In the centrosymmetric title compound, [Ag
2(NCS)
2(C
21H
21P)
4]·2CH
3CN, the Ag atom is coordinated by two phosphine ligands and two bridging thiocyanate ligands in a distorted tetrahedral configuration. The Ag—P bond distances are 2.4615 (7) and 2.5091 (7) Å, while the Ag—N and the Ag—S bond distances are 2.364 (2) and 2.3269 (18) Å, respectively. The crystal structure exhibits C—H
S hydrogen bonds.
Supporting information
CCDC reference: 672703
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.006 Å
- R factor = 0.043
- wR factor = 0.121
- Data-to-parameter ratio = 21.8
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Ag - P1 .. 16.58 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Ag - S_a .. 10.24 su
Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ag - P2 .. 9.28 su
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C132
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C131
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C134
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C234
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C02
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 6
0 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
8 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
8 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
2 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
The title compound was synthesized by heating one equivalent of
P(p-tol)3 (0.324 g, 1.06 mmol) with AgSCN (0.176 g, 1.06 mmol) in
acetonitrile (10.0 ml) under reflux. Recrystallization from acetone produced
white crystals suitable for X-ray diffraction in quantitative yield (0.486 g,
97.1%).
H atoms were positioned geometrically and refined using a riding model, with
fixed C—H distances of 0.93 Å (CH) [Uiso(H) = 1.2Ueq]
and 0.96 Å (CH3) [Uiso(H) = 1.5Ueq]. The highest
residual peak is 0.95 e located 0.78 Å from atom Ag and the deepest hole
-0.62 e, 0.75 Å from Ag. A Hirschfield test failure appeared in the
structure validation. Using a disordered model the U values of the Ag atoms
were refined to an 98.6% occupancy, allowing the structure to pass the
Hirschfield test.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).
Di-µ-thiocyanato-bis[bis(tri-
p-tolylphosphine)silver(I)] acetonitrile
disolvate
top
Crystal data top
[Ag2(NCS)2(C21H21P)4]·2C2H3N | Z = 1 |
Mr = 1631.49 | F(000) = 844 |
Triclinic, P1 | Dx = 1.322 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8842 (5) Å | Cell parameters from 5879 reflections |
b = 13.8418 (7) Å | θ = 2.3–23.8° |
c = 15.4048 (8) Å | µ = 0.65 mm−1 |
α = 75.839 (3)° | T = 100 K |
β = 69.345 (2)° | Cuboid, colourless |
γ = 72.833 (2)° | 0.43 × 0.28 × 0.18 mm |
V = 2049.11 (18) Å3 | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 10186 independent reflections |
Radiation source: fine-focus sealed tube | 7349 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 0 pixels mm-1 | θmax = 28.4°, θmin = 1.9° |
ω and ϕ scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −18→18 |
Tmin = 0.766, Tmax = 0.891 | l = −20→20 |
41388 measured reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.043 | w = 1/[σ2(Fo2) + (0.0549P)2 + 1.0074P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.121 | (Δ/σ)max = 0.002 |
S = 1.03 | Δρmax = 0.95 e Å−3 |
10186 reflections | Δρmin = −0.62 e Å−3 |
467 parameters | |
Crystal data top
[Ag2(NCS)2(C21H21P)4]·2C2H3N | γ = 72.833 (2)° |
Mr = 1631.49 | V = 2049.11 (18) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.8842 (5) Å | Mo Kα radiation |
b = 13.8418 (7) Å | µ = 0.65 mm−1 |
c = 15.4048 (8) Å | T = 100 K |
α = 75.839 (3)° | 0.43 × 0.28 × 0.18 mm |
β = 69.345 (2)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 10186 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 7349 reflections with I > 2σ(I) |
Tmin = 0.766, Tmax = 0.891 | Rint = 0.037 |
41388 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.95 e Å−3 |
10186 reflections | Δρmin = −0.62 e Å−3 |
467 parameters | |
Special details top
Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD
diffractometer using an exposure time of 10 s/frame. A total of 1408 frames
were collected with a frame width of 0.5° covering up to θ = 28.36° with
99.3% completeness accomplished. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N01 | 0.8035 (8) | 0.8517 (7) | 0.2119 (5) | 0.181 (3) | |
C02 | 0.8093 (6) | 0.7898 (6) | 0.2777 (6) | 0.123 (2) | |
C01 | 0.8191 (6) | 0.7107 (6) | 0.3612 (5) | 0.139 (2) | |
H01A | 0.8171 | 0.6448 | 0.3494 | 0.209* | |
H01B | 0.7428 | 0.7307 | 0.4159 | 0.209* | |
H01C | 0.9038 | 0.7043 | 0.3735 | 0.209* | |
P1 | 0.45861 (8) | 0.33722 (6) | 0.33462 (5) | 0.04830 (18) | |
P2 | 0.33522 (8) | 0.65463 (6) | 0.22390 (5) | 0.04649 (17) | |
Ag | 0.44006 (2) | 0.522764 (16) | 0.332532 (15) | 0.05329 (9) | |
N | 0.3217 (3) | 0.5219 (2) | 0.49407 (18) | 0.0596 (6) | |
S | 0.32370 (9) | 0.45764 (9) | 0.68088 (6) | 0.0755 (3) | |
C | 0.3244 (3) | 0.4944 (2) | 0.5702 (2) | 0.0517 (7) | |
C111 | 0.3066 (3) | 0.3150 (2) | 0.32640 (19) | 0.0498 (7) | |
C112 | 0.3026 (4) | 0.2392 (3) | 0.2849 (2) | 0.0657 (9) | |
H112 | 0.3842 | 0.194 | 0.2565 | 0.079* | |
C113 | 0.1803 (4) | 0.2281 (3) | 0.2841 (3) | 0.0740 (10) | |
H113 | 0.1801 | 0.1748 | 0.2553 | 0.089* | |
C114 | 0.0598 (3) | 0.2916 (3) | 0.3235 (3) | 0.0645 (9) | |
C115 | 0.0640 (4) | 0.3680 (3) | 0.3641 (3) | 0.0715 (10) | |
H115 | −0.0178 | 0.4138 | 0.3912 | 0.086* | |
C116 | 0.1839 (3) | 0.3799 (3) | 0.3665 (2) | 0.0642 (8) | |
H116 | 0.1832 | 0.4329 | 0.3959 | 0.077* | |
C117 | −0.0723 (4) | 0.2789 (4) | 0.3219 (3) | 0.0927 (13) | |
H11A | −0.0546 | 0.2318 | 0.2784 | 0.139* | |
H11B | −0.1256 | 0.3455 | 0.3012 | 0.139* | |
H11C | −0.1226 | 0.251 | 0.3851 | 0.139* | |
C121 | 0.5996 (3) | 0.2773 (2) | 0.2425 (2) | 0.0489 (6) | |
C122 | 0.6476 (3) | 0.1721 (2) | 0.2459 (2) | 0.0636 (8) | |
H122 | 0.6048 | 0.1272 | 0.2975 | 0.076* | |
C123 | 0.7569 (4) | 0.1320 (3) | 0.1748 (3) | 0.0730 (10) | |
H123 | 0.7876 | 0.0598 | 0.1784 | 0.088* | |
C124 | 0.8224 (3) | 0.1942 (3) | 0.0990 (3) | 0.0692 (9) | |
C125 | 0.7767 (3) | 0.2984 (3) | 0.0961 (2) | 0.0647 (8) | |
H125 | 0.8213 | 0.3428 | 0.045 | 0.078* | |
C126 | 0.6662 (3) | 0.3398 (2) | 0.1666 (2) | 0.0551 (7) | |
H126 | 0.6359 | 0.412 | 0.1627 | 0.066* | |
C127 | 0.9419 (5) | 0.1491 (4) | 0.0214 (3) | 0.1131 (17) | |
H12A | 0.9629 | 0.0742 | 0.0372 | 0.17* | |
H12B | 1.0203 | 0.1745 | 0.0148 | 0.17* | |
H12C | 0.9198 | 0.1692 | −0.0379 | 0.17* | |
C131 | 0.4852 (3) | 0.2517 (2) | 0.44051 (19) | 0.0495 (6) | |
C132 | 0.4380 (5) | 0.1640 (3) | 0.4788 (3) | 0.0909 (14) | |
H132 | 0.3838 | 0.1462 | 0.4512 | 0.109* | |
C133 | 0.4684 (5) | 0.1014 (3) | 0.5567 (3) | 0.0928 (14) | |
H133 | 0.4356 | 0.0408 | 0.5811 | 0.111* | |
C134 | 0.5437 (4) | 0.1239 (3) | 0.5997 (2) | 0.0649 (9) | |
C135 | 0.5942 (4) | 0.2076 (3) | 0.5603 (3) | 0.0726 (10) | |
H135 | 0.651 | 0.2234 | 0.587 | 0.087* | |
C136 | 0.5653 (3) | 0.2713 (3) | 0.4818 (3) | 0.0677 (9) | |
H136 | 0.6022 | 0.3301 | 0.4563 | 0.081* | |
C137 | 0.5763 (5) | 0.0539 (3) | 0.6853 (3) | 0.0930 (14) | |
H13A | 0.6359 | 0.0803 | 0.704 | 0.14* | |
H13B | 0.6215 | −0.0151 | 0.6701 | 0.14* | |
H13C | 0.4927 | 0.0513 | 0.7372 | 0.14* | |
C211 | 0.4437 (3) | 0.7267 (2) | 0.12818 (19) | 0.0473 (6) | |
C212 | 0.4250 (3) | 0.7632 (2) | 0.0403 (2) | 0.0551 (7) | |
H212 | 0.3579 | 0.7449 | 0.0256 | 0.066* | |
C213 | 0.5037 (4) | 0.8261 (3) | −0.0262 (2) | 0.0642 (9) | |
H213 | 0.4895 | 0.8503 | −0.0859 | 0.077* | |
C214 | 0.6017 (4) | 0.8542 (3) | −0.0077 (2) | 0.0619 (8) | |
C215 | 0.6228 (4) | 0.8157 (3) | 0.0789 (2) | 0.0670 (9) | |
H215 | 0.692 | 0.8323 | 0.0926 | 0.08* | |
C216 | 0.5443 (3) | 0.7530 (2) | 0.1462 (2) | 0.0591 (8) | |
H216 | 0.56 | 0.7279 | 0.2054 | 0.071* | |
C217 | 0.6843 (5) | 0.9264 (3) | −0.0789 (3) | 0.0908 (13) | |
H21A | 0.6912 | 0.977 | −0.0471 | 0.136* | |
H21B | 0.6401 | 0.9616 | −0.1273 | 0.136* | |
H21C | 0.7748 | 0.8872 | −0.1083 | 0.136* | |
C221 | 0.2629 (3) | 0.5939 (2) | 0.16666 (19) | 0.0477 (6) | |
C222 | 0.1265 (3) | 0.6102 (3) | 0.1810 (2) | 0.0644 (8) | |
H222 | 0.0655 | 0.6634 | 0.2143 | 0.077* | |
C223 | 0.0773 (4) | 0.5504 (3) | 0.1475 (3) | 0.0724 (9) | |
H223 | −0.0172 | 0.5634 | 0.1584 | 0.087* | |
C224 | 0.1611 (4) | 0.4726 (3) | 0.0990 (2) | 0.0675 (9) | |
C225 | 0.2979 (4) | 0.4586 (3) | 0.0817 (3) | 0.0719 (10) | |
H225 | 0.3588 | 0.4076 | 0.0457 | 0.086* | |
C226 | 0.3483 (4) | 0.5174 (3) | 0.1158 (2) | 0.0636 (8) | |
H226 | 0.443 | 0.505 | 0.1041 | 0.076* | |
C227 | 0.1079 (6) | 0.4033 (4) | 0.0663 (4) | 0.1025 (15) | |
H22A | 0.1084 | 0.4291 | 0.001 | 0.154* | |
H22B | 0.0154 | 0.4018 | 0.1062 | 0.154* | |
H22C | 0.1653 | 0.3339 | 0.0704 | 0.154* | |
C231 | 0.1978 (3) | 0.7558 (2) | 0.27808 (19) | 0.0471 (6) | |
C232 | 0.1569 (3) | 0.8513 (2) | 0.2292 (2) | 0.0623 (8) | |
H232 | 0.1986 | 0.8659 | 0.1634 | 0.075* | |
C233 | 0.0550 (4) | 0.9258 (3) | 0.2755 (3) | 0.0700 (9) | |
H233 | 0.0284 | 0.9908 | 0.2405 | 0.084* | |
C234 | −0.0082 (3) | 0.9086 (3) | 0.3703 (2) | 0.0612 (8) | |
C235 | 0.0337 (4) | 0.8138 (3) | 0.4184 (2) | 0.0696 (9) | |
H235 | −0.0086 | 0.7996 | 0.4841 | 0.084* | |
C236 | 0.1356 (4) | 0.7384 (2) | 0.3739 (2) | 0.0625 (8) | |
H236 | 0.163 | 0.6741 | 0.4096 | 0.075* | |
C237 | −0.1194 (4) | 0.9897 (3) | 0.4205 (3) | 0.0917 (13) | |
H23A | −0.0812 | 1.0264 | 0.4478 | 0.138* | |
H23B | −0.1868 | 0.9572 | 0.4705 | 0.138* | |
H23C | −0.1623 | 1.0381 | 0.3756 | 0.138* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N01 | 0.176 (6) | 0.208 (8) | 0.162 (7) | −0.054 (6) | −0.043 (5) | −0.035 (6) |
C02 | 0.085 (3) | 0.152 (6) | 0.142 (6) | −0.040 (4) | −0.012 (4) | −0.058 (5) |
C01 | 0.119 (5) | 0.161 (6) | 0.135 (5) | −0.059 (4) | −0.002 (4) | −0.040 (5) |
P1 | 0.0595 (4) | 0.0380 (4) | 0.0417 (4) | −0.0077 (3) | −0.0149 (3) | −0.0009 (3) |
P2 | 0.0560 (4) | 0.0399 (4) | 0.0413 (4) | −0.0059 (3) | −0.0193 (3) | −0.0018 (3) |
Ag | 0.06801 (16) | 0.04370 (13) | 0.04507 (13) | −0.00633 (10) | −0.02247 (11) | −0.00144 (9) |
N | 0.0651 (16) | 0.0592 (16) | 0.0476 (15) | −0.0068 (13) | −0.0157 (12) | −0.0075 (12) |
S | 0.0586 (5) | 0.1111 (8) | 0.0462 (4) | −0.0207 (5) | −0.0171 (4) | 0.0101 (5) |
C | 0.0435 (15) | 0.0527 (17) | 0.0484 (16) | −0.0051 (12) | −0.0091 (12) | −0.0039 (13) |
C111 | 0.0601 (17) | 0.0421 (15) | 0.0406 (14) | −0.0082 (13) | −0.0152 (13) | 0.0004 (12) |
C112 | 0.0627 (19) | 0.064 (2) | 0.072 (2) | −0.0011 (16) | −0.0241 (17) | −0.0237 (17) |
C113 | 0.076 (2) | 0.074 (2) | 0.083 (3) | −0.0118 (19) | −0.032 (2) | −0.026 (2) |
C114 | 0.0611 (19) | 0.061 (2) | 0.066 (2) | −0.0133 (16) | −0.0229 (17) | 0.0034 (16) |
C115 | 0.0570 (19) | 0.061 (2) | 0.081 (2) | −0.0087 (16) | −0.0077 (17) | −0.0101 (18) |
C116 | 0.066 (2) | 0.0511 (18) | 0.068 (2) | −0.0124 (15) | −0.0085 (16) | −0.0139 (16) |
C117 | 0.074 (3) | 0.093 (3) | 0.114 (4) | −0.024 (2) | −0.036 (2) | −0.007 (3) |
C121 | 0.0548 (16) | 0.0432 (15) | 0.0455 (15) | −0.0058 (12) | −0.0181 (13) | −0.0039 (12) |
C122 | 0.070 (2) | 0.0471 (18) | 0.065 (2) | −0.0076 (15) | −0.0195 (17) | −0.0023 (15) |
C123 | 0.073 (2) | 0.055 (2) | 0.085 (3) | 0.0096 (17) | −0.029 (2) | −0.0220 (19) |
C124 | 0.0568 (19) | 0.084 (3) | 0.061 (2) | 0.0048 (18) | −0.0210 (16) | −0.0220 (19) |
C125 | 0.0622 (19) | 0.072 (2) | 0.0479 (17) | −0.0096 (17) | −0.0127 (15) | −0.0012 (15) |
C126 | 0.0617 (18) | 0.0489 (17) | 0.0495 (16) | −0.0082 (14) | −0.0196 (14) | −0.0002 (13) |
C127 | 0.083 (3) | 0.135 (4) | 0.086 (3) | 0.023 (3) | −0.008 (2) | −0.040 (3) |
C131 | 0.0613 (17) | 0.0409 (15) | 0.0428 (14) | −0.0126 (13) | −0.0146 (13) | −0.0010 (12) |
C132 | 0.143 (4) | 0.090 (3) | 0.073 (2) | −0.071 (3) | −0.063 (3) | 0.028 (2) |
C133 | 0.149 (4) | 0.080 (3) | 0.075 (2) | −0.066 (3) | −0.060 (3) | 0.031 (2) |
C134 | 0.096 (3) | 0.0499 (18) | 0.0531 (18) | −0.0127 (17) | −0.0352 (18) | −0.0015 (14) |
C135 | 0.075 (2) | 0.075 (2) | 0.074 (2) | −0.0207 (19) | −0.0414 (19) | 0.0083 (19) |
C136 | 0.064 (2) | 0.066 (2) | 0.073 (2) | −0.0252 (17) | −0.0310 (18) | 0.0156 (17) |
C137 | 0.148 (4) | 0.068 (2) | 0.072 (2) | −0.022 (3) | −0.062 (3) | 0.013 (2) |
C211 | 0.0540 (16) | 0.0425 (15) | 0.0416 (14) | −0.0061 (12) | −0.0154 (12) | −0.0048 (11) |
C212 | 0.0676 (19) | 0.0540 (18) | 0.0439 (15) | −0.0122 (15) | −0.0212 (14) | −0.0037 (13) |
C213 | 0.087 (2) | 0.0565 (19) | 0.0389 (15) | −0.0092 (17) | −0.0183 (16) | −0.0004 (14) |
C214 | 0.071 (2) | 0.0533 (18) | 0.0509 (17) | −0.0140 (16) | −0.0068 (16) | −0.0083 (14) |
C215 | 0.068 (2) | 0.070 (2) | 0.065 (2) | −0.0237 (17) | −0.0210 (17) | −0.0043 (17) |
C216 | 0.070 (2) | 0.0566 (18) | 0.0508 (17) | −0.0150 (15) | −0.0249 (15) | 0.0020 (14) |
C217 | 0.107 (3) | 0.081 (3) | 0.067 (2) | −0.038 (2) | 0.000 (2) | 0.001 (2) |
C221 | 0.0601 (17) | 0.0393 (14) | 0.0428 (14) | −0.0066 (12) | −0.0210 (13) | −0.0024 (11) |
C222 | 0.0615 (19) | 0.070 (2) | 0.063 (2) | −0.0094 (16) | −0.0188 (16) | −0.0194 (17) |
C223 | 0.069 (2) | 0.085 (3) | 0.071 (2) | −0.024 (2) | −0.0254 (18) | −0.013 (2) |
C224 | 0.098 (3) | 0.0537 (19) | 0.062 (2) | −0.0219 (19) | −0.042 (2) | 0.0025 (16) |
C225 | 0.094 (3) | 0.0519 (19) | 0.075 (2) | 0.0012 (18) | −0.040 (2) | −0.0207 (17) |
C226 | 0.0651 (19) | 0.0539 (19) | 0.074 (2) | 0.0008 (15) | −0.0301 (17) | −0.0170 (16) |
C227 | 0.147 (4) | 0.080 (3) | 0.113 (4) | −0.039 (3) | −0.073 (3) | −0.008 (3) |
C231 | 0.0554 (16) | 0.0427 (15) | 0.0426 (14) | −0.0084 (12) | −0.0186 (12) | −0.0034 (11) |
C232 | 0.068 (2) | 0.0521 (18) | 0.0522 (17) | −0.0075 (15) | −0.0128 (15) | 0.0028 (14) |
C233 | 0.072 (2) | 0.0428 (17) | 0.078 (2) | −0.0015 (15) | −0.0184 (19) | −0.0009 (16) |
C234 | 0.0607 (18) | 0.0525 (18) | 0.071 (2) | −0.0077 (15) | −0.0196 (17) | −0.0173 (16) |
C235 | 0.082 (2) | 0.067 (2) | 0.0473 (17) | −0.0051 (18) | −0.0132 (17) | −0.0112 (16) |
C236 | 0.081 (2) | 0.0491 (18) | 0.0478 (17) | −0.0027 (16) | −0.0214 (16) | −0.0030 (14) |
C237 | 0.084 (3) | 0.071 (3) | 0.103 (3) | 0.002 (2) | −0.011 (2) | −0.031 (2) |
Geometric parameters (Å, º) top
N01—C02 | 1.163 (9) | C133—H133 | 0.95 |
C02—C01 | 1.485 (9) | C134—C135 | 1.345 (5) |
C01—H01A | 0.98 | C134—C137 | 1.519 (4) |
C01—H01B | 0.98 | C135—C136 | 1.387 (5) |
C01—H01C | 0.98 | C135—H135 | 0.95 |
P1—C111 | 1.821 (3) | C136—H136 | 0.95 |
P1—C131 | 1.825 (3) | C137—H13A | 0.98 |
P1—C121 | 1.829 (3) | C137—H13B | 0.98 |
P1—Ag | 2.5091 (8) | C137—H13C | 0.98 |
P2—C211 | 1.820 (3) | C211—C216 | 1.381 (4) |
P2—C221 | 1.830 (3) | C211—C212 | 1.389 (4) |
P2—C231 | 1.830 (3) | C212—C213 | 1.388 (4) |
P2—Ag | 2.4612 (7) | C212—H212 | 0.95 |
Ag—N | 2.363 (3) | C213—C214 | 1.372 (5) |
Ag—Si | 2.5955 (10) | C213—H213 | 0.95 |
N—C | 1.149 (4) | C214—C215 | 1.383 (5) |
S—C | 1.653 (3) | C214—C217 | 1.520 (5) |
S—Agi | 2.5955 (9) | C215—C216 | 1.389 (5) |
C111—C112 | 1.373 (4) | C215—H215 | 0.95 |
C111—C116 | 1.398 (4) | C216—H216 | 0.95 |
C112—C113 | 1.390 (5) | C217—H21A | 0.98 |
C112—H112 | 0.95 | C217—H21B | 0.98 |
C113—C114 | 1.371 (5) | C217—H21C | 0.98 |
C113—H113 | 0.95 | C221—C222 | 1.378 (4) |
C114—C115 | 1.372 (5) | C221—C226 | 1.382 (4) |
C114—C117 | 1.510 (5) | C222—C223 | 1.380 (5) |
C115—C116 | 1.376 (5) | C222—H222 | 0.95 |
C115—H115 | 0.95 | C223—C224 | 1.372 (5) |
C116—H116 | 0.95 | C223—H223 | 0.95 |
C117—H11A | 0.98 | C224—C225 | 1.379 (5) |
C117—H11B | 0.98 | C224—C227 | 1.511 (5) |
C117—H11C | 0.98 | C225—C226 | 1.383 (5) |
C121—C126 | 1.385 (4) | C225—H225 | 0.95 |
C121—C122 | 1.390 (4) | C226—H226 | 0.95 |
C122—C123 | 1.381 (5) | C227—H22A | 0.98 |
C122—H122 | 0.95 | C227—H22B | 0.98 |
C123—C124 | 1.377 (5) | C227—H22C | 0.98 |
C123—H123 | 0.95 | C231—C236 | 1.383 (4) |
C124—C125 | 1.375 (5) | C231—C232 | 1.383 (4) |
C124—C127 | 1.516 (5) | C232—C233 | 1.390 (5) |
C125—C126 | 1.389 (5) | C232—H232 | 0.95 |
C125—H125 | 0.95 | C233—C234 | 1.370 (5) |
C126—H126 | 0.95 | C233—H233 | 0.95 |
C127—H12A | 0.98 | C234—C235 | 1.373 (5) |
C127—H12B | 0.98 | C234—C237 | 1.512 (5) |
C127—H12C | 0.98 | C235—C236 | 1.386 (5) |
C131—C136 | 1.362 (4) | C235—H235 | 0.95 |
C131—C132 | 1.375 (4) | C236—H236 | 0.95 |
C132—C133 | 1.379 (5) | C237—H23A | 0.98 |
C132—H132 | 0.95 | C237—H23B | 0.98 |
C133—C134 | 1.357 (5) | C237—H23C | 0.98 |
| | | |
N01—C02—C01 | 179.1 (7) | C135—C134—C137 | 121.4 (3) |
C02—C01—H01A | 109.5 | C133—C134—C137 | 121.3 (3) |
C02—C01—H01B | 109.5 | C134—C135—C136 | 121.6 (3) |
H01A—C01—H01B | 109.5 | C134—C135—H135 | 119.2 |
C02—C01—H01C | 109.5 | C136—C135—H135 | 119.2 |
H01A—C01—H01C | 109.5 | C131—C136—C135 | 121.5 (3) |
H01B—C01—H01C | 109.5 | C131—C136—H136 | 119.2 |
C111—P1—C131 | 104.29 (13) | C135—C136—H136 | 119.2 |
C111—P1—C121 | 106.51 (13) | C134—C137—H13A | 109.5 |
C131—P1—C121 | 101.71 (13) | C134—C137—H13B | 109.5 |
C111—P1—Ag | 112.36 (10) | H13A—C137—H13B | 109.5 |
C131—P1—Ag | 115.15 (10) | C134—C137—H13C | 109.5 |
C121—P1—Ag | 115.59 (10) | H13A—C137—H13C | 109.5 |
C211—P2—C221 | 105.03 (13) | H13B—C137—H13C | 109.5 |
C211—P2—C231 | 102.62 (13) | C216—C211—C212 | 118.1 (3) |
C221—P2—C231 | 106.15 (13) | C216—C211—P2 | 118.0 (2) |
C211—P2—Ag | 117.54 (9) | C212—C211—P2 | 123.7 (2) |
C221—P2—Ag | 109.03 (9) | C213—C212—C211 | 120.4 (3) |
C231—P2—Ag | 115.44 (9) | C213—C212—H212 | 119.8 |
N—Ag—P2 | 115.81 (7) | C211—C212—H212 | 119.8 |
N—Ag—P1 | 95.55 (7) | C214—C213—C212 | 121.6 (3) |
P2—Ag—P1 | 119.75 (3) | C214—C213—H213 | 119.2 |
N—Ag—Si | 103.43 (7) | C212—C213—H213 | 119.2 |
P2—Ag—Si | 112.43 (3) | C213—C214—C215 | 118.0 (3) |
P1—Ag—Si | 107.61 (3) | C213—C214—C217 | 121.7 (3) |
C—N—Ag | 147.5 (2) | C215—C214—C217 | 120.3 (4) |
C—S—Agi | 100.60 (11) | C214—C215—C216 | 121.0 (3) |
N—C—S | 178.2 (3) | C214—C215—H215 | 119.5 |
C112—C111—C116 | 117.5 (3) | C216—C215—H215 | 119.5 |
C112—C111—P1 | 125.4 (2) | C211—C216—C215 | 120.9 (3) |
C116—C111—P1 | 117.2 (2) | C211—C216—H216 | 119.5 |
C111—C112—C113 | 120.5 (3) | C215—C216—H216 | 119.5 |
C111—C112—H112 | 119.7 | C214—C217—H21A | 109.5 |
C113—C112—H112 | 119.7 | C214—C217—H21B | 109.5 |
C114—C113—C112 | 122.0 (3) | H21A—C217—H21B | 109.5 |
C114—C113—H113 | 119 | C214—C217—H21C | 109.5 |
C112—C113—H113 | 119 | H21A—C217—H21C | 109.5 |
C113—C114—C115 | 117.4 (3) | H21B—C217—H21C | 109.5 |
C113—C114—C117 | 121.5 (4) | C222—C221—C226 | 117.7 (3) |
C115—C114—C117 | 121.1 (3) | C222—C221—P2 | 123.9 (2) |
C114—C115—C116 | 121.6 (3) | C226—C221—P2 | 117.9 (2) |
C114—C115—H115 | 119.2 | C221—C222—C223 | 120.9 (3) |
C116—C115—H115 | 119.2 | C221—C222—H222 | 119.5 |
C115—C116—C111 | 121.0 (3) | C223—C222—H222 | 119.5 |
C115—C116—H116 | 119.5 | C224—C223—C222 | 121.8 (4) |
C111—C116—H116 | 119.5 | C224—C223—H223 | 119.1 |
C114—C117—H11A | 109.5 | C222—C223—H223 | 119.1 |
C114—C117—H11B | 109.5 | C223—C224—C225 | 117.3 (3) |
H11A—C117—H11B | 109.5 | C223—C224—C227 | 122.3 (4) |
C114—C117—H11C | 109.5 | C225—C224—C227 | 120.4 (4) |
H11A—C117—H11C | 109.5 | C224—C225—C226 | 121.4 (3) |
H11B—C117—H11C | 109.5 | C224—C225—H225 | 119.3 |
C126—C121—C122 | 117.7 (3) | C226—C225—H225 | 119.3 |
C126—C121—P1 | 118.6 (2) | C221—C226—C225 | 120.9 (3) |
C122—C121—P1 | 123.7 (2) | C221—C226—H226 | 119.5 |
C123—C122—C121 | 120.6 (3) | C225—C226—H226 | 119.5 |
C123—C122—H122 | 119.7 | C224—C227—H22A | 109.5 |
C121—C122—H122 | 119.7 | C224—C227—H22B | 109.5 |
C124—C123—C122 | 121.6 (3) | H22A—C227—H22B | 109.5 |
C124—C123—H123 | 119.2 | C224—C227—H22C | 109.5 |
C122—C123—H123 | 119.2 | H22A—C227—H22C | 109.5 |
C125—C124—C123 | 118.0 (3) | H22B—C227—H22C | 109.5 |
C125—C124—C127 | 121.0 (4) | C236—C231—C232 | 117.8 (3) |
C123—C124—C127 | 121.0 (4) | C236—C231—P2 | 118.6 (2) |
C124—C125—C126 | 121.0 (3) | C232—C231—P2 | 123.5 (2) |
C124—C125—H125 | 119.5 | C231—C232—C233 | 120.5 (3) |
C126—C125—H125 | 119.5 | C231—C232—H232 | 119.8 |
C121—C126—C125 | 121.0 (3) | C233—C232—H232 | 119.8 |
C121—C126—H126 | 119.5 | C234—C233—C232 | 122.0 (3) |
C125—C126—H126 | 119.5 | C234—C233—H233 | 119 |
C124—C127—H12A | 109.5 | C232—C233—H233 | 119 |
C124—C127—H12B | 109.5 | C233—C234—C235 | 117.1 (3) |
H12A—C127—H12B | 109.5 | C233—C234—C237 | 121.9 (3) |
C124—C127—H12C | 109.5 | C235—C234—C237 | 121.0 (3) |
H12A—C127—H12C | 109.5 | C234—C235—C236 | 122.0 (3) |
H12B—C127—H12C | 109.5 | C234—C235—H235 | 119 |
C136—C131—C132 | 116.7 (3) | C236—C235—H235 | 119 |
C136—C131—P1 | 118.3 (2) | C231—C236—C235 | 120.6 (3) |
C132—C131—P1 | 124.9 (2) | C231—C236—H236 | 119.7 |
C131—C132—C133 | 120.8 (3) | C235—C236—H236 | 119.7 |
C131—C132—H132 | 119.6 | C234—C237—H23A | 109.5 |
C133—C132—H132 | 119.6 | C234—C237—H23B | 109.5 |
C134—C133—C132 | 122.1 (3) | H23A—C237—H23B | 109.5 |
C134—C133—H133 | 119 | C234—C237—H23C | 109.5 |
C132—C133—H133 | 119 | H23A—C237—H23C | 109.5 |
C135—C134—C133 | 117.2 (3) | H23B—C237—H23C | 109.5 |
| | | |
C211—P2—Ag—N | 134.40 (13) | C136—C131—C132—C133 | 1.7 (7) |
C221—P2—Ag—N | −106.31 (13) | P1—C131—C132—C133 | 177.0 (4) |
C231—P2—Ag—N | 13.01 (13) | C131—C132—C133—C134 | 1.0 (8) |
C211—P2—Ag—P1 | −112.01 (11) | C132—C133—C134—C135 | −3.4 (7) |
C221—P2—Ag—P1 | 7.28 (11) | C132—C133—C134—C137 | −179.9 (5) |
C231—P2—Ag—P1 | 126.61 (11) | C133—C134—C135—C136 | 3.1 (6) |
C211—P2—Ag—Si | 15.79 (11) | C137—C134—C135—C136 | 179.6 (4) |
C221—P2—Ag—Si | 135.08 (10) | C132—C131—C136—C135 | −1.9 (6) |
C231—P2—Ag—Si | −105.59 (11) | P1—C131—C136—C135 | −177.6 (3) |
C111—P1—Ag—N | 82.47 (12) | C134—C135—C136—C131 | −0.5 (6) |
C131—P1—Ag—N | −36.74 (13) | C221—P2—C211—C216 | −159.2 (2) |
C121—P1—Ag—N | −155.00 (12) | C231—P2—C211—C216 | 90.0 (3) |
C111—P1—Ag—P2 | −41.54 (10) | Ag—P2—C211—C216 | −37.8 (3) |
C131—P1—Ag—P2 | −160.75 (11) | C221—P2—C211—C212 | 25.7 (3) |
C121—P1—Ag—P2 | 80.99 (11) | C231—P2—C211—C212 | −85.1 (3) |
C111—P1—Ag—Si | −171.52 (10) | Ag—P2—C211—C212 | 147.1 (2) |
C131—P1—Ag—Si | 69.27 (11) | C216—C211—C212—C213 | −1.4 (5) |
C121—P1—Ag—Si | −48.99 (10) | P2—C211—C212—C213 | 173.6 (2) |
P2—Ag—N—C | −164.1 (4) | C211—C212—C213—C214 | 0.0 (5) |
P1—Ag—N—C | 69.0 (5) | C212—C213—C214—C215 | 1.7 (5) |
Si—Ag—N—C | −40.6 (5) | C212—C213—C214—C217 | −177.5 (3) |
C131—P1—C111—C112 | −85.8 (3) | C213—C214—C215—C216 | −2.0 (5) |
C121—P1—C111—C112 | 21.3 (3) | C217—C214—C215—C216 | 177.3 (4) |
Ag—P1—C111—C112 | 148.9 (3) | C212—C211—C216—C215 | 1.2 (5) |
C131—P1—C111—C116 | 93.6 (3) | P2—C211—C216—C215 | −174.2 (3) |
C121—P1—C111—C116 | −159.3 (2) | C214—C215—C216—C211 | 0.6 (5) |
Ag—P1—C111—C116 | −31.8 (3) | C211—P2—C221—C222 | −120.2 (3) |
C116—C111—C112—C113 | −0.4 (5) | C231—P2—C221—C222 | −12.0 (3) |
P1—C111—C112—C113 | 178.9 (3) | Ag—P2—C221—C222 | 113.0 (3) |
C111—C112—C113—C114 | 0.4 (6) | C211—P2—C221—C226 | 68.5 (3) |
C112—C113—C114—C115 | 0.3 (6) | C231—P2—C221—C226 | 176.7 (2) |
C112—C113—C114—C117 | 179.8 (4) | Ag—P2—C221—C226 | −58.3 (3) |
C113—C114—C115—C116 | −0.9 (5) | C226—C221—C222—C223 | 1.6 (5) |
C117—C114—C115—C116 | 179.5 (4) | P2—C221—C222—C223 | −169.7 (3) |
C114—C115—C116—C111 | 0.8 (5) | C221—C222—C223—C224 | 0.1 (6) |
C112—C111—C116—C115 | −0.2 (5) | C222—C223—C224—C225 | −2.3 (5) |
P1—C111—C116—C115 | −179.5 (3) | C222—C223—C224—C227 | 176.9 (4) |
C111—P1—C121—C126 | 110.7 (2) | C223—C224—C225—C226 | 3.0 (5) |
C131—P1—C121—C126 | −140.3 (2) | C227—C224—C225—C226 | −176.2 (3) |
Ag—P1—C121—C126 | −14.9 (3) | C222—C221—C226—C225 | −0.9 (5) |
C111—P1—C121—C122 | −71.8 (3) | P2—C221—C226—C225 | 171.0 (3) |
C131—P1—C121—C122 | 37.1 (3) | C224—C225—C226—C221 | −1.5 (5) |
Ag—P1—C121—C122 | 162.6 (2) | C211—P2—C231—C236 | −147.7 (3) |
C126—C121—C122—C123 | −0.9 (5) | C221—P2—C231—C236 | 102.3 (3) |
P1—C121—C122—C123 | −178.3 (3) | Ag—P2—C231—C236 | −18.6 (3) |
C121—C122—C123—C124 | 0.4 (6) | C211—P2—C231—C232 | 28.9 (3) |
C122—C123—C124—C125 | 0.6 (6) | C221—P2—C231—C232 | −81.1 (3) |
C122—C123—C124—C127 | −179.8 (4) | Ag—P2—C231—C232 | 158.0 (2) |
C123—C124—C125—C126 | −1.2 (5) | C236—C231—C232—C233 | −1.0 (5) |
C127—C124—C125—C126 | 179.3 (4) | P2—C231—C232—C233 | −177.6 (3) |
C122—C121—C126—C125 | 0.4 (5) | C231—C232—C233—C234 | 0.1 (6) |
P1—C121—C126—C125 | 178.0 (2) | C232—C233—C234—C235 | 0.3 (6) |
C124—C125—C126—C121 | 0.7 (5) | C232—C233—C234—C237 | −179.7 (4) |
C111—P1—C131—C136 | −160.5 (3) | C233—C234—C235—C236 | 0.2 (6) |
C121—P1—C131—C136 | 88.9 (3) | C237—C234—C235—C236 | −179.8 (4) |
Ag—P1—C131—C136 | −36.9 (3) | C232—C231—C236—C235 | 1.4 (5) |
C111—P1—C131—C132 | 24.2 (4) | P2—C231—C236—C235 | 178.2 (3) |
C121—P1—C131—C132 | −86.4 (4) | C234—C235—C236—C231 | −1.1 (6) |
Ag—P1—C131—C132 | 147.8 (3) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C01—H01A···Si | 0.98 | 2.59 | 3.443 (6) | 146 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Ag2(NCS)2(C21H21P)4]·2C2H3N |
Mr | 1631.49 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 10.8842 (5), 13.8418 (7), 15.4048 (8) |
α, β, γ (°) | 75.839 (3), 69.345 (2), 72.833 (2) |
V (Å3) | 2049.11 (18) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.65 |
Crystal size (mm) | 0.43 × 0.28 × 0.18 |
|
Data collection |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.766, 0.891 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 41388, 10186, 7349 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.668 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.121, 1.03 |
No. of reflections | 10186 |
No. of parameters | 467 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.95, −0.62 |
Selected geometric parameters (Å, º) topP1—Ag | 2.5091 (8) | N—C | 1.149 (4) |
P2—Ag | 2.4612 (7) | S—C | 1.653 (3) |
Ag—N | 2.363 (3) | S—Agi | 2.5955 (9) |
| | | |
N—Ag—P1 | 95.55 (7) | P1—Ag—Si | 107.61 (3) |
P2—Ag—P1 | 119.75 (3) | C—N—Ag | 147.5 (2) |
N—Ag—Si | 103.43 (7) | C—S—Agi | 100.60 (11) |
P2—Ag—Si | 112.43 (3) | N—C—S | 178.2 (3) |
| | | |
P2—Ag—N—C | −164.1 (4) | Si—Ag—N—C | −40.6 (5) |
P1—Ag—N—C | 69.0 (5) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C01—H01A···Si | 0.98 | 2.59 | 3.443 (6) | 146 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Silver(I) complexes of the type [AgLnX] (L is a tertiary phosphine or arsine, n = 1–4 and X is a coordinating or noncoordinating anion) were first prepared by Mann et al. (1937) and were the first crystallographic examples of metal phosphine complexes. These compounds display a rich diversity of structural types due to the interplay of parameters such as the geometric flexibility of Ag(I), the bite angle, the electronic properties of the group 15 donor ligand, the coordination of the supporting ligand, etc. (Meijboom et al., 2008).
We recently embarked on a structural research project aimed at the identification which roles the above mentioned properties play during the crystallization of simple silver(I) salts with Group 15 donor ligands. Initial focus on tri-p-tolylphosphine complexes (Meijboom et al., 2006; Meijboom, 2006; Meijboom & Muller, 2006; Venter et al., 2006; Meijboom, 2007) enable us to compare these structures with the isosteric triphenylphosphine complexes.
As part of the above mentioned series, we present here the title compound, (I), a silver(I) bis[tri(p-tolyl)phosphine] complex, of which only relatively few examples can be found in the literature [Cambridge Structural Database (CSD), Version 5.28, November 2006 update; Allen, 2002].
The Ag atom in compound (I) is surrounded by two phosphine ligands as well as an N and a S atom of two different thiocyanate ligands, forming a distorted tetrahedral configuration; selected geometric parameters are given in Table 1. The thiocyanate ligands form bridges to give a dimeric structure. In addition, some weak inter- and intramolecular interactions are observed (Table 2). All bond distances and angles are otherwise unremarkable.