Crystal structure of cyclo-bis-(μ4-2,2-di-allyl-malonato-κ(6) O (1),O (3):O (3):O (1'),O (3'):O (1'))tetra-kis-(triphenyl-phosphane-κP)tetra-silver(I).

In the tetra-nuclear mol-ecule of the title compound, [Ag4(C9H10O4)2(C18H15P)4], the Ag(I) ion is coordinated by one P and three O atoms in a considerably distorted tetra-hedral environment. The two 2,2-di-allyl-malonate anions bridge four Ag(I) ions in a μ4-(κ(6) O (1),O (3):O (3):O (1'),O (3'):O (1')) mode, setting up an Ag4O8P4 core (point group symmetry -4..) of corner-sharing tetra-hedra. The shortest intra-molecular Ag⋯Ag distance of 3.9510 (3) Å reveals that no direct d (10)⋯d (10) inter-actions are present. Four weak intra-molecular C-H⋯O hydrogen bonds are observed in the crystal structure of the title compound, which most likely stabilize the tetra-nuclear silver core.

Chemical context

Silver(I) carboxyl­ates of general type [AgO2CR] (n is the degree of aggregation) are of inter­est due to their versatile structures in the solid state and in solution, their synthetic methodologies and their manifold reaction behavior (see, for example: Schliebe et al., 2013 ▶; Jahn et al., 2010 ▶; Wang et al., 2008 ▶; Fernández et al., 2007 ▶; Olson et al., 2006 ▶; Szymańska et al., 2007 ▶). These metal-organic complexes are of importance not only in the field of basic research but also in multipurpose applications including, for example, metallization processes for micro- and nano-structured new materials in electronic systems and devices (e.g. using chemical vapour deposition, CVD), since silver possesses the highest electrical conductivity of any element (Jakob et al., 2010 ▶; Lang & Dietrich, 2013 ▶), catalytic processes (Steffan et al., 2009 ▶) and their use in biological studies (Djokić, 2008 ▶; Zhu et al., 2003 ▶).

The CVD process requires metal precursors possessing high vapour pressures. On a mol­ecular level this is typically achieved by designing low aggregated metal compounds. In the case of silver, this can be realized by the use of phosphanes as a Lewis base; however, the concomitant increase of the mol­ecular weight of the transition metal complex may decrease its vapour pressure. Circumventing this difficulty, we have investigated the use of olefines as ligands for silver(I) carboxyl­ates, in which the olefin is covalently bonded to the carboxyl­ate. In the context of this approach, the title compound [{(Ph3P)Ag}4{(O2C)2C(CH2CH=CH2)2}2], (I), was obtained by the reaction of the silver salt of 2,2-di­allyl­malonic acid with tri­phenyl­phosphane.

Structural commentary

The asymmetric unit of (I) contains one quarter of the mol­ecule which is completed by application of a fourfold screw axis as the symmetry element. The resulting tetra­nuclear silver core is decorated by four tri­phenyl­phosphane ligands, whereby the metal ions are bridged by two 2,2-di­allyl­malonate anions in a μ4-(κ6 O 1,O 3:O 3:O 1′,O 3′:O 1′) mode (Fig. 1 ▶). There is no example in the literature of a transition metal malonate displaying this type of coordination. The environment around silver, set up by one phospho­rus and three oxygen atoms, is best described as distorted tetra­hedral. Ag1 is oriented slightly above the plane of O1, P1 and O2ii [distance 0.2911 (10) Å], which is supported by the respective bond angles around Ag1 (Table 1 ▶) summing up to 354.3°. The O—Ag1—P1 angles are substanti­ally larger than the O—Ag1—O angles, which may be attributed to the chelating coordination of the malonate ligands and the bulkiness of the tri­phenyl­phosphane ligand. The Ag—O bond lengths are more than 0.2 Å shorter for the two oxygen atoms of the aforementioned plane than for the third apical oxygen atom (Table 1 ▶). However, the values are in the expected range for Ag—O bonds in silver carboxyl­ates.

Figure 1

The Ag4O8P4 core of the title compound with surrounding atoms. Displacement ellipsoids are displayed at the 50% probability level. The carbon atoms of the phenyl substituents except the ipso-carbon atoms and all hydrogen atoms have been omitted for clarity. [Symmetry codes: (A) –x + 1, –y + 1, z; (B) y, –x + 1, –z + 2; (C) –y + 1, x, –z + 2.]

Table 1

Selected bond lengths (Å) and bond angles (°)

Ag1—O1	2.323 (2)	O1—Ag1—O2i	82.45 (7)
Ag1—P1	2.3483 (8)	O1—Ag1—O2ii	90.28 (8)
Ag1—O2i	2.592 (2)	P1—Ag1—O2i	112.26 (5)
Ag1—O2ii	2.344 (2)	P1—Ag1—O2ii	115.95 (6)
O1—Ag1—P1	148.09 (6)	O2i—Ag1—O2ii	92.63 (10)

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

The cyclic corner-sharing arrangement of the described O3P tetra­hedra gives the tetra­nuclear structure of (I) (Fig. 2 ▶). The four silver ions are oriented in a butterfly-like arrangement, which delimits the title compound from Ag4O4 heterocubanes (Jakob et al., 2011 ▶; Zhang et al., 2008 ▶, Kühnert et al., 2007 ▶) in which the four silver ions form a tetra­hedron. In contrast, there are some similarities with [bis­(1,8-naphthalenedi­carboxyl­ato)][tetra­kis­(tri­phenyl­phosphane)silver(I)] (van der Ploeg et al., 1979 ▶); however, in the structure of this compound one silver ion is penta­coordinated.

Figure 2

Structure fragment showing the cyclic corner-sharing arrangement of the AgO3P polyhedra giving the tetra­nuclear silver core of composition Ag4O8P4.

Supra­molecular features

Four weak intra­molecular C—H⋯O hydrogen bonds (Steiner, 2002 ▶) are observed in the crystal structure of (I) (Table 2 ▶), which most likely stabilize the silver core.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O2i	0.93	2.51	3.351 (4)	150

Symmetry code: (i) .

In contrast to iridium and platinum complexes of 2,2-diallylmalonic acid and derivatives thereof, the C=C double bond does not coordinate the transition metal in (I). Furthermore, no obvious π–π stacking inter­actions are observed between the allyl and the phenyl substituents. Therefore, the packing seems to be dominated by dispersion forces (Fig. 3 ▶).

Figure 3

Packing diagram of the title compound along the c axis; voids in the structure are represented by red spheres [drawn using the CAVITYPLOT routine in PLATON (Spek, 2009 ▶)]. The hydrogen atoms have been omitted for clarity. Colour code: black (C), red (O), yellow (P), green (Ag).

Database survey

2,2-Di­allyl­malonic acid and derivatives thereof have only been used as ligands in four mononuclear platinum and one iridium complex, in which coordination of the transition metal occurs either through (O,O′)-, (O,alkene)- or (alkene,alkene′)-chelation (Berthon-Gelloz et al., 2007 ▶; Makino et al., 2004 ▶; Jung et al., 1999 ▶; Lee et al., 1999 ▶). To the best of our knowledge, no di­allyl­malonate silver(I) compounds have been described in the literature so far.

Synthesis and crystallization

Complex [{(Ph3P)Ag}4{(O2C)2C(CH2CH=CH2)2}2] was prepared by the addition of PPh3 (132 mg, 0.503 mmol) to a suspension of [(AgO2C)2C(CH2CH=CH2)2] (100 mg, 0.251 mmol) in di­chloro­methane (30 ml) at 273 K. After stirring for 2 h at this temperature, the reaction mixture was filtered through a pad of celite. Afterwards, all volatiles were removed in oil-pump vacuum, and (I) was obtained as a pale-grey solid. Colourless crystals of (I) were obtained by solvent diffusion of a chloro­form solution of (I) against pentane at ambient temperature. Yield: 230 mg (0.125 mmol, 99% based on [(AgO2C)2C(CH2CH=CH2)2]).

Analysis calculated for C90H80Ag4O8P4 (1844.96): C 58.59, H 4.37. Found: C 58.53, H 4.34. 1H NMR (500 MHz, CDCl3, 298 K, ppm): δ = 2.79 (d, 8H, 3 J HH = 6.5 Hz, CH 2CH=CH2), 4.97 (d, 4H, 3 J HH = 10.2 Hz, CH2CH=CH 2), 5.03 (d, 4H, 3 J HH = 17.1 Hz, CH2CH=CH 2), 5.90 (m, 4H, CH2CH=CH2), 7.30–7.51 (m, 60H, C6H5). 31P{1H} NMR (203 MHz, CDCl3, 298 K, ppm): δ = 15.7 (d, 1 J AgP = 680 Hz). IR (KBr, cm−1): ν = 1637 (w, C=C), 1559 (vs, C=O), 1440 (vs, P—Ph), 692 (vs), 521 (vs).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▶. C-bonded H atoms were placed in calculated positions and constrained to ride on their parent atoms, with U iso(H) = 1.2U eq(C) and a C—H distance of 0.93 Å for aromatic and vinylic as well as 0.97 Å for methyl­ene protons. The unit cell contains two voids of 34(1.4) Å3. Void volume calculation using the SQUEEZE routine in PLATON (Spek, 2009 ▶) gives a total electron count in the voids per cell of 3 e− Å−3 suggesting that no solvent mol­ecules occupy these voids. The Flack parameter is −0.051 (9); however, this ambiguity is resolved as the Flack parameter of the inverted structure is calculated to 1.052 (9). This indicates that the original absolute structure has been assigned correctly.

Table 3

Experimental details

Crystal data
Chemical formula	[Ag4(C9H10O4)2(C18H15P)4]
M r	1844.90
Crystal system, space group	Tetragonal, I
Temperature (K)	105
a, c (Å)	16.0462 (1), 15.3337 (2)
V (Å3)	3948.13 (7)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.12
Crystal size (mm)	0.2 × 0.1 × 0.1
Data collection
Diffractometer	Oxford Gemini S
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶)
T min, T max	0.903, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	21141, 4571, 4425
R int	0.034
(sin θ/λ)max (Å−1)	0.671
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.022, 0.048, 1.04
No. of reflections	4571
No. of parameters	240
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.40, −0.52
Absolute structure	Flack x determined using 1620 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons & Flack, 2004 ▶)
Absolute structure parameter	−0.051 (9)

Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2006 ▶), SHELXS2013, SHELXL2013 and SHELXTL (Sheldrick, 2008 ▶), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ▶), DIAMOND (Brandenburg, 1996 ▶), publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814019394/wm5047sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019394/wm5047Isup2.hkl

CCDC reference: 1021407

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ag4(C9H10O4)2(C18H15P)4]	Dx = 1.552 Mg m−3
Mr = 1844.90	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 14970 reflections
a = 16.0462 (1) Å	θ = 3.2–28.4°
c = 15.3337 (2) Å	µ = 1.12 mm−1
V = 3948.13 (7) Å3	T = 105 K
Z = 2	Block, colourless
F(000) = 1864	0.2 × 0.1 × 0.1 mm

Oxford Gemini S diffractometer	Rint = 0.034
ω scans	θmax = 28.5°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	h = −19→20
Tmin = 0.903, Tmax = 1.000	k = −21→21
21141 measured reflections	l = −19→20
4571 independent reflections	2 standard reflections every 50 reflections
4425 reflections with I > 2σ(I)	intensity decay: none

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.022	w = 1/[σ2(Fo2) + (0.0226P)2 + 1.5165P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.048	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.40 e Å−3
4571 reflections	Δρmin = −0.52 e Å−3
240 parameters	Absolute structure: Flack x determined using 1620 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
0 restraints	Absolute structure parameter: −0.051 (9)

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.

	x	y	z	Uiso*/Ueq
C1	0.42916 (19)	0.52013 (18)	1.13083 (19)	0.0162 (6)
C2	0.5000	0.5000	1.1958 (3)	0.0156 (8)
C3	0.4814 (2)	0.4235 (2)	1.2530 (2)	0.0205 (7)
H3A	0.4329	0.4350	1.2889	0.025*
H3B	0.4681	0.3765	1.2157	0.025*
C4	0.5527 (2)	0.4007 (2)	1.3107 (2)	0.0258 (7)
H4	0.6037	0.3908	1.2837	0.031*
C5	0.5502 (3)	0.3933 (3)	1.3962 (3)	0.0394 (9)
H5A	0.5005	0.4026	1.4259	0.047*
H5B	0.5980	0.3787	1.4269	0.047*
C6	0.3546 (2)	0.17708 (19)	0.9260 (2)	0.0189 (6)
C7	0.3733 (2)	0.2094 (2)	0.8438 (2)	0.0252 (7)
H7	0.4161	0.2480	0.8373	0.030*
C8	0.3276 (3)	0.1837 (2)	0.7717 (2)	0.0329 (9)
H8	0.3407	0.2047	0.7168	0.039*
C9	0.2631 (3)	0.1274 (2)	0.7803 (3)	0.0389 (10)
H9	0.2332	0.1102	0.7316	0.047*
C10	0.2434 (2)	0.0970 (2)	0.8615 (3)	0.0346 (9)
H10	0.1995	0.0597	0.8675	0.042*
C11	0.2883 (2)	0.1214 (2)	0.9348 (2)	0.0245 (7)
H11	0.2741	0.1007	0.9894	0.029*
C12	0.52112 (19)	0.17391 (19)	0.9931 (2)	0.0191 (6)
C13	0.58867 (19)	0.21305 (19)	1.0339 (2)	0.0230 (6)
H13	0.5799	0.2591	1.0696	0.028*
C14	0.6692 (2)	0.1829 (2)	1.0208 (2)	0.0295 (8)
H14	0.7140	0.2080	1.0489	0.035*
C15	0.6825 (2)	0.1156 (2)	0.9662 (3)	0.0292 (7)
H15	0.7361	0.0952	0.9580	0.035*
C16	0.6160 (2)	0.0786 (2)	0.9240 (2)	0.0267 (7)
H16	0.6252	0.0339	0.8866	0.032*
C17	0.5356 (2)	0.1078 (2)	0.9370 (2)	0.0223 (7)
H17	0.4913	0.0829	0.9079	0.027*
C18	0.38021 (19)	0.14737 (19)	1.1075 (2)	0.0184 (6)
C19	0.3973 (2)	0.0620 (2)	1.1117 (2)	0.0233 (7)
H19	0.4319	0.0376	1.0703	0.028*
C20	0.3628 (2)	0.0137 (2)	1.1771 (2)	0.0262 (7)
H20	0.3739	−0.0432	1.1794	0.031*
C21	0.3121 (2)	0.0500 (2)	1.2389 (2)	0.0258 (7)
H21	0.2889	0.0174	1.2828	0.031*
C22	0.2956 (2)	0.1343 (2)	1.2362 (2)	0.0264 (7)
H22	0.2616	0.1584	1.2784	0.032*
C23	0.3297 (2)	0.1832 (2)	1.1707 (2)	0.0207 (7)
H23	0.3187	0.2401	1.1690	0.025*
O1	0.36944 (13)	0.47026 (13)	1.12166 (14)	0.0186 (5)
O2	0.43925 (14)	0.58622 (14)	1.08654 (14)	0.0209 (5)
P1	0.41682 (5)	0.21258 (5)	1.01855 (5)	0.01656 (16)
Ag1	0.41599 (2)	0.35747 (2)	1.04012 (2)	0.01949 (7)

	U11	U22	U33	U12	U13	U23
C1	0.0177 (16)	0.0146 (15)	0.0163 (14)	0.0002 (11)	0.0004 (12)	−0.0030 (11)
C2	0.015 (2)	0.016 (2)	0.0154 (19)	−0.0020 (16)	0.000	0.000
C3	0.0228 (17)	0.0192 (16)	0.0195 (15)	−0.0003 (12)	0.0021 (12)	−0.0004 (12)
C4	0.0282 (19)	0.0209 (17)	0.0284 (18)	0.0034 (13)	−0.0007 (14)	0.0035 (14)
C5	0.050 (3)	0.036 (2)	0.032 (2)	0.0070 (18)	−0.0071 (18)	0.0058 (17)
C6	0.0192 (16)	0.0127 (15)	0.0250 (16)	0.0044 (12)	−0.0039 (12)	−0.0018 (12)
C7	0.0280 (19)	0.0247 (18)	0.0229 (17)	0.0059 (14)	−0.0026 (13)	−0.0032 (13)
C8	0.039 (2)	0.035 (2)	0.0250 (19)	0.0123 (17)	−0.0077 (15)	−0.0018 (16)
C9	0.044 (2)	0.030 (2)	0.042 (2)	0.0116 (17)	−0.0237 (18)	−0.0141 (17)
C10	0.030 (2)	0.0236 (19)	0.050 (2)	0.0006 (15)	−0.0192 (18)	0.0006 (16)
C11	0.0211 (16)	0.0192 (16)	0.0332 (19)	0.0003 (12)	−0.0092 (13)	0.0005 (13)
C12	0.0180 (16)	0.0188 (16)	0.0204 (15)	−0.0011 (12)	−0.0030 (12)	0.0062 (12)
C13	0.0220 (16)	0.0202 (15)	0.0270 (16)	−0.0026 (11)	−0.0015 (14)	0.0025 (14)
C14	0.0206 (17)	0.0303 (19)	0.038 (2)	−0.0044 (14)	−0.0021 (15)	0.0055 (15)
C15	0.0167 (15)	0.0308 (19)	0.040 (2)	0.0026 (12)	0.0062 (16)	0.0078 (17)
C16	0.0252 (18)	0.0231 (18)	0.0318 (18)	0.0028 (14)	0.0071 (14)	0.0032 (14)
C17	0.0214 (16)	0.0205 (16)	0.0250 (18)	−0.0005 (12)	−0.0008 (12)	0.0017 (12)
C18	0.0161 (16)	0.0179 (16)	0.0211 (16)	−0.0015 (11)	−0.0029 (12)	0.0004 (12)
C19	0.0237 (18)	0.0207 (17)	0.0256 (17)	0.0010 (13)	−0.0028 (13)	0.0011 (13)
C20	0.0294 (19)	0.0185 (17)	0.0306 (19)	−0.0010 (13)	−0.0052 (14)	0.0057 (14)
C21	0.0230 (18)	0.0268 (18)	0.0274 (18)	−0.0040 (14)	−0.0028 (14)	0.0097 (14)
C22	0.0217 (19)	0.0320 (19)	0.0255 (18)	0.0024 (14)	0.0021 (14)	0.0041 (14)
C23	0.0191 (17)	0.0198 (17)	0.0234 (17)	0.0030 (12)	−0.0014 (13)	0.0026 (13)
O1	0.0154 (11)	0.0168 (11)	0.0236 (12)	−0.0017 (8)	0.0018 (9)	−0.0032 (9)
O2	0.0212 (12)	0.0188 (11)	0.0225 (12)	−0.0024 (9)	−0.0047 (9)	0.0042 (9)
P1	0.0175 (4)	0.0137 (4)	0.0185 (4)	0.0000 (3)	−0.0015 (3)	0.0002 (3)
Ag1	0.02397 (13)	0.01337 (12)	0.02114 (11)	−0.00192 (9)	0.00038 (10)	0.00018 (9)

C1—O1	1.256 (3)	C13—C14	1.394 (5)
C1—O2	1.270 (4)	C13—H13	0.9300
C1—C2	1.545 (4)	C14—C15	1.383 (5)
C2—C3	1.539 (4)	C14—H14	0.9300
C2—C3i	1.539 (4)	C15—C16	1.382 (5)
C2—C1i	1.545 (4)	C15—H15	0.9300
C3—C4	1.492 (5)	C16—C17	1.386 (5)
C3—H3A	0.9700	C16—H16	0.9300
C3—H3B	0.9700	C17—H17	0.9300
C4—C5	1.318 (5)	C18—C23	1.387 (5)
C4—H4	0.9300	C18—C19	1.399 (4)
C5—H5A	0.9300	C18—P1	1.817 (3)
C5—H5B	0.9300	C19—C20	1.383 (5)
C6—C7	1.397 (5)	C19—H19	0.9300
C6—C11	1.397 (5)	C20—C21	1.378 (5)
C6—P1	1.825 (3)	C20—H20	0.9300
C7—C8	1.389 (5)	C21—C22	1.380 (5)
C7—H7	0.9300	C21—H21	0.9300
C8—C9	1.380 (6)	C22—C23	1.388 (5)
C8—H8	0.9300	C22—H22	0.9300
C9—C10	1.373 (6)	C23—H23	0.9300
C9—H9	0.9300	Ag1—O1	2.323 (2)
C10—C11	1.391 (5)	Ag1—P1	2.3483 (8)
C10—H10	0.9300	Ag1—O2i	2.592 (2)
C11—H11	0.9300	Ag1—O2ii	2.344 (2)
C12—C17	1.386 (5)	O2—Ag1iii	2.344 (2)
C12—C13	1.400 (4)	O2—Ag1i	2.592 (2)
C12—P1	1.827 (3)
O1—C1—O2	124.7 (3)	C15—C14—H14	120.0
O1—C1—C2	120.0 (2)	C13—C14—H14	120.0
O2—C1—C2	115.2 (2)	C16—C15—C14	120.0 (3)
C3—C2—C3i	110.4 (4)	C16—C15—H15	120.0
C3—C2—C1i	110.11 (16)	C14—C15—H15	120.0
C3i—C2—C1i	113.04 (17)	C15—C16—C17	120.3 (3)
C3—C2—C1	113.04 (17)	C15—C16—H16	119.8
C3i—C2—C1	110.10 (16)	C17—C16—H16	119.8
C1i—C2—C1	99.8 (3)	C12—C17—C16	120.3 (3)
C4—C3—C2	112.6 (3)	C12—C17—H17	119.9
C4—C3—H3A	109.1	C16—C17—H17	119.9
C2—C3—H3A	109.1	C23—C18—C19	119.2 (3)
C4—C3—H3B	109.1	C23—C18—P1	118.3 (2)
C2—C3—H3B	109.1	C19—C18—P1	122.4 (2)
H3A—C3—H3B	107.8	C20—C19—C18	120.3 (3)
C5—C4—C3	126.0 (4)	C20—C19—H19	119.9
C5—C4—H4	117.0	C18—C19—H19	119.9
C3—C4—H4	117.0	C21—C20—C19	119.8 (3)
C4—C5—H5A	120.0	C21—C20—H20	120.1
C4—C5—H5B	120.0	C19—C20—H20	120.1
H5A—C5—H5B	120.0	C20—C21—C22	120.5 (3)
C7—C6—C11	119.2 (3)	C20—C21—H21	119.7
C7—C6—P1	118.0 (3)	C22—C21—H21	119.7
C11—C6—P1	122.8 (3)	C21—C22—C23	120.0 (3)
C8—C7—C6	119.7 (3)	C21—C22—H22	120.0
C8—C7—H7	120.2	C23—C22—H22	120.0
C6—C7—H7	120.2	C18—C23—C22	120.1 (3)
C9—C8—C7	120.9 (4)	C18—C23—H23	119.9
C9—C8—H8	119.6	C22—C23—H23	119.9
C7—C8—H8	119.6	C1—O1—Ag1	108.13 (19)
C10—C9—C8	119.5 (3)	C1—O2—Ag1iii	111.05 (19)
C10—C9—H9	120.2	C1—O2—Ag1i	123.53 (19)
C8—C9—H9	120.2	Ag1iii—O2—Ag1i	106.22 (8)
C9—C10—C11	120.9 (4)	C18—P1—C6	103.13 (15)
C9—C10—H10	119.6	C18—P1—C12	105.12 (14)
C11—C10—H10	119.6	C6—P1—C12	103.22 (15)
C10—C11—C6	119.8 (3)	C18—P1—Ag1	117.56 (10)
C10—C11—H11	120.1	C6—P1—Ag1	114.54 (10)
C6—C11—H11	120.1	C12—P1—Ag1	111.81 (10)
C17—C12—C13	119.4 (3)	O1—Ag1—P1	148.09 (6)
C17—C12—P1	123.1 (2)	O1—Ag1—O2i	82.45 (7)
C13—C12—P1	117.5 (2)	O1—Ag1—O2ii	90.28 (8)
C14—C13—C12	119.8 (3)	P1—Ag1—O2i	112.26 (5)
C14—C13—H13	120.1	O2ii—Ag1—P1	115.95 (6)
C12—C13—H13	120.1	O2ii—Ag1—O2i	92.63 (10)
C15—C14—C13	120.1 (3)
O1—C1—C2—C3	−8.4 (4)	C19—C20—C21—C22	−0.2 (5)
O2—C1—C2—C3	175.2 (3)	C20—C21—C22—C23	0.3 (5)
O1—C1—C2—C3i	−132.4 (3)	C19—C18—C23—C22	−1.0 (5)
O2—C1—C2—C3i	51.2 (4)	P1—C18—C23—C22	175.4 (3)
O1—C1—C2—C1i	108.5 (3)	C21—C22—C23—C18	0.2 (5)
O2—C1—C2—C1i	−67.9 (2)	O2—C1—O1—Ag1	100.7 (3)
C3i—C2—C3—C4	−60.5 (2)	C2—C1—O1—Ag1	−75.4 (3)
C1i—C2—C3—C4	65.0 (4)	O1—C1—O2—Ag1iii	−17.0 (4)
C1—C2—C3—C4	175.6 (2)	C2—C1—O2—Ag1iii	159.23 (19)
C2—C3—C4—C5	124.2 (4)	O1—C1—O2—Ag1i	−144.9 (2)
C11—C6—C7—C8	−2.2 (5)	C2—C1—O2—Ag1i	31.3 (3)
P1—C6—C7—C8	179.7 (3)	C23—C18—P1—C6	−106.6 (3)
C6—C7—C8—C9	1.0 (5)	C19—C18—P1—C6	69.7 (3)
C7—C8—C9—C10	0.5 (6)	C23—C18—P1—C12	145.6 (3)
C8—C9—C10—C11	−0.8 (6)	C19—C18—P1—C12	−38.1 (3)
C9—C10—C11—C6	−0.4 (5)	C23—C18—P1—Ag1	20.5 (3)
C7—C6—C11—C10	1.9 (5)	C19—C18—P1—Ag1	−163.2 (2)
P1—C6—C11—C10	179.9 (3)	C7—C6—P1—C18	−173.8 (2)
C17—C12—C13—C14	−3.0 (5)	C11—C6—P1—C18	8.2 (3)
P1—C12—C13—C14	176.2 (3)	C7—C6—P1—C12	−64.5 (3)
C12—C13—C14—C15	1.4 (5)	C11—C6—P1—C12	117.5 (3)
C13—C14—C15—C16	0.5 (5)	C7—C6—P1—Ag1	57.3 (3)
C14—C15—C16—C17	−1.0 (5)	C11—C6—P1—Ag1	−120.7 (2)
C13—C12—C17—C16	2.5 (5)	C17—C12—P1—C18	85.6 (3)
P1—C12—C17—C16	−176.6 (2)	C13—C12—P1—C18	−93.6 (3)
C15—C16—C17—C12	−0.6 (5)	C17—C12—P1—C6	−22.2 (3)
C23—C18—C19—C20	1.2 (5)	C13—C12—P1—C6	158.7 (2)
P1—C18—C19—C20	−175.1 (3)	C17—C12—P1—Ag1	−145.8 (2)
C18—C19—C20—C21	−0.6 (5)	C13—C12—P1—Ag1	35.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O2i	0.93	2.51	3.351 (4)	150