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The title compounds, 1-cyano-2-hydroxy-N-[4-(methylsulfon­yl)phenyl]but-2-en­amide, C12H12N2O4S, PHI492, 1-cyano-2-hydroxy-N-[3-(methyl­sulfonyl)­phenyl]­but-2-en­amide, C12H12­N2O4S, PHI493, and N-[3-bromo-4-(trifluoro­methoxy)­phenyl]-1-cyano-2-hydroxybut-2-en­amide, C12H8Br­F3N2O3, PHI495, are potent inhibitors of Bruton's tyrosine kinase (BTK). The molecular structures of these compounds are similar and they display similar hydrogen-bonding networks and crystal packing. Examination of the crystal-packing interaction in the three compounds reveals an alternating direction of adjacent mol­ecules in the crystalline lattice due to intermolecular cyano–amide hydrogen bonding. PHI492, a positional isomer of PHI493, does not form intermolecular O—H...O hydrogen bonds between mol­ecules and crystallizes in a space group different from that of PHI493 and PHI495. The aromatic ring and the amide group of each mol­ecule form a conjugated π-system which ensures planarity, with further stabilization gained from intramolecular O—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009768/bk1544sup1.cif
Contains datablocks global, PHI493, PHI495, PHI492

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009768/bk1544PHI492sup2.hkl
Contains datablock PHI492

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009768/bk1544PHI493sup3.hkl
Contains datablock PHI493

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009768/bk1544PHI495sup4.hkl
Contains datablock PHI495

CCDC references: 152624; 152625; 152626

Comment top

The title compounds were designed and synthesized as part of our ongoing program on the development of tyrosine kinase inhibitors as anti-cancer agents. The development of inhibitors of the PTK (or BTK?) signaling pathway is an active area of translational (or transnational?) cancer research. The identification of the compounds was guided by structure-based drug design methods, which included the construction of the kinase homology model of BTK (Mahajan et al., 1999) and advanced docking procedures to generate novel molecules that are complementary in shape and electrostatics to the kinase domain topography. Based on these modeling studies, several leflunomide metabolite (LFM) analogs were synthesized and tested for their kinase inhibitory activity on BTK. The three title compounds, PHI492, PHI493 and PHI495, were subsequently found to have micromolar potency towards BTK. \sch

The X-ray crystal structures of PHI492, PHI493 and PHI495 (Figs. 1–3) show that all three molecules contain an intramolecular O—H···O hydrogen bond that locks the compounds in a planar conformation. The presence of this intramolecular hydrogen bond is consistent with the results from docking studies of LFM analogs at the catalytic sites of several protein tyrosine kinases (Ghosh et al., 1998; Ghosh, Narla et al., 1999; Mahajan et al., 1999). These studies reveal that the planar conformation of these inhibitors resulting from the intramolecular hydrogen bond would allow the molecules to fit snugly into the shallow catalytic sites of EGFR (define?) and BTK. This binding mode is such that the title compounds can maintain close contact with the hinge region of the receptor on the edge of the inhibitor, and the aromatic rings of the inhibitors are sandwiched between hydrophobic residues at the catalytic site of the receptor.

The electronegative SO2 group of PHI492 and PHI493 is involved in hydrogen bonding with Lys430 and Arg525, respectively, on BTK, while in PHI495 the CF3 group is oriented towards Val416. In all three crystal structures, the molecules pack to form hydrogen-bonded dimers about inversion centers.

Compound PHI492 does not display O—H···O intermolecular hydrogen bonds and the intramolecular O9···O7 distance is 2.534 (2) Å. The compound forms a centrosymmetrically related dimer via an N1—H1···N11i intermolecular hydrogen bond [N1···N11i 3.132 (2) Å; symmetry code: (i) 1 - x, 4 - y, -z]. In compound PHI493, the intramolecular O9···O7 hydrogen-bond distance is 2.510 (2)%A and the dimers are linked by an N1···N11ii intermolecular hydrogen bond [N1···N11ii 3.060 (2) Å; symmetry code: (ii) -1 - x, 2 - y, 1 - z] and an O7···O9iii intermolecular contact [O7···O9iii 3.046 (2) Å; symmetry code: (iii) -x, 3 - y, 1 - z]. In PHI495, the intramolecular O9···.·O7 distance is 2.508 (4) Å and the dimers are linked by an N1···N11v intermolecular hydrogen bond [N1···N11v 3.218 (5) Å; symmetry code: (v) 2 - x, 1 - y, -z] and an O7···O9iv intermolecular contact [O7···O9iv 3.027 (4) Å; symmetry code: (iv) 1 - x, -y, -z]. These hydrogen-bond interactions observed in the crystal packing are similar for the three title compounds and similar to the six other leflunomide metabolite analogs reported earlier (Ghosh, Zheng & Uckun, 1999; Ghosh & Uckun, 1999).

The dihedral angle of the plane of the phenyl ring with the plane formed by atoms N1, C7, C8, C9 and C10 is 2.3 (3)° for PHI492, 2.4 (3)° for PHI493, and 2.5 (7)° for PHI495. The planarity of the molecules is extended to the hydroxyl, cyano and methyl groups via the intramolecular O9—H9···O7 hydrogen bond. The mean-plane deviation for each of the molecules as a whole is 0.0422 Å for PHI492, 0.0368 Å for PHI493 and 0.0372 Å for PHI495.

There is no significant difference in the corresponding bond lengths and angles in the three structures. However, the C8—C11 (Csp2—Csp1) bond distances are 1.424 (3) Å for PHI492, 1.424 (2) Å for PHI493 and 1.427 (6) Å for PHI495, and are slightly longer than the expected Csp2—Csp1 bond length of 1.416 Å. The C11N11 bond distances, on the other hand, are significantly shorter than the expected CN bond length of 1.165 Å; they are 1.138 (2) Å for PHI492, 1.136 (2) Å for PHI493 and 1.134 (5) Å for PHI495. A similar lengthening of the C8—C11 bond and shortening of the CN bond has been observed in the molecular structures of the six LFM analogs reported earlier (Ghosh, Zheng & Uckun, 1999; Ghosh & Uckun, 1999).

Experimental top

PHI492 was crystallized through slow evaporation of an ethanol/dichloromethane/dimethylformamide solution (3:2:1 v/v/v); colorless prisms, suitable for diffraction, were obtained after 27 d. PHI493 was crystallized as colorless needles through slow evaporation of tetrahydrofuran. PHI495 was dissolved in acetonitrile and crystallized through vapor diffusion of diethylether at 277 K; colorless prisms, suitable for diffraction, were grown in 18 d.

Refinement top

The H atoms attached to the N and O atoms for all three compounds appeared well resolved in the difference Fourier maps but, with the exception of PHI495, proved difficult to refine freely. The positions of the hydroxyl and amide protons in PHI492 and PHI493 were refined by restrained methods using the DFIX command in SHELXL97? (Sheldrick, 1997), where the distances were restrained to 0.82 Å and 0.86 Å, respectively, and their Ueq values were allowed to refine freely. All H atoms attached to C atoms were placed in ideal positions and refined using a riding model with aromatic C—H = 0.96 Å, methyl C—H = 0.98 Å, and with fixed isotropic displacement parameters equal to 1.2 (1.5 for methyl-H atoms) times the equivalent isotropic displacement parameter of the atom to which they were attached. The methyl groups were allowed to rotate about their local threefold axis during refinement. The H atoms in the methyl group C10 of PHI493 and PHI495 were found to be rotationally disordered, in a 0.6:0.4 ratio in PHI493 and in a 0.3:0.7 ratio in PHI495. The major features in the final difference map of PHI495 were 1.1 Å from the Br atom.

Structure description top

The title compounds were designed and synthesized as part of our ongoing program on the development of tyrosine kinase inhibitors as anti-cancer agents. The development of inhibitors of the PTK (or BTK?) signaling pathway is an active area of translational (or transnational?) cancer research. The identification of the compounds was guided by structure-based drug design methods, which included the construction of the kinase homology model of BTK (Mahajan et al., 1999) and advanced docking procedures to generate novel molecules that are complementary in shape and electrostatics to the kinase domain topography. Based on these modeling studies, several leflunomide metabolite (LFM) analogs were synthesized and tested for their kinase inhibitory activity on BTK. The three title compounds, PHI492, PHI493 and PHI495, were subsequently found to have micromolar potency towards BTK. \sch

The X-ray crystal structures of PHI492, PHI493 and PHI495 (Figs. 1–3) show that all three molecules contain an intramolecular O—H···O hydrogen bond that locks the compounds in a planar conformation. The presence of this intramolecular hydrogen bond is consistent with the results from docking studies of LFM analogs at the catalytic sites of several protein tyrosine kinases (Ghosh et al., 1998; Ghosh, Narla et al., 1999; Mahajan et al., 1999). These studies reveal that the planar conformation of these inhibitors resulting from the intramolecular hydrogen bond would allow the molecules to fit snugly into the shallow catalytic sites of EGFR (define?) and BTK. This binding mode is such that the title compounds can maintain close contact with the hinge region of the receptor on the edge of the inhibitor, and the aromatic rings of the inhibitors are sandwiched between hydrophobic residues at the catalytic site of the receptor.

The electronegative SO2 group of PHI492 and PHI493 is involved in hydrogen bonding with Lys430 and Arg525, respectively, on BTK, while in PHI495 the CF3 group is oriented towards Val416. In all three crystal structures, the molecules pack to form hydrogen-bonded dimers about inversion centers.

Compound PHI492 does not display O—H···O intermolecular hydrogen bonds and the intramolecular O9···O7 distance is 2.534 (2) Å. The compound forms a centrosymmetrically related dimer via an N1—H1···N11i intermolecular hydrogen bond [N1···N11i 3.132 (2) Å; symmetry code: (i) 1 - x, 4 - y, -z]. In compound PHI493, the intramolecular O9···O7 hydrogen-bond distance is 2.510 (2)%A and the dimers are linked by an N1···N11ii intermolecular hydrogen bond [N1···N11ii 3.060 (2) Å; symmetry code: (ii) -1 - x, 2 - y, 1 - z] and an O7···O9iii intermolecular contact [O7···O9iii 3.046 (2) Å; symmetry code: (iii) -x, 3 - y, 1 - z]. In PHI495, the intramolecular O9···.·O7 distance is 2.508 (4) Å and the dimers are linked by an N1···N11v intermolecular hydrogen bond [N1···N11v 3.218 (5) Å; symmetry code: (v) 2 - x, 1 - y, -z] and an O7···O9iv intermolecular contact [O7···O9iv 3.027 (4) Å; symmetry code: (iv) 1 - x, -y, -z]. These hydrogen-bond interactions observed in the crystal packing are similar for the three title compounds and similar to the six other leflunomide metabolite analogs reported earlier (Ghosh, Zheng & Uckun, 1999; Ghosh & Uckun, 1999).

The dihedral angle of the plane of the phenyl ring with the plane formed by atoms N1, C7, C8, C9 and C10 is 2.3 (3)° for PHI492, 2.4 (3)° for PHI493, and 2.5 (7)° for PHI495. The planarity of the molecules is extended to the hydroxyl, cyano and methyl groups via the intramolecular O9—H9···O7 hydrogen bond. The mean-plane deviation for each of the molecules as a whole is 0.0422 Å for PHI492, 0.0368 Å for PHI493 and 0.0372 Å for PHI495.

There is no significant difference in the corresponding bond lengths and angles in the three structures. However, the C8—C11 (Csp2—Csp1) bond distances are 1.424 (3) Å for PHI492, 1.424 (2) Å for PHI493 and 1.427 (6) Å for PHI495, and are slightly longer than the expected Csp2—Csp1 bond length of 1.416 Å. The C11N11 bond distances, on the other hand, are significantly shorter than the expected CN bond length of 1.165 Å; they are 1.138 (2) Å for PHI492, 1.136 (2) Å for PHI493 and 1.134 (5) Å for PHI495. A similar lengthening of the C8—C11 bond and shortening of the CN bond has been observed in the molecular structures of the six LFM analogs reported earlier (Ghosh, Zheng & Uckun, 1999; Ghosh & Uckun, 1999).

Computing details top

For all compounds, data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of PHI492 showing the atomic numbering. Displacement ellipsoids are drawn at the 30% probability level and H atoms are displayed as small circles of arbitrary radii.
[Figure 2] Fig. 2. The structure of PHI493 showing the atomic numbering. Displacement ellipsoids are drawn at the 30% probability level and H atoms are displayed as small circles of arbitrary radii.
[Figure 3] Fig. 3. The structure of PHI495 showing the atomic numbering. Displacement ellipsoids are drawn at the 30% probability level and H atoms are displayed as small circles of arbitrary radii.
(PHI492) 1-cyano-2-hydroxy-N-[4-(methylsulfonyl)phenyl]but-2-enamide top
Crystal data top
C12H12N2O4SF(000) = 584
Mr = 280.30Dx = 1.492 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.8002 (10) ÅCell parameters from 5320 reflections
b = 5.5336 (6) Åθ = 1.6–26.4°
c = 25.852 (3) ŵ = 0.27 mm1
β = 97.644 (1)°T = 295 K
V = 1247.7 (2) Å3Prism, colorless
Z = 40.34 × 0.31 × 0.28 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2157 reflections with I > 2σ(I)
ω scansRint = 0.030
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
θmax = 26.4°, θmin = 1.6°
Tmin = 0.913, Tmax = 0.928h = 1110
10595 measured reflectionsk = 66
2503 independent reflectionsl = 3231
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.057P)2 + 0.5101P]
where P = (Fo2 + 2Fc2)/3
2503 reflections(Δ/σ)max = 0.003
182 parametersΔρmax = 0.23 e Å3
2 restraintsΔρmin = 0.45 e Å3
Crystal data top
C12H12N2O4SV = 1247.7 (2) Å3
Mr = 280.30Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.8002 (10) ŵ = 0.27 mm1
b = 5.5336 (6) ÅT = 295 K
c = 25.852 (3) Å0.34 × 0.31 × 0.28 mm
β = 97.644 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2503 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
2157 reflections with I > 2σ(I)
Tmin = 0.913, Tmax = 0.928Rint = 0.030
10595 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0442 restraints
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.23 e Å3
2503 reflectionsΔρmin = 0.45 e Å3
182 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.92302 (6)0.96106 (9)0.186661 (18)0.03941 (17)
O10.7903 (2)0.8542 (3)0.20405 (7)0.0594 (4)
O21.04355 (19)0.8031 (3)0.17545 (6)0.0555 (4)
O70.82385 (16)1.4044 (3)0.06543 (5)0.0446 (4)
O90.75956 (19)1.5746 (3)0.15671 (6)0.0540 (4)
H90.799 (3)1.485 (5)0.1335 (9)0.076 (9)*
N10.71869 (19)1.5741 (3)0.00206 (6)0.0389 (4)
H10.657 (2)1.682 (3)0.0096 (9)0.043 (6)*
N110.5095 (2)2.0899 (4)0.05154 (8)0.0566 (5)
C10.7722 (2)1.4183 (3)0.04377 (7)0.0347 (4)
C20.8655 (2)1.2177 (4)0.03973 (8)0.0404 (4)
H20.89601.17690.00780.048*
C30.9123 (2)1.0798 (3)0.08344 (8)0.0388 (4)
H30.97610.94750.08100.047*
C40.8650 (2)1.1370 (3)0.13082 (7)0.0337 (4)
C50.7714 (2)1.3354 (4)0.13495 (8)0.0413 (5)
H50.73891.37340.16680.050*
C60.7270 (2)1.4751 (4)0.09191 (8)0.0422 (5)
H60.66581.61000.09490.051*
C70.7434 (2)1.5618 (3)0.04842 (8)0.0355 (4)
C80.6686 (2)1.7474 (3)0.08386 (8)0.0366 (4)
C90.6804 (2)1.7415 (4)0.13599 (8)0.0405 (4)
C100.6065 (3)1.9207 (4)0.17414 (9)0.0530 (6)
H10A0.58291.84540.20770.079*
H10B0.67522.05370.17670.079*
H10C0.51381.97880.16270.079*
C110.5806 (2)1.9372 (4)0.06545 (8)0.0407 (4)
C120.9998 (3)1.1723 (4)0.23398 (8)0.0517 (5)
H12A1.05181.08840.26370.078*
H12B0.91841.26820.24460.078*
H12C1.07101.27540.21950.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0506 (3)0.0333 (3)0.0355 (3)0.0060 (2)0.0100 (2)0.00012 (18)
O10.0708 (10)0.0500 (9)0.0616 (10)0.0100 (8)0.0247 (8)0.0067 (8)
O20.0685 (10)0.0520 (9)0.0462 (8)0.0283 (8)0.0079 (7)0.0012 (7)
O70.0515 (8)0.0398 (8)0.0448 (8)0.0173 (6)0.0143 (6)0.0045 (6)
O90.0674 (10)0.0517 (9)0.0441 (9)0.0244 (8)0.0125 (8)0.0043 (7)
N10.0438 (9)0.0332 (8)0.0403 (9)0.0129 (7)0.0079 (7)0.0003 (7)
N110.0625 (12)0.0487 (11)0.0594 (12)0.0251 (10)0.0112 (10)0.0002 (9)
C10.0353 (9)0.0301 (9)0.0388 (10)0.0029 (7)0.0055 (7)0.0017 (7)
C20.0456 (10)0.0404 (10)0.0365 (10)0.0123 (9)0.0105 (8)0.0025 (8)
C30.0431 (10)0.0346 (10)0.0397 (10)0.0115 (8)0.0088 (8)0.0017 (8)
C40.0344 (9)0.0309 (9)0.0363 (9)0.0017 (7)0.0068 (7)0.0014 (7)
C50.0488 (11)0.0390 (10)0.0378 (10)0.0097 (9)0.0122 (9)0.0038 (8)
C60.0472 (11)0.0352 (10)0.0451 (11)0.0141 (9)0.0095 (9)0.0032 (8)
C70.0339 (9)0.0305 (9)0.0425 (10)0.0028 (7)0.0063 (8)0.0001 (8)
C80.0349 (9)0.0312 (9)0.0439 (11)0.0053 (8)0.0065 (8)0.0009 (8)
C90.0399 (10)0.0371 (10)0.0449 (11)0.0073 (8)0.0069 (8)0.0021 (8)
C100.0597 (13)0.0518 (13)0.0473 (12)0.0182 (11)0.0070 (10)0.0093 (10)
C110.0403 (10)0.0379 (10)0.0436 (11)0.0072 (8)0.0039 (8)0.0036 (8)
C120.0640 (13)0.0536 (13)0.0370 (11)0.0040 (11)0.0045 (10)0.0069 (9)
Geometric parameters (Å, º) top
S1—O21.4336 (15)C3—H30.9300
S1—O11.4339 (16)C4—C51.385 (3)
S1—C41.7596 (19)C5—C61.368 (3)
S1—C121.760 (2)C5—H50.9300
O7—C71.239 (2)C6—H60.9300
O9—C91.313 (2)C7—C81.472 (3)
O9—H90.819 (10)C8—C91.366 (3)
N1—C71.353 (3)C8—C111.424 (3)
N1—C11.412 (2)C9—C101.486 (3)
N1—H10.851 (10)C10—H10A0.9600
N11—C111.138 (2)C10—H10B0.9600
C1—C61.392 (3)C10—H10C0.9600
C1—C21.393 (2)C12—H12A0.9600
C2—C31.380 (3)C12—H12B0.9600
C2—H20.9300C12—H12C0.9600
C3—C41.382 (3)
O2—S1—O1117.86 (10)C5—C6—C1121.01 (17)
O2—S1—C4108.26 (9)C5—C6—H6119.5
O1—S1—C4109.02 (9)C1—C6—H6119.5
O2—S1—C12108.63 (11)O7—C7—N1123.37 (17)
O1—S1—C12108.03 (11)O7—C7—C8119.91 (17)
C4—S1—C12104.20 (10)N1—C7—C8116.72 (16)
C9—O9—H9109 (2)C9—C8—C11117.63 (17)
C7—N1—C1128.78 (16)C9—C8—C7120.73 (17)
C7—N1—H1116.6 (15)C11—C8—C7121.64 (17)
C1—N1—H1114.4 (15)O9—C9—C8122.25 (18)
C6—C1—C2119.22 (18)O9—C9—C10114.07 (18)
C6—C1—N1116.07 (16)C8—C9—C10123.69 (18)
C2—C1—N1124.71 (17)C9—C10—H10A109.5
C3—C2—C1119.60 (17)C9—C10—H10B109.5
C3—C2—H2120.2H10A—C10—H10B109.5
C1—C2—H2120.2C9—C10—H10C109.5
C2—C3—C4120.46 (17)H10A—C10—H10C109.5
C2—C3—H3119.8H10B—C10—H10C109.5
C4—C3—H3119.8N11—C11—C8178.9 (2)
C3—C4—C5120.13 (18)S1—C12—H12A109.5
C3—C4—S1120.80 (14)S1—C12—H12B109.5
C5—C4—S1119.07 (14)H12A—C12—H12B109.5
C6—C5—C4119.56 (17)S1—C12—H12C109.5
C6—C5—H5120.2H12A—C12—H12C109.5
C4—C5—H5120.2H12B—C12—H12C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O9—H9···O70.82 (1)1.80 (2)2.534 (2)148 (3)
N1—H1···N11i0.85 (1)2.31 (1)3.132 (2)164 (2)
Symmetry code: (i) x+1, y+4, z.
(PHI493) 1-cyano-2-hydroxy-N-[3-(methylsulfonyl)phenyl]but-2-enamide top
Crystal data top
C12H12N2O4SZ = 2
Mr = 280.30F(000) = 292
Triclinic, P1Dx = 1.450 Mg m3
a = 5.4734 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.4048 (6) ÅCell parameters from 4558 reflections
c = 11.5200 (6) Åθ = 2.0–25.7°
α = 115.478 (1)°µ = 0.26 mm1
β = 95.941 (1)°T = 295 K
γ = 93.035 (1)°Needle, colorless
V = 641.88 (6) Å30.55 × 0.35 × 0.17 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2428 independent reflections
Radiation source: fine-focus sealed tube2152 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 25.7°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 66
Tmin = 0.869, Tmax = 0.957k = 1313
6510 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0546P)2 + 0.1902P]
where P = (Fo2 + 2Fc2)/3
2428 reflections(Δ/σ)max = 0.002
182 parametersΔρmax = 0.22 e Å3
2 restraintsΔρmin = 0.28 e Å3
Crystal data top
C12H12N2O4Sγ = 93.035 (1)°
Mr = 280.30V = 641.88 (6) Å3
Triclinic, P1Z = 2
a = 5.4734 (3) ÅMo Kα radiation
b = 11.4048 (6) ŵ = 0.26 mm1
c = 11.5200 (6) ÅT = 295 K
α = 115.478 (1)°0.55 × 0.35 × 0.17 mm
β = 95.941 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2428 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
2152 reflections with I > 2σ(I)
Tmin = 0.869, Tmax = 0.957Rint = 0.022
6510 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0342 restraints
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.22 e Å3
2428 reflectionsΔρmin = 0.28 e Å3
182 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.18636 (8)0.72706 (4)0.08772 (4)0.04348 (16)
N10.1711 (3)1.13535 (12)0.39287 (14)0.0403 (3)
H10.247 (3)1.0773 (15)0.407 (2)0.054 (6)*
N110.6427 (4)1.10486 (15)0.57420 (18)0.0662 (5)
O10.1075 (3)0.67815 (13)0.17522 (14)0.0622 (4)
O20.4265 (3)0.70436 (14)0.04929 (16)0.0710 (5)
O70.1032 (3)1.35314 (11)0.44916 (14)0.0564 (4)
O90.3146 (3)1.51540 (11)0.62330 (14)0.0560 (4)
H90.223 (4)1.485 (2)0.5662 (18)0.074 (7)*
C10.0055 (3)1.08639 (15)0.30128 (15)0.0370 (4)
C20.1493 (4)1.16422 (16)0.26817 (18)0.0481 (4)
H2B0.14341.25420.30500.058*
C30.3124 (4)1.10813 (18)0.1803 (2)0.0586 (5)
H3A0.41511.16120.15890.070*
C40.3252 (4)0.97491 (18)0.12390 (19)0.0527 (5)
H4A0.43590.93780.06550.063*
C50.1686 (3)0.89833 (15)0.15682 (16)0.0394 (4)
C60.0049 (3)0.95122 (15)0.24385 (16)0.0395 (4)
H6A0.09820.89750.26430.047*
C70.2140 (3)1.26115 (15)0.46070 (16)0.0386 (4)
C80.3970 (3)1.28887 (15)0.55049 (15)0.0375 (4)
C90.4378 (3)1.41522 (15)0.62732 (16)0.0405 (4)
C100.6188 (4)1.45202 (18)0.72103 (19)0.0523 (5)
H10A0.71701.51440.70930.078*0.59 (2)
H10B0.53231.48990.80800.078*0.59 (2)
H10C0.72411.37560.70650.078*0.59 (2)
H10D0.59861.40550.77320.078*0.41 (2)
H10E0.78331.43000.67450.078*0.41 (2)
H10F0.59151.54430.77600.078*0.41 (2)
C110.5334 (3)1.18660 (16)0.56395 (17)0.0440 (4)
C120.0315 (4)0.66208 (19)0.05261 (19)0.0553 (5)
H12A0.03300.56880.09470.083*
H12B0.01120.69780.11050.083*
H12C0.19220.68400.02960.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0465 (3)0.0326 (2)0.0486 (3)0.01200 (17)0.01693 (18)0.01218 (19)
N10.0526 (8)0.0252 (6)0.0454 (8)0.0040 (6)0.0247 (6)0.0137 (6)
N110.0868 (13)0.0383 (8)0.0797 (12)0.0061 (8)0.0514 (10)0.0231 (8)
O10.0955 (11)0.0397 (7)0.0585 (8)0.0151 (7)0.0223 (8)0.0248 (6)
O20.0498 (8)0.0541 (8)0.0941 (11)0.0194 (6)0.0265 (8)0.0135 (8)
O70.0747 (9)0.0282 (6)0.0703 (9)0.0050 (6)0.0417 (7)0.0184 (6)
O90.0733 (9)0.0265 (6)0.0641 (9)0.0037 (6)0.0336 (7)0.0111 (6)
C10.0444 (9)0.0307 (8)0.0369 (8)0.0049 (6)0.0149 (7)0.0134 (6)
C20.0651 (11)0.0307 (8)0.0508 (10)0.0047 (7)0.0275 (9)0.0158 (7)
C30.0731 (13)0.0432 (10)0.0667 (12)0.0020 (9)0.0400 (10)0.0247 (9)
C40.0617 (11)0.0433 (10)0.0554 (11)0.0099 (8)0.0342 (9)0.0176 (8)
C50.0449 (9)0.0318 (8)0.0408 (9)0.0063 (6)0.0150 (7)0.0130 (7)
C60.0462 (9)0.0297 (8)0.0448 (9)0.0033 (6)0.0188 (7)0.0157 (7)
C70.0478 (9)0.0281 (8)0.0405 (8)0.0032 (6)0.0146 (7)0.0139 (7)
C80.0467 (9)0.0283 (7)0.0380 (8)0.0031 (6)0.0147 (7)0.0131 (6)
C90.0484 (9)0.0310 (8)0.0403 (9)0.0043 (7)0.0128 (7)0.0126 (7)
C100.0606 (11)0.0393 (9)0.0521 (10)0.0096 (8)0.0248 (9)0.0113 (8)
C110.0552 (10)0.0318 (8)0.0458 (9)0.0081 (7)0.0260 (8)0.0133 (7)
C120.0591 (12)0.0445 (10)0.0528 (11)0.0084 (8)0.0117 (9)0.0114 (8)
Geometric parameters (Å, º) top
S1—O21.4312 (14)C4—C51.384 (2)
S1—O11.4360 (14)C4—H4A0.9300
S1—C121.750 (2)C5—C61.377 (2)
S1—C51.7768 (16)C6—H6A0.9300
N1—C71.354 (2)C7—C81.463 (2)
N1—C11.412 (2)C8—C91.374 (2)
N1—H10.844 (9)C8—C111.425 (2)
N11—C111.136 (2)C9—C101.483 (2)
O7—C71.2472 (19)C10—H10A0.9600
O9—C91.316 (2)C10—H10B0.9600
O9—H90.833 (10)C10—H10C0.9600
C1—C21.389 (2)C10—H10D0.9600
C1—C61.399 (2)C10—H10E0.9600
C2—C31.386 (2)C10—H10F0.9600
C2—H2B0.9300C12—H12A0.9600
C3—C41.381 (3)C12—H12B0.9600
C3—H3A0.9300C12—H12C0.9600
O2—S1—O1118.71 (10)C11—C8—C7121.35 (14)
O2—S1—C12108.16 (10)O9—C9—C8121.60 (15)
O1—S1—C12107.80 (10)O9—C9—C10114.07 (14)
O2—S1—C5107.75 (8)C8—C9—C10124.33 (15)
O1—S1—C5108.60 (8)C9—C10—H10A109.5
C12—S1—C5105.01 (9)C9—C10—H10B109.5
C7—N1—C1127.91 (13)H10A—C10—H10B109.5
C7—N1—H1118.3 (14)C9—C10—H10C109.5
C1—N1—H1113.7 (14)H10A—C10—H10C109.5
C9—O9—H9107.1 (17)H10B—C10—H10C109.5
C2—C1—C6118.99 (14)C9—C10—H10D109.5
C2—C1—N1124.02 (14)H10A—C10—H10D141.1
C6—C1—N1116.97 (13)H10B—C10—H10D56.3
C3—C2—C1120.13 (15)H10C—C10—H10D56.3
C3—C2—H2B119.9C9—C10—H10E109.5
C1—C2—H2B119.9H10A—C10—H10E56.3
C4—C3—C2121.28 (16)H10B—C10—H10E141.1
C4—C3—H3A119.4H10C—C10—H10E56.3
C2—C3—H3A119.4H10D—C10—H10E109.5
C3—C4—C5118.02 (15)C9—C10—H10F109.5
C3—C4—H4A121.0H10A—C10—H10F56.3
C5—C4—H4A121.0H10B—C10—H10F56.3
C6—C5—C4122.02 (15)H10C—C10—H10F141.1
C6—C5—S1119.22 (12)H10D—C10—H10F109.5
C4—C5—S1118.73 (12)H10E—C10—H10F109.5
C5—C6—C1119.54 (14)N11—C11—C8179.7 (2)
C5—C6—H6A120.2S1—C12—H12A109.5
C1—C6—H6A120.2S1—C12—H12B109.5
O7—C7—N1122.34 (14)H12A—C12—H12B109.5
O7—C7—C8119.39 (14)S1—C12—H12C109.5
N1—C7—C8118.27 (13)H12A—C12—H12C109.5
C9—C8—C11117.83 (14)H12B—C12—H12C109.5
C9—C8—C7120.80 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N11i0.84 (1)2.24 (1)3.060 (2)164 (2)
O9—H9···O70.83 (1)1.75 (2)2.5102 (17)151 (2)
O9—H9···O7ii0.83 (1)2.57 (2)3.0464 (18)118 (2)
Symmetry codes: (i) x1, y+2, z+1; (ii) x, y+3, z+1.
(PHI495) 1-cyano-2-hydroxy-N-[3-bromo-4-(trifluromethoxy)phenyl]but-2-enamide top
Crystal data top
C12H8BrF3N2O3Z = 2
Mr = 365.11F(000) = 360
Triclinic, P1Dx = 1.750 Mg m3
Dm = 1.76 (2) Mg m3
Dm measured by flotation in phenyliodide and hexane
a = 5.2834 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.8265 (8) ÅCell parameters from 1906 reflections
c = 13.1634 (10) Åθ = 1.7–25.7°
α = 69.009 (1)°µ = 3.01 mm1
β = 81.085 (1)°T = 295 K
γ = 83.238 (1)°Needle, colorless
V = 692.91 (9) Å30.45 × 0.11 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2643 independent reflections
Radiation source: fine-focus sealed tube1364 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω scansθmax = 25.7°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 66
Tmin = 0.344, Tmax = 0.753k = 1313
7235 measured reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0639P)2]
where P = (Fo2 + 2Fc2)/3
2643 reflections(Δ/σ)max = 0.004
200 parametersΔρmax = 0.61 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
C12H8BrF3N2O3γ = 83.238 (1)°
Mr = 365.11V = 692.91 (9) Å3
Triclinic, P1Z = 2
a = 5.2834 (4) ÅMo Kα radiation
b = 10.8265 (8) ŵ = 3.01 mm1
c = 13.1634 (10) ÅT = 295 K
α = 69.009 (1)°0.45 × 0.11 × 0.10 mm
β = 81.085 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2643 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1364 reflections with I > 2σ(I)
Tmin = 0.344, Tmax = 0.753Rint = 0.037
7235 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.61 e Å3
2643 reflectionsΔρmin = 0.51 e Å3
200 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.18630 (13)0.49058 (6)0.37570 (5)0.1136 (4)
F10.2881 (9)0.0828 (5)0.5088 (3)0.1625 (17)
F20.3853 (8)0.2333 (4)0.5740 (3)0.1645 (17)
F30.0019 (9)0.1602 (5)0.5507 (3)0.1481 (16)
O40.1978 (6)0.2863 (4)0.4107 (3)0.0898 (10)
O70.5577 (5)0.1190 (3)0.0302 (2)0.0699 (9)
O90.8665 (6)0.0708 (3)0.1182 (3)0.0754 (10)
H90.727 (10)0.068 (5)0.070 (5)0.109 (19)*
N10.6152 (7)0.2897 (4)0.0847 (3)0.0552 (9)
H10.696 (7)0.355 (3)0.070 (3)0.042 (11)*
N111.1555 (8)0.4453 (4)0.0794 (3)0.0810 (12)
C10.4079 (7)0.2789 (4)0.1688 (3)0.0515 (10)
C20.2253 (8)0.1866 (4)0.1979 (3)0.0601 (11)
H20.23450.12500.16300.072*
C30.0286 (8)0.1882 (5)0.2803 (3)0.0700 (12)
H30.09720.12780.29970.084*
C40.0153 (8)0.2761 (5)0.3334 (3)0.0666 (12)
C50.1969 (9)0.3664 (4)0.3048 (3)0.0652 (12)
C60.3926 (8)0.3670 (4)0.2232 (3)0.0611 (11)
H60.51700.42800.20450.073*
C70.6795 (7)0.2146 (4)0.0208 (3)0.0518 (10)
C80.9063 (7)0.2481 (4)0.0615 (3)0.0507 (10)
C90.9902 (8)0.1735 (4)0.1260 (3)0.0582 (11)
C101.2180 (9)0.1980 (5)0.2098 (4)0.0747 (13)
H10A1.23440.13390.24580.112*0.29 (5)
H10B1.36900.19040.17520.112*0.29 (5)
H10C1.19820.28560.26280.112*0.29 (5)
H10D1.30000.27270.21010.112*0.71 (5)
H10E1.16540.21620.28070.112*0.71 (5)
H10F1.33620.12110.19310.112*0.71 (5)
C111.0481 (8)0.3575 (4)0.0728 (3)0.0568 (11)
C120.2141 (14)0.1923 (7)0.5082 (6)0.0981 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.1548 (7)0.1008 (5)0.0998 (5)0.0162 (4)0.0380 (4)0.0721 (4)
F10.192 (4)0.161 (4)0.140 (3)0.090 (3)0.061 (3)0.068 (3)
F20.175 (3)0.192 (4)0.109 (3)0.017 (3)0.084 (3)0.072 (3)
F30.137 (3)0.218 (5)0.070 (2)0.035 (3)0.002 (2)0.025 (3)
O40.076 (2)0.117 (3)0.068 (2)0.0010 (19)0.0266 (18)0.039 (2)
O70.0687 (18)0.078 (2)0.079 (2)0.0349 (17)0.0287 (15)0.0525 (17)
O90.071 (2)0.084 (2)0.091 (2)0.0331 (18)0.0266 (19)0.0607 (19)
N10.057 (2)0.060 (2)0.057 (2)0.0201 (19)0.0132 (17)0.0339 (19)
N110.088 (3)0.084 (3)0.081 (3)0.038 (2)0.017 (2)0.041 (2)
C10.050 (2)0.061 (3)0.047 (2)0.011 (2)0.0060 (19)0.025 (2)
C20.058 (3)0.071 (3)0.060 (3)0.017 (2)0.010 (2)0.036 (2)
C30.067 (3)0.087 (3)0.059 (3)0.026 (2)0.019 (2)0.033 (3)
C40.059 (3)0.082 (3)0.053 (3)0.000 (3)0.016 (2)0.026 (2)
C50.077 (3)0.066 (3)0.057 (3)0.000 (2)0.011 (2)0.036 (2)
C60.072 (3)0.061 (3)0.057 (3)0.018 (2)0.014 (2)0.033 (2)
C70.049 (2)0.061 (3)0.051 (2)0.015 (2)0.0087 (19)0.027 (2)
C80.050 (2)0.056 (2)0.049 (2)0.0156 (19)0.0088 (19)0.025 (2)
C90.060 (3)0.064 (3)0.055 (3)0.014 (2)0.008 (2)0.030 (2)
C100.073 (3)0.088 (3)0.068 (3)0.020 (3)0.024 (2)0.042 (3)
C110.060 (3)0.064 (3)0.052 (3)0.020 (2)0.011 (2)0.028 (2)
C120.096 (5)0.129 (5)0.074 (4)0.035 (4)0.033 (4)0.050 (4)
Geometric parameters (Å, º) top
Br1—C51.884 (4)C1—C61.372 (5)
F1—C121.288 (7)C1—C21.383 (5)
F2—C121.305 (6)C2—C31.384 (6)
F3—C121.286 (7)C3—C41.358 (6)
O4—C121.319 (7)C4—C51.365 (6)
O4—C41.418 (5)C5—C61.368 (5)
O7—C71.241 (5)C7—C81.469 (5)
O9—C91.320 (5)C8—C91.364 (5)
N1—C71.349 (5)C8—C111.427 (6)
N1—C11.415 (5)C9—C101.479 (6)
N11—C111.134 (5)
C12—O4—C4117.6 (4)O7—C7—C8119.7 (3)
C7—N1—C1128.8 (4)N1—C7—C8117.5 (4)
C6—C1—C2119.5 (3)C9—C8—C11118.7 (3)
C6—C1—N1116.4 (4)C9—C8—C7121.1 (4)
C2—C1—N1124.1 (4)C11—C8—C7120.2 (3)
C1—C2—C3118.4 (4)O9—C9—C8121.0 (4)
C4—C3—C2121.4 (4)O9—C9—C10114.0 (4)
C3—C4—C5119.9 (4)C8—C9—C10125.1 (4)
C3—C4—O4121.6 (4)N11—C11—C8177.9 (4)
C5—C4—O4118.2 (4)F3—C12—F1105.1 (7)
C4—C5—C6119.7 (4)F3—C12—F2108.6 (6)
C4—C5—Br1121.4 (3)F1—C12—F2106.6 (5)
C6—C5—Br1118.8 (3)F3—C12—O4114.2 (5)
C5—C6—C1121.0 (4)F1—C12—O4113.7 (6)
O7—C7—N1122.7 (4)F2—C12—O4108.2 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O9—H9···O70.89 (6)1.70 (6)2.508 (4)150 (5)
O9—H9···O7i0.89 (6)2.52 (5)3.027 (4)117 (4)
N1—H1···N11ii0.82 (3)2.44 (4)3.218 (5)161 (3)
Symmetry codes: (i) x+1, y, z; (ii) x+2, y+1, z.

Experimental details

(PHI492)(PHI493)(PHI495)
Crystal data
Chemical formulaC12H12N2O4SC12H12N2O4SC12H8BrF3N2O3
Mr280.30280.30365.11
Crystal system, space groupMonoclinic, P21/nTriclinic, P1Triclinic, P1
Temperature (K)295295295
a, b, c (Å)8.8002 (10), 5.5336 (6), 25.852 (3)5.4734 (3), 11.4048 (6), 11.5200 (6)5.2834 (4), 10.8265 (8), 13.1634 (10)
α, β, γ (°)90, 97.644 (1), 90115.478 (1), 95.941 (1), 93.035 (1)69.009 (1), 81.085 (1), 83.238 (1)
V3)1247.7 (2)641.88 (6)692.91 (9)
Z422
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.270.263.01
Crystal size (mm)0.34 × 0.31 × 0.280.55 × 0.35 × 0.170.45 × 0.11 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detectorBruker SMART CCD area-detectorBruker SMART CCD area-detector
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.913, 0.9280.869, 0.9570.344, 0.753
No. of measured, independent and
observed [I > 2σ(I)] reflections
10595, 2503, 2157 6510, 2428, 2152 7235, 2643, 1364
Rint0.0300.0220.037
(sin θ/λ)max1)0.6260.6100.611
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.113, 1.07 0.034, 0.102, 1.05 0.045, 0.131, 1.01
No. of reflections250324282643
No. of parameters182182200
No. of restraints220
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.450.22, 0.280.61, 0.51

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) for (PHI492) top
S1—O21.4336 (15)N1—C71.353 (3)
S1—O11.4339 (16)N1—C11.412 (2)
S1—C41.7596 (19)N11—C111.138 (2)
S1—C121.760 (2)C7—C81.472 (3)
O7—C71.239 (2)C8—C91.366 (3)
O9—C91.313 (2)C8—C111.424 (3)
O9—H90.819 (10)C9—C101.486 (3)
O2—S1—O1117.86 (10)O7—C7—N1123.37 (17)
O2—S1—C4108.26 (9)O7—C7—C8119.91 (17)
O1—S1—C4109.02 (9)N1—C7—C8116.72 (16)
O2—S1—C12108.63 (11)C9—C8—C11117.63 (17)
O1—S1—C12108.03 (11)C9—C8—C7120.73 (17)
C4—S1—C12104.20 (10)C11—C8—C7121.64 (17)
C7—N1—C1128.78 (16)O9—C9—C8122.25 (18)
C6—C1—N1116.07 (16)O9—C9—C10114.07 (18)
C2—C1—N1124.71 (17)C8—C9—C10123.69 (18)
C3—C4—S1120.80 (14)N11—C11—C8178.9 (2)
C5—C4—S1119.07 (14)
Hydrogen-bond geometry (Å, º) for (PHI492) top
D—H···AD—HH···AD···AD—H···A
O9—H9···O70.819 (10)1.800 (18)2.534 (2)148 (3)
N1—H1···N11i0.851 (10)2.307 (11)3.132 (2)164 (2)
Symmetry code: (i) x+1, y+4, z.
Selected geometric parameters (Å, º) for (PHI493) top
S1—O21.4312 (14)O7—C71.2472 (19)
S1—O11.4360 (14)O9—C91.316 (2)
S1—C121.750 (2)C7—C81.463 (2)
S1—C51.7768 (16)C8—C91.374 (2)
N1—C71.354 (2)C8—C111.425 (2)
N1—C11.412 (2)C9—C101.483 (2)
N11—C111.136 (2)
O2—S1—O1118.71 (10)O7—C7—N1122.34 (14)
O2—S1—C12108.16 (10)O7—C7—C8119.39 (14)
O1—S1—C12107.80 (10)N1—C7—C8118.27 (13)
O2—S1—C5107.75 (8)C9—C8—C11117.83 (14)
O1—S1—C5108.60 (8)C9—C8—C7120.80 (14)
C12—S1—C5105.01 (9)C11—C8—C7121.35 (14)
C7—N1—C1127.91 (13)O9—C9—C8121.60 (15)
C2—C1—N1124.02 (14)O9—C9—C10114.07 (14)
C6—C1—N1116.97 (13)C8—C9—C10124.33 (15)
C6—C5—S1119.22 (12)N11—C11—C8179.7 (2)
C4—C5—S1118.73 (12)
Hydrogen-bond geometry (Å, º) for (PHI493) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N11i0.844 (9)2.239 (11)3.060 (2)164.2 (19)
O9—H9···O70.833 (10)1.749 (15)2.5102 (17)151 (2)
O9—H9···O7ii0.833 (10)2.57 (2)3.0464 (18)117.5 (19)
Symmetry codes: (i) x1, y+2, z+1; (ii) x, y+3, z+1.
Selected geometric parameters (Å, º) for (PHI495) top
Br1—C51.884 (4)N1—C71.349 (5)
F1—C121.288 (7)N1—C11.415 (5)
F2—C121.305 (6)N11—C111.134 (5)
F3—C121.286 (7)C7—C81.469 (5)
O4—C121.319 (7)C8—C91.364 (5)
O4—C41.418 (5)C8—C111.427 (6)
O7—C71.241 (5)C9—C101.479 (6)
O9—C91.320 (5)
C12—O4—C4117.6 (4)C9—C8—C7121.1 (4)
C7—N1—C1128.8 (4)C11—C8—C7120.2 (3)
C6—C1—N1116.4 (4)O9—C9—C8121.0 (4)
C2—C1—N1124.1 (4)O9—C9—C10114.0 (4)
C3—C4—O4121.6 (4)C8—C9—C10125.1 (4)
C5—C4—O4118.2 (4)N11—C11—C8177.9 (4)
C4—C5—Br1121.4 (3)F3—C12—F1105.1 (7)
C6—C5—Br1118.8 (3)F3—C12—F2108.6 (6)
O7—C7—N1122.7 (4)F1—C12—F2106.6 (5)
O7—C7—C8119.7 (3)F3—C12—O4114.2 (5)
N1—C7—C8117.5 (4)F1—C12—O4113.7 (6)
C9—C8—C11118.7 (3)F2—C12—O4108.2 (6)
Hydrogen-bond geometry (Å, º) for (PHI495) top
D—H···AD—HH···AD···AD—H···A
O9—H9···O70.89 (6)1.70 (6)2.508 (4)150 (5)
O9—H9···O7i0.89 (6)2.52 (5)3.027 (4)117 (4)
N1—H1···N11ii0.82 (3)2.44 (4)3.218 (5)161 (3)
Symmetry codes: (i) x+1, y, z; (ii) x+2, y+1, z.
 

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