research papers
Here, the first accurate study is presented of the room-temperature and 100 K structures of one of the first organic spin liquids, κ-(BEDT-TTF)2Ag2(CN)3. It is shown that the monoclinic structure determined previously is only the average one. It is shown that the exact structure presents triclinic symmetry with two non-equivalent dimers in the unit cell. But surprisingly this does not lead to a sizeable charge disproportionation between dimers. The difference from the analogue compound κ-(BEDT-TTF)2Cu2(CN)3 which also presents a spin liquid phase is discussed in detail. The data provided here show the importance of the anionic layer and in particular the transition metal position in the process of symmetry breaking. The possible impact of the symmetry breaking, albeit weak, on the spin-liquid mechanism and the influence of various disorders on the physical properties of this system is also discussed.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520620005545/lo5067sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520620005545/lo5067100Ksup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520620005545/lo5067300Ksup3.hkl |
Computing details top
For both structures, data collection: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015); cell refinement: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015); data reduction: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015).
(100K) top
Crystal data top
C3Ag2N3·2(C10H8S8) | V = 1715.40 (6) Å3 |
Mr = 1063.17 | Z = 2 |
Triclinic, P1 | F(000) = 1050 |
Hall symbol: -P 1 | Dx = 2.058 Mg m−3 |
a = 15.0062 (3) Å | Synchrotron radiation, λ = 0.6717 Å |
b = 8.5820 (1) Å | Cell parameters from 29184 reflections |
c = 13.3243 (3) Å | θ = 2.6–32.3° |
α = 89.984 (2)° | µ = 1.79 mm−1 |
β = 91.447 (2)° | T = 100 K |
γ = 90.002 (1)° | Plate |
Data collection top
Xcalibur, Atlas diffractometer | 69664 independent reflections |
Radiation source: synchrotron | 57334 reflections with I > 3σ(I) |
Synchrotron monochromator | Rint = 0.041 |
Detector resolution: 10.2930 pixels mm-1 | θmax = 32.4°, θmin = 1.4° |
ω and φ scans | h = −23→23 |
Absorption correction: multi-scan CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | k = −12→13 |
Tmin = 0.933, Tmax = 1 | l = −20→20 |
69664 measured reflections |
Refinement top
Refinement on F | 16 constraints |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.075 | Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2) |
S = 2.54 | (Δ/σ)max = 0.019 |
69664 reflections | Δρmax = 1.18 e Å−3 |
397 parameters | Δρmin = −1.00 e Å−3 |
2 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ag1 | 0.993551 (5) | 0.259795 (9) | 0.124440 (6) | 0.03747 (3) | |
Ag2 | 0.006498 (5) | 0.759854 (9) | 0.375487 (6) | 0.03747 (3) | |
S1 | 0.541346 (14) | 0.02129 (3) | 0.245779 (13) | 0.02309 (5) | |
S2 | 0.375102 (13) | 0.76190 (2) | 0.377224 (14) | 0.02146 (5) | |
S3 | 0.624892 (13) | 0.26180 (2) | 0.122736 (13) | 0.02144 (5) | |
S4 | 0.462537 (13) | 0.26196 (3) | −0.031747 (14) | 0.02274 (5) | |
S5 | 0.458600 (14) | 0.52119 (3) | 0.254261 (14) | 0.02333 (5) | |
S6 | 0.537499 (13) | 0.76210 (3) | 0.531783 (14) | 0.02277 (5) | |
S7 | 0.367178 (14) | 0.03061 (3) | 0.088194 (15) | 0.02664 (6) | |
S8 | 0.632704 (14) | 0.53058 (3) | 0.411819 (15) | 0.02680 (6) | |
S9 | 0.788701 (13) | 0.29184 (3) | 0.246269 (14) | 0.02435 (6) | |
S10 | 0.211349 (13) | 0.79184 (3) | 0.253675 (15) | 0.02438 (6) | |
S11 | 0.689325 (17) | 0.00036 (3) | 0.394945 (17) | 0.03341 (7) | |
S12 | 0.310710 (17) | 0.50030 (3) | 0.105015 (17) | 0.03346 (7) | |
S13 | 0.685986 (18) | 0.83088 (3) | 0.67057 (2) | 0.03770 (8) | |
S14 | 0.314075 (18) | 0.33067 (3) | −0.17056 (2) | 0.03746 (8) | |
S15 | 0.197201 (17) | 0.05629 (4) | −0.02851 (3) | 0.04526 (9) | |
S16 | 0.802774 (17) | 0.55618 (4) | 0.52817 (3) | 0.04500 (9) | |
N1 | 1.01943 (7) | −0.06300 (15) | 0.22381 (8) | 0.0495 (4) | |
C2 | 1.01112 (7) | 0.03775 (15) | 0.18797 (8) | 0.0370 (3) | |
C3 | −0.01017 (7) | 0.53882 (16) | 0.31278 (8) | 0.0383 (3) | |
N4 | −0.01857 (7) | 0.43768 (15) | 0.27615 (8) | 0.0489 (3) | |
C5 | 0.99673 (7) | 0.44534 (12) | 0.02480 (7) | 0.0395 (3) | 0.5 |
N5 | 0.99673 (7) | 0.44534 (12) | 0.02480 (7) | 0.0395 (3) | 0.5 |
C6 | 0.00318 (7) | 0.94562 (12) | 0.47516 (7) | 0.0398 (3) | 0.5 |
N6 | 0.00318 (7) | 0.94562 (12) | 0.47516 (7) | 0.0398 (3) | 0.5 |
C7 | 0.53685 (5) | 0.64123 (10) | 0.42677 (5) | 0.0213 (2) | |
C8 | 0.46324 (5) | 0.14130 (10) | 0.07325 (5) | 0.0217 (2) | |
C9 | 0.35216 (6) | 0.22218 (10) | −0.06762 (6) | 0.0244 (2) | |
C10 | 0.68609 (5) | 0.19792 (9) | 0.22844 (5) | 0.0209 (2) | |
C11 | 0.46586 (5) | 0.63928 (9) | 0.36033 (5) | 0.02018 (19) | |
C12 | 0.31387 (5) | 0.69827 (9) | 0.27154 (5) | 0.02067 (19) | |
C13 | 0.64772 (6) | 0.72215 (10) | 0.56726 (6) | 0.0246 (2) | |
C14 | 0.64713 (6) | 0.08701 (10) | 0.28487 (6) | 0.0241 (2) | |
C15 | 0.53421 (5) | 0.13910 (9) | 0.13932 (5) | 0.02044 (19) | |
C16 | 0.35297 (6) | 0.58630 (10) | 0.21524 (6) | 0.0235 (2) | |
C17 | 0.30825 (6) | 0.11525 (11) | −0.01269 (6) | 0.0281 (2) | |
C18 | 0.69164 (6) | 0.61620 (11) | 0.51280 (6) | 0.0278 (2) | |
C19 | 0.16067 (6) | 0.67483 (11) | 0.15470 (6) | 0.0267 (2) | |
C20 | 0.77597 (6) | 0.13794 (11) | 0.42900 (6) | 0.0266 (2) | |
C21 | 0.83927 (6) | 0.17423 (11) | 0.34530 (6) | 0.0264 (2) | |
C22 | 0.20294 (8) | 0.25524 (14) | −0.19138 (10) | 0.0495 (4) | |
C23 | 0.22429 (6) | 0.63805 (11) | 0.07104 (6) | 0.0265 (2) | |
C24 | 0.15399 (7) | 0.22372 (14) | −0.09485 (10) | 0.0496 (4) | |
C25 | 0.84628 (7) | 0.72421 (14) | 0.59486 (10) | 0.0483 (4) | |
C26 | 0.79656 (9) | 0.75573 (14) | 0.69167 (10) | 0.0510 (4) | |
H1c19 | 0.138798 | 0.579417 | 0.182522 | 0.032* | |
H2c19 | 0.109245 | 0.727835 | 0.127272 | 0.032* | |
H1c20 | 0.749455 | 0.23282 | 0.452002 | 0.032* | |
H2c20 | 0.809217 | 0.099724 | 0.486382 | 0.032* | |
H1c21 | 0.860877 | 0.078678 | 0.317442 | 0.0316* | |
H2c21 | 0.890935 | 0.226714 | 0.372547 | 0.0316* | |
H1c22 | 0.168957 | 0.326885 | −0.232329 | 0.0594* | |
H2c22 | 0.205628 | 0.161157 | −0.230144 | 0.0594* | |
H1c23 | 0.250901 | 0.732814 | 0.047939 | 0.0318* | |
H2c23 | 0.191119 | 0.600185 | 0.013527 | 0.0318* | |
H1c24 | 0.091714 | 0.208684 | −0.110086 | 0.0596* | |
H2c24 | 0.158129 | 0.313614 | −0.052122 | 0.0596* | |
H1c25 | 0.908448 | 0.708744 | 0.610493 | 0.0579* | |
H2c25 | 0.842285 | 0.814135 | 0.552116 | 0.0579* | |
H1c26 | 0.830395 | 0.827187 | 0.732892 | 0.0612* | |
H2c26 | 0.793751 | 0.661611 | 0.730415 | 0.0612* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.03226 (5) | 0.03636 (6) | 0.04348 (5) | −0.00190 (4) | −0.00506 (3) | 0.00226 (4) |
Ag2 | 0.03222 (5) | 0.03643 (6) | 0.04344 (5) | 0.00124 (4) | −0.00512 (3) | −0.00289 (4) |
S1 | 0.02062 (9) | 0.02719 (11) | 0.02160 (8) | −0.00686 (8) | 0.00315 (6) | 0.00193 (7) |
S2 | 0.01732 (9) | 0.02526 (10) | 0.02177 (8) | 0.00431 (7) | −0.00026 (6) | −0.00427 (7) |
S3 | 0.01719 (9) | 0.02548 (10) | 0.02163 (8) | −0.00511 (8) | −0.00011 (6) | 0.00389 (7) |
S4 | 0.01687 (9) | 0.02642 (11) | 0.02482 (8) | −0.00312 (8) | −0.00155 (6) | 0.00125 (7) |
S5 | 0.02102 (9) | 0.02757 (11) | 0.02153 (8) | 0.00596 (8) | 0.00327 (6) | −0.00194 (7) |
S6 | 0.01687 (9) | 0.02657 (11) | 0.02476 (8) | 0.00258 (8) | −0.00145 (6) | −0.00138 (7) |
S7 | 0.01977 (10) | 0.03528 (12) | 0.02507 (8) | −0.00969 (8) | 0.00441 (7) | −0.00253 (8) |
S8 | 0.01966 (10) | 0.03576 (12) | 0.02519 (8) | 0.00900 (8) | 0.00432 (7) | 0.00251 (8) |
S9 | 0.01661 (9) | 0.02947 (12) | 0.02684 (8) | −0.00459 (8) | −0.00177 (6) | 0.00679 (7) |
S10 | 0.01666 (9) | 0.02962 (12) | 0.02676 (8) | 0.00359 (8) | −0.00166 (6) | −0.00678 (7) |
S11 | 0.03051 (12) | 0.03848 (13) | 0.03095 (10) | −0.00953 (10) | −0.00469 (8) | 0.01553 (9) |
S12 | 0.03072 (12) | 0.03850 (13) | 0.03089 (10) | 0.00840 (10) | −0.00479 (8) | −0.01556 (9) |
S13 | 0.03233 (13) | 0.03400 (13) | 0.04580 (13) | −0.00054 (10) | −0.01847 (10) | −0.00333 (10) |
S14 | 0.03156 (13) | 0.03444 (13) | 0.04542 (13) | −0.00041 (10) | −0.01785 (10) | 0.00331 (10) |
S15 | 0.01852 (11) | 0.04910 (17) | 0.06787 (18) | −0.00929 (11) | −0.00466 (11) | −0.00309 (13) |
S16 | 0.01820 (11) | 0.04893 (17) | 0.06759 (18) | 0.00859 (11) | −0.00439 (11) | 0.00299 (13) |
N1 | 0.0313 (5) | 0.0683 (8) | 0.0489 (5) | 0.0041 (5) | −0.0016 (4) | −0.0115 (5) |
C2 | 0.0203 (4) | 0.0531 (7) | 0.0378 (5) | −0.0040 (4) | 0.0040 (3) | −0.0107 (4) |
C3 | 0.0183 (4) | 0.0576 (7) | 0.0393 (5) | 0.0052 (4) | 0.0042 (3) | 0.0122 (5) |
N4 | 0.0301 (5) | 0.0683 (7) | 0.0481 (5) | −0.0031 (5) | 0.0010 (4) | 0.0144 (5) |
C5 | 0.0359 (5) | 0.0484 (6) | 0.0339 (4) | −0.0020 (4) | −0.0032 (3) | 0.0016 (4) |
N5 | 0.0359 (5) | 0.0484 (6) | 0.0339 (4) | −0.0020 (4) | −0.0032 (3) | 0.0016 (4) |
C6 | 0.0354 (5) | 0.0507 (6) | 0.0331 (4) | 0.0000 (4) | −0.0025 (3) | −0.0015 (4) |
N6 | 0.0354 (5) | 0.0507 (6) | 0.0331 (4) | 0.0000 (4) | −0.0025 (3) | −0.0015 (4) |
C7 | 0.0177 (3) | 0.0246 (4) | 0.0218 (3) | 0.0036 (3) | 0.0036 (2) | 0.0026 (3) |
C8 | 0.0176 (3) | 0.0261 (4) | 0.0215 (3) | −0.0050 (3) | 0.0040 (2) | −0.0027 (3) |
C9 | 0.0187 (4) | 0.0250 (4) | 0.0294 (3) | 0.0008 (3) | −0.0050 (3) | −0.0047 (3) |
C10 | 0.0164 (3) | 0.0246 (4) | 0.0215 (3) | −0.0028 (3) | 0.0005 (2) | 0.0028 (3) |
C11 | 0.0172 (3) | 0.0236 (4) | 0.0199 (3) | 0.0030 (3) | 0.0035 (2) | 0.0002 (2) |
C12 | 0.0162 (3) | 0.0246 (4) | 0.0213 (3) | 0.0028 (3) | 0.0005 (2) | −0.0026 (3) |
C13 | 0.0186 (4) | 0.0255 (4) | 0.0293 (3) | −0.0007 (3) | −0.0044 (3) | 0.0055 (3) |
C14 | 0.0207 (4) | 0.0285 (4) | 0.0231 (3) | −0.0047 (3) | 0.0008 (3) | 0.0037 (3) |
C15 | 0.0175 (3) | 0.0241 (4) | 0.0199 (3) | −0.0039 (3) | 0.0034 (2) | −0.0006 (2) |
C16 | 0.0201 (4) | 0.0276 (4) | 0.0228 (3) | 0.0035 (3) | 0.0007 (2) | −0.0049 (3) |
C17 | 0.0160 (3) | 0.0355 (5) | 0.0330 (4) | −0.0037 (3) | 0.0003 (3) | −0.0074 (3) |
C18 | 0.0166 (4) | 0.0340 (5) | 0.0327 (4) | 0.0020 (3) | 0.0003 (3) | 0.0064 (3) |
C19 | 0.0182 (4) | 0.0324 (5) | 0.0295 (3) | −0.0035 (3) | 0.0021 (3) | −0.0061 (3) |
C20 | 0.0245 (4) | 0.0323 (5) | 0.0232 (3) | −0.0001 (3) | 0.0007 (3) | 0.0016 (3) |
C21 | 0.0180 (4) | 0.0318 (5) | 0.0292 (3) | 0.0031 (3) | 0.0014 (3) | 0.0054 (3) |
C22 | 0.0399 (6) | 0.0364 (6) | 0.0704 (8) | 0.0008 (5) | −0.0322 (6) | −0.0070 (5) |
C23 | 0.0229 (4) | 0.0329 (5) | 0.0237 (3) | −0.0008 (3) | −0.0001 (3) | −0.0029 (3) |
C24 | 0.0219 (5) | 0.0448 (6) | 0.0816 (8) | 0.0076 (4) | −0.0119 (5) | −0.0259 (6) |
C25 | 0.0219 (5) | 0.0416 (6) | 0.0808 (8) | −0.0077 (4) | −0.0100 (5) | 0.0220 (6) |
C26 | 0.0422 (7) | 0.0378 (6) | 0.0713 (8) | −0.0034 (5) | −0.0339 (6) | 0.0078 (5) |
Geometric parameters (Å, º) top
Ag1—C2 | 2.0988 (13) | S10—C12 | 1.7464 (8) |
Ag1—C5 | 2.0742 (10) | S11—C14 | 1.7486 (8) |
Ag2—C3 | 2.0856 (13) | S12—C16 | 1.7485 (8) |
Ag2—C6 | 2.0767 (10) | S13—C13 | 1.7482 (9) |
S1—C14 | 1.7515 (9) | S14—C9 | 1.7419 (9) |
S1—C15 | 1.7428 (8) | S15—C17 | 1.7491 (9) |
S2—C11 | 1.7403 (8) | S16—C18 | 1.7525 (9) |
S2—C12 | 1.7494 (7) | N1—C2 | 0.9940 (18) |
S3—C10 | 1.7498 (8) | C3—N4 | 1.0022 (18) |
S3—C15 | 1.7391 (8) | C5—C5i | 1.1531 (14) |
S4—C8 | 1.7401 (8) | C6—C6ii | 1.1497 (14) |
S4—C9 | 1.7460 (9) | C7—C11 | 1.3680 (10) |
S5—C11 | 1.7404 (8) | C8—C15 | 1.3646 (10) |
S5—C16 | 1.7474 (8) | C9—C17 | 1.3550 (12) |
S6—C7 | 1.7419 (8) | C10—C14 | 1.3546 (11) |
S6—C13 | 1.7427 (9) | C12—C16 | 1.3613 (11) |
S7—C8 | 1.7420 (8) | C13—C18 | 1.3462 (12) |
S7—C17 | 1.7482 (9) | C19—C23 | 1.5191 (12) |
S8—C7 | 1.7393 (8) | C20—C21 | 1.5154 (12) |
S8—C18 | 1.7529 (9) | C22—C24 | 1.5213 (19) |
S9—C10 | 1.7490 (8) | C25—C26 | 1.5304 (19) |
C2—Ag1—C5 | 161.84 (4) | S9—C10—C14 | 129.73 (6) |
C3—Ag2—C6 | 161.84 (4) | S2—C11—S5 | 115.10 (4) |
C14—S1—C15 | 95.27 (4) | S2—C11—C7 | 120.53 (6) |
C11—S2—C12 | 95.96 (4) | S5—C11—C7 | 124.36 (6) |
C10—S3—C15 | 96.00 (4) | S2—C12—S10 | 114.15 (4) |
C8—S4—C9 | 95.18 (4) | S2—C12—C16 | 116.05 (6) |
C11—S5—C16 | 95.34 (4) | S10—C12—C16 | 129.79 (6) |
C7—S6—C13 | 94.97 (4) | S6—C13—S13 | 113.52 (5) |
C8—S7—C17 | 95.14 (4) | S6—C13—C18 | 117.45 (6) |
C7—S8—C18 | 94.92 (4) | S13—C13—C18 | 129.02 (7) |
Ag1—C2—N1 | 175.07 (11) | S1—C14—S11 | 114.76 (5) |
Ag2—C3—N4 | 174.46 (11) | S1—C14—C10 | 117.50 (6) |
Ag1—C5—C5i | 174.20 (9) | S11—C14—C10 | 127.74 (6) |
Ag2—C6—C6ii | 174.46 (9) | S1—C15—S3 | 114.98 (4) |
S6—C7—S8 | 115.43 (4) | S1—C15—C8 | 124.33 (6) |
S6—C7—C11 | 121.05 (6) | S3—C15—C8 | 120.68 (6) |
S8—C7—C11 | 123.50 (6) | S5—C16—S12 | 114.96 (5) |
S4—C8—S7 | 115.34 (4) | S5—C16—C12 | 117.52 (6) |
S4—C8—C15 | 121.04 (6) | S12—C16—C12 | 127.50 (6) |
S7—C8—C15 | 123.60 (6) | S7—C17—S15 | 115.75 (5) |
S4—C9—S14 | 113.65 (5) | S7—C17—C9 | 116.94 (6) |
S4—C9—C17 | 117.09 (6) | S15—C17—C9 | 127.27 (7) |
S14—C9—C17 | 129.25 (7) | S8—C18—S16 | 115.25 (5) |
S3—C10—S9 | 114.04 (4) | S8—C18—C13 | 116.91 (7) |
S3—C10—C14 | 116.22 (6) | S16—C18—C13 | 127.80 (7) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x, −y+2, −z+1. |
(300K) top
Crystal data top
C3Ag2N3·2(C10H8S8) | V = 1756.56 (6) Å3 |
Mr = 1063.17 | Z = 2 |
Triclinic, P1 | F(000) = 1050 |
Hall symbol: -P 1 | Dx = 2.055 Mg m−3 |
a = 15.0831 (3) Å | Synchrotron radiation, λ = 0.6717 Å |
b = 8.6447 (1) Å | Cell parameters from 26905 reflections |
c = 13.4755 (3) Å | θ = 2.6–32.0° |
α = 90.012 (2)° | µ = 1.75 mm−1 |
β = 91.364 (2)° | T = 293 K |
γ = 89.998 (1)° | Plate |
Data collection top
Xcalibur, Atlas diffractometer | 11624 independent reflections |
Radiation source: synchrotron | 9553 reflections with I > 3σ(I) |
Synchrotron monochromator | Rint = 0.049 |
Detector resolution: 10.2930 pixels mm-1 | θmax = 32.4°, θmin = 1.9° |
ω and φ scans | h = −23→23 |
Absorption correction: multi-scan CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | k = −12→13 |
Tmin = 0.893, Tmax = 1 | l = −21→21 |
11624 measured reflections |
Refinement top
Refinement on F | 16 constraints |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.067 | Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2) |
S = 2.41 | (Δ/σ)max = 0.019 |
11624 reflections | Δρmax = 1.18 e Å−3 |
397 parameters | Δρmin = −1.00 e Å−3 |
2 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ag1 | 0.99546 (2) | 0.26699 (4) | 0.12664 (3) | 0.07302 (11) | |
Ag2 | 0.00434 (3) | 0.76684 (4) | 0.37331 (3) | 0.07320 (11) | |
S1 | 0.54168 (4) | 0.02439 (9) | 0.24304 (5) | 0.04796 (17) | |
S2 | 0.37442 (4) | 0.76037 (9) | 0.37913 (4) | 0.04685 (16) | |
S3 | 0.62561 (4) | 0.26073 (9) | 0.12105 (5) | 0.04680 (17) | |
S4 | 0.46222 (4) | 0.26280 (9) | −0.03083 (5) | 0.04679 (17) | |
S5 | 0.45825 (4) | 0.52443 (9) | 0.25690 (4) | 0.04804 (17) | |
S6 | 0.53770 (4) | 0.76260 (9) | 0.53080 (5) | 0.04680 (17) | |
S7 | 0.36838 (5) | 0.03546 (11) | 0.08980 (5) | 0.0530 (2) | |
S8 | 0.63179 (4) | 0.53546 (10) | 0.41024 (5) | 0.05274 (19) | |
S9 | 0.78727 (4) | 0.29263 (10) | 0.24485 (6) | 0.0530 (2) | |
S10 | 0.21297 (5) | 0.79249 (10) | 0.25541 (5) | 0.0528 (2) | |
S11 | 0.68686 (6) | 0.00705 (13) | 0.39215 (6) | 0.0656 (3) | |
S12 | 0.31320 (7) | 0.50780 (13) | 0.10764 (6) | 0.0653 (3) | |
S13 | 0.68668 (8) | 0.83327 (15) | 0.66493 (10) | 0.0759 (4) | |
S14 | 0.31288 (8) | 0.33283 (14) | −0.16476 (10) | 0.0762 (3) | |
S15 | 0.19835 (7) | 0.0649 (2) | −0.02069 (16) | 0.0970 (6) | |
S16 | 0.80171 (6) | 0.56431 (19) | 0.52176 (14) | 0.0961 (5) | |
N1 | 1.0203 (3) | −0.0602 (5) | 0.2265 (4) | 0.0858 (16) | |
C2 | 1.0138 (3) | 0.0537 (5) | 0.1855 (3) | 0.0677 (12) | |
C3 | −0.0137 (3) | 0.5460 (6) | 0.3110 (3) | 0.0637 (11) | |
N4 | −0.0218 (3) | 0.4486 (6) | 0.2776 (4) | 0.0844 (16) | |
C5 | 0.9967 (3) | 0.4474 (5) | 0.0250 (3) | 0.0710 (12) | 0.5 |
N5 | 0.9967 (3) | 0.4474 (5) | 0.0250 (3) | 0.0710 (12) | 0.5 |
C6 | 0.0033 (3) | 0.9475 (5) | 0.4748 (3) | 0.0716 (12) | 0.5 |
N6 | 0.0033 (3) | 0.9475 (5) | 0.4748 (3) | 0.0716 (12) | 0.5 |
C7 | 0.53651 (15) | 0.6446 (3) | 0.42583 (15) | 0.0410 (5) | |
C8 | 0.46328 (15) | 0.1444 (3) | 0.07394 (16) | 0.0414 (6) | |
C9 | 0.35162 (17) | 0.2258 (4) | −0.0636 (2) | 0.0475 (7) | |
C10 | 0.68507 (15) | 0.1996 (3) | 0.22654 (16) | 0.0415 (6) | |
C11 | 0.46535 (15) | 0.6415 (3) | 0.36166 (15) | 0.0400 (5) | |
C12 | 0.31490 (15) | 0.6999 (3) | 0.27388 (15) | 0.0410 (6) | |
C13 | 0.64825 (17) | 0.7272 (3) | 0.5641 (2) | 0.0478 (7) | |
C14 | 0.64620 (16) | 0.0903 (3) | 0.28279 (16) | 0.0442 (6) | |
C15 | 0.53485 (15) | 0.1415 (3) | 0.13851 (15) | 0.0397 (5) | |
C16 | 0.35387 (17) | 0.5908 (3) | 0.21745 (16) | 0.0446 (6) | |
C17 | 0.30842 (18) | 0.1222 (4) | −0.0088 (2) | 0.0527 (8) | |
C18 | 0.69177 (16) | 0.6224 (4) | 0.5081 (2) | 0.0519 (8) | |
C19 | 0.1629 (2) | 0.6768 (5) | 0.1580 (3) | 0.0598 (10) | |
C20 | 0.7753 (2) | 0.1394 (5) | 0.4244 (2) | 0.0620 (10) | |
C21 | 0.83717 (19) | 0.1762 (4) | 0.3418 (2) | 0.0585 (9) | |
C22 | 0.2053 (4) | 0.2549 (8) | −0.1863 (5) | 0.103 (2) | |
C23 | 0.2247 (2) | 0.6397 (5) | 0.0756 (2) | 0.0596 (10) | |
C24 | 0.1547 (3) | 0.2204 (7) | −0.0945 (6) | 0.108 (3) | |
C25 | 0.8452 (3) | 0.7215 (7) | 0.5947 (6) | 0.106 (2) | |
C26 | 0.7940 (4) | 0.7525 (7) | 0.6882 (5) | 0.099 (2) | |
H1c19 | 0.140704 | 0.582428 | 0.18563 | 0.0718* | |
H2c19 | 0.111436 | 0.728975 | 0.131326 | 0.0718* | |
H1c20 | 0.750714 | 0.233603 | 0.449511 | 0.0745* | |
H2c20 | 0.808727 | 0.099628 | 0.480264 | 0.0745* | |
H1c21 | 0.858967 | 0.081753 | 0.31393 | 0.0703* | |
H2c21 | 0.888794 | 0.227871 | 0.368462 | 0.0703* | |
H1c22 | 0.171301 | 0.323867 | −0.228089 | 0.1233* | |
H2c22 | 0.20942 | 0.162877 | −0.225742 | 0.1233* | |
H1c23 | 0.249128 | 0.733826 | 0.050189 | 0.0715* | |
H2c23 | 0.19126 | 0.599812 | 0.019707 | 0.0715* | |
H1c24 | 0.093885 | 0.199274 | −0.112366 | 0.1298* | |
H2c24 | 0.151195 | 0.312101 | −0.054615 | 0.1298* | |
H1c25 | 0.90619 | 0.701428 | 0.612145 | 0.1268* | |
H2c25 | 0.846319 | 0.813536 | 0.554969 | 0.1268* | |
H1c26 | 0.827745 | 0.820181 | 0.73102 | 0.1182* | |
H2c26 | 0.788379 | 0.658178 | 0.72512 | 0.1182* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.07130 (18) | 0.06384 (19) | 0.08336 (19) | −0.00071 (15) | −0.01005 (14) | 0.01488 (15) |
Ag2 | 0.07145 (19) | 0.0641 (2) | 0.08349 (19) | 0.00328 (16) | −0.00996 (15) | −0.01224 (15) |
S1 | 0.0430 (3) | 0.0565 (4) | 0.0445 (2) | −0.0128 (3) | 0.00222 (19) | 0.0073 (2) |
S2 | 0.0410 (2) | 0.0541 (4) | 0.0452 (2) | 0.0111 (3) | −0.00503 (18) | −0.0117 (2) |
S3 | 0.0408 (2) | 0.0540 (4) | 0.0454 (2) | −0.0107 (3) | −0.00502 (18) | 0.0122 (2) |
S4 | 0.0376 (2) | 0.0522 (4) | 0.0502 (2) | −0.0059 (3) | −0.00499 (19) | 0.0057 (2) |
S5 | 0.0431 (3) | 0.0567 (4) | 0.0444 (2) | 0.0128 (3) | 0.00240 (18) | −0.0070 (2) |
S6 | 0.0374 (2) | 0.0526 (4) | 0.0501 (2) | 0.0059 (3) | −0.00472 (18) | −0.0057 (2) |
S7 | 0.0421 (3) | 0.0680 (5) | 0.0491 (3) | −0.0161 (3) | 0.0042 (2) | 0.0000 (3) |
S8 | 0.0420 (3) | 0.0673 (4) | 0.0490 (2) | 0.0160 (3) | 0.0043 (2) | 0.0006 (3) |
S9 | 0.0385 (2) | 0.0616 (4) | 0.0583 (3) | −0.0106 (3) | −0.0077 (2) | 0.0174 (3) |
S10 | 0.0382 (2) | 0.0613 (4) | 0.0583 (3) | 0.0104 (3) | −0.0076 (2) | −0.0165 (3) |
S11 | 0.0640 (4) | 0.0756 (6) | 0.0566 (3) | −0.0159 (4) | −0.0107 (3) | 0.0287 (4) |
S12 | 0.0629 (4) | 0.0759 (6) | 0.0564 (3) | 0.0163 (5) | −0.0100 (3) | −0.0279 (4) |
S13 | 0.0645 (5) | 0.0717 (7) | 0.0899 (7) | 0.0021 (5) | −0.0347 (5) | −0.0156 (6) |
S14 | 0.0657 (5) | 0.0723 (6) | 0.0890 (6) | −0.0017 (5) | −0.0343 (5) | 0.0156 (5) |
S15 | 0.0381 (4) | 0.1075 (11) | 0.1448 (14) | −0.0194 (6) | −0.0124 (5) | 0.0176 (10) |
S16 | 0.0385 (3) | 0.1070 (10) | 0.1420 (12) | 0.0194 (5) | −0.0132 (5) | −0.0184 (9) |
N1 | 0.079 (3) | 0.090 (3) | 0.088 (3) | 0.008 (2) | −0.005 (2) | −0.007 (2) |
C2 | 0.0520 (15) | 0.081 (3) | 0.0698 (18) | −0.0037 (18) | 0.0046 (13) | −0.0147 (18) |
C3 | 0.0531 (16) | 0.070 (2) | 0.0679 (17) | −0.0028 (18) | 0.0043 (13) | 0.0050 (16) |
N4 | 0.073 (3) | 0.087 (3) | 0.093 (3) | −0.015 (2) | −0.003 (2) | 0.003 (2) |
C5 | 0.077 (2) | 0.071 (2) | 0.0645 (16) | 0.0021 (19) | −0.0043 (14) | 0.0107 (17) |
N5 | 0.077 (2) | 0.071 (2) | 0.0645 (16) | 0.0021 (19) | −0.0043 (14) | 0.0107 (17) |
C6 | 0.077 (2) | 0.073 (3) | 0.0644 (16) | 0.001 (2) | −0.0076 (15) | −0.0109 (16) |
N6 | 0.077 (2) | 0.073 (3) | 0.0644 (16) | 0.001 (2) | −0.0076 (15) | −0.0109 (16) |
C7 | 0.0352 (8) | 0.0471 (12) | 0.0407 (7) | 0.0035 (9) | 0.0000 (6) | 0.0017 (8) |
C8 | 0.0344 (8) | 0.0479 (13) | 0.0420 (8) | −0.0051 (10) | 0.0003 (6) | −0.0025 (8) |
C9 | 0.0366 (9) | 0.0500 (15) | 0.0554 (11) | 0.0011 (11) | −0.0077 (8) | −0.0071 (10) |
C10 | 0.0346 (8) | 0.0486 (13) | 0.0413 (8) | −0.0038 (9) | −0.0009 (6) | 0.0066 (8) |
C11 | 0.0364 (8) | 0.0443 (12) | 0.0392 (7) | 0.0051 (9) | 0.0005 (6) | −0.0016 (7) |
C12 | 0.0358 (8) | 0.0465 (13) | 0.0405 (7) | 0.0047 (10) | −0.0014 (6) | −0.0065 (8) |
C13 | 0.0392 (10) | 0.0495 (15) | 0.0542 (11) | −0.0010 (11) | −0.0072 (8) | 0.0061 (10) |
C14 | 0.0413 (9) | 0.0514 (14) | 0.0398 (8) | −0.0062 (10) | 0.0000 (7) | 0.0079 (9) |
C15 | 0.0360 (8) | 0.0439 (12) | 0.0391 (7) | −0.0059 (9) | 0.0003 (6) | 0.0001 (8) |
C16 | 0.0412 (9) | 0.0523 (14) | 0.0403 (7) | 0.0062 (11) | −0.0008 (7) | −0.0089 (8) |
C17 | 0.0336 (9) | 0.0642 (19) | 0.0603 (13) | −0.0045 (12) | −0.0023 (9) | −0.0079 (13) |
C18 | 0.0328 (9) | 0.0615 (17) | 0.0611 (12) | 0.0060 (11) | −0.0023 (8) | 0.0068 (12) |
C19 | 0.0398 (11) | 0.076 (2) | 0.0635 (14) | −0.0018 (15) | −0.0010 (10) | −0.0167 (15) |
C20 | 0.0538 (14) | 0.084 (2) | 0.0479 (11) | 0.0055 (16) | 0.0000 (10) | 0.0104 (13) |
C21 | 0.0407 (10) | 0.074 (2) | 0.0613 (13) | 0.0084 (13) | 0.0005 (9) | 0.0170 (13) |
C22 | 0.075 (3) | 0.109 (5) | 0.121 (5) | 0.006 (3) | −0.052 (3) | −0.002 (4) |
C23 | 0.0516 (13) | 0.080 (2) | 0.0468 (10) | 0.0020 (16) | −0.0014 (9) | −0.0042 (12) |
C24 | 0.0494 (18) | 0.101 (4) | 0.173 (7) | 0.023 (3) | −0.027 (3) | −0.056 (4) |
C25 | 0.0487 (17) | 0.100 (4) | 0.167 (6) | −0.008 (2) | −0.018 (3) | 0.058 (4) |
C26 | 0.077 (3) | 0.102 (4) | 0.114 (4) | 0.001 (3) | −0.047 (3) | 0.015 (3) |
Geometric parameters (Å, º) top
Ag1—C2 | 2.024 (4) | C5—C5i | 1.138 (6) |
Ag1—C5 | 2.076 (4) | C5—N5 | 0 |
Ag1—N5 | 2.076 (4) | C5—N5i | 1.138 (6) |
Ag2—C3 | 2.101 (5) | N5—N5i | 1.138 (6) |
Ag2—C6 | 2.076 (4) | C6—C6ii | 1.140 (6) |
Ag2—N6 | 2.076 (4) | C6—N6 | 0 |
S1—C14 | 1.748 (3) | C6—N6ii | 1.140 (6) |
S1—C15 | 1.736 (2) | N6—N6ii | 1.140 (6) |
S2—C11 | 1.734 (2) | C7—C11 | 1.362 (3) |
S2—C12 | 1.741 (2) | C8—C15 | 1.371 (3) |
S3—C10 | 1.745 (2) | C9—C17 | 1.340 (4) |
S3—C15 | 1.734 (2) | C10—C14 | 1.354 (4) |
S4—C8 | 1.744 (3) | C12—C16 | 1.354 (4) |
S4—C9 | 1.745 (3) | C13—C18 | 1.358 (4) |
S5—C11 | 1.738 (2) | C19—C23 | 1.502 (5) |
S5—C16 | 1.747 (3) | C19—H1c19 | 0.96 |
S6—C7 | 1.744 (2) | C19—H2c19 | 0.96 |
S6—C13 | 1.744 (3) | C20—C21 | 1.503 (4) |
S7—C8 | 1.731 (3) | C20—H1c20 | 0.96 |
S7—C17 | 1.757 (3) | C20—H2c20 | 0.96 |
S8—C7 | 1.736 (2) | C21—H1c21 | 0.96 |
S8—C18 | 1.751 (3) | C21—H2c21 | 0.96 |
S9—C10 | 1.751 (2) | C22—C24 | 1.498 (10) |
S10—C12 | 1.746 (2) | C22—H1c22 | 0.96 |
S11—C14 | 1.739 (3) | C22—H2c22 | 0.96 |
S12—C16 | 1.743 (3) | C23—H1c23 | 0.96 |
S13—C13 | 1.728 (3) | C23—H2c23 | 0.96 |
S13—C26 | 1.783 (6) | C24—H1c24 | 0.96 |
S14—C9 | 1.738 (3) | C24—H2c24 | 0.96 |
S14—C22 | 1.775 (6) | C25—C26 | 1.517 (9) |
S15—C17 | 1.736 (3) | C25—H1c25 | 0.96 |
S15—C24 | 1.789 (7) | C25—H2c25 | 0.96 |
S16—C18 | 1.738 (3) | C26—H1c26 | 0.96 |
N1—C2 | 1.131 (6) | C26—H2c26 | 0.96 |
C3—N4 | 0.961 (7) | ||
C2—Ag1—C5 | 160.03 (17) | S2—C11—C7 | 121.07 (18) |
C2—Ag1—N5 | 160.03 (17) | S5—C11—C7 | 123.99 (18) |
C5—Ag1—N5 | 0.0 (5) | S2—C12—S10 | 114.44 (14) |
C3—Ag2—C6 | 160.75 (17) | S2—C12—C16 | 116.37 (18) |
C3—Ag2—N6 | 160.75 (17) | S10—C12—C16 | 129.18 (18) |
C6—Ag2—N6 | 0.0 (5) | S6—C13—S13 | 114.21 (16) |
C14—S1—C15 | 95.40 (12) | S6—C13—C18 | 116.5 (2) |
C11—S2—C12 | 96.07 (11) | S13—C13—C18 | 129.3 (2) |
C10—S3—C15 | 95.82 (11) | S1—C14—S11 | 114.96 (15) |
C8—S4—C9 | 95.00 (13) | S1—C14—C10 | 117.09 (17) |
C11—S5—C16 | 95.37 (11) | S11—C14—C10 | 127.95 (19) |
C7—S6—C13 | 95.58 (12) | S1—C15—S3 | 115.15 (12) |
C8—S7—C17 | 94.98 (13) | S1—C15—C8 | 123.81 (19) |
C7—S8—C18 | 95.17 (12) | S3—C15—C8 | 121.02 (18) |
C13—S13—C26 | 102.5 (2) | S5—C16—S12 | 114.82 (15) |
C9—S14—C22 | 102.4 (2) | S5—C16—C12 | 117.26 (17) |
C17—S15—C24 | 100.1 (2) | S12—C16—C12 | 127.92 (19) |
Ag1—C2—N1 | 173.3 (4) | S7—C17—S15 | 115.0 (2) |
Ag2—C3—N4 | 175.7 (5) | S7—C17—C9 | 117.0 (2) |
Ag1—C5—C5i | 173.5 (4) | S15—C17—C9 | 128.0 (2) |
Ag1—C5—N5 | 0 | S8—C18—S16 | 115.48 (18) |
Ag1—C5—N5i | 173.5 (4) | S8—C18—C13 | 117.18 (19) |
C5i—C5—N5 | 0 | S16—C18—C13 | 127.3 (2) |
C5i—C5—N5i | 0.0 (5) | C23—C19—H1c19 | 109.47 |
N5—C5—N5i | 0 | C23—C19—H2c19 | 109.47 |
Ag1—N5—C5 | 0 | H1c19—C19—H2c19 | 105 |
Ag1—N5—C5i | 173.5 (4) | C21—C20—H1c20 | 109.47 |
Ag1—N5—N5i | 173.5 (4) | C21—C20—H2c20 | 109.47 |
C5—N5—C5i | 0 | H1c20—C20—H2c20 | 103.12 |
C5—N5—N5i | 0 | C20—C21—H1c21 | 109.47 |
C5i—N5—N5i | 0.0 (5) | C20—C21—H2c21 | 109.47 |
Ag2—C6—C6ii | 173.7 (4) | H1c21—C21—H2c21 | 105.05 |
Ag2—C6—N6 | 0 | S14—C22—C24 | 115.0 (5) |
Ag2—C6—N6ii | 173.7 (4) | S14—C22—H1c22 | 109.47 |
C6ii—C6—N6 | 0 | S14—C22—H2c22 | 109.47 |
C6ii—C6—N6ii | 0.0 (5) | C24—C22—H1c22 | 109.47 |
N6—C6—N6ii | 0 | C24—C22—H2c22 | 109.47 |
Ag2—N6—C6 | 0 | H1c22—C22—H2c22 | 103.31 |
Ag2—N6—C6ii | 173.7 (4) | C19—C23—H1c23 | 109.47 |
Ag2—N6—N6ii | 173.7 (4) | C19—C23—H2c23 | 109.47 |
C6—N6—C6ii | 0 | H1c23—C23—H2c23 | 102.92 |
C6—N6—N6ii | 0 | S15—C24—C22 | 114.9 (4) |
C6ii—N6—N6ii | 0.0 (5) | S15—C24—H1c24 | 109.47 |
S6—C7—S8 | 115.05 (12) | S15—C24—H2c24 | 109.47 |
S6—C7—C11 | 121.26 (18) | C22—C24—H1c24 | 109.47 |
S8—C7—C11 | 123.69 (18) | C22—C24—H2c24 | 109.47 |
S4—C8—S7 | 115.33 (13) | H1c24—C24—H2c24 | 103.45 |
S4—C8—C15 | 121.10 (19) | C26—C25—H1c25 | 109.47 |
S7—C8—C15 | 123.57 (19) | C26—C25—H2c25 | 109.47 |
S4—C9—S14 | 113.72 (16) | H1c25—C25—H2c25 | 104.85 |
S4—C9—C17 | 117.2 (2) | S13—C26—C25 | 113.7 (4) |
S14—C9—C17 | 129.0 (2) | S13—C26—H1c26 | 109.47 |
S3—C10—S9 | 114.16 (14) | S13—C26—H2c26 | 109.47 |
S3—C10—C14 | 116.53 (18) | C25—C26—H1c26 | 109.47 |
S9—C10—C14 | 129.30 (18) | C25—C26—H2c26 | 109.47 |
S2—C11—S5 | 114.93 (12) | H1c26—C26—H2c26 | 104.93 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x, −y+2, −z+1. |