Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104009473/na1660sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104009473/na1660Isup2.hkl |
CCDC reference: 243583
The ligand was prepared by the literature method (McAuliffe et al., 1978; Pal et al., 1994), by the reaction of o-aminobenzenethiol and 1,2-dibromomethylbenzene (yield 58%; m.p. 371–373 K). Spectroscopic analysis: 1H NMR (CDCl3, δ, p.p.m.): 3.98 (SCH2–, 4H, s), 4.13 (NH2–, 4H, s), 6.62–6.72 (C—C6H4—C, 4H, m), 6.99–7.19 (N—C6H4—S, 8H, m). For the preparation of (I), a solution of AgNO3 (90 mg, 0.5 mmol) in methanol (10 ml) was carefully layered on a solution of L (140 mg, 0.5 mmol) in chloroform (10 ml), and the mixture was kept in darkness. Colourless single crystals of (I) suitable for X-ray analysis were obtained after about two weeks in 48% yield. Analysis calculated for (I): C 39.27, H 3.27, N 6.54%; found: C 38.95, H 3.32, N 6.33%. Spectroscopic analysis: IR (KBr pellet, ν, cm−1): 3447 (w), 3373 (m), 3270 (m), 3157 (w), 3064 (w), 2976 (w), 1606 (s), 1570 (m), 1479 (versus), 1447 (s), 1385 (versus), 1355 (versus), 1315 (s), 1233 (s), 1161 (m), 1044 (m), 1002 (m), 913 (m), 815 (m), 745 (versus), 692 (m).
H atoms were placed in geometric positions and refined using a riding model, with N—H distances of 0.90 Å and C—H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C,N). Please check added text and correct as necessary.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[Ag(C20H20N2S2)](NO3)·CHCl3 | Z = 2 |
Mr = 641.75 | F(000) = 644 |
Triclinic, P1 | Dx = 1.761 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.441 (6) Å | Cell parameters from 865 reflections |
b = 9.805 (6) Å | θ = 2.3–24.6° |
c = 13.936 (9) Å | µ = 1.37 mm−1 |
α = 102.385 (11)° | T = 293 K |
β = 98.580 (12)° | Block, colourless |
γ = 101.351 (11)° | 0.30 × 0.25 × 0.20 mm |
V = 1210.4 (13) Å3 |
Bruker SMART CCD area-detector diffractometer | 4269 independent reflections |
Radiation source: fine-focus sealed tube | 2561 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: empirical (using intensity measurements) via multi-scan [SADABS (Sheldrick, 1996; Blessing, 1995)] | h = −7→11 |
Tmin = 0.685, Tmax = 0.772 | k = −11→11 |
5074 measured reflections | l = −16→14 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2) + (0.0802P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.152 | (Δ/σ)max = 0.001 |
S = 0.96 | Δρmax = 1.20 e Å−3 |
4269 reflections | Δρmin = −0.65 e Å−3 |
298 parameters |
[Ag(C20H20N2S2)](NO3)·CHCl3 | γ = 101.351 (11)° |
Mr = 641.75 | V = 1210.4 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.441 (6) Å | Mo Kα radiation |
b = 9.805 (6) Å | µ = 1.37 mm−1 |
c = 13.936 (9) Å | T = 293 K |
α = 102.385 (11)° | 0.30 × 0.25 × 0.20 mm |
β = 98.580 (12)° |
Bruker SMART CCD area-detector diffractometer | 4269 independent reflections |
Absorption correction: empirical (using intensity measurements) via multi-scan [SADABS (Sheldrick, 1996; Blessing, 1995)] | 2561 reflections with I > 2σ(I) |
Tmin = 0.685, Tmax = 0.772 | Rint = 0.033 |
5074 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 0.96 | Δρmax = 1.20 e Å−3 |
4269 reflections | Δρmin = −0.65 e Å−3 |
298 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.50351 (6) | 0.74897 (6) | 0.98894 (4) | 0.0400 (2) | |
S1 | 0.6038 (2) | 0.53961 (19) | 0.90899 (14) | 0.0325 (5) | |
S2 | 0.66958 (18) | 0.97716 (19) | 0.97168 (13) | 0.0306 (4) | |
N1 | 0.5194 (7) | 0.2206 (6) | 0.8363 (4) | 0.0386 (15) | |
H1C | 0.6155 | 0.2501 | 0.8351 | 0.046* | |
H1D | 0.4917 | 0.1260 | 0.8063 | 0.046* | |
N2 | 0.7575 (6) | 1.2978 (6) | 1.0613 (5) | 0.0348 (15) | |
H2A | 0.7963 | 1.2829 | 1.0059 | 0.042* | |
H2B | 0.7916 | 1.3912 | 1.0937 | 0.042* | |
C1 | 0.7513 (7) | 0.5961 (8) | 0.8443 (6) | 0.0353 (18) | |
H1A | 0.8386 | 0.6504 | 0.8940 | 0.042* | |
H1B | 0.7751 | 0.5112 | 0.8066 | 0.042* | |
C2 | 0.7141 (7) | 0.6850 (7) | 0.7750 (6) | 0.0333 (18) | |
C3 | 0.6581 (8) | 0.6177 (9) | 0.6744 (6) | 0.042 (2) | |
H3A | 0.6469 | 0.5190 | 0.6525 | 0.051* | |
C4 | 0.6194 (10) | 0.6917 (9) | 0.6078 (6) | 0.059 (3) | |
H4A | 0.5780 | 0.6434 | 0.5414 | 0.071* | |
C5 | 0.6407 (10) | 0.8371 (9) | 0.6375 (7) | 0.057 (2) | |
H5A | 0.6147 | 0.8885 | 0.5915 | 0.068* | |
C6 | 0.7005 (8) | 0.9068 (8) | 0.7353 (6) | 0.043 (2) | |
H6A | 0.7138 | 1.0060 | 0.7556 | 0.051* | |
C7 | 0.7410 (7) | 0.8342 (7) | 0.8036 (5) | 0.0295 (17) | |
C8 | 0.8091 (7) | 0.9186 (7) | 0.9087 (5) | 0.0330 (17) | |
H8A | 0.8840 | 1.0015 | 0.9080 | 0.040* | |
H8B | 0.8560 | 0.8595 | 0.9446 | 0.040* | |
C9 | 0.4635 (8) | 0.4397 (8) | 0.8059 (5) | 0.0336 (17) | |
C10 | 0.3802 (8) | 0.5079 (9) | 0.7502 (6) | 0.042 (2) | |
H10A | 0.3944 | 0.6073 | 0.7696 | 0.050* | |
C11 | 0.2772 (9) | 0.4300 (10) | 0.6669 (6) | 0.051 (2) | |
H11A | 0.2204 | 0.4756 | 0.6299 | 0.061* | |
C12 | 0.2587 (9) | 0.2847 (11) | 0.6388 (6) | 0.055 (2) | |
H12A | 0.1911 | 0.2319 | 0.5808 | 0.067* | |
C13 | 0.3370 (8) | 0.2152 (9) | 0.6936 (6) | 0.044 (2) | |
H13A | 0.3207 | 0.1156 | 0.6738 | 0.053* | |
C14 | 0.4400 (7) | 0.2914 (7) | 0.7782 (5) | 0.0304 (17) | |
C15 | 0.7762 (7) | 1.0669 (7) | 1.0934 (5) | 0.0293 (16) | |
C16 | 0.8256 (8) | 0.9879 (8) | 1.1560 (6) | 0.0388 (19) | |
H16A | 0.8031 | 0.8881 | 1.1347 | 0.047* | |
C17 | 0.9074 (9) | 1.0555 (10) | 1.2492 (6) | 0.049 (2) | |
H17A | 0.9417 | 1.0021 | 1.2913 | 0.059* | |
C18 | 0.9390 (9) | 1.2018 (10) | 1.2805 (6) | 0.052 (2) | |
H18A | 0.9940 | 1.2479 | 1.3445 | 0.063* | |
C19 | 0.8902 (8) | 1.2811 (8) | 1.2185 (6) | 0.0396 (19) | |
H19A | 0.9121 | 1.3807 | 1.2411 | 0.048* | |
C20 | 0.8092 (7) | 1.2156 (7) | 1.1231 (5) | 0.0312 (17) | |
C21 | 0.8248 (9) | 0.2444 (8) | 0.5954 (6) | 0.045 (2) | |
H21A | 0.8803 | 0.2676 | 0.6644 | 0.054* | |
Cl1 | 0.6404 (3) | 0.2104 (3) | 0.5995 (2) | 0.0704 (7) | |
Cl2 | 0.8785 (3) | 0.3900 (3) | 0.5468 (2) | 0.0810 (8) | |
Cl3 | 0.8698 (3) | 0.0933 (3) | 0.5284 (2) | 0.0779 (8) | |
N3 | 0.0262 (8) | 0.6789 (8) | 0.1288 (6) | 0.0490 (18) | |
O1 | −0.0375 (10) | 0.6207 (10) | 0.1811 (7) | 0.124 (4) | |
O2 | −0.0298 (12) | 0.6992 (13) | 0.0539 (7) | 0.155 (5) | |
O3 | 0.1554 (7) | 0.7287 (7) | 0.1542 (6) | 0.083 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0382 (4) | 0.0380 (4) | 0.0417 (4) | 0.0040 (2) | 0.0109 (3) | 0.0083 (3) |
S1 | 0.0386 (11) | 0.0259 (10) | 0.0326 (11) | 0.0045 (8) | 0.0074 (8) | 0.0092 (8) |
S2 | 0.0294 (10) | 0.0270 (10) | 0.0318 (11) | 0.0024 (7) | 0.0071 (8) | 0.0032 (8) |
N1 | 0.048 (4) | 0.026 (3) | 0.040 (4) | 0.004 (3) | 0.011 (3) | 0.006 (3) |
N2 | 0.032 (3) | 0.021 (3) | 0.049 (4) | 0.001 (3) | 0.013 (3) | 0.007 (3) |
C1 | 0.028 (4) | 0.033 (4) | 0.048 (5) | 0.006 (3) | 0.014 (3) | 0.013 (4) |
C2 | 0.028 (4) | 0.032 (4) | 0.040 (5) | 0.004 (3) | 0.015 (3) | 0.007 (4) |
C3 | 0.046 (5) | 0.037 (5) | 0.039 (5) | −0.001 (4) | 0.015 (4) | 0.004 (4) |
C4 | 0.084 (7) | 0.053 (6) | 0.031 (5) | −0.006 (5) | 0.012 (4) | 0.011 (4) |
C5 | 0.076 (7) | 0.049 (6) | 0.050 (6) | 0.010 (5) | 0.010 (5) | 0.026 (5) |
C6 | 0.060 (5) | 0.034 (5) | 0.031 (5) | 0.007 (4) | 0.008 (4) | 0.007 (4) |
C7 | 0.023 (4) | 0.033 (4) | 0.029 (4) | 0.003 (3) | 0.007 (3) | 0.004 (3) |
C8 | 0.035 (4) | 0.031 (4) | 0.029 (4) | 0.006 (3) | 0.007 (3) | 0.001 (3) |
C9 | 0.039 (4) | 0.038 (5) | 0.024 (4) | 0.006 (3) | 0.009 (3) | 0.009 (3) |
C10 | 0.041 (5) | 0.047 (5) | 0.042 (5) | 0.018 (4) | 0.011 (4) | 0.011 (4) |
C11 | 0.042 (5) | 0.075 (7) | 0.036 (5) | 0.019 (5) | 0.003 (4) | 0.015 (5) |
C12 | 0.043 (5) | 0.080 (7) | 0.031 (5) | −0.004 (5) | −0.001 (4) | 0.011 (5) |
C13 | 0.036 (5) | 0.043 (5) | 0.042 (5) | −0.006 (4) | 0.010 (4) | 0.001 (4) |
C14 | 0.036 (4) | 0.029 (4) | 0.029 (4) | 0.004 (3) | 0.013 (3) | 0.011 (3) |
C15 | 0.026 (4) | 0.033 (4) | 0.028 (4) | 0.004 (3) | 0.010 (3) | 0.006 (3) |
C16 | 0.035 (4) | 0.041 (5) | 0.045 (5) | 0.008 (3) | 0.013 (4) | 0.017 (4) |
C17 | 0.045 (5) | 0.063 (6) | 0.048 (6) | 0.016 (4) | 0.010 (4) | 0.028 (5) |
C18 | 0.042 (5) | 0.070 (7) | 0.035 (5) | −0.003 (4) | 0.006 (4) | 0.007 (5) |
C19 | 0.036 (4) | 0.044 (5) | 0.034 (5) | 0.004 (4) | 0.010 (3) | 0.002 (4) |
C20 | 0.021 (4) | 0.031 (4) | 0.040 (5) | −0.001 (3) | 0.009 (3) | 0.009 (4) |
C21 | 0.049 (5) | 0.050 (5) | 0.039 (5) | 0.017 (4) | 0.015 (4) | 0.010 (4) |
Cl1 | 0.0543 (15) | 0.0685 (16) | 0.099 (2) | 0.0174 (12) | 0.0291 (13) | 0.0303 (15) |
Cl2 | 0.0844 (19) | 0.0671 (17) | 0.107 (2) | 0.0160 (14) | 0.0377 (16) | 0.0445 (16) |
Cl3 | 0.0744 (18) | 0.0579 (15) | 0.098 (2) | 0.0210 (13) | 0.0300 (15) | −0.0011 (15) |
N3 | 0.046 (5) | 0.061 (5) | 0.039 (5) | 0.010 (4) | 0.010 (4) | 0.011 (4) |
O1 | 0.136 (8) | 0.115 (7) | 0.110 (7) | −0.033 (6) | 0.074 (6) | 0.028 (6) |
O2 | 0.169 (10) | 0.259 (14) | 0.062 (6) | 0.107 (9) | 0.002 (6) | 0.055 (7) |
O3 | 0.043 (4) | 0.065 (4) | 0.123 (6) | −0.001 (3) | 0.019 (4) | −0.005 (4) |
Ag1—N2i | 2.383 (6) | C8—H8A | 0.9700 |
Ag1—N1ii | 2.436 (6) | C8—H8B | 0.9700 |
Ag1—S1 | 2.540 (2) | C9—C10 | 1.384 (10) |
Ag1—S2 | 2.546 (2) | C9—C14 | 1.386 (10) |
S1—C9 | 1.759 (7) | C10—C11 | 1.367 (11) |
S1—C1 | 1.829 (7) | C10—H10A | 0.9300 |
S2—C15 | 1.779 (7) | C11—C12 | 1.363 (12) |
S2—C8 | 1.806 (7) | C11—H11A | 0.9300 |
N1—C14 | 1.402 (9) | C12—C13 | 1.359 (12) |
N1—Ag1ii | 2.436 (6) | C12—H12A | 0.9300 |
N1—H1C | 0.9000 | C13—C14 | 1.374 (10) |
N1—H1D | 0.9000 | C13—H13A | 0.9300 |
N2—C20 | 1.398 (9) | C15—C16 | 1.375 (10) |
N2—Ag1i | 2.383 (6) | C15—C20 | 1.385 (9) |
N2—H2A | 0.9000 | C16—C17 | 1.361 (11) |
N2—H2B | 0.9000 | C16—H16A | 0.9300 |
C1—C2 | 1.482 (10) | C17—C18 | 1.364 (12) |
C1—H1A | 0.9700 | C17—H17A | 0.9300 |
C1—H1B | 0.9700 | C18—C19 | 1.369 (11) |
C2—C3 | 1.387 (10) | C18—H18A | 0.9300 |
C2—C7 | 1.391 (10) | C19—C20 | 1.379 (10) |
C3—C4 | 1.347 (11) | C19—H19A | 0.9300 |
C3—H3A | 0.9300 | C21—Cl1 | 1.718 (8) |
C4—C5 | 1.361 (12) | C21—Cl2 | 1.728 (9) |
C4—H4A | 0.9300 | C21—Cl3 | 1.738 (8) |
C5—C6 | 1.364 (11) | C21—H21A | 0.9800 |
C5—H5A | 0.9300 | N3—O2 | 1.172 (10) |
C6—C7 | 1.360 (10) | N3—O1 | 1.180 (9) |
C6—H6A | 0.9300 | N3—O3 | 1.189 (8) |
C7—C8 | 1.495 (9) | ||
N2i—Ag1—N1ii | 90.3 (2) | S2—C8—H8A | 109.7 |
N2i—Ag1—S1 | 111.83 (14) | C7—C8—H8B | 109.7 |
N1ii—Ag1—S1 | 118.04 (15) | S2—C8—H8B | 109.7 |
N2i—Ag1—S2 | 120.79 (15) | H8A—C8—H8B | 108.2 |
N1ii—Ag1—S2 | 108.66 (15) | C10—C9—C14 | 119.8 (7) |
S1—Ag1—S2 | 107.09 (8) | C10—C9—S1 | 120.7 (6) |
C9—S1—C1 | 100.3 (3) | C14—C9—S1 | 119.5 (6) |
C9—S1—Ag1 | 104.5 (2) | C11—C10—C9 | 120.3 (8) |
C1—S1—Ag1 | 112.0 (2) | C11—C10—H10A | 119.8 |
C15—S2—C8 | 100.9 (3) | C9—C10—H10A | 119.8 |
C15—S2—Ag1 | 106.6 (2) | C12—C11—C10 | 119.2 (8) |
C8—S2—Ag1 | 105.6 (2) | C12—C11—H11A | 120.4 |
C14—N1—Ag1ii | 117.9 (4) | C10—C11—H11A | 120.4 |
C14—N1—H1C | 107.8 | C13—C12—C11 | 121.4 (8) |
Ag1ii—N1—H1C | 107.8 | C13—C12—H12A | 119.3 |
C14—N1—H1D | 107.8 | C11—C12—H12A | 119.3 |
Ag1ii—N1—H1D | 107.8 | C12—C13—C14 | 120.3 (8) |
H1C—N1—H1D | 107.2 | C12—C13—H13A | 119.9 |
C20—N2—Ag1i | 115.8 (4) | C14—C13—H13A | 119.9 |
C20—N2—H2A | 108.3 | C13—C14—C9 | 119.0 (7) |
Ag1i—N2—H2A | 108.3 | C13—C14—N1 | 120.8 (7) |
C20—N2—H2B | 108.3 | C9—C14—N1 | 120.3 (6) |
Ag1i—N2—H2B | 108.3 | C16—C15—C20 | 121.1 (7) |
H2A—N2—H2B | 107.4 | C16—C15—S2 | 119.6 (5) |
C2—C1—S1 | 114.0 (5) | C20—C15—S2 | 119.4 (6) |
C2—C1—H1A | 108.8 | C17—C16—C15 | 120.1 (7) |
S1—C1—H1A | 108.8 | C17—C16—H16A | 120.0 |
C2—C1—H1B | 108.8 | C15—C16—H16A | 120.0 |
S1—C1—H1B | 108.8 | C16—C17—C18 | 119.8 (8) |
H1A—C1—H1B | 107.7 | C16—C17—H17A | 120.1 |
C3—C2—C7 | 117.6 (7) | C18—C17—H17A | 120.1 |
C3—C2—C1 | 118.6 (7) | C17—C18—C19 | 120.5 (8) |
C7—C2—C1 | 123.7 (7) | C17—C18—H18A | 119.8 |
C4—C3—C2 | 121.7 (8) | C19—C18—H18A | 119.8 |
C4—C3—H3A | 119.2 | C18—C19—C20 | 121.0 (8) |
C2—C3—H3A | 119.2 | C18—C19—H19A | 119.5 |
C3—C4—C5 | 120.1 (8) | C20—C19—H19A | 119.5 |
C3—C4—H4A | 119.9 | C19—C20—C15 | 117.6 (7) |
C5—C4—H4A | 119.9 | C19—C20—N2 | 120.4 (7) |
C4—C5—C6 | 119.5 (8) | C15—C20—N2 | 121.9 (6) |
C4—C5—H5A | 120.3 | Cl1—C21—Cl2 | 112.2 (5) |
C6—C5—H5A | 120.3 | Cl1—C21—Cl3 | 111.1 (5) |
C7—C6—C5 | 121.4 (7) | Cl2—C21—Cl3 | 110.5 (4) |
C7—C6—H6A | 119.3 | Cl1—C21—H21A | 107.6 |
C5—C6—H6A | 119.3 | Cl2—C21—H21A | 107.6 |
C6—C7—C2 | 119.6 (7) | Cl3—C21—H21A | 107.6 |
C6—C7—C8 | 118.2 (6) | O2—N3—O1 | 124.7 (11) |
C2—C7—C8 | 122.2 (7) | O2—N3—O3 | 115.6 (10) |
C7—C8—S2 | 110.0 (5) | O1—N3—O3 | 119.6 (9) |
C7—C8—H8A | 109.7 | ||
N2i—Ag1—S1—C9 | 19.0 (3) | C1—S1—C9—C14 | 98.1 (6) |
N1ii—Ag1—S1—C9 | 121.7 (3) | Ag1—S1—C9—C14 | −145.8 (5) |
S2—Ag1—S1—C9 | −115.4 (3) | C14—C9—C10—C11 | −1.4 (11) |
N2i—Ag1—S1—C1 | 126.7 (3) | S1—C9—C10—C11 | 176.3 (6) |
N1ii—Ag1—S1—C1 | −130.6 (3) | C9—C10—C11—C12 | −0.7 (12) |
S2—Ag1—S1—C1 | −7.7 (3) | C10—C11—C12—C13 | 2.2 (13) |
N2i—Ag1—S2—C15 | 123.1 (3) | C11—C12—C13—C14 | −1.6 (13) |
N1ii—Ag1—S2—C15 | 21.2 (3) | C12—C13—C14—C9 | −0.6 (11) |
S1—Ag1—S2—C15 | −107.4 (2) | C12—C13—C14—N1 | 178.8 (7) |
N2i—Ag1—S2—C8 | −130.1 (3) | C10—C9—C14—C13 | 2.0 (11) |
N1ii—Ag1—S2—C8 | 127.9 (3) | S1—C9—C14—C13 | −175.7 (5) |
S1—Ag1—S2—C8 | −0.6 (2) | C10—C9—C14—N1 | −177.4 (6) |
C9—S1—C1—C2 | 60.7 (6) | S1—C9—C14—N1 | 5.0 (9) |
Ag1—S1—C1—C2 | −49.7 (6) | Ag1ii—N1—C14—C13 | −120.1 (6) |
S1—C1—C2—C3 | −94.6 (7) | Ag1ii—N1—C14—C9 | 59.3 (8) |
S1—C1—C2—C7 | 89.6 (7) | C8—S2—C15—C16 | −72.7 (6) |
C7—C2—C3—C4 | −5.3 (11) | Ag1—S2—C15—C16 | 37.3 (6) |
C1—C2—C3—C4 | 178.7 (7) | C8—S2—C15—C20 | 106.7 (6) |
C2—C3—C4—C5 | 2.8 (13) | Ag1—S2—C15—C20 | −143.2 (5) |
C3—C4—C5—C6 | −0.5 (14) | C20—C15—C16—C17 | 0.5 (11) |
C4—C5—C6—C7 | 0.8 (13) | S2—C15—C16—C17 | 179.9 (6) |
C5—C6—C7—C2 | −3.4 (11) | C15—C16—C17—C18 | 0.6 (12) |
C5—C6—C7—C8 | 178.5 (7) | C16—C17—C18—C19 | −0.7 (12) |
C3—C2—C7—C6 | 5.5 (10) | C17—C18—C19—C20 | −0.4 (12) |
C1—C2—C7—C6 | −178.7 (7) | C18—C19—C20—C15 | 1.4 (11) |
C3—C2—C7—C8 | −176.5 (6) | C18—C19—C20—N2 | 178.7 (7) |
C1—C2—C7—C8 | −0.7 (10) | C16—C15—C20—C19 | −1.5 (10) |
C6—C7—C8—S2 | 74.4 (7) | S2—C15—C20—C19 | 179.1 (5) |
C2—C7—C8—S2 | −103.6 (7) | C16—C15—C20—N2 | −178.7 (6) |
C15—S2—C8—C7 | 178.0 (5) | S2—C15—C20—N2 | 1.9 (9) |
Ag1—S2—C8—C7 | 67.1 (5) | Ag1i—N2—C20—C19 | −118.3 (6) |
C1—S1—C9—C10 | −79.6 (6) | Ag1i—N2—C20—C15 | 58.8 (8) |
Ag1—S1—C9—C10 | 36.5 (6) |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···S1 | 0.90 | 2.83 | 2.977 (6) | 90 |
N2—H2A···S2 | 0.90 | 2.91 | 3.018 (6) | 88 |
N1—H1C···O3iii | 0.90 | 2.11 | 2.990 (9) | 165 |
C21—H21A···O1iii | 0.98 | 2.33 | 3.287 (13) | 165 |
C21—H21A···O3iii | 0.98 | 2.59 | 3.416 (12) | 142 |
N2—H2A···O3iv | 0.90 | 2.33 | 3.203 (10) | 164 |
N2—H2A···O2iv | 0.90 | 2.46 | 3.227 (12) | 144 |
N2—H2B···O1v | 0.90 | 2.44 | 3.303 (10) | 161 |
C1—H1A···O2vi | 0.97 | 2.29 | 3.152 (12) | 148 |
Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+2, −z+1; (v) x+1, y+1, z+1; (vi) x+1, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C20H20N2S2)](NO3)·CHCl3 |
Mr | 641.75 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.441 (6), 9.805 (6), 13.936 (9) |
α, β, γ (°) | 102.385 (11), 98.580 (12), 101.351 (11) |
V (Å3) | 1210.4 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.37 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) via multi-scan [SADABS (Sheldrick, 1996; Blessing, 1995)] |
Tmin, Tmax | 0.685, 0.772 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5074, 4269, 2561 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.152, 0.96 |
No. of reflections | 4269 |
No. of parameters | 298 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.20, −0.65 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···S1 | 0.90 | 2.83 | 2.977 (6) | 90 |
N2—H2A···S2 | 0.90 | 2.91 | 3.018 (6) | 88 |
N1—H1C···O3i | 0.90 | 2.11 | 2.990 (9) | 165 |
C21—H21A···O1i | 0.98 | 2.33 | 3.287 (13) | 165 |
C21—H21A···O3i | 0.98 | 2.59 | 3.416 (12) | 142 |
N2—H2A···O3ii | 0.90 | 2.33 | 3.203 (10) | 164 |
N2—H2A···O2ii | 0.90 | 2.46 | 3.227 (12) | 144 |
N2—H2B···O1iii | 0.90 | 2.44 | 3.303 (10) | 161 |
C1—H1A···O2iv | 0.97 | 2.29 | 3.152 (12) | 148 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x+1, y+1, z+1; (iv) x+1, y, z+1. |
As a favourable and fashionable connecting node for the construction of coordination polymers, the AgI ion shows a good coordination tendency with S or N donors. The study of Ag complexes of N-containing heterocyclic thioether ligands has mainly focused on pyridine derivatives (Sharma et al., 1999; Constable et al., 2002; Xie et al., 2004; Xie & Bu, 2003; Bu et al., 2003), although examples with other heterocyclic thioether ligands have also been reported (Hong et al., 2000; Zou et al., 2004). Dithioethers, a type of ditopic ligand, can be used as bridging ligands in the construction of coordination polymers with soft metal ions, and a series of bis(phenylthio)alkane and bis(heteroarylthio)alkane flexible ligands and their Ag complexes have been prepared and characterized (Li et al., 2003; Bu, Hou et al., 2002; Bu, Chen et al., 2002). In this paper, we report the crystal structure of the title novel Ag complex, (I), with a relatively rigid bis(heteroarylthioether) ligand, 1,2-phenylenebis(methylenethio-2-aniline) (L). \sch
Complex (I) is a one-dimensional metallopolymer, and the geometry at the AgI ion can be best described as a slightly distorted tetrahedron comprising the two S donors of the ligand and two N donors from two amino groups of two adjacent complexes, with the NO3− counteranion not taking part in coordination (Fig. 1). Ag—N bond distances are 2.382 (5) and 2.428 (5) Å, and Ag—S bond distances are 2.537 (2) and 2.546 (2) Å, which are in the ranges expected for such coordination (Carlucci et al., 1998; Engelhardt et al., 1985; Gotsis & White, 1987).
The coordination of the two S donors of the ligand to the Ag atom forms a seven-membered chelate ring (Ag1/S1/C1/C2/C7/C8/S2), with an S···S distance of 4.088 (2) Å. Atoms C1, S1, Ag1, S2 and C8 are almost coplanar. The two terminal aniline groups of the ligand are oriented in opposite directions relative to the chelate plane and are almost perpendicular to this plane, with dihedral angles of 82.3 (3) and 83.6 (4)°. These two planes are almost parallel to each other, with a dihedral angle of 14.5 (2)°, and the angles between them and the central o-phenylene linker are 23.1 (3) and 9.4 (2)°.
The coordination of the Ag atom to donors from three different ligands results in the assembly of an intriguing extended polymeric structure, which consists of a complex system of interconnected rings, as shown in Fig. 2. In addition, a ten-membered centrosymmetric dinuclear ring is formed by two Ag atoms linking with two N—C—C—S bridges, with an Ag···Ag interatomic distance of 4.945 (4) Å.