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ISSN: 2414-3146

1-(3′,6′-Dihy­dr­oxy-3-oxo-3H-spiro­[isobenzo­furan-1,9′-xanthen]-5-yl)-3-[4-({4-[1-(4-fluoro­phen­yl)-1H-imidazol-5-yl]pyridin-2-yl}amino)­phen­yl]thio­urea methanol monosolvate

aInstitute of Pharmaceutical Sciences, Department of Pharmaceutical and Medicinal Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany, and bDepartment of Organic Chemistry, Johannes Gutenberg-University Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
*Correspondence e-mail: pierre.koch@uni-tuebingen.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 14 May 2016; accepted 23 May 2016; online 27 May 2016)

The title compound, which crystallized as a methanol monosolvate, C41H27FN6O5S·CH3OH, was synthesized as a probe for a fluorescence polarization-based competition binding assay. The isobenzo­furan fused-ring system is close to planar and orientated almost perpendicular to the central ring of the xanthene system. The dihedral angle between the benzene rings of the xanthene system is 10.0 (2)°, indicating a butterfly-like orientation. A short intra­molecular C—F⋯π contact [F⋯π = 3.100 (4) Å and C—F⋯π = 139.9 (3)°] to the six-membered ring of the isobenzo­furan system may influence the mol­ecular conformation. The methanol solvent mol­ecule is disordered over two orientations in a 0.6:0.4 ratio. In the crystal, the components are linked by numerous hydrogen bonds, generating a three-dimensional network.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The title compound was synthesized by reaction of N1-{4-[1-(4-fluoro­phen­yl)-1H-imidazol-5-yl]pyridin-2-yl}benzene-1,4-di­amine and 5(6)-fluorescein-iso­thio­cyanate as a probe for a fluorescence polarization-based competition binding assay. The design and application of similar probes was recently published by our group (Ansideri et al., 2016[Ansideri, F., Lange, A., El-Gokha, A., Boeckler, F. M. & Koch, P. (2016). Anal. Biochem. 503, 28-40.]). As a commercially available isomeric mixture of the 5′- and 6′-isomers of fluorescein-iso­thio­cyanate had been used as a staring material, single-crystal analysis was performed to confirm the isolated isomer. X-ray data confirmed that solely the 5′-isomer was isolated. The title molecule is shown in Fig. 1[link].

[Figure 1]
Figure 1
The mol­ecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

The isobenzo­furan fused-ring system is almost planar (r.m.s. deviation = 0.038 Å) and almost perpendicular to the central ring of the xanthene system [dihedral angle = 86.44 (17)°]. The dihedral angle between the benzene rings of the xanthene system is 10.0 (2)°. The thio­urea unit of the mol­ecule makes dihedral angles of 53.64 (17)° and 56.3 (2)° with the isobenzo­furan ring system and the phenyl ring at the pyridine-C2 position, respectively. The imidazole ring makes a dihedral angle of 14.8 (3)° with the 4-fluoro­phenyl ring. The pyridine ring is almost perpendicular to the imidazole core, subtending a dihedral angle of 84.9 (3)°. A short intra­molecular C—F⋯π contact [F⋯π = 3.100 (4) Å and C—F⋯π = 139.9 (3)°] to the six-membered ring of the isobenzo­furan system may influence the mol­ecular conformation.

The crystal packing features numerous hydrogen bonds (Table 1[link]), generating a three-dimensional network, and incorporates one disordered mol­ecule of methanol.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O15—H15⋯N46i 0.84 1.84 2.667 (5) 168
O16—H16⋯O21ii 0.84 2.04 2.808 (5) 153
C22—H22⋯O15iii 0.95 2.59 3.315 (5) 133
C24—H24⋯S29iv 0.95 2.99 3.804 (5) 145
N26—H26⋯O15iii 1.09 2.17 3.061 (5) 138
N28—H28⋯N38v 1.17 1.94 3.069 (6) 162
C34—H34⋯O1Lvi 0.95 2.46 3.334 (9) 154
N36—H36⋯S29vii 0.88 2.64 3.437 (4) 152
C40—H40⋯O2Lviii 0.95 2.32 3.103 (12) 139
C45—H45⋯O17ii 0.95 2.49 3.379 (6) 155
C53—H53⋯S29ix 0.95 2.87 3.743 (6) 153
C1L—H2M⋯O21 0.98 2.56 3.267 (7) 129
O1L—H1L⋯S29x 0.84 2.46 3.202 (8) 147
Symmetry codes: (i) x, y-1, z; (ii) [-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]; (iii) [x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (iv) [-x+1, y, -z+{\script{1\over 2}}]; (v) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (vi) [-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]; (vii) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (viii) -x+1, -y+1, -z+1; (ix) [x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (x) -x+1, -y, -z+1.

Synthesis and crystallization

A solution of N1-{4-[1-(4-fluoro­phen­yl)-1H-imidazol-5-yl]pyridin-2-yl}benzene-1,4-di­amine (200 mg, 0.58 mmol) and 5(6)-fluorescein-iso­thio­cyanate (248 mg, 0.77 mmol) in acetone (30 ml) was stirred at 298 K for 48 h with light excluded. The mixture was evaporated to dryness and the residue was purified by flash chromatography (di­chloro­methane–ethanol 95:05–90:10) obtaining 160 mg of the desired product (yield 37%). Crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in methanol at 298 K.

1H NMR (250 MHz, DMSO-d6): δ 6.45 (dd, J1 = 5.3 Hz, J2 = 1.4 Hz, 1H), 6.53–6.63 (m, 5H), 6.67 (d, J = 2.0 Hz, 2H), 7.18 (d, J = 8.4 Hz, 1H), 7.27 (d, J = 8.9 Hz, 2H), 7.35–7.45 (m, 5H), 7.47 (d, J = 9.0 Hz, 2H), 7.82 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz), 8.00 (d, J = 1.0 Hz, 1H), 8.05 (d, J = 5.4 Hz, 1H), 8.17 (d, J = 1.9 Hz, 1H), 9.06 (br s, 1H), 9.94 (br s, 1H), 10.00 (s, 1H), 10.17 (s, 2H); 13C NMR (100 MHz, DMSO-d6) δ 83.6, 102.9, 108.3, 111.4, 113.3, 113.4, 117.3 (d, J = 22.9 Hz), 118.4, 119.1, 124.6, 125.7, 127.2, 128.7 (d, J = 8.8 Hz), 129.8, 130.8, 131.3, 132.7, 133.3 (d, J = 2.4 Hz), 138.4, 139.6, 141.8, 142.3, 148.5, 148.7, 152.8, 156.9, 160.5, 162.6 (d, J = 245.6 Hz), 169.6, 180.8. HPLC: t = 11.54 min, purity: 98% (λ = 254 nm).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The methanol solvent mol­ecule is disordered over two orientations in a 0.6:0.4 ratio.

Table 2
Experimental details

Crystal data
Chemical formula C41H27FN6O5S·CH4O
Mr 766.79
Crystal system, space group Monoclinic, C2/c
Temperature (K) 193
a, b, c (Å) 15.1825 (8), 17.7557 (7), 26.2236 (13)
β (°) 92.283 (4)
V3) 7063.6 (6)
Z 8
Radiation type Mo Kα
μ (mm−1) 0.16
Crystal size (mm) 0.09 × 0.08 × 0.07
 
Data collection
Diffractometer Stoe IPDS 2T
No. of measured, independent and observed [I > 2σ(I)] reflections 23065, 8960, 3244
Rint 0.085
(sin θ/λ)max−1) 0.674
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.240, 0.92
No. of reflections 8960
No. of parameters 516
No. of restraints 2
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.35, −0.38
Computer programs: X-AREA and X-RED (Stoe & Cie, 2011[Stoe & Cie (2011). X-RED and X-AREA. Stoe & Cie, Darmstadt, Darmstadt, Germany.], SIR2004 (Burla et al., 2005[Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.]) and SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]).

Structural data


Experimental top

A solution of N1-{4-[1-(4-fluorophenyl)-1H-imidazol-5-yl]pyridin-2-yl}benzene-1,4-diamine (200 mg, 0.58 mmol) and 5(6)-fluorescein-isothiocyanate (248 mg, 0.77 mmol) in acetone (30 ml) was stirred at 298 K for 48 h covered from light. The mixture was concentrated to dryness and the residue was purified by flash chromatography (dichloromethane–ethanol 95:05–90:10) obtaining 160 mg of the desired product (yield 37%). Crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in methanol at 298 K.

1H NMR (250 MHz, DMSO-d6): δ 6.45 (dd, J1 = 5.3 Hz, J2 = 1.4 Hz, 1H), 6.53–6.63 (m, 5H), 6.67 (d, J = 2.0 Hz, 2H), 7.18 (d, J = 8.4 Hz, 1H), 7.27 (d, J = 8.9 Hz, 2H), 7.35–7.45 (m, 5H), 7.47 (d, J = 9.0 Hz, 2H), 7.82 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz), 8.00 (d, J = 1.0 Hz, 1H), 8.05 (d, J = 5.4 Hz, 1H), 8.17 (d, J = 1.9 Hz, 1H), 9.06 (br s, 1H), 9.94 (br s, 1H), 10.00 (s, 1H), 10.17 (s, 2H); 13C NMR (100 MHz, DMSO-d6) δ 83.6, 102.9, 108.3, 111.4, 113.3, 113.4, 117.3 (d, J = 22.9 Hz), 118.4, 119.1, 124.6, 125.7, 127.2, 128.7 (d, J = 8.8 Hz), 129.8, 130.8, 131.3, 132.7, 133.3 (d, J = 2.4 Hz), 138.4, 139.6, 141.8, 142.3, 148.5, 148.7, 152.8, 156.9, 160.5, 162.6 (d, J = 245.6 Hz), 169.6, 180.8. HPLC: t = 11.54 min, purity: 98% (λ = 254 nm).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2.

Structure description top

The title compound was synthesized by reaction of N1-{4-[1-(4-fluorophenyl)-1H-imidazol-5-yl]pyridin-2-yl}benzene-1,4-diamine and 5(6)-fluorescein-isothiocyanate as a probe for a fluorescence polarization-based competition binding assay. The design and application of similar probes was recently published by our group (Ansideri et al., 2016). As a commercially available isomeric mixture of the 5'- and 6'-isomers of fluorescein-isothiocyanate had been used as a staring material, single-crystal analysis was performed to confirm the isolated isomer. X-ray data confirmed that solely the 5'-isomer was isolated.

The isobenzofuran fused-ring system is almost planar (r.m.s. deviation = 0.038 Å) and almost perpendicular to the central ring of the xanthene system [dihedral angle = 86.44 (17)°]. The dihedral angle between the benzene rings of the xanthene system is 10.0 (2)°. The thiourea unit of the molecule makes dihedral angles of 53.64 (17)° and 56.3 (2)° with the isobenzofuran ring system and the phenyl ring at the pyridine-C2 position, respectively. The imidazole ring makes a dihedral angle of 14.8 (3)° with the 4-fluorophenyl ring. The pyridine ring is almost perpendicular to the imidazole core, subtending a dihedral angle of 84.9 (3)°. A short intramolecular C—F···π contact [F···π = 3.100 (4) Å and C—F···π = 139.9 (3)°] to the six-membered ring of the isobenzofuran system may influence the molecular conformation.

The crystal packing features numerous hydrogen bonds (Table 1), generating a three-dimensional network, and incorporates one disordered molecule of methanol.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2011); cell refinement: X-AREA (Stoe & Cie, 2011; data reduction: X-RED (Stoe & Cie, 2011; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
1-(3',6'-Dihydroxy-3-oxo-3H-spiro[isobenzofuran-1,9'-xanthen]-5-yl)-3-[4-({4-[1-(4-fluorophenyl)-1H-imidazol-5-yl]pyridin-2-yl}amino)phenyl]thiourea; methanol top
Crystal data top
C41H27FN6O5S·CH4OF(000) = 3184
Mr = 766.79Dx = 1.442 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 15.1825 (8) ÅCell parameters from 7245 reflections
b = 17.7557 (7) Åθ = 2.3–27.9°
c = 26.2236 (13) ŵ = 0.16 mm1
β = 92.283 (4)°T = 193 K
V = 7063.6 (6) Å3Block, colourless
Z = 80.09 × 0.08 × 0.07 mm
Data collection top
Stoe IPDS 2T
diffractometer
3244 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focusRint = 0.085
Detector resolution: 6.67 pixels mm-1θmax = 28.6°, θmin = 2.3°
rotation method scansh = 2020
23065 measured reflectionsk = 2123
8960 independent reflectionsl = 3535
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.070 w = 1/[σ2(Fo2) + (0.110P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.240(Δ/σ)max < 0.001
S = 0.92Δρmax = 0.35 e Å3
8960 reflectionsΔρmin = 0.38 e Å3
516 parametersExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraintsExtinction coefficient: 0.00101 (19)
Crystal data top
C41H27FN6O5S·CH4OV = 7063.6 (6) Å3
Mr = 766.79Z = 8
Monoclinic, C2/cMo Kα radiation
a = 15.1825 (8) ŵ = 0.16 mm1
b = 17.7557 (7) ÅT = 193 K
c = 26.2236 (13) Å0.09 × 0.08 × 0.07 mm
β = 92.283 (4)°
Data collection top
Stoe IPDS 2T
diffractometer
3244 reflections with I > 2σ(I)
23065 measured reflectionsRint = 0.085
8960 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0702 restraints
wR(F2) = 0.240H-atom parameters constrained
S = 0.92Δρmax = 0.35 e Å3
8960 reflectionsΔρmin = 0.38 e Å3
516 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.7146 (3)0.0416 (2)0.45826 (18)0.0456 (10)
C20.7446 (3)0.0387 (2)0.45478 (17)0.0438 (9)
C30.6854 (3)0.0980 (2)0.45158 (19)0.0491 (11)
H30.62420.08740.45260.059*
C40.7120 (3)0.1717 (2)0.44691 (18)0.0485 (10)
H40.66980.21130.44570.058*
C50.8021 (3)0.1878 (2)0.44396 (18)0.0466 (10)
C60.8623 (3)0.1298 (2)0.44888 (19)0.0503 (11)
H60.92370.14020.44840.060*
C70.8333 (3)0.0563 (2)0.45448 (18)0.0469 (10)
O80.89947 (18)0.00298 (16)0.45973 (14)0.0535 (8)
C90.8766 (3)0.0723 (2)0.45771 (19)0.0467 (10)
C100.9461 (3)0.1221 (3)0.45871 (19)0.0519 (11)
H101.00500.10410.46170.062*
C110.9296 (3)0.1988 (3)0.4553 (2)0.0525 (11)
C120.8432 (3)0.2243 (3)0.4504 (2)0.0578 (12)
H120.83140.27670.44690.069*
C130.7748 (3)0.1734 (2)0.45061 (19)0.0523 (11)
H130.71580.19150.44810.063*
C140.7897 (3)0.0962 (2)0.45448 (18)0.0454 (10)
O150.83304 (19)0.25782 (16)0.43631 (13)0.0548 (8)
H150.79170.28560.42540.082*
O160.99968 (19)0.24600 (18)0.45616 (15)0.0636 (9)
H160.98450.28830.46720.095*
O170.67552 (18)0.05307 (17)0.51047 (12)0.0470 (7)
C180.5937 (3)0.0830 (2)0.50544 (18)0.0453 (10)
C190.5674 (3)0.0866 (2)0.45147 (18)0.0453 (10)
C200.6358 (3)0.0599 (2)0.42341 (18)0.0441 (10)
O210.5539 (2)0.10267 (18)0.54287 (13)0.0541 (8)
C220.4891 (3)0.1127 (2)0.42833 (18)0.0462 (10)
H220.44210.13050.44790.055*
C230.4827 (3)0.1116 (2)0.37583 (18)0.0470 (10)
C240.5513 (3)0.0831 (2)0.34715 (19)0.0488 (11)
H240.54470.08140.31100.059*
C250.6285 (3)0.0575 (3)0.37110 (19)0.0487 (11)
H250.67530.03870.35180.058*
N260.4075 (2)0.1462 (2)0.35115 (15)0.0497 (9)
H260.39890.20010.37030.060*
C270.3620 (3)0.1219 (3)0.30850 (18)0.0491 (11)
N280.3064 (2)0.1732 (2)0.28696 (16)0.0525 (9)
H280.25900.14110.25830.063*
S290.36943 (8)0.03475 (7)0.28470 (5)0.0582 (4)
C300.3108 (3)0.2532 (2)0.29427 (19)0.0511 (11)
C310.3902 (3)0.2919 (3)0.2939 (2)0.0591 (12)
H310.44380.26450.29240.071*
C320.3928 (3)0.3699 (3)0.2956 (2)0.0576 (12)
H320.44770.39550.29530.069*
C330.3145 (3)0.4108 (3)0.29767 (19)0.0513 (11)
C340.2351 (3)0.3715 (3)0.29846 (19)0.0527 (11)
H340.18120.39860.29950.063*
C350.2338 (3)0.2942 (3)0.29771 (19)0.0526 (11)
H350.17920.26840.29960.063*
N360.3091 (2)0.4896 (2)0.29414 (17)0.0570 (10)
H360.25620.50640.28500.068*
C370.3706 (3)0.5452 (3)0.30223 (19)0.0532 (11)
N380.3436 (3)0.6124 (3)0.2834 (2)0.0799 (15)
C390.3977 (5)0.6696 (4)0.2922 (4)0.126 (4)
H390.37830.71820.28150.151*
C400.4795 (5)0.6642 (4)0.3158 (3)0.115 (3)
H400.51730.70680.31770.138*
C410.5070 (3)0.5962 (3)0.3369 (2)0.0607 (13)
C420.4508 (3)0.5361 (3)0.32982 (19)0.0528 (11)
H420.46630.48820.34370.063*
C430.5906 (3)0.5970 (3)0.36659 (19)0.0534 (11)
N440.6417 (2)0.5368 (2)0.38405 (15)0.0509 (9)
C450.7124 (3)0.5661 (3)0.4102 (2)0.0561 (12)
H450.75840.53680.42570.067*
N460.7097 (2)0.6401 (2)0.41169 (16)0.0534 (9)
C470.6355 (3)0.6593 (3)0.38449 (19)0.0548 (11)
H470.61680.70970.37850.066*
C480.6348 (3)0.4580 (3)0.37468 (19)0.0523 (11)
C490.5898 (4)0.4127 (3)0.4064 (2)0.0721 (16)
H490.55840.43410.43350.087*
C500.5895 (4)0.3352 (3)0.3992 (3)0.0799 (18)
H500.55830.30300.42110.096*
C510.6341 (4)0.3071 (3)0.3607 (2)0.0675 (15)
C520.6814 (5)0.3505 (3)0.3291 (3)0.091 (2)
H520.71390.32860.30270.109*
C530.6807 (5)0.4272 (3)0.3365 (2)0.084 (2)
H530.71270.45900.31470.101*
F540.6336 (3)0.23112 (17)0.35271 (16)0.0939 (11)
C1L0.5122 (6)0.1316 (5)0.6625 (3)0.123 (3)
H1M0.46290.15540.64350.185*0.6
H2M0.54280.09710.64010.185*0.6
H3M0.55340.17050.67520.185*0.6
H4M0.57670.13370.66200.185*0.4
H5M0.48670.15730.63230.185*0.4
H6M0.49300.07890.66250.185*0.4
O1L0.4803 (5)0.0914 (5)0.7038 (3)0.111 (3)0.6
H1L0.52210.06810.71880.166*0.6
O2L0.4841 (7)0.1673 (5)0.7067 (3)0.081 (3)0.4
H2L0.43410.18640.70080.122*0.4
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0352 (19)0.044 (2)0.057 (3)0.0036 (17)0.0048 (18)0.006 (2)
C20.0364 (19)0.042 (2)0.052 (3)0.0047 (17)0.0059 (17)0.002 (2)
C30.0342 (19)0.043 (2)0.070 (3)0.0017 (17)0.0030 (19)0.002 (2)
C40.039 (2)0.038 (2)0.068 (3)0.0018 (17)0.0038 (19)0.003 (2)
C50.044 (2)0.034 (2)0.061 (3)0.0040 (17)0.003 (2)0.0025 (19)
C60.035 (2)0.043 (2)0.072 (3)0.0047 (17)0.003 (2)0.003 (2)
C70.036 (2)0.045 (2)0.059 (3)0.0005 (17)0.0040 (19)0.006 (2)
O80.0363 (14)0.0361 (15)0.087 (2)0.0002 (12)0.0070 (15)0.0041 (15)
C90.043 (2)0.035 (2)0.062 (3)0.0002 (17)0.005 (2)0.005 (2)
C100.035 (2)0.047 (2)0.073 (3)0.0026 (18)0.004 (2)0.009 (2)
C110.043 (2)0.045 (2)0.069 (3)0.0048 (19)0.002 (2)0.006 (2)
C120.045 (2)0.042 (2)0.085 (4)0.0045 (19)0.005 (2)0.004 (2)
C130.041 (2)0.040 (2)0.075 (3)0.0040 (18)0.008 (2)0.005 (2)
C140.038 (2)0.041 (2)0.056 (3)0.0026 (17)0.0028 (18)0.010 (2)
O150.0430 (15)0.0361 (15)0.085 (2)0.0058 (13)0.0048 (15)0.0086 (16)
O160.0409 (15)0.0425 (17)0.107 (3)0.0043 (13)0.0025 (17)0.0120 (18)
O170.0389 (14)0.0475 (17)0.0541 (19)0.0063 (12)0.0050 (13)0.0031 (14)
C180.037 (2)0.043 (2)0.055 (3)0.0050 (17)0.0051 (19)0.006 (2)
C190.037 (2)0.041 (2)0.058 (3)0.0024 (17)0.0013 (19)0.001 (2)
C200.038 (2)0.040 (2)0.054 (3)0.0023 (17)0.0015 (18)0.0023 (19)
O210.0514 (17)0.0521 (19)0.059 (2)0.0047 (15)0.0018 (15)0.0044 (16)
C220.037 (2)0.046 (2)0.055 (3)0.0064 (17)0.0010 (18)0.002 (2)
C230.0340 (19)0.045 (2)0.061 (3)0.0011 (17)0.0048 (18)0.002 (2)
C240.044 (2)0.046 (2)0.056 (3)0.0010 (18)0.003 (2)0.005 (2)
C250.038 (2)0.051 (3)0.057 (3)0.0035 (18)0.0034 (19)0.006 (2)
N260.0429 (18)0.046 (2)0.060 (2)0.0064 (16)0.0094 (17)0.0054 (18)
C270.042 (2)0.048 (2)0.056 (3)0.0002 (18)0.0078 (19)0.002 (2)
N280.046 (2)0.041 (2)0.069 (3)0.0028 (16)0.0160 (17)0.0009 (18)
S290.0543 (6)0.0454 (6)0.0736 (9)0.0011 (5)0.0144 (6)0.0027 (6)
C300.050 (2)0.039 (2)0.063 (3)0.0015 (19)0.010 (2)0.001 (2)
C310.044 (2)0.051 (3)0.082 (4)0.004 (2)0.007 (2)0.000 (3)
C320.044 (2)0.044 (2)0.084 (4)0.0012 (19)0.005 (2)0.003 (2)
C330.049 (2)0.041 (2)0.063 (3)0.0012 (19)0.006 (2)0.005 (2)
C340.044 (2)0.044 (2)0.070 (3)0.0028 (18)0.006 (2)0.004 (2)
C350.045 (2)0.048 (3)0.064 (3)0.0009 (19)0.005 (2)0.009 (2)
N360.043 (2)0.044 (2)0.083 (3)0.0023 (16)0.0078 (19)0.006 (2)
C370.050 (2)0.046 (3)0.063 (3)0.002 (2)0.009 (2)0.010 (2)
N380.079 (3)0.051 (3)0.107 (4)0.006 (2)0.039 (3)0.014 (3)
C390.119 (6)0.058 (4)0.192 (9)0.034 (4)0.103 (6)0.041 (5)
C400.108 (5)0.062 (4)0.170 (8)0.029 (4)0.081 (5)0.039 (4)
C410.063 (3)0.050 (3)0.068 (3)0.006 (2)0.022 (2)0.001 (2)
C420.056 (3)0.040 (2)0.062 (3)0.001 (2)0.007 (2)0.004 (2)
C430.055 (3)0.047 (2)0.057 (3)0.004 (2)0.007 (2)0.009 (2)
N440.054 (2)0.0402 (19)0.058 (2)0.0027 (17)0.0079 (17)0.0009 (18)
C450.048 (2)0.047 (3)0.073 (3)0.004 (2)0.012 (2)0.001 (2)
N460.049 (2)0.045 (2)0.065 (3)0.0013 (17)0.0119 (18)0.0027 (19)
C470.056 (3)0.047 (3)0.061 (3)0.006 (2)0.007 (2)0.002 (2)
C480.051 (2)0.043 (2)0.062 (3)0.007 (2)0.003 (2)0.004 (2)
C490.077 (3)0.049 (3)0.092 (4)0.005 (3)0.027 (3)0.010 (3)
C500.080 (4)0.046 (3)0.116 (5)0.005 (3)0.029 (4)0.011 (3)
C510.074 (3)0.036 (2)0.092 (4)0.005 (2)0.004 (3)0.007 (3)
C520.138 (6)0.053 (3)0.085 (5)0.015 (4)0.036 (4)0.016 (3)
C530.133 (6)0.053 (3)0.069 (4)0.027 (3)0.033 (4)0.011 (3)
F540.110 (3)0.0416 (17)0.130 (3)0.0085 (17)0.003 (2)0.0046 (18)
C1L0.151 (8)0.113 (6)0.108 (7)0.029 (6)0.026 (6)0.039 (5)
O1L0.099 (6)0.122 (7)0.111 (7)0.036 (5)0.006 (5)0.026 (6)
O2L0.108 (8)0.052 (6)0.086 (7)0.018 (5)0.027 (6)0.007 (5)
Geometric parameters (Å, º) top
C1—C21.501 (6)C31—H310.9500
C1—C141.503 (6)C32—C331.395 (6)
C1—C201.511 (6)C32—H320.9500
C1—O171.527 (5)C33—C341.394 (6)
C2—C71.383 (5)C33—N361.404 (6)
C2—C31.385 (6)C34—C351.374 (6)
C3—C41.376 (6)C34—H340.9500
C3—H30.9500C35—H350.9500
C4—C51.403 (6)N36—C371.371 (6)
C4—H40.9500N36—H360.8800
C5—O151.347 (5)C37—N381.348 (6)
C5—C61.380 (6)C37—C421.400 (6)
C6—C71.386 (6)N38—C391.322 (7)
C6—H60.9500C39—C401.368 (9)
C7—O81.383 (5)C39—H390.9500
O8—C91.382 (5)C40—C411.385 (8)
C9—C101.377 (6)C40—H400.9500
C9—C141.385 (6)C41—C421.375 (6)
C10—C111.387 (6)C41—C431.462 (7)
C10—H100.9500C42—H420.9500
C11—O161.354 (5)C43—C471.373 (6)
C11—C121.389 (6)C43—N441.388 (6)
C12—C131.378 (6)N44—C451.354 (6)
C12—H120.9500N44—C481.423 (6)
C13—C141.393 (6)C45—N461.314 (6)
C13—H130.9500C45—H450.9500
O15—H150.8400N46—C471.353 (6)
O16—H160.8400C47—H470.9500
O17—C181.354 (5)C48—C531.358 (7)
C18—O211.223 (5)C48—C491.360 (7)
C18—C191.456 (7)C49—C501.389 (7)
C19—C201.381 (6)C49—H490.9500
C19—C221.392 (6)C50—C511.333 (8)
C20—C251.372 (7)C50—H500.9500
C22—C231.376 (6)C51—C521.358 (8)
C22—H220.9500C51—F541.365 (6)
C23—C241.402 (6)C52—C531.376 (8)
C23—N261.429 (5)C52—H520.9500
C24—C251.384 (6)C53—H530.9500
C24—H240.9500C1L—O1L1.3998 (10)
C25—H250.9500C1L—O2L1.4009 (10)
N26—C271.362 (6)C1L—H1M0.9800
N26—H261.0913C1L—H2M0.9800
C27—N281.350 (6)C1L—H3M0.9800
C27—S291.675 (5)C1L—H4M0.9800
N28—C301.434 (6)C1L—H5M0.9800
N28—H281.1665C1L—H6M0.9800
C30—C351.383 (6)O1L—H1L0.8400
C30—C311.389 (6)O2L—H2L0.8400
C31—C321.386 (7)
C2—C1—C14112.1 (3)C32—C31—C30121.3 (4)
C2—C1—C20113.8 (4)C32—C31—H31119.4
C14—C1—C20113.9 (4)C30—C31—H31119.4
C2—C1—O17108.1 (4)C31—C32—C33119.8 (4)
C14—C1—O17107.2 (3)C31—C32—H32120.1
C20—C1—O17100.8 (3)C33—C32—H32120.1
C7—C2—C3117.3 (4)C34—C33—C32118.6 (4)
C7—C2—C1120.9 (4)C34—C33—N36116.8 (4)
C3—C2—C1121.8 (3)C32—C33—N36124.3 (4)
C4—C3—C2122.4 (4)C35—C34—C33120.7 (4)
C4—C3—H3118.8C35—C34—H34119.6
C2—C3—H3118.8C33—C34—H34119.6
C3—C4—C5119.2 (4)C34—C35—C30121.1 (4)
C3—C4—H4120.4C34—C35—H35119.5
C5—C4—H4120.4C30—C35—H35119.5
O15—C5—C6118.0 (4)C37—N36—C33132.1 (4)
O15—C5—C4122.8 (4)C37—N36—H36114.0
C6—C5—C4119.2 (4)C33—N36—H36114.0
C5—C6—C7120.0 (4)N38—C37—N36112.7 (4)
C5—C6—H6120.0N38—C37—C42122.5 (4)
C7—C6—H6120.0N36—C37—C42124.7 (4)
O8—C7—C2123.3 (4)C39—N38—C37116.0 (5)
O8—C7—C6115.0 (3)N38—C39—C40124.8 (6)
C2—C7—C6121.8 (4)N38—C39—H39117.6
C9—O8—C7118.5 (3)C40—C39—H39117.6
C10—C9—O8115.4 (4)C39—C40—C41119.7 (6)
C10—C9—C14122.2 (4)C39—C40—H40120.1
O8—C9—C14122.5 (4)C41—C40—H40120.1
C9—C10—C11119.5 (4)C42—C41—C40116.5 (5)
C9—C10—H10120.2C42—C41—C43126.9 (4)
C11—C10—H10120.2C40—C41—C43116.5 (4)
O16—C11—C12122.6 (4)C41—C42—C37120.1 (4)
O16—C11—C10117.8 (4)C41—C42—H42119.9
C12—C11—C10119.6 (4)C37—C42—H42119.9
C13—C12—C11119.7 (4)C47—C43—N44104.1 (4)
C13—C12—H12120.2C47—C43—C41126.7 (4)
C11—C12—H12120.2N44—C43—C41129.1 (4)
C12—C13—C14121.7 (4)C45—N44—C43107.0 (4)
C12—C13—H13119.1C45—N44—C48121.2 (4)
C14—C13—H13119.1C43—N44—C48131.5 (4)
C9—C14—C13117.3 (4)N46—C45—N44112.0 (4)
C9—C14—C1121.4 (4)N46—C45—H45124.0
C13—C14—C1121.2 (4)N44—C45—H45124.0
C5—O15—H15109.5C45—N46—C47105.2 (4)
C11—O16—H16109.5N46—C47—C43111.6 (4)
C18—O17—C1110.7 (3)N46—C47—H47124.2
O21—C18—O17120.9 (4)C43—C47—H47124.2
O21—C18—C19130.0 (4)C53—C48—C49119.9 (5)
O17—C18—C19109.1 (4)C53—C48—N44119.1 (4)
C20—C19—C22122.0 (4)C49—C48—N44120.8 (5)
C20—C19—C18108.7 (4)C48—C49—C50120.2 (5)
C22—C19—C18129.4 (4)C48—C49—H49119.9
C25—C20—C19120.7 (4)C50—C49—H49119.9
C25—C20—C1129.0 (4)C51—C50—C49118.3 (5)
C19—C20—C1110.2 (4)C51—C50—H50120.9
C23—C22—C19117.1 (4)C49—C50—H50120.9
C23—C22—H22121.4C50—C51—C52123.1 (5)
C19—C22—H22121.4C50—C51—F54119.1 (5)
C22—C23—C24121.2 (4)C52—C51—F54117.8 (5)
C22—C23—N26118.0 (4)C51—C52—C53118.0 (6)
C24—C23—N26120.6 (4)C51—C52—H52121.0
C25—C24—C23120.5 (5)C53—C52—H52121.0
C25—C24—H24119.7C48—C53—C52120.6 (5)
C23—C24—H24119.7C48—C53—H53119.7
C20—C25—C24118.5 (4)C52—C53—H53119.7
C20—C25—H25120.7O1L—C1L—H1M109.5
C24—C25—H25120.7O1L—C1L—H2M109.5
C27—N26—C23127.3 (4)H1M—C1L—H2M109.5
C27—N26—H26126.1O1L—C1L—H3M109.5
C23—N26—H26106.1H1M—C1L—H3M109.5
N28—C27—N26114.8 (4)H2M—C1L—H3M109.5
N28—C27—S29121.2 (4)O2L—C1L—H4M109.5
N26—C27—S29124.0 (3)O2L—C1L—H5M109.5
C27—N28—C30125.9 (4)H4M—C1L—H5M109.5
C27—N28—H28107.4O2L—C1L—H6M109.5
C30—N28—H28126.4H4M—C1L—H6M109.5
C35—C30—C31118.4 (4)H5M—C1L—H6M109.5
C35—C30—N28119.6 (4)C1L—O1L—H1L109.5
C31—C30—N28121.8 (4)C1L—O2L—H2L109.5
C14—C1—C2—C77.2 (6)C22—C23—C24—C252.0 (7)
C20—C1—C2—C7138.2 (4)N26—C23—C24—C25172.5 (4)
O17—C1—C2—C7110.7 (4)C19—C20—C25—C240.7 (7)
C14—C1—C2—C3172.6 (4)C1—C20—C25—C24174.6 (4)
C20—C1—C2—C341.6 (6)C23—C24—C25—C200.7 (7)
O17—C1—C2—C369.5 (5)C22—C23—N26—C27142.2 (5)
C7—C2—C3—C41.7 (7)C24—C23—N26—C2743.1 (7)
C1—C2—C3—C4178.1 (5)C23—N26—C27—N28166.0 (4)
C2—C3—C4—C51.6 (8)C23—N26—C27—S2916.3 (7)
C3—C4—C5—O15175.9 (5)N26—C27—N28—C3020.6 (7)
C3—C4—C5—C63.8 (7)S29—C27—N28—C30161.7 (4)
O15—C5—C6—C7177.1 (4)C27—N28—C30—C35141.9 (5)
C4—C5—C6—C72.7 (7)C27—N28—C30—C3143.5 (7)
C3—C2—C7—O8177.0 (4)C35—C30—C31—C321.6 (8)
C1—C2—C7—O83.2 (7)N28—C30—C31—C32173.1 (5)
C3—C2—C7—C62.9 (7)C30—C31—C32—C330.1 (9)
C1—C2—C7—C6176.9 (5)C31—C32—C33—C340.6 (8)
C5—C6—C7—O8179.2 (4)C31—C32—C33—N36173.1 (5)
C5—C6—C7—C20.7 (8)C32—C33—C34—C350.6 (8)
C2—C7—O8—C99.8 (7)N36—C33—C34—C35174.7 (5)
C6—C7—O8—C9170.3 (4)C33—C34—C35—C302.4 (8)
C7—O8—C9—C10174.6 (4)C31—C30—C35—C342.8 (8)
C7—O8—C9—C144.9 (7)N28—C30—C35—C34172.0 (5)
O8—C9—C10—C11178.0 (5)C34—C33—N36—C37165.4 (5)
C14—C9—C10—C111.5 (8)C32—C33—N36—C3720.9 (9)
C9—C10—C11—O16179.7 (4)C33—N36—C37—N38165.5 (5)
C9—C10—C11—C120.6 (8)C33—N36—C37—C4218.5 (9)
O16—C11—C12—C13178.9 (5)N36—C37—N38—C39176.4 (7)
C10—C11—C12—C132.0 (8)C42—C37—N38—C390.3 (9)
C11—C12—C13—C141.5 (8)C37—N38—C39—C404.4 (14)
C10—C9—C14—C132.0 (7)N38—C39—C40—C416.7 (16)
O8—C9—C14—C13177.5 (4)C39—C40—C41—C424.0 (12)
C10—C9—C14—C1174.3 (5)C39—C40—C41—C43173.0 (8)
O8—C9—C14—C16.2 (7)C40—C41—C42—C370.3 (9)
C12—C13—C14—C90.5 (8)C43—C41—C42—C37176.9 (5)
C12—C13—C14—C1175.8 (5)N38—C37—C42—C412.5 (8)
C2—C1—C14—C911.7 (6)N36—C37—C42—C41178.2 (5)
C20—C1—C14—C9142.7 (4)C42—C41—C43—C47162.3 (5)
O17—C1—C14—C9106.7 (5)C40—C41—C43—C4714.3 (9)
C2—C1—C14—C13172.1 (4)C42—C41—C43—N4416.3 (9)
C20—C1—C14—C1341.2 (6)C40—C41—C43—N44167.1 (6)
O17—C1—C14—C1369.4 (5)C47—C43—N44—C450.4 (5)
C2—C1—O17—C18127.2 (4)C41—C43—N44—C45179.2 (5)
C14—C1—O17—C18111.8 (4)C47—C43—N44—C48173.9 (5)
C20—C1—O17—C187.6 (4)C41—C43—N44—C487.3 (9)
C1—O17—C18—O21173.6 (4)C43—N44—C45—N461.1 (6)
C1—O17—C18—C196.0 (5)C48—N44—C45—N46175.4 (4)
O21—C18—C19—C20178.0 (5)N44—C45—N46—C471.3 (6)
O17—C18—C19—C201.5 (5)C45—N46—C47—C431.1 (6)
O21—C18—C19—C220.8 (8)N44—C43—C47—N460.4 (6)
O17—C18—C19—C22179.6 (4)C41—C43—C47—N46178.5 (5)
C22—C19—C20—C250.7 (7)C45—N44—C48—C5379.0 (7)
C18—C19—C20—C25179.6 (4)C43—N44—C48—C5393.6 (7)
C22—C19—C20—C1175.4 (4)C45—N44—C48—C4994.7 (6)
C18—C19—C20—C13.6 (5)C43—N44—C48—C4992.6 (7)
C2—C1—C20—C2562.3 (6)C53—C48—C49—C501.1 (9)
C14—C1—C20—C2567.8 (6)N44—C48—C49—C50174.8 (5)
O17—C1—C20—C25177.8 (4)C48—C49—C50—C510.0 (10)
C2—C1—C20—C19122.1 (4)C49—C50—C51—C521.6 (11)
C14—C1—C20—C19107.8 (4)C49—C50—C51—F54179.2 (6)
O17—C1—C20—C196.6 (4)C50—C51—C52—C532.0 (11)
C20—C19—C22—C230.6 (6)F54—C51—C52—C53178.8 (6)
C18—C19—C22—C23178.1 (4)C49—C48—C53—C520.7 (10)
C19—C22—C23—C241.9 (6)N44—C48—C53—C52174.5 (6)
C19—C22—C23—N26172.8 (4)C51—C52—C53—C480.7 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O15—H15···N46i0.841.842.667 (5)168
O16—H16···O21ii0.842.042.808 (5)153
C22—H22···O15iii0.952.593.315 (5)133
C24—H24···S29iv0.952.993.804 (5)145
N26—H26···O15iii1.092.173.061 (5)138
N28—H28···N38v1.171.943.069 (6)162
C34—H34···O1Lvi0.952.463.334 (9)154
N36—H36···S29vii0.882.643.437 (4)152
C40—H40···O2Lviii0.952.323.103 (12)139
C45—H45···O17ii0.952.493.379 (6)155
C53—H53···S29ix0.952.873.743 (6)153
C1L—H2M···O210.982.563.267 (7)129
O1L—H1L···S29x0.842.463.202 (8)147
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y+1/2, z+1; (iii) x1/2, y+1/2, z; (iv) x+1, y, z+1/2; (v) x+1/2, y1/2, z+1/2; (vi) x+1/2, y+1/2, z+1; (vii) x+1/2, y+1/2, z+1/2; (viii) x+1, y+1, z+1; (ix) x+1/2, y+1/2, z; (x) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O15—H15···N46i0.841.842.667 (5)168
O16—H16···O21ii0.842.042.808 (5)153
C22—H22···O15iii0.952.593.315 (5)133
C24—H24···S29iv0.952.993.804 (5)145
N26—H26···O15iii1.092.173.061 (5)138
N28—H28···N38v1.171.943.069 (6)162
C34—H34···O1Lvi0.952.463.334 (9)154
N36—H36···S29vii0.882.643.437 (4)152
C40—H40···O2Lviii0.952.323.103 (12)139
C45—H45···O17ii0.952.493.379 (6)155
C53—H53···S29ix0.952.873.743 (6)153
C1L—H2M···O210.982.563.267 (7)129
O1L—H1L···S29x0.842.463.202 (8)147
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y+1/2, z+1; (iii) x1/2, y+1/2, z; (iv) x+1, y, z+1/2; (v) x+1/2, y1/2, z+1/2; (vi) x+1/2, y+1/2, z+1; (vii) x+1/2, y+1/2, z+1/2; (viii) x+1, y+1, z+1; (ix) x+1/2, y+1/2, z; (x) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC41H27FN6O5S·CH4O
Mr766.79
Crystal system, space groupMonoclinic, C2/c
Temperature (K)193
a, b, c (Å)15.1825 (8), 17.7557 (7), 26.2236 (13)
β (°) 92.283 (4)
V3)7063.6 (6)
Z8
Radiation typeMo Kα
µ (mm1)0.16
Crystal size (mm)0.09 × 0.08 × 0.07
Data collection
DiffractometerStoe IPDS 2T
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
23065, 8960, 3244
Rint0.085
(sin θ/λ)max1)0.674
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.240, 0.92
No. of reflections8960
No. of parameters516
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.38

Computer programs: X-AREA (Stoe & Cie, 2011), X-AREA (Stoe & Cie, 2011, X-RED (Stoe & Cie, 2011, SIR2004 (Burla et al., 2005), SHELXL2014 (Sheldrick, 2015).

 

References

First citationAnsideri, F., Lange, A., El-Gokha, A., Boeckler, F. M. & Koch, P. (2016). Anal. Biochem. 503, 28–40.  CrossRef CAS PubMed Google Scholar
First citationBurla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationStoe & Cie (2011). X-RED and X-AREA. Stoe & Cie, Darmstadt, Darmstadt, Germany.  Google Scholar

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