catena-Poly[[tetra­kis(hexa­methyl­phospho­ramide-κO)bis­(nitrato-κ²O,O′)yttrium(III)] [silver(I)-di-μ-sulfido-tungstate(VI)(Ag—W)-di-μ-sulfido]]

The title salt of a one-dimensional anionic W/S/Ag polymer, {[Y(NO₃)₂(C₆H₁₈N₃OP)₄][WAgS₄]}_n was produced by the reaction of ammonium tetra­thio­tungstate(VI), silver(I) sulfide and yttrium(III) nitrate in hexa­methyl­phospho­ramide. The cation has the same structure as that in the isostructural Yb compound [Cao et al. (2007). Acta Cryst. E63, m2076–m2077]. Together with the two nitrate ligands, the cation is monovalent, which leads to the anionic chain having a monovalent repeat unit. This contrasts with solvent-coordinated rare-earth cations, which are trivalent and induce trivalent repeat units in the anionic chains. The polymeric {[WS₄Ag]ⁿ⁻}_n anion, with W—Ag—W and Ag—W—Ag angles of 162.684 (19) and 153.833 (10)°, respectively, presents a distorted linear configuration the same as that of the anionic chain in the isostructural Yb compound, suggesting that different rare-earth cations with the same coordination environments have the same influence on the arrangement of their anionic chains.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](g-S) = 0.002 Å
• R factor = 0.044
• wR factor = 0.085
• Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT761_ALERT_1_A CIF Contains no X-H Bonds ......................          ?
PLAT762_ALERT_1_A CIF Contains no X-Y-H or H-Y-H Angles ..........          ?

Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        N11

Alert level C
PLAT213_ALERT_2_C Atom C5      has ADP max/min Ratio .............       3.20 prola
PLAT213_ALERT_2_C Atom C6      has ADP max/min Ratio .............       3.90 oblat
PLAT213_ALERT_2_C Atom C8      has ADP max/min Ratio .............       3.70 prola
PLAT213_ALERT_2_C Atom C20     has ADP max/min Ratio .............       3.20 prola
PLAT213_ALERT_2_C Atom C23     has ADP max/min Ratio .............       3.10 prola
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.13 Ratio
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.57 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.11 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         P1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         P2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3
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         N8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        N10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        N12
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         W1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.01

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for W1          (9)       6.66
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ag1         (1)       1.16
PLAT794_ALERT_5_G Check Predicted Bond Valency for Y1          (3)       3.69

   2 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  17 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

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


checkCIF publication errors

Alert level A
PUBL022_ALERT_1_A There is a mismatched ~ on line 135
              the isostructural Yb compound~, suggesting that differernt rare-earth cations
              If you require a ~ then it should be escaped
              with a \, i.e. \~
              Otherwise there must be a matching closing ~, e.g. C~2~H~4~

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

S1. Comment

One-dimensional Mo(W)/S/Ag anionic polymers have attracted much attention for their configurational isomerism (Niu et al., 2004) and potential applications, especially in third-order nonlinear optical (NLO) materials. (Zhang et al., 2007, and references therein). Different solvent-coordinated rare-earth cations proved effective to obtain various configurations of anionic chains (Niu et al., 2004). The title compound {[Y(hmp)₄(NO₃)₂][WS₄Ag]}_n (hmp = hexamethylphosphoramide) with a wave-like anionic chain was prepared by following such route using Y(III)-hmp complex as counterion.

In possession of two nitrate ligands, the cation in the title compound is univalent (Fig. 1), which leads to an anionic chain with a univalent repeat unit, unlike other solvent-coordinated rare-earth cations, in literature (Niu et al., 2004), which are trivalent and induce trivalent repeat units. For example, [Nd(dmf)₈]³⁺ induces an anionic chain with a trivalent repeat unit [W₄S₁₆Ag₅]^3- (Huang et al., 1997).

As illustrated in Fig. 2, the anionic chain in the title compound has a distorted linear configuration with W—Ag—W and Ag—W—Ag angles of 162.684 (19) and 153.833 (10) °, deviating significantly from the ideal 180 °, which is observed in the reported compound {(γ-MePyH)[MoS₄Ag]}_n (179.3 (2)–180.0 (1) °)(Lang et al., 1993). Similar angles of 160.81 (7) and 153.41 (7) ° for W—Ag—W and Ag—W—Ag are found in another distorted linear chain in {[Yb(hmp)₄(NO₃)₂][WS₄Ag]}_n (Cao et al., 2007), which suggests that differernt rare earth cations with the same coordination environments will result in the same anionic structures.

Related literature

One example of a one-dimensional Mo/S/Ag anionic polymer with an almost ideal linear configuration is {(γ-MePyH)[MoS₄Ag]}_n (Lang et al., 1993). A more relevant analog of the title compound is {[Yb(hmp)₄(NO₃)₂][WS₄Ag]}_n (Cao et al., 2007), which has similar wave-like chains. For related literature, see: Huang et al. (1996); Niu et al. (2004); Zhang et al. (2007).

S2. Experimental

1 mmol A g₂S was added to a solution of [NH₄]₂WS₄ (2 mmol in 30 mL h mp) with thorough stir for 12 h. The solution underwent an additional stir for one minute after 1 mmol Y(NO₃)₃6H₂O was added. After filtration the orange-red filtrate was carefully laid on the surface with 30 ml i-PrOH. Red block crystals were obtained after ten days. Yield: 1.138 g in pure form, 42.2% (based on W). Analysis calculated for C₂₄H₇₂AgN₁₄O₁₀P₄S₄WY: C 21.36, H 5.38, N 14.53%; found: C 21.39, H 5.40, N 14.49%. IR: ν, cm^-1, 478.9 m, 447.4 s (W-µ₂-S).

S3. Refinement

Some N and P atoms have low U_eq as compared to neighbors and a few C atoms have large ADP max/min ratio. Splitting these atoms to resolve disorder will cause the refinement unstable or ADP non positive definite, so no further treatments were applied to these atoms. H atoms were positioned geometrically and refined with riding model, with U_iso = 1.5U_eq for methyl H atoms and 0.97 Å for C—H bonds.

Computing details

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of the cation in the title compound, with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted.
	Fig. 2. The molecular structure of a portion of the anionic chain in the title compound, with atom labels and 30% probability displacement ellipsoids.

catena-Poly[[tetrakis(hexamethylphosphoramide-κO)bis(nitrato- κ²O,O')yttrium(III)] [silver(I)-di-µ-sulfido-tungstate(VI)(Ag—W)-di-µ-sulfido]]

Crystal data

[Y(NO3)2(C6H18N3OP)4][WAgS4]	F(000) = 2712.0
Mr = 1349.74	Dx = 1.675 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 18559 reflections
a = 15.789 (3) Å	θ = 3.0–25.4°
b = 29.661 (6) Å	µ = 3.91 mm^−1
c = 11.430 (2) Å	T = 223 K
β = 90.83 (3)°	Block, red
V = 5352.3 (18) Å^3	0.50 × 0.45 × 0.32 mm
Z = 4

Data collection

Rigaku Mercury CCD diffractometer	9804 independent reflections
Radiation source: fine-focus sealed tube	9045 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 14.6306 pixels mm^-1	θmax = 25.4°, θmin = 3.0°
ω scans	h = −19→18
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −35→34
Tmin = 0.173, Tmax = 0.286	l = −13→13
49397 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.21	w = 1/[σ^2(Fo^2) + (0.0187P)^2 + 15.0729P] where P = (Fo^2 + 2Fc^2)/3
9783 reflections	(Δ/σ)max = 0.001
532 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −0.77 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
Y1	0.76115 (3)	0.082921 (16)	0.17150 (4)	0.02278 (12)
P1	0.70695 (12)	0.14734 (5)	−0.09585 (14)	0.0438 (4)
P2	0.54106 (9)	0.09577 (5)	0.26801 (14)	0.0342 (3)
P3	0.97701 (9)	0.13288 (5)	0.17952 (13)	0.0338 (3)
P4	0.80120 (10)	−0.02977 (5)	0.30019 (13)	0.0353 (4)
O1	0.7919 (2)	0.01860 (11)	0.2690 (3)	0.0339 (9)
O2	0.8953 (2)	0.10728 (12)	0.1756 (3)	0.0322 (9)
O3	0.7269 (2)	0.12720 (13)	0.0200 (3)	0.0371 (9)
O4	0.7473 (2)	0.15830 (12)	0.2613 (4)	0.0377 (9)
O5	0.7751 (2)	0.10306 (12)	0.3780 (3)	0.0369 (9)
O6	0.6976 (2)	0.02732 (13)	0.0357 (4)	0.0381 (9)
O7	0.8304 (2)	0.04127 (13)	0.0125 (3)	0.0372 (9)
O8	0.7633 (3)	0.00110 (17)	−0.1173 (4)	0.0650 (14)
O9	0.7713 (4)	0.17139 (17)	0.4459 (4)	0.0830 (19)
O10	0.6240 (2)	0.08090 (12)	0.2196 (3)	0.0338 (9)
N1	0.9766 (3)	0.17387 (18)	0.0847 (5)	0.0561 (15)
N2	1.0543 (3)	0.09826 (18)	0.1512 (4)	0.0399 (12)
N3	0.9927 (3)	0.1554 (2)	0.3074 (5)	0.0628 (18)
N4	0.7792 (3)	−0.03569 (17)	0.4397 (4)	0.0460 (13)
N5	0.7355 (4)	−0.06513 (17)	0.2348 (5)	0.0560 (15)
N6	0.8944 (4)	−0.0475 (2)	0.2622 (5)	0.0624 (17)
N7	0.6078 (5)	0.1388 (2)	−0.1297 (7)	0.091 (3)
N8	0.7640 (5)	0.1249 (2)	−0.1959 (5)	0.081 (2)
N9	0.7263 (5)	0.20028 (18)	−0.0935 (5)	0.0643 (18)
N10	0.4665 (3)	0.0697 (2)	0.1992 (5)	0.0626 (18)
N11	0.5156 (4)	0.14856 (19)	0.2598 (6)	0.0631 (17)
N12	0.5426 (4)	0.0871 (2)	0.4099 (5)	0.0603 (16)
N13	0.7646 (3)	0.14517 (17)	0.3638 (5)	0.0454 (13)
N14	0.7637 (3)	0.02239 (16)	−0.0259 (4)	0.0376 (12)
C1	0.9801 (5)	0.1285 (4)	0.4099 (7)	0.101 (4)
H1A	0.9527	0.1004	0.3880	0.151*
H1B	0.9446	0.1449	0.4640	0.151*
H1C	1.0344	0.1222	0.4470	0.151*
C2	1.0456 (4)	0.0655 (2)	0.0564 (6)	0.0548 (18)
H2A	0.9861	0.0614	0.0370	0.082*
H2B	1.0698	0.0369	0.0810	0.082*
H2C	1.0752	0.0765	−0.0118	0.082*
C3	1.0453 (5)	0.1839 (3)	0.0046 (7)	0.072 (2)
H3A	1.0869	0.1598	0.0082	0.107*
H3B	1.0719	0.2121	0.0270	0.107*
H3C	1.0227	0.1863	−0.0745	0.107*
C4	1.1419 (4)	0.1073 (3)	0.1885 (7)	0.065 (2)
H4A	1.1422	0.1294	0.2512	0.098*
H4B	1.1734	0.1190	0.1229	0.098*
H4C	1.1680	0.0796	0.2161	0.098*
C5	1.0340 (6)	0.1992 (4)	0.3275 (10)	0.122 (4)
H5A	1.0400	0.2148	0.2535	0.183*
H5B	1.0895	0.1945	0.3629	0.183*
H5C	0.9997	0.2173	0.3795	0.183*
C6	0.7278 (10)	0.1079 (5)	−0.3074 (8)	0.170 (7)
H6A	0.6667	0.1112	−0.3069	0.255*
H6B	0.7422	0.0763	−0.3163	0.255*
H6C	0.7507	0.1249	−0.3720	0.255*
C7	0.9100 (5)	0.2080 (3)	0.0883 (9)	0.082 (3)
H7A	0.8670	0.1988	0.1432	0.123*
H7B	0.8846	0.2114	0.0111	0.123*
H7C	0.9342	0.2366	0.1132	0.123*
C8	0.3773 (5)	0.0796 (4)	0.2200 (10)	0.144 (6)
H8A	0.3728	0.1080	0.2618	0.216*
H8B	0.3529	0.0557	0.2664	0.216*
H8C	0.3471	0.0818	0.1457	0.216*
C9	0.6478 (6)	−0.0669 (4)	0.2665 (10)	0.104 (3)
H9A	0.6414	−0.0552	0.3452	0.155*
H9B	0.6282	−0.0979	0.2636	0.155*
H9C	0.6145	−0.0488	0.2122	0.155*
C10	0.7551 (8)	0.2262 (3)	−0.1959 (8)	0.112 (4)
H10A	0.7741	0.2055	−0.2558	0.168*
H10B	0.8015	0.2458	−0.1725	0.168*
H10C	0.7086	0.2442	−0.2265	0.168*
C11	0.4713 (6)	0.0980 (5)	0.4814 (8)	0.131 (5)
H11A	0.4399	0.1227	0.4460	0.196*
H11B	0.4912	0.1068	0.5587	0.196*
H11C	0.4348	0.0719	0.4876	0.196*
C12	0.5528 (8)	0.1728 (4)	−0.1864 (12)	0.160 (6)
H12A	0.5838	0.2009	−0.1940	0.239*
H12B	0.5032	0.1778	−0.1391	0.239*
H12C	0.5354	0.1622	−0.2634	0.239*
C13	0.4851 (8)	0.1680 (4)	0.1525 (10)	0.140 (5)
H13A	0.4653	0.1443	0.1005	0.210*
H13B	0.5305	0.1845	0.1156	0.210*
H13C	0.4387	0.1885	0.1688	0.210*
C14	0.8032 (5)	−0.0008 (3)	0.5217 (6)	0.068 (2)
H14A	0.8055	0.0279	0.4814	0.102*
H14B	0.8584	−0.0077	0.5554	0.102*
H14C	0.7617	0.0008	0.5833	0.102*
C15	0.7738 (5)	−0.0808 (2)	0.4921 (6)	0.066 (2)
H15A	0.7577	−0.1025	0.4322	0.099*
H15B	0.7317	−0.0807	0.5530	0.099*
H15C	0.8284	−0.0891	0.5255	0.099*
C16	0.6951 (6)	0.2277 (2)	0.0057 (6)	0.069 (2)
H16A	0.6776	0.2079	0.0684	0.103*
H16B	0.6472	0.2458	−0.0204	0.103*
H16C	0.7400	0.2474	0.0339	0.103*
C17	0.8541 (7)	0.1225 (3)	−0.1835 (8)	0.100 (3)
H17A	0.8712	0.1346	−0.1079	0.151*
H17B	0.8802	0.1400	−0.2450	0.151*
H17C	0.8720	0.0913	−0.1891	0.151*
C18	0.5672 (6)	0.0961 (3)	−0.1161 (10)	0.107 (4)
H18A	0.6065	0.0751	−0.0796	0.160*
H18B	0.5497	0.0847	−0.1922	0.160*
H18C	0.5179	0.0996	−0.0672	0.160*
C19	0.5932 (5)	0.0498 (3)	0.4575 (7)	0.074 (2)
H19A	0.6407	0.0440	0.4067	0.111*
H19B	0.5583	0.0229	0.4623	0.111*
H19C	0.6141	0.0577	0.5350	0.111*
C20	0.5465 (6)	0.1826 (3)	0.3437 (12)	0.140 (6)
H20A	0.5670	0.1678	0.4142	0.210*
H20B	0.5007	0.2029	0.3631	0.210*
H20C	0.5923	0.1996	0.3091	0.210*
C21	0.4794 (5)	0.0279 (3)	0.1376 (8)	0.079 (3)
H21A	0.5396	0.0231	0.1266	0.118*
H21B	0.4509	0.0292	0.0619	0.118*
H21C	0.4564	0.0032	0.1827	0.118*
C22	0.7468 (7)	−0.0825 (3)	0.1202 (8)	0.105 (4)
H22A	0.8064	−0.0812	0.1007	0.158*
H22B	0.7143	−0.0646	0.0645	0.158*
H22C	0.7275	−0.1135	0.1171	0.158*
C23	0.9172 (7)	−0.0953 (3)	0.2798 (9)	0.113 (4)
H23A	0.8661	−0.1130	0.2890	0.169*
H23B	0.9526	−0.0982	0.3495	0.169*
H23C	0.9480	−0.1061	0.2125	0.169*
C24	0.9634 (5)	−0.0158 (3)	0.2480 (8)	0.076 (2)
H24A	0.9407	0.0143	0.2373	0.114*
H24B	0.9960	−0.0241	0.1800	0.114*
H24C	0.9998	−0.0164	0.3171	0.114*
W1	0.283016 (14)	0.227680 (7)	0.528018 (18)	0.02567 (7)
Ag1	0.28194 (4)	0.264566 (17)	0.28785 (4)	0.04883 (14)
S1	0.28226 (11)	0.30025 (5)	0.48562 (13)	0.0427 (4)
S2	0.28502 (11)	0.18418 (5)	0.37165 (12)	0.0391 (4)
S3	0.16900 (10)	0.21196 (6)	0.62861 (13)	0.0434 (4)
S4	0.39682 (10)	0.21320 (6)	0.63391 (13)	0.0458 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Y1	0.0208 (3)	0.0182 (2)	0.0293 (3)	0.0000 (2)	0.0008 (2)	0.0008 (2)
P1	0.0625 (11)	0.0335 (8)	0.0348 (9)	0.0083 (8)	−0.0171 (8)	0.0021 (7)
P2	0.0214 (7)	0.0355 (8)	0.0458 (9)	0.0016 (6)	0.0059 (6)	−0.0069 (7)
P3	0.0229 (7)	0.0428 (9)	0.0358 (8)	−0.0074 (6)	−0.0004 (6)	−0.0078 (7)
P4	0.0449 (9)	0.0235 (7)	0.0378 (8)	0.0080 (7)	0.0110 (7)	0.0088 (6)
O1	0.040 (2)	0.0202 (18)	0.042 (2)	0.0036 (17)	−0.0010 (17)	0.0057 (17)
O2	0.0229 (19)	0.035 (2)	0.039 (2)	−0.0053 (16)	−0.0012 (16)	−0.0013 (17)
O3	0.040 (2)	0.034 (2)	0.036 (2)	−0.0008 (18)	−0.0110 (18)	0.0082 (18)
O4	0.045 (2)	0.026 (2)	0.042 (2)	0.0064 (18)	−0.0023 (19)	−0.0024 (18)
O5	0.048 (2)	0.028 (2)	0.035 (2)	0.0040 (18)	0.0047 (18)	−0.0005 (17)
O6	0.031 (2)	0.033 (2)	0.050 (3)	−0.0012 (17)	−0.0020 (19)	−0.0081 (19)
O7	0.030 (2)	0.037 (2)	0.044 (2)	−0.0006 (18)	0.0008 (18)	−0.0082 (19)
O8	0.067 (3)	0.071 (3)	0.056 (3)	0.005 (3)	−0.004 (2)	−0.041 (3)
O9	0.149 (6)	0.050 (3)	0.049 (3)	0.020 (3)	−0.019 (3)	−0.028 (3)
O10	0.0194 (19)	0.033 (2)	0.049 (2)	0.0011 (16)	0.0035 (16)	−0.0067 (18)
N1	0.045 (3)	0.044 (3)	0.080 (4)	−0.012 (3)	0.013 (3)	0.011 (3)
N2	0.025 (3)	0.058 (3)	0.037 (3)	−0.001 (2)	−0.001 (2)	−0.011 (2)
N3	0.041 (3)	0.097 (5)	0.050 (4)	0.002 (3)	−0.010 (3)	−0.034 (3)
N4	0.062 (4)	0.038 (3)	0.039 (3)	0.007 (3)	0.009 (3)	0.012 (2)
N5	0.082 (4)	0.030 (3)	0.057 (4)	−0.011 (3)	0.018 (3)	−0.005 (3)
N6	0.058 (4)	0.055 (4)	0.075 (4)	0.026 (3)	0.025 (3)	0.029 (3)
N7	0.094 (6)	0.061 (4)	0.115 (6)	0.010 (4)	−0.068 (5)	0.018 (4)
N8	0.127 (7)	0.068 (4)	0.048 (4)	0.033 (4)	0.000 (4)	−0.007 (3)
N9	0.119 (6)	0.037 (3)	0.038 (3)	0.006 (3)	0.002 (3)	0.012 (3)
N10	0.027 (3)	0.081 (4)	0.080 (4)	−0.004 (3)	0.006 (3)	−0.045 (4)
N11	0.048 (4)	0.041 (3)	0.100 (5)	0.012 (3)	0.013 (3)	−0.003 (3)
N12	0.046 (3)	0.087 (5)	0.048 (3)	0.014 (3)	0.011 (3)	−0.010 (3)
N13	0.055 (3)	0.038 (3)	0.043 (3)	0.006 (3)	0.001 (3)	−0.009 (3)
N14	0.040 (3)	0.031 (3)	0.042 (3)	0.006 (2)	−0.002 (2)	−0.006 (2)
C1	0.066 (6)	0.195 (12)	0.040 (5)	0.022 (6)	−0.013 (4)	−0.003 (6)
C2	0.038 (4)	0.071 (5)	0.056 (4)	0.000 (3)	0.012 (3)	−0.019 (4)
C3	0.070 (5)	0.066 (5)	0.080 (6)	−0.022 (4)	0.020 (4)	0.006 (4)
C4	0.024 (3)	0.104 (6)	0.067 (5)	0.006 (4)	−0.007 (3)	−0.016 (4)
C5	0.091 (7)	0.118 (9)	0.157 (11)	−0.026 (6)	−0.025 (7)	−0.093 (8)
C6	0.31 (2)	0.169 (13)	0.037 (5)	−0.011 (13)	0.000 (8)	−0.049 (7)
C7	0.073 (6)	0.051 (5)	0.124 (8)	0.008 (4)	0.019 (5)	0.024 (5)
C8	0.028 (4)	0.221 (13)	0.183 (11)	−0.013 (6)	0.015 (5)	−0.156 (11)
C9	0.069 (6)	0.115 (8)	0.127 (9)	−0.025 (6)	−0.005 (6)	−0.027 (7)
C10	0.213 (13)	0.063 (6)	0.060 (6)	0.018 (7)	0.027 (7)	0.033 (5)
C11	0.095 (8)	0.240 (15)	0.059 (6)	0.075 (9)	0.027 (5)	−0.009 (7)
C12	0.164 (12)	0.129 (10)	0.182 (13)	0.066 (9)	−0.107 (10)	0.007 (9)
C13	0.195 (13)	0.109 (9)	0.119 (9)	0.094 (9)	0.057 (9)	0.044 (7)
C14	0.096 (6)	0.068 (5)	0.041 (4)	0.006 (5)	−0.005 (4)	0.002 (4)
C15	0.094 (6)	0.051 (4)	0.054 (4)	0.013 (4)	0.027 (4)	0.029 (4)
C16	0.121 (7)	0.033 (4)	0.053 (5)	0.010 (4)	0.003 (4)	−0.001 (3)
C17	0.112 (8)	0.107 (8)	0.085 (7)	0.043 (7)	0.043 (6)	0.011 (6)
C18	0.082 (7)	0.081 (7)	0.155 (10)	−0.008 (5)	−0.074 (7)	−0.001 (7)
C19	0.061 (5)	0.097 (7)	0.063 (5)	0.002 (5)	0.000 (4)	0.017 (5)
C20	0.069 (6)	0.070 (6)	0.281 (17)	−0.003 (5)	0.012 (8)	−0.098 (9)
C21	0.041 (4)	0.069 (5)	0.127 (8)	−0.010 (4)	0.016 (4)	−0.053 (5)
C22	0.135 (9)	0.086 (7)	0.095 (7)	−0.047 (6)	0.032 (6)	−0.040 (6)
C23	0.143 (9)	0.083 (7)	0.115 (8)	0.081 (7)	0.070 (7)	0.049 (6)
C24	0.039 (4)	0.079 (6)	0.110 (7)	0.004 (4)	−0.006 (4)	−0.014 (5)
W1	0.03217 (13)	0.02568 (12)	0.01909 (11)	0.00287 (9)	−0.00250 (8)	−0.00114 (9)
Ag1	0.0780 (4)	0.0470 (3)	0.0214 (2)	0.0006 (3)	−0.0012 (2)	0.0028 (2)
S1	0.0713 (11)	0.0254 (7)	0.0312 (8)	0.0047 (7)	0.0005 (7)	−0.0022 (6)
S2	0.0597 (10)	0.0293 (7)	0.0283 (7)	−0.0007 (7)	−0.0002 (7)	−0.0057 (6)
S3	0.0385 (9)	0.0605 (10)	0.0314 (8)	−0.0081 (8)	0.0016 (6)	−0.0014 (7)
S4	0.0395 (9)	0.0649 (11)	0.0328 (8)	0.0174 (8)	−0.0084 (7)	−0.0053 (8)

Geometric parameters (Å, º)

Y1—O3	2.233 (4)	N2—C2	1.460 (8)
Y1—O2	2.238 (3)	N2—C4	1.466 (7)
Y1—O10	2.243 (3)	N3—C1	1.432 (11)
Y1—O1	2.259 (3)	N3—C5	1.472 (10)
Y1—O5	2.441 (4)	N4—C14	1.443 (9)
Y1—O7	2.466 (4)	N4—C15	1.470 (8)
Y1—O6	2.468 (4)	N5—C22	1.421 (10)
Y1—O4	2.471 (4)	N5—C9	1.438 (10)
P1—O3	1.483 (4)	N6—C24	1.449 (9)
P1—N9	1.600 (6)	N6—C23	1.477 (9)
P1—N8	1.610 (7)	N7—C18	1.428 (11)
P1—N7	1.627 (7)	N7—C12	1.476 (10)
P2—O10	1.495 (4)	N8—C17	1.429 (11)
P2—N10	1.605 (5)	N8—C6	1.479 (11)
P2—N11	1.619 (6)	N9—C10	1.477 (9)
P2—N12	1.642 (6)	N9—C16	1.486 (9)
P3—O2	1.497 (4)	N10—C21	1.442 (8)
P3—N3	1.622 (5)	N10—C8	1.462 (9)
P3—N1	1.628 (6)	N11—C13	1.432 (12)
P3—N2	1.631 (5)	N11—C20	1.472 (11)
P4—O1	1.485 (4)	N12—C11	1.436 (9)
P4—N6	1.628 (6)	N12—C19	1.466 (9)
P4—N4	1.646 (5)	W1—S4	2.1943 (16)
P4—N5	1.647 (6)	W1—S3	2.2000 (16)
O4—N13	1.260 (6)	W1—S2	2.2050 (14)
O5—N13	1.270 (6)	W1—S1	2.2063 (15)
O6—N14	1.275 (6)	W1—Ag1	2.9549 (7)
O7—N14	1.266 (6)	W1—Ag1^i	2.9791 (7)
O8—N14	1.221 (6)	Ag1—S1	2.4960 (16)
O9—N13	1.222 (6)	Ag1—S2	2.5698 (16)
N1—C3	1.460 (8)	Ag1—S3^ii	2.6236 (17)
N1—C7	1.462 (9)	Ag1—S4^ii	2.6293 (18)
O3—Y1—O2	92.57 (14)	N13—O5—Y1	96.2 (3)
O3—Y1—O10	88.97 (14)	N14—O6—Y1	95.5 (3)
O2—Y1—O10	157.01 (13)	N14—O7—Y1	95.8 (3)
O3—Y1—O1	157.99 (14)	P2—O10—Y1	159.5 (2)
O2—Y1—O1	93.76 (14)	C3—N1—C7	114.7 (6)
O10—Y1—O1	93.32 (14)	C3—N1—P3	125.0 (5)
O3—Y1—O5	128.53 (13)	C7—N1—P3	119.7 (5)
O2—Y1—O5	80.13 (14)	C2—N2—C4	114.6 (5)
O10—Y1—O5	81.00 (14)	C2—N2—P3	120.2 (4)
O1—Y1—O5	73.37 (13)	C4—N2—P3	122.1 (5)
O3—Y1—O7	80.11 (14)	C1—N3—C5	115.4 (7)
O2—Y1—O7	75.36 (13)	C1—N3—P3	119.2 (6)
O10—Y1—O7	127.40 (13)	C5—N3—P3	124.5 (7)
O1—Y1—O7	81.14 (13)	C14—N4—C15	113.9 (6)
O5—Y1—O7	143.13 (13)	C14—N4—P4	119.7 (5)
O3—Y1—O6	79.26 (14)	C15—N4—P4	120.4 (4)
O2—Y1—O6	127.21 (13)	C22—N5—C9	110.7 (7)
O10—Y1—O6	75.60 (13)	C22—N5—P4	124.2 (5)
O1—Y1—O6	80.13 (13)	C9—N5—P4	120.8 (5)
O5—Y1—O6	143.31 (13)	C24—N6—C23	117.1 (7)
O7—Y1—O6	51.85 (13)	C24—N6—P4	120.3 (5)
O3—Y1—O4	76.59 (14)	C23—N6—P4	119.5 (5)
O2—Y1—O4	77.82 (13)	C18—N7—C12	113.1 (8)
O10—Y1—O4	80.25 (13)	C18—N7—P1	123.0 (5)
O1—Y1—O4	125.37 (13)	C12—N7—P1	123.7 (7)
O5—Y1—O4	52.00 (12)	C17—N8—C6	116.1 (9)
O7—Y1—O4	143.34 (13)	C17—N8—P1	121.1 (6)
O6—Y1—O4	145.91 (13)	C6—N8—P1	122.7 (8)
O3—Y1—N13	102.53 (15)	C10—N9—C16	115.4 (6)
O2—Y1—N13	76.64 (15)	C10—N9—P1	123.9 (5)
O10—Y1—N13	80.63 (15)	C16—N9—P1	119.0 (5)
O1—Y1—N13	99.44 (15)	C21—N10—C8	113.3 (6)
O5—Y1—N13	26.10 (13)	C21—N10—P2	123.1 (5)
O7—Y1—N13	151.97 (14)	C8—N10—P2	121.6 (5)
O6—Y1—N13	156.14 (14)	C13—N11—C20	112.7 (8)
O4—Y1—N13	25.94 (13)	C13—N11—P2	121.3 (6)
O3—Y1—N14	76.44 (14)	C20—N11—P2	123.1 (7)
O2—Y1—N14	101.15 (14)	C11—N12—C19	112.7 (7)
O10—Y1—N14	101.51 (14)	C11—N12—P2	121.7 (6)
O1—Y1—N14	81.66 (14)	C19—N12—P2	119.0 (5)
O5—Y1—N14	155.02 (13)	O9—N13—O4	122.1 (5)
O7—Y1—N14	25.90 (12)	O9—N13—O5	121.2 (5)
O6—Y1—N14	26.11 (13)	O4—N13—O5	116.7 (5)
O4—Y1—N14	152.93 (13)	O8—N14—O7	121.3 (5)
N13—Y1—N14	177.56 (15)	O8—N14—O6	122.5 (5)
O3—P1—N9	110.0 (3)	O7—N14—O6	116.2 (4)
O3—P1—N8	110.8 (3)	S4—W1—S3	109.87 (6)
N9—P1—N8	108.0 (4)	S4—W1—S2	108.14 (6)
O3—P1—N7	109.9 (3)	S3—W1—S2	108.73 (6)
N9—P1—N7	109.9 (4)	S4—W1—S1	108.29 (7)
N8—P1—N7	108.3 (4)	S3—W1—S1	108.65 (7)
O10—P2—N10	108.4 (2)	S2—W1—S1	113.14 (6)
O10—P2—N11	118.8 (3)	Ag1—W1—Ag1^i	153.833 (10)
N10—P2—N11	105.0 (3)	S1—Ag1—S2	93.22 (5)
O10—P2—N12	108.6 (3)	S1—Ag1—S3^ii	120.54 (6)
N10—P2—N12	114.1 (3)	S2—Ag1—S3^ii	120.92 (6)
N11—P2—N12	102.1 (3)	S1—Ag1—S4^ii	120.49 (6)
O2—P3—N3	110.9 (3)	S2—Ag1—S4^ii	118.21 (6)
O2—P3—N1	111.3 (3)	S3^ii—Ag1—S4^ii	86.43 (5)
N3—P3—N1	107.0 (3)	S1—Ag1—W1	46.82 (4)
O2—P3—N2	108.7 (2)	S2—Ag1—W1	46.40 (3)
N3—P3—N2	109.4 (3)	S3^ii—Ag1—W1	137.51 (4)
N1—P3—N2	109.5 (3)	S4^ii—Ag1—W1	136.04 (4)
O1—P4—N6	109.5 (3)	S1—Ag1—W1^ii	150.48 (4)
O1—P4—N4	108.3 (2)	S2—Ag1—W1^ii	116.29 (4)
N6—P4—N4	115.4 (3)	S3^ii—Ag1—W1^ii	45.70 (4)
O1—P4—N5	116.6 (3)	S4^ii—Ag1—W1^ii	45.54 (4)
N6—P4—N5	103.8 (3)	W1—Ag1—W1^ii	162.684 (19)
N4—P4—N5	103.4 (3)	W1—S1—Ag1	77.59 (5)
P4—O1—Y1	162.6 (2)	W1—S2—Ag1	76.04 (5)
P3—O2—Y1	168.3 (2)	W1—S3—Ag1^i	75.71 (5)
P1—O3—Y1	167.3 (3)	W1—S4—Ag1^i	75.68 (5)
N13—O4—Y1	95.0 (3)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2.