New solvates and a salt of the anti-HIV compound etravirine

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.

Computing details

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)

Crystal data

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) Å^3	Needle, colourless
Z = 4	0.3 × 0.02 × 0.02 mm

Data collection

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

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.066	H-atom parameters constrained
wR(F^2) = 0.214	w = 1/[σ^2(Fo^2) + (0.1282P)^2 + 0.5303P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

Crystal data

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) Å^3	0.1 × 0.03 × 0.01 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.210	w = 1/[σ^2(Fo^2) + (0.146P)^2 + 0.1471P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

Crystal data

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) Å^3	0.15 × 0.02 × 0.01 mm

Data collection

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

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.155	w = 1/[σ^2(Fo^2) + (0.085P)^2 + 0.2663P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

Crystal data

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) Å^3	Plate, colourless
Z = 8	0.16 × 0.09 × 0.01 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.132	w = 1/[σ^2(Fo^2) + (0.0323P)^2 + 7.2848P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—C2^i	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—C2^i	110.3 (4)
C18B—C19B—C20B	120.8 (4)	O1—C2—C1^i	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)

Crystal data

C20H16BrN6O^2+·0.5C2O4^2^−	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) Å^3	Plate, colourless
Z = 8	0.3 × 0.1 × 0.01 mm

Data collection

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

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—C0AA^i	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—C0AA^i	118.3 (3)
C23—C16—C25	124.6 (3)	O3—C0AA—C0AA^i	117.3 (3)
C25—C16—O4	116.7 (3)

Symmetry code: (i) −x+1/2, y, −z.