catena-Poly[[(acetonitrile-κN)silver(I)]-di-μ-trifluoro­methane­sulfonato-κ⁴O:O′-[(acetonitrile-κN)silver(I)]-μ-tetra­phenyl­diphosphine-κ²P:P′]

The silver(I)-based title polymer, [Ag₂(CF₃SO₃)₂(C₂₈H₂₆N₂P₂)]_n, has been synthesized and structurally characterized. The compound shows the formation of a centrosymmetric eight-membered Ag/O/S/O/Ag/O/S/O ring situated around an inversion center, with the Ag^I ions bridged by two trifluoro­methane­sulfonate ions in a staggered conformation. The rings are then linked by tetra­phenyl­diphosphine ligands into a one-dimensional polymer. The rings have an Ag...Ag separation of 5.419 (5) Å and are linked by a 2.2206 (15) Å P—P bond. All Ag^I ions have pseudo-tetra­hedral geometry, with a coordination environment consisting of two O atoms from two symmetry-related trifluoro­methane­sulfonate ions, a P atom from a phosphine ligand and an N atom from an acetonitrile ligand.

Key indicators

• Single-crystal X-ray study
• T = 105 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.040
• wR factor = 0.112
• Data-to-parameter ratio = 19.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT094_ALERT_2_B Ratio of Maximum / Minimum Residual Density ....       6.44
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C13

Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14

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

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

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S1. Comment

The title polymer contains Ag^I ions in pseudo tetrahedral geometry bridged by a rigid bidentate diphosphine (DPP) ligand (Klausmeyer et al., 2004). The distorted tetrahedral angles range from 140.60 (10) to 86.61 (13)°. The Ag^I ion is stabilized by the soft donor phosphorus, from DPP, and 2 hard oxo ligands, from trifluoromethanesulfonate. The structure contains an 8-membered ring containing the silvers and the anions (Fig. 1). This ring is situated on an inversion center. The rings are then linked by the diphosphine ligand through the silvers into a one-dimensional polymer which boasts a 'Ring—P—P—Ring' design resembling a staircase (Fig. 2). The extended packing structure indicates that F atoms on the trifluoromethanesulfonate ion form a 3.186 (4) Å interaction with a C—H group on a neighboring 'staircase' polymer.

Related literature

For the preparation of the diphosphine ligand, see: Klausmeyer et al. (2004).

S2. Experimental

The DPP ligand is an impurity formed in the synthesis of PCP-31 (Klausmeyer et al., 2004). Then combined with an equivalent of Ag(I)OTF in 10 ml CH₃CN, a clear colorless solution results. Colorless blocks of the title compound were obtained by the slow diffusion of ether into a CH₃CN solution containing the complex at 278 K.

S3. Refinement

H atoms were included in calculated positions and refined as riding on their parent atoms, with C—H bond lengths fixed to 0.95 (aromatic CH), or 0.98 Å (methyl CH₃). Isotropic displacement parameters were fixed for H atoms: U_iso(H) = 1.5U_eq(C15) for the methyl group and U_iso(H) = 1.2U_eq(carrier C) for phenyl groups. In the last difference map, the highest residual peak, 1.47 e.Å^-3, is found at 1.03 Å from Ag1.

Computing details

Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2003).

Figures

	Fig. 1. Thermal ellipsoid plot of the monomer unit of the title compound. Displacement ellipsoids are shown at the 30% probability level and the labeling scheme is given for the asymmetric unit. Non-labeled atoms are generated by symmetry code 1 - x, 2 - y, -z.
	Fig. 2. Ball-and-Stick diagram displaying the 'Ring-P—P-Ring' pattern observed in the extended structure of the title polymer. H atoms have been omitted for clarity.

catena-Poly[[(acetonitrile-κN)silver(I)]-di-µ- trifluoromethanesulfonato-κ⁴O:O'-[(acetonitrile-κN)silver(I)]-µ- tetraphenyldiphosphine-κ²P:P']

Crystal data

[Ag2(CF3SO3)2(C28H26N2P2)]	F(000) = 956
Mr = 483.16	Dx = 1.771 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8448 reflections
a = 10.1128 (2) Å	θ = 2.3–28.0°
b = 17.4753 (3) Å	µ = 1.36 mm^−1
c = 10.5053 (2) Å	T = 105 K
β = 102.599 (1)°	Rod, colourless
V = 1811.84 (6) Å^3	0.21 × 0.17 × 0.10 mm
Z = 4

Data collection

Bruker X8 APEX diffractometer	4502 independent reflections
Radiation source: fine-focus sealed tube	3588 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.760, Tmax = 0.873	k = −23→23
28681 measured reflections	l = −14→12

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0619P)^2 + 1.0373P] where P = (Fo^2 + 2Fc^2)/3
4502 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 1.47 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

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

	x	y	z	Uiso*/Ueq
Ag1	0.61713 (3)	1.022971 (14)	0.25471 (3)	0.05425 (11)
P1	0.50042 (7)	0.96768 (4)	0.40910 (7)	0.03942 (17)
S3	0.57444 (9)	0.87763 (4)	0.03092 (8)	0.05077 (19)
C7	0.3200 (3)	0.95576 (16)	0.3394 (3)	0.0439 (6)
C8	0.2762 (4)	0.9755 (2)	0.2101 (4)	0.0623 (9)
H8	0.3393	0.9941	0.1624	0.075*
C1	0.5731 (3)	0.87625 (16)	0.4756 (3)	0.0442 (6)
C2	0.6818 (4)	0.8485 (2)	0.4273 (4)	0.0607 (8)
H2	0.7138	0.8765	0.3627	0.073*
C6	0.5306 (4)	0.83521 (19)	0.5713 (4)	0.0590 (8)
H6	0.4571	0.8535	0.6057	0.071*
C4	0.6990 (4)	0.7402 (2)	0.5701 (5)	0.0736 (11)
H4	0.7425	0.6938	0.6028	0.088*
C5	0.5950 (4)	0.7669 (2)	0.6178 (4)	0.0667 (10)
H5	0.5649	0.7390	0.6838	0.080*
C12	0.2260 (4)	0.9294 (3)	0.4062 (4)	0.0729 (11)
H12	0.2548	0.9145	0.4949	0.087*
C13	0.6961 (5)	0.8024 (3)	0.0321 (4)	0.0731 (11)
C9	0.1401 (5)	0.9684 (3)	0.1490 (5)	0.0819 (13)
H9	0.1112	0.9812	0.0593	0.098*
C11	0.0889 (4)	0.9245 (3)	0.3452 (5)	0.0830 (13)
H11	0.0245	0.9081	0.3932	0.100*
C3	0.7430 (4)	0.7802 (3)	0.4734 (5)	0.0757 (11)
H3	0.8154	0.7607	0.4387	0.091*
C10	0.0478 (4)	0.9433 (2)	0.2168 (5)	0.0735 (12)
H10	−0.0450	0.9388	0.1745	0.088*
F2	0.7758 (4)	0.8166 (3)	−0.0462 (4)	0.1362 (14)
F3	0.6357 (4)	0.73743 (16)	−0.0037 (4)	0.1363 (15)
F1	0.7723 (3)	0.7912 (2)	0.1497 (3)	0.1225 (12)
O2	0.4961 (3)	0.85106 (17)	0.1200 (3)	0.0738 (7)
O1	0.6587 (3)	0.94232 (16)	0.0761 (3)	0.0799 (8)
N1	0.8058 (3)	1.0888 (2)	0.2480 (4)	0.0730 (9)
C14	0.8980 (4)	1.1225 (2)	0.2413 (4)	0.0650 (9)
O3	0.5061 (4)	0.88004 (19)	−0.1030 (3)	0.0885 (10)
C15	1.0188 (5)	1.1660 (3)	0.2352 (6)	0.0971 (16)
H15A	1.0059	1.2196	0.2572	0.146*
H15B	1.0353	1.1630	0.1468	0.146*
H15C	1.0966	1.1447	0.2974	0.146*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.05592 (17)	0.05287 (16)	0.05747 (17)	−0.00550 (10)	0.02006 (12)	0.00355 (10)
P1	0.0370 (4)	0.0361 (3)	0.0438 (4)	−0.0028 (3)	0.0059 (3)	0.0003 (3)
S3	0.0570 (4)	0.0431 (4)	0.0537 (4)	0.0051 (3)	0.0155 (4)	0.0008 (3)
C7	0.0388 (14)	0.0346 (13)	0.0553 (17)	−0.0022 (11)	0.0039 (12)	−0.0029 (12)
C8	0.0480 (18)	0.073 (2)	0.062 (2)	0.0061 (16)	0.0032 (16)	0.0082 (17)
C1	0.0421 (14)	0.0360 (13)	0.0508 (16)	0.0020 (11)	0.0018 (12)	0.0001 (12)
C2	0.0521 (18)	0.063 (2)	0.066 (2)	0.0107 (16)	0.0090 (16)	0.0091 (17)
C6	0.064 (2)	0.0435 (16)	0.073 (2)	0.0015 (14)	0.0228 (18)	0.0042 (15)
C4	0.063 (2)	0.0495 (19)	0.097 (3)	0.0097 (17)	−0.007 (2)	0.016 (2)
C5	0.075 (2)	0.0462 (18)	0.077 (2)	−0.0031 (17)	0.011 (2)	0.0162 (17)
C12	0.056 (2)	0.096 (3)	0.063 (2)	−0.024 (2)	0.0046 (17)	0.011 (2)
C13	0.079 (3)	0.073 (3)	0.072 (2)	0.023 (2)	0.027 (2)	0.002 (2)
C9	0.056 (2)	0.102 (4)	0.073 (3)	0.009 (2)	−0.016 (2)	0.010 (2)
C11	0.049 (2)	0.094 (3)	0.104 (3)	−0.023 (2)	0.013 (2)	0.012 (3)
C3	0.059 (2)	0.073 (3)	0.094 (3)	0.0232 (19)	0.014 (2)	0.009 (2)
C10	0.0448 (19)	0.062 (2)	0.098 (3)	0.0001 (16)	−0.017 (2)	−0.002 (2)
F2	0.122 (3)	0.182 (4)	0.134 (3)	0.054 (2)	0.090 (2)	0.022 (3)
F3	0.177 (4)	0.0536 (17)	0.182 (4)	0.0202 (19)	0.046 (3)	−0.0193 (19)
F1	0.102 (2)	0.163 (3)	0.099 (2)	0.071 (2)	0.0145 (17)	0.024 (2)
O2	0.0638 (16)	0.0796 (18)	0.0868 (19)	−0.0078 (14)	0.0355 (15)	−0.0007 (15)
O1	0.102 (2)	0.0586 (15)	0.090 (2)	−0.0251 (15)	0.0457 (18)	−0.0175 (14)
N1	0.0616 (19)	0.071 (2)	0.089 (2)	−0.0154 (16)	0.0215 (17)	−0.0050 (18)
C14	0.059 (2)	0.068 (2)	0.069 (2)	−0.0121 (17)	0.0172 (18)	−0.0080 (18)
O3	0.111 (2)	0.081 (2)	0.0627 (17)	0.0280 (18)	−0.0042 (16)	0.0076 (14)
C15	0.068 (3)	0.105 (4)	0.123 (4)	−0.028 (3)	0.031 (3)	−0.007 (3)

Geometric parameters (Å, º)

Ag1—N1	2.242 (3)	C4—C5	1.344 (6)
Ag1—P1	2.4068 (8)	C4—C3	1.383 (6)
Ag1—O1	2.455 (3)	C4—H4	0.9500
Ag1—O3^i	2.470 (3)	C5—H5	0.9500
P1—C7	1.824 (3)	C12—C11	1.398 (5)
P1—C1	1.832 (3)	C12—H12	0.9500
P1—P1^ii	2.2206 (15)	C13—F2	1.295 (5)
S3—O3	1.427 (3)	C13—F3	1.305 (5)
S3—O2	1.429 (3)	C13—F1	1.320 (5)
S3—O1	1.433 (3)	C9—C10	1.365 (7)
S3—C13	1.799 (4)	C9—H9	0.9500
C7—C8	1.378 (5)	C11—C10	1.362 (7)
C7—C12	1.378 (5)	C11—H11	0.9500
C8—C9	1.392 (6)	C3—H3	0.9500
C8—H8	0.9500	C10—H10	0.9500
C1—C6	1.378 (5)	N1—C14	1.118 (5)
C1—C2	1.394 (5)	C14—C15	1.452 (6)
C2—C3	1.383 (5)	O3—Ag1^i	2.470 (3)
C2—H2	0.9500	C15—H15A	0.9800
C6—C5	1.396 (5)	C15—H15B	0.9800
C6—H6	0.9500	C15—H15C	0.9800
N1—Ag1—P1	140.60 (10)	C3—C4—H4	119.9
N1—Ag1—O1	88.97 (11)	C4—C5—C6	120.6 (4)
P1—Ag1—O1	118.38 (7)	C4—C5—H5	119.7
N1—Ag1—O3^i	86.61 (13)	C6—C5—H5	119.7
P1—Ag1—O3^i	117.23 (9)	C7—C12—C11	120.8 (4)
O1—Ag1—O3^i	92.72 (11)	C7—C12—H12	119.6
C7—P1—C1	109.67 (13)	C11—C12—H12	119.6
C7—P1—P1^ii	102.26 (11)	F2—C13—F3	107.5 (4)
C1—P1—P1^ii	101.08 (11)	F2—C13—F1	107.8 (4)
C7—P1—Ag1	111.71 (11)	F3—C13—F1	106.4 (4)
C1—P1—Ag1	113.08 (11)	F2—C13—S3	112.0 (3)
P1^ii—P1—Ag1	118.02 (5)	F3—C13—S3	110.9 (3)
O3—S3—O2	115.9 (2)	F1—C13—S3	111.9 (3)
O3—S3—O1	115.4 (2)	C10—C9—C8	120.6 (4)
O2—S3—O1	114.45 (17)	C10—C9—H9	119.7
O3—S3—C13	102.2 (2)	C8—C9—H9	119.7
O2—S3—C13	103.52 (19)	C10—C11—C12	119.8 (4)
O1—S3—C13	102.6 (2)	C10—C11—H11	120.1
C8—C7—C12	118.5 (3)	C12—C11—H11	120.1
C8—C7—P1	116.4 (3)	C4—C3—C2	120.1 (4)
C12—C7—P1	125.0 (3)	C4—C3—H3	119.9
C7—C8—C9	120.3 (4)	C2—C3—H3	119.9
C7—C8—H8	119.8	C11—C10—C9	119.9 (4)
C9—C8—H8	119.8	C11—C10—H10	120.0
C6—C1—C2	118.7 (3)	C9—C10—H10	120.0
C6—C1—P1	124.7 (2)	S3—O1—Ag1	121.18 (17)
C2—C1—P1	116.6 (3)	C14—N1—Ag1	177.9 (4)
C3—C2—C1	120.1 (4)	N1—C14—C15	178.9 (5)
C3—C2—H2	120.0	S3—O3—Ag1^i	136.42 (19)
C1—C2—H2	120.0	C14—C15—H15A	109.5
C1—C6—C5	120.3 (3)	C14—C15—H15B	109.5
C1—C6—H6	119.9	H15A—C15—H15B	109.5
C5—C6—H6	119.9	C14—C15—H15C	109.5
C5—C4—C3	120.1 (3)	H15A—C15—H15C	109.5
C5—C4—H4	119.9	H15B—C15—H15C	109.5

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