Download citation
Download citation
link to html
New salt forms of the anti­oxidant drug emoxypine (EMX, 2-ethyl-6-methyl­pyridin-3-ol) with pharmaceutically acceptable maleic (Mlt), malonic (Mln) and adipic (Adp) acids were obtained {emoxypinium maleate, C8H12NO+·C4H3O4, [EMX+Mlt], emoxypinium malonate, C8H12NO+·C3H3O4, [EMX+Mln], and emoxypinium adipate, C8H12NO+·C6H9O4, [EMX+Adp]} and their crystal structures determined. The mol­ecular packing in the three EMX salts was studied by means of solid-state density functional theory (DFT), followed by QTAIMC (quantum theory of atoms in mol­ecules and crystals) analysis. It was found that the major contribution to the packing energy comes from pyridine–carboxyl­ate and hy­droxy–carboxyl­ate heterosynthons forming infinite one-dimensional ribbons, with [EMX+Adp] additionally stabilized by hydrogen-bonded C(9) chains of Adp ions. The melting processes of the [EMX+Mlt] (1:1), [EMX+Mln] (1:1) and [EMX+Adp] (1:1) salts were studied and the fusion enthalpy was found to increase with the increase of the calculated lattice energy. The dissolution process of the EMX salts in buffer (pH 7.4) was also studied. It was found that the formation of binary crystals of EMX with di­carb­oxy­lic acids increases the EMX solubility by more than 30 times compared to its pure form.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618007386/yf3142sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229618007386/yf3142Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229618007386/yf3142IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229618007386/yf3142IIIsup4.hkl
Contains datablock III

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618007386/yf3142Isup5.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618007386/yf3142IIsup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618007386/yf3142IIIsup7.cml
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618007386/yf3142sup8.pdf
Additional figures and tables

CCDC references: 1836239; 1836241; 1836240

Computing details top

For all structures, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2-Ethyl-3-hydroxy-6-methylpyridin-1-ium 3-carboxyprop-2-enoate (I) top
Crystal data top
C8H12NO+·C4H3O4F(000) = 1072
Mr = 253.25Dx = 1.356 Mg m3
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 6269 reflections
a = 26.571 (3) Åθ = 3.0–30.1°
b = 6.9074 (8) ŵ = 0.11 mm1
c = 13.5152 (16) ÅT = 150 K
V = 2480.6 (5) Å3Parallelepiped, colourless
Z = 80.35 × 0.20 × 0.20 mm
Data collection top
Bruker SMART APEXII
diffractometer
2713 independent reflections
Radiation source: fine-focus sealed tube2282 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ω scansθmax = 27.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 3333
Tmin = 0.964, Tmax = 0.979k = 88
19445 measured reflectionsl = 1716
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: difference Fourier map
wR(F2) = 0.101All H-atom parameters refined
S = 1.04 w = 1/[σ2(Fo2) + (0.0506P)2 + 0.7672P]
where P = (Fo2 + 2Fc2)/3
2713 reflections(Δ/σ)max < 0.001
223 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.19 e Å3
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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.23337 (3)0.51028 (14)0.25508 (7)0.0328 (2)
H20.2066 (8)0.492 (3)0.2909 (13)0.057 (5)*
N10.36097 (4)0.57375 (14)0.32811 (8)0.0253 (2)
H10.3918 (6)0.588 (2)0.2955 (11)0.037 (4)*
C10.31985 (4)0.56061 (17)0.27019 (9)0.0246 (3)
C20.27330 (4)0.52561 (17)0.31535 (9)0.0257 (3)
C30.27151 (5)0.51191 (18)0.41811 (9)0.0294 (3)
C40.31499 (5)0.53136 (18)0.47344 (9)0.0293 (3)
C50.36080 (5)0.56154 (17)0.42794 (9)0.0276 (3)
C60.41005 (6)0.5867 (3)0.48088 (11)0.0394 (3)
C70.32582 (5)0.5779 (2)0.16069 (9)0.0293 (3)
C80.32970 (6)0.3791 (2)0.11233 (10)0.0412 (4)
H30.2400 (6)0.488 (2)0.4490 (11)0.033 (4)*
H40.3130 (6)0.524 (2)0.5448 (12)0.039 (4)*
H610.4111 (8)0.505 (3)0.5358 (18)0.079 (7)*
H620.4123 (8)0.718 (3)0.5043 (16)0.085 (7)*
H630.4384 (7)0.563 (3)0.4393 (15)0.060 (5)*
H710.3554 (6)0.659 (2)0.1477 (11)0.037 (4)*
H720.2954 (6)0.648 (2)0.1362 (11)0.039 (4)*
H810.2974 (7)0.301 (3)0.1274 (12)0.059 (5)*
H820.3334 (6)0.391 (3)0.0408 (13)0.049 (5)*
H830.3600 (6)0.312 (2)0.1389 (12)0.049 (5)*
O110.51272 (4)0.55390 (18)0.29968 (7)0.0456 (3)
H110.5546 (9)0.540 (3)0.2876 (16)0.083 (7)*
O120.44379 (3)0.59189 (18)0.21062 (8)0.0479 (3)
O130.65378 (3)0.55089 (16)0.14008 (7)0.0394 (3)
O140.60222 (4)0.52160 (17)0.26715 (7)0.0422 (3)
C110.48987 (5)0.5836 (2)0.21751 (10)0.0329 (3)
C120.51939 (5)0.6098 (2)0.12445 (10)0.0371 (3)
C130.56863 (5)0.5967 (2)0.10733 (10)0.0338 (3)
C140.61100 (4)0.55363 (18)0.17691 (9)0.0265 (3)
H120.4980 (6)0.642 (2)0.0678 (12)0.046 (4)*
H130.5794 (6)0.614 (2)0.0406 (12)0.041 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0171 (4)0.0484 (6)0.0329 (5)0.0021 (4)0.0017 (3)0.0017 (4)
N10.0185 (5)0.0295 (5)0.0279 (5)0.0003 (4)0.0020 (4)0.0006 (4)
C10.0201 (5)0.0265 (6)0.0271 (6)0.0005 (4)0.0016 (4)0.0014 (4)
C20.0191 (5)0.0273 (6)0.0308 (6)0.0007 (4)0.0019 (4)0.0007 (5)
C30.0254 (6)0.0306 (6)0.0320 (7)0.0009 (5)0.0092 (5)0.0004 (5)
C40.0328 (6)0.0305 (6)0.0247 (6)0.0005 (5)0.0037 (5)0.0003 (5)
C50.0281 (6)0.0280 (6)0.0268 (6)0.0005 (5)0.0013 (5)0.0028 (5)
C60.0315 (7)0.0538 (9)0.0329 (7)0.0023 (6)0.0064 (6)0.0047 (7)
C70.0201 (6)0.0413 (7)0.0264 (6)0.0001 (5)0.0021 (4)0.0078 (5)
C80.0424 (8)0.0549 (9)0.0262 (7)0.0094 (7)0.0031 (6)0.0026 (6)
O110.0258 (5)0.0780 (8)0.0329 (5)0.0000 (5)0.0072 (4)0.0056 (5)
O120.0184 (5)0.0698 (8)0.0557 (7)0.0039 (4)0.0079 (4)0.0079 (6)
O130.0173 (4)0.0647 (7)0.0363 (5)0.0045 (4)0.0007 (4)0.0083 (5)
O140.0233 (5)0.0745 (8)0.0287 (5)0.0030 (5)0.0019 (3)0.0090 (5)
C110.0213 (6)0.0386 (7)0.0388 (7)0.0008 (5)0.0057 (5)0.0011 (6)
C120.0209 (6)0.0590 (9)0.0315 (7)0.0058 (6)0.0019 (5)0.0045 (6)
C130.0231 (6)0.0527 (8)0.0256 (6)0.0042 (6)0.0007 (5)0.0053 (6)
C140.0192 (5)0.0308 (6)0.0296 (6)0.0004 (4)0.0015 (4)0.0017 (5)
Geometric parameters (Å, º) top
O1—C21.3419 (14)C7—C81.524 (2)
O1—H20.87 (2)C7—H710.979 (15)
N1—C11.3471 (15)C7—H720.999 (16)
N1—C51.3519 (16)C8—H811.035 (18)
N1—H10.936 (16)C8—H820.976 (18)
C1—C21.4004 (16)C8—H830.995 (17)
C1—C71.4932 (17)O11—C111.2821 (16)
C2—C31.3928 (18)O11—H111.13 (2)
C3—C41.3827 (18)O12—C111.2294 (16)
C3—H30.951 (15)O13—C141.2412 (15)
C4—C51.3795 (17)O14—C141.2612 (16)
C4—H40.968 (16)C11—C121.4932 (18)
C5—C61.5014 (18)C12—C131.3318 (18)
C6—H610.94 (2)C12—H120.981 (16)
C6—H620.96 (2)C13—C141.4967 (17)
C6—H630.95 (2)C13—H130.954 (16)
C2—O1—H2108.7 (12)C1—C7—H71107.9 (9)
C1—N1—C5124.96 (10)C8—C7—H71112.5 (9)
C1—N1—H1116.4 (9)C1—C7—H72106.3 (8)
C5—N1—H1118.6 (9)C8—C7—H72110.5 (9)
N1—C1—C2118.34 (11)H71—C7—H72108.2 (13)
N1—C1—C7118.97 (10)C7—C8—H81109.4 (10)
C2—C1—C7122.66 (11)C7—C8—H82110.7 (10)
O1—C2—C3124.96 (11)H81—C8—H82108.9 (13)
O1—C2—C1116.58 (11)C7—C8—H83108.6 (10)
C3—C2—C1118.45 (11)H81—C8—H83110.8 (14)
C4—C3—C2120.28 (11)H82—C8—H83108.4 (13)
C4—C3—H3121.1 (9)C11—O11—H11110.8 (11)
C2—C3—H3118.6 (9)C14—O14—H11111.6 (9)
C5—C4—C3120.72 (11)O12—C11—O11123.00 (12)
C5—C4—H4120.0 (9)O12—C11—C12116.98 (12)
C3—C4—H4119.3 (9)O11—C11—C12120.02 (11)
N1—C5—C4117.21 (11)C13—C12—C11130.85 (12)
N1—C5—C6117.73 (11)C13—C12—H12116.7 (9)
C4—C5—C6125.04 (12)C11—C12—H12112.4 (9)
C5—C6—H61109.6 (14)C12—C13—C14130.03 (12)
C5—C6—H62108.7 (13)C12—C13—H13116.9 (9)
H61—C6—H62107.9 (18)C14—C13—H13113.1 (9)
C5—C6—H63112.8 (12)O13—C14—O14123.67 (11)
H61—C6—H63109.9 (17)O13—C14—C13116.10 (11)
H62—C6—H63107.8 (16)O14—C14—C13120.23 (11)
C1—C7—C8111.12 (11)
C5—N1—C1—C22.13 (18)C1—N1—C5—C6177.81 (12)
C5—N1—C1—C7179.69 (12)C3—C4—C5—N10.90 (18)
N1—C1—C2—O1178.93 (10)C3—C4—C5—C6179.29 (13)
C7—C1—C2—O10.81 (18)N1—C1—C7—C895.66 (14)
N1—C1—C2—C31.91 (17)C2—C1—C7—C882.44 (15)
C7—C1—C2—C3179.97 (12)O12—C11—C12—C13175.27 (16)
O1—C2—C3—C4179.51 (12)O11—C11—C12—C134.6 (3)
C1—C2—C3—C40.43 (19)C11—C12—C13—C141.0 (3)
C2—C3—C4—C51.00 (19)C12—C13—C14—O13179.87 (16)
C1—N1—C5—C40.70 (18)C12—C13—C14—O140.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11···O141.13 (2)1.30 (2)2.4288 (14)176 (2)
O1—H2···O13i0.87 (2)1.71 (2)2.5804 (13)178.5 (19)
N1—H1···O120.936 (16)1.795 (17)2.7165 (14)167.5 (14)
Symmetry code: (i) x1/2, y+1, z+1/2.
2-Ethyl-3-hydroxy-6-methylpyridin-1-ium 3-carboxypropanoate (II) top
Crystal data top
C8H12NO+·C3H3O4Z = 4
Mr = 241.24F(000) = 512
Triclinic, P1Dx = 1.377 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.9211 (7) ÅCell parameters from 5243 reflections
b = 10.5301 (8) Åθ = 2.5–30.6°
c = 13.7175 (10) ŵ = 0.11 mm1
α = 80.0535 (11)°T = 150 K
β = 86.3313 (11)°Prism, colourless
γ = 66.5117 (10)°0.40 × 0.20 × 0.05 mm
V = 1164.07 (15) Å3
Data collection top
Bruker SMART APEXII
diffractometer
5599 independent reflections
Radiation source: fine-focus sealed tube4307 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ω scansθmax = 28.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1111
Tmin = 0.958, Tmax = 0.995k = 1313
12144 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: difference Fourier map
wR(F2) = 0.108All H-atom parameters refined
S = 1.03 w = 1/[σ2(Fo2) + (0.0632P)2 + 0.1019P]
where P = (Fo2 + 2Fc2)/3
5599 reflections(Δ/σ)max < 0.001
427 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.23 e Å3
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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.25059 (11)0.94822 (10)0.49431 (6)0.0303 (2)
H120.324 (2)0.866 (2)0.4794 (13)0.053 (5)*
N10.27799 (11)1.14462 (10)0.67428 (7)0.0191 (2)
H110.2147 (18)1.2292 (16)0.6934 (11)0.032 (4)*
C110.21972 (13)1.11105 (12)0.59834 (8)0.0194 (2)
C120.31050 (14)0.98134 (12)0.56914 (8)0.0210 (2)
C130.45557 (14)0.89267 (12)0.61915 (9)0.0225 (2)
C140.50934 (14)0.93460 (13)0.69542 (9)0.0228 (2)
C150.41919 (14)1.06403 (12)0.72318 (8)0.0210 (2)
C160.46939 (17)1.11937 (15)0.80301 (10)0.0278 (3)
C170.06539 (14)1.21647 (13)0.54769 (9)0.0253 (3)
C180.10265 (19)1.30767 (18)0.45902 (12)0.0439 (4)
H130.5167 (17)0.8008 (15)0.5993 (10)0.028 (4)*
H140.6073 (17)0.8775 (14)0.7317 (10)0.024 (3)*
H1610.496 (2)1.055 (2)0.8627 (15)0.064 (6)*
H1620.568 (3)1.137 (2)0.7861 (14)0.071 (6)*
H1630.388 (2)1.202 (2)0.8186 (14)0.062 (6)*
H1710.0018 (18)1.1681 (16)0.5262 (11)0.036 (4)*
H1720.0015 (18)1.2712 (16)0.5950 (11)0.037 (4)*
H1810.173 (2)1.245 (2)0.4109 (15)0.068 (6)*
H1820.001 (2)1.3805 (19)0.4255 (13)0.057 (5)*
H1830.156 (2)1.3620 (19)0.4801 (14)0.059 (5)*
N20.83343 (12)0.11657 (10)0.17789 (7)0.0205 (2)
H210.7931 (19)0.1931 (17)0.2111 (12)0.039 (4)*
O20.71557 (11)0.00878 (9)0.01610 (6)0.0281 (2)
H220.759 (2)0.092 (2)0.0455 (15)0.068 (6)*
C210.74586 (14)0.11303 (12)0.10278 (8)0.0206 (2)
C220.80482 (14)0.00756 (12)0.05829 (8)0.0205 (2)
C230.94858 (14)0.11854 (12)0.09343 (9)0.0222 (2)
C241.03252 (14)0.10822 (13)0.17156 (9)0.0224 (2)
C250.97484 (13)0.01199 (12)0.21409 (8)0.0208 (2)
C261.05829 (16)0.03354 (15)0.29668 (10)0.0282 (3)
C270.59039 (15)0.23649 (13)0.07126 (9)0.0269 (3)
C280.60503 (18)0.32019 (14)0.02888 (10)0.0326 (3)
H230.9861 (16)0.2020 (14)0.0647 (9)0.020 (3)*
H241.1283 (17)0.1833 (15)0.1985 (10)0.027 (4)*
H2611.107 (2)0.1014 (19)0.2734 (13)0.056 (5)*
H2620.985 (2)0.0716 (18)0.3475 (13)0.047 (5)*
H2631.142 (2)0.058 (2)0.3272 (13)0.059 (5)*
H2710.502 (2)0.2003 (17)0.0657 (12)0.043 (4)*
H2720.5614 (17)0.2958 (15)0.1213 (11)0.031 (4)*
H2810.498 (2)0.3990 (17)0.0499 (12)0.046 (4)*
H2820.6397 (18)0.2554 (16)0.0781 (11)0.037 (4)*
H2830.688 (2)0.3614 (18)0.0290 (13)0.052 (5)*
O310.47446 (13)0.44831 (11)0.27092 (8)0.0418 (3)
H310.393 (3)0.539 (2)0.3028 (16)0.087 (7)*
O320.74168 (13)0.32588 (10)0.28866 (8)0.0410 (3)
O330.47330 (12)0.71824 (10)0.44915 (7)0.0385 (2)
O340.33650 (12)0.65525 (11)0.35028 (8)0.0406 (3)
C310.61609 (17)0.42311 (13)0.30669 (9)0.0283 (3)
C320.62348 (16)0.51936 (13)0.37450 (10)0.0254 (3)
C330.46522 (16)0.64055 (13)0.39291 (9)0.0267 (3)
H3210.6670 (19)0.4621 (16)0.4395 (12)0.038 (4)*
H3220.6975 (19)0.5572 (16)0.3481 (11)0.036 (4)*
O411.18702 (11)0.57232 (10)0.14240 (8)0.0366 (2)
H411.147 (3)0.493 (2)0.0999 (16)0.084 (7)*
O421.06394 (11)0.61278 (9)0.26157 (7)0.0320 (2)
O430.79442 (11)0.21875 (9)0.10746 (7)0.0324 (2)
O441.04830 (11)0.36617 (10)0.06211 (7)0.0340 (2)
C411.06034 (15)0.54701 (12)0.19505 (9)0.0241 (3)
C420.90252 (16)0.43260 (14)0.17060 (11)0.0294 (3)
C430.91565 (15)0.33013 (12)0.10873 (8)0.0239 (3)
H4210.842 (2)0.3832 (19)0.2290 (14)0.059 (5)*
H4220.838 (2)0.4797 (19)0.1307 (13)0.056 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0282 (5)0.0316 (5)0.0297 (5)0.0040 (4)0.0066 (4)0.0182 (4)
N10.0195 (5)0.0172 (5)0.0195 (5)0.0047 (4)0.0006 (4)0.0065 (4)
C110.0184 (5)0.0208 (6)0.0184 (5)0.0064 (4)0.0001 (4)0.0048 (4)
C120.0208 (5)0.0228 (6)0.0199 (5)0.0074 (5)0.0005 (4)0.0080 (4)
C130.0217 (6)0.0191 (6)0.0249 (6)0.0048 (5)0.0016 (4)0.0078 (5)
C140.0199 (6)0.0221 (6)0.0239 (6)0.0051 (5)0.0032 (4)0.0035 (5)
C150.0213 (5)0.0227 (6)0.0197 (5)0.0090 (5)0.0022 (4)0.0035 (4)
C160.0290 (7)0.0287 (7)0.0260 (6)0.0090 (5)0.0077 (5)0.0086 (5)
C170.0197 (6)0.0265 (6)0.0254 (6)0.0015 (5)0.0048 (5)0.0097 (5)
C180.0335 (8)0.0404 (9)0.0431 (9)0.0044 (7)0.0106 (7)0.0096 (7)
N20.0216 (5)0.0201 (5)0.0209 (5)0.0073 (4)0.0003 (4)0.0082 (4)
O20.0281 (5)0.0272 (5)0.0280 (4)0.0051 (4)0.0080 (4)0.0133 (4)
C210.0199 (5)0.0218 (6)0.0202 (5)0.0069 (4)0.0000 (4)0.0068 (4)
C220.0214 (5)0.0214 (6)0.0194 (5)0.0076 (5)0.0005 (4)0.0071 (4)
C230.0243 (6)0.0187 (6)0.0230 (6)0.0064 (5)0.0013 (4)0.0070 (4)
C240.0204 (6)0.0223 (6)0.0216 (5)0.0049 (5)0.0016 (4)0.0036 (4)
C250.0199 (5)0.0240 (6)0.0194 (5)0.0090 (5)0.0002 (4)0.0046 (4)
C260.0274 (6)0.0337 (7)0.0255 (6)0.0120 (6)0.0055 (5)0.0083 (5)
C270.0218 (6)0.0239 (6)0.0306 (6)0.0008 (5)0.0031 (5)0.0124 (5)
C280.0317 (7)0.0248 (7)0.0349 (7)0.0030 (6)0.0072 (6)0.0058 (6)
O310.0443 (6)0.0359 (6)0.0473 (6)0.0107 (5)0.0108 (5)0.0211 (5)
O320.0459 (6)0.0291 (5)0.0450 (6)0.0050 (4)0.0010 (5)0.0229 (4)
O330.0390 (5)0.0326 (5)0.0442 (6)0.0073 (4)0.0044 (4)0.0253 (4)
O340.0287 (5)0.0366 (6)0.0541 (6)0.0048 (4)0.0041 (4)0.0193 (5)
C310.0392 (7)0.0212 (6)0.0251 (6)0.0110 (5)0.0018 (5)0.0084 (5)
C320.0272 (6)0.0232 (6)0.0275 (6)0.0094 (5)0.0046 (5)0.0115 (5)
C330.0300 (6)0.0227 (6)0.0274 (6)0.0093 (5)0.0060 (5)0.0088 (5)
O410.0276 (5)0.0338 (5)0.0433 (5)0.0010 (4)0.0053 (4)0.0185 (4)
O420.0382 (5)0.0233 (5)0.0330 (5)0.0068 (4)0.0004 (4)0.0140 (4)
O430.0335 (5)0.0265 (5)0.0354 (5)0.0044 (4)0.0047 (4)0.0164 (4)
O440.0295 (5)0.0362 (5)0.0374 (5)0.0084 (4)0.0067 (4)0.0175 (4)
C410.0292 (6)0.0177 (5)0.0246 (6)0.0083 (5)0.0018 (5)0.0048 (5)
C420.0276 (7)0.0257 (6)0.0333 (7)0.0041 (5)0.0049 (5)0.0147 (5)
C430.0286 (6)0.0234 (6)0.0212 (6)0.0106 (5)0.0014 (5)0.0069 (5)
Geometric parameters (Å, º) top
O1—C121.3430 (13)C23—H230.953 (14)
O1—H120.901 (19)C24—C251.3802 (16)
N1—C151.3477 (15)C24—H240.945 (14)
N1—C111.3504 (14)C25—C261.4902 (16)
N1—H110.918 (15)C26—H2610.979 (18)
C11—C121.3956 (16)C26—H2620.950 (17)
C11—C171.4994 (16)C26—H2630.991 (18)
C12—C131.3951 (16)C27—C281.527 (2)
C13—C141.3829 (16)C27—H2711.012 (16)
C13—H130.979 (14)C27—H2720.962 (15)
C14—C151.3841 (16)C28—H2811.005 (17)
C14—H140.953 (14)C28—H2820.991 (16)
C15—C161.4934 (16)C28—H2830.995 (18)
C16—H1610.94 (2)O31—C311.2940 (17)
C16—H1620.97 (2)O31—H311.09 (2)
C16—H1630.93 (2)O32—C311.2257 (15)
C17—C181.520 (2)O33—C331.2417 (15)
C17—H1710.986 (15)O34—C331.2639 (16)
C17—H1720.957 (16)C31—C321.5113 (16)
C18—H1811.02 (2)C32—C331.5215 (17)
C18—H1820.999 (18)C32—H3210.991 (16)
C18—H1830.966 (19)C32—H3220.924 (16)
N2—C211.3465 (14)O41—C411.2914 (16)
N2—C251.3545 (15)O41—H411.04 (2)
N2—H210.927 (17)O42—C411.2288 (14)
O2—C221.3388 (14)O43—C431.2406 (15)
O2—H220.96 (2)O44—C431.2683 (15)
C21—C221.3984 (16)C41—C421.5078 (17)
C21—C271.4986 (16)C42—C431.5257 (16)
C22—C231.3902 (16)C42—H4210.944 (19)
C23—C241.3888 (16)C42—H4220.985 (18)
C12—O1—H12108.6 (11)C25—C24—H24117.9 (8)
C15—N1—C11125.23 (10)C23—C24—H24121.6 (8)
C15—N1—H11118.6 (9)N2—C25—C24117.49 (10)
C11—N1—H11116.2 (9)N2—C25—C26118.34 (10)
N1—C11—C12117.75 (10)C24—C25—C26124.18 (11)
N1—C11—C17118.57 (10)C25—C26—H261111.0 (10)
C12—C11—C17123.63 (10)C25—C26—H262112.7 (10)
O1—C12—C13123.55 (10)H261—C26—H262105.0 (14)
O1—C12—C11117.31 (10)C25—C26—H263109.7 (11)
C13—C12—C11119.13 (10)H261—C26—H263110.9 (14)
C14—C13—C12120.07 (11)H262—C26—H263107.4 (14)
C14—C13—H13121.5 (8)C21—C27—C28112.70 (10)
C12—C13—H13118.5 (8)C21—C27—H271108.0 (9)
C13—C14—C15120.33 (11)C28—C27—H271108.2 (9)
C13—C14—H14123.0 (8)C21—C27—H272108.1 (9)
C15—C14—H14116.7 (8)C28—C27—H272109.9 (8)
N1—C15—C14117.45 (10)H271—C27—H272109.9 (12)
N1—C15—C16118.48 (10)C27—C28—H281111.0 (9)
C14—C15—C16124.08 (11)C27—C28—H282108.0 (9)
C15—C16—H161112.3 (12)H281—C28—H282109.5 (12)
C15—C16—H162112.2 (12)C27—C28—H283113.1 (10)
H161—C16—H162104.6 (16)H281—C28—H283107.8 (13)
C15—C16—H163113.1 (12)H282—C28—H283107.5 (13)
H161—C16—H163106.1 (16)C31—O31—H31103.1 (12)
H162—C16—H163107.9 (16)C33—O34—H31101.0 (9)
C11—C17—C18111.01 (11)O32—C31—O31123.34 (12)
C11—C17—H171110.0 (9)O32—C31—C32119.43 (12)
C18—C17—H171109.8 (9)O31—C31—C32117.23 (11)
C11—C17—H172108.5 (9)C31—C32—C33117.58 (11)
C18—C17—H172111.8 (9)C31—C32—H321108.4 (9)
H171—C17—H172105.6 (12)C33—C32—H321107.7 (9)
C17—C18—H181108.5 (11)C31—C32—H322107.7 (9)
C17—C18—H182112.2 (10)C33—C32—H322107.5 (9)
H181—C18—H182110.5 (15)H321—C32—H322107.5 (13)
C17—C18—H183110.4 (11)O33—C33—O34124.93 (12)
H181—C18—H183111.7 (16)O33—C33—C32116.76 (12)
H182—C18—H183103.5 (15)O34—C33—C32118.31 (11)
C21—N2—C25125.04 (10)C41—O41—H41103.5 (12)
C21—N2—H21119.2 (10)C43—O44—H41100.7 (9)
C25—N2—H21115.7 (10)O42—C41—O41122.92 (11)
C22—O2—H22115.1 (12)O42—C41—C42120.08 (11)
N2—C21—C22117.81 (10)O41—C41—C42116.99 (10)
N2—C21—C27119.08 (10)C41—C42—C43116.76 (11)
C22—C21—C27123.11 (10)C41—C42—H421110.1 (11)
O2—C22—C23123.86 (10)C43—C42—H421110.2 (11)
O2—C22—C21116.74 (10)C41—C42—H422106.5 (11)
C23—C22—C21119.39 (10)C43—C42—H422105.7 (10)
C24—C23—C22119.83 (10)H421—C42—H422107.0 (15)
C24—C23—H23121.0 (8)O43—C43—O44125.41 (11)
C22—C23—H23119.2 (8)O43—C43—C42117.02 (11)
C25—C24—C23120.43 (11)O44—C43—C42117.57 (11)
C15—N1—C11—C121.50 (18)N2—C21—C22—C230.76 (17)
C15—N1—C11—C17176.24 (11)C27—C21—C22—C23178.72 (11)
N1—C11—C12—O1179.24 (10)O2—C22—C23—C24179.54 (11)
C17—C11—C12—O13.13 (18)C21—C22—C23—C240.47 (18)
N1—C11—C12—C130.19 (17)C22—C23—C24—C250.51 (18)
C17—C11—C12—C13177.81 (11)C21—N2—C25—C240.89 (17)
O1—C12—C13—C14179.87 (11)C21—N2—C25—C26179.01 (11)
C11—C12—C13—C141.14 (18)C23—C24—C25—N21.16 (17)
C12—C13—C14—C150.53 (18)C23—C24—C25—C26178.74 (12)
C11—N1—C15—C142.11 (18)N2—C21—C27—C28108.67 (13)
C11—N1—C15—C16177.54 (11)C22—C21—C27—C2871.86 (16)
C13—C14—C15—N11.02 (18)O32—C31—C32—C33178.67 (12)
C13—C14—C15—C16178.60 (12)O31—C31—C32—C331.77 (18)
N1—C11—C17—C1892.62 (14)C31—C32—C33—O33179.68 (11)
C12—C11—C17—C1884.99 (16)C31—C32—C33—O340.52 (18)
C25—N2—C21—C220.07 (17)O42—C41—C42—C43163.63 (12)
C25—N2—C21—C27179.43 (11)O41—C41—C42—C4317.38 (18)
N2—C21—C22—O2179.89 (10)C41—C42—C43—O43163.73 (12)
C27—C21—C22—O20.42 (17)C41—C42—C43—O4417.02 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O31—H31···O341.09 (2)1.38 (2)2.4410 (13)162 (2)
O41—H41···O441.04 (2)1.44 (2)2.4428 (12)162 (2)
O1—H12···O330.901 (19)1.69 (2)2.5925 (13)175.0 (17)
O2—H22···O430.96 (2)1.62 (2)2.5610 (12)167.6 (19)
N2—H21···O320.927 (17)1.800 (17)2.7196 (13)170.9 (15)
N1—H11···O42i0.918 (15)1.850 (16)2.7604 (13)171.1 (13)
Symmetry code: (i) x1, y+2, z+1.
2-Ethyl-3-hydroxy-6-methylpyridin-1-ium 6-carboxyhexanoate (III) top
Crystal data top
C8H12NO+·C6H9O4Z = 2
Mr = 283.32F(000) = 304
Triclinic, P1Dx = 1.316 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.7831 (17) ÅCell parameters from 2982 reflections
b = 8.9442 (17) Åθ = 2.4–30.3°
c = 9.6114 (18) ŵ = 0.10 mm1
α = 77.301 (3)°T = 150 K
β = 76.142 (3)°Prism, colourless
γ = 85.677 (3)°0.45 × 0.40 × 0.30 mm
V = 714.9 (2) Å3
Data collection top
Bruker SMART APEXII
diffractometer
3122 independent reflections
Radiation source: fine-focus sealed tube2569 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ω scansθmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1111
Tmin = 0.957, Tmax = 0.971k = 1111
6841 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: difference Fourier map
wR(F2) = 0.114All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0678P)2 + 0.0968P]
where P = (Fo2 + 2Fc2)/3
3122 reflections(Δ/σ)max < 0.001
265 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.22 e Å3
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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.20593 (11)0.62338 (11)0.11713 (10)0.0292 (2)
H20.228 (2)0.700 (2)0.047 (2)0.064 (6)*
N10.13170 (12)0.45634 (12)0.23947 (11)0.0211 (2)
H10.153 (2)0.375 (2)0.306 (2)0.041 (5)*
C10.01767 (14)0.47705 (14)0.22500 (13)0.0208 (3)
C20.05585 (15)0.60828 (14)0.12762 (13)0.0221 (3)
C30.06186 (16)0.71071 (15)0.05091 (14)0.0245 (3)
C40.21377 (16)0.68091 (15)0.06912 (14)0.0249 (3)
C50.25044 (14)0.55150 (14)0.16525 (13)0.0227 (3)
C60.41058 (16)0.50777 (18)0.19083 (16)0.0296 (3)
C70.13652 (15)0.36075 (14)0.31264 (14)0.0243 (3)
C80.24304 (19)0.41427 (18)0.44312 (17)0.0348 (3)
H30.0377 (18)0.8016 (19)0.0186 (18)0.034 (4)*
H40.2981 (18)0.7486 (18)0.0168 (17)0.027 (4)*
H610.410 (3)0.493 (2)0.285 (3)0.067 (6)*
H620.447 (2)0.420 (2)0.154 (2)0.047 (5)*
H630.487 (2)0.585 (2)0.143 (2)0.049 (5)*
H710.0840 (18)0.2653 (18)0.3421 (17)0.031 (4)*
H720.1990 (19)0.3413 (18)0.2460 (19)0.036 (4)*
H810.180 (2)0.430 (2)0.510 (2)0.053 (5)*
H820.296 (2)0.512 (2)0.413 (2)0.052 (5)*
H830.321 (2)0.339 (2)0.4962 (19)0.040 (4)*
O110.00039 (12)0.15146 (13)0.59754 (12)0.0434 (3)
H110.051 (3)0.068 (3)0.692 (3)0.088 (8)*
O120.22294 (11)0.23943 (11)0.45206 (10)0.0300 (2)
O130.89348 (11)0.04695 (12)0.81496 (12)0.0393 (3)
O140.68104 (11)0.17891 (11)0.93355 (10)0.0315 (2)
C110.15037 (15)0.15899 (14)0.56614 (14)0.0248 (3)
C120.23604 (15)0.06199 (16)0.67565 (16)0.0278 (3)
C130.40362 (14)0.10703 (14)0.65759 (14)0.0223 (3)
C140.48701 (14)0.00703 (14)0.76002 (14)0.0232 (3)
C150.65418 (15)0.03752 (15)0.74244 (15)0.0244 (3)
C160.74819 (14)0.07165 (14)0.83756 (14)0.0237 (3)
H1210.239 (2)0.044 (2)0.658 (2)0.047 (5)*
H1220.175 (2)0.0607 (19)0.770 (2)0.039 (4)*
H1310.4583 (18)0.1133 (17)0.5562 (18)0.028 (4)*
H1320.4040 (18)0.2086 (18)0.6765 (17)0.031 (4)*
H1410.4301 (19)0.0117 (18)0.8594 (19)0.034 (4)*
H1420.4890 (16)0.1073 (17)0.7352 (16)0.023 (4)*
H1510.7129 (18)0.0471 (18)0.6417 (19)0.032 (4)*
H1520.6544 (19)0.138 (2)0.7678 (19)0.039 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0238 (5)0.0301 (5)0.0287 (5)0.0001 (4)0.0120 (4)0.0106 (4)
N10.0235 (6)0.0200 (5)0.0181 (5)0.0001 (4)0.0079 (4)0.0032 (4)
C10.0231 (6)0.0208 (6)0.0174 (6)0.0003 (5)0.0070 (5)0.0003 (5)
C20.0239 (6)0.0228 (6)0.0184 (6)0.0021 (5)0.0078 (5)0.0005 (5)
C30.0303 (7)0.0217 (6)0.0186 (6)0.0003 (5)0.0075 (5)0.0040 (5)
C40.0272 (7)0.0245 (6)0.0201 (6)0.0049 (5)0.0050 (5)0.0023 (5)
C50.0235 (6)0.0250 (6)0.0185 (6)0.0015 (5)0.0055 (5)0.0011 (5)
C60.0230 (7)0.0375 (8)0.0244 (7)0.0015 (6)0.0056 (5)0.0022 (6)
C70.0253 (6)0.0210 (6)0.0248 (6)0.0021 (5)0.0100 (5)0.0040 (5)
C80.0350 (8)0.0315 (8)0.0292 (7)0.0033 (6)0.0004 (6)0.0050 (6)
O110.0224 (5)0.0530 (7)0.0418 (6)0.0050 (5)0.0145 (4)0.0269 (5)
O120.0259 (5)0.0304 (5)0.0279 (5)0.0019 (4)0.0110 (4)0.0119 (4)
O130.0226 (5)0.0459 (6)0.0404 (6)0.0045 (4)0.0153 (4)0.0205 (5)
O140.0254 (5)0.0316 (5)0.0313 (5)0.0018 (4)0.0124 (4)0.0134 (4)
C110.0220 (6)0.0229 (6)0.0273 (7)0.0020 (5)0.0113 (5)0.0064 (5)
C120.0216 (7)0.0282 (7)0.0285 (7)0.0028 (5)0.0111 (6)0.0118 (6)
C130.0204 (6)0.0203 (6)0.0238 (7)0.0004 (5)0.0088 (5)0.0049 (5)
C140.0197 (6)0.0229 (6)0.0234 (7)0.0004 (5)0.0079 (5)0.0059 (5)
C150.0214 (6)0.0229 (6)0.0260 (7)0.0007 (5)0.0103 (5)0.0059 (5)
C160.0219 (6)0.0241 (6)0.0228 (6)0.0005 (5)0.0087 (5)0.0033 (5)
Geometric parameters (Å, º) top
O1—C21.3405 (15)C8—H820.97 (2)
O1—H20.90 (2)C8—H830.970 (18)
N1—C11.3470 (16)O11—C111.2892 (16)
N1—C51.3533 (16)O11—H111.07 (3)
N1—H10.90 (2)O12—C111.2303 (15)
C1—C21.4050 (16)O13—C161.2701 (16)
C1—C71.4962 (17)O14—C161.2470 (16)
C2—C31.3901 (18)C11—C121.5187 (16)
C3—C41.3856 (19)C12—C131.5149 (18)
C3—H30.977 (17)C12—H1210.994 (19)
C4—C51.3832 (17)C12—H1220.933 (18)
C4—H40.961 (16)C13—C141.5290 (16)
C5—C61.4940 (18)C13—H1310.970 (16)
C6—H610.89 (2)C13—H1320.965 (16)
C6—H620.931 (19)C14—C151.5109 (18)
C6—H630.96 (2)C14—H1410.959 (17)
C7—C81.520 (2)C14—H1420.975 (15)
C7—H710.958 (16)C15—C161.5227 (16)
C7—H720.986 (17)C15—H1510.971 (16)
C8—H810.98 (2)C15—H1520.984 (17)
C2—O1—H2115.9 (13)C7—C8—H83110.9 (10)
C1—N1—C5125.04 (11)H81—C8—H83108.5 (15)
C1—N1—H1117.5 (11)H82—C8—H83109.0 (15)
C5—N1—H1117.4 (11)C11—O11—H11115.9 (13)
N1—C1—C2118.33 (11)O12—C11—O11122.00 (11)
N1—C1—C7119.23 (10)O12—C11—C12120.95 (11)
C2—C1—C7122.44 (11)O11—C11—C12117.04 (11)
O1—C2—C3125.40 (11)C13—C12—C11114.88 (11)
O1—C2—C1115.97 (11)C13—C12—H121107.7 (10)
C3—C2—C1118.63 (11)C11—C12—H121105.2 (11)
C4—C3—C2120.02 (11)C13—C12—H122112.8 (10)
C4—C3—H3120.3 (9)C11—C12—H122108.3 (11)
C2—C3—H3119.6 (9)H121—C12—H122107.4 (15)
C5—C4—C3121.00 (12)C12—C13—C14111.48 (10)
C5—C4—H4116.9 (9)C12—C13—H131108.6 (9)
C3—C4—H4122.1 (9)C14—C13—H131110.8 (9)
N1—C5—C4116.95 (11)C12—C13—H132109.4 (9)
N1—C5—C6117.92 (11)C14—C13—H132110.1 (9)
C4—C5—C6125.12 (12)H131—C13—H132106.4 (13)
C5—C6—H61110.7 (14)C15—C14—C13111.65 (10)
C5—C6—H62109.7 (11)C15—C14—H141109.8 (10)
H61—C6—H62111.1 (18)C13—C14—H141109.1 (10)
C5—C6—H63113.4 (11)C15—C14—H142108.3 (8)
H61—C6—H63105.5 (17)C13—C14—H142108.1 (9)
H62—C6—H63106.3 (15)H141—C14—H142109.9 (13)
C1—C7—C8112.50 (11)C14—C15—C16115.48 (10)
C1—C7—H71109.4 (9)C14—C15—H151111.2 (9)
C8—C7—H71111.7 (9)C16—C15—H151106.9 (9)
C1—C7—H72107.1 (10)C14—C15—H152109.4 (10)
C8—C7—H72110.2 (9)C16—C15—H152106.4 (10)
H71—C7—H72105.6 (13)H151—C15—H152107.1 (14)
C7—C8—H81109.1 (11)O14—C16—O13123.05 (11)
C7—C8—H82111.7 (11)O14—C16—C15119.66 (11)
H81—C8—H82107.5 (15)O13—C16—C15117.29 (11)
C5—N1—C1—C21.12 (18)C3—C4—C5—N10.17 (19)
C5—N1—C1—C7179.02 (11)C3—C4—C5—C6178.91 (13)
N1—C1—C2—O1179.93 (10)N1—C1—C7—C8103.03 (14)
C7—C1—C2—O10.21 (18)C2—C1—C7—C876.83 (16)
N1—C1—C2—C30.09 (18)O12—C11—C12—C1317.5 (2)
C7—C1—C2—C3179.77 (12)O11—C11—C12—C13163.33 (13)
O1—C2—C3—C4178.77 (12)C11—C12—C13—C14173.44 (12)
C1—C2—C3—C41.25 (19)C12—C13—C14—C15179.96 (12)
C2—C3—C4—C51.3 (2)C13—C14—C15—C16178.57 (12)
C1—N1—C5—C41.07 (18)C14—C15—C16—O147.79 (19)
C1—N1—C5—C6177.76 (12)C14—C15—C16—O13172.81 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11···O13i1.07 (3)1.40 (3)2.4639 (15)176 (2)
O1—H2···O14ii0.90 (2)1.66 (2)2.5355 (12)163 (2)
N1—H1···O120.90 (2)1.83 (2)2.7181 (14)167.6 (16)
Symmetry codes: (i) x1, y, z; (ii) x1, y+1, z1.
Geometric parameters (Å, °), graph-set notations and QTAIMC energies (EHB)* of hydrogen bonds in the studied salt forms of EMX top
InteractionD—HH···AD···AD—H···AEHB (kJ mol-1)Graph-set notation
[EMX+Mlt] (1:1)
O11—H11···O14*1.13 (2)1.30 (2)2.4288 (14)176 (2)88.2E(7)
O1—H12···O-13i0.87 (2)1.71 (2)2.5804 (13)178.5 (19)54.1D
N+1—H1···O120.936 (16)1.795 (17)2.7165 (14)167.5 (14)36.8D
[EMX+Mln] (1:1)
O31—H31···O34*1.09 (2)1.38 (2)2.4410 (13)162 (2)68.9E(6)
O41—H41···O44*1.04 (2)1.44 (2)2.4428 (12)162 (2)65.1E(6)
O1—H12···O-330.901 (19)1.69 (2)2.5925 (13)175.0 (17)53.6D
O2—H22···O-430.96 (2)1.62 (2)2.5610 (12)167.6 (19)51.5D
N+2—H21···O320.927 (17)1.800 (17)2.7196 (13)170.9 (15)34.8D
N+1—H11···O42ii0.918 (15)1.850 (16)2.7604 (13)171.1 (13)30.9D
[EMX+Adp] (1:1)
O11—H11···O-13iii1.07 (3)1.40 (3)2.4639 (15)176 (2)72.5C(9)
O1—H2···O14iv0.90 (2)1.66 (2)2.5355 (12)163 (2)59.9D
N+1—H1···O120.90 (2)1.83 (2)2.7181 (14)167.6 (16)36.3D
Note: (*) intramolecular hydrogen bond.

Symmetry codes: (i) x-1/2, -y+1, -z+1/2; (ii) x-1, y+2, z+1; (iii) x-1, y, z; (iv) x-1, y+1, z-1.
Contributions of different types of stabilizing noncovalent interactions into the lattice energy* of studied EMX salts top
Crystal[EMX+Mlt][EMX+Mln][EMX+Adp]
Elatt226.3213.7315.8
ΣE(Hydrogen bonds)90.8 (40.1%)85.4 (39.9%)168.8 (53.4%)
ΣE(C—H···O)70.1 (31.0%)80.1 (37.5%)88.6 (28.1%)
ΣE(C—H···π)9.0 (4.0%)10.2 (4.8%)16.3 (5.2%)
ΣE(H···H)29.7 (13.1%)15.4 (7.2%)26.3 (8.3%)
ΣE(ππ)26.6 (11.8%)22.7 (10.6%)15.9 (5.0%)
E(EMX–EMX)49.0 (21.7%)41.8 (19.5%)25.6 (8.1%)
E(EMX–acid)167.7 (74.1%)153.0 (71.6%)192.1 (60.8%)
E(acid–acid)9.5 (4.2%)18.9 (8.9%)98.1 (31.1%)
Note: (*) all the energies are given in kJ mol-1 and % of Elatt value
Thermophysical data for emoxypine salts top
Tfus (salt) (°C) (onset)ΔHfusTa (kJ mol-1)Tfus (acid) (°C)
[EMX+Mln] (1:1)124.8±0.227.4±0.6135.60
[EMX+Mlt] (1:1)133.2±0.334.8±0.6142.70
[EMX+Adp] (1:1)115.8±0.553.5±1.1151.92
EMX168.8116.6-
Note: (a) for the salts, the values correspond to a mole of molecules in the asymmetric unit.
Solubilities at 25°C for EMX salts and pure EMX in pH 7.4 media top
Solubility (mol l-1)Solid phase recovered after solubility experimenta
[EMX+Mln] (1:1)1.8±0.1amorphous
[EMX+Mlt] (1:1)1.7±0.1[EMX+Mlt]
[EMX+Adp] (1:1)0.38±0.05[EMX+Adp]
EMX0.047±0.01EMX
Note: (a) the residual materials were identified by DSC and PXRD analyses (Fig. S2–S5 in the supporting information).
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds