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

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 Au^I atom [N-Au-P = 176.94 (6)°], with Au-N and Au-P bond lengths of 2.070 (2) and 2.2338 (7) Å, 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.

Key indicators

• Single-crystal X-ray study
• T = 125 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.027
• wR factor = 0.059
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.35 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        N5'
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C3
PLAT411_ALERT_2_C Short Inter H...H Contact  H5B    ..  H1A     ..       2.06 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          5
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT234_ALERT_4_C Large Hirshfeld Difference C1'    --  C2'     ..       0.19 Ang.
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         N1'
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          N1
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C2 H5
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              N O3
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          5
              C H3
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          6
              N O3
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          7
              C H2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        939

Alert level G
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................       7.00 Perc.
PLAT432_ALERT_2_G Short Inter X...Y Contact  O1'    ..  C2'     ..       3.00 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  N5'    ..  C3'     ..       1.96 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  N5'    ..  C4'     ..       2.54 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C1'    ..  C4'     ..       2.44 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C1'    ..  C3'     ..       2.50 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C3'    ..  C4'     ..       1.80 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C3'    ..  C5      ..       2.69 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C4'    ..  C5      ..       3.00 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C5     ..  C1      ..       2.47 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C5     ..  O2      ..       2.95 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C6     ..  O3      ..       3.01 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  O3     ..  C4      ..       3.01 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  N5     ..  C1      ..       1.80 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  N5     ..  C2      ..       2.64 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C1     ..  C3      ..       2.53 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C2     ..  C3      ..       3.04 Ang.
PLAT773_ALERT_2_G Check long C-C Bond in CIF: C3'    --  C4'     .       1.80 Ang.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................      38.00 Perc.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         10
PLAT793_ALERT_4_G The Model has Chirality at C8      (Verify) ....          S
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  15 ALERT level C = Check and explain
  24 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  21 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
  12 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

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 (triphenylphosphine)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.

Related literature

For related structures, see: Karle & Karle (1988); Oleksyn & Serda (1993); Orlow et al. (2005); Borissova et al. (2008); Thwaite et al. (2004). For background to the metal coordination chemistry of chloroquine, see: Sánchez-Delgado et al. (1996); Navarro et 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).

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 U_iso(H) = 1.2, 1.5 and 1.2 × U_eq(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 U_iso(H) = 1.2 × U_eq(N). The presence of a residual electron density peak and the proximity of a nitrate anion indicated that N5 was protonated. Hydrogen atoms on N5 were included in calculated positions and were refined using a riding model at N–H = 0.93 Å and U_iso(H) = 1.2 × U_eq(N) .

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).

Figures

Fig. 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	Z = 2
Mr = 904.13	F(000) = 904
Triclinic, P1	Dx = 1.638 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.2456 (5) Å	Cell parameters from 9914 reflections
b = 13.1914 (6) Å	θ = 2.6–28.2°
c = 13.6301 (7) Å	µ = 4.18 mm^−1
α = 85.866 (1)°	T = 125 K
β = 88.126 (1)°	Plate, colourless
γ = 86.510 (1)°	0.34 × 0.14 × 0.05 mm
V = 1833.22 (15) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	10116 independent reflections
Radiation source: fine-focus sealed tube	8781 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 30.4°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −13→14
Tmin = 0.331, Tmax = 0.818	k = −18→18
25641 measured reflections	l = −18→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.059	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0268P)^2 + 0.224P] where P = (Fo^2 + 2Fc^2)/3
10116 reflections	(Δ/σ)max = 0.002
535 parameters	Δρmax = 0.79 e Å^−3
1 restraint	Δρmin = −0.84 e Å^−3

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 (Ų)

	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)
N1	−0.7853 (8)	0.3049 (6)	0.0355 (8)	0.0249 (19)	0.481 (4)
O1	−0.6757 (6)	0.2555 (6)	0.0027 (5)	0.0508 (16)	0.481 (4)
O2	−0.8285 (6)	0.3795 (4)	−0.0104 (4)	0.0542 (16)	0.481 (4)
O3	−0.8277 (5)	0.2750 (4)	0.1169 (4)	0.0433 (13)	0.481 (4)
N5	−0.1929 (19)	0.3572 (7)	0.1579 (14)	0.0312 (18)	0.481 (4)
H5	−0.2154	0.3451	0.2242	0.037*	0.481 (4)
C1	−0.3183 (7)	0.4390 (6)	0.0986 (5)	0.0272 (14)	0.481 (4)
H1A	−0.3322	0.5034	0.1316	0.033*	0.481 (4)
H1B	−0.2942	0.4552	0.0286	0.033*	0.481 (4)
C2	−0.4399 (6)	0.3793 (6)	0.1079 (5)	0.0415 (17)	0.481 (4)
H2A	−0.5135	0.4207	0.0791	0.062*	0.481 (4)
H2B	−0.4599	0.3615	0.1776	0.062*	0.481 (4)
H2C	−0.4251	0.3169	0.0732	0.062*	0.481 (4)
C3	−0.1635 (9)	0.2834 (7)	0.1254 (7)	0.0293 (18)	0.481 (4)
H3A	−0.2504	0.2552	0.1216	0.035*	0.481 (4)
H3B	−0.1239	0.2453	0.1834	0.035*	0.481 (4)
C4	−0.0910 (9)	0.2302 (8)	0.0440 (7)	0.058 (2)	0.481 (4)
H4A	−0.0945	0.1564	0.0570	0.087*	0.481 (4)
H4B	0.0004	0.2484	0.0409	0.087*	0.481 (4)
H4C	−0.1318	0.2512	−0.0189	0.087*	0.481 (4)
N1'	0.3290 (7)	0.3177 (6)	0.0098 (5)	0.0373 (13)	0.519 (4)
O1'	0.3781 (6)	0.2933 (5)	−0.0668 (5)	0.0708 (18)	0.519 (4)
O2'	0.3890 (6)	0.3670 (4)	0.0672 (3)	0.0610 (16)	0.519 (4)
O3'	0.2288 (17)	0.3057 (12)	0.0391 (12)	0.113 (5)	0.519 (4)
N5'	−0.2021 (18)	0.3913 (6)	0.1539 (13)	0.0312 (18)	0.519 (4)
H5'	−0.2375	0.3987	0.2168	0.037*	0.519 (4)
C1'	−0.3049 (9)	0.3885 (8)	0.0918 (8)	0.064 (3)	0.519 (4)
H1'A	−0.3527	0.3256	0.1036	0.076*	0.519 (4)
H1'B	−0.2777	0.3981	0.0216	0.076*	0.519 (4)
C2'	−0.3838 (8)	0.4842 (7)	0.1296 (7)	0.069 (2)	0.519 (4)
H2'A	−0.4691	0.4922	0.0987	0.104*	0.519 (4)
H2'B	−0.3350	0.5450	0.1126	0.104*	0.519 (4)
H2'C	−0.3965	0.4753	0.2012	0.104*	0.519 (4)
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)
O4	−0.2598 (2)	0.32863 (15)	0.35104 (16)	0.0399 (5)
O5	−0.2412 (2)	0.40230 (17)	0.48672 (16)	0.0449 (6)
O6	−0.3220 (2)	0.48678 (17)	0.35888 (18)	0.0484 (6)
N3	0.5210 (2)	0.23408 (16)	0.49707 (16)	0.0218 (4)
N4	0.2893 (3)	0.38262 (19)	0.27767 (19)	0.0354 (6)
H4	0.293 (3)	0.362 (2)	0.2210 (16)	0.042*
C5	−0.0876 (3)	0.4451 (3)	0.1452 (2)	0.0432 (8)
H5A	−0.0406	0.4419	0.0808	0.052*
H5B	−0.1337	0.5131	0.1473	0.052*
C6	0.0088 (3)	0.4291 (3)	0.2274 (2)	0.0407 (8)
H6A	0.0440	0.3574	0.2321	0.049*
H6B	−0.0361	0.4433	0.2908	0.049*
C7	0.1203 (3)	0.4995 (2)	0.2076 (2)	0.0292 (6)
H7A	0.1600	0.4880	0.1418	0.035*
H7B	0.0840	0.5709	0.2059	0.035*
C8	0.2266 (3)	0.4855 (2)	0.2828 (2)	0.0288 (6)
H8A	0.1857	0.4916	0.3499	0.035*
C9	0.3271 (3)	0.5659 (2)	0.2646 (3)	0.0411 (8)
H9A	0.3988	0.5513	0.3103	0.062*
H9B	0.2854	0.6333	0.2749	0.062*
H9C	0.3618	0.5649	0.1968	0.062*
C10	0.3611 (2)	0.3343 (2)	0.3491 (2)	0.0252 (5)
C11	0.3767 (2)	0.3752 (2)	0.43949 (19)	0.0239 (5)
H11A	0.3325	0.4381	0.4536	0.029*
C12	0.4565 (3)	0.3237 (2)	0.50772 (19)	0.0244 (5)
H12A	0.4666	0.3545	0.5677	0.029*
C13	0.5037 (2)	0.18783 (19)	0.41085 (18)	0.0206 (5)
C14	0.5651 (2)	0.09074 (19)	0.39948 (19)	0.0235 (5)
H14A	0.6166	0.0578	0.4505	0.028*
C15	0.5501 (2)	0.04404 (19)	0.3141 (2)	0.0243 (5)
Cl	0.63057 (7)	−0.07417 (5)	0.29880 (5)	0.03084 (15)
C16	0.4726 (3)	0.0892 (2)	0.2383 (2)	0.0286 (6)
H16A	0.4626	0.0554	0.1800	0.034*
C17	0.4113 (3)	0.1831 (2)	0.2497 (2)	0.0294 (6)
H17A	0.3580	0.2138	0.1987	0.035*
C18	0.4253 (2)	0.2355 (2)	0.33543 (19)	0.0241 (5)
C19	0.9009 (3)	0.00417 (19)	0.64813 (19)	0.0238 (5)
C20	0.8238 (3)	−0.0623 (2)	0.6048 (2)	0.0294 (6)
H20A	0.7337	−0.0443	0.5955	0.035*
C21	0.8771 (3)	−0.1545 (2)	0.5750 (2)	0.0354 (7)
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au	0.02601 (6)	0.02376 (5)	0.02042 (5)	−0.00079 (4)	−0.00528 (4)	−0.00233 (4)
P	0.0256 (3)	0.0196 (3)	0.0201 (3)	0.0005 (3)	−0.0027 (3)	−0.0022 (2)
N1	0.017 (3)	0.023 (4)	0.038 (5)	−0.010 (3)	0.004 (3)	−0.020 (3)
O1	0.039 (3)	0.067 (5)	0.049 (4)	0.010 (3)	−0.014 (3)	−0.022 (3)
O2	0.075 (4)	0.049 (3)	0.035 (3)	0.023 (3)	−0.007 (3)	0.004 (2)
O3	0.053 (3)	0.047 (3)	0.029 (3)	0.011 (2)	−0.013 (2)	−0.004 (2)
N5	0.036 (3)	0.033 (6)	0.0265 (19)	−0.015 (5)	−0.0003 (17)	−0.006 (5)
C1	0.026 (3)	0.035 (4)	0.021 (3)	0.004 (3)	−0.003 (2)	−0.005 (3)
C2	0.028 (3)	0.052 (4)	0.046 (4)	−0.013 (3)	−0.008 (3)	−0.005 (3)
C3	0.035 (4)	0.027 (5)	0.027 (4)	−0.016 (3)	0.002 (3)	−0.001 (3)
C4	0.052 (6)	0.066 (7)	0.057 (6)	−0.005 (5)	0.003 (4)	−0.012 (5)
N1'	0.041 (4)	0.040 (3)	0.030 (3)	−0.001 (3)	−0.009 (3)	0.000 (3)
O1'	0.065 (4)	0.102 (5)	0.047 (3)	0.013 (3)	−0.012 (3)	−0.031 (3)
O2'	0.085 (4)	0.068 (4)	0.033 (3)	−0.022 (3)	−0.013 (3)	−0.004 (2)
O3'	0.128 (12)	0.129 (11)	0.080 (10)	0.012 (9)	−0.019 (8)	0.005 (8)
N5'	0.036 (3)	0.033 (6)	0.0265 (19)	−0.015 (5)	−0.0003 (17)	−0.006 (5)
C1'	0.046 (5)	0.065 (6)	0.084 (7)	0.005 (5)	−0.008 (4)	−0.035 (6)
C2'	0.048 (5)	0.095 (7)	0.064 (6)	0.005 (5)	−0.013 (4)	−0.004 (5)
C3'	0.107 (8)	0.036 (6)	0.034 (6)	−0.009 (5)	0.008 (5)	−0.003 (4)
C4'	0.063 (5)	0.045 (5)	0.041 (4)	−0.003 (4)	0.006 (4)	−0.019 (4)
N2	0.0287 (12)	0.0258 (12)	0.0328 (13)	−0.0032 (10)	0.0054 (10)	−0.0056 (10)
O4	0.0540 (14)	0.0294 (11)	0.0370 (12)	−0.0050 (10)	0.0130 (10)	−0.0117 (9)
O5	0.0638 (15)	0.0386 (12)	0.0328 (12)	0.0051 (11)	−0.0117 (11)	−0.0076 (10)
O6	0.0619 (16)	0.0328 (12)	0.0491 (15)	0.0070 (11)	−0.0092 (12)	0.0009 (11)
N3	0.0228 (11)	0.0217 (11)	0.0211 (11)	−0.0007 (8)	−0.0012 (8)	−0.0028 (8)
N4	0.0446 (15)	0.0291 (13)	0.0328 (14)	0.0132 (11)	−0.0171 (12)	−0.0108 (11)
C5	0.0322 (16)	0.067 (2)	0.0310 (17)	−0.0116 (15)	−0.0027 (13)	0.0044 (15)
C6	0.0334 (16)	0.059 (2)	0.0311 (16)	−0.0192 (15)	−0.0072 (13)	0.0057 (15)
C7	0.0296 (14)	0.0244 (14)	0.0326 (15)	0.0005 (11)	−0.0038 (12)	0.0040 (11)
C8	0.0270 (14)	0.0220 (13)	0.0377 (16)	0.0044 (11)	−0.0064 (12)	−0.0065 (11)
C9	0.0358 (17)	0.0388 (18)	0.051 (2)	−0.0078 (14)	−0.0045 (15)	−0.0112 (15)
C10	0.0225 (13)	0.0260 (13)	0.0276 (14)	0.0022 (10)	−0.0064 (11)	−0.0060 (11)
C11	0.0236 (13)	0.0218 (12)	0.0271 (14)	0.0013 (10)	−0.0017 (10)	−0.0079 (10)
C12	0.0272 (13)	0.0250 (13)	0.0220 (13)	−0.0041 (10)	−0.0009 (10)	−0.0056 (10)
C13	0.0198 (12)	0.0216 (12)	0.0204 (12)	−0.0013 (9)	0.0002 (9)	−0.0016 (10)
C14	0.0217 (12)	0.0242 (13)	0.0241 (13)	0.0018 (10)	−0.0008 (10)	−0.0013 (10)
C15	0.0213 (12)	0.0227 (13)	0.0291 (14)	0.0019 (10)	0.0013 (10)	−0.0061 (11)
Cl	0.0286 (3)	0.0248 (3)	0.0391 (4)	0.0053 (3)	0.0004 (3)	−0.0085 (3)
C16	0.0318 (14)	0.0289 (14)	0.0264 (14)	0.0016 (11)	−0.0039 (11)	−0.0110 (11)
C17	0.0323 (14)	0.0305 (15)	0.0256 (14)	0.0058 (12)	−0.0100 (11)	−0.0063 (11)
C18	0.0236 (13)	0.0246 (13)	0.0247 (13)	0.0019 (10)	−0.0053 (10)	−0.0066 (10)
C19	0.0305 (14)	0.0215 (12)	0.0190 (12)	−0.0017 (10)	0.0046 (10)	−0.0005 (10)
C20	0.0379 (16)	0.0239 (13)	0.0263 (14)	−0.0007 (12)	−0.0026 (12)	−0.0020 (11)
C21	0.0530 (19)	0.0236 (14)	0.0304 (16)	−0.0055 (13)	0.0011 (14)	−0.0058 (12)
C22	0.0485 (18)	0.0225 (14)	0.0348 (17)	−0.0008 (13)	0.0175 (14)	−0.0048 (12)
C23	0.0317 (16)	0.0336 (17)	0.062 (2)	−0.0004 (13)	0.0200 (15)	−0.0089 (15)
C24	0.0295 (15)	0.0284 (15)	0.0488 (19)	−0.0063 (12)	0.0112 (13)	−0.0113 (13)
C25	0.0253 (13)	0.0210 (12)	0.0213 (13)	0.0001 (10)	−0.0001 (10)	−0.0046 (10)
C26	0.0330 (15)	0.0281 (14)	0.0243 (14)	−0.0010 (11)	−0.0017 (11)	−0.0039 (11)
C27	0.0391 (17)	0.0326 (16)	0.0377 (17)	−0.0075 (13)	0.0088 (14)	−0.0051 (13)
C28	0.0296 (15)	0.0389 (17)	0.0482 (19)	−0.0058 (13)	0.0041 (14)	−0.0204 (15)
C29	0.0290 (15)	0.0386 (17)	0.0389 (17)	0.0035 (13)	−0.0087 (13)	−0.0187 (14)
C30	0.0359 (15)	0.0286 (14)	0.0243 (14)	0.0030 (12)	−0.0037 (12)	−0.0069 (11)
C31	0.0235 (13)	0.0289 (14)	0.0219 (13)	−0.0018 (10)	−0.0021 (10)	−0.0048 (11)
C32	0.0295 (14)	0.0279 (14)	0.0315 (15)	−0.0012 (11)	−0.0007 (12)	−0.0068 (12)
C33	0.0378 (17)	0.0485 (19)	0.0396 (18)	−0.0014 (15)	0.0138 (14)	−0.0165 (15)
C34	0.0420 (19)	0.067 (2)	0.0250 (16)	−0.0028 (17)	0.0085 (14)	0.0003 (15)
C35	0.0392 (18)	0.061 (2)	0.0348 (18)	0.0052 (16)	0.0036 (14)	0.0191 (16)
C36	0.0309 (15)	0.0408 (17)	0.0303 (16)	0.0082 (13)	0.0044 (12)	0.0061 (13)

Geometric parameters (Å, º)

Au—N3	2.070 (2)	C7—C8	1.513 (4)
Au—P	2.2338 (7)	C7—H7A	0.9900
P—C25	1.809 (3)	C7—H7B	0.9900
P—C19	1.814 (3)	C8—C9	1.526 (4)
P—C31	1.816 (3)	C8—H8A	1.0000
N1—O2	1.197 (12)	C9—H9A	0.9800
N1—O3	1.226 (12)	C9—H9B	0.9800
N1—O1	1.343 (11)	C9—H9C	0.9800
N5—C3	1.119 (17)	C10—C11	1.398 (4)
N5—C5	1.628 (16)	C10—C18	1.445 (3)
N5—C1	1.801 (18)	C11—C12	1.373 (4)
N5—H5	0.9300	C11—H11A	0.9500
C1—C2	1.511 (10)	C12—H12A	0.9500
C1—H1A	0.9900	C13—C14	1.409 (3)
C1—H1B	0.9900	C13—C18	1.413 (3)
C2—H2A	0.9800	C14—C15	1.373 (4)
C2—H2B	0.9800	C14—H14A	0.9500
C2—H2C	0.9800	C15—C16	1.400 (4)
C3—C4	1.507 (14)	C15—Cl	1.742 (3)
C3—H3A	0.9900	C16—C17	1.371 (4)
C3—H3B	0.9900	C16—H16A	0.9500
C4—H4A	0.9800	C17—C18	1.415 (4)
C4—H4B	0.9800	C17—H17A	0.9500
C4—H4C	0.9800	C19—C24	1.388 (4)
N1'—O3'	1.105 (16)	C19—C20	1.389 (4)
N1'—O1'	1.201 (9)	C20—C21	1.385 (4)
N1'—O2'	1.251 (8)	C20—H20A	0.9500
N5'—C1'	1.38 (2)	C21—C22	1.381 (4)
N5'—C5	1.405 (17)	C21—H21A	0.9500
N5'—C3'	1.959 (14)	C22—C23	1.377 (4)
N5'—H5'	0.9300	C22—H22A	0.9500
C1'—C2'	1.567 (12)	C23—C24	1.392 (4)
C1'—H1'A	0.9900	C23—H23A	0.9500
C1'—H1'B	0.9900	C24—H24A	0.9500
C2'—H2'A	0.9800	C25—C26	1.393 (4)
C2'—H2'B	0.9800	C25—C30	1.398 (4)
C2'—H2'C	0.9800	C26—C27	1.388 (4)
C3'—C4'	1.803 (14)	C26—H26A	0.9500
C3'—H3'A	0.9900	C27—C28	1.386 (5)
C3'—H3'B	0.9900	C27—H27A	0.9500
C4'—H4'A	0.9800	C28—C29	1.380 (5)
C4'—H4'B	0.9800	C28—H28A	0.9500
C4'—H4'C	0.9800	C29—C30	1.380 (4)
N2—O6	1.238 (3)	C29—H29A	0.9500
N2—O5	1.241 (3)	C30—H30A	0.9500
N2—O4	1.264 (3)	C31—C36	1.393 (4)
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
N3—Au—P	176.94 (6)	N4—C8—C9	110.7 (2)
C25—P—C19	105.97 (12)	C7—C8—C9	111.3 (2)
C25—P—C31	105.86 (12)	N4—C8—H8A	108.8
C19—P—C31	104.78 (12)	C7—C8—H8A	108.8
C25—P—Au	115.47 (9)	C9—C8—H8A	108.8
C19—P—Au	110.06 (9)	C8—C9—H9A	109.5
C31—P—Au	113.88 (9)	C8—C9—H9B	109.5
O2—N1—O3	123.8 (7)	H9A—C9—H9B	109.5
O2—N1—O1	119.5 (9)	C8—C9—H9C	109.5
O3—N1—O1	116.3 (9)	H9A—C9—H9C	109.5
C3—N5—C5	116.5 (15)	H9B—C9—H9C	109.5
C3—N5—C1	118.2 (15)	N4—C10—C11	122.5 (2)
C5—N5—C1	92.3 (6)	N4—C10—C18	120.5 (2)
C3—N5—H5	109.6	C11—C10—C18	116.9 (2)
C5—N5—H5	109.6	C12—C11—C10	119.5 (2)
C1—N5—H5	109.6	C12—C11—H11A	120.3
C2—C1—N5	105.1 (7)	C10—C11—H11A	120.3
C2—C1—H1A	110.7	N3—C12—C11	125.6 (2)
N5—C1—H1A	110.7	N3—C12—H12A	117.2
C2—C1—H1B	110.7	C11—C12—H12A	117.2
N5—C1—H1B	110.7	N3—C13—C14	118.6 (2)
H1A—C1—H1B	108.8	N3—C13—C18	121.4 (2)
N5—C3—C4	147.4 (12)	C14—C13—C18	120.0 (2)
N5—C3—H3A	99.9	C15—C14—C13	119.5 (2)
C4—C3—H3A	99.9	C15—C14—H14A	120.3
N5—C3—H3B	99.9	C13—C14—H14A	120.3
C4—C3—H3B	99.9	C14—C15—C16	121.8 (2)
H3A—C3—H3B	104.2	C14—C15—Cl	119.3 (2)
O3'—N1'—O1'	128.3 (11)	C16—C15—Cl	118.9 (2)
O3'—N1'—O2'	110.2 (11)	C17—C16—C15	118.8 (2)
O1'—N1'—O2'	121.5 (7)	C17—C16—H16A	120.6
C1'—N5'—C5	131.5 (12)	C15—C16—H16A	120.6
C1'—N5'—C3'	95.6 (9)	C16—C17—C18	121.8 (3)
C5—N5'—C3'	105.3 (10)	C16—C17—H17A	119.1
C1'—N5'—H5'	107.3	C18—C17—H17A	119.1
C5—N5'—H5'	107.3	C13—C18—C17	118.1 (2)
C3'—N5'—H5'	107.3	C13—C18—C10	119.2 (2)
N5'—C1'—C2'	95.8 (8)	C17—C18—C10	122.6 (2)
N5'—C1'—H1'A	112.6	C24—C19—C20	118.9 (2)
C2'—C1'—H1'A	112.6	C24—C19—P	122.4 (2)
N5'—C1'—H1'B	112.6	C20—C19—P	118.6 (2)
C2'—C1'—H1'B	112.6	C21—C20—C19	120.7 (3)
H1'A—C1'—H1'B	110.1	C21—C20—H20A	119.7
C1'—C2'—H2'A	109.5	C19—C20—H20A	119.7
C1'—C2'—H2'B	109.5	C22—C21—C20	119.8 (3)
H2'A—C2'—H2'B	109.5	C22—C21—H21A	120.1
C1'—C2'—H2'C	109.5	C20—C21—H21A	120.1
H2'A—C2'—H2'C	109.5	C23—C22—C21	120.2 (3)
H2'B—C2'—H2'C	109.5	C23—C22—H22A	119.9
C4'—C3'—N5'	84.7 (7)	C21—C22—H22A	119.9
C4'—C3'—H3'A	114.5	C22—C23—C24	120.0 (3)
N5'—C3'—H3'A	114.5	C22—C23—H23A	120.0
C4'—C3'—H3'B	114.5	C24—C23—H23A	120.0
N5'—C3'—H3'B	114.5	C19—C24—C23	120.3 (3)
H3'A—C3'—H3'B	111.6	C19—C24—H24A	119.9
C3'—C4'—H4'A	109.5	C23—C24—H24A	119.9
C3'—C4'—H4'B	109.5	C26—C25—C30	119.0 (2)
H4'A—C4'—H4'B	109.5	C26—C25—P	119.4 (2)
C3'—C4'—H4'C	109.5	C30—C25—P	121.4 (2)
H4'A—C4'—H4'C	109.5	C27—C26—C25	119.9 (3)
H4'B—C4'—H4'C	109.5	C27—C26—H26A	120.1
O6—N2—O5	121.2 (2)	C25—C26—H26A	120.1
O6—N2—O4	118.8 (3)	C28—C27—C26	120.3 (3)
O5—N2—O4	120.0 (2)	C28—C27—H27A	119.9
C12—N3—C13	117.2 (2)	C26—C27—H27A	119.9
C12—N3—Au	119.89 (17)	C29—C28—C27	120.2 (3)
C13—N3—Au	121.94 (16)	C29—C28—H28A	119.9
C10—N4—C8	124.3 (2)	C27—C28—H28A	119.9
C10—N4—H4	120 (2)	C30—C29—C28	119.8 (3)
C8—N4—H4	114 (2)	C30—C29—H29A	120.1
N5'—C5—C6	118.1 (7)	C28—C29—H29A	120.1
C6—C5—N5	109.3 (7)	C29—C30—C25	120.7 (3)
N5'—C5—H5A	114.5	C29—C30—H30A	119.7
C6—C5—H5A	109.8	C25—C30—H30A	119.7
N5—C5—H5A	109.8	C36—C31—C32	119.2 (3)
N5'—C5—H5B	95.0	C36—C31—P	121.4 (2)
C6—C5—H5B	109.8	C32—C31—P	119.4 (2)
N5—C5—H5B	109.8	C33—C32—C31	120.0 (3)
H5A—C5—H5B	108.3	C33—C32—H32A	120.0
C5—C6—C7	109.9 (3)	C31—C32—H32A	120.0
C5—C6—H6A	109.7	C32—C33—C34	120.2 (3)
C7—C6—H6A	109.7	C32—C33—H33A	119.9
C5—C6—H6B	109.7	C34—C33—H33A	119.9
C7—C6—H6B	109.7	C35—C34—C33	120.0 (3)
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
C3—N5—C1—C2	63.6 (16)	N4—C10—C18—C13	178.0 (3)
C5—N5—C1—C2	−174.5 (7)	C11—C10—C18—C13	−2.7 (4)
C5—N5—C3—C4	−34 (3)	N4—C10—C18—C17	−3.0 (4)
C1—N5—C3—C4	74 (3)	C11—C10—C18—C17	176.3 (3)
C5—N5'—C1'—C2'	−85.5 (15)	C25—P—C19—C24	20.4 (3)
C3'—N5'—C1'—C2'	158.3 (8)	C31—P—C19—C24	−91.3 (2)
C1'—N5'—C3'—C4'	54.7 (10)	Au—P—C19—C24	145.9 (2)
C5—N5'—C3'—C4'	−81.1 (10)	C25—P—C19—C20	−163.2 (2)
C1'—N5'—C5—C6	−178.7 (11)	C31—P—C19—C20	85.1 (2)
C3'—N5'—C5—C6	−66.6 (11)	Au—P—C19—C20	−37.7 (2)
C1'—N5'—C5—N5	−122 (6)	C24—C19—C20—C21	1.5 (4)
C3'—N5'—C5—N5	−10 (5)	P—C19—C20—C21	−175.1 (2)
C3—N5—C5—N5'	146 (7)	C19—C20—C21—C22	1.2 (4)
C1—N5—C5—N5'	23 (5)	C20—C21—C22—C23	−2.6 (5)
C3—N5—C5—C6	−85.2 (15)	C21—C22—C23—C24	1.3 (5)
C1—N5—C5—C6	151.6 (6)	C20—C19—C24—C23	−2.8 (4)
N5'—C5—C6—C7	−175.9 (7)	P—C19—C24—C23	173.6 (2)
N5—C5—C6—C7	170.8 (7)	C22—C23—C24—C19	1.4 (5)
C5—C6—C7—C8	−176.8 (3)	C19—P—C25—C26	98.4 (2)
C10—N4—C8—C7	−161.2 (3)	C31—P—C25—C26	−150.7 (2)
C10—N4—C8—C9	76.5 (4)	Au—P—C25—C26	−23.7 (2)
C6—C7—C8—N4	64.2 (3)	C19—P—C25—C30	−76.8 (2)
C6—C7—C8—C9	−173.9 (3)	C31—P—C25—C30	34.1 (2)
C8—N4—C10—C11	4.3 (5)	Au—P—C25—C30	161.09 (19)
C8—N4—C10—C18	−176.5 (3)	C30—C25—C26—C27	3.7 (4)
N4—C10—C11—C12	−177.1 (3)	P—C25—C26—C27	−171.6 (2)
C18—C10—C11—C12	3.6 (4)	C25—C26—C27—C28	−2.0 (4)
C13—N3—C12—C11	−1.6 (4)	C26—C27—C28—C29	−0.9 (5)
Au—N3—C12—C11	167.6 (2)	C27—C28—C29—C30	1.9 (4)
C10—C11—C12—N3	−1.6 (4)	C28—C29—C30—C25	−0.2 (4)
C12—N3—C13—C14	−176.8 (2)	C26—C25—C30—C29	−2.7 (4)
Au—N3—C13—C14	14.3 (3)	P—C25—C30—C29	172.5 (2)
C12—N3—C13—C18	2.6 (4)	C25—P—C31—C36	−89.6 (3)
Au—N3—C13—C18	−166.36 (19)	C19—P—C31—C36	22.2 (3)
N3—C13—C14—C15	−179.4 (2)	Au—P—C31—C36	142.5 (2)
C18—C13—C14—C15	1.2 (4)	C25—P—C31—C32	90.7 (2)
C13—C14—C15—C16	−1.5 (4)	C19—P—C31—C32	−157.5 (2)
C13—C14—C15—Cl	177.96 (19)	Au—P—C31—C32	−37.2 (2)
C14—C15—C16—C17	0.7 (4)	C36—C31—C32—C33	1.5 (4)
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···O3^i	0.84 (2)	2.32 (3)	3.013 (5)	140 (3)

Symmetry code: (i) x+1, y, z.