The novel title silver(I) coordination polymer, catena-poly[[acetonitrilesilver(I)]-di-μ-4-[N-(diphenylphosphino)aminomethyl]pyridine-κ2N1:P;κ2P:N1-[acetonitrilesilver(I)]-μ3-4-[N,N-bis(diphenylphosphino)aminomethyl]pyridine-κ3N1:P:P′-bis[acetonitrilesilver(I)(Ag—Ag)]-μ3-4-[N,N-bis(diphenylphosphino)aminomethyl]pyridine-κ3P:P′:N1] tetrakis(tetrafluoroborate) acetonitrile trisolvate], {[Ag4(C2H3N)4(C18H17N2P)2(C30H26N2P2)2](BF4)4·3C2H3N}n, is formed by the self-assembly of the Ph2P(4-NHCH2C5H4N) and (Ph2P)2(4-NCH2C5H4N) ligands with silver tetrafluoroborate. The polymer consists of alternating rings (which lie about inversion centers) bridged by the pyridyl rings of the bis-phosphine-substituted ligands, with anions hydrogen bonded the length of the chain. Two distinctly different metal coordination environments exist in the polymer, viz. distorted tetrahedral and trigonal geometries.
Supporting information
CCDC reference: 256999
Compound (I) was prepared by the dilute addition of chlorodiphenylphosphine to a solution of 1:1 4-aminomethylpyridine and triethylamine. Triethylamine (0.13 ml, 0.92 mmol) was added to a stirred solution of 4-aminomethylpyridine (0.100 g, 0.92 mmol) in toluene (50 ml). This solution was stirred for 10 min and then cooled to 273 K. A solution of chlorodiphenylphosphine (0.204 g, 0.92 mmol) in toluene (50 ml) was then added dropwise over a period of 1 h. The resulting solution was stirred for an additional hour and then filtered cold through celite. This solution was then dried in vacuo to leave (I) as a colorless oil. Compound (II) was prepared by the addition of two equivalents of chlorodiphenylphosphine to a solution of 1:2 4-aminomethylpyridine and triethylamine. Triethylamine (1.3 ml, 9.2 mmol) was added to a stirred solution of 4-aminomethylpyridine (0.500 g, 4.6 mmol) in toluene (15 ml). This solution was stirred for 10 min and then cooled to 273 K. A solution of chlorodiphenylphosphine (2.04 g, 9.2 mmol) in toluene (10 ml) was then added dropwise over the period of 10 min. The solution was stirred for 30 min and then allowed to warm to room temperature. This cloudy suspension was then filtered through celite and dried in vacuo to leave (II) as a clear yellow oil. The ligand mixture was prepared by adding a solution of chlorodiphenylphosphine (2.04 g, 9.24 mmol) dropwise over a period of 10 min to a stirred solution of aminomethylpyridine (1.00 g, 9.25 mmol) and triethylamine (1.3 ml, 9.33 mmol) in toluene (20 ml) at 273 K. This solution was allowed to warm to room temperature and filtered through celite. The solvent was removed in vacuo to leave the Ph2P(4-NHCH2C5H4N)/ (Ph2P)2(4-NCH2C5H4N) mixture as a yellow oil. This mixture (0.10 g) was then added to a solution of AgBF4 (0.67 g, 3.44 mmol) in CH3CN (5 ml), stirred for 5 min, and precipitated with ether to leave the coodination polymer (III) as a white solid. Diffraction-quality crystals were obtained by redissolving (III) in acetonitrile and slowly diffusing ether into this solution at 278 K.
H atoms were included in calculated positions (C—H = 0.930 Å), except for atom H1, which was located and refined isotropically; isotropic displacement parameters for all other H atoms were fixed [Uiso(H) = 1.2Uiso(C)].
Data collection: APEX2 (Bruker,2003); cell refinement: APEX2; 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 (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.
catena-poly[[[acetonitrilesilver(I)]-di-µ-4-[N– (diphenylphosphino)aminomethyl]pyridine-
κ2N1:
P;
κ2P:
N1– [acetonitrilesilver(I)]-µ
3– 4-[
N,
N-bis(diphenylphosphino)aminomethyl]pyridine-
κ3N1:
P:
P'- bis[acetonitrilesilver(I)(Ag—Ag)]-µ
3-4-[N,
N- bis(diphenylphosphino)aminomethyl]pyridine-
κ3P:
P':
N1] tetrakis(tetrafluoroborate) acetonitrile trisolvate]
top
Crystal data top
[Ag4(C18H17N2P)2(C30H26N2P2)2(C2H3N)4](BF4)4·3C2H3N | Z = 1 |
Mr = 2726.80 | F(000) = 1380 |
Triclinic, P1 | Dx = 1.501 Mg m−3 |
a = 13.2233 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.6535 (11) Å | Cell parameters from 5178 reflections |
c = 16.7275 (12) Å | θ = 2.4–25.6° |
α = 97.085 (2)° | µ = 0.80 mm−1 |
β = 104.690 (2)° | T = 110 K |
γ = 101.691 (3)° | Parallelpiped, colorless |
V = 3017.6 (4) Å3 | 0.14 × 0.08 × 0.06 mm |
Data collection top
Bruker X8 APEX CCD area detector diffractometer | 12262 independent reflections |
Radiation source: fine-focus sealed tube | 8973 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; sheldrick, 1996) SADABS | h = −16→14 |
Tmin = 0.899, Tmax = 0.956 | k = −17→18 |
32743 measured reflections | l = −18→20 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0191P)2 + 1.5905P] where P = (Fo2 + 2Fc2)/3 |
12262 reflections | (Δ/σ)max = 0.003 |
748 parameters | Δρmax = 0.56 e Å−3 |
1 restraint | Δρmin = −0.57 e Å−3 |
Crystal data top
[Ag4(C18H17N2P)2(C30H26N2P2)2(C2H3N)4](BF4)4·3C2H3N | γ = 101.691 (3)° |
Mr = 2726.80 | V = 3017.6 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 13.2233 (8) Å | Mo Kα radiation |
b = 14.6535 (11) Å | µ = 0.80 mm−1 |
c = 16.7275 (12) Å | T = 110 K |
α = 97.085 (2)° | 0.14 × 0.08 × 0.06 mm |
β = 104.690 (2)° | |
Data collection top
Bruker X8 APEX CCD area detector diffractometer | 12262 independent reflections |
Absorption correction: multi-scan (SADABS; sheldrick, 1996) SADABS | 8973 reflections with I > 2σ(I) |
Tmin = 0.899, Tmax = 0.956 | Rint = 0.053 |
32743 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.56 e Å−3 |
12262 reflections | Δρmin = −0.57 e Å−3 |
748 parameters | |
Special details top
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) top | x | y | z | Uiso*/Ueq | |
Ag1 | 0.257495 (19) | 0.620771 (17) | 0.091629 (15) | 0.01907 (7) | |
Ag2 | 0.038645 (18) | 1.090798 (17) | 0.469909 (15) | 0.01632 (7) | |
N1 | 0.2560 (2) | 0.6736 (2) | −0.10425 (17) | 0.0191 (6) | |
H1 | 0.279 (3) | 0.706 (2) | −0.1347 (19) | 0.030 (11)* | |
N2 | −0.0904 (2) | 0.44917 (18) | −0.10172 (16) | 0.0191 (6) | |
N3 | 0.18475 (19) | 0.92324 (18) | 0.44893 (15) | 0.0143 (6) | |
N4 | 0.2921 (2) | 0.72002 (19) | 0.22606 (16) | 0.0193 (6) | |
N5 | 0.3363 (2) | 0.5097 (2) | 0.16511 (18) | 0.0285 (7) | |
N6 | −0.0668 (2) | 1.0881 (2) | 0.33601 (18) | 0.0247 (7) | |
N7 | 0.3122 (3) | 0.4941 (3) | 0.4160 (3) | 0.0644 (12) | |
N8 | 0.5739 (4) | 0.5756 (3) | 0.3770 (3) | 0.0763 (14) | |
N9 | 0.1468 (3) | 0.2685 (2) | 0.4568 (2) | 0.0397 (8) | |
P1 | 0.32959 (6) | 0.70034 (6) | −0.00295 (5) | 0.01605 (18) | |
P2 | 0.20609 (6) | 1.04305 (6) | 0.47491 (5) | 0.01434 (17) | |
P3 | 0.05239 (6) | 0.86031 (6) | 0.42751 (5) | 0.01416 (17) | |
B1 | 0.0904 (3) | 0.2000 (3) | 0.0825 (3) | 0.0238 (9) | |
B2 | 0.6903 (3) | 0.2583 (3) | 0.2907 (3) | 0.0247 (9) | |
F1 | 0.13713 (18) | 0.13086 (16) | 0.05474 (14) | 0.0452 (6) | |
F2 | 0.03382 (19) | 0.23233 (17) | 0.01449 (13) | 0.0497 (6) | |
F3 | 0.17106 (15) | 0.27536 (14) | 0.13528 (13) | 0.0371 (5) | |
F4 | 0.02184 (19) | 0.16616 (19) | 0.12762 (15) | 0.0628 (8) | |
F5 | 0.6432 (2) | 0.33251 (18) | 0.30028 (17) | 0.0640 (8) | |
F6 | 0.68971 (16) | 0.20822 (17) | 0.35520 (14) | 0.0502 (7) | |
F7 | 0.79607 (15) | 0.29258 (15) | 0.29025 (12) | 0.0371 (5) | |
F8 | 0.63338 (16) | 0.19828 (16) | 0.21421 (13) | 0.0410 (6) | |
C1 | 0.2115 (3) | 0.5738 (2) | −0.1442 (2) | 0.0214 (7) | |
H1A | 0.2640 | 0.5380 | −0.1243 | 0.026* | |
H1B | 0.1989 | 0.5684 | −0.2045 | 0.026* | |
C2 | 0.1070 (2) | 0.5307 (2) | −0.12661 (19) | 0.0183 (7) | |
C3 | 0.0335 (2) | 0.5844 (2) | −0.11886 (19) | 0.0182 (7) | |
H3 | 0.0490 | 0.6486 | −0.1217 | 0.022* | |
C4 | −0.0634 (2) | 0.5408 (2) | −0.10688 (19) | 0.0187 (7) | |
H4 | −0.1123 | 0.5772 | −0.1022 | 0.022* | |
C5 | −0.0187 (2) | 0.3981 (2) | −0.1085 (2) | 0.0207 (7) | |
H5 | −0.0356 | 0.3343 | −0.1044 | 0.025* | |
C6 | 0.0792 (2) | 0.4358 (2) | −0.12116 (19) | 0.0189 (7) | |
H6 | 0.1263 | 0.3976 | −0.1260 | 0.023* | |
C7 | 0.3351 (2) | 0.8257 (2) | 0.02146 (19) | 0.0160 (7) | |
C8 | 0.4307 (3) | 0.8970 (2) | 0.05331 (19) | 0.0196 (7) | |
H8 | 0.4969 | 0.8821 | 0.0590 | 0.023* | |
C9 | 0.4264 (3) | 0.9907 (2) | 0.0766 (2) | 0.0255 (8) | |
H9 | 0.4900 | 1.0380 | 0.0980 | 0.031* | |
C10 | 0.3284 (3) | 1.0138 (2) | 0.0681 (2) | 0.0264 (8) | |
H10 | 0.3261 | 1.0764 | 0.0832 | 0.032* | |
C11 | 0.2329 (3) | 0.9430 (3) | 0.0369 (2) | 0.0263 (8) | |
H11 | 0.1669 | 0.9583 | 0.0312 | 0.032* | |
C12 | 0.2364 (3) | 0.8507 (2) | 0.01463 (19) | 0.0200 (7) | |
H12 | 0.1724 | 0.8038 | −0.0054 | 0.024* | |
C13 | 0.4664 (2) | 0.6921 (2) | 0.0014 (2) | 0.0188 (7) | |
C14 | 0.5220 (3) | 0.7311 (2) | −0.0519 (2) | 0.0262 (8) | |
H14 | 0.4899 | 0.7654 | −0.0898 | 0.031* | |
C15 | 0.6235 (3) | 0.7196 (3) | −0.0492 (2) | 0.0305 (9) | |
H15 | 0.6599 | 0.7471 | −0.0845 | 0.037* | |
C16 | 0.6716 (3) | 0.6671 (3) | 0.0057 (2) | 0.0337 (9) | |
H16 | 0.7397 | 0.6585 | 0.0069 | 0.040* | |
C17 | 0.6177 (3) | 0.6277 (3) | 0.0586 (3) | 0.0423 (11) | |
H17 | 0.6496 | 0.5925 | 0.0958 | 0.051* | |
C18 | 0.5159 (3) | 0.6404 (3) | 0.0567 (2) | 0.0293 (9) | |
H18 | 0.4805 | 0.6139 | 0.0929 | 0.035* | |
C19 | 0.2779 (2) | 0.8781 (2) | 0.45709 (19) | 0.0165 (7) | |
H19A | 0.2738 | 0.8347 | 0.4961 | 0.020* | |
H19B | 0.3440 | 0.9272 | 0.4816 | 0.020* | |
C20 | 0.2849 (2) | 0.8246 (2) | 0.37623 (19) | 0.0150 (7) | |
C21 | 0.3009 (2) | 0.8689 (2) | 0.3095 (2) | 0.0187 (7) | |
H21 | 0.3103 | 0.9342 | 0.3142 | 0.022* | |
C22 | 0.3025 (2) | 0.8142 (2) | 0.2366 (2) | 0.0198 (7) | |
H22 | 0.3114 | 0.8443 | 0.1922 | 0.024* | |
C23 | 0.2817 (3) | 0.6790 (2) | 0.2914 (2) | 0.0230 (8) | |
H23 | 0.2764 | 0.6141 | 0.2862 | 0.028* | |
C24 | 0.2783 (2) | 0.7282 (2) | 0.3664 (2) | 0.0194 (7) | |
H24 | 0.2717 | 0.6965 | 0.4103 | 0.023* | |
C25 | 0.2842 (2) | 1.0895 (2) | 0.40690 (19) | 0.0163 (7) | |
C26 | 0.3963 (2) | 1.1041 (2) | 0.4273 (2) | 0.0202 (7) | |
H26 | 0.4349 | 1.0976 | 0.4802 | 0.024* | |
C27 | 0.4500 (3) | 1.1284 (2) | 0.3689 (2) | 0.0245 (8) | |
H27 | 0.5245 | 1.1378 | 0.3827 | 0.029* | |
C28 | 0.3931 (3) | 1.1386 (2) | 0.2899 (2) | 0.0268 (8) | |
H28 | 0.4293 | 1.1544 | 0.2507 | 0.032* | |
C29 | 0.2824 (3) | 1.1255 (2) | 0.2695 (2) | 0.0246 (8) | |
H29 | 0.2444 | 1.1327 | 0.2166 | 0.030* | |
C30 | 0.2276 (2) | 1.1013 (2) | 0.3279 (2) | 0.0185 (7) | |
H30 | 0.1533 | 1.0929 | 0.3141 | 0.022* | |
C31 | 0.3019 (2) | 1.0801 (2) | 0.57932 (19) | 0.0172 (7) | |
C32 | 0.3178 (2) | 1.0172 (2) | 0.6351 (2) | 0.0213 (7) | |
H32 | 0.2826 | 0.9533 | 0.6184 | 0.026* | |
C33 | 0.3869 (3) | 1.0513 (3) | 0.7159 (2) | 0.0263 (8) | |
H33 | 0.3991 | 1.0094 | 0.7528 | 0.032* | |
C34 | 0.4374 (3) | 1.1456 (3) | 0.7421 (2) | 0.0299 (9) | |
H34 | 0.4829 | 1.1673 | 0.7965 | 0.036* | |
C35 | 0.4209 (3) | 1.2087 (3) | 0.6877 (2) | 0.0286 (8) | |
H35 | 0.4554 | 1.2726 | 0.7057 | 0.034* | |
C36 | 0.3526 (2) | 1.1766 (2) | 0.6060 (2) | 0.0227 (8) | |
H36 | 0.3409 | 1.2190 | 0.5697 | 0.027* | |
C37 | 0.0598 (2) | 0.7376 (2) | 0.4263 (2) | 0.0179 (7) | |
C38 | 0.0953 (2) | 0.7097 (2) | 0.5037 (2) | 0.0203 (7) | |
H38 | 0.1131 | 0.7533 | 0.5535 | 0.024* | |
C39 | 0.1039 (3) | 0.6178 (2) | 0.5063 (2) | 0.0242 (8) | |
H39 | 0.1293 | 0.6001 | 0.5578 | 0.029* | |
C40 | 0.0750 (3) | 0.5517 (2) | 0.4326 (2) | 0.0277 (8) | |
H40 | 0.0808 | 0.4898 | 0.4346 | 0.033* | |
C41 | 0.0372 (3) | 0.5783 (2) | 0.3559 (2) | 0.0254 (8) | |
H41 | 0.0170 | 0.5338 | 0.3065 | 0.030* | |
C42 | 0.0294 (2) | 0.6704 (2) | 0.3524 (2) | 0.0222 (8) | |
H42 | 0.0040 | 0.6877 | 0.3007 | 0.027* | |
C43 | −0.0154 (2) | 0.8606 (2) | 0.31859 (19) | 0.0170 (7) | |
C44 | 0.0384 (3) | 0.8844 (2) | 0.2596 (2) | 0.0212 (7) | |
H44 | 0.1132 | 0.9044 | 0.2763 | 0.025* | |
C45 | −0.0184 (3) | 0.8786 (3) | 0.1763 (2) | 0.0272 (8) | |
H45 | 0.0182 | 0.8945 | 0.1373 | 0.033* | |
C46 | −0.1291 (3) | 0.8494 (3) | 0.1516 (2) | 0.0311 (9) | |
H46 | −0.1674 | 0.8451 | 0.0958 | 0.037* | |
C47 | −0.1836 (3) | 0.8264 (3) | 0.2094 (2) | 0.0304 (9) | |
H47 | −0.2584 | 0.8064 | 0.1922 | 0.036* | |
C48 | −0.1279 (2) | 0.8328 (2) | 0.2927 (2) | 0.0212 (7) | |
H48 | −0.1654 | 0.8187 | 0.3315 | 0.025* | |
C49 | 0.3636 (3) | 0.4570 (2) | 0.2043 (2) | 0.0264 (8) | |
C50 | 0.3979 (3) | 0.3889 (3) | 0.2559 (2) | 0.0385 (10) | |
H50A | 0.4050 | 0.4125 | 0.3136 | 0.058* | |
H50B | 0.4661 | 0.3802 | 0.2505 | 0.058* | |
H50C | 0.3452 | 0.3293 | 0.2373 | 0.058* | |
C51 | −0.1174 (3) | 1.0846 (2) | 0.2691 (2) | 0.0231 (8) | |
C52 | −0.1806 (3) | 1.0812 (3) | 0.1834 (2) | 0.0321 (9) | |
H52A | −0.2130 | 1.1341 | 0.1815 | 0.048* | |
H52B | −0.2360 | 1.0232 | 0.1648 | 0.048* | |
H52C | −0.1344 | 1.0838 | 0.1472 | 0.048* | |
C53 | 0.3770 (4) | 0.5547 (3) | 0.4630 (3) | 0.0455 (11) | |
C54 | 0.4577 (4) | 0.6332 (3) | 0.5205 (3) | 0.0571 (13) | |
H54A | 0.4727 | 0.6845 | 0.4914 | 0.086* | |
H54B | 0.5225 | 0.6131 | 0.5419 | 0.086* | |
H54C | 0.4314 | 0.6539 | 0.5663 | 0.086* | |
C55 | 0.6578 (4) | 0.5711 (3) | 0.3707 (3) | 0.0540 (12) | |
C56 | 0.7613 (4) | 0.5659 (4) | 0.3633 (3) | 0.0742 (16) | |
H56A | 0.7660 | 0.5010 | 0.3572 | 0.111* | |
H56B | 0.8157 | 0.6024 | 0.4128 | 0.111* | |
H56C | 0.7723 | 0.5909 | 0.3149 | 0.111* | |
C57 | 0.1200 (3) | 0.2906 (2) | 0.3921 (3) | 0.0309 (9) | |
C58 | 0.0844 (3) | 0.3173 (3) | 0.3112 (2) | 0.0411 (10) | |
H58A | 0.0856 | 0.2685 | 0.2678 | 0.062* | |
H58B | 0.1315 | 0.3758 | 0.3097 | 0.062* | |
H58C | 0.0123 | 0.3252 | 0.3024 | 0.062* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag1 | 0.02314 (14) | 0.01886 (14) | 0.01753 (14) | 0.00476 (10) | 0.00909 (11) | 0.00574 (11) |
Ag2 | 0.01565 (12) | 0.02180 (14) | 0.01429 (14) | 0.00750 (10) | 0.00623 (10) | 0.00462 (10) |
N1 | 0.0206 (15) | 0.0213 (16) | 0.0150 (15) | 0.0029 (12) | 0.0061 (12) | 0.0039 (13) |
N2 | 0.0200 (14) | 0.0210 (15) | 0.0156 (15) | 0.0047 (12) | 0.0036 (12) | 0.0046 (12) |
N3 | 0.0120 (13) | 0.0184 (14) | 0.0144 (14) | 0.0060 (11) | 0.0048 (11) | 0.0044 (11) |
N4 | 0.0209 (14) | 0.0222 (16) | 0.0167 (15) | 0.0057 (12) | 0.0079 (12) | 0.0045 (12) |
N5 | 0.0335 (17) | 0.0285 (18) | 0.0284 (18) | 0.0147 (14) | 0.0108 (14) | 0.0075 (15) |
N6 | 0.0217 (15) | 0.0315 (18) | 0.0192 (17) | 0.0069 (13) | 0.0022 (13) | 0.0050 (13) |
N7 | 0.065 (3) | 0.048 (3) | 0.088 (3) | 0.016 (2) | 0.033 (3) | 0.015 (2) |
N8 | 0.062 (3) | 0.068 (3) | 0.102 (4) | 0.012 (2) | 0.033 (3) | 0.011 (3) |
N9 | 0.047 (2) | 0.032 (2) | 0.046 (2) | 0.0114 (16) | 0.0185 (18) | 0.0125 (17) |
P1 | 0.0157 (4) | 0.0186 (4) | 0.0155 (4) | 0.0053 (3) | 0.0056 (3) | 0.0050 (4) |
P2 | 0.0131 (4) | 0.0180 (4) | 0.0124 (4) | 0.0046 (3) | 0.0041 (3) | 0.0024 (3) |
P3 | 0.0131 (4) | 0.0177 (4) | 0.0121 (4) | 0.0041 (3) | 0.0042 (3) | 0.0023 (3) |
B1 | 0.024 (2) | 0.026 (2) | 0.023 (2) | 0.0091 (17) | 0.0091 (18) | 0.0022 (18) |
B2 | 0.023 (2) | 0.032 (2) | 0.021 (2) | 0.0075 (18) | 0.0059 (18) | 0.0091 (19) |
F1 | 0.0576 (15) | 0.0422 (14) | 0.0453 (15) | 0.0318 (12) | 0.0168 (12) | 0.0063 (11) |
F2 | 0.0572 (15) | 0.0588 (16) | 0.0328 (14) | 0.0379 (13) | −0.0034 (11) | 0.0025 (12) |
F3 | 0.0284 (11) | 0.0348 (13) | 0.0417 (14) | 0.0016 (9) | 0.0049 (10) | 0.0049 (10) |
F4 | 0.0494 (15) | 0.079 (2) | 0.0530 (16) | −0.0169 (13) | 0.0343 (13) | −0.0018 (14) |
F5 | 0.0604 (17) | 0.0521 (17) | 0.080 (2) | 0.0347 (14) | 0.0112 (15) | −0.0025 (14) |
F6 | 0.0278 (12) | 0.0762 (18) | 0.0423 (14) | −0.0049 (11) | 0.0023 (10) | 0.0402 (13) |
F7 | 0.0258 (11) | 0.0541 (15) | 0.0292 (12) | −0.0028 (10) | 0.0112 (9) | 0.0134 (11) |
F8 | 0.0365 (12) | 0.0480 (15) | 0.0294 (13) | 0.0012 (10) | 0.0039 (10) | 0.0004 (11) |
C1 | 0.0208 (17) | 0.0242 (19) | 0.0182 (18) | 0.0053 (14) | 0.0062 (14) | −0.0010 (15) |
C2 | 0.0200 (17) | 0.0221 (18) | 0.0112 (17) | 0.0059 (14) | 0.0016 (13) | 0.0015 (14) |
C3 | 0.0208 (17) | 0.0137 (17) | 0.0184 (18) | 0.0030 (13) | 0.0042 (14) | 0.0026 (14) |
C4 | 0.0204 (17) | 0.0201 (18) | 0.0165 (18) | 0.0085 (14) | 0.0045 (14) | 0.0026 (14) |
C5 | 0.0240 (18) | 0.0195 (18) | 0.0186 (18) | 0.0066 (14) | 0.0037 (15) | 0.0070 (14) |
C6 | 0.0187 (17) | 0.0200 (18) | 0.0174 (18) | 0.0079 (14) | 0.0022 (14) | 0.0014 (14) |
C7 | 0.0192 (16) | 0.0196 (18) | 0.0099 (17) | 0.0068 (13) | 0.0026 (13) | 0.0053 (13) |
C8 | 0.0222 (17) | 0.0264 (19) | 0.0136 (17) | 0.0083 (14) | 0.0077 (14) | 0.0074 (15) |
C9 | 0.034 (2) | 0.0191 (19) | 0.023 (2) | 0.0041 (15) | 0.0111 (16) | 0.0029 (15) |
C10 | 0.047 (2) | 0.0201 (19) | 0.0199 (19) | 0.0165 (17) | 0.0155 (17) | 0.0055 (15) |
C11 | 0.031 (2) | 0.034 (2) | 0.021 (2) | 0.0185 (17) | 0.0107 (16) | 0.0095 (16) |
C12 | 0.0219 (17) | 0.0222 (19) | 0.0162 (18) | 0.0065 (14) | 0.0035 (14) | 0.0065 (14) |
C13 | 0.0194 (17) | 0.0155 (17) | 0.0191 (18) | 0.0046 (13) | 0.0034 (14) | −0.0018 (14) |
C14 | 0.0275 (19) | 0.030 (2) | 0.030 (2) | 0.0134 (16) | 0.0146 (16) | 0.0125 (17) |
C15 | 0.0243 (19) | 0.038 (2) | 0.030 (2) | 0.0058 (17) | 0.0121 (17) | −0.0004 (18) |
C16 | 0.0200 (19) | 0.038 (2) | 0.042 (2) | 0.0129 (17) | 0.0072 (18) | −0.0033 (19) |
C17 | 0.031 (2) | 0.048 (3) | 0.052 (3) | 0.0212 (19) | 0.004 (2) | 0.019 (2) |
C18 | 0.0252 (19) | 0.035 (2) | 0.030 (2) | 0.0095 (16) | 0.0076 (16) | 0.0121 (17) |
C19 | 0.0133 (15) | 0.0224 (18) | 0.0149 (17) | 0.0061 (13) | 0.0040 (13) | 0.0044 (14) |
C20 | 0.0114 (15) | 0.0201 (17) | 0.0153 (17) | 0.0061 (13) | 0.0056 (13) | 0.0017 (14) |
C21 | 0.0162 (16) | 0.0199 (18) | 0.0218 (19) | 0.0078 (13) | 0.0058 (14) | 0.0039 (15) |
C22 | 0.0170 (16) | 0.028 (2) | 0.0181 (18) | 0.0066 (14) | 0.0086 (14) | 0.0076 (15) |
C23 | 0.0261 (18) | 0.0221 (19) | 0.025 (2) | 0.0098 (15) | 0.0124 (16) | 0.0037 (15) |
C24 | 0.0225 (17) | 0.0236 (19) | 0.0173 (18) | 0.0082 (14) | 0.0108 (14) | 0.0080 (15) |
C25 | 0.0176 (16) | 0.0144 (16) | 0.0168 (18) | 0.0046 (13) | 0.0050 (14) | 0.0014 (13) |
C26 | 0.0165 (16) | 0.0220 (18) | 0.0208 (19) | 0.0039 (14) | 0.0040 (14) | 0.0034 (15) |
C27 | 0.0163 (17) | 0.028 (2) | 0.029 (2) | 0.0007 (14) | 0.0094 (15) | 0.0047 (16) |
C28 | 0.030 (2) | 0.027 (2) | 0.029 (2) | 0.0044 (16) | 0.0185 (17) | 0.0104 (16) |
C29 | 0.033 (2) | 0.026 (2) | 0.0188 (19) | 0.0086 (15) | 0.0113 (16) | 0.0082 (15) |
C30 | 0.0176 (16) | 0.0197 (18) | 0.0222 (19) | 0.0089 (13) | 0.0079 (14) | 0.0061 (14) |
C31 | 0.0125 (15) | 0.0238 (18) | 0.0146 (17) | 0.0043 (13) | 0.0048 (13) | −0.0006 (14) |
C32 | 0.0167 (16) | 0.029 (2) | 0.0197 (19) | 0.0072 (14) | 0.0074 (14) | 0.0047 (15) |
C33 | 0.0181 (17) | 0.043 (2) | 0.0194 (19) | 0.0104 (16) | 0.0041 (15) | 0.0095 (17) |
C34 | 0.0194 (18) | 0.053 (3) | 0.0139 (18) | 0.0059 (17) | 0.0042 (15) | −0.0013 (18) |
C35 | 0.0212 (18) | 0.029 (2) | 0.027 (2) | −0.0019 (15) | 0.0050 (16) | −0.0061 (17) |
C36 | 0.0212 (18) | 0.027 (2) | 0.0189 (19) | 0.0053 (15) | 0.0046 (15) | 0.0029 (15) |
C37 | 0.0148 (16) | 0.0193 (18) | 0.0211 (19) | 0.0049 (13) | 0.0070 (14) | 0.0044 (14) |
C38 | 0.0215 (17) | 0.0217 (18) | 0.0188 (18) | 0.0046 (14) | 0.0082 (14) | 0.0041 (14) |
C39 | 0.0241 (18) | 0.028 (2) | 0.024 (2) | 0.0082 (15) | 0.0083 (15) | 0.0102 (16) |
C40 | 0.0282 (19) | 0.0190 (19) | 0.037 (2) | 0.0051 (15) | 0.0117 (17) | 0.0055 (17) |
C41 | 0.0265 (19) | 0.023 (2) | 0.022 (2) | 0.0030 (15) | 0.0065 (16) | −0.0055 (15) |
C42 | 0.0200 (17) | 0.026 (2) | 0.0206 (19) | 0.0054 (14) | 0.0055 (15) | 0.0037 (15) |
C43 | 0.0188 (16) | 0.0151 (17) | 0.0180 (18) | 0.0069 (13) | 0.0056 (14) | 0.0015 (14) |
C44 | 0.0180 (17) | 0.029 (2) | 0.0172 (18) | 0.0050 (14) | 0.0069 (14) | 0.0052 (15) |
C45 | 0.030 (2) | 0.038 (2) | 0.0152 (19) | 0.0070 (16) | 0.0096 (16) | 0.0053 (16) |
C46 | 0.032 (2) | 0.043 (2) | 0.017 (2) | 0.0123 (17) | 0.0008 (16) | 0.0066 (17) |
C47 | 0.0190 (18) | 0.043 (2) | 0.022 (2) | 0.0071 (16) | −0.0018 (16) | −0.0024 (17) |
C48 | 0.0153 (16) | 0.029 (2) | 0.0196 (19) | 0.0057 (14) | 0.0061 (14) | 0.0037 (15) |
C49 | 0.0255 (19) | 0.023 (2) | 0.027 (2) | 0.0061 (16) | 0.0052 (16) | −0.0022 (17) |
C50 | 0.048 (2) | 0.032 (2) | 0.033 (2) | 0.0190 (19) | 0.0010 (19) | 0.0068 (18) |
C51 | 0.0175 (17) | 0.029 (2) | 0.024 (2) | 0.0071 (14) | 0.0059 (16) | 0.0061 (16) |
C52 | 0.027 (2) | 0.050 (3) | 0.020 (2) | 0.0126 (18) | 0.0014 (16) | 0.0108 (18) |
C53 | 0.048 (3) | 0.041 (3) | 0.055 (3) | 0.021 (2) | 0.016 (2) | 0.017 (2) |
C54 | 0.062 (3) | 0.052 (3) | 0.052 (3) | 0.026 (2) | −0.002 (2) | 0.008 (2) |
C55 | 0.055 (3) | 0.039 (3) | 0.060 (3) | 0.003 (2) | 0.016 (3) | −0.001 (2) |
C56 | 0.058 (3) | 0.065 (4) | 0.098 (4) | 0.018 (3) | 0.030 (3) | −0.014 (3) |
C57 | 0.038 (2) | 0.0172 (19) | 0.039 (3) | 0.0059 (16) | 0.0175 (19) | 0.0006 (17) |
C58 | 0.059 (3) | 0.034 (2) | 0.033 (2) | 0.014 (2) | 0.016 (2) | 0.0062 (19) |
Geometric parameters (Å, º) top
Ag1—N2i | 2.297 (3) | C19—H19B | 0.9700 |
Ag1—P1 | 2.3540 (8) | C20—C24 | 1.383 (4) |
Ag1—N5 | 2.403 (3) | C20—C21 | 1.398 (4) |
Ag1—N4 | 2.405 (3) | C21—C22 | 1.383 (4) |
Ag2—N6 | 2.309 (3) | C21—H21 | 0.9300 |
Ag2—P2 | 2.4387 (8) | C22—H22 | 0.9300 |
Ag2—P3ii | 2.4496 (8) | C23—C24 | 1.384 (4) |
Ag2—Ag2ii | 3.0363 (5) | C23—H23 | 0.9300 |
N1—C1 | 1.464 (4) | C24—H24 | 0.9300 |
N1—P1 | 1.679 (3) | C25—C30 | 1.394 (4) |
N1—H1 | 0.810 (18) | C25—C26 | 1.398 (4) |
N2—C4 | 1.337 (4) | C26—C27 | 1.386 (4) |
N2—C5 | 1.339 (4) | C26—H26 | 0.9300 |
N2—Ag1i | 2.297 (3) | C27—C28 | 1.388 (5) |
N3—C19 | 1.496 (4) | C27—H27 | 0.9300 |
N3—P2 | 1.703 (3) | C28—C29 | 1.382 (5) |
N3—P3 | 1.729 (2) | C28—H28 | 0.9300 |
N4—C23 | 1.334 (4) | C29—C30 | 1.395 (4) |
N4—C22 | 1.343 (4) | C29—H29 | 0.9300 |
N5—C49 | 1.130 (4) | C30—H30 | 0.9300 |
N6—C51 | 1.139 (4) | C31—C32 | 1.398 (4) |
N7—C53 | 1.149 (5) | C31—C36 | 1.399 (4) |
N8—C55 | 1.154 (6) | C32—C33 | 1.391 (4) |
N9—C57 | 1.157 (5) | C32—H32 | 0.9300 |
P1—C7 | 1.815 (3) | C33—C34 | 1.369 (5) |
P1—C13 | 1.821 (3) | C33—H33 | 0.9300 |
P2—C31 | 1.821 (3) | C34—C35 | 1.385 (5) |
P2—C25 | 1.824 (3) | C34—H34 | 0.9300 |
P3—C43 | 1.816 (3) | C35—C36 | 1.395 (4) |
P3—C37 | 1.819 (3) | C35—H35 | 0.9300 |
P3—Ag2ii | 2.4496 (8) | C36—H36 | 0.9300 |
B1—F4 | 1.377 (4) | C37—C42 | 1.396 (4) |
B1—F1 | 1.381 (4) | C37—C38 | 1.400 (4) |
B1—F2 | 1.386 (4) | C38—C39 | 1.380 (4) |
B1—F3 | 1.394 (4) | C38—H38 | 0.9300 |
B2—F5 | 1.370 (5) | C39—C40 | 1.385 (5) |
B2—F6 | 1.378 (4) | C39—H39 | 0.9300 |
B2—F7 | 1.389 (4) | C40—C41 | 1.387 (5) |
B2—F8 | 1.394 (4) | C40—H40 | 0.9300 |
C1—C2 | 1.514 (4) | C41—C42 | 1.382 (4) |
C1—H1A | 0.9700 | C41—H41 | 0.9300 |
C1—H1B | 0.9700 | C42—H42 | 0.9300 |
C2—C6 | 1.385 (4) | C43—C44 | 1.393 (4) |
C2—C3 | 1.390 (4) | C43—C48 | 1.397 (4) |
C3—C4 | 1.386 (4) | C44—C45 | 1.389 (4) |
C3—H3 | 0.9300 | C44—H44 | 0.9300 |
C4—H4 | 0.9300 | C45—C46 | 1.376 (5) |
C5—C6 | 1.380 (4) | C45—H45 | 0.9300 |
C5—H5 | 0.9300 | C46—C47 | 1.378 (5) |
C6—H6 | 0.9300 | C46—H46 | 0.9300 |
C7—C8 | 1.400 (4) | C47—C48 | 1.382 (4) |
C7—C12 | 1.407 (4) | C47—H47 | 0.9300 |
C8—C9 | 1.397 (4) | C48—H48 | 0.9300 |
C8—H8 | 0.9300 | C49—C50 | 1.464 (5) |
C9—C10 | 1.382 (5) | C50—H50A | 0.9600 |
C9—H9 | 0.9300 | C50—H50B | 0.9600 |
C10—C11 | 1.395 (5) | C50—H50C | 0.9600 |
C10—H10 | 0.9300 | C51—C52 | 1.453 (5) |
C11—C12 | 1.370 (5) | C52—H52A | 0.9600 |
C11—H11 | 0.9300 | C52—H52B | 0.9600 |
C12—H12 | 0.9300 | C52—H52C | 0.9600 |
C13—C18 | 1.388 (4) | C53—C54 | 1.447 (6) |
C13—C14 | 1.397 (4) | C54—H54A | 0.9600 |
C14—C15 | 1.377 (5) | C54—H54B | 0.9600 |
C14—H14 | 0.9300 | C54—H54C | 0.9600 |
C15—C16 | 1.383 (5) | C55—C56 | 1.422 (6) |
C15—H15 | 0.9300 | C56—H56A | 0.9600 |
C16—C17 | 1.381 (5) | C56—H56B | 0.9600 |
C16—H16 | 0.9300 | C56—H56C | 0.9600 |
C17—C18 | 1.388 (5) | C57—C58 | 1.445 (5) |
C17—H17 | 0.9300 | C58—H58A | 0.9600 |
C18—H18 | 0.9300 | C58—H58B | 0.9600 |
C19—C20 | 1.511 (4) | C58—H58C | 0.9600 |
C19—H19A | 0.9700 | | |
| | | |
N2i—Ag1—P1 | 137.72 (7) | C21—C20—C19 | 122.6 (3) |
N2i—Ag1—N5 | 91.09 (9) | C22—C21—C20 | 118.9 (3) |
P1—Ag1—N5 | 123.89 (7) | C22—C21—H21 | 120.5 |
N2i—Ag1—N4 | 88.78 (9) | C20—C21—H21 | 120.5 |
P1—Ag1—N4 | 113.03 (6) | N4—C22—C21 | 123.9 (3) |
N5—Ag1—N4 | 87.89 (9) | N4—C22—H22 | 118.1 |
N6—Ag2—P2 | 114.45 (7) | C21—C22—H22 | 118.1 |
N6—Ag2—P3ii | 109.33 (7) | N4—C23—C24 | 123.2 (3) |
P2—Ag2—P3ii | 136.21 (3) | N4—C23—H23 | 118.4 |
N6—Ag2—Ag2ii | 110.36 (7) | C24—C23—H23 | 118.4 |
P2—Ag2—Ag2ii | 87.66 (2) | C20—C24—C23 | 120.2 (3) |
P3ii—Ag2—Ag2ii | 76.18 (2) | C20—C24—H24 | 119.9 |
C1—N1—P1 | 118.9 (2) | C23—C24—H24 | 119.9 |
C1—N1—H1 | 113 (3) | C30—C25—C26 | 119.3 (3) |
P1—N1—H1 | 115 (3) | C30—C25—P2 | 117.7 (2) |
C4—N2—C5 | 117.2 (3) | C26—C25—P2 | 122.7 (2) |
C4—N2—Ag1i | 121.6 (2) | C27—C26—C25 | 120.2 (3) |
C5—N2—Ag1i | 121.1 (2) | C27—C26—H26 | 119.9 |
C19—N3—P2 | 120.53 (19) | C25—C26—H26 | 119.9 |
C19—N3—P3 | 123.8 (2) | C26—C27—C28 | 120.3 (3) |
P2—N3—P3 | 115.08 (14) | C26—C27—H27 | 119.8 |
C23—N4—C22 | 116.7 (3) | C28—C27—H27 | 119.8 |
C23—N4—Ag1 | 118.6 (2) | C29—C28—C27 | 119.9 (3) |
C22—N4—Ag1 | 123.5 (2) | C29—C28—H28 | 120.0 |
C49—N5—Ag1 | 171.6 (3) | C27—C28—H28 | 120.0 |
C51—N6—Ag2 | 177.9 (3) | C28—C29—C30 | 120.2 (3) |
N1—P1—C7 | 100.97 (14) | C28—C29—H29 | 119.9 |
N1—P1—C13 | 108.00 (14) | C30—C29—H29 | 119.9 |
C7—P1—C13 | 106.34 (14) | C25—C30—C29 | 120.1 (3) |
N1—P1—Ag1 | 116.89 (10) | C25—C30—H30 | 120.0 |
C7—P1—Ag1 | 109.48 (10) | C29—C30—H30 | 120.0 |
C13—P1—Ag1 | 113.92 (11) | C32—C31—C36 | 119.9 (3) |
N3—P2—C31 | 107.18 (14) | C32—C31—P2 | 122.1 (2) |
N3—P2—C25 | 104.23 (13) | C36—C31—P2 | 117.7 (2) |
C31—P2—C25 | 103.23 (14) | C33—C32—C31 | 119.3 (3) |
N3—P2—Ag2 | 111.85 (8) | C33—C32—H32 | 120.4 |
C31—P2—Ag2 | 111.73 (10) | C31—C32—H32 | 120.4 |
C25—P2—Ag2 | 117.71 (10) | C34—C33—C32 | 121.0 (3) |
N3—P3—C43 | 107.69 (13) | C34—C33—H33 | 119.5 |
N3—P3—C37 | 104.60 (13) | C32—C33—H33 | 119.5 |
C43—P3—C37 | 103.12 (14) | C33—C34—C35 | 120.2 (3) |
N3—P3—Ag2ii | 114.26 (9) | C33—C34—H34 | 119.9 |
C43—P3—Ag2ii | 115.57 (10) | C35—C34—H34 | 119.9 |
C37—P3—Ag2ii | 110.48 (10) | C34—C35—C36 | 120.3 (3) |
F4—B1—F1 | 111.3 (3) | C34—C35—H35 | 119.9 |
F4—B1—F2 | 109.5 (3) | C36—C35—H35 | 119.9 |
F1—B1—F2 | 109.9 (3) | C35—C36—C31 | 119.4 (3) |
F4—B1—F3 | 107.8 (3) | C35—C36—H36 | 120.3 |
F1—B1—F3 | 109.0 (3) | C31—C36—H36 | 120.3 |
F2—B1—F3 | 109.2 (3) | C42—C37—C38 | 119.2 (3) |
F5—B2—F6 | 110.8 (3) | C42—C37—P3 | 122.9 (2) |
F5—B2—F7 | 109.6 (3) | C38—C37—P3 | 117.9 (2) |
F6—B2—F7 | 109.2 (3) | C39—C38—C37 | 120.2 (3) |
F5—B2—F8 | 108.9 (3) | C39—C38—H38 | 119.9 |
F6—B2—F8 | 109.4 (3) | C37—C38—H38 | 119.9 |
F7—B2—F8 | 108.9 (3) | C38—C39—C40 | 120.3 (3) |
N1—C1—C2 | 113.0 (3) | C38—C39—H39 | 119.8 |
N1—C1—H1A | 109.0 | C40—C39—H39 | 119.8 |
C2—C1—H1A | 109.0 | C39—C40—C41 | 119.7 (3) |
N1—C1—H1B | 109.0 | C39—C40—H40 | 120.2 |
C2—C1—H1B | 109.0 | C41—C40—H40 | 120.2 |
H1A—C1—H1B | 107.8 | C42—C41—C40 | 120.5 (3) |
C6—C2—C3 | 117.6 (3) | C42—C41—H41 | 119.7 |
C6—C2—C1 | 121.4 (3) | C40—C41—H41 | 119.7 |
C3—C2—C1 | 120.9 (3) | C41—C42—C37 | 120.0 (3) |
C4—C3—C2 | 118.8 (3) | C41—C42—H42 | 120.0 |
C4—C3—H3 | 120.6 | C37—C42—H42 | 120.0 |
C2—C3—H3 | 120.6 | C44—C43—C48 | 118.7 (3) |
N2—C4—C3 | 123.6 (3) | C44—C43—P3 | 123.8 (2) |
N2—C4—H4 | 118.2 | C48—C43—P3 | 117.5 (2) |
C3—C4—H4 | 118.2 | C45—C44—C43 | 120.8 (3) |
N2—C5—C6 | 122.9 (3) | C45—C44—H44 | 119.6 |
N2—C5—H5 | 118.6 | C43—C44—H44 | 119.6 |
C6—C5—H5 | 118.6 | C46—C45—C44 | 119.7 (3) |
C5—C6—C2 | 119.8 (3) | C46—C45—H45 | 120.1 |
C5—C6—H6 | 120.1 | C44—C45—H45 | 120.1 |
C2—C6—H6 | 120.1 | C45—C46—C47 | 120.2 (3) |
C8—C7—C12 | 118.6 (3) | C45—C46—H46 | 119.9 |
C8—C7—P1 | 124.3 (2) | C47—C46—H46 | 119.9 |
C12—C7—P1 | 116.9 (2) | C46—C47—C48 | 120.6 (3) |
C9—C8—C7 | 119.9 (3) | C46—C47—H47 | 119.7 |
C9—C8—H8 | 120.1 | C48—C47—H47 | 119.7 |
C7—C8—H8 | 120.1 | C47—C48—C43 | 120.1 (3) |
C10—C9—C8 | 120.5 (3) | C47—C48—H48 | 120.0 |
C10—C9—H9 | 119.7 | C43—C48—H48 | 120.0 |
C8—C9—H9 | 119.7 | N5—C49—C50 | 179.1 (4) |
C9—C10—C11 | 119.9 (3) | C49—C50—H50A | 109.5 |
C9—C10—H10 | 120.1 | C49—C50—H50B | 109.5 |
C11—C10—H10 | 120.1 | H50A—C50—H50B | 109.5 |
C12—C11—C10 | 120.0 (3) | C49—C50—H50C | 109.5 |
C12—C11—H11 | 120.0 | H50A—C50—H50C | 109.5 |
C10—C11—H11 | 120.0 | H50B—C50—H50C | 109.5 |
C11—C12—C7 | 121.2 (3) | N6—C51—C52 | 179.0 (4) |
C11—C12—H12 | 119.4 | C51—C52—H52A | 109.5 |
C7—C12—H12 | 119.4 | C51—C52—H52B | 109.5 |
C18—C13—C14 | 118.0 (3) | H52A—C52—H52B | 109.5 |
C18—C13—P1 | 119.0 (2) | C51—C52—H52C | 109.5 |
C14—C13—P1 | 122.9 (2) | H52A—C52—H52C | 109.5 |
C15—C14—C13 | 121.2 (3) | H52B—C52—H52C | 109.5 |
C15—C14—H14 | 119.4 | N7—C53—C54 | 178.2 (5) |
C13—C14—H14 | 119.4 | C53—C54—H54A | 109.5 |
C14—C15—C16 | 120.2 (3) | C53—C54—H54B | 109.5 |
C14—C15—H15 | 119.9 | H54A—C54—H54B | 109.5 |
C16—C15—H15 | 119.9 | C53—C54—H54C | 109.5 |
C17—C16—C15 | 119.5 (3) | H54A—C54—H54C | 109.5 |
C17—C16—H16 | 120.3 | H54B—C54—H54C | 109.5 |
C15—C16—H16 | 120.3 | N8—C55—C56 | 179.7 (7) |
C16—C17—C18 | 120.3 (3) | C55—C56—H56A | 109.5 |
C16—C17—H17 | 119.9 | C55—C56—H56B | 109.5 |
C18—C17—H17 | 119.9 | H56A—C56—H56B | 109.5 |
C17—C18—C13 | 120.9 (3) | C55—C56—H56C | 109.5 |
C17—C18—H18 | 119.6 | H56A—C56—H56C | 109.5 |
C13—C18—H18 | 119.6 | H56B—C56—H56C | 109.5 |
N3—C19—C20 | 115.6 (2) | N9—C57—C58 | 178.8 (4) |
N3—C19—H19A | 108.4 | C57—C58—H58A | 109.5 |
C20—C19—H19A | 108.4 | C57—C58—H58B | 109.5 |
N3—C19—H19B | 108.4 | H58A—C58—H58B | 109.5 |
C20—C19—H19B | 108.4 | C57—C58—H58C | 109.5 |
H19A—C19—H19B | 107.4 | H58A—C58—H58C | 109.5 |
C24—C20—C21 | 116.9 (3) | H58B—C58—H58C | 109.5 |
C24—C20—C19 | 120.4 (3) | | |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F7iii | 0.81 (2) | 2.54 (3) | 3.136 (3) | 131 (3) |
N1—H1···F8iii | 0.81 (2) | 2.38 (2) | 3.186 (3) | 173 (3) |
Symmetry code: (iii) −x+1, −y+1, −z. |
Experimental details
Crystal data |
Chemical formula | [Ag4(C18H17N2P)2(C30H26N2P2)2(C2H3N)4](BF4)4·3C2H3N |
Mr | 2726.80 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 110 |
a, b, c (Å) | 13.2233 (8), 14.6535 (11), 16.7275 (12) |
α, β, γ (°) | 97.085 (2), 104.690 (2), 101.691 (3) |
V (Å3) | 3017.6 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.14 × 0.08 × 0.06 |
|
Data collection |
Diffractometer | Bruker X8 APEX CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) SADABS |
Tmin, Tmax | 0.899, 0.956 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32743, 12262, 8973 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.626 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.081, 1.02 |
No. of reflections | 12262 |
No. of parameters | 748 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.56, −0.57 |
Selected geometric parameters (Å, º) topAg1—N2i | 2.297 (3) | Ag2—N6 | 2.309 (3) |
Ag1—P1 | 2.3540 (8) | Ag2—P2 | 2.4387 (8) |
Ag1—N5 | 2.403 (3) | Ag2—P3ii | 2.4496 (8) |
Ag1—N4 | 2.405 (3) | Ag2—Ag2ii | 3.0363 (5) |
| | | |
N2i—Ag1—P1 | 137.72 (7) | N6—Ag2—P2 | 114.45 (7) |
N2i—Ag1—N5 | 91.09 (9) | N6—Ag2—P3ii | 109.33 (7) |
P1—Ag1—N5 | 123.89 (7) | P2—Ag2—P3ii | 136.21 (3) |
N2i—Ag1—N4 | 88.78 (9) | N6—Ag2—Ag2ii | 110.36 (7) |
P1—Ag1—N4 | 113.03 (6) | P2—Ag2—Ag2ii | 87.66 (2) |
N5—Ag1—N4 | 87.89 (9) | P3ii—Ag2—Ag2ii | 76.18 (2) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F7iii | 0.810 (18) | 2.54 (3) | 3.136 (3) | 131 (3) |
N1—H1···F8iii | 0.810 (18) | 2.381 (19) | 3.186 (3) | 173 (3) |
Symmetry code: (iii) −x+1, −y+1, −z. |
Silver-based coordination polymers have received a great deal of attention in recent years, owing particularly to the abundant chemistry that these compounds possess (Batten et al., 1999; Muthu et al.,2002; Reger et al., 2003). Silver(I) phosphine and pyridine complexes have been constructed that demonstrate a wealth of novel electronic, medicinal and structural properties (Blake et al., 1999; Khlobystov et al., 2001). A large number of these polymers constructed of pyridyl donors and other conjugated systems have exhibited luminescent properties (Tong et al., 2002; Zhang et al., 2002; Zheng et al., 2001), and these compounds are of interest for possible use in light emitting devices (LEDs). Other studies of pyridyl-substituted phosphine–silver complexes have demonstrated the variability of the silver coordination environment (Klausmeyer et al., 2004, and references therein; Seward et al., 2003).
Pyridyl-substituted phosphines are an interesting species in that they display the relatively harder and softer donors of the pyridyl N atom and the tertiary phosphine group, respectively, in a single molecule. By adding an amine linkage between these two moeties, it is possible to expand further the chemistry of an already intriguing ligand by imparting such features as pH dependence on the coordination chemistry and luminescence (Dollberg & Turro, 2001) and added coordination ability of the ligand by having the extra donor.
We have synthesized two new pyridyl-substituted aminophosphine ligands that, when coordinated to silver tetrafluoroborate, self-assemble into a polymeric structure of strictly repeating units. Ph2P(4-NHCH2C5H4N), (I), and (Ph2P)2(4-NCH2C5H4N), (II), have been obtained by the reaction of 4-methylaminopyridine with one and two equivalents of chlorodiphenylphosphine, respectively, as shown in the scheme. Compound (I) is obtained in a relatively pure form by the slow addition of chlorodiphenylphosphine to a chilled solution of 4-aminomethylpyridine and triethylamine. Rapid addition or an excess of phosphine causes a mixture of (I) and (II) to result, while addition of a full second equivalent causes only the disubstituted ligand, (II), to be formed.
Reaction of the (I)–(II) mixture that results from the rapid combination of ligand components with silver(I) tetrafluoroborate yields the coordination polymer (III), shown in Fig. 1. The polymeric backbone of (III) is perpetuated by the repetition of the two distinct rings shown in Fig. 2; one consists of a head-to-tail-type coordination of (I) around the distorted tetrahedron of atom Ag1, and the other, smaller, ring is constructed by the head-to-head η2,µ2-action of the disubstituted ligand (II) coordinated to the trigonal atom Ag2. The rings alternate in position in the polymer and are joined by the outstretched pyridyl group of ligand (II), which completes the coordination sphere of atom Ag1.
The molecular structure of the unique portion of (III) is shown in Fig. 3. Steric distortions around the metal centers are immediately apparent. Angles around the distorted tetrahedral Ag1 atom range from the acute 87.89 (9)° angle that involves the coordinated acetonitrile group and the pyridyl extension of the disubstituted ligand, to the 137.72 (7)° separation of atom P1 and its symmetry-equivalent N-donor, N2i [symmetry code: (i) ?]. Also of interest are the lengths of the bonds to atom Ag1. The Ag1—N2i distance is already slightly elongated at 2.297 (3) Å, while the bonds to atoms N4 and N5 are exceptionally long at 2.405 (3) and 2.403 (3) Å, respectively (Muthu et al., 2001). The Ag1—P1 bond is typical at 2.3540 (8) Å (Carnalli et al., 1988). Atom Ag2 is in a trigonal environment with respect to the two phosphorus and acetonitrile N-atom donors. Atom Ag2 deviates from the N6/P2/P3ii plane [symmetry code: (ii) ?] by only 0.0156 (9) Å. The N6—Ag2—P2 and N6—Ag2—P3ii angles are 114.45 (7) and 109.33 (7)°, respectively, and the P2—Ag2—P3ii angle is 136.21 (3)°. It is also seen that atom P3 holds a symmetry-equivalent Ag atom in place, close enough to form a substantial silver–silver interaction with atom Ag2, with the separation at a close 3.0363 (5) Å (Chen et al., 2002). This interaction extends nearly perpendicular to the plane formed by the three ligands surrounding atom Ag2. The Ag2—N6 bond is again lengthy at 2.309 (3) Å, while the Ag2—P2 and Ag2—P3ii bonds are slightly extended at 2.4387 (8) and 2.4496 (8) Å. The BF4− anions are dispersed between the polymer strands, half being held in place by hydrogen-bonding with atom N1. The N1—H1 vector appears to bisect the F7—B2—F8 angle equally, with D—H···A distances of 3.136 (3) and 3.183 (6) Å for N1—H1···F7 and N1—H1···F8, respectively.