The structures of three compounds with potential antimalarial activity are reported. In
N,
N-diethyl-
N′-(7-iodoquinolin-4-yl)ethane-1,2-diamine, C
15H
20IN
3, (I), the molecules are linked into ribbons by N—H
N and C—H
N hydrogen bonds. In
N-(7-bromoquinolin-4-yl)-
N′,
N′-diethylethane-1,2-diamine dihydrate, C
15H
20BrN
3·2H
2O, (II), two aminoquinoline molecules and four water molecules form an
R54(13) hydrogen-bonded ring which links to its neighbours to form a
T5(2) one-dimensional infinite tape with pendant hydrogen bonds to the aminoquinolines. The phosphate salt 7-chloro-4-[2-(diethylammonio)ethylamino]quinolinium bis(dihydrogenphosphate) phosphoric acid, C
15H
22ClN
32+·2H
2PO
4−·H
3PO
4, (III), was prepared in order to establish the protonation sites of these compounds. The phosphate ions form a two-dimensional hydrogen-bonded sheet, while the aminoquinoline cations are linked to the phosphates by N—H
O hydrogen bonds from each of their three N atoms. While the conformation of the quinoline region hardly varies between (I), (II) and (III), the amino side chain is much more flexible and adopts a significantly different conformation in each case. Aromatic π–π stacking interactions are the only supramolecular interactions seen in all three structures.
Supporting information
CCDC references: 299647; 299648; 299649
Compounds (I)–(III) were synthesized for an earlier study by reaction of N,N-diethylethanediamine with the corresponding 7-substituted 4-chloroquinolines (Kaschula et al., 2002). Single crystals of the free base forms of (I) and (II) were obtained by dissolving the respective compounds (ca 12 mg) in a minimum volume of diethyl ether and allowing slow evaporation of the solvent in the refrigerator (283 K). Compound (III) (ca 10 mg) was dissolved in a dilute solution of phosphoric acid to facilitate the formation of the diprotic species. An aliquot of n-hexane was added to the solution and the vial placed in the refrigerator (283 K) to allow slow mixing of the solvent layers. Needle-like crystals formed in the aqueous layer within one week.
H atoms attached to N or O atoms were located in difference maps and included in the refinements with independent displacement parameters. All other H atoms were placed in geometrically calculated positions and refined as riding atoms, with C—H = 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for methyl groups. [Please check added text] Since there are only four protonation sites on the two quinoline molecules in (III), it seems reasonable to surmise that four of the six phosphates exist as H2PO4−, each having donated one proton. In dilute aqueous solution, phosphoric acid behaves as a strong acid but only one of its H atoms is readily ionisable. The pKa values are 2.15, 7.20 and 12.37 for the successive loss of protons (Weast, 1974). The remaining two phosphates are most likely in the form H3PO4, and the location of the H atoms in the difference Fourier map seemed to confirm this.
For all compounds, data collection: COLLECT (Nonius, 1997); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: POV-RAY (Cason, 2003); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
(I)
N,
N-diethyl-
N'-(7-iodoquinolin-4-yl)ethane-1,2-diamine
top
Crystal data top
C15H20IN3 | Dx = 1.597 Mg m−3 |
Mr = 369.24 | Melting point = 359–360 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 9238 reflections |
a = 13.2379 (7) Å | θ = 3.1–27.2° |
b = 7.8883 (4) Å | µ = 2.08 mm−1 |
c = 29.4118 (17) Å | T = 114 K |
V = 3071.3 (3) Å3 | Plate, pale yellow |
Z = 8 | 0.10 × 0.10 × 0.02 mm |
F(000) = 1472 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3328 independent reflections |
Radiation source: fine-focus sealed tube | 2401 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ω and ϕ scans | θmax = 27.2°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −16→16 |
Tmin = 0.820, Tmax = 0.961 | k = −9→10 |
34000 measured reflections | l = −37→37 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0361P)2 + 3.0942P] where P = (Fo2 + 2Fc2)/3 |
3328 reflections | (Δ/σ)max = 0.001 |
178 parameters | Δρmax = 1.14 e Å−3 |
0 restraints | Δρmin = −1.02 e Å−3 |
Crystal data top
C15H20IN3 | V = 3071.3 (3) Å3 |
Mr = 369.24 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.2379 (7) Å | µ = 2.08 mm−1 |
b = 7.8883 (4) Å | T = 114 K |
c = 29.4118 (17) Å | 0.10 × 0.10 × 0.02 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3328 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2401 reflections with I > 2σ(I) |
Tmin = 0.820, Tmax = 0.961 | Rint = 0.053 |
34000 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 1.14 e Å−3 |
3328 reflections | Δρmin = −1.02 e Å−3 |
178 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. The structure was solved by direct methods and refined on F2 using SHELX97 (Sheldrick, 1997) within the X-SEED interface (Barbour, 2003). A weighting scheme based on P = (Fo2 + 2Fc2)/3 was employed in order to reduce statistical bias (Wilson, 1976). Molecular geometry and supramolecular interactions were analysed with the aid of PLATON (Spek, 2003). Diagrams were prepared using POV-RAY (Cason, 2003) within the X-SEED interface. Bond lengths and angles are in agreement with typical literature values. 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 > σ(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. [Wilson, A. J. C. (1976). Acta Cryst. A32, 994–996.] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 0.834275 (18) | 0.19709 (3) | 0.407928 (7) | 0.03463 (10) | |
N1 | 0.93606 (18) | 0.4940 (4) | 0.24943 (9) | 0.0256 (6) | |
N11 | 0.6361 (2) | 0.5477 (4) | 0.20344 (9) | 0.0231 (6) | |
N14 | 0.60814 (18) | 0.6236 (4) | 0.07778 (8) | 0.0228 (6) | |
C2 | 0.9124 (2) | 0.5623 (4) | 0.20984 (11) | 0.0262 (8) | |
H2 | 0.9669 | 0.6002 | 0.1915 | 0.031* | |
C3 | 0.8157 (2) | 0.5843 (4) | 0.19239 (11) | 0.0231 (7) | |
H3 | 0.8062 | 0.6371 | 0.1637 | 0.028* | |
C4 | 0.7327 (2) | 0.5282 (4) | 0.21748 (10) | 0.0195 (7) | |
C5 | 0.7535 (2) | 0.4482 (4) | 0.26032 (9) | 0.0193 (7) | |
C6 | 0.6775 (2) | 0.3821 (4) | 0.28907 (10) | 0.0221 (7) | |
H6 | 0.6090 | 0.3864 | 0.2795 | 0.027* | |
C7 | 0.7005 (2) | 0.3124 (4) | 0.33017 (11) | 0.0249 (7) | |
H7 | 0.6483 | 0.2691 | 0.3491 | 0.030* | |
C8 | 0.8010 (2) | 0.3049 (4) | 0.34443 (10) | 0.0230 (7) | |
C9 | 0.8777 (2) | 0.3648 (4) | 0.31738 (10) | 0.0230 (7) | |
H9 | 0.9458 | 0.3575 | 0.3274 | 0.028* | |
C10 | 0.8552 (2) | 0.4370 (4) | 0.27475 (11) | 0.0199 (7) | |
C12 | 0.6089 (2) | 0.6359 (4) | 0.16168 (10) | 0.0226 (7) | |
H12A | 0.6521 | 0.7377 | 0.1585 | 0.027* | |
H12B | 0.5379 | 0.6744 | 0.1639 | 0.027* | |
C13 | 0.6207 (2) | 0.5256 (4) | 0.11947 (10) | 0.0235 (7) | |
H13A | 0.6885 | 0.4728 | 0.1196 | 0.028* | |
H13B | 0.5699 | 0.4337 | 0.1202 | 0.028* | |
C15 | 0.5007 (2) | 0.6630 (5) | 0.07024 (12) | 0.0332 (9) | |
H15A | 0.4688 | 0.6905 | 0.0998 | 0.040* | |
H15B | 0.4665 | 0.5612 | 0.0579 | 0.040* | |
C16 | 0.4846 (3) | 0.8095 (5) | 0.03789 (12) | 0.0374 (9) | |
H16A | 0.5199 | 0.9099 | 0.0494 | 0.056* | |
H16B | 0.4123 | 0.8338 | 0.0354 | 0.056* | |
H16C | 0.5114 | 0.7797 | 0.0079 | 0.056* | |
C17 | 0.6496 (2) | 0.5320 (5) | 0.03847 (11) | 0.0304 (8) | |
H17A | 0.6277 | 0.5902 | 0.0103 | 0.036* | |
H17B | 0.6208 | 0.4162 | 0.0380 | 0.036* | |
C18 | 0.7630 (3) | 0.5194 (5) | 0.03847 (13) | 0.0394 (9) | |
H18A | 0.7922 | 0.6324 | 0.0427 | 0.059* | |
H18B | 0.7859 | 0.4725 | 0.0094 | 0.059* | |
H18C | 0.7848 | 0.4449 | 0.0633 | 0.059* | |
H11 | 0.590 (3) | 0.521 (5) | 0.2212 (12) | 0.034 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.04390 (16) | 0.03291 (17) | 0.02708 (14) | −0.00529 (12) | −0.01132 (10) | 0.00636 (10) |
N1 | 0.0170 (14) | 0.0312 (17) | 0.0286 (15) | −0.0018 (13) | 0.0007 (12) | −0.0003 (13) |
N11 | 0.0142 (13) | 0.0335 (18) | 0.0216 (14) | −0.0001 (13) | −0.0005 (11) | 0.0019 (12) |
N14 | 0.0193 (14) | 0.0294 (17) | 0.0196 (13) | 0.0025 (12) | 0.0016 (11) | 0.0025 (12) |
C2 | 0.0198 (16) | 0.027 (2) | 0.0321 (19) | −0.0035 (15) | 0.0066 (14) | −0.0016 (15) |
C3 | 0.0208 (17) | 0.0249 (19) | 0.0238 (16) | −0.0030 (14) | 0.0008 (13) | 0.0002 (14) |
C4 | 0.0160 (16) | 0.0193 (18) | 0.0232 (15) | −0.0002 (14) | 0.0001 (12) | −0.0049 (13) |
C5 | 0.0167 (15) | 0.0205 (17) | 0.0208 (15) | −0.0003 (13) | 0.0006 (13) | −0.0058 (13) |
C6 | 0.0160 (15) | 0.027 (2) | 0.0231 (16) | −0.0005 (14) | 0.0008 (12) | −0.0037 (14) |
C7 | 0.0235 (16) | 0.029 (2) | 0.0222 (16) | −0.0039 (15) | 0.0020 (13) | −0.0003 (15) |
C8 | 0.0296 (16) | 0.0232 (18) | 0.0161 (15) | 0.0003 (15) | −0.0053 (12) | 0.0042 (14) |
C9 | 0.0184 (15) | 0.0230 (19) | 0.0276 (17) | 0.0004 (14) | −0.0049 (13) | −0.0017 (14) |
C10 | 0.0154 (15) | 0.0175 (18) | 0.0269 (16) | 0.0004 (13) | 0.0007 (12) | −0.0046 (14) |
C12 | 0.0190 (16) | 0.0266 (19) | 0.0221 (16) | 0.0019 (14) | −0.0027 (12) | 0.0008 (14) |
C13 | 0.0184 (16) | 0.029 (2) | 0.0231 (17) | −0.0014 (15) | −0.0004 (13) | 0.0009 (14) |
C15 | 0.0177 (16) | 0.046 (2) | 0.0357 (19) | 0.0019 (17) | −0.0042 (15) | 0.0115 (17) |
C16 | 0.0309 (19) | 0.042 (2) | 0.039 (2) | 0.0103 (18) | −0.0082 (16) | 0.0008 (18) |
C17 | 0.035 (2) | 0.034 (2) | 0.0219 (17) | 0.0040 (16) | 0.0004 (14) | 0.0026 (15) |
C18 | 0.041 (2) | 0.032 (2) | 0.045 (2) | 0.0079 (18) | 0.0196 (18) | 0.0042 (18) |
Geometric parameters (Å, º) top
I1—C8 | 2.099 (3) | C8—C9 | 1.373 (4) |
N1—C2 | 1.321 (4) | C9—C10 | 1.409 (4) |
N1—C10 | 1.379 (4) | C9—H9 | 0.9500 |
N11—C4 | 1.353 (4) | C12—C13 | 1.524 (4) |
N11—C12 | 1.457 (4) | C12—H12A | 0.9900 |
N11—H11 | 0.83 (3) | C12—H12B | 0.9900 |
N14—C13 | 1.459 (4) | C13—H13A | 0.9900 |
N14—C17 | 1.470 (4) | C13—H13B | 0.9900 |
N14—C15 | 1.473 (4) | C15—C16 | 1.512 (5) |
C2—C3 | 1.390 (4) | C15—H15A | 0.9900 |
C2—H2 | 0.9500 | C15—H15B | 0.9900 |
C3—C4 | 1.396 (4) | C16—H16A | 0.9800 |
C3—H3 | 0.9500 | C16—H16B | 0.9800 |
C4—C5 | 1.436 (4) | C16—H16C | 0.9800 |
C5—C6 | 1.413 (4) | C17—C18 | 1.505 (4) |
C5—C10 | 1.415 (4) | C17—H17A | 0.9900 |
C6—C7 | 1.362 (4) | C17—H17B | 0.9900 |
C6—H6 | 0.9500 | C18—H18A | 0.9800 |
C7—C8 | 1.397 (4) | C18—H18B | 0.9800 |
C7—H7 | 0.9500 | C18—H18C | 0.9800 |
| | | |
C2—N1—C10 | 115.2 (3) | N11—C12—H12A | 109.0 |
C4—N11—C12 | 123.0 (3) | C13—C12—H12A | 109.0 |
C4—N11—H11 | 119 (2) | N11—C12—H12B | 109.0 |
C12—N11—H11 | 118 (2) | C13—C12—H12B | 109.0 |
C13—N14—C17 | 111.0 (3) | H12A—C12—H12B | 107.8 |
C13—N14—C15 | 110.4 (2) | N14—C13—C12 | 111.8 (3) |
C17—N14—C15 | 110.2 (3) | N14—C13—H13A | 109.3 |
N1—C2—C3 | 126.5 (3) | C12—C13—H13A | 109.3 |
N1—C2—H2 | 116.7 | N14—C13—H13B | 109.3 |
C3—C2—H2 | 116.7 | C12—C13—H13B | 109.3 |
C2—C3—C4 | 119.3 (3) | H13A—C13—H13B | 107.9 |
C2—C3—H3 | 120.3 | N14—C15—C16 | 113.0 (3) |
C4—C3—H3 | 120.3 | N14—C15—H15A | 109.0 |
N11—C4—C3 | 123.1 (3) | C16—C15—H15A | 109.0 |
N11—C4—C5 | 119.9 (3) | N14—C15—H15B | 109.0 |
C3—C4—C5 | 116.9 (3) | C16—C15—H15B | 109.0 |
C6—C5—C10 | 118.4 (3) | H15A—C15—H15B | 107.8 |
C6—C5—C4 | 123.4 (3) | C15—C16—H16A | 109.5 |
C10—C5—C4 | 118.2 (3) | C15—C16—H16B | 109.5 |
C7—C6—C5 | 121.4 (3) | H16A—C16—H16B | 109.5 |
C7—C6—H6 | 119.3 | C15—C16—H16C | 109.5 |
C5—C6—H6 | 119.3 | H16A—C16—H16C | 109.5 |
C6—C7—C8 | 119.8 (3) | H16B—C16—H16C | 109.5 |
C6—C7—H7 | 120.1 | N14—C17—C18 | 113.9 (3) |
C8—C7—H7 | 120.1 | N14—C17—H17A | 108.8 |
C9—C8—C7 | 121.0 (3) | C18—C17—H17A | 108.8 |
C9—C8—I1 | 120.0 (2) | N14—C17—H17B | 108.8 |
C7—C8—I1 | 119.0 (2) | C18—C17—H17B | 108.8 |
C8—C9—C10 | 119.9 (3) | H17A—C17—H17B | 107.7 |
C8—C9—H9 | 120.0 | C17—C18—H18A | 109.5 |
C10—C9—H9 | 120.0 | C17—C18—H18B | 109.5 |
N1—C10—C9 | 116.7 (3) | H18A—C18—H18B | 109.5 |
N1—C10—C5 | 123.8 (3) | C17—C18—H18C | 109.5 |
C9—C10—C5 | 119.5 (3) | H18A—C18—H18C | 109.5 |
N11—C12—C13 | 112.9 (3) | H18B—C18—H18C | 109.5 |
| | | |
C10—N1—C2—C3 | 1.4 (5) | C2—N1—C10—C9 | −179.4 (3) |
N1—C2—C3—C4 | −1.2 (5) | C2—N1—C10—C5 | 0.3 (4) |
C12—N11—C4—C3 | −2.8 (5) | C8—C9—C10—N1 | −179.9 (3) |
C12—N11—C4—C5 | 176.5 (3) | C8—C9—C10—C5 | 0.4 (5) |
C2—C3—C4—N11 | 178.6 (3) | C6—C5—C10—N1 | 178.8 (3) |
C2—C3—C4—C5 | −0.6 (4) | C4—C5—C10—N1 | −2.0 (4) |
N11—C4—C5—C6 | 1.9 (4) | C6—C5—C10—C9 | −1.5 (4) |
C3—C4—C5—C6 | −178.8 (3) | C4—C5—C10—C9 | 177.7 (3) |
N11—C4—C5—C10 | −177.2 (3) | C4—N11—C12—C13 | 80.7 (4) |
C3—C4—C5—C10 | 2.1 (4) | C17—N14—C13—C12 | 162.5 (3) |
C10—C5—C6—C7 | 1.4 (5) | C15—N14—C13—C12 | −75.0 (3) |
C4—C5—C6—C7 | −177.7 (3) | N11—C12—C13—N14 | −171.2 (2) |
C5—C6—C7—C8 | −0.3 (5) | C13—N14—C15—C16 | 160.6 (3) |
C6—C7—C8—C9 | −0.9 (5) | C17—N14—C15—C16 | −76.5 (4) |
C6—C7—C8—I1 | 179.9 (2) | C13—N14—C17—C18 | −69.9 (4) |
C7—C8—C9—C10 | 0.8 (5) | C15—N14—C17—C18 | 167.5 (3) |
I1—C8—C9—C10 | 180.0 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N1i | 0.83 (3) | 2.22 (3) | 3.019 (4) | 161 (3) |
C6—H6···N1i | 0.95 | 2.59 | 3.504 (4) | 163 |
Symmetry code: (i) x−1/2, y, −z+1/2. |
(II)
N-(7-bromoquinolin-4-yl)-
N',
N'-diethylethane-1,2-diamine dihydrate
top
Crystal data top
C15H20BrN3·2H2O | F(000) = 1488 |
Mr = 358.28 | Dx = 1.435 Mg m−3 |
Monoclinic, C2/c | Melting point = 340–341 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 28.0177 (4) Å | Cell parameters from 8774 reflections |
b = 6.8221 (9) Å | θ = 1.6–26.4° |
c = 18.9339 (4) Å | µ = 2.49 mm−1 |
β = 113.61 (3)° | T = 113 K |
V = 3316.1 (9) Å3 | Plate, colourless |
Z = 8 | 0.13 × 0.10 × 0.10 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3403 independent reflections |
Radiation source: fine-focus sealed tube | 2470 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
ω and ϕ scans | θmax = 26.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −34→34 |
Tmin = 0.738, Tmax = 0.789 | k = −8→8 |
26586 measured reflections | l = −23→23 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0305P)2 + 3.5408P] where P = (Fo2 + 2Fc2)/3 |
3403 reflections | (Δ/σ)max = 0.002 |
212 parameters | Δρmax = 0.38 e Å−3 |
5 restraints | Δρmin = −0.51 e Å−3 |
Crystal data top
C15H20BrN3·2H2O | V = 3316.1 (9) Å3 |
Mr = 358.28 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 28.0177 (4) Å | µ = 2.49 mm−1 |
b = 6.8221 (9) Å | T = 113 K |
c = 18.9339 (4) Å | 0.13 × 0.10 × 0.10 mm |
β = 113.61 (3)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3403 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2470 reflections with I > 2σ(I) |
Tmin = 0.738, Tmax = 0.789 | Rint = 0.074 |
26586 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 5 restraints |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.38 e Å−3 |
3403 reflections | Δρmin = −0.51 e Å−3 |
212 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. The structure was solved by direct methods and refined on F2 using SHELX97 (Sheldrick, 1997) within the X-SEED interface (Barbour, 2003). A weighting scheme based on P = (Fo2 + 2Fc2)/3 was employed in order to reduce statistical bias (Wilson, 1976). Molecular geometry and supramolecular interactions were analysed with the aid of PLATON (Spek, 2003). Diagrams were prepared using POV-RAY (Cason, 2003) within the X-SEED interface. Bond lengths and angles are in agreement with typical literature values. 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 > σ(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. [Wilson, A. J. C. (1976). Acta Cryst. A32, 994–996.] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.059437 (10) | 0.97961 (4) | 0.340318 (17) | 0.03556 (11) | |
O1 | 0.29418 (8) | 1.2080 (3) | 0.29291 (12) | 0.0275 (4) | |
N1 | 0.23553 (8) | 0.9821 (3) | 0.57984 (11) | 0.0219 (5) | |
O2 | 0.19338 (7) | 1.1306 (3) | 0.18035 (11) | 0.0258 (4) | |
C2 | 0.28697 (10) | 0.9862 (3) | 0.61193 (14) | 0.0221 (5) | |
H2 | 0.3032 | 0.9789 | 0.6666 | 0.027* | |
C3 | 0.31936 (10) | 1.0004 (3) | 0.57244 (14) | 0.0211 (5) | |
H3 | 0.3561 | 1.0040 | 0.6001 | 0.025* | |
C4 | 0.29786 (9) | 1.0094 (3) | 0.49231 (14) | 0.0188 (5) | |
C5 | 0.24186 (9) | 1.0027 (3) | 0.45438 (13) | 0.0180 (5) | |
C6 | 0.21440 (9) | 1.0026 (3) | 0.37340 (14) | 0.0203 (5) | |
H6 | 0.2334 | 1.0087 | 0.3416 | 0.024* | |
C7 | 0.16129 (10) | 0.9940 (3) | 0.33976 (14) | 0.0221 (5) | |
H7 | 0.1434 | 0.9918 | 0.2852 | 0.027* | |
C8 | 0.13353 (9) | 0.9883 (3) | 0.38726 (14) | 0.0223 (5) | |
C9 | 0.15807 (9) | 0.9859 (3) | 0.46556 (14) | 0.0211 (5) | |
H9 | 0.1383 | 0.9809 | 0.4962 | 0.025* | |
C10 | 0.21297 (9) | 0.9908 (3) | 0.50103 (14) | 0.0183 (5) | |
N11 | 0.32747 (8) | 1.0191 (3) | 0.45075 (12) | 0.0207 (5) | |
H11 | 0.3144 (10) | 1.055 (4) | 0.4047 (15) | 0.025 (8)* | |
C12 | 0.38398 (9) | 1.0288 (4) | 0.48757 (15) | 0.0221 (5) | |
H12A | 0.3976 | 0.9087 | 0.5184 | 0.026* | |
H12B | 0.3945 | 1.1426 | 0.5229 | 0.026* | |
C13 | 0.40721 (10) | 1.0483 (3) | 0.42820 (15) | 0.0221 (6) | |
H13A | 0.3895 | 1.1571 | 0.3928 | 0.027* | |
H13B | 0.4444 | 1.0841 | 0.4550 | 0.027* | |
N14 | 0.40334 (8) | 0.8709 (3) | 0.38220 (11) | 0.0199 (5) | |
C15 | 0.40570 (11) | 0.9224 (4) | 0.30768 (15) | 0.0277 (6) | |
H15A | 0.3785 | 1.0216 | 0.2820 | 0.033* | |
H15B | 0.3968 | 0.8039 | 0.2747 | 0.033* | |
C16 | 0.45759 (12) | 1.0017 (4) | 0.31104 (19) | 0.0387 (7) | |
H16C | 0.4684 | 1.1135 | 0.3464 | 0.058* | |
H16A | 0.4535 | 1.0439 | 0.2595 | 0.058* | |
H16B | 0.4841 | 0.8985 | 0.3294 | 0.058* | |
C17 | 0.44336 (10) | 0.7282 (4) | 0.42671 (15) | 0.0256 (6) | |
H17A | 0.4400 | 0.7018 | 0.4760 | 0.031* | |
H17B | 0.4782 | 0.7865 | 0.4391 | 0.031* | |
C18 | 0.44002 (11) | 0.5357 (4) | 0.38517 (18) | 0.0322 (6) | |
H18A | 0.4046 | 0.4829 | 0.3682 | 0.048* | |
H17C | 0.4648 | 0.4422 | 0.4202 | 0.048* | |
H18B | 0.4484 | 0.5574 | 0.3403 | 0.048* | |
H11W | 0.3026 (11) | 1.338 (4) | 0.3064 (17) | 0.047 (9)* | |
H12W | 0.2655 (11) | 1.192 (4) | 0.2616 (17) | 0.040 (10)* | |
H21W | 0.1678 (11) | 1.207 (4) | 0.1614 (17) | 0.045 (10)* | |
H22W | 0.2038 (12) | 1.109 (5) | 0.1430 (17) | 0.049 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.01681 (15) | 0.0525 (2) | 0.03318 (17) | 0.00043 (13) | 0.00561 (12) | −0.00042 (15) |
O1 | 0.0272 (12) | 0.0288 (12) | 0.0230 (11) | 0.0006 (9) | 0.0063 (10) | −0.0012 (9) |
N1 | 0.0254 (12) | 0.0208 (11) | 0.0190 (11) | −0.0015 (9) | 0.0083 (10) | −0.0007 (9) |
O2 | 0.0218 (11) | 0.0341 (11) | 0.0215 (11) | 0.0064 (9) | 0.0087 (9) | 0.0024 (8) |
C2 | 0.0236 (14) | 0.0236 (13) | 0.0159 (12) | −0.0007 (11) | 0.0044 (11) | 0.0002 (11) |
C3 | 0.0191 (13) | 0.0209 (13) | 0.0196 (13) | −0.0012 (10) | 0.0040 (11) | 0.0000 (11) |
C4 | 0.0230 (13) | 0.0133 (12) | 0.0213 (12) | 0.0015 (10) | 0.0101 (11) | −0.0007 (10) |
C5 | 0.0185 (12) | 0.0149 (12) | 0.0185 (12) | −0.0008 (10) | 0.0051 (10) | −0.0008 (10) |
C6 | 0.0218 (13) | 0.0189 (13) | 0.0199 (13) | 0.0008 (11) | 0.0082 (11) | 0.0001 (10) |
C7 | 0.0237 (14) | 0.0227 (14) | 0.0185 (13) | 0.0011 (11) | 0.0068 (11) | 0.0001 (11) |
C8 | 0.0175 (13) | 0.0192 (13) | 0.0259 (14) | 0.0018 (10) | 0.0043 (11) | 0.0000 (11) |
C9 | 0.0217 (13) | 0.0192 (13) | 0.0250 (14) | −0.0012 (10) | 0.0121 (12) | 0.0004 (11) |
C10 | 0.0226 (13) | 0.0130 (12) | 0.0210 (13) | −0.0010 (10) | 0.0105 (11) | −0.0017 (10) |
N11 | 0.0175 (11) | 0.0273 (12) | 0.0157 (11) | 0.0001 (9) | 0.0049 (9) | 0.0008 (10) |
C12 | 0.0168 (13) | 0.0235 (13) | 0.0240 (13) | 0.0000 (10) | 0.0062 (11) | −0.0025 (11) |
C13 | 0.0161 (13) | 0.0211 (13) | 0.0272 (14) | −0.0015 (10) | 0.0065 (12) | −0.0012 (11) |
N14 | 0.0171 (11) | 0.0210 (11) | 0.0206 (12) | −0.0002 (9) | 0.0064 (10) | 0.0010 (9) |
C15 | 0.0293 (16) | 0.0304 (15) | 0.0241 (15) | 0.0018 (12) | 0.0116 (13) | 0.0013 (12) |
C16 | 0.0435 (18) | 0.0345 (17) | 0.0511 (19) | −0.0024 (14) | 0.0326 (16) | 0.0005 (14) |
C17 | 0.0213 (15) | 0.0254 (14) | 0.0270 (15) | 0.0004 (11) | 0.0063 (13) | 0.0013 (11) |
C18 | 0.0254 (15) | 0.0264 (15) | 0.0419 (17) | 0.0015 (12) | 0.0103 (14) | −0.0012 (13) |
Geometric parameters (Å, º) top
Br1—C8 | 1.904 (3) | N11—C12 | 1.454 (3) |
O1—H11W | 0.93 (3) | N11—H11 | 0.84 (2) |
O1—H12W | 0.79 (3) | C12—C13 | 1.514 (3) |
N1—C2 | 1.321 (3) | C12—H12A | 0.9900 |
N1—C10 | 1.369 (3) | C12—H12B | 0.9900 |
O2—H21W | 0.84 (3) | C13—N14 | 1.470 (3) |
O2—H22W | 0.88 (3) | C13—H13A | 0.9900 |
C2—C3 | 1.391 (3) | C13—H13B | 0.9900 |
C2—H2 | 0.9500 | N14—C17 | 1.469 (3) |
C3—C4 | 1.392 (3) | N14—C15 | 1.481 (3) |
C3—H3 | 0.9500 | C15—C16 | 1.529 (4) |
C4—N11 | 1.354 (3) | C15—H15A | 0.9900 |
C4—C5 | 1.441 (3) | C15—H15B | 0.9900 |
C5—C6 | 1.413 (3) | C16—H16C | 0.9800 |
C5—C10 | 1.419 (3) | C16—H16A | 0.9800 |
C6—C7 | 1.366 (3) | C16—H16B | 0.9800 |
C6—H6 | 0.9500 | C17—C18 | 1.514 (4) |
C7—C8 | 1.405 (3) | C17—H17A | 0.9900 |
C7—H7 | 0.9500 | C17—H17B | 0.9900 |
C8—C9 | 1.362 (4) | C18—H18A | 0.9800 |
C9—C10 | 1.411 (3) | C18—H17C | 0.9800 |
C9—H9 | 0.9500 | C18—H18B | 0.9800 |
| | | |
H11W—O1—H12W | 114 (3) | N11—C12—H12B | 109.4 |
C2—N1—C10 | 116.3 (2) | C13—C12—H12B | 109.4 |
H21W—O2—H22W | 105 (3) | H12A—C12—H12B | 108.0 |
N1—C2—C3 | 125.5 (2) | N14—C13—C12 | 114.6 (2) |
N1—C2—H2 | 117.3 | N14—C13—H13A | 108.6 |
C3—C2—H2 | 117.3 | C12—C13—H13A | 108.6 |
C2—C3—C4 | 119.9 (2) | N14—C13—H13B | 108.6 |
C2—C3—H3 | 120.1 | C12—C13—H13B | 108.6 |
C4—C3—H3 | 120.1 | H13A—C13—H13B | 107.6 |
N11—C4—C3 | 122.5 (2) | C17—N14—C13 | 110.35 (19) |
N11—C4—C5 | 120.7 (2) | C17—N14—C15 | 112.87 (19) |
C3—C4—C5 | 116.8 (2) | C13—N14—C15 | 110.40 (19) |
C6—C5—C10 | 118.5 (2) | N14—C15—C16 | 116.7 (2) |
C6—C5—C4 | 123.5 (2) | N14—C15—H15A | 108.1 |
C10—C5—C4 | 118.0 (2) | C16—C15—H15A | 108.1 |
C7—C6—C5 | 121.6 (2) | N14—C15—H15B | 108.1 |
C7—C6—H6 | 119.2 | C16—C15—H15B | 108.1 |
C5—C6—H6 | 119.2 | H15A—C15—H15B | 107.3 |
C6—C7—C8 | 118.8 (2) | C15—C16—H16C | 109.5 |
C6—C7—H7 | 120.6 | C15—C16—H16A | 109.5 |
C8—C7—H7 | 120.6 | H16C—C16—H16A | 109.5 |
C9—C8—C7 | 122.0 (2) | C15—C16—H16B | 109.5 |
C9—C8—Br1 | 119.25 (19) | H16C—C16—H16B | 109.5 |
C7—C8—Br1 | 118.78 (19) | H16A—C16—H16B | 109.5 |
C8—C9—C10 | 119.8 (2) | N14—C17—C18 | 113.7 (2) |
C8—C9—H9 | 120.1 | N14—C17—H17A | 108.8 |
C10—C9—H9 | 120.1 | C18—C17—H17A | 108.8 |
N1—C10—C9 | 117.2 (2) | N14—C17—H17B | 108.8 |
N1—C10—C5 | 123.5 (2) | C18—C17—H17B | 108.8 |
C9—C10—C5 | 119.3 (2) | H17A—C17—H17B | 107.7 |
C4—N11—C12 | 121.8 (2) | C17—C18—H18A | 109.5 |
C4—N11—H11 | 120.4 (19) | C17—C18—H17C | 109.5 |
C12—N11—H11 | 115.1 (19) | H18A—C18—H17C | 109.5 |
N11—C12—C13 | 110.9 (2) | C17—C18—H18B | 109.5 |
N11—C12—H12A | 109.4 | H18A—C18—H18B | 109.5 |
C13—C12—H12A | 109.4 | H17C—C18—H18B | 109.5 |
| | | |
C10—N1—C2—C3 | 0.6 (3) | C8—C9—C10—N1 | −178.1 (2) |
N1—C2—C3—C4 | −0.7 (4) | C8—C9—C10—C5 | 1.4 (3) |
C2—C3—C4—N11 | −178.6 (2) | C6—C5—C10—N1 | 177.4 (2) |
C2—C3—C4—C5 | −0.2 (3) | C4—C5—C10—N1 | −1.2 (3) |
N11—C4—C5—C6 | 1.0 (3) | C6—C5—C10—C9 | −2.1 (3) |
C3—C4—C5—C6 | −177.4 (2) | C4—C5—C10—C9 | 179.4 (2) |
N11—C4—C5—C10 | 179.4 (2) | C3—C4—N11—C12 | −2.6 (3) |
C3—C4—C5—C10 | 1.0 (3) | C5—C4—N11—C12 | 179.1 (2) |
C10—C5—C6—C7 | 0.8 (3) | C4—N11—C12—C13 | −177.3 (2) |
C4—C5—C6—C7 | 179.3 (2) | N11—C12—C13—N14 | −70.9 (3) |
C5—C6—C7—C8 | 1.1 (3) | C12—C13—N14—C17 | −78.3 (3) |
C6—C7—C8—C9 | −1.8 (4) | C12—C13—N14—C15 | 156.2 (2) |
C6—C7—C8—Br1 | 179.21 (18) | C17—N14—C15—C16 | −56.2 (3) |
C7—C8—C9—C10 | 0.5 (4) | C13—N14—C15—C16 | 67.9 (3) |
Br1—C8—C9—C10 | 179.55 (16) | C13—N14—C17—C18 | 176.5 (2) |
C2—N1—C10—C9 | 179.8 (2) | C15—N14—C17—C18 | −59.5 (3) |
C2—N1—C10—C5 | 0.4 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O1 | 0.84 (2) | 2.22 (3) | 3.038 (3) | 166 (3) |
O1—H11W···O2i | 0.93 (3) | 2.01 (3) | 2.924 (3) | 169 (3) |
O1—H12W···O2 | 0.79 (3) | 2.03 (3) | 2.824 (3) | 176 (3) |
O2—H22W···N1ii | 0.88 (3) | 1.86 (3) | 2.722 (3) | 166 (3) |
O2—H21W···N14i | 0.84 (3) | 2.14 (3) | 2.977 (3) | 172 (3) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, −y+2, z−1/2. |
(III) 7-chloro-4-[2-(diethylammonio)ethylamino]quinolinium bis(dihydrogenphosphate) phosphoric acid
top
Crystal data top
C15H22ClN32+·2H2O4P−·H3O4P | Z = 4 |
Mr = 571.77 | F(000) = 1192 |
Triclinic, P1 | Dx = 1.643 Mg m−3 |
Hall symbol: -P 1 | Melting point = 466–468 K |
a = 11.0960 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.6481 (3) Å | Cell parameters from 9976 reflections |
c = 15.1797 (4) Å | θ = 1.5–26.8° |
α = 79.552 (1)° | µ = 0.44 mm−1 |
β = 88.019 (1)° | T = 113 K |
γ = 72.336 (1)° | Plate, colourless |
V = 2311.38 (9) Å3 | 0.25 × 0.15 × 0.04 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 9766 independent reflections |
Radiation source: fine-focus sealed tube | 6450 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.128 |
ω and ϕ scans | θmax = 26.8°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −14→13 |
Tmin = 0.898, Tmax = 0.984 | k = −18→18 |
42956 measured reflections | l = −19→19 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0549P)2] where P = (Fo2 + 2Fc2)/3 |
9766 reflections | (Δ/σ)max = 0.001 |
697 parameters | Δρmax = 0.54 e Å−3 |
14 restraints | Δρmin = −0.75 e Å−3 |
Crystal data top
C15H22ClN32+·2H2O4P−·H3O4P | γ = 72.336 (1)° |
Mr = 571.77 | V = 2311.38 (9) Å3 |
Triclinic, P1 | Z = 4 |
a = 11.0960 (2) Å | Mo Kα radiation |
b = 14.6481 (3) Å | µ = 0.44 mm−1 |
c = 15.1797 (4) Å | T = 113 K |
α = 79.552 (1)° | 0.25 × 0.15 × 0.04 mm |
β = 88.019 (1)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 9766 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 6450 reflections with I > 2σ(I) |
Tmin = 0.898, Tmax = 0.984 | Rint = 0.128 |
42956 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 14 restraints |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.54 e Å−3 |
9766 reflections | Δρmin = −0.75 e Å−3 |
697 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. The structure was solved by direct methods and refined on F2 using SHELX97 (Sheldrick, 1997) within the X-SEED interface (Barbour, 2003). A weighting scheme based on P = (Fo2 + 2Fc2)/3 was employed in order to reduce statistical bias (Wilson, 1976). Molecular geometry and supramolecular interactions were analysed with the aid of PLATON (Spek, 2003). Diagrams were prepared using POV-RAY (Cason, 2003) within the X-SEED interface. Bond lengths and angles are in agreement with typical literature values. 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 > σ(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. [Wilson, A. J. C. (1976). Acta Cryst. A32, 994–996.] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1A | 1.03866 (7) | 0.65341 (6) | 0.23778 (5) | 0.0239 (2) | |
N1A | 1.1493 (2) | 0.54579 (19) | 0.57057 (18) | 0.0201 (6) | |
H1A | 1.235 (3) | 0.511 (2) | 0.554 (2) | 0.026 (9)* | |
C2A | 1.1225 (3) | 0.5429 (2) | 0.6573 (2) | 0.0208 (7) | |
H2A | 1.1867 | 0.5064 | 0.7007 | 0.025* | |
C3A | 1.0065 (3) | 0.5904 (2) | 0.6858 (2) | 0.0201 (7) | |
H3A | 0.9925 | 0.5887 | 0.7481 | 0.024* | |
C4A | 0.9065 (3) | 0.6423 (2) | 0.6233 (2) | 0.0166 (7) | |
C5A | 0.9349 (3) | 0.6455 (2) | 0.5296 (2) | 0.0172 (7) | |
C6A | 0.8446 (3) | 0.6958 (2) | 0.4590 (2) | 0.0186 (7) | |
H6A | 0.7605 | 0.7290 | 0.4732 | 0.022* | |
C7A | 0.8771 (3) | 0.6970 (2) | 0.3721 (2) | 0.0216 (7) | |
H7A | 0.8156 | 0.7309 | 0.3260 | 0.026* | |
C8A | 1.0003 (3) | 0.6487 (2) | 0.3496 (2) | 0.0195 (7) | |
C9A | 1.0918 (3) | 0.5993 (2) | 0.4147 (2) | 0.0201 (7) | |
H9A | 1.1756 | 0.5674 | 0.3989 | 0.024* | |
C10A | 1.0584 (3) | 0.5972 (2) | 0.5051 (2) | 0.0171 (7) | |
N11A | 0.7903 (2) | 0.68560 (19) | 0.65015 (17) | 0.0179 (6) | |
H11A | 0.717 (4) | 0.224 (3) | 0.616 (3) | 0.052 (12)* | |
C12A | 0.7586 (3) | 0.6956 (2) | 0.7431 (2) | 0.0182 (7) | |
H12A | 0.6812 | 0.7516 | 0.7426 | 0.022* | |
H12B | 0.8279 | 0.7118 | 0.7700 | 0.022* | |
C13A | 0.7368 (3) | 0.6076 (2) | 0.8039 (2) | 0.0183 (7) | |
H13A | 0.7897 | 0.5479 | 0.7834 | 0.022* | |
H13B | 0.7655 | 0.6054 | 0.8655 | 0.022* | |
N14A | 0.6013 (2) | 0.6068 (2) | 0.80656 (17) | 0.0174 (6) | |
H14A | 0.557 (3) | 0.661 (2) | 0.822 (2) | 0.017 (9)* | |
C15A | 0.5531 (3) | 0.6001 (2) | 0.7172 (2) | 0.0203 (7) | |
H15A | 0.6041 | 0.5382 | 0.6995 | 0.024* | |
H15B | 0.5644 | 0.6543 | 0.6715 | 0.024* | |
C16A | 0.4156 (3) | 0.6045 (2) | 0.7183 (2) | 0.0278 (8) | |
H16A | 0.4063 | 0.5441 | 0.7535 | 0.042* | |
H16B | 0.3848 | 0.6124 | 0.6568 | 0.042* | |
H16C | 0.3663 | 0.6599 | 0.7452 | 0.042* | |
C17A | 0.5809 (3) | 0.5299 (2) | 0.8822 (2) | 0.0229 (7) | |
H17A | 0.6203 | 0.5352 | 0.9379 | 0.028* | |
H17B | 0.4889 | 0.5435 | 0.8920 | 0.028* | |
C18A | 0.6348 (3) | 0.4266 (2) | 0.8652 (2) | 0.0260 (8) | |
H18A | 0.5948 | 0.4200 | 0.8111 | 0.039* | |
H18B | 0.6181 | 0.3811 | 0.9166 | 0.039* | |
H18C | 0.7263 | 0.4117 | 0.8571 | 0.039* | |
Cl1B | 1.03743 (8) | 0.13997 (6) | 0.26036 (5) | 0.0260 (2) | |
N1B | 1.1423 (2) | 0.05115 (19) | 0.59475 (17) | 0.0185 (6) | |
H1B | 1.223 (3) | 0.023 (2) | 0.580 (2) | 0.025 (9)* | |
C2B | 1.1139 (3) | 0.0530 (2) | 0.6806 (2) | 0.0189 (7) | |
H2B | 1.1781 | 0.0202 | 0.7251 | 0.023* | |
C3B | 0.9960 (3) | 0.1003 (2) | 0.7070 (2) | 0.0191 (7) | |
H3B | 0.9802 | 0.1018 | 0.7687 | 0.023* | |
C4B | 0.8974 (3) | 0.1469 (2) | 0.6426 (2) | 0.0165 (7) | |
C5B | 0.9287 (3) | 0.1463 (2) | 0.5495 (2) | 0.0173 (7) | |
C6B | 0.8393 (3) | 0.1916 (2) | 0.4777 (2) | 0.0214 (7) | |
H6B | 0.7544 | 0.2242 | 0.4907 | 0.026* | |
C7B | 0.8727 (3) | 0.1893 (2) | 0.3911 (2) | 0.0214 (7) | |
H7B | 0.8117 | 0.2201 | 0.3441 | 0.026* | |
C8B | 0.9981 (3) | 0.1409 (2) | 0.3715 (2) | 0.0199 (7) | |
C9B | 1.0885 (3) | 0.0953 (2) | 0.4381 (2) | 0.0196 (7) | |
H9B | 1.1729 | 0.0630 | 0.4238 | 0.024* | |
C10B | 1.0532 (3) | 0.0977 (2) | 0.5278 (2) | 0.0167 (7) | |
N11B | 0.7792 (2) | 0.18997 (18) | 0.66548 (17) | 0.0176 (6) | |
H11B | 0.728 (4) | 0.715 (3) | 0.609 (3) | 0.049 (12)* | |
C12B | 0.7424 (3) | 0.1960 (2) | 0.7584 (2) | 0.0190 (7) | |
H12C | 0.6617 | 0.2490 | 0.7580 | 0.023* | |
H12D | 0.8073 | 0.2142 | 0.7883 | 0.023* | |
C13B | 0.7260 (3) | 0.1029 (2) | 0.8138 (2) | 0.0183 (7) | |
H13C | 0.7844 | 0.0464 | 0.7916 | 0.022* | |
H13D | 0.7509 | 0.0987 | 0.8768 | 0.022* | |
N14B | 0.5940 (2) | 0.09551 (19) | 0.81179 (17) | 0.0171 (6) | |
H14B | 0.546 (3) | 0.155 (2) | 0.828 (2) | 0.019 (9)* | |
C15B | 0.5517 (3) | 0.0942 (2) | 0.7189 (2) | 0.0192 (7) | |
H17C | 0.6099 | 0.0375 | 0.6967 | 0.023* | |
H17D | 0.5566 | 0.1539 | 0.6782 | 0.023* | |
C16B | 0.4181 (3) | 0.0885 (2) | 0.7166 (2) | 0.0243 (8) | |
H18D | 0.4177 | 0.0220 | 0.7417 | 0.036* | |
H18E | 0.3861 | 0.1058 | 0.6545 | 0.036* | |
H18F | 0.3639 | 0.1339 | 0.7522 | 0.036* | |
C17B | 0.5781 (3) | 0.0122 (2) | 0.8809 (2) | 0.0221 (7) | |
H15C | 0.4868 | 0.0190 | 0.8867 | 0.026* | |
H15D | 0.6103 | 0.0164 | 0.9395 | 0.026* | |
C18B | 0.6462 (3) | −0.0869 (2) | 0.8584 (2) | 0.0258 (8) | |
H16D | 0.6128 | −0.0925 | 0.8014 | 0.039* | |
H16E | 0.6329 | −0.1377 | 0.9060 | 0.039* | |
H16F | 0.7369 | −0.0946 | 0.8534 | 0.039* | |
P1C | 0.04913 (7) | 0.11808 (6) | 0.97748 (5) | 0.0168 (2) | |
O2C | 0.11285 (19) | 0.04409 (15) | 0.92098 (14) | 0.0192 (5) | |
O3C | 0.11599 (19) | 0.19243 (15) | 0.98368 (14) | 0.0202 (5) | |
O4C | −0.08912 (19) | 0.16847 (15) | 0.93799 (14) | 0.0204 (5) | |
H4C | −0.154 (3) | 0.197 (3) | 0.981 (3) | 0.059 (13)* | |
O5C | 0.0351 (2) | 0.07007 (15) | 1.07751 (14) | 0.0202 (5) | |
H5C | −0.024 (4) | 0.031 (3) | 1.085 (3) | 0.074 (15)* | |
P1D | 0.47262 (7) | 0.37797 (6) | 0.58040 (5) | 0.0171 (2) | |
O2D | 0.5658 (2) | 0.42734 (16) | 0.61219 (14) | 0.0237 (5) | |
H2D | 0.574 (5) | 0.482 (3) | 0.562 (3) | 0.11 (2)* | |
O3D | 0.54951 (19) | 0.28257 (15) | 0.55642 (15) | 0.0234 (5) | |
O4D | 0.3870 (2) | 0.36299 (18) | 0.66206 (16) | 0.0284 (6) | |
H4D | 0.416 (6) | 0.339 (5) | 0.720 (3) | 0.16 (3)* | |
O5D | 0.38181 (19) | 0.44600 (15) | 0.50729 (14) | 0.0195 (5) | |
P1E | 0.08354 (8) | 0.59654 (6) | 0.93870 (5) | 0.0182 (2) | |
O2E | 0.2019 (2) | 0.62296 (17) | 0.90365 (15) | 0.0284 (6) | |
H2E | 0.226 (4) | 0.679 (3) | 0.918 (3) | 0.097 (18)* | |
O3E | 0.0982 (2) | 0.57117 (15) | 1.04258 (14) | 0.0215 (5) | |
H3E | 0.032 (3) | 0.549 (3) | 1.065 (3) | 0.061 (14)* | |
O4E | 0.07182 (19) | 0.51287 (15) | 0.89873 (14) | 0.0194 (5) | |
O5E | −0.0384 (2) | 0.68249 (16) | 0.91437 (15) | 0.0237 (5) | |
H5E | −0.071 (4) | 0.727 (3) | 0.948 (3) | 0.050 (13)* | |
P1F | 0.33922 (7) | 0.81462 (6) | 0.89529 (5) | 0.0164 (2) | |
O2F | 0.47519 (18) | 0.75201 (14) | 0.90124 (13) | 0.0183 (5) | |
O3F | 0.24895 (19) | 0.76555 (15) | 0.94554 (14) | 0.0218 (5) | |
O4F | 0.2932 (2) | 0.84771 (16) | 0.79549 (14) | 0.0234 (5) | |
H4F | 0.364 (3) | 0.847 (3) | 0.749 (2) | 0.039 (10)* | |
O5F | 0.3323 (2) | 0.90787 (16) | 0.93465 (15) | 0.0227 (5) | |
H5F | 0.259 (3) | 0.955 (3) | 0.931 (3) | 0.067 (15)* | |
P1G | 0.48709 (7) | 0.88015 (6) | 0.59041 (5) | 0.0174 (2) | |
O2G | 0.59085 (19) | 0.92980 (16) | 0.60234 (14) | 0.0202 (5) | |
H2G | 0.605 (4) | 0.968 (3) | 0.549 (3) | 0.079 (16)* | |
O3G | 0.55876 (19) | 0.80070 (16) | 0.53399 (15) | 0.0206 (5) | |
H3G | 0.516 (3) | 0.772 (3) | 0.504 (3) | 0.063 (14)* | |
O4G | 0.4602 (2) | 0.83212 (16) | 0.68111 (14) | 0.0274 (6) | |
O5G | 0.37415 (18) | 0.95214 (15) | 0.53753 (14) | 0.0202 (5) | |
P1H | 0.34869 (7) | 0.29833 (6) | 0.88708 (5) | 0.0175 (2) | |
O2H | 0.2345 (2) | 0.37879 (17) | 0.83702 (14) | 0.0254 (5) | |
H2H | 0.177 (4) | 0.432 (3) | 0.862 (3) | 0.067 (14)* | |
O3H | 0.3185 (2) | 0.20034 (16) | 0.90912 (16) | 0.0281 (6) | |
H3H | 0.237 (3) | 0.194 (3) | 0.941 (3) | 0.068 (14)* | |
O4H | 0.46035 (18) | 0.28290 (15) | 0.82823 (14) | 0.0190 (5) | |
O5H | 0.3664 (2) | 0.33338 (16) | 0.97447 (15) | 0.0248 (5) | |
H5H | 0.428 (5) | 0.300 (4) | 1.019 (3) | 0.13 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1A | 0.0266 (4) | 0.0299 (5) | 0.0146 (4) | −0.0084 (4) | −0.0017 (3) | −0.0018 (3) |
N1A | 0.0165 (14) | 0.0196 (15) | 0.0187 (15) | 0.0001 (12) | −0.0058 (12) | 0.0019 (12) |
C2A | 0.0201 (17) | 0.0228 (18) | 0.0164 (17) | −0.0052 (14) | −0.0067 (14) | 0.0035 (14) |
C3A | 0.0220 (17) | 0.0221 (18) | 0.0147 (16) | −0.0067 (14) | −0.0071 (14) | 0.0022 (13) |
C4A | 0.0190 (16) | 0.0148 (16) | 0.0153 (16) | −0.0064 (13) | −0.0049 (14) | 0.0024 (13) |
C5A | 0.0189 (16) | 0.0136 (16) | 0.0172 (16) | −0.0039 (13) | −0.0047 (14) | 0.0017 (13) |
C6A | 0.0162 (16) | 0.0203 (17) | 0.0167 (17) | −0.0031 (13) | −0.0017 (14) | −0.0010 (13) |
C7A | 0.0199 (17) | 0.0237 (18) | 0.0176 (18) | −0.0041 (14) | −0.0100 (14) | 0.0032 (14) |
C8A | 0.0249 (17) | 0.0186 (17) | 0.0146 (16) | −0.0068 (14) | −0.0029 (14) | −0.0006 (13) |
C9A | 0.0173 (16) | 0.0177 (17) | 0.0236 (18) | −0.0031 (13) | −0.0027 (15) | −0.0022 (14) |
C10A | 0.0177 (16) | 0.0144 (16) | 0.0172 (17) | −0.0040 (13) | −0.0056 (14) | 0.0017 (13) |
N11A | 0.0178 (14) | 0.0210 (15) | 0.0126 (14) | −0.0043 (12) | −0.0038 (12) | 0.0010 (11) |
C12A | 0.0194 (16) | 0.0181 (17) | 0.0160 (16) | −0.0033 (13) | −0.0045 (14) | −0.0035 (13) |
C13A | 0.0161 (16) | 0.0217 (17) | 0.0160 (16) | −0.0043 (13) | −0.0046 (13) | −0.0017 (13) |
N14A | 0.0195 (14) | 0.0184 (15) | 0.0123 (14) | −0.0032 (12) | −0.0054 (12) | −0.0014 (11) |
C15A | 0.0245 (17) | 0.0204 (17) | 0.0135 (16) | −0.0048 (14) | −0.0083 (14) | 0.0012 (13) |
C16A | 0.0247 (18) | 0.0253 (19) | 0.032 (2) | −0.0047 (15) | −0.0119 (16) | −0.0043 (16) |
C17A | 0.0243 (17) | 0.0227 (18) | 0.0219 (18) | −0.0105 (15) | −0.0013 (15) | 0.0017 (14) |
C18A | 0.0302 (18) | 0.0221 (18) | 0.0256 (19) | −0.0088 (15) | −0.0066 (16) | −0.0010 (15) |
Cl1B | 0.0310 (5) | 0.0310 (5) | 0.0154 (4) | −0.0093 (4) | 0.0003 (4) | −0.0032 (3) |
N1B | 0.0144 (14) | 0.0190 (15) | 0.0188 (15) | −0.0012 (12) | −0.0049 (12) | −0.0010 (11) |
C2B | 0.0190 (16) | 0.0190 (17) | 0.0167 (17) | −0.0053 (14) | −0.0083 (14) | 0.0028 (13) |
C3B | 0.0206 (17) | 0.0210 (17) | 0.0145 (16) | −0.0066 (14) | −0.0046 (14) | 0.0017 (13) |
C4B | 0.0182 (16) | 0.0141 (16) | 0.0156 (16) | −0.0055 (13) | −0.0039 (14) | 0.0031 (13) |
C5B | 0.0207 (16) | 0.0154 (16) | 0.0147 (16) | −0.0051 (13) | −0.0047 (14) | 0.0009 (13) |
C6B | 0.0150 (16) | 0.0244 (18) | 0.0212 (18) | −0.0022 (14) | −0.0063 (14) | −0.0006 (14) |
C7B | 0.0228 (17) | 0.0214 (18) | 0.0157 (17) | −0.0016 (14) | −0.0070 (14) | 0.0004 (14) |
C8B | 0.0257 (17) | 0.0205 (17) | 0.0137 (16) | −0.0082 (14) | −0.0004 (14) | −0.0015 (13) |
C9B | 0.0160 (16) | 0.0198 (17) | 0.0217 (18) | −0.0044 (13) | −0.0011 (14) | −0.0016 (14) |
C10B | 0.0178 (16) | 0.0152 (16) | 0.0149 (16) | −0.0040 (13) | −0.0085 (14) | 0.0026 (13) |
N11B | 0.0177 (14) | 0.0215 (15) | 0.0107 (13) | −0.0031 (12) | −0.0040 (12) | 0.0003 (11) |
C12B | 0.0203 (16) | 0.0201 (17) | 0.0156 (16) | −0.0038 (14) | −0.0034 (14) | −0.0037 (13) |
C13B | 0.0157 (15) | 0.0237 (18) | 0.0140 (16) | −0.0052 (13) | −0.0079 (13) | 0.0003 (13) |
N14B | 0.0168 (13) | 0.0180 (15) | 0.0148 (14) | −0.0031 (12) | −0.0058 (11) | −0.0012 (11) |
C15B | 0.0216 (17) | 0.0225 (17) | 0.0126 (16) | −0.0054 (14) | −0.0070 (14) | −0.0015 (13) |
C16B | 0.0206 (17) | 0.0266 (19) | 0.0244 (19) | −0.0048 (15) | −0.0085 (15) | −0.0036 (15) |
C17B | 0.0262 (17) | 0.0260 (19) | 0.0150 (17) | −0.0117 (15) | −0.0026 (14) | 0.0009 (14) |
C18B | 0.0286 (18) | 0.0224 (18) | 0.0246 (19) | −0.0088 (15) | −0.0103 (16) | 0.0042 (15) |
P1C | 0.0180 (4) | 0.0173 (4) | 0.0136 (4) | −0.0044 (3) | −0.0046 (3) | 0.0000 (3) |
O2C | 0.0213 (11) | 0.0179 (12) | 0.0166 (11) | −0.0040 (9) | −0.0030 (10) | −0.0014 (9) |
O3C | 0.0203 (11) | 0.0209 (12) | 0.0197 (12) | −0.0067 (10) | −0.0020 (10) | −0.0030 (10) |
O4C | 0.0165 (11) | 0.0237 (12) | 0.0164 (12) | 0.0004 (10) | −0.0068 (10) | −0.0017 (10) |
O5C | 0.0247 (12) | 0.0189 (12) | 0.0140 (11) | −0.0042 (10) | −0.0072 (10) | 0.0017 (9) |
P1D | 0.0170 (4) | 0.0179 (4) | 0.0136 (4) | −0.0024 (3) | −0.0045 (3) | 0.0002 (3) |
O2D | 0.0299 (13) | 0.0239 (13) | 0.0179 (12) | −0.0107 (10) | −0.0119 (10) | 0.0017 (10) |
O3D | 0.0219 (11) | 0.0222 (12) | 0.0240 (12) | −0.0017 (10) | −0.0082 (10) | −0.0057 (10) |
O4D | 0.0213 (12) | 0.0409 (15) | 0.0171 (13) | −0.0049 (11) | −0.0008 (11) | 0.0021 (11) |
O5D | 0.0178 (11) | 0.0201 (12) | 0.0150 (11) | −0.0003 (9) | −0.0065 (9) | 0.0031 (9) |
P1E | 0.0218 (4) | 0.0168 (4) | 0.0150 (4) | −0.0052 (3) | −0.0038 (4) | −0.0005 (3) |
O2E | 0.0332 (13) | 0.0276 (14) | 0.0290 (14) | −0.0138 (11) | 0.0076 (11) | −0.0096 (11) |
O3E | 0.0260 (13) | 0.0217 (12) | 0.0157 (12) | −0.0068 (10) | −0.0082 (10) | 0.0000 (9) |
O4E | 0.0220 (11) | 0.0176 (12) | 0.0174 (12) | −0.0031 (9) | −0.0042 (9) | −0.0039 (9) |
O5E | 0.0300 (13) | 0.0179 (12) | 0.0178 (12) | 0.0017 (10) | −0.0091 (11) | −0.0025 (10) |
P1F | 0.0174 (4) | 0.0163 (4) | 0.0139 (4) | −0.0029 (3) | −0.0041 (3) | −0.0012 (3) |
O2F | 0.0174 (11) | 0.0200 (12) | 0.0144 (11) | −0.0004 (9) | −0.0051 (9) | −0.0034 (9) |
O3F | 0.0238 (12) | 0.0222 (12) | 0.0191 (12) | −0.0071 (10) | 0.0003 (10) | −0.0026 (10) |
O4F | 0.0223 (12) | 0.0305 (13) | 0.0127 (12) | −0.0030 (10) | −0.0056 (10) | 0.0006 (10) |
O5F | 0.0196 (12) | 0.0197 (12) | 0.0271 (13) | −0.0021 (10) | −0.0046 (11) | −0.0059 (10) |
P1G | 0.0175 (4) | 0.0180 (4) | 0.0137 (4) | −0.0017 (3) | −0.0040 (3) | −0.0005 (3) |
O2G | 0.0209 (11) | 0.0226 (12) | 0.0160 (12) | −0.0050 (10) | −0.0072 (10) | −0.0015 (10) |
O3G | 0.0169 (11) | 0.0226 (12) | 0.0207 (12) | −0.0014 (10) | −0.0063 (10) | −0.0064 (10) |
O4G | 0.0320 (13) | 0.0277 (13) | 0.0171 (12) | −0.0050 (11) | 0.0002 (11) | 0.0031 (10) |
O5G | 0.0167 (11) | 0.0191 (12) | 0.0201 (12) | −0.0003 (9) | −0.0064 (10) | 0.0006 (9) |
P1H | 0.0177 (4) | 0.0191 (4) | 0.0138 (4) | −0.0029 (3) | −0.0048 (4) | −0.0017 (3) |
O2H | 0.0216 (12) | 0.0288 (13) | 0.0166 (12) | 0.0076 (10) | −0.0082 (10) | −0.0050 (10) |
O3H | 0.0287 (13) | 0.0257 (13) | 0.0311 (14) | −0.0097 (11) | 0.0053 (11) | −0.0064 (11) |
O4H | 0.0204 (11) | 0.0198 (12) | 0.0159 (11) | −0.0052 (9) | −0.0025 (9) | −0.0021 (9) |
O5H | 0.0274 (13) | 0.0264 (13) | 0.0155 (12) | 0.0022 (10) | −0.0094 (11) | −0.0066 (10) |
Geometric parameters (Å, º) top
Cl1A—C8A | 1.730 (3) | N11B—H11A | 0.99 (4) |
N1A—C2A | 1.336 (4) | C12B—C13B | 1.525 (4) |
N1A—C10A | 1.382 (4) | C12B—H12C | 0.9900 |
N1A—H1A | 0.98 (3) | C12B—H12D | 0.9900 |
C2A—C3A | 1.362 (4) | C13B—N14B | 1.503 (4) |
C2A—H2A | 0.9500 | C13B—H13C | 0.9900 |
C3A—C4A | 1.417 (4) | C13B—H13D | 0.9900 |
C3A—H3A | 0.9500 | N14B—C15B | 1.507 (4) |
C4A—N11A | 1.338 (4) | N14B—C17B | 1.507 (4) |
C4A—C5A | 1.442 (4) | N14B—H14B | 0.95 (3) |
C5A—C10A | 1.411 (4) | C15B—C16B | 1.512 (4) |
C5A—C6A | 1.427 (4) | C15B—H17C | 0.9900 |
C6A—C7A | 1.354 (4) | C15B—H17D | 0.9900 |
C6A—H6A | 0.9500 | C16B—H18D | 0.9800 |
C7A—C8A | 1.398 (4) | C16B—H18E | 0.9800 |
C7A—H7A | 0.9500 | C16B—H18F | 0.9800 |
C8A—C9A | 1.376 (4) | C17B—C18B | 1.513 (4) |
C9A—C10A | 1.406 (4) | C17B—H15C | 0.9900 |
C9A—H9A | 0.9500 | C17B—H15D | 0.9900 |
N11A—C12A | 1.465 (4) | C18B—H16D | 0.9800 |
N11A—H11B | 0.90 (4) | C18B—H16E | 0.9800 |
C12A—C13A | 1.521 (4) | C18B—H16F | 0.9800 |
C12A—H12A | 0.9900 | P1C—O2C | 1.497 (2) |
C12A—H12B | 0.9900 | P1C—O3C | 1.509 (2) |
C13A—N14A | 1.505 (4) | P1C—O4C | 1.573 (2) |
C13A—H13A | 0.9900 | P1C—O5C | 1.577 (2) |
C13A—H13B | 0.9900 | O3C—H3H | 1.47 (3) |
N14A—C15A | 1.506 (4) | O4C—H4C | 1.01 (3) |
N14A—C17A | 1.519 (4) | O5C—H5C | 0.99 (3) |
N14A—H14A | 0.87 (3) | P1D—O3D | 1.501 (2) |
C15A—C16A | 1.507 (4) | P1D—O5D | 1.519 (2) |
C15A—H15A | 0.9900 | P1D—O4D | 1.560 (2) |
C15A—H15B | 0.9900 | P1D—O2D | 1.562 (2) |
C16A—H16A | 0.9800 | O2D—H2D | 1.02 (4) |
C16A—H16B | 0.9800 | O4D—H4D | 0.92 (4) |
C16A—H16C | 0.9800 | P1E—O4E | 1.503 (2) |
C17A—C18A | 1.516 (4) | P1E—O2E | 1.531 (2) |
C17A—H17A | 0.9900 | P1E—O5E | 1.544 (2) |
C17A—H17B | 0.9900 | P1E—O3E | 1.556 (2) |
C18A—H18A | 0.9800 | O2E—H2E | 1.00 (4) |
C18A—H18B | 0.9800 | O3E—H3E | 0.92 (3) |
C18A—H18C | 0.9800 | O5E—H5E | 0.88 (3) |
Cl1B—C8B | 1.729 (3) | P1F—O2F | 1.505 (2) |
N1B—C2B | 1.333 (4) | P1F—O3F | 1.512 (2) |
N1B—C10B | 1.373 (4) | P1F—O4F | 1.558 (2) |
N1B—H1B | 0.90 (3) | P1F—O5F | 1.568 (2) |
C2B—C3B | 1.367 (4) | O4F—H4F | 1.04 (3) |
C2B—H2B | 0.9500 | O5F—H5F | 0.88 (3) |
C3B—C4B | 1.413 (4) | P1G—O4G | 1.492 (2) |
C3B—H3B | 0.9500 | P1G—O5G | 1.513 (2) |
C4B—N11B | 1.336 (4) | P1G—O2G | 1.568 (2) |
C4B—C5B | 1.444 (4) | P1G—O3G | 1.573 (2) |
C5B—C10B | 1.407 (4) | O2G—H2G | 0.94 (3) |
C5B—C6B | 1.423 (4) | O3G—H3G | 0.90 (3) |
C6B—C7B | 1.357 (4) | O4G—H4F | 1.45 (3) |
C6B—H6B | 0.9500 | P1H—O4H | 1.487 (2) |
C7B—C8B | 1.406 (4) | P1H—O5H | 1.545 (2) |
C7B—H7B | 0.9500 | P1H—O3H | 1.547 (2) |
C8B—C9B | 1.376 (4) | P1H—O2H | 1.551 (2) |
C9B—C10B | 1.407 (4) | O2H—H2H | 0.97 (3) |
C9B—H9B | 0.9500 | O3H—H3H | 1.04 (3) |
N11B—C12B | 1.465 (4) | O5H—H5H | 0.93 (4) |
| | | |
C2A—N1A—C10A | 120.8 (3) | C10B—C9B—H9B | 120.7 |
C2A—N1A—H1A | 118.8 (19) | N1B—C10B—C5B | 119.9 (3) |
C10A—N1A—H1A | 120.4 (19) | N1B—C10B—C9B | 119.0 (3) |
N1A—C2A—C3A | 122.5 (3) | C5B—C10B—C9B | 121.1 (3) |
N1A—C2A—H2A | 118.8 | C4B—N11B—C12B | 123.0 (3) |
C3A—C2A—H2A | 118.8 | C4B—N11B—H11A | 117 (2) |
C2A—C3A—C4A | 120.5 (3) | C12B—N11B—H11A | 120 (2) |
C2A—C3A—H3A | 119.7 | N11B—C12B—C13B | 115.1 (3) |
C4A—C3A—H3A | 119.7 | N11B—C12B—H12C | 108.5 |
N11A—C4A—C3A | 121.5 (3) | C13B—C12B—H12C | 108.5 |
N11A—C4A—C5A | 121.4 (3) | N11B—C12B—H12D | 108.5 |
C3A—C4A—C5A | 117.1 (3) | C13B—C12B—H12D | 108.5 |
C10A—C5A—C6A | 117.3 (3) | H12C—C12B—H12D | 107.5 |
C10A—C5A—C4A | 119.1 (3) | N14B—C13B—C12B | 114.5 (2) |
C6A—C5A—C4A | 123.6 (3) | N14B—C13B—H13C | 108.6 |
C7A—C6A—C5A | 120.9 (3) | C12B—C13B—H13C | 108.6 |
C7A—C6A—H6A | 119.5 | N14B—C13B—H13D | 108.6 |
C5A—C6A—H6A | 119.5 | C12B—C13B—H13D | 108.6 |
C6A—C7A—C8A | 120.6 (3) | H13C—C13B—H13D | 107.6 |
C6A—C7A—H7A | 119.7 | C13B—N14B—C15B | 112.2 (2) |
C8A—C7A—H7A | 119.7 | C13B—N14B—C17B | 111.7 (2) |
C9A—C8A—C7A | 121.2 (3) | C15B—N14B—C17B | 113.3 (2) |
C9A—C8A—Cl1A | 119.6 (2) | C13B—N14B—H14B | 101.6 (18) |
C7A—C8A—Cl1A | 119.1 (2) | C15B—N14B—H14B | 107.7 (18) |
C8A—C9A—C10A | 118.5 (3) | C17B—N14B—H14B | 109.6 (19) |
C8A—C9A—H9A | 120.7 | N14B—C15B—C16B | 112.2 (3) |
C10A—C9A—H9A | 120.7 | N14B—C15B—H17C | 109.2 |
N1A—C10A—C9A | 118.7 (3) | C16B—C15B—H17C | 109.2 |
N1A—C10A—C5A | 119.9 (3) | N14B—C15B—H17D | 109.2 |
C9A—C10A—C5A | 121.4 (3) | C16B—C15B—H17D | 109.2 |
C4A—N11A—C12A | 124.1 (3) | H17C—C15B—H17D | 107.9 |
C4A—N11A—H11B | 119 (3) | C15B—C16B—H18D | 109.5 |
C12A—N11A—H11B | 116 (3) | C15B—C16B—H18E | 109.5 |
N11A—C12A—C13A | 116.5 (3) | H18D—C16B—H18E | 109.5 |
N11A—C12A—H12A | 108.2 | C15B—C16B—H18F | 109.5 |
C13A—C12A—H12A | 108.2 | H18D—C16B—H18F | 109.5 |
N11A—C12A—H12B | 108.2 | H18E—C16B—H18F | 109.5 |
C13A—C12A—H12B | 108.2 | N14B—C17B—C18B | 113.4 (3) |
H12A—C12A—H12B | 107.3 | N14B—C17B—H15C | 108.9 |
N14A—C13A—C12A | 114.4 (2) | C18B—C17B—H15C | 108.9 |
N14A—C13A—H13A | 108.7 | N14B—C17B—H15D | 108.9 |
C12A—C13A—H13A | 108.7 | C18B—C17B—H15D | 108.9 |
N14A—C13A—H13B | 108.7 | H15C—C17B—H15D | 107.7 |
C12A—C13A—H13B | 108.7 | C17B—C18B—H16D | 109.5 |
H13A—C13A—H13B | 107.6 | C17B—C18B—H16E | 109.5 |
C13A—N14A—C15A | 112.5 (2) | H16D—C18B—H16E | 109.5 |
C13A—N14A—C17A | 111.7 (2) | C17B—C18B—H16F | 109.5 |
C15A—N14A—C17A | 112.9 (2) | H16D—C18B—H16F | 109.5 |
C13A—N14A—H14A | 107 (2) | H16E—C18B—H16F | 109.5 |
C15A—N14A—H14A | 109 (2) | O2C—P1C—O3C | 115.00 (12) |
C17A—N14A—H14A | 103 (2) | O2C—P1C—O4C | 106.63 (12) |
N14A—C15A—C16A | 112.7 (3) | O3C—P1C—O4C | 111.18 (12) |
N14A—C15A—H15A | 109.0 | O2C—P1C—O5C | 112.34 (12) |
C16A—C15A—H15A | 109.0 | O3C—P1C—O5C | 105.16 (12) |
N14A—C15A—H15B | 109.0 | O4C—P1C—O5C | 106.27 (12) |
C16A—C15A—H15B | 109.0 | P1C—O3C—H3H | 125.1 (17) |
H15A—C15A—H15B | 107.8 | P1C—O4C—H4C | 116 (2) |
C15A—C16A—H16A | 109.5 | P1C—O5C—H5C | 114 (3) |
C15A—C16A—H16B | 109.5 | O3D—P1D—O5D | 115.12 (12) |
H16A—C16A—H16B | 109.5 | O3D—P1D—O4D | 111.56 (13) |
C15A—C16A—H16C | 109.5 | O5D—P1D—O4D | 104.57 (12) |
H16A—C16A—H16C | 109.5 | O3D—P1D—O2D | 107.98 (12) |
H16B—C16A—H16C | 109.5 | O5D—P1D—O2D | 111.77 (12) |
C18A—C17A—N14A | 114.0 (3) | O4D—P1D—O2D | 105.43 (13) |
C18A—C17A—H17A | 108.8 | P1D—O2D—H2D | 109 (3) |
N14A—C17A—H17A | 108.8 | P1D—O4D—H4D | 125 (4) |
C18A—C17A—H17B | 108.8 | O4E—P1E—O2E | 109.70 (13) |
N14A—C17A—H17B | 108.8 | O4E—P1E—O5E | 107.96 (12) |
H17A—C17A—H17B | 107.6 | O2E—P1E—O5E | 112.11 (13) |
C17A—C18A—H18A | 109.5 | O4E—P1E—O3E | 112.34 (12) |
C17A—C18A—H18B | 109.5 | O2E—P1E—O3E | 106.65 (13) |
H18A—C18A—H18B | 109.5 | O5E—P1E—O3E | 108.12 (13) |
C17A—C18A—H18C | 109.5 | P1E—O2E—H2E | 124 (3) |
H18A—C18A—H18C | 109.5 | P1E—O3E—H3E | 108 (3) |
H18B—C18A—H18C | 109.5 | P1E—O5E—H5E | 124 (3) |
C2B—N1B—C10B | 121.1 (3) | O2F—P1F—O3F | 114.26 (12) |
C2B—N1B—H1B | 119 (2) | O2F—P1F—O4F | 110.17 (12) |
C10B—N1B—H1B | 119 (2) | O3F—P1F—O4F | 107.91 (12) |
N1B—C2B—C3B | 122.4 (3) | O2F—P1F—O5F | 107.62 (12) |
N1B—C2B—H2B | 118.8 | O3F—P1F—O5F | 108.67 (13) |
C3B—C2B—H2B | 118.8 | O4F—P1F—O5F | 108.03 (12) |
C2B—C3B—C4B | 120.1 (3) | P1F—O4F—H4F | 115.5 (19) |
C2B—C3B—H3B | 120.0 | P1F—O5F—H5F | 118 (3) |
C4B—C3B—H3B | 120.0 | O4G—P1G—O5G | 115.93 (13) |
N11B—C4B—C3B | 122.2 (3) | O4G—P1G—O2G | 107.56 (13) |
N11B—C4B—C5B | 120.4 (3) | O5G—P1G—O2G | 110.76 (12) |
C3B—C4B—C5B | 117.4 (3) | O4G—P1G—O3G | 109.84 (13) |
C10B—C5B—C6B | 117.7 (3) | O5G—P1G—O3G | 110.13 (12) |
C10B—C5B—C4B | 119.0 (3) | O2G—P1G—O3G | 101.64 (12) |
C6B—C5B—C4B | 123.3 (3) | P1G—O2G—H2G | 112 (3) |
C7B—C6B—C5B | 121.4 (3) | P1G—O3G—H3G | 121 (3) |
C7B—C6B—H6B | 119.3 | P1G—O4G—H4F | 139.6 (14) |
C5B—C6B—H6B | 119.3 | O4H—P1H—O5H | 114.84 (12) |
C6B—C7B—C8B | 119.6 (3) | O4H—P1H—O3H | 106.73 (13) |
C6B—C7B—H7B | 120.2 | O5H—P1H—O3H | 110.16 (13) |
C8B—C7B—H7B | 120.2 | O4H—P1H—O2H | 109.77 (12) |
C9B—C8B—C7B | 121.6 (3) | O5H—P1H—O2H | 105.22 (12) |
C9B—C8B—Cl1B | 120.1 (2) | O3H—P1H—O2H | 110.14 (13) |
C7B—C8B—Cl1B | 118.3 (2) | P1H—O2H—H2H | 126 (2) |
C8B—C9B—C10B | 118.6 (3) | P1H—O3H—H3H | 122 (2) |
C8B—C9B—H9B | 120.7 | P1H—O5H—H5H | 126 (4) |
| | | |
C10A—N1A—C2A—C3A | −0.6 (5) | C10B—N1B—C2B—C3B | 0.3 (5) |
N1A—C2A—C3A—C4A | 2.7 (5) | N1B—C2B—C3B—C4B | 2.1 (5) |
C2A—C3A—C4A—N11A | 176.8 (3) | C2B—C3B—C4B—N11B | 176.7 (3) |
C2A—C3A—C4A—C5A | −2.5 (4) | C2B—C3B—C4B—C5B | −3.0 (4) |
N11A—C4A—C5A—C10A | −178.8 (3) | N11B—C4B—C5B—C10B | −178.0 (3) |
C3A—C4A—C5A—C10A | 0.4 (4) | C3B—C4B—C5B—C10B | 1.7 (4) |
N11A—C4A—C5A—C6A | 1.5 (5) | N11B—C4B—C5B—C6B | 1.2 (5) |
C3A—C4A—C5A—C6A | −179.2 (3) | C3B—C4B—C5B—C6B | −179.1 (3) |
C10A—C5A—C6A—C7A | −0.2 (4) | C10B—C5B—C6B—C7B | −0.7 (5) |
C4A—C5A—C6A—C7A | 179.4 (3) | C4B—C5B—C6B—C7B | −180.0 (3) |
C5A—C6A—C7A—C8A | 0.0 (5) | C5B—C6B—C7B—C8B | 0.2 (5) |
C6A—C7A—C8A—C9A | −0.4 (5) | C6B—C7B—C8B—C9B | 0.1 (5) |
C6A—C7A—C8A—Cl1A | −179.0 (2) | C6B—C7B—C8B—Cl1B | −179.6 (2) |
C7A—C8A—C9A—C10A | 0.9 (5) | C7B—C8B—C9B—C10B | 0.1 (5) |
Cl1A—C8A—C9A—C10A | 179.5 (2) | Cl1B—C8B—C9B—C10B | 179.9 (2) |
C2A—N1A—C10A—C9A | 179.0 (3) | C2B—N1B—C10B—C5B | −1.7 (4) |
C2A—N1A—C10A—C5A | −1.5 (4) | C2B—N1B—C10B—C9B | 178.7 (3) |
C8A—C9A—C10A—N1A | 178.5 (3) | C6B—C5B—C10B—N1B | −178.7 (3) |
C8A—C9A—C10A—C5A | −1.1 (4) | C4B—C5B—C10B—N1B | 0.6 (4) |
C6A—C5A—C10A—N1A | −178.8 (3) | C6B—C5B—C10B—C9B | 1.0 (4) |
C4A—C5A—C10A—N1A | 1.5 (4) | C4B—C5B—C10B—C9B | −179.7 (3) |
C6A—C5A—C10A—C9A | 0.7 (4) | C8B—C9B—C10B—N1B | 179.0 (3) |
C4A—C5A—C10A—C9A | −178.9 (3) | C8B—C9B—C10B—C5B | −0.7 (4) |
C3A—C4A—N11A—C12A | 8.7 (4) | C3B—C4B—N11B—C12B | 2.4 (5) |
C5A—C4A—N11A—C12A | −172.1 (3) | C5B—C4B—N11B—C12B | −177.9 (3) |
C4A—N11A—C12A—C13A | −81.8 (4) | C4B—N11B—C12B—C13B | −78.0 (4) |
N11A—C12A—C13A—N14A | −91.1 (3) | N11B—C12B—C13B—N14B | −91.1 (3) |
C12A—C13A—N14A—C15A | 64.0 (3) | C12B—C13B—N14B—C15B | 62.4 (3) |
C12A—C13A—N14A—C17A | −167.8 (3) | C12B—C13B—N14B—C17B | −169.1 (3) |
C13A—N14A—C15A—C16A | −177.0 (3) | C13B—N14B—C15B—C16B | −179.0 (3) |
C17A—N14A—C15A—C16A | 55.4 (4) | C17B—N14B—C15B—C16B | 53.3 (3) |
C13A—N14A—C17A—C18A | −73.7 (3) | C13B—N14B—C17B—C18B | −71.3 (3) |
C15A—N14A—C17A—C18A | 54.3 (3) | C15B—N14B—C17B—C18B | 56.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O5Di | 0.98 (3) | 1.81 (3) | 2.787 (3) | 171 (3) |
N11A—H11B···O3G | 0.90 (4) | 2.14 (4) | 3.026 (3) | 167 (4) |
N14A—H14A···O2F | 0.87 (3) | 1.95 (3) | 2.777 (3) | 158 (3) |
N1B—H1B···O5Gii | 0.90 (3) | 1.85 (3) | 2.742 (3) | 169 (3) |
N11B—H11A···O3D | 0.99 (4) | 1.97 (4) | 2.908 (3) | 158 (3) |
N14B—H14B···O4H | 0.95 (3) | 1.82 (3) | 2.747 (3) | 165 (3) |
O4C—H4C···O3Fiii | 1.01 (3) | 1.56 (3) | 2.563 (3) | 176 (4) |
O5C—H5C···O2Civ | 0.99 (3) | 1.69 (4) | 2.672 (3) | 168 (4) |
O2D—H2D···O5Dv | 1.02 (4) | 1.53 (4) | 2.536 (3) | 167 (5) |
O4D—H4D···O4H | 0.92 (4) | 1.71 (4) | 2.625 (3) | 172 (6) |
O2E—H2E···O3F | 1.00 (4) | 1.49 (4) | 2.491 (3) | 174 (5) |
O3E—H3E···O4Eiii | 0.92 (3) | 1.69 (3) | 2.601 (3) | 169 (4) |
O5E—H5E···O3Ciii | 0.88 (3) | 1.66 (3) | 2.544 (3) | 173 (4) |
O4F—H4F···O4G | 1.04 (3) | 1.45 (3) | 2.483 (3) | 171 (3) |
O5F—H5F···O2Cvi | 0.88 (3) | 1.74 (3) | 2.625 (3) | 177 (4) |
O2G—H2G···O5Gvii | 0.94 (3) | 1.65 (4) | 2.582 (3) | 172 (5) |
O3G—H3G···O3Dv | 0.90 (3) | 1.63 (3) | 2.535 (3) | 175 (4) |
O2H—H2H···O4E | 0.97 (3) | 1.56 (3) | 2.528 (3) | 173 (4) |
O3H—H3H···O3C | 1.04 (3) | 1.47 (3) | 2.506 (3) | 176 (4) |
O5H—H5H···O2Fviii | 0.93 (4) | 1.57 (4) | 2.501 (3) | 176 (6) |
Symmetry codes: (i) x+1, y, z; (ii) x+1, y−1, z; (iii) −x, −y+1, −z+2; (iv) −x, −y, −z+2; (v) −x+1, −y+1, −z+1; (vi) x, y+1, z; (vii) −x+1, −y+2, −z+1; (viii) −x+1, −y+1, −z+2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C15H20IN3 | C15H20BrN3·2H2O | C15H22ClN32+·2H2O4P−·H3O4P |
Mr | 369.24 | 358.28 | 571.77 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 114 | 113 | 113 |
a, b, c (Å) | 13.2379 (7), 7.8883 (4), 29.4118 (17) | 28.0177 (4), 6.8221 (9), 18.9339 (4) | 11.0960 (2), 14.6481 (3), 15.1797 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 113.61 (3), 90 | 79.552 (1), 88.019 (1), 72.336 (1) |
V (Å3) | 3071.3 (3) | 3316.1 (9) | 2311.38 (9) |
Z | 8 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 2.08 | 2.49 | 0.44 |
Crystal size (mm) | 0.10 × 0.10 × 0.02 | 0.13 × 0.10 × 0.10 | 0.25 × 0.15 × 0.04 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) | Multi-scan (SADABS; Sheldrick, 2000) | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.820, 0.961 | 0.738, 0.789 | 0.898, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34000, 3328, 2401 | 26586, 3403, 2470 | 42956, 9766, 6450 |
Rint | 0.053 | 0.074 | 0.128 |
(sin θ/λ)max (Å−1) | 0.642 | 0.626 | 0.635 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.081, 1.05 | 0.037, 0.080, 1.04 | 0.054, 0.140, 1.00 |
No. of reflections | 3328 | 3403 | 9766 |
No. of parameters | 178 | 212 | 697 |
No. of restraints | 0 | 5 | 14 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.14, −1.02 | 0.38, −0.51 | 0.54, −0.75 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N1i | 0.83 (3) | 2.22 (3) | 3.019 (4) | 161 (3) |
C6—H6···N1i | 0.95 | 2.59 | 3.504 (4) | 163 |
Symmetry code: (i) x−1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O1 | 0.84 (2) | 2.22 (3) | 3.038 (3) | 166 (3) |
O1—H11W···O2i | 0.93 (3) | 2.01 (3) | 2.924 (3) | 169 (3) |
O1—H12W···O2 | 0.79 (3) | 2.03 (3) | 2.824 (3) | 176 (3) |
O2—H22W···N1ii | 0.88 (3) | 1.86 (3) | 2.722 (3) | 166 (3) |
O2—H21W···N14i | 0.84 (3) | 2.14 (3) | 2.977 (3) | 172 (3) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, −y+2, z−1/2. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O5Di | 0.98 (3) | 1.81 (3) | 2.787 (3) | 171 (3) |
N11A—H11B···O3G | 0.90 (4) | 2.14 (4) | 3.026 (3) | 167 (4) |
N14A—H14A···O2F | 0.87 (3) | 1.95 (3) | 2.777 (3) | 158 (3) |
N1B—H1B···O5Gii | 0.90 (3) | 1.85 (3) | 2.742 (3) | 169 (3) |
N11B—H11A···O3D | 0.99 (4) | 1.97 (4) | 2.908 (3) | 158 (3) |
N14B—H14B···O4H | 0.95 (3) | 1.82 (3) | 2.747 (3) | 165 (3) |
O4C—H4C···O3Fiii | 1.01 (3) | 1.56 (3) | 2.563 (3) | 176 (4) |
O5C—H5C···O2Civ | 0.99 (3) | 1.69 (4) | 2.672 (3) | 168 (4) |
O2D—H2D···O5Dv | 1.02 (4) | 1.53 (4) | 2.536 (3) | 167 (5) |
O4D—H4D···O4H | 0.92 (4) | 1.71 (4) | 2.625 (3) | 172 (6) |
O2E—H2E···O3F | 1.00 (4) | 1.49 (4) | 2.491 (3) | 174 (5) |
O3E—H3E···O4Eiii | 0.92 (3) | 1.69 (3) | 2.601 (3) | 169 (4) |
O5E—H5E···O3Ciii | 0.88 (3) | 1.66 (3) | 2.544 (3) | 173 (4) |
O4F—H4F···O4G | 1.04 (3) | 1.45 (3) | 2.483 (3) | 171 (3) |
O5F—H5F···O2Cvi | 0.88 (3) | 1.74 (3) | 2.625 (3) | 177 (4) |
O2G—H2G···O5Gvii | 0.94 (3) | 1.65 (4) | 2.582 (3) | 172 (5) |
O3G—H3G···O3Dv | 0.90 (3) | 1.63 (3) | 2.535 (3) | 175 (4) |
O2H—H2H···O4E | 0.97 (3) | 1.56 (3) | 2.528 (3) | 173 (4) |
O3H—H3H···O3C | 1.04 (3) | 1.47 (3) | 2.506 (3) | 176 (4) |
O5H—H5H···O2Fviii | 0.93 (4) | 1.57 (4) | 2.501 (3) | 176 (6) |
Symmetry codes: (i) x+1, y, z; (ii) x+1, y−1, z; (iii) −x, −y+1, −z+2; (iv) −x, −y, −z+2; (v) −x+1, −y+1, −z+1; (vi) x, y+1, z; (vii) −x+1, −y+2, −z+1; (viii) −x+1, −y+1, −z+2. |
Selected torsion angles (°) topCompound | τ1 | τ2 | τ3 | τ4 | τ5 | τ6 |
(I) | -2.8 (2) | 80.6 (4) | -171.2 (2) | -74.8 (3) | 160.6 (3) | -69.9 (4) |
(II) | -2.6 (3) | -177.2 (2) | -70.9 (3) | 156.2 (2) | 67.9 (3) | 176.5 (2) |
(IIIA) | 8.6 (3) | -81.5 (4) | -91.3 (3) | 64.1 (3) | -177.0 (3) | -74.2 (3) |
(IIIB) | 2.4 (2) | 78.0 (4) | 91.2 (3) | 62.5 (3) | 178.9 (2) | 71.1 (3) |
τ1 = C3—C4—N11—C12 τ2 = C4—N11—C12—C13 τ3 = N11—C12—C13—N14 τ4 = C12—C13—N14—C15 τ5 = C13—N14—C15—C16 τ6 = C13—N14—C17—C18 |
Quinoline antimalarial drugs, such as chloroquine, quinine, amodiaquine and mefloquine, have been used as effective treatments for malaria (Tilley et al., 2001). Until the onset of parasite resistance, chloroquine was especially valuable, owing to its affordability, limited toxicity and potency. It is believed to accumulate in its diprotonated state in the acidic environment of the Plasmodium food vacuole in an infected red blood cell, unable to re-cross the lipid membrane. The drug activity is understood to arise from complex formation between the 4-aminoquinoline drug and its target, haematin, thus preventing the haematin from aggregating to crystalline haemozoin (Egan et al., 1994). The structure–activity relationships for a series of aminoquinolines have been investigated in order to determine which molecular constituents confer antimalarial activity (Kaschula et al., 2002). A 4-aminoquinoline nucleus provides a planar electron-rich conjugated system able to associate with the porphyrin dimer. A moderately electron-withdrawing and strongly lipophilic group at position 7 is needed to maximize the drug activity, while the terminal amino group is basic and helps to ensure that the drug accumulates in the acidic food vacuole.
Molecular modelling provides a useful probe for investigating these complexes and crystallographic studies can provide complementary information about the structure of 4-aminoquinoline compounds. As part of an ongoing study into the mechanism of antimalarial drug activity, we have elucidated the crystal structures of three short-chain 4-aminoquinolines, viz. N,N-diethyl-N'-(7-iodoquinolin-4-yl)ethane-1,2-diamine, (I), N-(7-bromoquinolin-4-yl)-N',N'-diethylethane-1,2-diamine dihydrate, (II), and 7-chloro-4-[2-(diethylammonio)ethylamino]quinolinium bis(dihydrogenphosphate) phosphoric acid, (III) (see scheme). This class of compounds has been shown to inhibit the formation of synthetic β-haematin and to exhibit antiplasmodial activity in vitro (Kaschula et al., 2002), and they are therefore potential antimalarials. While this class of compounds forms complexes with haematin and prevents its aggregation to crystalline haemozoin, complexes between the drug molecule and haematin are notoriously difficult to crystallize. Molecular modelling using computational methods may provide a means of studying such interactions in solution.
The crystal structures obtained in this study are valuable for comparison with the structures generated using molecular modelling. The intermolecular parameters determined from the crystal structures were compared with those of related compounds generated using molecular modelling. The results of these computational investigations will be reported separately.
The iodo-compound, (I), is shown in Fig. 1. The bromoquinoline derivative crystallizes with two water molecules to form (II) (Fig. 2). The asymmetric unit of (III) consists of two crystallographically independent quinoline molecules (labelled A and B), and six phosphate ions (Fig. 3); structural refinement confirmed that the diprotic salt of N'-(7-chloroquinolin-4-yl)-N,N-diethyl-1,2-ethanediamine had crystallized.
The molecular conformations of compounds (I)-(III) can be defined in terms of six torsion angles, which are given in Table 1. The quinoline rings are planar in each case. Thus, the only conformational differences arise within the diamine side chain. The N11—C12 bond is nearly coplanar with the ring system in each case, with the greatest deviation being in molecule A of (III). The torsion angles C4—N11—C12—C13 (τ2) and N11—C12—C13—N14 (τ3) show that for (I), the side chain is in the more extended conformation induced by the gauche and anti conformations in τ2 and τ3, respectively. In (II), these torsion angles are anti and gauche, while in (III) they are both gauche, in each case resulting in the side chain folding back to a greater degree. The three different side chain conformations are shown in Fig. 4. NMR-constrained molecular mechanics and molecular dynamics/simulated annealing studies (Leed et al., 2002) have found that, on complexation with haematin, the aliphatic side chains of chloroquine, quinine and quinidine fold back to interact with the tetrapyrrole. It should be noted that the more extended conformation observed in this study may therefore change significantly on complexation.
In the supramolecular structure of (I), quinoline atom N1 of the molecule at (x, y, z) acts as a hydrogen-bond acceptor to the 4-amino group (atom N11) and quinoline atom C6 of the molecule at (1/2 + x, y, 1/2 − z), generating an R21(7) ring (Table 2) (Bernstein et al., 1995). Propagation by a twofold screw axis generates a ribbon of molecules parallel to [100] (Fig. 5). Perpendicular to the ribbons, molecules stack in parallel orientations to allow π–π interactions between adjacent quinoline rings (centroid separations are between 3.82 and 4.53 Å)
Intermolecular hydrogen bonds are prominent in the crystal structure of (II) (Table 3). Two aminoquinoline molecules and four water molecules form an R54(13) hydrogen-bonded ring. These rings then form a linked network with shared O1—H···O2 edges. This network is illustrated in Fig. 6 as green dotted lines. O2—H···N1(quinoline) hydrogen-bonded chains (shown as red dotted lines in Fig. 6) are pendant to these rings. It is worth noting that this arrangement allows each aminoquinoline N atom to act as either a hydrogen-bond acceptor (N1 and N14) or donor (N11). Water is potentially capable of participating in four hydrogen bonds but frequently shows a three-coordinate configuration (Jeffrey & Maluszynska, 1990). This is illustrated in the case of (II), where atom O1 donates two hydrogen bonds but accepts one, while atom O2 participates in a full quota of four hydrogen bonds. Infantes et al. (2002, 2003) have investigated the role of water molecules in stabilizing hydrated crystal structures of organic compounds. The hydrogen-bonded rings in (II) form the relatively common one-dimensional infinite tapes denoted by Infantes as T5(2). Aromatic stacking is again significant in this structure (centroid separations 3.57 and 3.58 Å). In addition, a Br···Br interaction [distance 3.6967 (5) Å; sum of radii 3.70 Å (Reference?)] is also evident.
The phosphate salt of (III) was prepared in order to confirm that protonation of these compounds occurs at the terminal amine and quinoline N atoms. The conformations of aminoquinoline molecules A and B are essentially identical but there are six crystallographically independent phosphate ions in the asymmetric unit. As in (I) and (II), there is an extended network of hydrogen bonds stabilizing the structure. A list of `strong' hydrogen bonds is given in Table 4; there are also a large number of C—H···O interactions, but these have not been detailed. Aromatic stacking also plays a role in the crystal packing, which takes the form of stacks of aminoquinoline and phosphate ions. The phosphate ions form a two-dimensional hydrogen-bonded sheet parallel to [111], similar to those reported for anilinium phosphate salts (Paxão et al., 2000; Mahmoudkhani & Langer, 2002). We note that all hydrogen bonds within this sheet are of the form P—O—H···O═P, with correspondingly short O···O distances (2.48–2.67 Å). This phenomenon has been noted previously: shorter bonds (ca 2.5 Å) connect P—O—H and P═O groups, while longer distances (ca 2.8 Å) link P—O—H moieties on adjacent molecules (Greenwood & Earnshaw, 1984; Dega-Szafran et al., 2000). In addition, P—O bond lengths corroborate the assignment of P—O—H (between 1.53 and 1.58 Å) and P═ O bonds (between 1.49 and 1.52 Å) within the phosphates. Aminoquinoline cations are linked to the phosphate anions via N—H···O—P hydrogen bonds. The aromatic ends of the quinolines point towards the phosphate layer and stack with their Cl atoms in alternating directions (centroid separations are in the range 3.65–3.95 Å). These features are illustrated in Fig. 7.
In conclusion, the molecular constituents of (I)–(III) potentially allow four different types of direction-specific intermolecular interactions. These are N—H···N and C—H···N hydrogen bonds, halogen interactions and aromatic π–π stacking interactions. In fact, the only interaction observed in all three structures is the last of these. In (I), N—H···N and C—H···N hydrogen bonds govern the supramolecular network, while in (II) and (III) the stronger hydrogen-bonding capability of O atoms (in water molecules or phosphate ions) dominates. The molecular conformation of the quinoline nucleus hardly varies between the three structures, while the amino side-chain is found to be much more flexible. The conformations of these three related 7-haloaminoquinolines and the patterns in their supramolecular networks suggest there is a subtle interplay between the weak direction-specific interactions between molecules. Weak forces of the type seen here, which depend on molecular polarizability, are not easy to model computationally, especially in the prediction of supramolecular structures. The variation in the supramolecular aggregation observed in these compounds suggests that experimental results of the type reported here are likely to be of prime importance for some time to come.
The observation of the two protonation sites in (III) is important. The terminal amine N atom has been previously recognized as a site of protonation but some uncertainty existed as to whether the second protonation site is the 4-amino or the quinoline N atom. This study provides evidence that the second protonation site is indeed the latter.