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In 2,4-diamino-5-(4-chlorophenyl)-6-ethylpyrimidin-1-ium (pyrimethaminium, PMNH) 4-methylbenzoate, C
12H
14ClN
4+·C
8H
7O
2−, (I), pyrimethaminium 3-hydroxypicolinate, C
12H
14ClN
4+·C
6H
4NO
3−, (II), and pyrimethaminium 2,4-dichlorobenzoate, C
12H
14ClN
4+·C
7H
3Cl
2O
2−, (III), the PMNH cations interact with the carboxylate groups of the corresponding anion
via nearly parallel N—H
O hydrogen bonds, forming
R22(8) ring motifs. A description of the observed arrays of quadruple hydrogen bonds in (I) and (II) in terms of hydrogen donors and acceptors (the
DA model), their graph-set motifs and the resulting supramolecular ladder is given. In (III), supramolecular chains along the
b axis and helical chains along the
a axis are formed
via N—H
O hydrogen bonds involving the 2-amino and 4-amino groups of the PMNH cation, respectively. Weak Cl
Cl interactions are also found in (III).
Supporting information
CCDC references: 774075; 774076; 774077
Compounds (I)–(III) were prepared by mixing hot methanol solutions (20 ml) of
pyrimethamine (62 mg; Shah Pharma Chemicals, India) with hot aqueous solutions
(Volume?) of the corresponding acid [4-methylbenzoic acid (34 mg, Loba Chemie)
for (I), 3-hydroxypicolinic acid (34 mg, Loba Chemie) for (II) and
2,4-dichlorobenzoic acid (47 mg, Loba Chemie) for (III)] in a 1:1 molar ratio,
and warming for 30 min over a water bath. Each solution was cooled slowly and
kept at room temperature. After a few days, colourless crystals were obtained
in each case.
All H atoms were positioned geometrically and refined using a riding model, with
C—H = 0.93–0.97 Å and N—H = 0.86 Å in (I)–(III), and O—H = 0.82 Å in (II), and with Uiso(H) = 1.5Ueq(C,O) for OH groups in
(II) and for all methyl groups, and Uiso(H) = 1.2Ueq(C,N)
for all other H atoms.
For all compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
(I) 2,4-diamino-5-(4-chlorophenyl)-6-ethylpyrimidin-1-ium 4-methylbenzoate
top
Crystal data top
C12H14ClN4+·C8H7O2− | F(000) = 1616 |
Mr = 384.86 | Dx = 1.247 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3398 reflections |
a = 17.1373 (3) Å | θ = 1.8–24.5° |
b = 16.4776 (3) Å | µ = 0.21 mm−1 |
c = 16.6127 (3) Å | T = 293 K |
β = 119.080 (1)° | Prism, colourless |
V = 4099.77 (13) Å3 | 0.15 × 0.12 × 0.12 mm |
Z = 8 | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 3398 independent reflections |
Radiation source: fine-focus sealed tube | 2474 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 24.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −19→19 |
Tmin = 0.970, Tmax = 0.975 | k = −19→19 |
32486 measured reflections | l = −19→19 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.144 | w = 1/[σ2(Fo2) + (0.0658P)2 + 3.2788P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3398 reflections | Δρmax = 0.42 e Å−3 |
247 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc* = kFc[1+0.001Fc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0027 (4) |
Crystal data top
C12H14ClN4+·C8H7O2− | V = 4099.77 (13) Å3 |
Mr = 384.86 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.1373 (3) Å | µ = 0.21 mm−1 |
b = 16.4776 (3) Å | T = 293 K |
c = 16.6127 (3) Å | 0.15 × 0.12 × 0.12 mm |
β = 119.080 (1)° | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 3398 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2474 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.975 | Rint = 0.038 |
32486 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.42 e Å−3 |
3398 reflections | Δρmin = −0.39 e Å−3 |
247 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user
for potential systematic errors. Weighted R-factors wR and all
goodnesses of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The observed criterion of F2 > σ(F2)
is used only for calculating -R-factor-obs 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 | x | y | z | Uiso*/Ueq | |
Cl1 | 0.30822 (8) | 0.39451 (7) | 0.04367 (7) | 0.1284 (5) | |
N1 | 0.48427 (13) | 0.14845 (13) | 0.52582 (12) | 0.0611 (7) | |
N2 | 0.44626 (15) | 0.11987 (15) | 0.63640 (14) | 0.0813 (9) | |
N3 | 0.35105 (12) | 0.19873 (12) | 0.51388 (12) | 0.0528 (6) | |
N4 | 0.26177 (13) | 0.28077 (13) | 0.39515 (13) | 0.0667 (8) | |
C2 | 0.42561 (15) | 0.15605 (15) | 0.55722 (15) | 0.0554 (8) | |
C4 | 0.33485 (14) | 0.23610 (14) | 0.43547 (15) | 0.0506 (7) | |
C5 | 0.39374 (15) | 0.22935 (14) | 0.39751 (15) | 0.0534 (8) | |
C6 | 0.46936 (15) | 0.18496 (15) | 0.44614 (15) | 0.0576 (8) | |
C7 | 0.54004 (18) | 0.17130 (18) | 0.41872 (19) | 0.0742 (10) | |
C8 | 0.5349 (3) | 0.0906 (3) | 0.3791 (3) | 0.1290 (19) | |
C9 | 0.37267 (15) | 0.27061 (15) | 0.30981 (16) | 0.0564 (8) | |
C10 | 0.41131 (18) | 0.34358 (17) | 0.30932 (19) | 0.0703 (10) | |
C11 | 0.3911 (2) | 0.38150 (18) | 0.2270 (2) | 0.0799 (11) | |
C12 | 0.3324 (2) | 0.3462 (2) | 0.1463 (2) | 0.0776 (11) | |
C13 | 0.2929 (2) | 0.2741 (2) | 0.1443 (2) | 0.0900 (11) | |
C14 | 0.3130 (2) | 0.23686 (18) | 0.22632 (18) | 0.0759 (10) | |
O1 | 0.64302 (12) | 0.09524 (12) | 0.75217 (12) | 0.0764 (7) | |
O2 | 0.61921 (13) | 0.05308 (13) | 0.61543 (13) | 0.0884 (8) | |
C15 | 0.74092 (15) | −0.00252 (15) | 0.74470 (16) | 0.0580 (8) | |
C16 | 0.76369 (17) | −0.04889 (16) | 0.68968 (19) | 0.0667 (9) | |
C17 | 0.8389 (2) | −0.09686 (19) | 0.7290 (3) | 0.0904 (14) | |
C18 | 0.8935 (2) | −0.0998 (2) | 0.8236 (3) | 0.1095 (16) | |
C19 | 0.8693 (2) | −0.0547 (3) | 0.8768 (2) | 0.1027 (14) | |
C20 | 0.79429 (17) | −0.00652 (19) | 0.83934 (18) | 0.0764 (10) | |
C21 | 0.66182 (16) | 0.05275 (16) | 0.70211 (16) | 0.0591 (8) | |
C22 | 0.9769 (3) | −0.1533 (4) | 0.8658 (4) | 0.192 (3) | |
H1 | 0.53190 | 0.12010 | 0.55650 | 0.0730* | |
H2A | 0.41120 | 0.12410 | 0.65960 | 0.0980* | |
H2B | 0.49470 | 0.09210 | 0.66460 | 0.0980* | |
H4A | 0.22750 | 0.28470 | 0.41930 | 0.0800* | |
H4B | 0.24850 | 0.30590 | 0.34470 | 0.0800* | |
H7A | 0.53400 | 0.21220 | 0.37400 | 0.0890* | |
H7B | 0.59840 | 0.17790 | 0.47250 | 0.0890* | |
H8A | 0.53850 | 0.04980 | 0.42210 | 0.1930* | |
H8B | 0.58350 | 0.08390 | 0.36640 | 0.1930* | |
H8C | 0.47930 | 0.08530 | 0.32300 | 0.1930* | |
H10 | 0.45140 | 0.36780 | 0.36480 | 0.0840* | |
H11 | 0.41770 | 0.43070 | 0.22710 | 0.0960* | |
H13 | 0.25290 | 0.25040 | 0.08850 | 0.1080* | |
H14 | 0.28570 | 0.18780 | 0.22540 | 0.0910* | |
H16 | 0.72800 | −0.04760 | 0.62600 | 0.0800* | |
H17 | 0.85340 | −0.12790 | 0.69130 | 0.1090* | |
H19 | 0.90470 | −0.05660 | 0.94050 | 0.1230* | |
H20 | 0.77950 | 0.02330 | 0.87750 | 0.0910* | |
H22A | 0.96980 | −0.19640 | 0.82390 | 0.2880* | |
H22B | 0.98530 | −0.17580 | 0.92270 | 0.2880* | |
H22C | 1.02810 | −0.12120 | 0.87720 | 0.2880* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.1810 (11) | 0.1438 (9) | 0.0940 (7) | 0.0300 (7) | 0.0932 (7) | 0.0522 (6) |
N1 | 0.0549 (11) | 0.0839 (14) | 0.0490 (11) | 0.0213 (10) | 0.0288 (9) | 0.0102 (10) |
N2 | 0.0817 (15) | 0.1171 (19) | 0.0622 (13) | 0.0446 (14) | 0.0484 (12) | 0.0364 (13) |
N3 | 0.0491 (11) | 0.0684 (12) | 0.0463 (10) | 0.0099 (9) | 0.0274 (9) | 0.0073 (9) |
N4 | 0.0601 (12) | 0.0950 (16) | 0.0580 (12) | 0.0274 (11) | 0.0389 (10) | 0.0266 (11) |
C2 | 0.0545 (13) | 0.0689 (15) | 0.0479 (13) | 0.0099 (12) | 0.0290 (11) | 0.0040 (11) |
C4 | 0.0480 (12) | 0.0623 (14) | 0.0456 (12) | 0.0039 (11) | 0.0259 (10) | 0.0035 (10) |
C5 | 0.0514 (13) | 0.0672 (15) | 0.0479 (12) | 0.0050 (11) | 0.0291 (11) | 0.0042 (11) |
C6 | 0.0554 (13) | 0.0745 (16) | 0.0494 (13) | 0.0068 (12) | 0.0306 (11) | 0.0024 (11) |
C7 | 0.0702 (16) | 0.098 (2) | 0.0689 (17) | 0.0213 (15) | 0.0451 (14) | 0.0120 (15) |
C8 | 0.142 (3) | 0.149 (4) | 0.138 (3) | 0.000 (3) | 0.101 (3) | −0.038 (3) |
C9 | 0.0544 (13) | 0.0725 (16) | 0.0537 (14) | 0.0113 (12) | 0.0353 (12) | 0.0078 (11) |
C10 | 0.0693 (16) | 0.0784 (18) | 0.0685 (17) | 0.0022 (14) | 0.0377 (14) | 0.0082 (14) |
C11 | 0.084 (2) | 0.0795 (19) | 0.099 (2) | 0.0102 (16) | 0.0624 (19) | 0.0246 (17) |
C12 | 0.089 (2) | 0.098 (2) | 0.0673 (19) | 0.0240 (17) | 0.0550 (17) | 0.0249 (16) |
C13 | 0.110 (2) | 0.107 (2) | 0.0544 (17) | −0.003 (2) | 0.0411 (17) | 0.0100 (16) |
C14 | 0.0881 (19) | 0.0864 (19) | 0.0568 (16) | −0.0091 (15) | 0.0381 (15) | 0.0066 (14) |
O1 | 0.0703 (11) | 0.1006 (14) | 0.0644 (11) | 0.0182 (10) | 0.0375 (9) | −0.0077 (10) |
O2 | 0.0814 (13) | 0.1205 (17) | 0.0544 (11) | 0.0424 (12) | 0.0261 (10) | 0.0025 (10) |
C15 | 0.0539 (13) | 0.0667 (15) | 0.0588 (14) | 0.0059 (11) | 0.0317 (12) | 0.0124 (11) |
C16 | 0.0681 (16) | 0.0658 (16) | 0.0751 (17) | 0.0087 (13) | 0.0419 (14) | 0.0075 (13) |
C17 | 0.097 (2) | 0.081 (2) | 0.124 (3) | 0.0313 (17) | 0.078 (2) | 0.0307 (19) |
C18 | 0.090 (2) | 0.132 (3) | 0.130 (3) | 0.056 (2) | 0.072 (2) | 0.078 (3) |
C19 | 0.075 (2) | 0.157 (3) | 0.080 (2) | 0.035 (2) | 0.0407 (17) | 0.061 (2) |
C20 | 0.0655 (16) | 0.107 (2) | 0.0627 (16) | 0.0114 (15) | 0.0359 (14) | 0.0235 (15) |
C21 | 0.0543 (13) | 0.0722 (16) | 0.0533 (15) | 0.0071 (12) | 0.0281 (12) | 0.0016 (12) |
C22 | 0.150 (4) | 0.246 (6) | 0.214 (6) | 0.136 (4) | 0.116 (4) | 0.146 (5) |
Geometric parameters (Å, º) top
Cl1—C12 | 1.739 (3) | C7—H7B | 0.9700 |
O1—C21 | 1.243 (3) | C7—H7A | 0.9700 |
O2—C21 | 1.259 (3) | C8—H8C | 0.9600 |
N1—C6 | 1.360 (3) | C8—H8A | 0.9600 |
N1—C2 | 1.345 (4) | C8—H8B | 0.9600 |
N2—C2 | 1.326 (3) | C10—H10 | 0.9300 |
N3—C4 | 1.342 (3) | C11—H11 | 0.9300 |
N3—C2 | 1.323 (3) | C13—H13 | 0.9300 |
N4—C4 | 1.320 (3) | C14—H14 | 0.9300 |
N1—H1 | 0.8600 | C15—C16 | 1.385 (4) |
N2—H2B | 0.8600 | C15—C20 | 1.384 (4) |
N2—H2A | 0.8600 | C15—C21 | 1.495 (4) |
N4—H4A | 0.8600 | C16—C17 | 1.376 (5) |
N4—H4B | 0.8600 | C17—C18 | 1.385 (6) |
C4—C5 | 1.431 (4) | C18—C19 | 1.364 (6) |
C5—C9 | 1.485 (3) | C18—C22 | 1.529 (7) |
C5—C6 | 1.360 (4) | C19—C20 | 1.376 (5) |
C6—C7 | 1.504 (4) | C16—H16 | 0.9300 |
C7—C8 | 1.467 (6) | C17—H17 | 0.9300 |
C9—C14 | 1.378 (4) | C19—H19 | 0.9300 |
C9—C10 | 1.375 (4) | C20—H20 | 0.9300 |
C10—C11 | 1.386 (4) | C22—H22A | 0.9600 |
C11—C12 | 1.355 (4) | C22—H22B | 0.9600 |
C12—C13 | 1.360 (5) | C22—H22C | 0.9600 |
C13—C14 | 1.377 (4) | | |
| | | |
Cl1···C19i | 3.507 (4) | C14···H4B | 2.9100 |
Cl1···H19i | 3.0100 | C16···H14xi | 3.0200 |
Cl1···H13ii | 3.0600 | C16···H11iii | 3.0900 |
O1···N4iii | 3.043 (3) | C17···H11iii | 3.0600 |
O1···N2 | 2.988 (3) | C17···H14xi | 2.9900 |
O1···N2iv | 2.947 (3) | C21···H1 | 2.6100 |
O2···N1 | 2.586 (3) | C21···H2B | 2.7000 |
O1···H2B | 2.2300 | H1···O1 | 2.8900 |
O1···H20 | 2.5400 | H1···O2 | 1.7300 |
O1···H2Aiv | 2.1400 | H1···C8 | 3.0100 |
O1···H4Biii | 2.3600 | H1···H2B | 2.2300 |
O1···H1 | 2.8900 | H1···H7B | 2.3900 |
O2···H1 | 1.7300 | H1···H8A | 2.5700 |
O2···H16 | 2.4400 | H1···C21 | 2.6100 |
O2···H2B | 2.7100 | H2A···H4Av | 2.5700 |
O2···H8A | 2.8100 | H2A···O1iv | 2.1400 |
N1···O2 | 2.586 (3) | H2B···O1 | 2.2300 |
N1···C21 | 3.415 (3) | H2B···H1 | 2.2300 |
N2···O1iv | 2.947 (3) | H2B···C8xi | 3.0800 |
N2···O1 | 2.988 (3) | H2B···O2 | 2.7100 |
N2···N2iv | 3.299 (3) | H2B···C21 | 2.7000 |
N3···N4v | 2.996 (3) | H4A···N3v | 2.1400 |
N4···N3v | 2.996 (3) | H4A···H2Av | 2.5700 |
N4···O1vi | 3.043 (3) | H4A···C2v | 3.0000 |
N4···C14 | 3.399 (4) | H4A···C4v | 3.1000 |
N1···H8A | 2.8300 | H4B···C14 | 2.9100 |
N3···H4Av | 2.1400 | H4B···O1vi | 2.3600 |
C2···C22vii | 3.496 (7) | H4B···C9 | 2.5300 |
C7···C10 | 3.512 (4) | H7A···C9 | 2.6200 |
C10···C7 | 3.512 (4) | H7A···C10 | 2.8400 |
C10···C20vi | 3.529 (4) | H7B···H1 | 2.3900 |
C11···C16vi | 3.383 (4) | H8A···O2 | 2.8100 |
C11···C11viii | 3.427 (5) | H8A···H1 | 2.5700 |
C11···C15vi | 3.380 (4) | H8A···N1 | 2.8300 |
C14···N4 | 3.399 (4) | H11···C16vi | 3.0900 |
C15···C11iii | 3.380 (4) | H11···C17vi | 3.0600 |
C16···C11iii | 3.383 (4) | H11···H11viii | 2.5400 |
C19···Cl1ix | 3.507 (4) | H11···C11viii | 3.0900 |
C20···C10iii | 3.529 (4) | H13···Cl1ii | 3.0600 |
C21···N1 | 3.415 (3) | H14···C16xi | 3.0200 |
C22···C2x | 3.496 (7) | H14···C17xi | 2.9900 |
C2···H22Avii | 3.1000 | H16···O2 | 2.4400 |
C2···H4Av | 3.0000 | H17···H22A | 2.4200 |
C4···H4Av | 3.1000 | H19···H22B | 2.5000 |
C6···H22Bvii | 2.9900 | H19···Cl1ix | 3.0100 |
C8···H1 | 3.0100 | H20···O1 | 2.5400 |
C8···H2Bxi | 3.0800 | H22A···H17 | 2.4200 |
C9···H7A | 2.6200 | H22A···C2x | 3.1000 |
C9···H4B | 2.5300 | H22B···H19 | 2.5000 |
C10···H7A | 2.8400 | H22B···C6x | 2.9900 |
C11···H11viii | 3.0900 | | |
| | | |
C2—N1—C6 | 120.9 (2) | C7—C8—H8C | 109.00 |
C2—N3—C4 | 117.5 (2) | H8A—C8—H8B | 110.00 |
C2—N1—H1 | 120.00 | H8A—C8—H8C | 109.00 |
C6—N1—H1 | 119.00 | H8B—C8—H8C | 110.00 |
C2—N2—H2A | 120.00 | C9—C10—H10 | 120.00 |
C2—N2—H2B | 120.00 | C11—C10—H10 | 120.00 |
H2A—N2—H2B | 120.00 | C10—C11—H11 | 120.00 |
H4A—N4—H4B | 120.00 | C12—C11—H11 | 120.00 |
C4—N4—H4A | 120.00 | C12—C13—H13 | 121.00 |
C4—N4—H4B | 120.00 | C14—C13—H13 | 121.00 |
N1—C2—N3 | 123.0 (2) | C9—C14—H14 | 119.00 |
N2—C2—N3 | 120.0 (3) | C13—C14—H14 | 119.00 |
N1—C2—N2 | 117.0 (2) | C16—C15—C20 | 118.7 (3) |
N3—C4—N4 | 116.5 (2) | C16—C15—C21 | 120.4 (2) |
N3—C4—C5 | 122.3 (2) | C20—C15—C21 | 120.9 (2) |
N4—C4—C5 | 121.2 (2) | C15—C16—C17 | 120.2 (3) |
C4—C5—C6 | 116.9 (2) | C16—C17—C18 | 121.3 (3) |
C4—C5—C9 | 120.7 (2) | C17—C18—C19 | 117.7 (4) |
C6—C5—C9 | 122.4 (2) | C17—C18—C22 | 120.4 (4) |
N1—C6—C5 | 119.3 (2) | C19—C18—C22 | 121.9 (4) |
N1—C6—C7 | 115.5 (2) | C18—C19—C20 | 122.2 (3) |
C5—C6—C7 | 125.2 (2) | C15—C20—C19 | 119.9 (3) |
C6—C7—C8 | 113.0 (3) | O1—C21—O2 | 124.6 (3) |
C5—C9—C10 | 121.2 (2) | O1—C21—C15 | 119.8 (2) |
C5—C9—C14 | 120.7 (2) | O2—C21—C15 | 115.6 (2) |
C10—C9—C14 | 118.1 (2) | C15—C16—H16 | 120.00 |
C9—C10—C11 | 120.7 (3) | C17—C16—H16 | 120.00 |
C10—C11—C12 | 119.5 (3) | C16—C17—H17 | 119.00 |
Cl1—C12—C11 | 118.8 (3) | C18—C17—H17 | 119.00 |
Cl1—C12—C13 | 119.8 (2) | C18—C19—H19 | 119.00 |
C11—C12—C13 | 121.4 (3) | C20—C19—H19 | 119.00 |
C12—C13—C14 | 118.9 (3) | C15—C20—H20 | 120.00 |
C9—C14—C13 | 121.5 (3) | C19—C20—H20 | 120.00 |
C6—C7—H7A | 109.00 | C18—C22—H22A | 109.00 |
C6—C7—H7B | 109.00 | C18—C22—H22B | 110.00 |
C8—C7—H7A | 109.00 | C18—C22—H22C | 109.00 |
C8—C7—H7B | 109.00 | H22A—C22—H22B | 110.00 |
H7A—C7—H7B | 108.00 | H22A—C22—H22C | 109.00 |
C7—C8—H8A | 109.00 | H22B—C22—H22C | 109.00 |
C7—C8—H8B | 109.00 | | |
| | | |
C6—N1—C2—N2 | −178.6 (2) | C14—C9—C10—C11 | −0.5 (5) |
C6—N1—C2—N3 | −0.1 (4) | C5—C9—C14—C13 | −179.8 (3) |
C2—N1—C6—C5 | −0.4 (4) | C10—C9—C14—C13 | 0.7 (5) |
C2—N1—C6—C7 | −179.8 (2) | C9—C10—C11—C12 | 0.2 (5) |
C4—N3—C2—N1 | −0.5 (3) | C10—C11—C12—Cl1 | −179.7 (3) |
C4—N3—C2—N2 | 178.0 (2) | C10—C11—C12—C13 | −0.1 (6) |
C2—N3—C4—N4 | −177.6 (2) | Cl1—C12—C13—C14 | 180.0 (3) |
C2—N3—C4—C5 | 1.6 (3) | C11—C12—C13—C14 | 0.4 (6) |
N3—C4—C5—C6 | −2.0 (3) | C12—C13—C14—C9 | −0.7 (5) |
N3—C4—C5—C9 | 179.0 (2) | C20—C15—C16—C17 | −1.0 (4) |
N4—C4—C5—C6 | 177.1 (2) | C21—C15—C16—C17 | 177.0 (3) |
N4—C4—C5—C9 | −1.9 (3) | C16—C15—C20—C19 | 1.3 (5) |
C4—C5—C6—N1 | 1.3 (3) | C21—C15—C20—C19 | −176.7 (3) |
C4—C5—C6—C7 | −179.3 (2) | C16—C15—C21—O1 | −178.6 (3) |
C9—C5—C6—N1 | −179.7 (2) | C16—C15—C21—O2 | 0.4 (4) |
C9—C5—C6—C7 | −0.4 (4) | C20—C15—C21—O1 | −0.7 (4) |
C4—C5—C9—C10 | 99.0 (3) | C20—C15—C21—O2 | 178.3 (3) |
C4—C5—C9—C14 | −80.5 (3) | C15—C16—C17—C18 | −0.3 (5) |
C6—C5—C9—C10 | −79.9 (3) | C16—C17—C18—C19 | 1.3 (6) |
C6—C5—C9—C14 | 100.6 (3) | C16—C17—C18—C22 | −179.8 (4) |
N1—C6—C7—C8 | 76.8 (3) | C17—C18—C19—C20 | −1.0 (6) |
C5—C6—C7—C8 | −102.6 (3) | C22—C18—C19—C20 | −179.9 (4) |
C5—C9—C10—C11 | −180.0 (3) | C18—C19—C20—C15 | −0.3 (6) |
Symmetry codes: (i) x−1/2, y+1/2, z−1; (ii) −x+1/2, −y+1/2, −z; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+1, y, −z+3/2; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z−1/2; (vii) −x+3/2, y+1/2, −z+3/2; (viii) −x+1, y, −z+1/2; (ix) x+1/2, y−1/2, z+1; (x) −x+3/2, y−1/2, −z+3/2; (xi) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 1.73 | 2.586 (3) | 173 |
N2—H2A···O1iv | 0.86 | 2.14 | 2.947 (3) | 157 |
N2—H2B···O1 | 0.86 | 2.23 | 2.988 (3) | 147 |
N4—H4A···N3v | 0.86 | 2.14 | 2.996 (3) | 176 |
N4—H4B···O1vi | 0.86 | 2.36 | 3.043 (3) | 136 |
Symmetry codes: (iv) −x+1, y, −z+3/2; (v) −x+1/2, −y+1/2, −z+1; (vi) x−1/2, −y+1/2, z−1/2. |
(II) 2,4-diamino-(
p-chlorophenyl)-6-ethylpyrimidinium 3-hydroxypicolinate'
top
Crystal data top
C12H14ClN4+·C6H4NO3− | F(000) = 808 |
Mr = 387.82 | Dx = 1.387 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5622 reflections |
a = 11.2563 (3) Å | θ = 1.9–30.4° |
b = 14.3968 (4) Å | µ = 0.24 mm−1 |
c = 11.7902 (3) Å | T = 293 K |
β = 103.625 (1)° | Prism, colourless |
V = 1856.89 (9) Å3 | 0.22 × 0.20 × 0.18 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX II CCD area detector diffractometer | 5622 independent reflections |
Radiation source: fine-focus sealed tube | 3927 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 30.4°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −15→15 |
Tmin = 0.950, Tmax = 0.959 | k = −20→20 |
21858 measured reflections | l = −15→16 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0709P)2 + 0.5158P] where P = (Fo2 + 2Fc2)/3 |
5622 reflections | (Δ/σ)max = 0.001 |
246 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
C12H14ClN4+·C6H4NO3− | V = 1856.89 (9) Å3 |
Mr = 387.82 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.2563 (3) Å | µ = 0.24 mm−1 |
b = 14.3968 (4) Å | T = 293 K |
c = 11.7902 (3) Å | 0.22 × 0.20 × 0.18 mm |
β = 103.625 (1)° | |
Data collection top
Bruker SMART APEX II CCD area detector diffractometer | 5622 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 3927 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.959 | Rint = 0.028 |
21858 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.39 e Å−3 |
5622 reflections | Δρmin = −0.35 e Å−3 |
246 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the
rounded fractional coordinates. All su's are estimated
from the variances of the (full) variance-covariance matrix.
The cell esds are taken into account in the estimation of
distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for
potential systematic errors. Weighted R-factors wR and all goodnesses of fit S
are based on F2, conventional R-factors R are based on F, with F set to zero
for negative F2. The observed criterion of F2 > 2sigma(F2) is used only
for calculating -R-factor-obs 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 | x | y | z | Uiso*/Ueq | |
Cl1 | 0.66240 (6) | 0.62306 (4) | 1.38986 (4) | 0.0694 (2) | |
N1 | 0.82081 (12) | 0.54460 (9) | 0.75791 (11) | 0.0375 (4) | |
N2 | 0.96003 (13) | 0.58674 (10) | 0.65198 (12) | 0.0423 (4) | |
N3 | 0.96070 (12) | 0.66575 (9) | 0.82133 (13) | 0.0416 (4) | |
N4 | 0.95778 (15) | 0.74277 (11) | 0.98868 (15) | 0.0585 (6) | |
C2 | 0.91478 (14) | 0.59983 (10) | 0.74512 (13) | 0.0352 (4) | |
C4 | 0.91457 (14) | 0.67436 (11) | 0.91553 (15) | 0.0401 (5) | |
C5 | 0.82281 (14) | 0.61243 (11) | 0.93933 (14) | 0.0369 (4) | |
C6 | 0.77637 (14) | 0.54923 (11) | 0.85573 (13) | 0.0357 (4) | |
C7 | 0.68328 (16) | 0.47616 (12) | 0.86360 (16) | 0.0464 (5) | |
C8 | 0.7442 (3) | 0.38982 (17) | 0.9185 (3) | 0.0912 (12) | |
C9 | 0.78431 (14) | 0.61809 (11) | 1.05183 (13) | 0.0371 (4) | |
C10 | 0.86250 (18) | 0.59219 (16) | 1.15633 (17) | 0.0577 (7) | |
C11 | 0.8264 (2) | 0.59431 (17) | 1.26033 (17) | 0.0626 (7) | |
C12 | 0.71056 (17) | 0.62210 (12) | 1.26052 (15) | 0.0450 (5) | |
C13 | 0.63071 (18) | 0.64809 (18) | 1.15934 (17) | 0.0623 (7) | |
C14 | 0.66868 (18) | 0.64717 (17) | 1.05624 (16) | 0.0604 (7) | |
O1 | 0.89470 (11) | 0.40927 (9) | 0.54067 (11) | 0.0504 (4) | |
O2 | 0.71175 (11) | 0.43050 (9) | 0.57770 (10) | 0.0477 (4) | |
O3 | 0.51752 (11) | 0.39159 (12) | 0.42491 (13) | 0.0606 (5) | |
N5 | 0.79256 (12) | 0.33747 (10) | 0.32772 (12) | 0.0414 (4) | |
C15 | 0.71958 (14) | 0.36663 (10) | 0.39545 (13) | 0.0348 (4) | |
C16 | 0.59211 (14) | 0.36258 (12) | 0.35892 (15) | 0.0416 (5) | |
C17 | 0.54154 (17) | 0.32534 (15) | 0.24937 (16) | 0.0550 (6) | |
C18 | 0.61739 (19) | 0.29373 (17) | 0.18254 (17) | 0.0613 (7) | |
C19 | 0.74202 (18) | 0.30191 (15) | 0.22363 (16) | 0.0552 (6) | |
C20 | 0.78153 (14) | 0.40452 (10) | 0.51336 (13) | 0.0361 (4) | |
H1 | 0.78890 | 0.50620 | 0.70340 | 0.0450* | |
H2A | 1.01900 | 0.62100 | 0.64120 | 0.0510* | |
H2B | 0.93040 | 0.54400 | 0.60240 | 0.0510* | |
H4A | 1.01310 | 0.77930 | 0.97460 | 0.0700* | |
H4B | 0.93060 | 0.75070 | 1.05030 | 0.0700* | |
H7A | 0.62870 | 0.49950 | 0.90960 | 0.0560* | |
H7B | 0.63480 | 0.46210 | 0.78600 | 0.0560* | |
H8A | 0.80480 | 0.37060 | 0.87800 | 0.1370* | |
H8B | 0.68440 | 0.34160 | 0.91380 | 0.1370* | |
H8C | 0.78280 | 0.40180 | 0.99880 | 0.1370* | |
H10 | 0.94140 | 0.57290 | 1.15640 | 0.0690* | |
H11 | 0.88050 | 0.57700 | 1.32960 | 0.0750* | |
H13 | 0.55160 | 0.66620 | 1.15990 | 0.0750* | |
H14 | 0.61490 | 0.66670 | 0.98790 | 0.0730* | |
H3 | 0.55830 | 0.41250 | 0.48660 | 0.0910* | |
H17 | 0.45720 | 0.32200 | 0.22180 | 0.0660* | |
H18 | 0.58500 | 0.26700 | 0.11010 | 0.0740* | |
H19 | 0.79270 | 0.28180 | 0.17670 | 0.0660* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0910 (4) | 0.0813 (4) | 0.0453 (3) | 0.0149 (3) | 0.0348 (3) | 0.0063 (2) |
N1 | 0.0422 (7) | 0.0389 (7) | 0.0336 (6) | −0.0089 (5) | 0.0133 (5) | −0.0064 (5) |
N2 | 0.0446 (7) | 0.0464 (7) | 0.0403 (7) | −0.0052 (6) | 0.0191 (6) | −0.0020 (6) |
N3 | 0.0420 (7) | 0.0364 (7) | 0.0514 (8) | −0.0057 (5) | 0.0208 (6) | −0.0068 (6) |
N4 | 0.0592 (10) | 0.0552 (9) | 0.0695 (11) | −0.0239 (7) | 0.0323 (8) | −0.0289 (8) |
C2 | 0.0372 (7) | 0.0331 (7) | 0.0374 (7) | 0.0008 (6) | 0.0129 (6) | 0.0027 (6) |
C4 | 0.0371 (8) | 0.0379 (8) | 0.0476 (9) | −0.0035 (6) | 0.0147 (7) | −0.0085 (7) |
C5 | 0.0367 (7) | 0.0387 (8) | 0.0379 (8) | −0.0028 (6) | 0.0140 (6) | −0.0041 (6) |
C6 | 0.0382 (7) | 0.0358 (7) | 0.0354 (7) | −0.0031 (6) | 0.0132 (6) | −0.0017 (6) |
C7 | 0.0496 (9) | 0.0480 (9) | 0.0463 (9) | −0.0161 (7) | 0.0208 (7) | −0.0087 (7) |
C8 | 0.0942 (19) | 0.0500 (12) | 0.128 (3) | −0.0174 (12) | 0.0234 (17) | 0.0184 (14) |
C9 | 0.0390 (8) | 0.0388 (8) | 0.0347 (7) | −0.0011 (6) | 0.0113 (6) | −0.0047 (6) |
C10 | 0.0469 (10) | 0.0817 (14) | 0.0449 (10) | 0.0213 (9) | 0.0114 (8) | 0.0027 (9) |
C11 | 0.0654 (12) | 0.0847 (15) | 0.0368 (9) | 0.0300 (11) | 0.0100 (8) | 0.0077 (9) |
C12 | 0.0557 (10) | 0.0462 (9) | 0.0364 (8) | 0.0040 (7) | 0.0174 (7) | −0.0011 (7) |
C13 | 0.0453 (10) | 0.1000 (17) | 0.0438 (10) | 0.0204 (10) | 0.0149 (8) | −0.0011 (10) |
C14 | 0.0477 (10) | 0.0974 (16) | 0.0351 (9) | 0.0231 (10) | 0.0075 (7) | 0.0031 (9) |
O1 | 0.0370 (6) | 0.0601 (8) | 0.0513 (7) | 0.0040 (5) | 0.0046 (5) | −0.0165 (6) |
O2 | 0.0473 (7) | 0.0586 (7) | 0.0405 (6) | −0.0020 (5) | 0.0167 (5) | −0.0113 (5) |
O3 | 0.0372 (6) | 0.0900 (11) | 0.0571 (8) | 0.0004 (6) | 0.0162 (6) | −0.0172 (7) |
N5 | 0.0393 (7) | 0.0477 (7) | 0.0392 (7) | −0.0016 (6) | 0.0133 (5) | −0.0068 (6) |
C15 | 0.0365 (7) | 0.0340 (7) | 0.0343 (7) | −0.0004 (6) | 0.0094 (6) | −0.0008 (6) |
C16 | 0.0372 (8) | 0.0470 (9) | 0.0412 (8) | 0.0011 (6) | 0.0104 (6) | 0.0008 (7) |
C17 | 0.0394 (9) | 0.0755 (14) | 0.0461 (10) | −0.0024 (8) | 0.0018 (7) | −0.0070 (9) |
C18 | 0.0573 (11) | 0.0815 (15) | 0.0412 (9) | −0.0047 (10) | 0.0041 (8) | −0.0170 (9) |
C19 | 0.0527 (10) | 0.0729 (13) | 0.0418 (9) | −0.0012 (9) | 0.0147 (8) | −0.0159 (9) |
C20 | 0.0394 (8) | 0.0333 (7) | 0.0359 (7) | 0.0020 (6) | 0.0095 (6) | −0.0013 (6) |
Geometric parameters (Å, º) top
Cl1—C12 | 1.7347 (19) | C9—C10 | 1.386 (3) |
O1—C20 | 1.240 (2) | C9—C14 | 1.380 (3) |
O2—C20 | 1.270 (2) | C10—C11 | 1.380 (3) |
O3—C16 | 1.339 (2) | C11—C12 | 1.364 (3) |
O3—H3 | 0.8200 | C12—C13 | 1.366 (3) |
N1—C6 | 1.363 (2) | C13—C14 | 1.380 (3) |
N1—C2 | 1.360 (2) | C7—H7B | 0.9700 |
N2—C2 | 1.328 (2) | C7—H7A | 0.9700 |
N3—C4 | 1.338 (2) | C8—H8B | 0.9600 |
N3—C2 | 1.325 (2) | C8—H8A | 0.9600 |
N4—C4 | 1.324 (2) | C8—H8C | 0.9600 |
N1—H1 | 0.8600 | C10—H10 | 0.9300 |
N2—H2A | 0.8600 | C11—H11 | 0.9300 |
N2—H2B | 0.8600 | C13—H13 | 0.9300 |
N4—H4A | 0.8600 | C14—H14 | 0.9300 |
N4—H4B | 0.8600 | C15—C16 | 1.399 (2) |
N5—C15 | 1.341 (2) | C15—C20 | 1.503 (2) |
N5—C19 | 1.328 (2) | C16—C17 | 1.391 (3) |
C4—C5 | 1.441 (2) | C17—C18 | 1.369 (3) |
C5—C6 | 1.353 (2) | C18—C19 | 1.377 (3) |
C5—C9 | 1.492 (2) | C17—H17 | 0.9300 |
C6—C7 | 1.503 (2) | C18—H18 | 0.9300 |
C7—C8 | 1.492 (3) | C19—H19 | 0.9300 |
| | | |
Cl1···C20i | 3.5913 (16) | C19···H2Aiv | 3.0000 |
Cl1···O3ii | 3.3165 (15) | C19···H8Axii | 3.0600 |
O1···N4iii | 2.982 (2) | C20···H1 | 2.6600 |
O1···N5 | 2.7082 (19) | C20···H4Aiii | 2.9100 |
O1···N2iv | 3.0962 (19) | C20···H2B | 2.6700 |
O1···N2 | 2.8873 (19) | C20···H3 | 2.4600 |
O2···O3 | 2.5462 (19) | H1···O1 | 2.8500 |
O2···N1 | 2.7370 (18) | H1···O2 | 1.8800 |
O3···O2 | 2.5462 (19) | H1···C20 | 2.6600 |
O3···Cl1ii | 3.3165 (15) | H1···H2B | 2.2700 |
O1···H4Aiii | 2.1700 | H1···H7B | 2.2700 |
O1···H2Aiv | 2.5900 | H2A···C15iv | 3.0800 |
O1···H2B | 2.0800 | H2A···N4vi | 2.6400 |
O1···H11v | 2.6400 | H2A···H4Avi | 2.4200 |
O1···H1 | 2.8500 | H2A···C19iv | 3.0000 |
O2···H3 | 1.8200 | H2A···O1iv | 2.5900 |
O2···H1 | 1.8800 | H2A···N5iv | 2.1500 |
O2···H7B | 2.8300 | H2A···H4Bvi | 2.2500 |
O2···H2B | 2.9100 | H2B···C20 | 2.6700 |
N1···O2 | 2.7370 (18) | H2B···O2 | 2.9100 |
N2···O1 | 2.8873 (19) | H2B···H1 | 2.2700 |
N2···N4vi | 3.116 (2) | H2B···O1 | 2.0800 |
N2···O1iv | 3.0962 (19) | H3···O2 | 1.8200 |
N2···N5iv | 2.948 (2) | H3···C20 | 2.4600 |
N4···N2vii | 3.116 (2) | H4A···H2Avii | 2.4200 |
N4···C10 | 3.280 (3) | H4A···O1viii | 2.1700 |
N4···O1viii | 2.982 (2) | H4A···C20viii | 2.9100 |
N5···N2iv | 2.948 (2) | H4A···N5viii | 2.9200 |
N5···O1 | 2.7082 (19) | H4B···C9 | 2.5200 |
N1···H8A | 2.9000 | H4B···H2Avii | 2.2500 |
N2···H4Bvi | 2.6100 | H4B···C10 | 2.7900 |
N2···H11v | 2.9400 | H4B···N2vii | 2.6100 |
N3···H19iv | 2.8700 | H7A···H14 | 2.6000 |
N4···H2Avii | 2.6400 | H7A···C9 | 2.7200 |
N5···H2Aiv | 2.1500 | H7A···C14 | 2.7100 |
N5···H4Aiii | 2.9200 | H7B···O2 | 2.8300 |
C7···C14 | 3.380 (3) | H7B···H1 | 2.2700 |
C8···C19ix | 3.588 (4) | H8A···N1 | 2.9000 |
C10···N4 | 3.280 (3) | H8A···C19ix | 3.0600 |
C13···C17x | 3.523 (3) | H8B···C15ix | 3.0400 |
C14···C7 | 3.380 (3) | H8B···H13ii | 2.6000 |
C17···C13xi | 3.523 (3) | H10···C2v | 3.0400 |
C19···C8xii | 3.588 (4) | H11···N2v | 2.9400 |
C20···Cl1xiii | 3.5913 (16) | H11···O1v | 2.6400 |
C2···H10v | 3.0400 | H13···C17x | 2.8300 |
C9···H7A | 2.7200 | H13···H8Bii | 2.6000 |
C9···H4B | 2.5200 | H14···H18xiv | 2.4700 |
C10···H4B | 2.7900 | H14···H7A | 2.6000 |
C14···H7A | 2.7100 | H14···C17xiv | 2.9400 |
C15···H8Bxii | 3.0400 | H14···C18xiv | 2.9500 |
C15···H2Aiv | 3.0800 | H14···H17xiv | 2.4200 |
C17···H13xi | 2.8300 | H17···H14xiv | 2.4200 |
C17···H14xiv | 2.9400 | H18···H14xiv | 2.4700 |
C18···H14xiv | 2.9500 | H19···N3iv | 2.8700 |
| | | |
C16—O3—H3 | 109.00 | C8—C7—H7A | 109.00 |
C2—N1—C6 | 121.03 (13) | C8—C7—H7B | 110.00 |
C2—N3—C4 | 117.61 (14) | H7A—C7—H7B | 108.00 |
C2—N1—H1 | 119.00 | C6—C7—H7B | 109.00 |
C6—N1—H1 | 119.00 | C7—C8—H8B | 109.00 |
C2—N2—H2A | 120.00 | H8A—C8—H8B | 109.00 |
C2—N2—H2B | 120.00 | H8A—C8—H8C | 109.00 |
H2A—N2—H2B | 120.00 | C7—C8—H8C | 109.00 |
C4—N4—H4A | 120.00 | H8B—C8—H8C | 110.00 |
C4—N4—H4B | 120.00 | C7—C8—H8A | 109.00 |
H4A—N4—H4B | 120.00 | C11—C10—H10 | 119.00 |
C15—N5—C19 | 118.82 (15) | C9—C10—H10 | 119.00 |
N2—C2—N3 | 119.86 (15) | C10—C11—H11 | 120.00 |
N1—C2—N2 | 117.94 (14) | C12—C11—H11 | 120.00 |
N1—C2—N3 | 122.20 (14) | C12—C13—H13 | 120.00 |
N3—C4—C5 | 122.71 (15) | C14—C13—H13 | 120.00 |
N3—C4—N4 | 117.05 (15) | C13—C14—H14 | 119.00 |
N4—C4—C5 | 120.24 (16) | C9—C14—H14 | 119.00 |
C4—C5—C6 | 116.48 (15) | N5—C15—C16 | 122.11 (14) |
C4—C5—C9 | 120.73 (14) | N5—C15—C20 | 116.65 (14) |
C6—C5—C9 | 122.78 (15) | C16—C15—C20 | 121.24 (14) |
N1—C6—C7 | 114.73 (14) | O3—C16—C15 | 123.11 (15) |
C5—C6—C7 | 125.53 (15) | O3—C16—C17 | 118.98 (16) |
N1—C6—C5 | 119.59 (15) | C15—C16—C17 | 117.90 (16) |
C6—C7—C8 | 110.74 (18) | C16—C17—C18 | 119.24 (18) |
C5—C9—C14 | 121.62 (14) | C17—C18—C19 | 119.40 (19) |
C5—C9—C10 | 121.28 (15) | N5—C19—C18 | 122.50 (18) |
C10—C9—C14 | 117.08 (16) | O1—C20—C15 | 118.98 (14) |
C9—C10—C11 | 121.72 (19) | O2—C20—C15 | 116.22 (14) |
C10—C11—C12 | 119.31 (19) | O1—C20—O2 | 124.80 (14) |
Cl1—C12—C13 | 119.21 (15) | C16—C17—H17 | 120.00 |
Cl1—C12—C11 | 120.03 (14) | C18—C17—H17 | 120.00 |
C11—C12—C13 | 120.76 (18) | C17—C18—H18 | 120.00 |
C12—C13—C14 | 119.34 (19) | C19—C18—H18 | 120.00 |
C9—C14—C13 | 121.78 (18) | N5—C19—H19 | 119.00 |
C6—C7—H7A | 110.00 | C18—C19—H19 | 119.00 |
| | | |
C6—N1—C2—N2 | 174.80 (14) | N1—C6—C7—C8 | 87.0 (2) |
C6—N1—C2—N3 | −5.8 (2) | C5—C9—C10—C11 | −177.86 (19) |
C2—N1—C6—C5 | 2.8 (2) | C14—C9—C10—C11 | 0.7 (3) |
C2—N1—C6—C7 | −172.89 (14) | C5—C9—C14—C13 | 176.7 (2) |
C4—N3—C2—N1 | 2.6 (2) | C10—C9—C14—C13 | −1.8 (3) |
C4—N3—C2—N2 | −178.01 (15) | C9—C10—C11—C12 | 0.4 (3) |
C2—N3—C4—N4 | −177.41 (15) | C10—C11—C12—C13 | −0.3 (3) |
C2—N3—C4—C5 | 3.2 (2) | C10—C11—C12—Cl1 | 178.72 (17) |
C19—N5—C15—C20 | 178.81 (15) | Cl1—C12—C13—C14 | −179.84 (18) |
C15—N5—C19—C18 | −0.1 (3) | C11—C12—C13—C14 | −0.8 (3) |
C19—N5—C15—C16 | −1.4 (2) | C12—C13—C14—C9 | 1.9 (4) |
N3—C4—C5—C6 | −5.9 (2) | N5—C15—C16—O3 | −179.76 (16) |
N3—C4—C5—C9 | 173.08 (15) | N5—C15—C16—C17 | 1.2 (2) |
N4—C4—C5—C6 | 174.78 (16) | C20—C15—C16—O3 | 0.0 (3) |
N4—C4—C5—C9 | −6.3 (2) | C20—C15—C16—C17 | −179.05 (16) |
C4—C5—C6—C7 | 177.89 (15) | N5—C15—C20—O1 | 1.9 (2) |
C4—C5—C9—C10 | −69.3 (2) | N5—C15—C20—O2 | −178.84 (14) |
C9—C5—C6—N1 | −176.28 (14) | C16—C15—C20—O1 | −177.92 (15) |
C9—C5—C6—C7 | −1.0 (3) | C16—C15—C20—O2 | 1.4 (2) |
C4—C5—C6—N1 | 2.7 (2) | O3—C16—C17—C18 | −178.61 (19) |
C6—C5—C9—C14 | −68.9 (2) | C15—C16—C17—C18 | 0.5 (3) |
C4—C5—C9—C14 | 112.3 (2) | C16—C17—C18—C19 | −1.9 (3) |
C6—C5—C9—C10 | 109.6 (2) | C17—C18—C19—N5 | 1.7 (3) |
C5—C6—C7—C8 | −88.4 (2) | | |
Symmetry codes: (i) x, y, z+1; (ii) −x+1, −y+1, −z+2; (iii) −x+2, y−1/2, −z+3/2; (iv) −x+2, −y+1, −z+1; (v) −x+2, −y+1, −z+2; (vi) x, −y+3/2, z−1/2; (vii) x, −y+3/2, z+1/2; (viii) −x+2, y+1/2, −z+3/2; (ix) x, −y+1/2, z+1/2; (x) −x+1, y+1/2, −z+3/2; (xi) −x+1, y−1/2, −z+3/2; (xii) x, −y+1/2, z−1/2; (xiii) x, y, z−1; (xiv) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 1.88 | 2.7370 (18) | 175 |
N2—H2A···O1iv | 0.86 | 2.59 | 3.0962 (19) | 119 |
N2—H2A···N5iv | 0.86 | 2.15 | 2.948 (2) | 154 |
N2—H2B···O1 | 0.86 | 2.08 | 2.8873 (19) | 157 |
O3—H3···O2 | 0.82 | 1.82 | 2.5462 (19) | 146 |
N4—H4A···O1viii | 0.86 | 2.17 | 2.982 (2) | 158 |
N4—H4B···N2vii | 0.86 | 2.61 | 3.116 (2) | 118 |
Symmetry codes: (iv) −x+2, −y+1, −z+1; (vii) x, −y+3/2, z+1/2; (viii) −x+2, y+1/2, −z+3/2. |
(III) 2,4-diamino-(4-chlorophenyl)-6-ethylpyrimidinium 2,4-dichlorobenzoate
top
Crystal data top
C12H14ClN4+·C7H3Cl2O2− | F(000) = 1808 |
Mr = 439.72 | Dx = 1.430 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 5639 reflections |
a = 14.3808 (2) Å | θ = 1.8–29.4° |
b = 12.6799 (2) Å | µ = 0.47 mm−1 |
c = 22.4021 (3) Å | T = 293 K |
V = 4084.96 (10) Å3 | Prism, colourless |
Z = 8 | 0.25 × 0.22 × 0.20 mm |
Data collection top
Bruker SMART APEX II CCD area-detector diffractometer | 5639 independent reflections |
Radiation source: fine-focus sealed tube | 3791 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 29.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −11→19 |
Tmin = 0.891, Tmax = 0.912 | k = −12→17 |
26496 measured reflections | l = −30→30 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0442P)2 + 1.8433P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
5639 reflections | Δρmax = 0.48 e Å−3 |
255 parameters | Δρmin = −0.51 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc* = kFc[1+0.001Fc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0016 (3) |
Crystal data top
C12H14ClN4+·C7H3Cl2O2− | V = 4084.96 (10) Å3 |
Mr = 439.72 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.3808 (2) Å | µ = 0.47 mm−1 |
b = 12.6799 (2) Å | T = 293 K |
c = 22.4021 (3) Å | 0.25 × 0.22 × 0.20 mm |
Data collection top
Bruker SMART APEX II CCD area-detector diffractometer | 5639 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 3791 reflections with I > 2σ(I) |
Tmin = 0.891, Tmax = 0.912 | Rint = 0.033 |
26496 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.48 e Å−3 |
5639 reflections | Δρmin = −0.51 e Å−3 |
255 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional
coordinates. All su's are estimated from the variances of the (full)
variance-covariance matrix. The cell esds are taken into account in the
estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for
potential systematic errors. Weighted R-factors wR and all goodnesses of fit S
are based on F2, conventional R-factors R are based on F, with F set to zero
for negative F2. The observed criterion of F2 > 2sigma(F2) is used only
for calculating -R-factor-obs 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 | x | y | z | Uiso*/Ueq | |
Cl1 | 1.16200 (5) | 0.33814 (6) | 0.20424 (3) | 0.0878 (3) | |
N1 | 0.83136 (10) | 0.58234 (10) | 0.46549 (6) | 0.0349 (4) | |
N2 | 0.80363 (11) | 0.73723 (12) | 0.51484 (7) | 0.0462 (5) | |
N3 | 0.92006 (10) | 0.73383 (11) | 0.44467 (6) | 0.0386 (4) | |
N4 | 1.03918 (11) | 0.72461 (12) | 0.37804 (7) | 0.0504 (5) | |
C2 | 0.85241 (11) | 0.68540 (13) | 0.47439 (7) | 0.0348 (5) | |
C4 | 0.96752 (12) | 0.67725 (13) | 0.40467 (8) | 0.0371 (5) | |
C5 | 0.94500 (11) | 0.57010 (13) | 0.39029 (7) | 0.0354 (5) | |
C6 | 0.87640 (11) | 0.52406 (12) | 0.42301 (7) | 0.0331 (5) | |
C7 | 0.84999 (12) | 0.40996 (13) | 0.41939 (8) | 0.0394 (5) | |
C8 | 0.90786 (17) | 0.34450 (17) | 0.46207 (11) | 0.0662 (8) | |
C9 | 0.99831 (12) | 0.51108 (13) | 0.34432 (7) | 0.0372 (5) | |
C10 | 1.08977 (13) | 0.48089 (15) | 0.35500 (9) | 0.0484 (6) | |
C11 | 1.14047 (14) | 0.42735 (16) | 0.31203 (10) | 0.0547 (7) | |
C12 | 1.09873 (15) | 0.40420 (15) | 0.25855 (9) | 0.0514 (7) | |
C13 | 1.00845 (15) | 0.43143 (16) | 0.24713 (8) | 0.0521 (6) | |
C14 | 0.95886 (13) | 0.48576 (15) | 0.28998 (8) | 0.0448 (6) | |
Cl2 | 0.69947 (4) | 0.35207 (5) | 0.65836 (3) | 0.0674 (2) | |
Cl3 | 0.33345 (6) | 0.32074 (7) | 0.69141 (5) | 0.1177 (4) | |
O1 | 0.70611 (9) | 0.46896 (10) | 0.53099 (6) | 0.0513 (4) | |
O2 | 0.66023 (10) | 0.61880 (10) | 0.57229 (7) | 0.0623 (5) | |
C15 | 0.57511 (11) | 0.46659 (13) | 0.59459 (7) | 0.0363 (5) | |
C16 | 0.58815 (13) | 0.38883 (14) | 0.63712 (8) | 0.0422 (6) | |
C17 | 0.51428 (16) | 0.34230 (15) | 0.66646 (10) | 0.0570 (7) | |
C18 | 0.42618 (15) | 0.37455 (18) | 0.65230 (12) | 0.0638 (8) | |
C19 | 0.40979 (14) | 0.45014 (18) | 0.60983 (11) | 0.0625 (8) | |
C20 | 0.48434 (13) | 0.49682 (16) | 0.58148 (9) | 0.0486 (6) | |
C21 | 0.65385 (12) | 0.52255 (13) | 0.56385 (8) | 0.0378 (5) | |
H1 | 0.78900 | 0.55310 | 0.48690 | 0.0420* | |
H2A | 0.81560 | 0.80250 | 0.52200 | 0.0550* | |
H2B | 0.75990 | 0.70570 | 0.53400 | 0.0550* | |
H4A | 1.05290 | 0.78870 | 0.38690 | 0.0600* | |
H4B | 1.07160 | 0.69100 | 0.35200 | 0.0600* | |
H7A | 0.85930 | 0.38480 | 0.37890 | 0.0470* | |
H7B | 0.78460 | 0.40200 | 0.42910 | 0.0470* | |
H8A | 0.97250 | 0.35180 | 0.45220 | 0.0990* | |
H8B | 0.89010 | 0.27170 | 0.45890 | 0.0990* | |
H8C | 0.89770 | 0.36850 | 0.50220 | 0.0990* | |
H10 | 1.11730 | 0.49690 | 0.39150 | 0.0580* | |
H11 | 1.20170 | 0.40750 | 0.31930 | 0.0660* | |
H13 | 0.98080 | 0.41360 | 0.21100 | 0.0620* | |
H14 | 0.89780 | 0.50570 | 0.28210 | 0.0540* | |
H17 | 0.52420 | 0.29040 | 0.69510 | 0.0680* | |
H19 | 0.34930 | 0.46970 | 0.60030 | 0.0750* | |
H20 | 0.47380 | 0.54920 | 0.55320 | 0.0580* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.1036 (5) | 0.0906 (5) | 0.0691 (4) | 0.0491 (4) | 0.0325 (4) | −0.0026 (3) |
N1 | 0.0362 (7) | 0.0280 (7) | 0.0405 (7) | −0.0031 (6) | 0.0069 (6) | −0.0021 (5) |
N2 | 0.0525 (9) | 0.0296 (7) | 0.0564 (9) | −0.0025 (7) | 0.0152 (7) | −0.0075 (7) |
N3 | 0.0412 (8) | 0.0296 (7) | 0.0449 (8) | −0.0041 (6) | 0.0036 (6) | −0.0020 (6) |
N4 | 0.0505 (9) | 0.0386 (8) | 0.0620 (10) | −0.0132 (7) | 0.0177 (8) | −0.0076 (7) |
C2 | 0.0363 (8) | 0.0284 (8) | 0.0396 (8) | 0.0003 (7) | −0.0012 (6) | −0.0012 (6) |
C4 | 0.0373 (8) | 0.0325 (8) | 0.0414 (8) | −0.0038 (7) | 0.0009 (7) | 0.0012 (7) |
C5 | 0.0347 (8) | 0.0325 (8) | 0.0390 (8) | −0.0020 (7) | 0.0016 (7) | −0.0036 (7) |
C6 | 0.0335 (8) | 0.0294 (8) | 0.0364 (8) | −0.0004 (6) | −0.0022 (6) | −0.0028 (6) |
C7 | 0.0431 (9) | 0.0305 (8) | 0.0445 (9) | −0.0048 (7) | 0.0052 (7) | −0.0055 (7) |
C8 | 0.0732 (15) | 0.0431 (11) | 0.0823 (16) | 0.0058 (11) | −0.0038 (13) | 0.0134 (11) |
C9 | 0.0365 (9) | 0.0320 (8) | 0.0431 (9) | −0.0030 (7) | 0.0061 (7) | −0.0012 (7) |
C10 | 0.0412 (10) | 0.0493 (11) | 0.0547 (11) | −0.0004 (8) | −0.0008 (8) | −0.0080 (9) |
C11 | 0.0393 (10) | 0.0507 (11) | 0.0740 (14) | 0.0086 (8) | 0.0094 (10) | −0.0012 (10) |
C12 | 0.0619 (13) | 0.0417 (10) | 0.0506 (11) | 0.0148 (9) | 0.0212 (9) | 0.0036 (8) |
C13 | 0.0662 (13) | 0.0520 (11) | 0.0380 (9) | 0.0120 (10) | 0.0043 (9) | −0.0013 (8) |
C14 | 0.0436 (10) | 0.0488 (10) | 0.0419 (9) | 0.0083 (8) | 0.0026 (8) | −0.0008 (8) |
Cl2 | 0.0547 (3) | 0.0690 (4) | 0.0784 (4) | 0.0048 (3) | −0.0097 (3) | 0.0230 (3) |
Cl3 | 0.0870 (5) | 0.0880 (5) | 0.1782 (9) | −0.0426 (4) | 0.0789 (6) | −0.0259 (5) |
O1 | 0.0563 (8) | 0.0334 (7) | 0.0642 (8) | −0.0011 (6) | 0.0258 (7) | −0.0041 (6) |
O2 | 0.0612 (9) | 0.0311 (7) | 0.0946 (11) | −0.0042 (6) | 0.0317 (8) | −0.0089 (7) |
C15 | 0.0349 (8) | 0.0320 (8) | 0.0419 (8) | −0.0021 (7) | 0.0040 (7) | −0.0068 (7) |
C16 | 0.0421 (10) | 0.0336 (9) | 0.0509 (10) | −0.0020 (7) | 0.0051 (8) | −0.0017 (7) |
C17 | 0.0668 (14) | 0.0374 (10) | 0.0669 (13) | −0.0107 (9) | 0.0211 (11) | 0.0014 (9) |
C18 | 0.0489 (12) | 0.0490 (12) | 0.0935 (17) | −0.0204 (10) | 0.0317 (12) | −0.0228 (12) |
C19 | 0.0344 (10) | 0.0610 (13) | 0.0921 (17) | −0.0033 (9) | 0.0055 (10) | −0.0252 (13) |
C20 | 0.0404 (10) | 0.0467 (10) | 0.0588 (11) | 0.0038 (8) | −0.0023 (8) | −0.0088 (9) |
C21 | 0.0378 (9) | 0.0311 (8) | 0.0444 (9) | 0.0018 (7) | 0.0045 (7) | 0.0007 (7) |
Geometric parameters (Å, º) top
Cl1—C12 | 1.735 (2) | C10—C11 | 1.385 (3) |
Cl2—C16 | 1.7339 (19) | C11—C12 | 1.372 (3) |
Cl3—C18 | 1.735 (3) | C12—C13 | 1.368 (3) |
O1—C21 | 1.252 (2) | C13—C14 | 1.380 (3) |
O2—C21 | 1.238 (2) | C7—H7A | 0.9700 |
N1—C6 | 1.368 (2) | C7—H7B | 0.9700 |
N1—C2 | 1.356 (2) | C8—H8A | 0.9600 |
N2—C2 | 1.321 (2) | C8—H8B | 0.9600 |
N3—C2 | 1.329 (2) | C8—H8C | 0.9600 |
N3—C4 | 1.336 (2) | C10—H10 | 0.9300 |
N4—C4 | 1.334 (2) | C11—H11 | 0.9300 |
N1—H1 | 0.8600 | C13—H13 | 0.9300 |
N2—H2A | 0.8600 | C14—H14 | 0.9300 |
N2—H2B | 0.8600 | C15—C16 | 1.384 (2) |
N4—H4A | 0.8600 | C15—C20 | 1.392 (2) |
N4—H4B | 0.8600 | C15—C21 | 1.503 (2) |
C4—C5 | 1.433 (2) | C16—C17 | 1.382 (3) |
C5—C9 | 1.486 (2) | C17—C18 | 1.369 (3) |
C5—C6 | 1.361 (2) | C18—C19 | 1.371 (3) |
C6—C7 | 1.498 (2) | C19—C20 | 1.380 (3) |
C7—C8 | 1.515 (3) | C17—H17 | 0.9300 |
C9—C10 | 1.391 (3) | C19—H19 | 0.9300 |
C9—C14 | 1.381 (2) | C20—H20 | 0.9300 |
| | | |
Cl1···C19i | 3.570 (2) | C2···H8Aviii | 3.0400 |
Cl1···Cl3ii | 3.1969 (11) | C4···H8Cviii | 2.9100 |
Cl2···O1 | 3.2168 (15) | C9···H4B | 2.5200 |
Cl3···Cl1iii | 3.1969 (11) | C9···H7A | 2.6800 |
Cl2···H2Aiv | 3.1300 | C10···H4B | 2.6800 |
Cl3···H7Av | 3.0700 | C12···H17xi | 2.8800 |
O1···N1 | 2.7321 (19) | C14···H7A | 2.7700 |
O1···C7 | 3.330 (2) | C15···H2Aiv | 3.0700 |
O1···Cl2 | 3.2168 (15) | C20···H4Avi | 2.9800 |
O1···N2iv | 2.964 (2) | C21···H1 | 2.6300 |
O2···N4vi | 2.866 (2) | C21···H2B | 2.8600 |
O2···N2 | 2.857 (2) | C21···H4Avi | 3.0100 |
O1···H1 | 1.8800 | C21···H2Aiv | 2.9800 |
O1···H2Aiv | 2.1400 | H1···H7B | 2.3100 |
O1···H7B | 2.6800 | H1···O1 | 1.8800 |
O2···H4Avi | 2.1400 | H1···O2 | 2.7900 |
O2···H1 | 2.7900 | H1···C21 | 2.6300 |
O2···H2B | 2.0000 | H1···H2B | 2.2400 |
O2···H20 | 2.8500 | H2A···O1vii | 2.1400 |
N1···O1 | 2.7321 (19) | H2A···C15vii | 3.0700 |
N2···O2 | 2.857 (2) | H2A···Cl2vii | 3.1300 |
N2···O1vii | 2.964 (2) | H2A···C21vii | 2.9800 |
N3···C8viii | 3.388 (3) | H2B···H1 | 2.2400 |
N4···C10 | 3.217 (2) | H2B···O2 | 2.0000 |
N4···O2ix | 2.866 (2) | H2B···C21 | 2.8600 |
N3···H20ix | 2.8600 | H4A···O2ix | 2.1400 |
C4···C8viii | 3.493 (3) | H4A···C20ix | 2.9800 |
C7···C14 | 3.432 (3) | H4A···C21ix | 3.0100 |
C7···O1 | 3.330 (2) | H4B···C9 | 2.5200 |
C8···C4viii | 3.493 (3) | H4B···C10 | 2.6800 |
C8···N3viii | 3.388 (3) | H7A···Cl3xi | 3.0700 |
C10···N4 | 3.217 (2) | H7A···C9 | 2.6800 |
C13···C18i | 3.384 (3) | H7A···C14 | 2.7700 |
C13···C17i | 3.407 (3) | H7B···O1 | 2.6800 |
C14···C17i | 3.544 (3) | H7B···H1 | 2.3100 |
C14···C7 | 3.432 (3) | H8A···C2viii | 3.0400 |
C17···C14x | 3.544 (3) | H8C···C4viii | 2.9100 |
C17···C13x | 3.407 (3) | H17···C12v | 2.8800 |
C18···C13x | 3.384 (3) | H20···O2 | 2.8500 |
C19···Cl1x | 3.570 (2) | H20···N3vi | 2.8600 |
| | | |
C2—N1—C6 | 121.14 (14) | H7A—C7—H7B | 108.00 |
C2—N3—C4 | 117.51 (14) | C7—C8—H8A | 109.00 |
C2—N1—H1 | 119.00 | C7—C8—H8B | 110.00 |
C6—N1—H1 | 119.00 | C7—C8—H8C | 109.00 |
C2—N2—H2A | 120.00 | H8A—C8—H8B | 109.00 |
C2—N2—H2B | 120.00 | H8A—C8—H8C | 109.00 |
H2A—N2—H2B | 120.00 | H8B—C8—H8C | 109.00 |
H4A—N4—H4B | 120.00 | C9—C10—H10 | 120.00 |
C4—N4—H4A | 120.00 | C11—C10—H10 | 120.00 |
C4—N4—H4B | 120.00 | C10—C11—H11 | 121.00 |
N1—C2—N3 | 122.34 (15) | C12—C11—H11 | 121.00 |
N2—C2—N3 | 120.16 (15) | C12—C13—H13 | 120.00 |
N1—C2—N2 | 117.50 (15) | C14—C13—H13 | 120.00 |
N3—C4—N4 | 116.95 (15) | C9—C14—H14 | 119.00 |
N3—C4—C5 | 122.99 (15) | C13—C14—H14 | 119.00 |
N4—C4—C5 | 120.06 (15) | C16—C15—C20 | 117.94 (16) |
C4—C5—C6 | 116.71 (15) | C16—C15—C21 | 123.34 (15) |
C4—C5—C9 | 121.10 (14) | C20—C15—C21 | 118.67 (15) |
C6—C5—C9 | 122.09 (15) | Cl2—C16—C15 | 120.37 (14) |
N1—C6—C5 | 119.10 (14) | Cl2—C16—C17 | 117.68 (15) |
N1—C6—C7 | 116.06 (14) | C15—C16—C17 | 121.85 (17) |
C5—C6—C7 | 124.68 (15) | C16—C17—C18 | 118.3 (2) |
C6—C7—C8 | 110.83 (15) | Cl3—C18—C17 | 118.48 (19) |
C5—C9—C10 | 120.49 (15) | Cl3—C18—C19 | 119.55 (17) |
C5—C9—C14 | 121.07 (15) | C17—C18—C19 | 121.9 (2) |
C10—C9—C14 | 118.44 (16) | C18—C19—C20 | 119.07 (19) |
C9—C10—C11 | 120.87 (18) | C15—C20—C19 | 120.90 (18) |
C10—C11—C12 | 118.78 (19) | O1—C21—O2 | 125.45 (17) |
Cl1—C12—C11 | 119.10 (16) | O1—C21—C15 | 117.72 (15) |
Cl1—C12—C13 | 119.25 (15) | O2—C21—C15 | 116.81 (16) |
C11—C12—C13 | 121.65 (19) | C16—C17—H17 | 121.00 |
C12—C13—C14 | 119.11 (18) | C18—C17—H17 | 121.00 |
C9—C14—C13 | 121.13 (17) | C18—C19—H19 | 120.00 |
C6—C7—H7A | 109.00 | C20—C19—H19 | 120.00 |
C6—C7—H7B | 110.00 | C15—C20—H20 | 120.00 |
C8—C7—H7A | 110.00 | C19—C20—H20 | 120.00 |
C8—C7—H7B | 110.00 | | |
| | | |
C6—N1—C2—N2 | 177.74 (15) | C10—C9—C14—C13 | 0.3 (3) |
C6—N1—C2—N3 | −3.1 (2) | C9—C10—C11—C12 | −0.2 (3) |
C2—N1—C6—C5 | 1.6 (2) | C10—C11—C12—Cl1 | 179.47 (15) |
C2—N1—C6—C7 | 177.30 (14) | C10—C11—C12—C13 | −0.9 (3) |
C4—N3—C2—N1 | 0.4 (2) | Cl1—C12—C13—C14 | −178.77 (15) |
C2—N3—C4—C5 | 3.8 (2) | C11—C12—C13—C14 | 1.6 (3) |
C2—N3—C4—N4 | −175.64 (15) | C12—C13—C14—C9 | −1.2 (3) |
C4—N3—C2—N2 | 179.46 (16) | C20—C15—C16—Cl2 | −176.73 (14) |
N3—C4—C5—C9 | 178.42 (15) | C20—C15—C16—C17 | −0.5 (3) |
N3—C4—C5—C6 | −5.1 (2) | C21—C15—C16—Cl2 | 0.8 (2) |
N4—C4—C5—C6 | 174.30 (16) | C21—C15—C16—C17 | 177.04 (17) |
N4—C4—C5—C9 | −2.2 (2) | C16—C15—C20—C19 | −0.4 (3) |
C4—C5—C6—N1 | 2.2 (2) | C21—C15—C20—C19 | −178.01 (18) |
C9—C5—C6—C7 | 3.4 (3) | C16—C15—C21—O1 | 64.5 (2) |
C4—C5—C9—C10 | 69.9 (2) | C16—C15—C21—O2 | −117.1 (2) |
C4—C5—C9—C14 | −109.5 (2) | C20—C15—C21—O1 | −118.03 (19) |
C6—C5—C9—C10 | −106.3 (2) | C20—C15—C21—O2 | 60.5 (2) |
C6—C5—C9—C14 | 74.3 (2) | Cl2—C16—C17—C18 | 176.69 (17) |
C4—C5—C6—C7 | −173.04 (15) | C15—C16—C17—C18 | 0.4 (3) |
C9—C5—C6—N1 | 178.65 (14) | C16—C17—C18—Cl3 | −177.10 (16) |
N1—C6—C7—C8 | −87.32 (19) | C16—C17—C18—C19 | 0.7 (3) |
C5—C6—C7—C8 | 88.1 (2) | Cl3—C18—C19—C20 | 176.24 (18) |
C5—C9—C10—C11 | −178.95 (17) | C17—C18—C19—C20 | −1.5 (4) |
C14—C9—C10—C11 | 0.5 (3) | C18—C19—C20—C15 | 1.3 (3) |
C5—C9—C14—C13 | 179.66 (17) | | |
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x+1, −y+1/2, z−1/2; (iii) x−1, −y+1/2, z+1/2; (iv) −x+3/2, y−1/2, z; (v) x−1/2, −y+1/2, −z+1; (vi) x−1/2, −y+3/2, −z+1; (vii) −x+3/2, y+1/2, z; (viii) −x+2, −y+1, −z+1; (ix) x+1/2, −y+3/2, −z+1; (x) −x+3/2, −y+1, z+1/2; (xi) x+1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 1.88 | 2.7321 (19) | 171 |
N2—H2A···O1vii | 0.86 | 2.14 | 2.964 (2) | 159 |
N2—H2B···O2 | 0.86 | 2.00 | 2.857 (2) | 174 |
N4—H4A···O2ix | 0.86 | 2.14 | 2.866 (2) | 141 |
Symmetry codes: (vii) −x+3/2, y+1/2, z; (ix) x+1/2, −y+3/2, −z+1. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C12H14ClN4+·C8H7O2− | C12H14ClN4+·C6H4NO3− | C12H14ClN4+·C7H3Cl2O2− |
Mr | 384.86 | 387.82 | 439.72 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/c | Orthorhombic, Pbca |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 17.1373 (3), 16.4776 (3), 16.6127 (3) | 11.2563 (3), 14.3968 (4), 11.7902 (3) | 14.3808 (2), 12.6799 (2), 22.4021 (3) |
α, β, γ (°) | 90, 119.080 (1), 90 | 90, 103.625 (1), 90 | 90, 90, 90 |
V (Å3) | 4099.77 (13) | 1856.89 (9) | 4084.96 (10) |
Z | 8 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.21 | 0.24 | 0.47 |
Crystal size (mm) | 0.15 × 0.12 × 0.12 | 0.22 × 0.20 × 0.18 | 0.25 × 0.22 × 0.20 |
|
Data collection |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer | Bruker SMART APEX II CCD area detector diffractometer | Bruker SMART APEX II CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) | Multi-scan (SADABS; Bruker, 2008) | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.970, 0.975 | 0.950, 0.959 | 0.891, 0.912 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32486, 3398, 2474 | 21858, 5622, 3927 | 26496, 5639, 3791 |
Rint | 0.038 | 0.028 | 0.033 |
(sin θ/λ)max (Å−1) | 0.583 | 0.713 | 0.691 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.144, 1.04 | 0.051, 0.153, 1.05 | 0.042, 0.118, 1.01 |
No. of reflections | 3398 | 5622 | 5639 |
No. of parameters | 247 | 246 | 255 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.39 | 0.39, −0.35 | 0.48, −0.51 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.8600 | 1.7300 | 2.586 (3) | 173.00 |
N2—H2A···O1i | 0.8600 | 2.1400 | 2.947 (3) | 157.00 |
N2—H2B···O1 | 0.8600 | 2.2300 | 2.988 (3) | 147.00 |
N4—H4A···N3ii | 0.8600 | 2.1400 | 2.996 (3) | 176.00 |
N4—H4B···O1iii | 0.8600 | 2.3600 | 3.043 (3) | 136.00 |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1/2, −y+1/2, −z+1; (iii) x−1/2, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.8600 | 1.8800 | 2.7370 (18) | 175.00 |
N2—H2A···N5i | 0.8600 | 2.1500 | 2.948 (2) | 154.00 |
N2—H2B···O1 | 0.8600 | 2.0800 | 2.8873 (19) | 157.00 |
O3—H3···O2 | 0.8200 | 1.8200 | 2.5462 (19) | 146.00 |
N4—H4A···O1ii | 0.8600 | 2.1700 | 2.982 (2) | 158.00 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, y+1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.8600 | 1.8800 | 2.7321 (19) | 171.00 |
N2—H2A···O1i | 0.8600 | 2.1400 | 2.964 (2) | 159.00 |
N2—H2B···O2 | 0.8600 | 2.0000 | 2.857 (2) | 174.00 |
N4—H4A···O2ii | 0.8600 | 2.1400 | 2.866 (2) | 141.00 |
Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) x+1/2, −y+3/2, −z+1. |
Selected geometric parameters in (I), (II) and (III) (Å, °) top | (I) | (II) | (III) |
Cl1—C12 | 1.739 (3) | 1.7347 (19) | 1.735 (2) |
N1—C2 | 1.345 (4) | 1.360 (2) | 1.356 (2) |
N1—C6 | 1.360 (3) | 1.363 (2) | 1.368 (2) |
N3—C2 | 1.323 (3) | 1.325 (2) | 1.329 (2) |
N3—C4 | 1.342 (3) | 1.338 (2) | 1.336 (2) |
C5—C9 | 1.485 (3) | 1.492 (2) | 1.486 (2) |
| | | |
C2—N1—C6 | 120.9 (2) | 121.03 (13) | 121.14 (14) |
C2—N3—C4 | 117.5 (2) | 117.61 (14) | 117.51 (14) |
| | | |
C5—C6—C7—C8 | -102.6 (3) | -88.4 (2) | 88.1 (2) |
Cl···Cl interactions (Å, °) in (III) topX—I···J | I—J | X—I···J |
C12-Cl1···Cl3i | 3.1969 (11) | 140.52 (8) |
C18-Cl3···Cl1ii | 3.1969 (11) | 152.35 (10) |
Symmetry codes: (i) 1 + x, 1/2 - y, -1/2 + z; (ii) -1 + x, 1/2 - y, 1/2 + z. |
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Pyrimethamine (PMN) is an antifolate drug used in the treatment of malaria. In the chemotherapy of malaria and neoplastic diseases, substituted 2,4-diaminopyrimidines are widely employed as metabolic inhibitors of pathways leading to the synthesis of proteins and nucleic acids (Hitchings & Burchall, 1965). PMN acts against malarial parasites by selectively inhibiting their dihydrofolate reductase–thymidylate synthase (Sardarian et al., 2003). PMN is also used along with other drugs for the treatment of opportunistic infections in patients suffering from AIDS (Tanaka et al., 2004). 2-Aminopyrimidine and its derivatives form good adducts as they readily form hydrogen-bonded patterns through their stereochemically associated amine group and ring N atom (Lynch et al., 2000). The crystal structures of PMN (Sethuraman & Thomas Muthiah, 2002) and many of its salts have been reported from our laboratory (Sethuraman et al., 2003; Stanley et al., 2005). The present study of the title salts, pyrimethaminium 4-methylbenzoate, (I), pyrimethaminium 3-hydroxypicolinate, (II), and pyrimethaminium 2,4-dichlorobenzoate, (III), was undertaken to obtain more information regarding patterns of hydrogen bonding in these types of compounds.
Views of compounds (I)–(III) are shown in Figs. 1–3 and comparitive geometric parameters are given in Table 1. In these compounds, the asymmetric unit contains one pyrimethaminium cation, together with a 4-methylbenzoate anion in (I), a 3-hydroxypicolinate anion in (II) and a 2,4-dichlorobenzoate anion in (III). As expected, in all three crystal structures the PMNH cations are protonated at the N1 position. The dihedral angle between the 2,4-diaminopyrimidine and 4-chlorophenyl planes is 80.11 (14)° in (I), 68.28 (9)° in (II) and 72.50 (8)° in (III). These values are close to those observed in modelling studies of dihydrofolate reductase pyrimethamine (DHFR–PMN) complexes (Sansom et al., 1989). Such modelling studies of DHFR–PMN complexes indicate that this dihedral angle is important for the proper docking of the drug molecule at the active site of the enzyme (Sansom et al., 1989). By contrast, the value of the C5—C6—C7—C8 torsion angle (Table 1), representing the deviation of the ethyl group from the pyrimidine plane, is not very important, as it does not affect the overall binding energy of the enzyme–drug complex (Sansom et al., 1989).
In each of (I)–(III), the carboxylate group of the respective anion (4-methylbenzoate, 3-hydroxypicolinate and 2,4-dichlorobenzoate, respectively) interacts with the protonated pyrimidine moiety of PMNH in a linear fashion through a pair of N—H···O hydrogen bonds, to form an eight-membered R22(8) ring motif (Etter, 1990; Bernstein et al., 1995) (Figs. 1–3). This motif has been observed in modelling studies of DHFR–PMN complexes (Sansom et al., 1989), and it is one of the 24 most frequently observed motifs in organic crystal structures (Allen et al., 1998).
In (I), the R22(8) motifs are crosslinked via N—H···O hydrogen bonds to produce a DDAA array (where D is a hydrogen-bond donor and A is a hydrogen-bond acceptor) of quadruple hydrogen bonds (Table 1); this can be represented by the graph-set notations R22(8) and R42(8) (see Fig. 4). The inversion-centre-related PMNH cations are also base-paired via N—H···N hydrogen bonds involving the unprotonated pyrimidine N atom and the 4-amino group (Table 2). This type of base pairing, also with an R22(8) motif, has been observed in many diaminopyrimidinecarboxylate salts (Stanley et al., 2005). In addition to the base pairing, a hydrogen-bonded acceptor (O1) bridges the 4-amino and 2-amino groups on the sides of the pairing, leading to a complementary linear DADA array of quadruple hydrogen bonds with rings having graph-set notation R22(8) and R32(8). In general, only one of the motifs (DADA or DDAA array) has been identified at any one time in diaminopyrimidinecarboxylate salts. Here, both the DADA and DDAA array motifs co-exist in an alternating manner to form a hydrogen-bonded supramolecular ladder (Fig. 4).
In (II) (Table 3), inversion-related molecules are connected via N2—H···N5 hydrogen bonds to form an array with an R44(14) ring motif. This array is futher crosslinked via N—H···O hydrogen bonds (Fig. 5). A typical intramolecular hydrogen bond exists between the hydroxy and carboxylate groups of the 3-hydroxypicolinate anion to form a six-membered hydrogen-bonded ring [S(6), Fig. 2].
In (III), the 2-amino group of the PMNH cation interacts with one of the carboxylate O atoms (O1) through an N—H···O hydrogen bond, to form a supramolecular chain motif C21(6) along the b axis (Fig. 6). In addition, the 4-amino group of the PMNH cation interacts with one of the carboxylate O atoms (O2) through an N—H···O hydrogen bond, to form a helical chain along the a axis (Fig. 7) with motif C21(8). Details of these hydrogen bonds are given in Table 4. Further, the cations and anions are linked by weak Cl···Cl interactions (Table 5) which are not observed in compounds (I) and (II).
In conclusion, in all three crystal stuctures the PMNH cation interacts with the carboxylate O atoms via N—H···O hydrogen bonds to form the frequently observed hydrogen-bonded eight-membered R22(8) ring motif. In compound (I), the R22(8) motifs are further bridged by N—H···O hydrogen bonds on either side, forming a DDAA array of quadruple hydrogen bonds. In (I), N4—H···N3 base pairing is observed, while there is none in compounds (II) and (III). In (I), both DADA and DDAA array motifs co-exist in an alternating manner to form a hydrogen-bonded supramolecular ladder. Thus, it appears that the variation in supramolecular organization depends in part on the nature of the side chain attached to the anionic ring, viz. 4-methylbenzoate, 3-hydroxypicolinate or 2,4-dichlorobenzoate.