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Four new solvates of the anti-HIV compound etravirine [systematic name: 4-({6-amino-5-bromo-2-[(4-cyanophenyl)amino]pyrimidin-4-yl}oxy)-3,5-dimethylbenzonitrile, C20H15BrN6O] with dimethyl sulfoxide (C2H6OS, two distinct monosolvates), 1,4-dioxane (C4H8O2, the 0.75-solvate) and N,N-dimethylacetamide (C4H9NO, the monosolvate), which exhibit conversion to the same anhydrous etravirine phase upon desolvation, and a stable etravirinium oxalate salt {6-amino-5-bromo-4-(4-cyano-2,6-dimethylphenoxy)-2-[(4-cyanophenyl)amino]pyrimidin-1-ium hemioxalate, C20H16BrN6O+·0.5C2O42−} were obtained. The crystal structures were solved by single-crystal X-ray diffraction and analyzed by powder X-ray diffraction, and the intermolecular interactions were explored by Hirshfeld surface analysis. Lattice energies were evaluated using the atom–atom force field Coulomb–London–Pauli (AA CLP) approximation, which distributes the total energy as four separate contributions: Coulombic, polarization, dispersion and repulsion. The formation of the solvates and the oxalate salt was further characterized by thermal analysis and IR spectroscopy.
Supporting information
CCDC references: 2086675; 2086673; 2086672; 2086674; 2086671
Data collection: CrysAlis PRO (Agilent, 2012) for ETR-DMSO1, ETR-DMA, ETR-Dioxan; CrysAlis PRO (Oxford Diffraction, 2010) for ETR-DMSO2; CrysAlis PRO (Rigaku OD, 2019) for ETR-Oxalic. Cell refinement: CrysAlis PRO (Agilent, 2012) for ETR-DMSO1, ETR-DMA, ETR-Dioxan; CrysAlis PRO (Oxford Diffraction, 2010) for ETR-DMSO2; CrysAlis PRO (Rigaku OD, 2019) for ETR-Oxalic. Data reduction: CrysAlis PRO (Agilent, 2012) for ETR-DMSO1, ETR-DMA, ETR-Dioxan; CrysAlis PRO (Oxford Diffraction, 2010) for ETR-DMSO2; CrysAlis PRO (Rigaku OD, 2019) for ETR-Oxalic. Program(s) used to solve structure: SHELXD (Sheldrick, 2008) for ETR-DMSO1; SHELXS (Sheldrick, 2008) for ETR-DMSO2, ETR-Dioxan; SHELXT (Sheldrick, 2015a) for ETR-DMA; olex2.solve (Bourhis et al., 2015) for ETR-Oxalic. For all structures, program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
4-({6-Amino-5-bromo-2-[(4-cyanophenyl)amino]pyrimidin-4-yl}oxy)-3,5-dimethylbenzonitrile dimethyl sulfoxide monosolvate (ETR-DMSO1)
top
Crystal data top
C20H15BrN6O·C2H6OS | F(000) = 1048 |
Mr = 513.42 | Dx = 1.392 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 9.2801 (6) Å | Cell parameters from 3301 reflections |
b = 15.4330 (9) Å | θ = 3.9–71.3° |
c = 17.1702 (11) Å | µ = 3.33 mm−1 |
β = 95.116 (6)° | T = 293 K |
V = 2449.3 (3) Å3 | Needle, colourless |
Z = 4 | 0.3 × 0.02 × 0.02 mm |
Data collection top
Agilent SuperNova Dual Source diffractometer with an Eos detector | 4663 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 3590 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.046 |
Detector resolution: 16.4335 pixels mm-1 | θmax = 71.7°, θmin = 3.9° |
ω scans | h = −11→8 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = −18→14 |
Tmin = 0.387, Tmax = 1.000 | l = −14→21 |
8978 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.066 | H-atom parameters constrained |
wR(F2) = 0.214 | w = 1/[σ2(Fo2) + (0.1282P)2 + 0.5303P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
4663 reflections | Δρmax = 0.79 e Å−3 |
293 parameters | Δρmin = −0.75 e Å−3 |
0 restraints | |
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. |
Refinement. Suitable single crystals were coated in inert oil (Paratone-N) and
mounted in the goniometer using a fine nyloon loop. The data collection was
acquired with a SuperNova diffractometer (tube operating at 50 kV and 0.8 mA),
equipped with dual microsources (Mo and Cu) using Cu Kα radiation, Eos CCD
detector at room temperature and CrysAlis PRO software (Rigaku, 2015). All
data were corrected for Lorentzian, polarization, and absorption effects. The
empirical absorption correction was accomplished using the multi-scan method
by spherical harmonics in the SCALE3 ABSPACK scaling algorithm (Rigaku, 2015).
The structures of ETR–DMA and ETR-oxalic were solved by SHELXT (Sheldrick,
2015) solution program with Intrinsic Phasing, ETR–DMSO1 was solved with
SHELXD (Sheldrick, 2008) by Dual Space, while the ETR–DMSO2 and ETR–Dioxane
were solved by SHELXS (Sheldrick, 2008) program using Direct Methods. The
structures were further refined with SHELXL (Sheldrick, 2015) refinement
package using least-squares minimization, which are implemented in Olex2
software (Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.63939 (6) | 0.45526 (3) | 0.18484 (3) | 0.0815 (3) | |
C8 | 0.9723 (4) | 0.2995 (2) | 0.0659 (2) | 0.0527 (8) | |
C5 | 1.1080 (4) | 0.1658 (2) | 0.0405 (2) | 0.0576 (8) | |
C14 | 0.6383 (4) | 0.1208 (3) | 0.1788 (2) | 0.0658 (10) | |
N2 | 1.0728 (4) | 0.2528 (2) | 0.0300 (2) | 0.0620 (8) | |
H2 | 1.119750 | 0.280629 | −0.002984 | 0.074* | |
O1 | 0.7168 (3) | 0.26599 (19) | 0.20069 (18) | 0.0690 (8) | |
N5 | 0.8938 (3) | 0.25682 (19) | 0.11601 (18) | 0.0563 (7) | |
C9 | 0.8612 (4) | 0.4301 (2) | 0.0802 (2) | 0.0557 (8) | |
C11 | 0.7983 (4) | 0.3043 (2) | 0.1491 (2) | 0.0549 (8) | |
C12 | 0.7374 (4) | 0.1778 (3) | 0.2155 (2) | 0.0605 (9) | |
C15 | 0.6485 (5) | 0.0339 (3) | 0.2002 (3) | 0.0701 (11) | |
H15 | 0.582808 | −0.005979 | 0.177087 | 0.084* | |
O2 | 0.7257 (3) | −0.3226 (2) | 0.0764 (2) | 0.0801 (9) | |
C4 | 1.1572 (5) | 0.1216 (3) | −0.0229 (2) | 0.0670 (10) | |
H4 | 1.162758 | 0.150434 | −0.070126 | 0.080* | |
N3 | 0.9605 (3) | 0.38274 (19) | 0.04555 (18) | 0.0567 (7) | |
C19 | 0.8458 (5) | 0.1525 (3) | 0.2726 (2) | 0.0667 (10) | |
C2 | 1.1918 (5) | −0.0074 (3) | 0.0534 (3) | 0.0701 (10) | |
C3 | 1.1975 (5) | 0.0363 (3) | −0.0168 (3) | 0.0725 (11) | |
H3 | 1.228743 | 0.007674 | −0.059823 | 0.087* | |
C10 | 0.7788 (4) | 0.3912 (2) | 0.1352 (2) | 0.0566 (8) | |
C18 | 0.8538 (5) | 0.0655 (3) | 0.2916 (3) | 0.0752 (11) | |
H18 | 0.925508 | 0.046191 | 0.328860 | 0.090* | |
N4 | 0.8474 (4) | 0.5133 (2) | 0.0595 (2) | 0.0708 (9) | |
H4A | 0.900290 | 0.534518 | 0.025454 | 0.085* | |
H4B | 0.785658 | 0.545688 | 0.080073 | 0.085* | |
C7 | 1.1442 (5) | 0.0366 (3) | 0.1171 (3) | 0.0778 (13) | |
H7 | 1.139613 | 0.007752 | 0.164372 | 0.093* | |
C1 | 1.2338 (6) | −0.0970 (3) | 0.0588 (4) | 0.0881 (14) | |
C6 | 1.1040 (5) | 0.1220 (3) | 0.1108 (2) | 0.0702 (11) | |
H6 | 1.073745 | 0.150859 | 0.153995 | 0.084* | |
N6 | 0.7769 (8) | −0.1550 (4) | 0.2933 (4) | 0.142 (3) | |
C13 | 0.5237 (6) | 0.1517 (4) | 0.1184 (3) | 0.0937 (16) | |
H13A | 0.466595 | 0.195659 | 0.140560 | 0.141* | |
H13B | 0.462604 | 0.103992 | 0.101089 | 0.141* | |
H13C | 0.568280 | 0.175314 | 0.074713 | 0.141* | |
C20 | 0.9503 (6) | 0.2166 (4) | 0.3120 (3) | 0.0905 (15) | |
H20A | 1.007268 | 0.241892 | 0.273963 | 0.136* | |
H20B | 1.012732 | 0.187493 | 0.351276 | 0.136* | |
H20C | 0.897531 | 0.261268 | 0.336076 | 0.136* | |
C21 | 0.5375 (8) | −0.2815 (6) | 0.1709 (4) | 0.126 (3) | |
H21A | 0.576751 | −0.333106 | 0.195805 | 0.190* | |
H21B | 0.434243 | −0.281425 | 0.171819 | 0.190* | |
H21C | 0.577519 | −0.231560 | 0.198174 | 0.190* | |
N1 | 1.2702 (7) | −0.1671 (3) | 0.0641 (4) | 0.122 (2) | |
S1 | 0.58124 (13) | −0.27884 (7) | 0.07405 (6) | 0.0692 (3) | |
C17 | 0.7680 (7) | −0.0842 (4) | 0.2766 (4) | 0.0975 (16) | |
C16 | 0.7562 (5) | 0.0066 (3) | 0.2559 (3) | 0.0748 (11) | |
C22 | 0.4522 (8) | −0.3545 (5) | 0.0378 (5) | 0.145 (3) | |
H22A | 0.471265 | −0.371208 | −0.014164 | 0.217* | |
H22B | 0.357508 | −0.329286 | 0.036623 | 0.217* | |
H22C | 0.457013 | −0.404670 | 0.071013 | 0.217* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0887 (4) | 0.0730 (4) | 0.0887 (4) | 0.0235 (2) | 0.0405 (3) | 0.0040 (2) |
C8 | 0.0519 (18) | 0.0504 (18) | 0.0576 (18) | 0.0005 (14) | 0.0151 (15) | −0.0008 (14) |
C5 | 0.0579 (19) | 0.0518 (19) | 0.066 (2) | 0.0037 (15) | 0.0196 (16) | 0.0012 (15) |
C14 | 0.066 (2) | 0.074 (3) | 0.059 (2) | 0.0000 (19) | 0.0168 (17) | 0.0087 (17) |
N2 | 0.073 (2) | 0.0473 (15) | 0.0707 (19) | 0.0065 (14) | 0.0350 (16) | 0.0074 (13) |
O1 | 0.0698 (17) | 0.0608 (16) | 0.0818 (18) | 0.0115 (13) | 0.0355 (14) | 0.0139 (13) |
N5 | 0.0576 (17) | 0.0500 (15) | 0.0641 (17) | 0.0038 (13) | 0.0213 (14) | 0.0034 (12) |
C9 | 0.0561 (19) | 0.0484 (17) | 0.0634 (19) | 0.0028 (15) | 0.0103 (15) | −0.0001 (15) |
C11 | 0.0535 (19) | 0.057 (2) | 0.0558 (18) | 0.0022 (15) | 0.0154 (15) | 0.0046 (14) |
C12 | 0.061 (2) | 0.062 (2) | 0.0618 (19) | 0.0060 (17) | 0.0241 (16) | 0.0086 (16) |
C15 | 0.074 (3) | 0.070 (3) | 0.068 (2) | −0.005 (2) | 0.015 (2) | 0.0039 (18) |
O2 | 0.0771 (19) | 0.0703 (18) | 0.099 (2) | 0.0187 (15) | 0.0408 (17) | 0.0151 (16) |
C4 | 0.076 (2) | 0.061 (2) | 0.068 (2) | 0.0067 (19) | 0.0273 (19) | 0.0022 (17) |
N3 | 0.0621 (17) | 0.0474 (15) | 0.0629 (16) | 0.0043 (13) | 0.0190 (14) | 0.0033 (12) |
C19 | 0.068 (2) | 0.072 (2) | 0.062 (2) | 0.002 (2) | 0.0141 (18) | −0.0008 (17) |
C2 | 0.066 (2) | 0.052 (2) | 0.094 (3) | 0.0071 (18) | 0.019 (2) | 0.0054 (19) |
C3 | 0.079 (3) | 0.059 (2) | 0.083 (3) | 0.0084 (19) | 0.031 (2) | −0.0092 (19) |
C10 | 0.061 (2) | 0.0495 (18) | 0.0609 (19) | 0.0061 (15) | 0.0150 (16) | −0.0013 (14) |
C18 | 0.074 (3) | 0.081 (3) | 0.070 (2) | 0.017 (2) | 0.001 (2) | 0.006 (2) |
N4 | 0.077 (2) | 0.0499 (17) | 0.091 (2) | 0.0123 (16) | 0.0349 (18) | 0.0070 (16) |
C7 | 0.086 (3) | 0.069 (3) | 0.082 (3) | 0.019 (2) | 0.030 (2) | 0.019 (2) |
C1 | 0.087 (3) | 0.062 (3) | 0.120 (4) | 0.015 (2) | 0.034 (3) | 0.010 (3) |
C6 | 0.083 (3) | 0.064 (2) | 0.066 (2) | 0.016 (2) | 0.024 (2) | 0.0084 (18) |
N6 | 0.166 (6) | 0.077 (3) | 0.176 (6) | 0.014 (4) | −0.028 (5) | 0.021 (4) |
C13 | 0.089 (3) | 0.106 (4) | 0.084 (3) | −0.001 (3) | −0.005 (3) | 0.027 (3) |
C20 | 0.090 (4) | 0.094 (4) | 0.086 (3) | −0.009 (3) | 0.003 (3) | −0.012 (3) |
C21 | 0.112 (5) | 0.178 (8) | 0.097 (4) | 0.025 (5) | 0.051 (4) | −0.011 (4) |
N1 | 0.131 (4) | 0.071 (3) | 0.172 (5) | 0.036 (3) | 0.045 (4) | 0.021 (3) |
S1 | 0.0759 (7) | 0.0577 (5) | 0.0776 (6) | 0.0129 (5) | 0.0268 (5) | 0.0115 (4) |
C17 | 0.113 (4) | 0.073 (3) | 0.104 (4) | 0.009 (3) | −0.004 (3) | 0.010 (3) |
C16 | 0.083 (3) | 0.065 (3) | 0.078 (3) | 0.008 (2) | 0.014 (2) | 0.008 (2) |
C22 | 0.115 (5) | 0.109 (5) | 0.198 (9) | 0.019 (4) | −0.061 (5) | −0.045 (5) |
Geometric parameters (Å, º) top
Br1—C10 | 1.891 (3) | C12—C19 | 1.396 (6) |
C8—N2 | 1.368 (4) | C15—C16 | 1.386 (7) |
C8—N5 | 1.348 (4) | O2—S1 | 1.499 (3) |
C8—N3 | 1.333 (5) | C4—C3 | 1.368 (6) |
C5—N2 | 1.390 (5) | C19—C18 | 1.382 (7) |
C5—C4 | 1.396 (5) | C19—C20 | 1.503 (7) |
C5—C6 | 1.386 (5) | C2—C3 | 1.386 (6) |
C14—C12 | 1.383 (6) | C2—C7 | 1.392 (6) |
C14—C15 | 1.391 (6) | C2—C1 | 1.438 (6) |
C14—C13 | 1.497 (6) | C18—C16 | 1.387 (7) |
O1—C11 | 1.351 (4) | C7—C6 | 1.373 (6) |
O1—C12 | 1.395 (5) | C1—N1 | 1.135 (7) |
N5—C11 | 1.318 (5) | N6—C17 | 1.130 (7) |
C9—N3 | 1.355 (5) | C21—S1 | 1.746 (6) |
C9—C10 | 1.402 (5) | S1—C22 | 1.747 (7) |
C9—N4 | 1.335 (5) | C17—C16 | 1.447 (7) |
C11—C10 | 1.372 (5) | | |
| | | |
N5—C8—N2 | 117.3 (3) | C8—N3—C9 | 116.6 (3) |
N3—C8—N2 | 115.7 (3) | C12—C19—C20 | 121.9 (4) |
N3—C8—N5 | 127.0 (3) | C18—C19—C12 | 117.2 (4) |
N2—C5—C4 | 117.5 (3) | C18—C19—C20 | 120.9 (4) |
C6—C5—N2 | 123.9 (3) | C3—C2—C7 | 119.0 (4) |
C6—C5—C4 | 118.5 (4) | C3—C2—C1 | 119.6 (4) |
C12—C14—C15 | 117.8 (4) | C7—C2—C1 | 121.4 (4) |
C12—C14—C13 | 121.1 (4) | C4—C3—C2 | 120.3 (4) |
C15—C14—C13 | 121.2 (4) | C9—C10—Br1 | 121.1 (3) |
C8—N2—C5 | 127.8 (3) | C11—C10—Br1 | 121.1 (3) |
C11—O1—C12 | 118.1 (3) | C11—C10—C9 | 117.7 (3) |
C11—N5—C8 | 115.2 (3) | C19—C18—C16 | 120.9 (4) |
N3—C9—C10 | 119.8 (3) | C6—C7—C2 | 120.6 (4) |
N4—C9—N3 | 117.0 (3) | N1—C1—C2 | 178.2 (8) |
N4—C9—C10 | 123.1 (3) | C7—C6—C5 | 120.6 (4) |
O1—C11—C10 | 118.0 (3) | O2—S1—C21 | 104.3 (3) |
N5—C11—O1 | 118.5 (3) | O2—S1—C22 | 107.0 (3) |
N5—C11—C10 | 123.5 (3) | C21—S1—C22 | 96.5 (5) |
C14—C12—O1 | 117.5 (4) | N6—C17—C16 | 179.5 (8) |
C14—C12—C19 | 123.4 (4) | C15—C16—C18 | 120.5 (4) |
O1—C12—C19 | 118.6 (4) | C15—C16—C17 | 119.9 (5) |
C16—C15—C14 | 120.2 (4) | C18—C16—C17 | 119.6 (5) |
C3—C4—C5 | 121.0 (4) | | |
4-({6-Amino-5-bromo-2-[(4-cyanophenyl)amino]pyrimidin-4-yl}oxy)-3,5-dimethylbenzonitrile dimethyl sulfoxide monosolvate (ETR-DMSO2)
top
Crystal data top
C20H15BrN6O·C2H6OS | Z = 2 |
Mr = 513.42 | F(000) = 524 |
Triclinic, P1 | Dx = 1.439 Mg m−3 |
a = 8.6953 (5) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 9.3336 (8) Å | Cell parameters from 4741 reflections |
c = 15.1494 (11) Å | θ = 3.0–70.9° |
α = 96.181 (6)° | µ = 3.45 mm−1 |
β = 102.323 (6)° | T = 293 K |
γ = 95.632 (6)° | Needle, colourless |
V = 1184.87 (15) Å3 | 0.1 × 0.03 × 0.01 mm |
Data collection top
Oxford Diffraction SuperNova Dual Source diffractometer with an Eos detector | 4449 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 3732 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.038 |
Detector resolution: 16.4335 pixels mm-1 | θmax = 71.0°, θmin = 3.0° |
ω scans | h = −10→7 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −11→11 |
Tmin = 0.482, Tmax = 1.000 | l = −18→18 |
7279 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.069 | H-atom parameters constrained |
wR(F2) = 0.210 | w = 1/[σ2(Fo2) + (0.146P)2 + 0.1471P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.003 |
4449 reflections | Δρmax = 0.66 e Å−3 |
294 parameters | Δρmin = −1.68 e Å−3 |
0 restraints | |
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. |
Refinement. Suitable single crystals were coated in inert oil (Paratone-N) and
mounted in the goniometer using a fine nyloon loop. The data collection was
acquired with a SuperNova diffractometer (tube operating at 50 kV and 0.8 mA),
equipped with dual microsources (Mo and Cu) using Cu Kα radiation, Eos CCD
detector at room temperature and CrysAlis PRO software (Rigaku, 2015). All
data were corrected for Lorentzian, polarization, and absorption effects. The
empirical absorption correction was accomplished using the multi-scan method
by spherical harmonics in the SCALE3 ABSPACK scaling algorithm (Rigaku, 2015).
The structures of ETR–DMA and ETR-oxalic were solved by SHELXT (Sheldrick,
2015) solution program with Intrinsic Phasing, ETR–DMSO1 was solved with
SHELXD (Sheldrick, 2008) by Dual Space, while the ETR–DMSO2 and ETR–Dioxane
were solved by SHELXS (Sheldrick, 2008) program using Direct Methods. The
structures were further refined with SHELXL (Sheldrick, 2015) refinement
package using least-squares minimization, which are implemented in Olex2
software (Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.15142 (4) | 0.39515 (5) | 0.07791 (3) | 0.0631 (2) | |
S1 | 0.71828 (12) | −0.04858 (11) | 0.43617 (9) | 0.0661 (3) | |
O1 | 0.4480 (3) | 0.2464 (3) | 0.09151 (18) | 0.0495 (6) | |
N5 | 0.6174 (3) | 0.3974 (3) | 0.2109 (2) | 0.0411 (6) | |
N3 | 0.5264 (4) | 0.6065 (3) | 0.2789 (2) | 0.0445 (6) | |
C11 | 0.4745 (4) | 0.3661 (3) | 0.1554 (2) | 0.0405 (7) | |
C10 | 0.3519 (4) | 0.4473 (3) | 0.1570 (2) | 0.0433 (7) | |
C8 | 0.6366 (4) | 0.5184 (3) | 0.2701 (2) | 0.0397 (7) | |
C12 | 0.5562 (4) | 0.1440 (3) | 0.1054 (2) | 0.0417 (7) | |
N2 | 0.7791 (3) | 0.5617 (3) | 0.3291 (2) | 0.0469 (7) | |
H2 | 0.782232 | 0.639829 | 0.365459 | 0.056* | |
C6 | 0.9480 (4) | 0.3774 (4) | 0.2881 (3) | 0.0508 (8) | |
H6 | 0.867907 | 0.329941 | 0.240004 | 0.061* | |
C9 | 0.3826 (4) | 0.5704 (3) | 0.2233 (3) | 0.0447 (7) | |
N4 | 0.2721 (4) | 0.6596 (3) | 0.2330 (3) | 0.0565 (8) | |
H4A | 0.179273 | 0.610360 | 0.219284 | 0.068* | |
H4B | 0.291873 | 0.700055 | 0.288675 | 0.068* | |
C5 | 0.9215 (4) | 0.5005 (3) | 0.3406 (2) | 0.0415 (7) | |
C14 | 0.6851 (4) | 0.1546 (4) | 0.0652 (3) | 0.0507 (8) | |
O2 | 0.8308 (4) | −0.1614 (3) | 0.4448 (3) | 0.0795 (10) | |
C2 | 1.2145 (4) | 0.3938 (4) | 0.3787 (3) | 0.0474 (8) | |
C19 | 0.5195 (4) | 0.0338 (4) | 0.1541 (3) | 0.0487 (8) | |
N1 | 1.4800 (5) | 0.2875 (5) | 0.4136 (3) | 0.0765 (12) | |
C18 | 0.6217 (6) | −0.0717 (4) | 0.1645 (3) | 0.0592 (10) | |
H18 | 0.600663 | −0.148393 | 0.196396 | 0.071* | |
C1 | 1.3639 (5) | 0.3362 (4) | 0.3989 (3) | 0.0556 (9) | |
C7 | 1.0937 (5) | 0.3258 (4) | 0.3076 (3) | 0.0546 (9) | |
H7 | 1.110565 | 0.243678 | 0.272127 | 0.066* | |
C16 | 0.7547 (5) | −0.0636 (5) | 0.1278 (3) | 0.0615 (11) | |
C3 | 1.1896 (5) | 0.5181 (4) | 0.4305 (3) | 0.0553 (9) | |
H3 | 1.270341 | 0.565683 | 0.478185 | 0.066* | |
C13 | 0.7171 (6) | 0.2766 (6) | 0.0127 (3) | 0.0724 (12) | |
H13A | 0.620990 | 0.289252 | −0.029014 | 0.109* | |
H13B | 0.795840 | 0.254414 | −0.020776 | 0.109* | |
H13C | 0.755032 | 0.364396 | 0.054061 | 0.109* | |
C4 | 1.0453 (4) | 0.5708 (4) | 0.4110 (3) | 0.0525 (9) | |
H4 | 1.030124 | 0.654759 | 0.445415 | 0.063* | |
C22 | 0.7398 (7) | 0.0439 (5) | 0.5481 (4) | 0.0793 (14) | |
H22A | 0.700005 | −0.021129 | 0.585320 | 0.119* | |
H22B | 0.681042 | 0.125759 | 0.545185 | 0.119* | |
H22C | 0.849919 | 0.076755 | 0.574066 | 0.119* | |
C15 | 0.7854 (5) | 0.0477 (5) | 0.0777 (3) | 0.0603 (10) | |
H15 | 0.873735 | 0.050676 | 0.052169 | 0.072* | |
C20 | 0.3756 (6) | 0.0299 (5) | 0.1952 (4) | 0.0746 (13) | |
H20A | 0.393232 | 0.105933 | 0.245565 | 0.112* | |
H20B | 0.357626 | −0.062407 | 0.216216 | 0.112* | |
H20C | 0.284447 | 0.043625 | 0.149931 | 0.112* | |
C21 | 0.8112 (7) | 0.0968 (6) | 0.3918 (4) | 0.0763 (13) | |
H21A | 0.914895 | 0.128674 | 0.429735 | 0.114* | |
H21B | 0.748422 | 0.175961 | 0.390546 | 0.114* | |
H21C | 0.820433 | 0.064351 | 0.331007 | 0.114* | |
N6 | 0.9503 (8) | −0.2524 (8) | 0.1575 (4) | 0.135 (3) | |
C17 | 0.8632 (7) | −0.1693 (7) | 0.1446 (4) | 0.0883 (18) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0347 (3) | 0.0633 (3) | 0.0793 (4) | 0.0092 (2) | −0.0134 (2) | 0.0061 (2) |
S1 | 0.0390 (5) | 0.0490 (5) | 0.0952 (8) | 0.0085 (4) | −0.0059 (5) | −0.0183 (5) |
O1 | 0.0355 (13) | 0.0372 (11) | 0.0623 (14) | 0.0082 (10) | −0.0125 (11) | −0.0088 (10) |
N5 | 0.0278 (14) | 0.0336 (12) | 0.0542 (15) | 0.0050 (10) | −0.0043 (11) | −0.0022 (11) |
N3 | 0.0387 (16) | 0.0331 (13) | 0.0575 (16) | 0.0098 (11) | 0.0023 (13) | −0.0010 (11) |
C11 | 0.0341 (17) | 0.0321 (14) | 0.0488 (17) | 0.0033 (12) | −0.0026 (13) | 0.0019 (12) |
C10 | 0.0280 (15) | 0.0371 (15) | 0.0584 (18) | 0.0052 (12) | −0.0058 (13) | 0.0084 (13) |
C8 | 0.0326 (16) | 0.0297 (13) | 0.0519 (17) | 0.0041 (12) | 0.0014 (13) | 0.0011 (12) |
C12 | 0.0300 (16) | 0.0338 (14) | 0.0503 (17) | 0.0054 (12) | −0.0085 (13) | −0.0092 (12) |
N2 | 0.0348 (15) | 0.0356 (13) | 0.0598 (16) | 0.0064 (11) | −0.0038 (12) | −0.0127 (12) |
C6 | 0.0348 (18) | 0.0469 (18) | 0.059 (2) | 0.0085 (14) | −0.0073 (15) | −0.0128 (15) |
C9 | 0.0370 (18) | 0.0347 (15) | 0.064 (2) | 0.0109 (13) | 0.0081 (15) | 0.0121 (14) |
N4 | 0.0424 (17) | 0.0478 (17) | 0.080 (2) | 0.0188 (14) | 0.0103 (16) | 0.0080 (15) |
C5 | 0.0358 (17) | 0.0350 (15) | 0.0473 (16) | 0.0036 (12) | −0.0007 (13) | −0.0018 (12) |
C14 | 0.0332 (18) | 0.055 (2) | 0.0535 (19) | −0.0026 (15) | −0.0025 (15) | −0.0066 (15) |
O2 | 0.0551 (19) | 0.0501 (16) | 0.112 (3) | 0.0151 (14) | −0.0111 (17) | −0.0297 (16) |
C2 | 0.0336 (17) | 0.0426 (17) | 0.060 (2) | 0.0060 (13) | −0.0022 (15) | 0.0063 (14) |
C19 | 0.044 (2) | 0.0376 (16) | 0.0578 (19) | 0.0008 (14) | 0.0063 (16) | −0.0079 (14) |
N1 | 0.037 (2) | 0.073 (2) | 0.107 (3) | 0.0165 (17) | −0.0084 (19) | −0.001 (2) |
C18 | 0.065 (3) | 0.0424 (18) | 0.061 (2) | 0.0117 (17) | −0.0038 (19) | −0.0013 (16) |
C1 | 0.035 (2) | 0.049 (2) | 0.074 (2) | 0.0052 (15) | −0.0024 (17) | 0.0032 (17) |
C7 | 0.046 (2) | 0.0448 (18) | 0.064 (2) | 0.0142 (15) | −0.0028 (17) | −0.0091 (16) |
C16 | 0.051 (2) | 0.060 (2) | 0.062 (2) | 0.0237 (19) | −0.0087 (18) | −0.0138 (18) |
C3 | 0.0374 (19) | 0.051 (2) | 0.064 (2) | 0.0005 (15) | −0.0085 (16) | −0.0049 (16) |
C13 | 0.062 (3) | 0.078 (3) | 0.071 (3) | −0.006 (2) | 0.007 (2) | 0.014 (2) |
C4 | 0.0398 (19) | 0.0403 (17) | 0.065 (2) | 0.0022 (14) | −0.0046 (16) | −0.0133 (15) |
C22 | 0.088 (4) | 0.058 (3) | 0.094 (4) | 0.010 (2) | 0.031 (3) | −0.003 (2) |
C15 | 0.0344 (19) | 0.079 (3) | 0.060 (2) | 0.0141 (18) | 0.0029 (17) | −0.014 (2) |
C20 | 0.066 (3) | 0.059 (2) | 0.102 (4) | 0.002 (2) | 0.032 (3) | 0.006 (2) |
C21 | 0.070 (3) | 0.078 (3) | 0.071 (3) | 0.010 (2) | 0.003 (2) | −0.006 (2) |
N6 | 0.121 (5) | 0.139 (5) | 0.132 (5) | 0.097 (5) | −0.024 (4) | −0.013 (4) |
C17 | 0.079 (4) | 0.095 (4) | 0.083 (3) | 0.052 (3) | −0.009 (3) | −0.007 (3) |
Geometric parameters (Å, º) top
Br1—C10 | 1.878 (3) | C6—C7 | 1.384 (5) |
S1—O2 | 1.504 (3) | C9—N4 | 1.352 (4) |
S1—C22 | 1.781 (5) | C5—C4 | 1.396 (5) |
S1—C21 | 1.778 (6) | C14—C13 | 1.495 (6) |
O1—C11 | 1.364 (4) | C14—C15 | 1.390 (6) |
O1—C12 | 1.407 (4) | C2—C1 | 1.439 (5) |
N5—C11 | 1.329 (4) | C2—C7 | 1.380 (5) |
N5—C8 | 1.338 (4) | C2—C3 | 1.391 (5) |
N3—C8 | 1.341 (4) | C19—C18 | 1.389 (5) |
N3—C9 | 1.339 (5) | C19—C20 | 1.512 (6) |
C11—C10 | 1.369 (4) | N1—C1 | 1.137 (5) |
C10—C9 | 1.406 (5) | C18—C16 | 1.386 (7) |
C8—N2 | 1.359 (4) | C16—C15 | 1.388 (7) |
C12—C14 | 1.385 (5) | C16—C17 | 1.436 (6) |
C12—C19 | 1.379 (5) | C3—C4 | 1.377 (5) |
N2—C5 | 1.400 (4) | N6—C17 | 1.139 (6) |
C6—C5 | 1.392 (4) | | |
| | | |
O2—S1—C22 | 106.2 (2) | C6—C5—N2 | 125.4 (3) |
O2—S1—C21 | 106.3 (2) | C6—C5—C4 | 118.6 (3) |
C21—S1—C22 | 96.6 (2) | C4—C5—N2 | 116.0 (3) |
C11—O1—C12 | 116.6 (2) | C12—C14—C13 | 121.8 (4) |
C11—N5—C8 | 115.0 (3) | C12—C14—C15 | 116.7 (4) |
C9—N3—C8 | 117.2 (3) | C15—C14—C13 | 121.5 (4) |
O1—C11—C10 | 117.5 (3) | C7—C2—C1 | 120.3 (3) |
N5—C11—O1 | 118.1 (3) | C7—C2—C3 | 119.1 (3) |
N5—C11—C10 | 124.4 (3) | C3—C2—C1 | 120.6 (3) |
C11—C10—Br1 | 122.3 (3) | C12—C19—C18 | 117.1 (4) |
C11—C10—C9 | 116.3 (3) | C12—C19—C20 | 121.2 (4) |
C9—C10—Br1 | 121.4 (2) | C18—C19—C20 | 121.7 (4) |
N5—C8—N3 | 126.4 (3) | C16—C18—C19 | 120.5 (4) |
N5—C8—N2 | 119.8 (3) | N1—C1—C2 | 178.2 (5) |
N3—C8—N2 | 113.8 (3) | C2—C7—C6 | 121.3 (3) |
C14—C12—O1 | 118.7 (3) | C18—C16—C15 | 120.5 (4) |
C19—C12—O1 | 116.6 (3) | C18—C16—C17 | 119.0 (5) |
C19—C12—C14 | 124.6 (3) | C15—C16—C17 | 120.4 (5) |
C8—N2—C5 | 130.9 (3) | C4—C3—C2 | 119.9 (3) |
C7—C6—C5 | 119.9 (3) | C3—C4—C5 | 121.2 (3) |
N3—C9—C10 | 120.7 (3) | C16—C15—C14 | 120.6 (4) |
N3—C9—N4 | 116.7 (3) | N6—C17—C16 | 179.3 (9) |
N4—C9—C10 | 122.6 (3) | | |
4-({6-Amino-5-bromo-2-[(4-cyanophenyl)amino]pyrimidin-4-yl}oxy)-3,5-dimethylbenzonitrile dimethylacetamide monosolvate (ETR-DMA)
top
Crystal data top
C20H15BrN6O·C4H9NO | Z = 2 |
Mr = 522.41 | F(000) = 536 |
Triclinic, P1 | Dx = 1.368 Mg m−3 |
a = 8.8344 (4) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 11.2114 (7) Å | Cell parameters from 3881 reflections |
c = 13.3205 (8) Å | θ = 3.4–71.2° |
α = 100.065 (5)° | µ = 2.49 mm−1 |
β = 98.949 (4)° | T = 293 K |
γ = 96.828 (4)° | Needle, colourless |
V = 1268.67 (13) Å3 | 0.15 × 0.02 × 0.01 mm |
Data collection top
Agilent SuperNova Dual Source diffractometer with an Eos detector | 4816 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 3796 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.034 |
Detector resolution: 16.4335 pixels mm-1 | θmax = 71.3°, θmin = 4.1° |
ω scans | h = −4→10 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = −13→12 |
Tmin = 0.642, Tmax = 1.000 | l = −16→16 |
7959 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters constrained |
wR(F2) = 0.155 | w = 1/[σ2(Fo2) + (0.085P)2 + 0.2663P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.002 |
4816 reflections | Δρmax = 0.57 e Å−3 |
312 parameters | Δρmin = −0.70 e Å−3 |
0 restraints | |
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. |
Refinement. Suitable single crystals were coated in inert oil (Paratone-N) and
mounted in the goniometer using a fine nyloon loop. The data collection was
acquired with a SuperNova diffractometer (tube operating at 50 kV and 0.8 mA),
equipped with dual microsources (Mo and Cu) using Cu Kα radiation, Eos CCD
detector at room temperature and CrysAlis PRO software (Rigaku, 2015). All
data were corrected for Lorentzian, polarization, and absorption effects. The
empirical absorption correction was accomplished using the multi-scan method
by spherical harmonics in the SCALE3 ABSPACK scaling algorithm (Rigaku, 2015).
The structures of ETR–DMA and ETR-oxalic were solved by SHELXT (Sheldrick,
2015) solution program with Intrinsic Phasing, ETR–DMSO1 was solved with
SHELXD (Sheldrick, 2008) by Dual Space, while the ETR–DMSO2 and ETR–Dioxane
were solved by SHELXS (Sheldrick, 2008) program using Direct Methods. The
structures were further refined with SHELXL (Sheldrick, 2015) refinement
package using least-squares minimization, which are implemented in Olex2
software (Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.99907 (4) | 0.15393 (4) | 0.22480 (3) | 0.07163 (19) | |
O1 | 0.6798 (2) | 0.1847 (2) | 0.12166 (16) | 0.0556 (6) | |
N3 | 0.8182 (3) | 0.4310 (2) | 0.3926 (2) | 0.0511 (6) | |
N5 | 0.6282 (3) | 0.3393 (2) | 0.24243 (19) | 0.0488 (6) | |
O2 | 1.3082 (3) | 0.2307 (3) | 0.4992 (2) | 0.0844 (8) | |
N4 | 1.0479 (3) | 0.3562 (3) | 0.4267 (2) | 0.0623 (8) | |
H4A | 1.071274 | 0.409270 | 0.483864 | 0.075* | |
H4B | 1.111176 | 0.306567 | 0.410349 | 0.075* | |
N2 | 0.5860 (3) | 0.5017 (3) | 0.3637 (2) | 0.0608 (7) | |
H2 | 0.626041 | 0.553981 | 0.419616 | 0.073* | |
C10 | 0.8685 (3) | 0.2659 (3) | 0.2696 (2) | 0.0469 (6) | |
C11 | 0.7253 (3) | 0.2649 (3) | 0.2131 (2) | 0.0454 (6) | |
C8 | 0.6799 (3) | 0.4203 (3) | 0.3305 (2) | 0.0483 (7) | |
C9 | 0.9129 (3) | 0.3510 (3) | 0.3631 (2) | 0.0482 (6) | |
C12 | 0.5276 (3) | 0.1827 (3) | 0.0695 (2) | 0.0494 (7) | |
C19 | 0.5028 (3) | 0.2582 (3) | −0.0007 (2) | 0.0533 (7) | |
C14 | 0.4140 (4) | 0.0976 (3) | 0.0885 (2) | 0.0515 (7) | |
C16 | 0.2341 (3) | 0.1677 (3) | −0.0348 (3) | 0.0545 (7) | |
C2 | 0.1335 (4) | 0.5484 (3) | 0.2485 (3) | 0.0593 (8) | |
N1 | −0.1493 (4) | 0.5759 (3) | 0.1854 (3) | 0.0834 (10) | |
C18 | 0.3510 (4) | 0.2514 (3) | −0.0524 (3) | 0.0548 (7) | |
H18 | 0.328358 | 0.302864 | −0.098515 | 0.066* | |
C15 | 0.2644 (4) | 0.0904 (3) | 0.0335 (2) | 0.0551 (7) | |
H15 | 0.184876 | 0.033406 | 0.042796 | 0.066* | |
C5 | 0.4341 (3) | 0.5128 (3) | 0.3204 (3) | 0.0540 (7) | |
N6 | −0.0466 (4) | 0.1526 (4) | −0.1336 (3) | 0.0902 (11) | |
C17 | 0.0774 (4) | 0.1599 (3) | −0.0905 (3) | 0.0663 (9) | |
C1 | −0.0243 (4) | 0.5639 (3) | 0.2121 (3) | 0.0664 (9) | |
C13 | 0.4490 (5) | 0.0183 (4) | 0.1664 (3) | 0.0725 (10) | |
H13A | 0.534184 | −0.023364 | 0.151542 | 0.109* | |
H13B | 0.359359 | −0.040889 | 0.162881 | 0.109* | |
H13C | 0.475735 | 0.068351 | 0.234721 | 0.109* | |
N7 | 1.2628 (5) | 0.0317 (4) | 0.5058 (3) | 0.0943 (12) | |
C4 | 0.3636 (4) | 0.5986 (4) | 0.3778 (3) | 0.0737 (11) | |
H4 | 0.417647 | 0.645123 | 0.440640 | 0.088* | |
C6 | 0.3510 (4) | 0.4434 (4) | 0.2278 (3) | 0.0704 (11) | |
H6 | 0.395377 | 0.383898 | 0.189505 | 0.085* | |
C7 | 0.2015 (4) | 0.4623 (4) | 0.1922 (3) | 0.0680 (10) | |
H7 | 0.146815 | 0.416150 | 0.129358 | 0.082* | |
C3 | 0.2146 (4) | 0.6149 (4) | 0.3422 (4) | 0.0800 (12) | |
H3 | 0.167889 | 0.671510 | 0.381877 | 0.096* | |
C20 | 0.6330 (5) | 0.3460 (4) | −0.0205 (4) | 0.0825 (12) | |
H20A | 0.671369 | 0.407889 | 0.040748 | 0.124* | |
H20B | 0.595291 | 0.383895 | −0.076785 | 0.124* | |
H20C | 0.715176 | 0.302054 | −0.037963 | 0.124* | |
C22 | 1.2772 (5) | 0.1462 (5) | 0.5473 (4) | 0.0835 (12) | |
C23 | 1.2883 (8) | 0.0000 (6) | 0.3988 (4) | 0.122 (2) | |
H23A | 1.317892 | 0.073575 | 0.374538 | 0.183* | |
H23B | 1.194429 | −0.044439 | 0.355373 | 0.183* | |
H23C | 1.369172 | −0.049979 | 0.396368 | 0.183* | |
C24 | 1.2238 (10) | −0.0699 (6) | 0.5572 (5) | 0.148 (3) | |
H24A | 1.213686 | −0.038105 | 0.627215 | 0.222* | |
H24B | 1.304527 | −0.120208 | 0.557705 | 0.222* | |
H24C | 1.127711 | −0.118148 | 0.520547 | 0.222* | |
C21 | 1.2543 (11) | 0.1796 (6) | 0.6572 (5) | 0.155 (3) | |
H21A | 1.350717 | 0.183476 | 0.703165 | 0.233* | |
H21B | 1.178285 | 0.118664 | 0.670685 | 0.233* | |
H21C | 1.219412 | 0.257895 | 0.668106 | 0.233* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0587 (2) | 0.0744 (3) | 0.0708 (3) | 0.03088 (19) | −0.00470 (18) | −0.01485 (19) |
O1 | 0.0432 (10) | 0.0617 (13) | 0.0484 (11) | 0.0165 (9) | −0.0081 (8) | −0.0167 (10) |
N3 | 0.0451 (12) | 0.0501 (14) | 0.0467 (13) | 0.0112 (10) | −0.0084 (10) | −0.0086 (11) |
N5 | 0.0406 (11) | 0.0488 (13) | 0.0466 (13) | 0.0083 (10) | −0.0050 (10) | −0.0083 (11) |
O2 | 0.0846 (19) | 0.0757 (19) | 0.087 (2) | 0.0142 (15) | −0.0097 (15) | 0.0198 (16) |
N4 | 0.0524 (14) | 0.0606 (16) | 0.0585 (16) | 0.0207 (12) | −0.0193 (12) | −0.0121 (13) |
N2 | 0.0489 (13) | 0.0621 (16) | 0.0549 (16) | 0.0178 (12) | −0.0114 (11) | −0.0209 (13) |
C10 | 0.0420 (13) | 0.0446 (15) | 0.0489 (15) | 0.0117 (11) | −0.0002 (12) | −0.0012 (12) |
C11 | 0.0429 (13) | 0.0452 (15) | 0.0415 (14) | 0.0069 (11) | 0.0003 (11) | −0.0032 (12) |
C8 | 0.0434 (14) | 0.0490 (16) | 0.0454 (15) | 0.0105 (12) | −0.0023 (11) | −0.0036 (12) |
C9 | 0.0426 (13) | 0.0464 (15) | 0.0492 (16) | 0.0089 (11) | −0.0044 (12) | 0.0015 (12) |
C12 | 0.0422 (13) | 0.0525 (17) | 0.0426 (15) | 0.0121 (12) | −0.0045 (11) | −0.0123 (12) |
C19 | 0.0482 (15) | 0.0544 (17) | 0.0489 (17) | 0.0052 (13) | 0.0009 (13) | −0.0035 (13) |
C14 | 0.0553 (16) | 0.0544 (17) | 0.0373 (14) | 0.0115 (13) | 0.0011 (12) | −0.0064 (12) |
C16 | 0.0451 (15) | 0.0541 (17) | 0.0536 (17) | 0.0073 (13) | −0.0042 (13) | −0.0068 (14) |
C2 | 0.0454 (15) | 0.0511 (17) | 0.080 (2) | 0.0126 (13) | 0.0038 (15) | 0.0114 (16) |
N1 | 0.0559 (17) | 0.068 (2) | 0.121 (3) | 0.0166 (15) | −0.0062 (18) | 0.020 (2) |
C18 | 0.0513 (16) | 0.0539 (18) | 0.0513 (17) | 0.0086 (13) | −0.0041 (13) | 0.0005 (14) |
C15 | 0.0483 (15) | 0.0565 (18) | 0.0513 (17) | 0.0033 (13) | 0.0025 (13) | −0.0051 (14) |
C5 | 0.0475 (15) | 0.0517 (17) | 0.0560 (18) | 0.0133 (13) | 0.0013 (13) | −0.0046 (14) |
N6 | 0.0551 (17) | 0.086 (2) | 0.116 (3) | 0.0072 (16) | −0.0149 (18) | 0.013 (2) |
C17 | 0.0509 (18) | 0.063 (2) | 0.076 (2) | 0.0090 (15) | −0.0050 (16) | 0.0028 (18) |
C1 | 0.0519 (18) | 0.0528 (19) | 0.093 (3) | 0.0140 (14) | 0.0013 (17) | 0.0169 (18) |
C13 | 0.081 (2) | 0.078 (3) | 0.055 (2) | 0.015 (2) | 0.0033 (18) | 0.0104 (18) |
N7 | 0.125 (3) | 0.080 (3) | 0.075 (2) | 0.017 (2) | 0.014 (2) | 0.008 (2) |
C4 | 0.0541 (18) | 0.072 (2) | 0.078 (2) | 0.0183 (17) | −0.0022 (17) | −0.0237 (19) |
C6 | 0.0554 (18) | 0.081 (2) | 0.061 (2) | 0.0296 (17) | −0.0085 (15) | −0.0195 (18) |
C7 | 0.0532 (17) | 0.077 (2) | 0.062 (2) | 0.0190 (16) | −0.0082 (15) | −0.0054 (18) |
C3 | 0.0563 (19) | 0.070 (2) | 0.099 (3) | 0.0219 (17) | 0.0014 (19) | −0.021 (2) |
C20 | 0.061 (2) | 0.085 (3) | 0.093 (3) | −0.010 (2) | −0.001 (2) | 0.023 (2) |
C22 | 0.078 (3) | 0.086 (3) | 0.078 (3) | 0.023 (2) | −0.003 (2) | 0.001 (2) |
C23 | 0.171 (6) | 0.126 (5) | 0.070 (3) | 0.048 (4) | 0.029 (3) | −0.004 (3) |
C24 | 0.245 (9) | 0.083 (4) | 0.112 (5) | −0.011 (5) | 0.030 (5) | 0.032 (3) |
C21 | 0.264 (10) | 0.112 (5) | 0.089 (4) | 0.032 (6) | 0.059 (5) | −0.010 (4) |
Geometric parameters (Å, º) top
Br1—C10 | 1.887 (3) | C14—C13 | 1.501 (5) |
O1—C11 | 1.353 (3) | C16—C18 | 1.387 (5) |
O1—C12 | 1.410 (3) | C16—C15 | 1.380 (5) |
N3—C8 | 1.344 (3) | C16—C17 | 1.450 (4) |
N3—C9 | 1.348 (4) | C2—C1 | 1.444 (4) |
N5—C11 | 1.321 (4) | C2—C7 | 1.372 (5) |
N5—C8 | 1.331 (4) | C2—C3 | 1.377 (5) |
O2—C22 | 1.260 (6) | N1—C1 | 1.138 (4) |
N4—C9 | 1.340 (4) | C5—C4 | 1.389 (5) |
N2—C8 | 1.368 (4) | C5—C6 | 1.383 (5) |
N2—C5 | 1.405 (4) | N6—C17 | 1.141 (5) |
C10—C11 | 1.366 (4) | N7—C22 | 1.289 (6) |
C10—C9 | 1.400 (4) | N7—C23 | 1.467 (6) |
C12—C19 | 1.376 (5) | N7—C24 | 1.463 (7) |
C12—C14 | 1.384 (5) | C4—C3 | 1.373 (5) |
C19—C18 | 1.395 (4) | C6—C7 | 1.386 (4) |
C19—C20 | 1.509 (5) | C22—C21 | 1.497 (7) |
C14—C15 | 1.394 (4) | | |
| | | |
C11—O1—C12 | 116.4 (2) | C15—C14—C13 | 121.2 (3) |
C8—N3—C9 | 116.6 (2) | C18—C16—C17 | 119.4 (3) |
C11—N5—C8 | 115.8 (2) | C15—C16—C18 | 121.3 (3) |
C8—N2—C5 | 129.8 (3) | C15—C16—C17 | 119.4 (3) |
C11—C10—Br1 | 121.2 (2) | C7—C2—C1 | 120.0 (3) |
C11—C10—C9 | 117.5 (3) | C7—C2—C3 | 119.2 (3) |
C9—C10—Br1 | 121.4 (2) | C3—C2—C1 | 120.8 (3) |
O1—C11—C10 | 118.8 (2) | C16—C18—C19 | 119.9 (3) |
N5—C11—O1 | 117.8 (2) | C16—C15—C14 | 120.1 (3) |
N5—C11—C10 | 123.4 (3) | C4—C5—N2 | 116.2 (3) |
N3—C8—N2 | 115.0 (2) | C6—C5—N2 | 124.9 (3) |
N5—C8—N3 | 126.4 (3) | C6—C5—C4 | 118.9 (3) |
N5—C8—N2 | 118.6 (2) | N6—C17—C16 | 179.0 (5) |
N3—C9—C10 | 120.1 (2) | N1—C1—C2 | 178.5 (5) |
N4—C9—N3 | 117.5 (3) | C22—N7—C23 | 117.8 (5) |
N4—C9—C10 | 122.4 (3) | C22—N7—C24 | 125.2 (5) |
C19—C12—O1 | 119.0 (3) | C24—N7—C23 | 117.0 (5) |
C19—C12—C14 | 124.5 (3) | C3—C4—C5 | 120.4 (3) |
C14—C12—O1 | 116.4 (3) | C5—C6—C7 | 120.1 (3) |
C12—C19—C18 | 117.1 (3) | C2—C7—C6 | 120.7 (3) |
C12—C19—C20 | 121.8 (3) | C4—C3—C2 | 120.8 (3) |
C18—C19—C20 | 121.0 (3) | O2—C22—N7 | 122.8 (5) |
C12—C14—C15 | 117.1 (3) | O2—C22—C21 | 118.9 (5) |
C12—C14—C13 | 121.7 (3) | N7—C22—C21 | 118.2 (5) |
4-({6-Amino-5-bromo-2-[(4-cyanophenyl)amino]pyrimidin-4-yl}oxy)-3,5-dimethylbenzonitrile 1,4-dioxane 0.75-solvate (ETR-Dioxan)
top
Crystal data top
C20H15BrN6O·0.75C4H8O2 | F(000) = 2048 |
Mr = 501.37 | Dx = 1.438 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 8.7721 (1) Å | Cell parameters from 6939 reflections |
b = 22.3659 (4) Å | θ = 3.8–71.2° |
c = 23.6458 (6) Å | µ = 2.71 mm−1 |
β = 93.364 (2)° | T = 293 K |
V = 4631.21 (15) Å3 | Plate, colourless |
Z = 8 | 0.16 × 0.09 × 0.01 mm |
Data collection top
Agilent SuperNova Dual Source diffractometer with an Eos detector | 8738 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 6403 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.038 |
Detector resolution: 16.4335 pixels mm-1 | θmax = 71.6°, θmin = 3.8° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = −22→27 |
Tmin = 0.235, Tmax = 1.000 | l = −28→20 |
16860 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0323P)2 + 7.2848P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.003 |
8738 reflections | Δρmax = 0.53 e Å−3 |
590 parameters | Δρmin = −0.58 e Å−3 |
0 restraints | |
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. |
Refinement. Suitable single crystals were coated in inert oil (Paratone-N) and
mounted in the goniometer using a fine nyloon loop. The data collection was
acquired with a SuperNova diffractometer (tube operating at 50 kV and 0.8 mA),
equipped with dual microsources (Mo and Cu) using Cu Kα radiation, Eos CCD
detector at room temperature and CrysAlis PRO software (Rigaku, 2015). All
data were corrected for Lorentzian, polarization, and absorption effects. The
empirical absorption correction was accomplished using the multi-scan method
by spherical harmonics in the SCALE3 ABSPACK scaling algorithm (Rigaku, 2015).
The structures of ETR–DMA and ETR-oxalic were solved by SHELXT (Sheldrick,
2015) solution program with Intrinsic Phasing, ETR–DMSO1 was solved with
SHELXD (Sheldrick, 2008) by Dual Space, while the ETR–DMSO2 and ETR–Dioxane
were solved by SHELXS (Sheldrick, 2008) program using Direct Methods. The
structures were further refined with SHELXL (Sheldrick, 2015) refinement
package using least-squares minimization, which are implemented in Olex2
software (Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1B | 0.28181 (5) | 0.43494 (2) | 0.23068 (2) | 0.06270 (16) | |
Br1A | 0.20258 (6) | 0.84723 (2) | 0.00872 (3) | 0.0797 (2) | |
O1A | −0.0947 (3) | 0.85388 (11) | −0.06322 (13) | 0.0528 (7) | |
N3A | −0.0297 (3) | 0.68709 (14) | 0.00298 (14) | 0.0448 (8) | |
N5B | 0.6974 (3) | 0.36134 (14) | 0.28047 (14) | 0.0459 (8) | |
O1B | 0.6072 (3) | 0.45831 (12) | 0.27755 (13) | 0.0547 (7) | |
C12A | −0.2250 (4) | 0.86093 (16) | −0.09930 (18) | 0.0444 (9) | |
C9A | 0.0762 (4) | 0.72990 (18) | 0.01507 (17) | 0.0445 (9) | |
C16A | −0.4791 (4) | 0.87437 (18) | −0.16950 (18) | 0.0484 (10) | |
N5A | −0.1782 (3) | 0.75726 (14) | −0.05312 (14) | 0.0425 (7) | |
N3B | 0.5402 (3) | 0.28129 (15) | 0.24391 (15) | 0.0510 (8) | |
N2A | −0.2536 (3) | 0.65868 (14) | −0.04259 (15) | 0.0488 (8) | |
H2A | −0.223270 | 0.623259 | −0.033315 | 0.059* | |
C11B | 0.5830 (4) | 0.39851 (17) | 0.26768 (16) | 0.0425 (9) | |
C8B | 0.6669 (4) | 0.30423 (18) | 0.26858 (17) | 0.0459 (9) | |
C10B | 0.4437 (4) | 0.38070 (18) | 0.24502 (17) | 0.0434 (9) | |
C8A | −0.1496 (4) | 0.70364 (16) | −0.03024 (16) | 0.0411 (8) | |
N4A | 0.1971 (4) | 0.71433 (16) | 0.04834 (15) | 0.0581 (10) | |
H4AA | 0.205336 | 0.678403 | 0.061123 | 0.070* | |
H4AB | 0.267160 | 0.740186 | 0.057079 | 0.070* | |
O2 | 0.2863 (3) | 0.59495 (15) | 0.08574 (13) | 0.0672 (9) | |
C5B | 0.9215 (4) | 0.26712 (19) | 0.31020 (17) | 0.0477 (9) | |
C11A | −0.0728 (4) | 0.79803 (16) | −0.04052 (16) | 0.0415 (9) | |
C2A | −0.6993 (4) | 0.66099 (19) | −0.11478 (17) | 0.0457 (9) | |
N2B | 0.7769 (4) | 0.26191 (15) | 0.28298 (16) | 0.0574 (10) | |
H2B | 0.751709 | 0.225964 | 0.273479 | 0.069* | |
C4A | −0.4667 (4) | 0.60989 (17) | −0.08897 (17) | 0.0450 (9) | |
H4A | −0.409906 | 0.574748 | −0.087585 | 0.054* | |
C10A | 0.0566 (4) | 0.78749 (17) | −0.00720 (17) | 0.0452 (9) | |
C19B | 0.8665 (4) | 0.49181 (18) | 0.28596 (17) | 0.0472 (9) | |
N1A | −0.9777 (4) | 0.6611 (2) | −0.15632 (19) | 0.0796 (13) | |
C19A | −0.3594 (5) | 0.87846 (17) | −0.07561 (18) | 0.0478 (9) | |
N4B | 0.2986 (4) | 0.29813 (17) | 0.20503 (16) | 0.0640 (11) | |
H4BA | 0.291772 | 0.260615 | 0.197302 | 0.077* | |
H4BB | 0.223307 | 0.321581 | 0.196087 | 0.077* | |
N6B | 1.2369 (5) | 0.51967 (19) | 0.44185 (18) | 0.0702 (11) | |
C5A | −0.4007 (4) | 0.66224 (16) | −0.06791 (16) | 0.0400 (8) | |
C16B | 0.9909 (4) | 0.50108 (17) | 0.37911 (17) | 0.0460 (9) | |
C15B | 0.8575 (5) | 0.48390 (18) | 0.40365 (18) | 0.0510 (10) | |
H15B | 0.855212 | 0.481972 | 0.442877 | 0.061* | |
C17B | 1.1272 (5) | 0.51245 (19) | 0.41416 (19) | 0.0538 (10) | |
C2B | 1.2134 (5) | 0.2670 (2) | 0.36269 (19) | 0.0597 (12) | |
C7A | −0.6346 (4) | 0.71352 (19) | −0.0936 (2) | 0.0579 (12) | |
H7A | −0.691676 | 0.748592 | −0.095061 | 0.069* | |
C18A | −0.4879 (4) | 0.88475 (18) | −0.11232 (19) | 0.0501 (10) | |
H18A | −0.580389 | 0.896027 | −0.098234 | 0.060* | |
C6B | 0.9958 (5) | 0.3203 (2) | 0.3229 (2) | 0.0719 (15) | |
H6B | 0.947802 | 0.356467 | 0.314025 | 0.086* | |
C12B | 0.7379 (4) | 0.47276 (16) | 0.31203 (18) | 0.0454 (9) | |
C15A | −0.3417 (5) | 0.85902 (18) | −0.19182 (18) | 0.0506 (10) | |
H15A | −0.337048 | 0.853551 | −0.230674 | 0.061* | |
C18B | 0.9937 (4) | 0.50591 (18) | 0.32072 (18) | 0.0488 (10) | |
H18B | 1.082250 | 0.518819 | 0.304723 | 0.059* | |
C14B | 0.7284 (4) | 0.46970 (17) | 0.37020 (18) | 0.0476 (9) | |
C4B | 0.9942 (5) | 0.2138 (2) | 0.32481 (19) | 0.0581 (11) | |
H4B | 0.944516 | 0.177666 | 0.317193 | 0.070* | |
C9B | 0.4268 (4) | 0.32009 (19) | 0.23107 (17) | 0.0471 (9) | |
C14A | −0.2117 (4) | 0.85181 (17) | −0.15656 (18) | 0.0465 (9) | |
C6A | −0.4876 (4) | 0.71447 (18) | −0.0705 (2) | 0.0559 (11) | |
H6A | −0.445692 | 0.750063 | −0.056412 | 0.067* | |
C7B | 1.1411 (5) | 0.3201 (2) | 0.3488 (2) | 0.0739 (15) | |
H7B | 1.190618 | 0.356083 | 0.356903 | 0.089* | |
C17A | −0.6164 (5) | 0.8782 (2) | −0.2063 (2) | 0.0588 (11) | |
C13A | −0.0619 (5) | 0.8331 (2) | −0.1787 (2) | 0.0717 (14) | |
H13D | 0.018106 | 0.858212 | −0.162556 | 0.108* | |
H13E | −0.066892 | 0.837015 | −0.219202 | 0.108* | |
H13F | −0.041264 | 0.792270 | −0.168503 | 0.108* | |
C3A | −0.6140 (4) | 0.60890 (18) | −0.11181 (17) | 0.0485 (10) | |
H3A | −0.656645 | 0.573209 | −0.125310 | 0.058* | |
C1B | 1.3681 (6) | 0.2672 (2) | 0.3876 (2) | 0.0780 (16) | |
C6 | 0.3881 (6) | 0.5797 (3) | 0.0438 (2) | 0.0792 (16) | |
H6C | 0.365711 | 0.603841 | 0.010268 | 0.095* | |
H6D | 0.373627 | 0.538032 | 0.033313 | 0.095* | |
N6A | −0.7258 (5) | 0.8799 (2) | −0.23454 (18) | 0.0786 (13) | |
N1B | 1.4888 (5) | 0.2660 (3) | 0.4069 (2) | 0.113 (2) | |
C13B | 0.5836 (5) | 0.4505 (2) | 0.3960 (2) | 0.0703 (14) | |
H13A | 0.572441 | 0.407948 | 0.392570 | 0.105* | |
H13B | 0.497944 | 0.469828 | 0.376511 | 0.105* | |
H13C | 0.587814 | 0.461529 | 0.435266 | 0.105* | |
C3B | 1.1391 (5) | 0.2138 (2) | 0.3504 (2) | 0.0656 (13) | |
H3B | 1.187219 | 0.177680 | 0.359570 | 0.079* | |
C20B | 0.8708 (5) | 0.4958 (3) | 0.22233 (19) | 0.0737 (14) | |
H20A | 0.878473 | 0.456375 | 0.206773 | 0.110* | |
H20B | 0.957608 | 0.519086 | 0.212763 | 0.110* | |
H20C | 0.779027 | 0.514604 | 0.206985 | 0.110* | |
C1A | −0.8553 (5) | 0.6609 (2) | −0.13833 (19) | 0.0571 (11) | |
O3 | 0.5833 (4) | 0.5561 (2) | 0.11432 (17) | 0.1089 (16) | |
C3 | 0.3209 (6) | 0.5622 (2) | 0.1354 (2) | 0.0704 (14) | |
H3C | 0.305161 | 0.519959 | 0.127906 | 0.085* | |
H3D | 0.252886 | 0.574156 | 0.164278 | 0.085* | |
C4 | 0.4808 (6) | 0.5724 (3) | 0.1563 (2) | 0.096 (2) | |
H4C | 0.495018 | 0.614265 | 0.165947 | 0.115* | |
H4D | 0.503020 | 0.548942 | 0.190279 | 0.115* | |
C5 | 0.5468 (6) | 0.5892 (3) | 0.0642 (2) | 0.0886 (19) | |
H5A | 0.614022 | 0.577173 | 0.035110 | 0.106* | |
H5B | 0.563381 | 0.631398 | 0.071729 | 0.106* | |
C20A | −0.3673 (6) | 0.8877 (2) | −0.0131 (2) | 0.0727 (14) | |
H20D | −0.372486 | 0.849597 | 0.005376 | 0.109* | |
H20E | −0.456622 | 0.910643 | −0.005965 | 0.109* | |
H20F | −0.277898 | 0.908750 | 0.001285 | 0.109* | |
O1 | 0.1284 (3) | 0.46292 (14) | 0.01220 (15) | 0.0664 (9) | |
C1 | 0.0707 (6) | 0.4738 (2) | −0.0444 (2) | 0.0750 (15) | |
H1A | −0.002189 | 0.442904 | −0.056020 | 0.090* | |
H1B | 0.153800 | 0.472487 | −0.069717 | 0.090* | |
C2 | 0.0056 (5) | 0.4661 (2) | 0.0486 (2) | 0.0743 (14) | |
H2C | 0.043845 | 0.459204 | 0.087413 | 0.089* | |
H2D | −0.068346 | 0.435156 | 0.038443 | 0.089* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1B | 0.0341 (2) | 0.0604 (3) | 0.0919 (4) | 0.0118 (2) | −0.0107 (2) | 0.0097 (3) |
Br1A | 0.0521 (3) | 0.0548 (3) | 0.1273 (5) | −0.0198 (2) | −0.0365 (3) | 0.0045 (3) |
O1A | 0.0373 (14) | 0.0385 (14) | 0.080 (2) | −0.0072 (11) | −0.0202 (14) | 0.0106 (14) |
N3A | 0.0313 (16) | 0.0430 (17) | 0.058 (2) | −0.0041 (13) | −0.0115 (15) | 0.0074 (15) |
N5B | 0.0306 (16) | 0.0429 (18) | 0.063 (2) | 0.0035 (13) | −0.0101 (15) | 0.0000 (15) |
O1B | 0.0333 (14) | 0.0432 (15) | 0.085 (2) | 0.0033 (12) | −0.0194 (14) | 0.0018 (14) |
C12A | 0.0328 (19) | 0.0302 (18) | 0.069 (3) | −0.0031 (14) | −0.0065 (18) | 0.0050 (17) |
C9A | 0.0290 (18) | 0.050 (2) | 0.054 (2) | −0.0020 (16) | −0.0068 (17) | 0.0001 (18) |
C16A | 0.039 (2) | 0.046 (2) | 0.060 (3) | 0.0013 (17) | −0.0018 (19) | 0.0072 (19) |
N5A | 0.0274 (15) | 0.0397 (17) | 0.059 (2) | −0.0041 (12) | −0.0118 (14) | 0.0048 (15) |
N3B | 0.0333 (17) | 0.0472 (19) | 0.070 (2) | 0.0045 (14) | −0.0179 (16) | −0.0013 (17) |
N2A | 0.0284 (16) | 0.0362 (16) | 0.080 (2) | −0.0023 (13) | −0.0148 (16) | 0.0087 (16) |
C11B | 0.0304 (18) | 0.046 (2) | 0.050 (2) | 0.0005 (16) | −0.0050 (16) | 0.0038 (18) |
C8B | 0.0304 (19) | 0.050 (2) | 0.056 (2) | 0.0038 (16) | −0.0134 (17) | 0.0019 (19) |
C10B | 0.0276 (18) | 0.048 (2) | 0.054 (2) | 0.0073 (15) | −0.0045 (16) | 0.0075 (18) |
C8A | 0.0273 (18) | 0.040 (2) | 0.055 (2) | −0.0035 (15) | −0.0054 (16) | 0.0014 (17) |
N4A | 0.0368 (18) | 0.058 (2) | 0.076 (3) | −0.0066 (16) | −0.0256 (17) | 0.0118 (19) |
O2 | 0.0536 (18) | 0.079 (2) | 0.069 (2) | 0.0129 (16) | 0.0032 (15) | 0.0186 (17) |
C5B | 0.034 (2) | 0.052 (2) | 0.056 (3) | 0.0082 (17) | −0.0083 (18) | −0.0028 (19) |
C11A | 0.0301 (18) | 0.0389 (19) | 0.055 (2) | −0.0005 (15) | −0.0035 (17) | 0.0034 (17) |
C2A | 0.0282 (18) | 0.055 (2) | 0.052 (2) | −0.0034 (16) | −0.0079 (17) | 0.0021 (19) |
N2B | 0.0348 (17) | 0.0440 (19) | 0.090 (3) | 0.0070 (15) | −0.0242 (18) | −0.0066 (18) |
C4A | 0.038 (2) | 0.038 (2) | 0.058 (2) | 0.0001 (16) | −0.0061 (18) | −0.0020 (18) |
C10A | 0.0340 (19) | 0.040 (2) | 0.060 (3) | −0.0086 (16) | −0.0087 (18) | −0.0016 (18) |
C19B | 0.038 (2) | 0.049 (2) | 0.054 (2) | 0.0017 (17) | −0.0022 (18) | −0.0029 (19) |
N1A | 0.043 (2) | 0.095 (3) | 0.097 (3) | 0.004 (2) | −0.031 (2) | −0.005 (3) |
C19A | 0.046 (2) | 0.038 (2) | 0.059 (3) | −0.0025 (17) | 0.0024 (19) | −0.0035 (18) |
N4B | 0.0366 (19) | 0.056 (2) | 0.096 (3) | 0.0004 (16) | −0.0268 (19) | −0.004 (2) |
N6B | 0.059 (2) | 0.070 (3) | 0.080 (3) | −0.009 (2) | −0.013 (2) | −0.007 (2) |
C5A | 0.0285 (18) | 0.041 (2) | 0.050 (2) | −0.0035 (15) | −0.0037 (16) | 0.0032 (17) |
C16B | 0.043 (2) | 0.038 (2) | 0.057 (3) | 0.0000 (16) | −0.0005 (18) | −0.0043 (18) |
C15B | 0.054 (2) | 0.046 (2) | 0.053 (2) | −0.0012 (19) | 0.006 (2) | 0.0003 (19) |
C17B | 0.048 (2) | 0.048 (2) | 0.066 (3) | −0.0049 (19) | −0.001 (2) | −0.007 (2) |
C2B | 0.040 (2) | 0.071 (3) | 0.066 (3) | 0.012 (2) | −0.020 (2) | −0.003 (2) |
C7A | 0.033 (2) | 0.047 (2) | 0.093 (3) | 0.0060 (17) | −0.008 (2) | −0.001 (2) |
C18A | 0.034 (2) | 0.045 (2) | 0.071 (3) | 0.0065 (17) | 0.0040 (19) | 0.000 (2) |
C6B | 0.046 (3) | 0.051 (3) | 0.115 (4) | 0.006 (2) | −0.030 (3) | 0.003 (3) |
C12B | 0.036 (2) | 0.0335 (19) | 0.066 (3) | 0.0030 (15) | −0.0032 (18) | −0.0009 (18) |
C15A | 0.048 (2) | 0.052 (2) | 0.053 (2) | 0.0007 (18) | 0.0048 (19) | 0.0033 (19) |
C18B | 0.036 (2) | 0.046 (2) | 0.065 (3) | −0.0026 (17) | 0.0065 (19) | −0.0026 (19) |
C14B | 0.039 (2) | 0.039 (2) | 0.065 (3) | 0.0000 (16) | 0.0056 (19) | 0.0043 (19) |
C4B | 0.047 (2) | 0.051 (2) | 0.074 (3) | 0.0090 (19) | −0.018 (2) | −0.001 (2) |
C9B | 0.0321 (19) | 0.055 (2) | 0.052 (2) | −0.0023 (17) | −0.0085 (17) | 0.0024 (19) |
C14A | 0.034 (2) | 0.041 (2) | 0.065 (3) | 0.0008 (16) | 0.0059 (18) | 0.0043 (19) |
C6A | 0.033 (2) | 0.039 (2) | 0.094 (3) | −0.0031 (16) | −0.011 (2) | −0.007 (2) |
C7B | 0.047 (3) | 0.062 (3) | 0.108 (4) | 0.001 (2) | −0.032 (3) | −0.006 (3) |
C17A | 0.043 (2) | 0.065 (3) | 0.068 (3) | 0.001 (2) | 0.000 (2) | 0.011 (2) |
C13A | 0.046 (3) | 0.073 (3) | 0.097 (4) | 0.004 (2) | 0.018 (2) | −0.004 (3) |
C3A | 0.043 (2) | 0.047 (2) | 0.054 (2) | −0.0059 (18) | −0.0080 (18) | −0.0047 (19) |
C1B | 0.055 (3) | 0.079 (4) | 0.095 (4) | 0.018 (3) | −0.033 (3) | −0.011 (3) |
C6 | 0.071 (3) | 0.105 (5) | 0.063 (3) | 0.013 (3) | 0.006 (3) | 0.012 (3) |
N6A | 0.047 (2) | 0.106 (4) | 0.081 (3) | −0.001 (2) | −0.011 (2) | 0.018 (3) |
N1B | 0.062 (3) | 0.115 (4) | 0.154 (5) | 0.025 (3) | −0.062 (3) | −0.020 (4) |
C13B | 0.050 (3) | 0.072 (3) | 0.090 (4) | −0.006 (2) | 0.017 (2) | 0.011 (3) |
C3B | 0.055 (3) | 0.064 (3) | 0.076 (3) | 0.021 (2) | −0.018 (2) | 0.002 (2) |
C20B | 0.058 (3) | 0.104 (4) | 0.058 (3) | −0.005 (3) | −0.004 (2) | 0.002 (3) |
C1A | 0.041 (2) | 0.062 (3) | 0.066 (3) | −0.001 (2) | −0.012 (2) | −0.003 (2) |
O3 | 0.064 (2) | 0.180 (5) | 0.083 (3) | 0.047 (3) | 0.007 (2) | 0.034 (3) |
C3 | 0.067 (3) | 0.079 (3) | 0.065 (3) | 0.012 (3) | 0.006 (2) | 0.014 (3) |
C4 | 0.070 (4) | 0.159 (6) | 0.058 (3) | 0.021 (4) | 0.000 (3) | 0.015 (4) |
C5 | 0.061 (3) | 0.131 (5) | 0.075 (4) | 0.016 (3) | 0.015 (3) | 0.026 (4) |
C20A | 0.064 (3) | 0.086 (4) | 0.068 (3) | 0.001 (3) | 0.001 (2) | −0.013 (3) |
O1 | 0.0391 (16) | 0.0557 (18) | 0.103 (3) | 0.0099 (14) | −0.0052 (16) | 0.0131 (17) |
C1 | 0.054 (3) | 0.076 (4) | 0.095 (4) | 0.016 (3) | 0.002 (3) | 0.009 (3) |
C2 | 0.057 (3) | 0.070 (3) | 0.095 (4) | 0.009 (2) | 0.003 (3) | 0.026 (3) |
Geometric parameters (Å, º) top
Br1B—C10B | 1.883 (3) | C4A—C5A | 1.385 (5) |
Br1A—C10A | 1.874 (4) | C4A—C3A | 1.372 (5) |
O1A—C12A | 1.395 (4) | C19B—C12B | 1.384 (5) |
O1A—C11A | 1.369 (4) | C19B—C18B | 1.382 (5) |
N3A—C9A | 1.353 (5) | C19B—C20B | 1.510 (6) |
N3A—C8A | 1.328 (4) | N1A—C1A | 1.132 (5) |
N5B—C11B | 1.324 (4) | C19A—C18A | 1.389 (6) |
N5B—C8B | 1.332 (5) | C19A—C20A | 1.498 (6) |
O1B—C11B | 1.372 (4) | N4B—C9B | 1.343 (5) |
O1B—C12B | 1.405 (4) | N6B—C17B | 1.143 (5) |
C12A—C19A | 1.390 (5) | C5A—C6A | 1.394 (5) |
C12A—C14A | 1.381 (6) | C16B—C15B | 1.391 (5) |
C9A—N4A | 1.330 (5) | C16B—C17B | 1.437 (6) |
C9A—C10A | 1.398 (5) | C16B—C18B | 1.386 (5) |
C16A—C18A | 1.379 (6) | C15B—C14B | 1.380 (6) |
C16A—C15A | 1.387 (5) | C2B—C7B | 1.376 (6) |
C16A—C17A | 1.446 (6) | C2B—C1B | 1.447 (6) |
N5A—C8A | 1.333 (5) | C2B—C3B | 1.380 (6) |
N5A—C11A | 1.320 (4) | C7A—C6A | 1.371 (5) |
N3B—C8B | 1.328 (5) | C6B—C7B | 1.381 (6) |
N3B—C9B | 1.341 (5) | C12B—C14B | 1.384 (6) |
N2A—C8A | 1.377 (4) | C15A—C14A | 1.382 (6) |
N2A—C5A | 1.393 (4) | C14B—C13B | 1.503 (5) |
C11B—C10B | 1.365 (5) | C4B—C3B | 1.376 (6) |
C8B—N2B | 1.380 (5) | C14A—C13A | 1.502 (5) |
C10B—C9B | 1.401 (6) | C17A—N6A | 1.137 (5) |
O2—C6 | 1.415 (6) | C1B—N1B | 1.129 (6) |
O2—C3 | 1.402 (5) | C6—C5 | 1.462 (7) |
C5B—N2B | 1.393 (5) | O3—C4 | 1.425 (6) |
C5B—C6B | 1.381 (6) | O3—C5 | 1.418 (6) |
C5B—C4B | 1.387 (5) | C3—C4 | 1.477 (7) |
C11A—C10A | 1.364 (5) | O1—C1 | 1.425 (6) |
C2A—C7A | 1.386 (5) | O1—C2 | 1.420 (6) |
C2A—C3A | 1.384 (5) | C1—C2i | 1.501 (6) |
C2A—C1A | 1.446 (5) | | |
| | | |
C11A—O1A—C12A | 115.7 (3) | C18A—C19A—C12A | 116.9 (4) |
C8A—N3A—C9A | 116.0 (3) | C18A—C19A—C20A | 121.3 (4) |
C11B—N5B—C8B | 114.5 (3) | N2A—C5A—C6A | 123.8 (3) |
C11B—O1B—C12B | 115.8 (3) | C4A—C5A—N2A | 117.6 (3) |
C19A—C12A—O1A | 118.0 (4) | C4A—C5A—C6A | 118.5 (3) |
C14A—C12A—O1A | 118.0 (3) | C15B—C16B—C17B | 120.0 (4) |
C14A—C12A—C19A | 124.0 (4) | C18B—C16B—C15B | 120.1 (4) |
N3A—C9A—C10A | 120.3 (3) | C18B—C16B—C17B | 119.9 (4) |
N4A—C9A—N3A | 117.0 (4) | C14B—C15B—C16B | 120.5 (4) |
N4A—C9A—C10A | 122.7 (4) | N6B—C17B—C16B | 177.9 (5) |
C18A—C16A—C15A | 121.0 (4) | C7B—C2B—C1B | 120.1 (5) |
C18A—C16A—C17A | 119.2 (4) | C7B—C2B—C3B | 119.3 (4) |
C15A—C16A—C17A | 119.8 (4) | C3B—C2B—C1B | 120.6 (4) |
C11A—N5A—C8A | 114.6 (3) | C6A—C7A—C2A | 120.9 (4) |
C8B—N3B—C9B | 116.1 (3) | C16A—C18A—C19A | 120.4 (4) |
C8A—N2A—C5A | 129.4 (3) | C7B—C6B—C5B | 120.3 (4) |
N5B—C11B—O1B | 117.7 (3) | C19B—C12B—O1B | 118.1 (4) |
N5B—C11B—C10B | 123.7 (4) | C19B—C12B—C14B | 123.8 (4) |
C10B—C11B—O1B | 118.5 (3) | C14B—C12B—O1B | 118.1 (3) |
N5B—C8B—N2B | 118.5 (3) | C14A—C15A—C16A | 120.3 (4) |
N3B—C8B—N5B | 128.0 (3) | C19B—C18B—C16B | 120.9 (4) |
N3B—C8B—N2B | 113.5 (4) | C15B—C14B—C12B | 117.6 (4) |
C11B—C10B—Br1B | 122.1 (3) | C15B—C14B—C13B | 121.2 (4) |
C11B—C10B—C9B | 117.0 (3) | C12B—C14B—C13B | 121.2 (4) |
C9B—C10B—Br1B | 120.9 (3) | C3B—C4B—C5B | 120.6 (4) |
N3A—C8A—N5A | 127.9 (3) | N3B—C9B—C10B | 120.4 (3) |
N3A—C8A—N2A | 114.4 (3) | N3B—C9B—N4B | 117.2 (4) |
N5A—C8A—N2A | 117.6 (3) | N4B—C9B—C10B | 122.4 (4) |
C3—O2—C6 | 110.3 (4) | C12A—C14A—C15A | 117.4 (4) |
C6B—C5B—N2B | 125.3 (4) | C12A—C14A—C13A | 120.6 (4) |
C6B—C5B—C4B | 118.9 (4) | C15A—C14A—C13A | 122.0 (4) |
C4B—C5B—N2B | 115.8 (4) | C7A—C6A—C5A | 120.2 (4) |
N5A—C11A—O1A | 117.5 (3) | C2B—C7B—C6B | 120.6 (5) |
N5A—C11A—C10A | 124.0 (3) | N6A—C17A—C16A | 178.2 (5) |
C10A—C11A—O1A | 118.5 (3) | C4A—C3A—C2A | 120.0 (4) |
C7A—C2A—C1A | 119.9 (4) | N1B—C1B—C2B | 178.4 (6) |
C3A—C2A—C7A | 119.1 (3) | O2—C6—C5 | 111.2 (4) |
C3A—C2A—C1A | 120.9 (4) | C4B—C3B—C2B | 120.3 (4) |
C8B—N2B—C5B | 131.4 (4) | N1A—C1A—C2A | 179.3 (6) |
C3A—C4A—C5A | 121.3 (4) | C5—O3—C4 | 109.1 (4) |
C9A—C10A—Br1A | 120.9 (3) | O2—C3—C4 | 110.7 (4) |
C11A—C10A—Br1A | 121.9 (3) | O3—C4—C3 | 110.7 (5) |
C11A—C10A—C9A | 117.2 (3) | O3—C5—C6 | 111.3 (5) |
C12B—C19B—C20B | 122.0 (4) | C2—O1—C1 | 108.7 (3) |
C18B—C19B—C12B | 117.1 (4) | O1—C1—C2i | 110.3 (4) |
C18B—C19B—C20B | 120.8 (4) | O1—C2—C1i | 110.9 (4) |
C12A—C19A—C20A | 121.7 (4) | | |
Symmetry code: (i) −x, −y+1, −z. |
6-Amino-5-bromo-4-(4-cyano-2,6-dimethylphenoxy)-2-[(4-cyanophenyl)amino]pyrimidin-1-ium hemioxalate (ETR-Oxalic)
top
Crystal data top
C20H16BrN6O2+·0.5C2O42− | F(000) = 1944 |
Mr = 480.31 | Dx = 1.532 Mg m−3 |
Monoclinic, I2/a | Mo Kα radiation, λ = 0.71073 Å |
a = 15.5664 (6) Å | Cell parameters from 4815 reflections |
b = 15.3769 (7) Å | θ = 3.8–28.1° |
c = 18.4445 (8) Å | µ = 2.01 mm−1 |
β = 109.359 (4)° | T = 293 K |
V = 4165.3 (3) Å3 | Plate, colourless |
Z = 8 | 0.3 × 0.1 × 0.01 mm |
Data collection top
Rigaku OD SuperNova Dual source diffractometer with an Eos detector | 4747 independent reflections |
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source | 3352 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.033 |
Detector resolution: 16.4335 pixels mm-1 | θmax = 28.8°, θmin = 2.9° |
ω scans | h = −19→19 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2019) | k = −13→20 |
Tmin = 0.382, Tmax = 1.000 | l = −24→24 |
10364 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.88 | (Δ/σ)max = 0.005 |
4747 reflections | Δρmax = 0.53 e Å−3 |
282 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | |
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. |
Refinement. Suitable single crystals were coated in inert oil (Paratone-N) and
mounted in the goniometer using a fine nyloon loop. The data collection was
acquired with a SuperNova diffractometer (tube operating at 50 kV and 0.8 mA),
equipped with dual microsources (Mo and Cu) using Cu Kα radiation, Eos CCD
detector at room temperature and CrysAlis PRO software (Rigaku, 2015). All
data were corrected for Lorentzian, polarization, and absorption effects. The
empirical absorption correction was accomplished using the multi-scan method
by spherical harmonics in the SCALE3 ABSPACK scaling algorithm (Rigaku, 2015).
The structures of ETR–DMA and ETR-oxalic were solved by SHELXT (Sheldrick,
2015) solution program with Intrinsic Phasing, ETR–DMSO1 was solved with
SHELXD (Sheldrick, 2008) by Dual Space, while the ETR–DMSO2 and ETR–Dioxane
were solved by SHELXS (Sheldrick, 2008) program using Direct Methods. The
structures were further refined with SHELXL (Sheldrick, 2015) refinement
package using least-squares minimization, which are implemented in Olex2
software (Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.27127 (2) | 0.38911 (2) | 0.76223 (2) | 0.05078 (15) | |
O2 | 0.22996 (14) | 0.52090 (16) | 0.08766 (10) | 0.0509 (6) | |
O3 | 0.13128 (13) | 0.51047 (14) | −0.02912 (10) | 0.0403 (5) | |
O4 | 0.35286 (14) | 0.36338 (15) | 0.63667 (11) | 0.0462 (5) | |
N5 | 0.65497 (15) | 0.41316 (16) | 0.77575 (12) | 0.0351 (5) | |
H5 | 0.690244 | 0.438004 | 0.816546 | 0.042* | |
N6 | 0.54447 (14) | 0.44167 (15) | 0.82892 (11) | 0.0306 (5) | |
H6 | 0.586599 | 0.462038 | 0.868283 | 0.037* | |
N7 | 0.50290 (16) | 0.39032 (15) | 0.70238 (12) | 0.0342 (5) | |
N8 | 0.44297 (16) | 0.46193 (18) | 0.89364 (12) | 0.0443 (6) | |
H8A | 0.487442 | 0.479994 | 0.932404 | 0.053* | |
H8B | 0.388820 | 0.459895 | 0.896165 | 0.053* | |
C9 | 0.7032 (2) | 0.3047 (2) | 0.61344 (16) | 0.0474 (8) | |
H9 | 0.673007 | 0.282297 | 0.564807 | 0.057* | |
C10 | 0.7964 (2) | 0.29792 (19) | 0.64360 (16) | 0.0399 (7) | |
C11 | 0.56607 (18) | 0.41467 (17) | 0.76703 (14) | 0.0303 (6) | |
C12 | 0.39078 (19) | 0.40625 (18) | 0.76422 (15) | 0.0335 (6) | |
C13 | 0.45786 (18) | 0.43724 (18) | 0.83002 (14) | 0.0307 (6) | |
C14 | 0.41795 (19) | 0.38764 (18) | 0.70223 (15) | 0.0337 (6) | |
C16 | 0.37744 (19) | 0.3571 (2) | 0.56968 (15) | 0.0397 (7) | |
C17 | 0.8466 (2) | 0.25452 (19) | 0.60077 (17) | 0.0448 (7) | |
C18 | 0.6534 (2) | 0.3442 (2) | 0.65381 (15) | 0.0457 (7) | |
H18 | 0.590455 | 0.349207 | 0.632270 | 0.055* | |
C19 | 0.4105 (2) | 0.3404 (3) | 0.43520 (18) | 0.0583 (10) | |
C21 | 0.6985 (2) | 0.37645 (18) | 0.72723 (15) | 0.0334 (6) | |
C22 | 0.3969 (2) | 0.4224 (3) | 0.46069 (19) | 0.0566 (9) | |
H22 | 0.399016 | 0.471232 | 0.431607 | 0.068* | |
C23 | 0.3801 (2) | 0.4315 (2) | 0.52991 (17) | 0.0472 (8) | |
C24 | 0.8420 (2) | 0.3321 (2) | 0.71589 (17) | 0.0445 (7) | |
H24 | 0.905116 | 0.329196 | 0.736319 | 0.053* | |
C25 | 0.3898 (3) | 0.2744 (2) | 0.54579 (19) | 0.0563 (9) | |
N26 | 0.4423 (3) | 0.3312 (4) | 0.30620 (19) | 0.1122 (17) | |
C27 | 0.4290 (2) | 0.3347 (4) | 0.36320 (19) | 0.0781 (14) | |
C28 | 0.7926 (2) | 0.3704 (2) | 0.75696 (17) | 0.0403 (7) | |
H28 | 0.823022 | 0.392553 | 0.805641 | 0.048* | |
C29 | 0.4077 (3) | 0.2688 (3) | 0.4766 (2) | 0.0663 (10) | |
H29 | 0.418016 | 0.214575 | 0.458660 | 0.080* | |
C31 | 0.3862 (5) | 0.1957 (3) | 0.5935 (3) | 0.110 (2) | |
H31A | 0.426672 | 0.203999 | 0.645097 | 0.165* | |
H31B | 0.404406 | 0.145132 | 0.571777 | 0.165* | |
H31C | 0.325188 | 0.188005 | 0.593975 | 0.165* | |
C34 | 0.3671 (3) | 0.5202 (3) | 0.5610 (2) | 0.0752 (12) | |
H34A | 0.313157 | 0.519632 | 0.575323 | 0.113* | |
H34B | 0.361038 | 0.563530 | 0.522152 | 0.113* | |
H34C | 0.418901 | 0.533551 | 0.605247 | 0.113* | |
C0AA | 0.21047 (17) | 0.51754 (18) | 0.01702 (14) | 0.0311 (6) | |
N2 | 0.8851 (2) | 0.2202 (2) | 0.56672 (17) | 0.0611 (8) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0326 (2) | 0.0742 (3) | 0.0481 (2) | −0.00861 (14) | 0.01677 (15) | −0.01373 (15) |
O2 | 0.0368 (11) | 0.0954 (17) | 0.0212 (9) | −0.0114 (11) | 0.0105 (8) | −0.0040 (10) |
O3 | 0.0293 (10) | 0.0661 (14) | 0.0227 (9) | −0.0005 (9) | 0.0050 (7) | 0.0034 (9) |
O4 | 0.0309 (11) | 0.0755 (15) | 0.0300 (10) | −0.0111 (10) | 0.0072 (8) | −0.0183 (10) |
N5 | 0.0290 (12) | 0.0529 (14) | 0.0231 (10) | −0.0037 (10) | 0.0083 (9) | −0.0100 (10) |
N6 | 0.0278 (11) | 0.0431 (13) | 0.0191 (9) | −0.0011 (10) | 0.0055 (8) | −0.0057 (10) |
N7 | 0.0320 (12) | 0.0477 (14) | 0.0220 (11) | −0.0017 (10) | 0.0078 (9) | −0.0085 (10) |
N8 | 0.0301 (12) | 0.0772 (18) | 0.0263 (11) | 0.0010 (12) | 0.0103 (9) | −0.0107 (12) |
C9 | 0.0513 (19) | 0.066 (2) | 0.0279 (14) | 0.0013 (16) | 0.0166 (13) | −0.0048 (14) |
C10 | 0.0506 (17) | 0.0401 (16) | 0.0366 (15) | 0.0063 (14) | 0.0247 (13) | 0.0075 (13) |
C11 | 0.0320 (14) | 0.0364 (14) | 0.0218 (12) | −0.0013 (12) | 0.0081 (10) | −0.0022 (11) |
C12 | 0.0285 (14) | 0.0463 (16) | 0.0255 (13) | −0.0013 (12) | 0.0088 (10) | −0.0082 (12) |
C13 | 0.0319 (14) | 0.0358 (14) | 0.0255 (12) | 0.0033 (11) | 0.0110 (10) | −0.0003 (11) |
C14 | 0.0311 (14) | 0.0420 (15) | 0.0255 (13) | −0.0020 (12) | 0.0061 (10) | −0.0057 (11) |
C16 | 0.0328 (15) | 0.0576 (19) | 0.0245 (13) | −0.0033 (14) | 0.0038 (11) | −0.0137 (14) |
C17 | 0.0578 (18) | 0.0446 (18) | 0.0378 (15) | 0.0102 (15) | 0.0235 (14) | 0.0095 (14) |
C18 | 0.0384 (16) | 0.070 (2) | 0.0287 (14) | 0.0024 (15) | 0.0116 (12) | −0.0042 (15) |
C19 | 0.0406 (18) | 0.100 (3) | 0.0317 (16) | 0.0063 (19) | 0.0083 (13) | −0.0162 (19) |
C21 | 0.0347 (14) | 0.0417 (16) | 0.0270 (13) | −0.0028 (12) | 0.0143 (11) | −0.0008 (12) |
C22 | 0.053 (2) | 0.077 (2) | 0.0378 (17) | 0.0050 (19) | 0.0118 (14) | 0.0061 (18) |
C23 | 0.0382 (17) | 0.061 (2) | 0.0386 (16) | 0.0032 (15) | 0.0074 (13) | −0.0084 (16) |
C24 | 0.0342 (15) | 0.058 (2) | 0.0443 (16) | 0.0054 (14) | 0.0172 (13) | 0.0023 (15) |
C25 | 0.068 (2) | 0.0544 (19) | 0.0446 (18) | −0.0044 (18) | 0.0154 (16) | −0.0143 (16) |
N26 | 0.055 (2) | 0.239 (6) | 0.0427 (18) | 0.012 (3) | 0.0166 (15) | −0.024 (3) |
C27 | 0.0408 (19) | 0.151 (4) | 0.0392 (19) | 0.010 (2) | 0.0088 (15) | −0.020 (2) |
C28 | 0.0359 (16) | 0.0525 (19) | 0.0327 (15) | −0.0011 (13) | 0.0118 (12) | −0.0058 (13) |
C29 | 0.075 (3) | 0.074 (3) | 0.047 (2) | 0.003 (2) | 0.0152 (17) | −0.028 (2) |
C31 | 0.189 (6) | 0.052 (3) | 0.095 (4) | −0.013 (3) | 0.057 (4) | −0.011 (3) |
C34 | 0.094 (3) | 0.061 (2) | 0.066 (2) | 0.018 (2) | 0.020 (2) | −0.005 (2) |
C0AA | 0.0314 (14) | 0.0398 (15) | 0.0205 (11) | −0.0022 (12) | 0.0066 (10) | −0.0002 (11) |
N2 | 0.077 (2) | 0.0617 (17) | 0.0567 (17) | 0.0227 (16) | 0.0385 (16) | 0.0058 (15) |
Geometric parameters (Å, º) top
Br1—C12 | 1.867 (3) | C12—C14 | 1.374 (4) |
O2—C0AA | 1.237 (3) | C16—C23 | 1.367 (5) |
O3—C0AA | 1.249 (3) | C16—C25 | 1.381 (5) |
O4—C14 | 1.348 (3) | C17—N2 | 1.132 (4) |
O4—C16 | 1.413 (3) | C18—C21 | 1.394 (4) |
N5—C11 | 1.339 (3) | C19—C22 | 1.386 (5) |
N5—C21 | 1.407 (3) | C19—C27 | 1.452 (4) |
N6—C11 | 1.358 (3) | C19—C29 | 1.348 (6) |
N6—C13 | 1.357 (3) | C21—C28 | 1.387 (4) |
N7—C11 | 1.323 (3) | C22—C23 | 1.393 (4) |
N7—C14 | 1.322 (4) | C23—C34 | 1.519 (5) |
N8—C13 | 1.325 (3) | C24—C28 | 1.377 (4) |
C9—C10 | 1.375 (4) | C25—C29 | 1.397 (5) |
C9—C18 | 1.381 (4) | C25—C31 | 1.507 (6) |
C10—C17 | 1.445 (4) | N26—C27 | 1.138 (4) |
C10—C24 | 1.389 (4) | C0AA—C0AAi | 1.556 (5) |
C12—C13 | 1.397 (4) | | |
| | | |
C14—O4—C16 | 117.6 (2) | N2—C17—C10 | 179.3 (4) |
C11—N5—C21 | 128.8 (2) | C9—C18—C21 | 119.2 (3) |
C13—N6—C11 | 121.4 (2) | C22—C19—C27 | 117.6 (4) |
C14—N7—C11 | 117.0 (2) | C29—C19—C22 | 120.9 (3) |
C10—C9—C18 | 121.4 (3) | C29—C19—C27 | 121.5 (4) |
C9—C10—C17 | 120.2 (3) | C18—C21—N5 | 124.5 (3) |
C9—C10—C24 | 119.6 (3) | C28—C21—N5 | 116.4 (3) |
C24—C10—C17 | 120.2 (3) | C28—C21—C18 | 119.1 (3) |
N5—C11—N6 | 116.0 (2) | C19—C22—C23 | 119.9 (4) |
N7—C11—N5 | 122.2 (2) | C16—C23—C22 | 117.1 (3) |
N7—C11—N6 | 121.8 (2) | C16—C23—C34 | 121.2 (3) |
C13—C12—Br1 | 121.22 (19) | C22—C23—C34 | 121.7 (3) |
C14—C12—Br1 | 122.3 (2) | C28—C24—C10 | 119.3 (3) |
C14—C12—C13 | 116.5 (2) | C16—C25—C29 | 116.1 (3) |
N6—C13—C12 | 117.7 (2) | C16—C25—C31 | 121.1 (3) |
N8—C13—N6 | 117.7 (2) | C29—C25—C31 | 122.8 (4) |
N8—C13—C12 | 124.6 (2) | N26—C27—C19 | 178.9 (5) |
O4—C14—C12 | 117.2 (3) | C24—C28—C21 | 121.4 (3) |
N7—C14—O4 | 117.7 (2) | C19—C29—C25 | 121.4 (3) |
N7—C14—C12 | 125.1 (2) | O2—C0AA—O3 | 124.3 (2) |
C23—C16—O4 | 118.5 (3) | O2—C0AA—C0AAi | 118.3 (3) |
C23—C16—C25 | 124.6 (3) | O3—C0AA—C0AAi | 117.3 (3) |
C25—C16—O4 | 116.7 (3) | | |
Symmetry code: (i) −x+1/2, y, −z. |
Interaction energies (kJ mol-1) for selected contacts topEele is electrostatic, Epol is polarization, Edisp
is dispersion, Erep is repulsion and Etot is the total
energy. |
Crystal | Interaction pair | Contact | Eele | Epol | Edisp | Erep | Etot |
ETR | ETR–ETR | N2—H2···N6 | -23.2 | -10.3 | -73.8 | 41.5 | -63.1 |
| | N4—H4A···C18 | | | | | |
| | N4—H4A···C19 | | | | | |
| ETR–ETR | N4—H4B···N1 | -30.3 | -7.6 | -6.8 | 15.3 | -29.6 |
| ETR–ETR | C13—H13C···Br1 | -6.6 | -5.3 | -50.1 | 23.5 | -36.2 |
ETR–DMSO1 | ETR–DMSO | N2—H2···O2 | -43.7 | -15.9 | -13.6 | 26.4 | -45.8 |
| ETR–ETR | N4—H4A···N3 | -41.7 | -15.5 | -20.6 | 40.7 | -38.1 |
| ETR–DMSO | N4—H4B···O2 | -40.0 | -13.0 | -13.7 | 23.4 | -42.6 |
ETR–DMSO2 | ETR–DMSO | N2—H2···O2 | -54.9 | -19.4 | -12.3 | 28.7 | -56.5 |
| | C4—H4···O2 | | | | | |
| ETR–ETR | C4···C4 (π–π) | -14.4 | -2.7 | -26.1 | 10.5 | -31.4 |
| DMSO–DMSO | C21—H21A···O2 | -39.0 | -12.1 | -15.0 | 12.7 | -50.8 |
| ETR–ETR | C3—H3···N1 | -23.9 | -5.0 | -9.8 | 11.7 | -27.0 |
| ETR–DMSO | C21—H21B···N1 | -14.9 | -3.8 | -5.7 | 4.9 | -18.9 |
ETR–DMA | ETR–DMA | N2—H2···O2 | -30.8 | -9.0 | -16.0 | 11.4 | -42.4 |
| | C4—H4···O2 | | | | | |
| ETR–ETR | N4—H4A···N3 | -45.3 | -16.0 | -21.9 | 46.2 | -37.0 |
| ETR–DMA | N4—H4B···O2 | -26.5 | -6.9 | -12.5 | 11.7 | -33.3 |
ETR–Dioxane | ETR–Dioxane | N4A—H4AA···O2 | -30.0 | -9.5 | -11.6 | 21.5 | -30.0 |
| ETR–Dioxane | N2A—H2A···O1 | -30.2 | -7.7 | -18.8 | 20.0 | -36.6 |
| Dioxane–Dioxane | C1—H1A···O2 | -5.2 | -2.5 | -15.3 | 7.4 | -14.7 |
| ETR–ETR | Br1A···N6B | -2.6 | -2.1 | -48.0 | 18.7 | -32.1 |
ETR–Oxalate | ETR–Oxalate | N3—H3···O2 | -132.6 | -36.1 | -23.3 | 125.6 | -77.7 |
| ETR–ETR | Br1···N6 | -11.6 | -2.3 | -51.0 | 35.4 | -30.6 |
| ETR–Oxalate | N4—H4A···O3 | -23.0 | -6.2 | -11.3 | 24.1 | -18.1 |
Partitioned and total lattice energies (kJ mol-1) topEcoul is the Coulombic term, Epol is the polarization term,
Edisp is the dispersion term, Eatt is the attraction term
(the sum of the Coulombic, polarization and dispersion terms), Erep
is the repulsion term and Elatt is the CLP crystal lattice energy. |
Structure | Ecoul | Epol | Edisp | Eatt | Erep | Elatt |
ETR | -12.1 | -52.5 | -198.5 | -263.1 | 81.4 | -200.1 |
ETR–DMSO1 | -24.2 | -37.0 | -111.9 | -173.3 | 51.8 | -121.4 |
ETR–DMSO2 | -19.1 | -37.1 | -110.0 | -166.2 | 61.1 | -105.0 |
ETR–DMA | -28.6 | -36.2 | -114.3 | -179.1 | 40.4 | -138.6 |
ETR–Dioxane | -12.9 | -15.4 | -66.4 | -94.7 | 30.1 | -64.7 |
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