (7) |
C25—C24—H24A | 108.6 | O34—C56—C57 | 102.5 (6) |
N3—C24—H24B | 108.6 | O34—C56—H56A | 111.3 |
C25—C24—H24B | 108.6 | C57—C56—H56A | 111.3 |
H24A—C24—H24B | 107.6 | O34—C56—H56B | 111.3 |
O4—C25—C24 | 117.1 (2) | C57—C56—H56B | 111.3 |
O4—C25—H25A | 108.0 | H56A—C56—H56B | 109.2 |
C24—C25—H25A | 108.0 | N33—C57—C56 | 112.7 (5) |
O4—C25—H25B | 108.0 | N33—C57—H57A | 109.0 |
C24—C25—H25B | 108.0 | C56—C57—H57A | 109.0 |
H25A—C25—H25B | 107.3 | N33—C57—H57B | 109.0 |
C25—O4—C26 | 112.8 (2) | C56—C57—H57B | 109.0 |
O4—C26—C27 | 117.0 (3) | H57A—C57—H57B | 107.8 |
O4—C26—H26A | 108.0 | N33—C54'—C55' | 112.4 (7) |
C27—C26—H26A | 108.0 | N33—C54'—H54C | 109.1 |
O4—C26—H26B | 108.0 | C55'—C54'—H54C | 109.1 |
C27—C26—H26B | 108.0 | N33—C54'—H54D | 109.1 |
H26A—C26—H26B | 107.3 | C55'—C54'—H54D | 109.1 |
N3—C27—C26 | 115.1 (2) | H54C—C54'—H54D | 107.9 |
N3—C27—H27A | 108.5 | O34'—C55'—C54' | 125.0 (10) |
C26—C27—H27A | 108.5 | O34'—C55'—H55C | 106.1 |
N3—C27—H27B | 108.5 | C54'—C55'—H55C | 106.1 |
C26—C27—H27B | 108.5 | O34'—C55'—H55D | 106.1 |
H27A—C27—H27B | 107.5 | C54'—C55'—H55D | 106.1 |
S31—C31—H31A | 109.5 | H55C—C55'—H55D | 106.3 |
S31—C31—H31B | 109.5 | C56'—O34'—C55' | 97.6 (11) |
H31A—C31—H31B | 109.5 | O34'—C56'—C57' | 126.0 (13) |
S31—C31—H31C | 109.5 | O34'—C56'—H56C | 105.8 |
H31A—C31—H31C | 109.5 | C57'—C56'—H56C | 105.8 |
H31B—C31—H31C | 109.5 | O34'—C56'—H56D | 105.8 |
O31—S31—O32 | 118.48 (13) | C57'—C56'—H56D | 105.8 |
O31—S31—C31 | 108.69 (14) | H56C—C56'—H56D | 106.2 |
O32—S31—C31 | 107.68 (13) | N33—C57'—C56' | 108.6 (9) |
O31—S31—C32 | 107.74 (11) | N33—C57'—H57C | 110.0 |
O32—S31—C32 | 107.97 (10) | C56'—C57'—H57C | 110.0 |
C31—S31—C32 | 105.56 (12) | N33—C57'—H57D | 110.0 |
C33—C32—C37 | 121.14 (18) | C56'—C57'—H57D | 110.0 |
C33—C32—S31 | 119.29 (16) | H57C—C57'—H57D | 108.4 |
C37—C32—S31 | 119.53 (15) | | |
| | | |
O1—S1—C2—C7 | 118.63 (18) | C33—C34—C35—N31 | −179.50 (18) |
O2—S1—C2—C7 | −10.2 (2) | C34—C35—C36—C37 | 1.0 (3) |
C1—S1—C2—C7 | −126.33 (18) | N31—C35—C36—C37 | 179.91 (18) |
O1—S1—C2—C3 | −58.82 (19) | C35—C36—C37—C32 | −0.8 (3) |
O2—S1—C2—C3 | 172.37 (17) | C33—C32—C37—C36 | 0.2 (3) |
C1—S1—C2—C3 | 56.2 (2) | S31—C32—C37—C36 | −177.62 (16) |
C7—C2—C3—C4 | 1.9 (3) | C34—C35—N31—N32 | 47.5 (3) |
S1—C2—C3—C4 | 179.29 (16) | C36—C35—N31—N32 | −131.4 (2) |
C2—C3—C4—C5 | −0.5 (3) | C34—C35—N31—C40 | −132.3 (2) |
C3—C4—C5—C6 | −1.3 (3) | C36—C35—N31—C40 | 48.8 (3) |
C3—C4—C5—N1 | −179.71 (18) | C40—N31—N32—C38 | −0.4 (2) |
C4—C5—C6—C7 | 1.7 (3) | C35—N31—N32—C38 | 179.82 (18) |
N1—C5—C6—C7 | −179.87 (18) | N31—N32—C38—C39 | 0.4 (2) |
C5—C6—C7—C2 | −0.3 (3) | N31—N32—C38—C47 | −179.60 (19) |
C3—C2—C7—C6 | −1.5 (3) | N32—C38—C39—C40 | −0.2 (3) |
S1—C2—C7—C6 | −178.95 (16) | C47—C38—C39—C40 | 179.7 (2) |
C4—C5—N1—C10 | −35.7 (3) | N32—N31—C40—C39 | 0.2 (2) |
C6—C5—N1—C10 | 145.9 (2) | C35—N31—C40—C39 | −180.0 (2) |
C4—C5—N1—N2 | 141.44 (19) | N32—N31—C40—C41 | −177.12 (18) |
C6—C5—N1—N2 | −37.0 (3) | C35—N31—C40—C41 | 2.7 (3) |
C10—N1—N2—C8 | −0.2 (2) | C38—C39—C40—N31 | 0.0 (2) |
C5—N1—N2—C8 | −177.78 (17) | C38—C39—C40—C41 | 177.3 (2) |
N1—N2—C8—C9 | 0.3 (2) | N31—C40—C41—C42 | 35.7 (3) |
N1—N2—C8—C17 | 179.89 (18) | C39—C40—C41—C42 | −141.1 (2) |
N2—C8—C9—C10 | −0.4 (2) | N31—C40—C41—C46 | −148.6 (2) |
C17—C8—C9—C10 | −179.9 (2) | C39—C40—C41—C46 | 34.6 (3) |
N2—N1—C10—C9 | −0.1 (2) | C46—C41—C42—C43 | 1.5 (3) |
C5—N1—C10—C9 | 177.18 (19) | C40—C41—C42—C43 | 177.14 (19) |
N2—N1—C10—C11 | 176.59 (18) | C41—C42—C43—C44 | −1.1 (3) |
C5—N1—C10—C11 | −6.2 (3) | C42—C43—C44—C45 | −0.1 (4) |
C8—C9—C10—N1 | 0.3 (2) | C43—C44—C45—C46 | 0.9 (4) |
C8—C9—C10—C11 | −176.2 (2) | C44—C45—C46—C41 | −0.5 (4) |
N1—C10—C11—C12 | 125.2 (2) | C42—C41—C46—C45 | −0.7 (4) |
C9—C10—C11—C12 | −58.9 (3) | C40—C41—C46—C45 | −176.6 (2) |
N1—C10—C11—C16 | −56.0 (3) | N32—C38—C47—O33 | −161.5 (2) |
C9—C10—C11—C16 | 119.9 (3) | C39—C38—C47—O33 | 18.6 (4) |
C16—C11—C12—C13 | −0.2 (3) | C38—C47—O33—C48 | 179.5 (2) |
C10—C11—C12—C13 | 178.6 (2) | C47—O33—C48—C49 | 171.4 (2) |
C11—C12—C13—C14 | −0.2 (4) | C47—O33—C48—C53 | −9.1 (4) |
C12—C13—C14—C15 | 0.8 (4) | O33—C48—C49—C50 | 179.6 (2) |
C13—C14—C15—C16 | −1.1 (4) | C53—C48—C49—C50 | 0.0 (4) |
C14—C15—C16—C11 | 0.6 (4) | C48—C49—C50—C51 | −1.0 (4) |
C12—C11—C16—C15 | 0.0 (3) | C49—C50—C51—C52 | 0.7 (4) |
C10—C11—C16—C15 | −178.8 (2) | C50—C51—C52—N33 | 178.6 (2) |
N2—C8—C17—O3 | −159.8 (2) | C50—C51—C52—C53 | 0.6 (4) |
C9—C8—C17—O3 | 19.7 (3) | O33—C48—C53—C52 | −178.3 (2) |
C8—C17—O3—C18 | 172.4 (2) | C49—C48—C53—C52 | 1.2 (4) |
C17—O3—C18—C23 | 1.0 (3) | N33—C52—C53—C48 | −179.5 (2) |
C17—O3—C18—C19 | −176.8 (2) | C51—C52—C53—C48 | −1.5 (4) |
O3—C18—C19—C20 | 176.5 (2) | C51—C52—N33—C57 | 157.1 (4) |
C23—C18—C19—C20 | −1.2 (4) | C53—C52—N33—C57 | −25.0 (5) |
C18—C19—C20—C21 | 0.1 (4) | C51—C52—N33—C54 | 3.1 (5) |
C19—C20—C21—C22 | 0.1 (4) | C53—C52—N33—C54 | −179.0 (4) |
C20—C21—C22—N3 | −176.3 (2) | C51—C52—N33—C57' | 174.9 (7) |
C20—C21—C22—C23 | 0.8 (4) | C53—C52—N33—C57' | −7.2 (8) |
O3—C18—C23—C22 | −175.4 (2) | C51—C52—N33—C54' | 41.4 (5) |
C19—C18—C23—C22 | 2.2 (3) | C53—C52—N33—C54' | −140.7 (5) |
N3—C22—C23—C18 | 175.3 (2) | C52—N33—C54—C55 | −169.1 (4) |
C21—C22—C23—C18 | −1.9 (3) | C57—N33—C54—C55 | 34.6 (7) |
C21—C22—N3—C27 | −164.1 (3) | C57'—N33—C54—C55 | 19.7 (11) |
C23—C22—N3—C27 | 18.8 (4) | C54'—N33—C54—C55 | 100.2 (10) |
C21—C22—N3—C24 | −11.0 (4) | N33—C54—C55—O34 | −46.6 (8) |
C23—C22—N3—C24 | 172.0 (2) | C54—C55—O34—C56 | 68.7 (6) |
C22—N3—C24—C25 | 167.7 (3) | C55—O34—C56—C57 | −75.6 (5) |
C27—N3—C24—C25 | −37.7 (4) | C52—N33—C57—C56 | 157.8 (4) |
N3—C24—C25—O4 | 43.2 (4) | C54—N33—C57—C56 | −46.3 (7) |
C24—C25—O4—C26 | −46.2 (4) | C57'—N33—C57—C56 | 84 (3) |
C25—O4—C26—C27 | 45.1 (4) | C54'—N33—C57—C56 | −77.1 (6) |
C22—N3—C27—C26 | −168.7 (3) | O34—C56—C57—N33 | 66.6 (6) |
C24—N3—C27—C26 | 37.0 (4) | C52—N33—C54'—C55' | −174.8 (7) |
O4—C26—C27—N3 | −41.6 (4) | C57—N33—C54'—C55' | 55.3 (8) |
O31—S31—C32—C33 | −148.51 (18) | C54—N33—C54'—C55' | −67.0 (10) |
O32—S31—C32—C33 | −19.5 (2) | C57'—N33—C54'—C55' | 49.7 (11) |
C31—S31—C32—C33 | 95.5 (2) | N33—C54'—C55'—O34' | −22.5 (17) |
O31—S31—C32—C37 | 29.4 (2) | C54'—C55'—O34'—C56' | −27.0 (17) |
O32—S31—C32—C37 | 158.44 (17) | C55'—O34'—C56'—C57' | 61.6 (14) |
C31—S31—C32—C37 | −86.6 (2) | C52—N33—C57'—C56' | −159.1 (8) |
C37—C32—C33—C34 | 0.2 (3) | C57—N33—C57'—C56' | −43.8 (18) |
S31—C32—C33—C34 | 178.07 (16) | C54—N33—C57'—C56' | 12.5 (14) |
C32—C33—C34—C35 | 0.0 (3) | C54'—N33—C57'—C56' | −24.0 (13) |
C33—C34—C35—C36 | −0.6 (3) | O34'—C56'—C57'—N33 | −38.0 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O2 | 0.93 | 2.50 | 2.887 (3) | 105 |
C24—H24A···O31i | 0.97 | 2.57 | 3.378 (4) | 141 |
C27—H27B···O32ii | 0.97 | 2.55 | 3.427 (4) | 151 |
C31—H31A···O34iii | 0.96 | 2.53 | 3.489 (8) | 174 |
C33—H33···O32 | 0.93 | 2.57 | 2.925 (3) | 103 |
C46—H46···O1iv | 0.93 | 2.40 | 3.223 (4) | 148 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1, y+1, z−1; (iii) x−1, y−1, z; (iv) −x+1, −y, −z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C17H16N2O2S | C19H18N2O4S | C27H27N3O4S |
Mr | 312.39 | 370.41 | 489.59 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, Pca21 | Triclinic, P1 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 11.007 (1), 13.061 (1), 24.298 (1) | 19.479 (1), 5.610 (1), 33.586 (3) | 10.325 (2), 13.874 (2), 18.094 (2) |
α, β, γ (°) | 90, 112.652 (5), 90 | 90, 90, 90 | 100.823 (9), 104.704 (8), 91.888 (11) |
V (Å3) | 3223.7 (4) | 3670.2 (8) | 2453.6 (7) |
Z | 8 | 8 | 4 |
Radiation type | Cu Kα | Cu Kα | Cu Kα |
µ (mm−1) | 1.85 | 1.80 | 1.49 |
Crystal size (mm) | 0.35 × 0.30 × 0.20 | 0.42 × 0.05 × 0.04 | 0.40 × 0.28 × 0.24 |
|
Data collection |
Diffractometer | Enraf–Nonius CAD-4 diffractometer | Enraf–Nonius CAD-4 diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Analytical (Alcock, 1970) | Analytical (Alcock, 1970) | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.563, 0.708 | 0.519, 0.932 | 0.587, 0.716 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11113, 6323, 5480 | 6078, 3651, 2391 | 15978, 9997, 8261 |
Rint | 0.028 | 0.028 | 0.018 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.624 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.118, 1.03 | 0.038, 0.102, 1.01 | 0.056, 0.168, 1.04 |
No. of reflections | 6323 | 3651 | 9997 |
No. of parameters | 402 | 475 | 646 |
No. of restraints | 0 | 1 | 766 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.30 | 0.18, −0.18 | 0.47, −0.39 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O22i | 0.960 | 2.390 | 3.344 (3) | 173.00 |
C7—H7···O1 | 0.930 | 2.580 | 2.939 (2) | 104.00 |
C23—H23···O1 | 0.930 | 2.560 | 3.083 (3) | 116.00 |
C27—H27···O22 | 0.930 | 2.550 | 2.921 (2) | 104.00 |
C30—H30···O2ii | 0.930 | 2.530 | 3.436 (2) | 165.00 |
Symmetry codes: (i) x−1, y, z; (ii) x, −y+1/2, z−1/2. |
Analysis of C–H···π interactions for I topX–H···Cg | H···Cg | X–H···Cg | X···Cg |
C1–H1···Cg4i | 2.70 | 152 | 3.577 (2) |
C4–H4···Cg2ii | 2.81 | 120 | 3.379 (2) |
C21–H21B···Cg6iii | 2.79 | 146 | 3.624 (2) |
C24–H24···Cg1i | 2.85 | 120 | 3.411 (2) |
Notes: Cg1 and Cg2 are the centroids of the five-membered N1-N2-C8-C10-C11 and N21-N22-C28-C30-C31 rings, respectively. Cg4 and Cg6 denote the centroids of the C12-C17 and C32-C37 phenyl rings.
Symmetry codes: (i)1 − x, 1/2 + y, 1/2 − z; (ii) 1 − x, −1/2 + y, 1/2 − z; (iii) 2 − x, −1/2 + y, 1/2 − z |
Selected torsion angles (º) for (II) topN1—C10—C11—C12 | −32.9 (6) | C30—N21—C25—C24 | 63.5 (6) |
C10—N1—C5—C6 | −64.8 (6) | C32—C31—C30—N21 | 27.1 (6) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1C···N22 | 0.960 | 2.580 | 3.515 (6) | 164.00 |
C7—H7···O2 | 0.930 | 2.550 | 2.908 (6) | 103.00 |
C21—H21A···N2i | 0.960 | 2.600 | 3.545 (7) | 169.00 |
C23—H23···O1ii | 0.930 | 2.470 | 3.292 (6) | 147.00 |
C23—H23···O22 | 0.930 | 2.540 | 2.907 (6) | 104.00 |
Symmetry codes: (i) x+1/2, −y+1, z; (ii) x, y+1, z. |
Analysis of C–H···π interactions for II topX–H···Cg | H···Cg | X–H···Cg | X···Cg |
C14–H14···Cg6i | 2.88 | 135 | 3.597 (6) |
C34–H34···Cg4ii | 2.95 | 138 | 3.694 (6) |
Notes: Cg4 and Cg6 denote the centroids of the C11-C16 and C31-C36 phenyl rings.
Symmetry codes: (i)1/2 − x, y, 1/2 + z; (ii) 1/2 − x, 1 + y, −1/2 + z |
Selected torsion angles (º) for (III) topC4—C5—N1—C10 | −35.7 (3) | C36—C35—N31—C40 | 48.8 (3) |
N1—C10—C11—C16 | −56.0 (3) | N31—C40—C41—C42 | 35.7 (3) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O2 | 0.930 | 2.500 | 2.887 (3) | 105.00 |
C24—H24A···O31i | 0.970 | 2.570 | 3.378 (4) | 141.00 |
C27—H27B···O32ii | 0.970 | 2.550 | 3.427 (4) | 151.00 |
C31—H31A···O34iii | 0.960 | 2.530 | 3.489 (8) | 174.00 |
C33—H33···O32 | 0.930 | 2.570 | 2.925 (3) | 103.00 |
C46—H46···O1iv | 0.930 | 2.400 | 3.223 (4) | 148.00 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1, y+1, z−1; (iii) x−1, y−1, z; (iv) −x+1, −y, −z. |
Analysis of C–H···π interactions for III topX–H···Cg | H···Cg | X–H···Cg | X···Cg |
C4–H4···Cg1i | 3.04 | 118 | 3.580 (2) |
C15–H15···Cg6ii | 2.78 | 153 | 3.631 (3) |
C26–H26A···Cg8iii | 3.02 | 156 | 3.926 (3) |
C27–H27A···Cg1iv | 2.90 | 149 | 3.763 (4) |
C34–H34···Cg10v | 2.78 | 143 | 3.571 (2) |
C36–H36···Cg11vi | 2.92 | 138 | 3.669 (2) |
C42–H42···Cg2v | 2.91 | 118 | 3.445 (2) |
Notes: Cg1 and Cg2 are the centroids of the five-membered N1-N2-C8-C9-C10 and N31-N32-C29-C29-C30 rings, respectively. Cg6, Cg8, Cg10 and Cg11 denote the centroids of the C2-C7, C18-C23, C41-C47 and C48-C53 phenyl rings, respectively.
Symmetry codes: (i) 2 − x, 1 − y, −z; (ii) 1 − x, 1 − y, −z; (iii) 3 − x, 2 − y, −z; (iv) 2 − x, 2 − y, −z; (v) −x, −y, 1 − z; (vi) 1 − x, −y, 1 − z |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
The three title compounds, i.e. C17H16N2O2S (I), C19H18N2O4S, (II), and C27H27N3O4S, (III), have been investigated as part of a project aimed at the design of new dual 5-LOX/COX-2 inhibitors (Barbey et al., 2002; Pommery et al., 2004). Besides selective COX-2 inhibition, this strategy appears to be a promising approach to providing safer non-steroidal anti-inflammatory drugs (Charlier & Michaux, 2003). Moreover, it opens up new perspectives in the prophylactic treatment of several types of cancer (Romano & Claria, 2003). Celecoxib, (IV), a selective COX-2 inhibitor, was used as a starting point to investigate several pharmacomodulations and subsequently to study the influence of various substituents on COX-2 and 5-LOX inhibition. While totally inactive against 5-LOX, the three title compounds exhibit different results regarding COX-2 inhibition. Indeed, in contrast to (III), (I) and (II), which are structurally closer to celecoxib, show an unexpected inactivity towards COX-2 (Barbey et al., 2002; Pommery et al., 2004). Crystal structure determination for the three compounds was carried out in order to elucidate their structural properties and to allow comparison with the previously reported structure of celecoxib (Vasu Dev, 1999), as deposited in the Cambridge Structural Database (CSD; refcode DIBBUL; Allen, 2002).
In all three crystal structures, the asymmetric unit includes two independent molecules, which differ slightly in conformation, whereas the parent compound, (IV), has only one (Fig. 1). Except for those influenced by the different nature of the moieties characteristic to each compound, the geometric parameters (bond lengths and angles) in the three studied molecules do not differ considerably from those in (IV).
Compound (I) (Fig. 2) crystallizes in space group P21/c. The two independent molecules are related by a non-crystallographic pseudo-twofold rotational axis (rotation of −177.70° about the b axis). Superimposition of all non-H atoms in both molecules with the quaternion transformation method (Mackay, 1984) gives a weighted (unit weight) r.m.s. fit of 0.16 Å (0.12 Å). The two vicinal phenyl rings are twisted with respect to the plane of the pyrazole ring. The extent of this deviation is not exactly the same for the two independent molecules. The C11—N1—C5—C6 and C13—C12—C11—N1 torsion angles are 39.3 (2) and 47.0 (2)°, respectively, and the C31—N21—C25—C26 and C33—C32—C31—N21 angles are −40.8 (2) and −54.7 (2)°, respectively. These orientations are quite different from that observed in celecoxib, whose two phenyl rings are almost perpendicular (the C6—C5—C3—N2 and C3—N2—C12—C17 torsion angles are 16.0 (8) and 98.8 (6)°, respectively). Weak intramolecular interactions in each residue of the asymmetric unit, involving a phenyl H atom (H7 and H27) and a sulfonyl O atom (O1 and O22, respectively), influence the conformation of the sulfonyl moiety with respect to the phenyl ring (Table 1). This kind of interaction is also found in celecoxib, between the H atom attached to atom C16 and sulfonyl atom O2. In the crystal packing (Fig. 3), cohesion is achieved by, in addition to van der Waals interactions, weak C—H···O hydrogen bonds and C—H···π interactions (Table 1 and Table 2).
Compound (II) (Fig. 4) crystallizes in space group Pca21. The ethyl ester chain is completely extended, with all the non-H atoms coplanar. The two residues in the asymmetric unit can be almost perfectly superimposed on one another (weighted and unit weight r.m.s. fit values of 0.065 and 0.050 Å, respectively). As observed for (I), both molecules are related by a non-crystallographic pseudo-twofold rotational axis (rotation of −179.2° about the c axis). The two vicinal phenyl rings are not perpendicular, in contrast to the situation in celecoxib (Table 3). Here again, in both asymmetric unit residues, a weak intramolecular hydrogen bond is observed, involving a phenyl H atom (H7 and H23) and one of the sulfonyl O atoms (O2 and O22; Table 4). While no classic hydrogen bond is found in the crystal packing (Fig. 5), the methyl atom (C1 and C21) of each methylsulfonyl group is involved in a weak intermolecular C—H···N interaction with the pyrazole N atom (N2 and N22) of an adjacent molecule (Table 4). Additional weak C—H···O and C—H···π contacts occur. Surprisingly, none of these intermolecular interactions involve the ethyl ester chain (Table 4 and Table 5).
Like celecoxib, compound (III) (Fig. 6) crystallizes in space group P-1. One of the residues in the asymmetric unit exhibits disorder in its morpholine moiety, as evidenced by the Ueq values. Among the three studied compounds, the two independent molecules in (III) display the most different conformations (weighted and unit weight r.m.s. fit values of 0.55 and 0.36 Å, respectively). The two vicinal phenyl rings are almost perpendicular when the two asymmetric-unit residues are superimposed. The torsion angles differ slightly from those observed for (I) and (II) (Table 6). However, both independent molecules exhibit a weak intramolecular hydrogen bond between a phenyl H atom (H7 and H33) and one of the sulfonyl O atoms (O2 and O32; Table 7). In the crystal packing (Fig. 7), several intermolecular interactions exist between symmetry-related molecules, notably C—H···O and C—H···π contacts, especially involving the morpholine moiety (Table 7 and Table 8). This additional fragment could represent an important anchoring point inside the COX-2 active site, partly explaining the higher COX-2 inhibitory potency of (III) compared with that of (I) or (II).