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{4 [(7 Chloro 4 quinol­yl)amino] N,N di­ethyl­penta­naminium}(tri­phenyl­phos­phine)gold(I) dinitrate

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{4-[(7-Chloro-4-quinolyl)amino]-

N

,

N

-di-

ethylpentanaminium}(triphenylphos-phine)gold(I) dinitrate

Marina Hitosugi-Levesque and Joseph M. Tanski*

Department of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA Correspondence e-mail: jotanski@vassar.edu

Received 27 July 2010; accepted 3 August 2010

Key indicators: single-crystal X-ray study;T= 125 K; mean(C–C) = 0.004 A˚; disorder in main residue;Rfactor = 0.027;wRfactor = 0.059; data-to-parameter ratio = 18.9.

The title compound, [Au(C18H27ClN3)(C18H15P)](NO3)2, is a

coordination complex of gold(I) triphenylphosphine with the N atom in the quinoline ring of the common antimalarial compound chloroquine (CQ). The pendant diethylamino group of the CQ ligand was found to be protonated. The complex exhibits a nearly linear coordination geometry around the AuIatom [N—Au—P = 176.94 (6)], with Au—N and Au—P bond lengths of 2.070 (2) and 2.2338 (7) A˚ , respectively. The diethylammonium group and one of the two nitrate counter-ions are disordered with occupancy ratios of 0.519 (4):0.481 (4). The nitrate anions are hydrogen bound to both the amino and ammonium groups of the N,N -diethylpentanaminium fragment of the CQ.

Related literature

For related structures, see: Karle & Karle (1988); Oleksyn & Serda (1993); Orlow et al. (2005); Borissova et al. (2008); Thwaiteet al.(2004). For background to the metal coordina-tion chemistry of chloroquine, see: Sa´nchez-Delgado et al. (1996); Navarroet al.(1997, 2004). Widespread use of CQ has led to cross-resistance, limiting the efficacy of CQ-related treatments for malaria, see: World Health Organization (2010).

Experimental

Crystal data

[Au(C18H27ClN3)(C18H15P)](NO3)2

Mr= 904.13 Triclinic,P1

a= 10.2456 (5) A˚

b= 13.1914 (6) A˚

c= 13.6301 (7) A˚ = 85.866 (1) = 88.126 (1)

= 86.510 (1)

V= 1833.22 (15) A˚3

Z= 2

MoKradiation = 4.18 mm1

T= 125 K

0.340.140.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007)

Tmin= 0.331,Tmax= 0.818

25641 measured reflections 10116 independent reflections 8781 reflections withI> 2(I)

Rint= 0.030

Refinement

R[F2> 2(F2)] = 0.027

wR(F2) = 0.059

S= 1.02 10116 reflections 535 parameters 1 restraint

H atoms treated by a mixture of independent and constrained refinement

max= 0.79 e A˚

3

min=0.84 e A˚

[image:1.610.316.565.368.424.2]

3

Table 1

Hydrogen-bond geometry (A˚ ,).

D—H A D—H H A D A D—H A

N5—H5 O4 0.93 1.77 2.70 (2) 177

N50—H50 O4 0.93 2.00 2.81 (2) 144

N4—H4 O20

0.84 (2) 2.28 (2) 3.030 (6) 149 (3) N4—H4 O3i

0.84 (2) 2.32 (3) 3.013 (5) 140 (3)

Symmetry code: (i)xþ1;y;z.

Data collection:APEX2(Bruker, 2007); cell refinement:SAINT (Bruker, 2007); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL(Sheldrick, 2008); software used to prepare material for publication:SHELXTL.

This work was supported by Vassar College. X-ray facilities were provided by the US National Science Foundation (grant No. 0521237 to JMT).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2313).

References

Borissova, A. O., Korlyukov, A. A., Antipin, M. Y. & Lyssenko, K. A. (2008).J. Phys. Chem. A,112, 11519–11522.

Bruker (2007).APEX2,SAINTandSADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Karle, J. M. & Karle, I. L. (1988).Acta Cryst.C44, 1605–1608.

Navarro, M., Sa´nchez-Delgado, R. A. & Pe´rez, H. (1997).J. Med. Chem.40, 1937–1939.

Navarro, M., Va´squez, F., Sa´nchez-Delgado, R. A., Pe´rez, H., Sinou, V. & Schre´vel, J. (2004).J. Med. Chem.47, 5204–5209.

Oleksyn, B. J. & Serda, P. (1993).Acta Cryst.B49, 530–534.

Orlow, A., Kalinowska-Tluscik, J. & Oleksyn, B. J. (2005).Acta Cryst.A61, c277–c278.

Acta Crystallographica Section E Structure Reports

Online

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Sa´nchez-Delgado, R. A., Navarro, M., Pe´rez, H. & Urbino, J. A. (1996).J. Med. Chem.39, 1095–1099.

Sheldrick, G. M. (2008).Acta Cryst.A64, 112–122.

Thwaite, S. E., Schier, A. & Schmidbaur, H. (2004).Inorg. Chim. Acta,357, 1549–1557.

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supporting information

Acta Cryst. (2010). E66, m1098–m1099 [https://doi.org/10.1107/S1600536810031144]

{4-[(7-Chloro-4-quinolyl)amino]-

N

,

N

-diethylpentanaminium}(triphenyl-phosphine)gold(I) dinitrate

Marina Hitosugi-Levesque and Joseph M. Tanski

S1. Comment

Chloroquine (CQ) has been used in treatments against the malaria parasites Plasmodium falciparum and Plasmodium vivax. Wide use of CQ has led to cross-resistance, limiting the efficacy of CQ related treatments. (World Health

Organization, 2010). Complexing CQ with metal containing fragments such as gold(I) triphenylphosphine and gold (III) tetrachloride can enhance its ability to combat CQ-resistant strains of malaria (Navarro et al. 1997; Navarro et al. 2004), as can CQ complexes of Rh and Ru (Sánchez-Delgado et al. 1996). While some of the biological effects of coordinating metals to chloroquine and ts derivatives have been reported, a lack of structure-activity correlation remains.

In the title complex (Fig. 1) gold(I) is coordinated to the nitrogen atom in the quinoline ring as proposed earlier

(Navarro et al. 1997). The complex exhibits a nearly linear coordination geometry around gold, with an N—Au—P angle of 176.94 (6)°. The Au—N and Au—P bond distance are 2.070 (2) Å and 2.2338 (7) Å, respectively. These bond

distances are similar to those found in thre structure of (triphenylphosphine)gold(I) chloride, with Au—P 2.2313 (4) Å (Borissova et al., 2008), as well as the Au—N and Au—P distances in the structure of the cationic pyridine adduct (tri-phenylphosphine)gold(I) pyridine tetrafluoroborate, with Au—N 2.073 (3) Å and Au—P 2.2364 (8) Å (Thwaite et al., 2004). The pendant diethylamino group (N4) of the CQ ligand in the title complex was found to be protonated, and the nitrate anions are hydrogen bound to both the N1 amino and N4 ammonium groups of the 1,4-pentanediamine fragment of the CQ.

S2. Experimental

[(CQ)Au(PPh3)][NO3] was prepared from chloroquine (CQ) free base and triphenylphosphine (PPh3) according to

literature procedure (Navarro et al., 2004). The protonated title complex, [C36H42AuClPN3](NO3)2 was obtained by

diffusion of diethyl ether into an acetone solution of [(CQ)Au(PPh3)][NO3] over a period of two weeks. All manipulations

were carried out under nitrogen using common Schlenck technique. X-ray diffraction quality crystals were separated as colorless plates.

S3. Refinement

Hydrogen atoms on carbon were included in calculated positions and were refined using a riding model at C–H = 0.95, 0.98 and 0.99 Å and Uiso(H) = 1.2, 1.5 and 1.2 × Ueq(C) of the aryl, methyl and methylene C-atoms, respectively. The

hydrogen atom on N4 was refined semi-freely with the help of a distance restraint at N–H = 0.88 Å and Uiso(H) = 1.2 ×

Ueq(N). The presence of a residual electron density peak and the proximity of a nitrate anion indicated that N5 was

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[image:4.610.133.477.73.224.2]

Figure 1

A view of the title complex, with displacement ellipsoids shown at the 50% probability level. H atoms on carbon have been omitted for clarity; primed atoms represent the disordered fraction of the NO3 ion and the diethylammonium group.

{4-[(7-Chloro-4-quinolyl)amino]-N,N- diethylpentanaminium}(triphenylphosphine)gold(I) dinitrate

Crystal data

[Au(C18H27ClN3)(C18H15P)](NO3)2

Mr = 904.13

Triclinic, P1 Hall symbol: -P 1 a = 10.2456 (5) Å b = 13.1914 (6) Å c = 13.6301 (7) Å α = 85.866 (1)° β = 88.126 (1)° γ = 86.510 (1)° V = 1833.22 (15) Å3

Z = 2 F(000) = 904 Dx = 1.638 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 9914 reflections θ = 2.6–28.2°

µ = 4.18 mm−1

T = 125 K Plate, colourless 0.34 × 0.14 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Bruker, 2007) Tmin = 0.331, Tmax = 0.818

25641 measured reflections 10116 independent reflections 8781 reflections with I > 2σ(I) Rint = 0.030

θmax = 30.4°, θmin = 1.5°

h = −13→14 k = −18→18 l = −18→19

Refinement Refinement on F2

Least-squares matrix: full R[F2 > 2σ(F2)] = 0.027

wR(F2) = 0.059

S = 1.02

10116 reflections 535 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2(F

o2) + (0.0268P)2 + 0.224P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.002

Δρmax = 0.79 e Å−3

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Special details

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. 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq Occ. (<1)

Au 0.665037 (10) 0.182061 (8) 0.594476 (7) 0.02328 (4) P 0.82288 (7) 0.11891 (5) 0.69465 (5) 0.02176 (13)

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C3′ −0.1431 (14) 0.2479 (8) 0.1467 (8) 0.059 (3) 0.519 (4) H3′A −0.0571 0.2290 0.1760 0.071* 0.519 (4) H3′B −0.2092 0.1990 0.1694 0.071* 0.519 (4) C4′ −0.1367 (9) 0.2780 (6) 0.0156 (6) 0.0492 (19) 0.519 (4) H4′A −0.1384 0.2152 −0.0185 0.074* 0.519 (4) H4′B −0.0560 0.3117 −0.0029 0.074* 0.519 (4) H4′C −0.2124 0.3236 −0.0032 0.074* 0.519 (4) N2 −0.2745 (2) 0.40668 (18) 0.39973 (18) 0.0290 (5)

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H21A 0.8240 −0.1989 0.5444 0.042* C22 1.0076 (3) −0.1817 (2) 0.5899 (2) 0.0356 (7) H22A 1.0434 −0.2461 0.5720 0.043* C23 1.0859 (3) −0.1158 (2) 0.6308 (3) 0.0428 (8) H23A 1.1761 −0.1342 0.6397 0.051* C24 1.0332 (3) −0.0222 (2) 0.6590 (2) 0.0352 (7) H24A 1.0879 0.0238 0.6858 0.042* C25 0.9531 (3) 0.20251 (19) 0.71033 (19) 0.0224 (5) C26 0.9777 (3) 0.2794 (2) 0.6378 (2) 0.0284 (6) H26A 0.9194 0.2936 0.5851 0.034* C27 1.0875 (3) 0.3353 (2) 0.6425 (2) 0.0363 (7) H27A 1.1058 0.3862 0.5919 0.044* C28 1.1707 (3) 0.3170 (2) 0.7209 (2) 0.0380 (7) H28A 1.2464 0.3548 0.7233 0.046* C29 1.1439 (3) 0.2440 (2) 0.7953 (2) 0.0348 (7) H29A 1.1995 0.2330 0.8499 0.042* C30 1.0360 (3) 0.1870 (2) 0.7902 (2) 0.0295 (6) H30A 1.0179 0.1367 0.8414 0.035* C31 0.7642 (2) 0.0799 (2) 0.81795 (19) 0.0246 (5) C32 0.6619 (3) 0.1374 (2) 0.8616 (2) 0.0294 (6) H32A 0.6227 0.1955 0.8263 0.035* C33 0.6179 (3) 0.1098 (3) 0.9562 (2) 0.0417 (8) H33A 0.5484 0.1490 0.9858 0.050* C34 0.6748 (3) 0.0252 (3) 1.0080 (2) 0.0452 (8) H34A 0.6456 0.0073 1.0735 0.054* C35 0.7737 (3) −0.0329 (3) 0.9646 (2) 0.0466 (9) H35A 0.8114 −0.0916 0.9999 0.056* C36 0.8185 (3) −0.0065 (2) 0.8699 (2) 0.0350 (7) H36A 0.8864 −0.0472 0.8403 0.042*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

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Geometric parameters (Å, º)

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N3—C12 1.334 (3) C31—C32 1.399 (4) N3—C13 1.384 (3) C32—C33 1.384 (4) N4—C10 1.340 (3) C32—H32A 0.9500 N4—C8 1.471 (3) C33—C34 1.385 (5) N4—H4 0.839 (18) C33—H33A 0.9500 C5—C6 1.513 (4) C34—C35 1.377 (5) C5—H5A 0.9900 C34—H34A 0.9500 C5—H5B 0.9900 C35—C36 1.383 (4) C6—C7 1.521 (4) C35—H35A 0.9500 C6—H6A 0.9900 C36—H36A 0.9500 C6—H6B 0.9900

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H6A—C6—H6B 108.2 C35—C34—H34A 120.0 C8—C7—C6 114.3 (2) C33—C34—H34A 120.0 C8—C7—H7A 108.7 C34—C35—C36 120.5 (3) C6—C7—H7A 108.7 C34—C35—H35A 119.8 C8—C7—H7B 108.7 C36—C35—H35A 119.8 C6—C7—H7B 108.7 C35—C36—C31 120.0 (3) H7A—C7—H7B 107.6 C35—C36—H36A 120.0 N4—C8—C7 108.4 (2) C31—C36—H36A 120.0

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Cl—C15—C16—C17 −178.8 (2) P—C31—C32—C33 −178.7 (2) C15—C16—C17—C18 0.5 (4) C31—C32—C33—C34 0.0 (5) N3—C13—C18—C17 −179.5 (2) C32—C33—C34—C35 −1.3 (5) C14—C13—C18—C17 −0.1 (4) C33—C34—C35—C36 1.1 (6) N3—C13—C18—C10 −0.4 (4) C34—C35—C36—C31 0.4 (5) C14—C13—C18—C10 178.9 (2) C32—C31—C36—C35 −1.7 (5) C16—C17—C18—C13 −0.8 (4) P—C31—C36—C35 178.5 (3) C16—C17—C18—C10 −179.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A N5—H5···O4 0.93 1.77 2.70 (2) 177 N5′—H5′···O4 0.93 2.00 2.81 (2) 144 N4—H4···O2′ 0.84 (2) 2.28 (2) 3.030 (6) 149 (3) N4—H4···O3i 0.84 (2) 2.32 (3) 3.013 (5) 140 (3)

Figure

Table 1
Figure 1A view of the title complex, with displacement ellipsoids shown at the 50% probability level

References

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