Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102000665/ob1051sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102000665/ob1051Isup2.hkl |
CCDC reference: 182976
The ligand was synthesized according to the procedure published by Ibrahim et al. (2001), with slight modifications. To a solution containing bz3tren in acetonitrile was added a solution of an equimolar amount of silver perchlorate dissolved in acetonitrile. Slow evaporation of the resulting solution in the dark afforded colourless crystals of (I), suitable for X-ray crystallographic analysis.
H atoms were added at calculated positions, with C—H = 0.96 Å and N—H = 0.90 Å, and refined using a riding model, with Uiso = 1.2Ueq of the parent atom.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SHELXTL (Siemens, 1996); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A perspective view of compound (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity. |
[Ag(C27H36N4)]ClO4 | F(000) = 1288 |
Mr = 623.92 | Dx = 1.420 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 16.0287 (11) Å | Cell parameters from 9303 reflections |
b = 9.6132 (7) Å | θ = 2.2–28.3° |
c = 20.2697 (15) Å | µ = 0.82 mm−1 |
β = 110.906 (1)° | T = 296 K |
V = 2917.7 (4) Å3 | Block, colourless |
Z = 4 | 0.5 × 0.4 × 0.4 mm |
Siemens SMART Query CCD area-detector diffractometer | 4068 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 28.3°, θmin = 2.2° |
ϕ and ω scans | h = −15→21 |
9303 measured reflections | k = −12→11 |
5264 independent reflections | l = −26→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0536P)2 + 0.2006P] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
5264 reflections | Δρmax = 0.32 e Å−3 |
334 parameters | Δρmin = −0.31 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 1637 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (3) |
[Ag(C27H36N4)]ClO4 | V = 2917.7 (4) Å3 |
Mr = 623.92 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 16.0287 (11) Å | µ = 0.82 mm−1 |
b = 9.6132 (7) Å | T = 296 K |
c = 20.2697 (15) Å | 0.5 × 0.4 × 0.4 mm |
β = 110.906 (1)° |
Siemens SMART Query CCD area-detector diffractometer | 4068 reflections with I > 2σ(I) |
9303 measured reflections | Rint = 0.026 |
5264 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.090 | Δρmax = 0.32 e Å−3 |
S = 0.99 | Δρmin = −0.31 e Å−3 |
5264 reflections | Absolute structure: Flack (1983), 1637 Friedel pairs |
334 parameters | Absolute structure parameter: 0.02 (3) |
2 restraints |
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 | ||
Ag | −0.89617 (4) | −0.25974 (2) | −0.53959 (4) | 0.07364 (11) | |
Cl | −0.76646 (9) | −0.73679 (11) | −0.62325 (7) | 0.0846 (3) | |
O1 | −0.8309 (6) | −0.6945 (8) | −0.6863 (3) | 0.204 (3) | |
O2 | −0.6881 (4) | −0.6625 (6) | −0.6064 (4) | 0.190 (3) | |
O3 | −0.8010 (6) | −0.7116 (8) | −0.5720 (5) | 0.193 (3) | |
O4 | −0.7507 (4) | −0.8764 (4) | −0.6254 (3) | 0.166 (2) | |
N1 | −0.9306 (3) | −0.2523 (3) | −0.6703 (3) | 0.0856 (11) | |
N2 | −1.0202 (2) | −0.4070 (3) | −0.5875 (2) | 0.0799 (9) | |
H2 | −1.0693 | −0.3568 | −0.5921 | 0.096* | |
N3 | −0.9216 (3) | −0.0226 (3) | −0.5708 (2) | 0.0836 (10) | |
H3 | −0.8685 | 0.0177 | −0.5639 | 0.100* | |
N4 | −0.7686 (2) | −0.3534 (4) | −0.5547 (2) | 0.0833 (10) | |
H4 | −0.7759 | −0.4463 | −0.5587 | 0.100* | |
C1 | −1.0154 (4) | −0.3236 (6) | −0.7013 (3) | 0.0980 (14) | |
H1A | −1.0216 | −0.3543 | −0.7479 | 0.118* | |
H1B | −1.0628 | −0.2591 | −0.7058 | 0.118* | |
C2 | −1.0250 (4) | −0.4465 (5) | −0.6591 (3) | 0.0956 (14) | |
H2A | −1.0813 | −0.4910 | −0.6833 | 0.115* | |
H2B | −0.9786 | −0.5124 | −0.6555 | 0.115* | |
C3 | −1.0206 (4) | −0.5302 (4) | −0.5438 (3) | 0.0980 (15) | |
H3A | −0.9694 | −0.5869 | −0.5388 | 0.118* | |
H3B | −1.0731 | −0.5846 | −0.5671 | 0.118* | |
C4 | −1.0190 (3) | −0.4887 (4) | −0.4729 (3) | 0.0822 (12) | |
C5 | −1.0963 (4) | −0.4507 (5) | −0.4620 (3) | 0.1003 (15) | |
H5 | −1.1525 | −0.4520 | −0.5006 | 0.120* | |
C6 | −1.0928 (5) | −0.4115 (6) | −0.3965 (4) | 0.1142 (18) | |
H6 | −1.1471 | −0.3858 | −0.3898 | 0.137* | |
C7 | −1.0151 (6) | −0.4076 (7) | −0.3407 (4) | 0.1215 (19) | |
H7 | −1.0144 | −0.3804 | −0.2950 | 0.146* | |
C8 | −0.9379 (5) | −0.4428 (7) | −0.3503 (4) | 0.1138 (18) | |
H8 | −0.8822 | −0.4389 | −0.3113 | 0.137* | |
C9 | −0.9394 (4) | −0.4838 (5) | −0.4156 (4) | 0.1003 (16) | |
H9 | −0.8847 | −0.5094 | −0.4216 | 0.120* | |
C10 | −0.9340 (4) | −0.1043 (5) | −0.6886 (3) | 0.1036 (15) | |
H10A | −0.9681 | −0.0933 | −0.7380 | 0.124* | |
H10B | −0.8745 | −0.0718 | −0.6804 | 0.124* | |
C11 | −0.9748 (4) | −0.0168 (5) | −0.6468 (3) | 0.1044 (17) | |
H11A | −0.9788 | 0.0778 | −0.6627 | 0.125* | |
H11B | −1.0342 | −0.0492 | −0.6547 | 0.125* | |
C12 | −0.9651 (4) | 0.0544 (6) | −0.5290 (4) | 0.1089 (17) | |
H12A | −1.0242 | 0.0184 | −0.5391 | 0.131* | |
H12B | −0.9704 | 0.1506 | −0.5427 | 0.131* | |
C13 | −0.9143 (3) | 0.0437 (4) | −0.4523 (3) | 0.0931 (14) | |
C14 | −0.9284 (4) | −0.0650 (6) | −0.4117 (4) | 0.1063 (18) | |
H14 | −0.9729 | −0.1342 | −0.4336 | 0.128* | |
C15 | −0.8793 (5) | −0.0739 (7) | −0.3408 (4) | 0.121 (2) | |
H15 | −0.8902 | −0.1498 | −0.3141 | 0.146* | |
C16 | −0.8164 (5) | 0.0208 (8) | −0.3076 (4) | 0.128 (2) | |
H16 | −0.7823 | 0.0127 | −0.2580 | 0.153* | |
C17 | −0.8024 (5) | 0.1290 (8) | −0.3463 (5) | 0.139 (3) | |
H17 | −0.7583 | 0.1979 | −0.3234 | 0.166* | |
C18 | −0.8505 (5) | 0.1411 (6) | −0.4177 (4) | 0.1154 (18) | |
H18 | −0.8394 | 0.2182 | −0.4435 | 0.138* | |
C19 | −0.8551 (4) | −0.3254 (6) | −0.6809 (3) | 0.1004 (15) | |
H19A | −0.8506 | −0.2949 | −0.7246 | 0.120* | |
H19B | −0.8674 | −0.4234 | −0.6849 | 0.120* | |
C20 | −0.7670 (4) | −0.3012 (6) | −0.6222 (4) | 0.1043 (16) | |
H20A | −0.7205 | −0.3474 | −0.6332 | 0.125* | |
H20B | −0.7540 | −0.2034 | −0.6182 | 0.125* | |
C21 | −0.6828 (4) | −0.3262 (7) | −0.4956 (4) | 0.1114 (17) | |
H21A | −0.6350 | −0.3708 | −0.5055 | 0.134* | |
H21B | −0.6713 | −0.2279 | −0.4922 | 0.134* | |
C22 | −0.6845 (3) | −0.3779 (5) | −0.4270 (3) | 0.0893 (13) | |
C23 | −0.7132 (4) | −0.2928 (6) | −0.3852 (4) | 0.1009 (17) | |
H23 | −0.7318 | −0.1994 | −0.4000 | 0.121* | |
C24 | −0.7154 (4) | −0.3422 (8) | −0.3214 (4) | 0.1166 (19) | |
H24 | −0.7373 | −0.2830 | −0.2931 | 0.140* | |
C25 | −0.6876 (4) | −0.4700 (8) | −0.2987 (4) | 0.122 (2) | |
H25 | −0.6890 | −0.5022 | −0.2543 | 0.147* | |
C26 | −0.6574 (4) | −0.5542 (7) | −0.3388 (4) | 0.126 (2) | |
H26 | −0.6367 | −0.6460 | −0.3222 | 0.151* | |
C27 | −0.6556 (4) | −0.5099 (6) | −0.4038 (4) | 0.1125 (18) | |
H27 | −0.6345 | −0.5708 | −0.4320 | 0.135* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag | 0.07163 (16) | 0.06678 (15) | 0.09265 (19) | 0.0029 (2) | 0.04170 (13) | 0.0023 (3) |
Cl | 0.0949 (8) | 0.0745 (6) | 0.0857 (7) | 0.0068 (6) | 0.0337 (6) | 0.0030 (6) |
O1 | 0.251 (8) | 0.190 (5) | 0.133 (5) | 0.090 (6) | 0.022 (5) | 0.030 (4) |
O2 | 0.164 (5) | 0.143 (4) | 0.296 (9) | −0.051 (4) | 0.121 (5) | −0.027 (5) |
O3 | 0.211 (7) | 0.244 (6) | 0.177 (6) | −0.038 (6) | 0.134 (6) | −0.039 (5) |
O4 | 0.158 (4) | 0.090 (3) | 0.187 (5) | 0.016 (3) | −0.014 (4) | −0.031 (3) |
N1 | 0.092 (3) | 0.083 (2) | 0.094 (3) | 0.0038 (17) | 0.047 (2) | 0.0094 (17) |
N2 | 0.077 (2) | 0.0642 (18) | 0.105 (3) | −0.0026 (15) | 0.0404 (19) | 0.0011 (17) |
N3 | 0.083 (2) | 0.0603 (17) | 0.119 (3) | 0.0085 (14) | 0.051 (2) | 0.0036 (16) |
N4 | 0.074 (2) | 0.074 (2) | 0.118 (3) | 0.0019 (16) | 0.053 (2) | −0.0054 (18) |
C1 | 0.108 (4) | 0.096 (3) | 0.088 (3) | 0.009 (3) | 0.033 (3) | 0.000 (3) |
C2 | 0.094 (3) | 0.084 (3) | 0.107 (4) | −0.009 (2) | 0.035 (3) | −0.013 (3) |
C3 | 0.113 (4) | 0.059 (2) | 0.128 (4) | −0.017 (2) | 0.051 (3) | −0.004 (2) |
C4 | 0.087 (3) | 0.0555 (19) | 0.111 (4) | −0.0090 (18) | 0.043 (3) | 0.014 (2) |
C5 | 0.086 (3) | 0.090 (3) | 0.124 (5) | 0.003 (2) | 0.036 (3) | 0.015 (3) |
C6 | 0.111 (4) | 0.105 (4) | 0.151 (6) | 0.002 (3) | 0.075 (4) | 0.008 (4) |
C7 | 0.153 (6) | 0.114 (4) | 0.120 (5) | −0.002 (4) | 0.075 (5) | 0.017 (3) |
C8 | 0.114 (5) | 0.116 (4) | 0.104 (5) | 0.005 (3) | 0.030 (4) | 0.020 (3) |
C9 | 0.085 (3) | 0.092 (3) | 0.126 (5) | 0.003 (2) | 0.040 (3) | 0.015 (3) |
C10 | 0.125 (4) | 0.090 (3) | 0.103 (4) | 0.009 (3) | 0.050 (3) | 0.023 (3) |
C11 | 0.119 (4) | 0.074 (3) | 0.129 (5) | 0.016 (3) | 0.054 (4) | 0.024 (3) |
C12 | 0.107 (4) | 0.082 (3) | 0.150 (5) | 0.027 (3) | 0.060 (4) | −0.001 (3) |
C13 | 0.095 (3) | 0.066 (2) | 0.144 (5) | 0.008 (2) | 0.073 (3) | −0.013 (3) |
C14 | 0.100 (4) | 0.079 (3) | 0.168 (6) | 0.000 (3) | 0.081 (4) | −0.011 (3) |
C15 | 0.148 (6) | 0.097 (4) | 0.155 (7) | 0.012 (4) | 0.098 (5) | 0.009 (4) |
C16 | 0.139 (6) | 0.138 (5) | 0.139 (6) | 0.007 (4) | 0.090 (5) | −0.022 (4) |
C17 | 0.158 (6) | 0.133 (5) | 0.163 (7) | −0.042 (5) | 0.104 (6) | −0.061 (5) |
C18 | 0.147 (5) | 0.088 (3) | 0.145 (6) | −0.016 (3) | 0.093 (4) | −0.020 (3) |
C19 | 0.122 (4) | 0.094 (3) | 0.110 (4) | 0.010 (3) | 0.071 (3) | −0.002 (3) |
C20 | 0.096 (4) | 0.103 (3) | 0.145 (5) | 0.003 (3) | 0.081 (4) | −0.001 (3) |
C21 | 0.070 (3) | 0.130 (4) | 0.146 (5) | −0.009 (3) | 0.052 (3) | −0.015 (4) |
C22 | 0.058 (2) | 0.091 (3) | 0.119 (4) | −0.007 (2) | 0.032 (2) | −0.013 (3) |
C23 | 0.078 (3) | 0.091 (3) | 0.131 (5) | −0.001 (2) | 0.033 (3) | −0.021 (3) |
C24 | 0.098 (4) | 0.126 (5) | 0.121 (5) | −0.001 (3) | 0.034 (4) | −0.028 (4) |
C25 | 0.095 (4) | 0.138 (6) | 0.115 (5) | −0.012 (4) | 0.015 (3) | −0.005 (4) |
C26 | 0.097 (4) | 0.106 (4) | 0.156 (7) | 0.003 (3) | 0.023 (4) | 0.009 (4) |
C27 | 0.084 (3) | 0.099 (4) | 0.156 (6) | 0.007 (3) | 0.045 (3) | −0.020 (4) |
Ag—N4 | 2.353 (3) | C25—C26 | 1.354 (9) |
Ag—N2 | 2.350 (3) | C26—C27 | 1.393 (9) |
Ag—N3 | 2.362 (3) | N2—H2 | 0.900 |
Ag—N1 | 2.507 (5) | N3—H3 | 0.900 |
Cl—O3 | 1.363 (7) | N4—H4 | 0.900 |
Cl—O4 | 1.370 (4) | C1—H1A | 0.960 |
Cl—O2 | 1.377 (5) | C1—H1B | 0.960 |
Cl—O1 | 1.388 (6) | C2—H2A | 0.960 |
N1—C1 | 1.450 (7) | C2—H2B | 0.960 |
N1—C10 | 1.467 (6) | C3—H3A | 0.960 |
N1—C19 | 1.479 (7) | C3—H3B | 0.960 |
N2—C2 | 1.475 (6) | C5—H5 | 0.960 |
N2—C3 | 1.480 (6) | C6—H6 | 0.960 |
N3—C11 | 1.472 (7) | C7—H7 | 0.960 |
N3—C12 | 1.473 (6) | C8—H8 | 0.960 |
N4—C20 | 1.465 (7) | C9—H9 | 0.960 |
N4—C21 | 1.490 (7) | C10—H10A | 0.960 |
C1—C2 | 1.500 (8) | C10—H10B | 0.960 |
C3—C4 | 1.482 (7) | C11—H11A | 0.960 |
C4—C5 | 1.383 (7) | C11—H11B | 0.960 |
C4—C9 | 1.387 (7) | C12—H12A | 0.960 |
C5—C6 | 1.362 (8) | C12—H12B | 0.960 |
C6—C7 | 1.351 (9) | C14—H14 | 0.960 |
C7—C8 | 1.362 (9) | C15—H15 | 0.960 |
C8—C9 | 1.371 (9) | C16—H16 | 0.960 |
C10—C11 | 1.500 (7) | C17—H17 | 0.960 |
C12—C13 | 1.479 (8) | C18—H18 | 0.960 |
C13—C18 | 1.380 (8) | C19—H19A | 0.960 |
C13—C14 | 1.397 (8) | C19—H19B | 0.960 |
C14—C15 | 1.373 (9) | C20—H20A | 0.960 |
C15—C16 | 1.347 (9) | C20—H20B | 0.960 |
C16—C17 | 1.369 (10) | C21—H21A | 0.960 |
C17—C18 | 1.380 (9) | C21—H21B | 0.960 |
C19—C20 | 1.506 (8) | C23—H23 | 0.960 |
C21—C22 | 1.486 (8) | C24—H24 | 0.960 |
C22—C23 | 1.370 (8) | C25—H25 | 0.960 |
C22—C27 | 1.376 (7) | C26—H26 | 0.960 |
C23—C24 | 1.390 (9) | C27—H27 | 0.960 |
C24—C25 | 1.331 (9) | ||
N4—Ag—N2 | 111.22 (13) | C2—C1—H1B | 108.9 |
N4—Ag—N3 | 114.19 (13) | H1A—C1—H1B | 107.7 |
N2—Ag—N3 | 115.53 (13) | N2—C2—H2A | 109.2 |
N4—Ag—N1 | 75.34 (14) | N2—C2—H2B | 109.2 |
N2—Ag—N1 | 75.27 (14) | C1—C2—H2A | 109.2 |
N3—Ag—N1 | 74.79 (13) | C1—C2—H2B | 109.2 |
O3—Cl—O4 | 109.2 (4) | H2A—C2—H2B | 107.9 |
O3—Cl—O2 | 107.5 (5) | N2—C3—H3A | 109.4 |
O4—Cl—O2 | 110.7 (4) | N2—C3—H3B | 109.4 |
O3—Cl—O1 | 106.2 (6) | C4—C3—H3A | 109.4 |
O4—Cl—O1 | 110.1 (4) | C4—C3—H3B | 109.4 |
O2—Cl—O1 | 112.9 (5) | H3A—C3—H3B | 108.0 |
C1—N1—C10 | 113.8 (4) | C4—C5—H5 | 120.0 |
C1—N1—C19 | 113.6 (4) | C6—C5—H5 | 120.0 |
C10—N1—C19 | 112.5 (4) | C5—C6—H6 | 119.0 |
C1—N1—Ag | 105.3 (3) | C7—C6—H6 | 119.0 |
C10—N1—Ag | 105.6 (3) | C6—C7—H7 | 120.5 |
C19—N1—Ag | 105.0 (3) | C8—C7—H7 | 120.5 |
C2—N2—C3 | 111.9 (4) | C7—C8—H8 | 119.9 |
C2—N2—Ag | 107.6 (3) | C9—C8—H8 | 119.9 |
C3—N2—Ag | 114.7 (3) | C4—C9—H9 | 119.6 |
C11—N3—C12 | 111.5 (4) | C8—C9—H9 | 119.6 |
C11—N3—Ag | 107.3 (3) | N1—C10—H10A | 109.1 |
C12—N3—Ag | 113.8 (3) | N1—C10—H10B | 109.1 |
C20—N4—C21 | 111.8 (4) | C11—C10—H10A | 109.1 |
C20—N4—Ag | 107.2 (3) | C11—C10—H10B | 109.1 |
C21—N4—Ag | 115.1 (3) | H10A—C10—H10B | 107.8 |
N1—C1—C2 | 113.3 (4) | N3—C11—H11A | 109.3 |
N2—C2—C1 | 112.3 (4) | N3—C11—H11B | 109.4 |
N2—C3—C4 | 111.3 (4) | C10—C11—H11A | 109.4 |
C5—C4—C9 | 117.7 (5) | C10—C11—H11B | 109.4 |
C5—C4—C3 | 121.3 (5) | H11A—C11—H11B | 108.0 |
C9—C4—C3 | 120.9 (5) | N3—C12—H12A | 109.2 |
C6—C5—C4 | 120.1 (5) | N3—C12—H12B | 109.2 |
C7—C6—C5 | 121.9 (6) | C13—C12—H12A | 109.2 |
C6—C7—C8 | 119.1 (7) | C13—C12—H12B | 109.2 |
C7—C8—C9 | 120.3 (6) | H12A—C12—H12B | 107.9 |
C8—C9—C4 | 120.8 (6) | C13—C14—H14 | 119.7 |
N1—C10—C11 | 112.6 (4) | C15—C14—H14 | 119.7 |
N3—C11—C10 | 111.4 (4) | C14—C15—H15 | 119.1 |
N3—C12—C13 | 111.9 (4) | C16—C15—H15 | 119.1 |
C18—C13—C14 | 117.0 (6) | C15—C16—H16 | 120.9 |
C18—C13—C12 | 121.1 (5) | C17—C16—H16 | 120.9 |
C14—C13—C12 | 121.9 (5) | C16—C17—H17 | 119.3 |
C15—C14—C13 | 120.7 (6) | C18—C17—H17 | 119.3 |
C16—C15—C14 | 121.9 (7) | C13—C18—H18 | 119.7 |
C15—C16—C17 | 118.2 (8) | C17—C18—H18 | 119.7 |
C16—C17—C18 | 121.4 (7) | N1—C19—H19A | 108.9 |
C17—C18—C13 | 120.7 (6) | N1—C19—H19B | 108.9 |
N1—C19—C20 | 113.3 (4) | C20—C19—H19A | 108.9 |
N4—C20—C19 | 111.2 (4) | C20—C19—H19B | 108.9 |
C22—C21—N4 | 111.9 (4) | H19A—C19—H19B | 107.8 |
C23—C22—C27 | 119.0 (6) | N4—C20—H20A | 109.4 |
C23—C22—C21 | 120.1 (5) | N4—C20—H20B | 109.4 |
C27—C22—C21 | 120.9 (6) | C19—C20—H20A | 109.4 |
C22—C23—C24 | 119.8 (6) | C19—C20—H20B | 109.4 |
C25—C24—C23 | 121.3 (7) | H20A—C20—H20B | 108.0 |
C24—C25—C26 | 119.5 (7) | N4—C21—H21A | 109.2 |
C25—C26—C27 | 121.1 (7) | N4—C21—H21B | 109.2 |
C22—C27—C26 | 119.2 (6) | C22—C21—H21A | 109.2 |
C2—N2—H2 | 107.5 | C22—C21—H21B | 109.2 |
C3—N2—H2 | 107.5 | H21A—C21—H21B | 107.9 |
Ag—N2—H2 | 107.5 | C22—C23—H23 | 120.1 |
C12—N3—H3 | 108.0 | C24—C23—H23 | 120.1 |
Ag—N3—H3 | 108.0 | C23—C24—H24 | 119.4 |
C11—N3—H3 | 108.0 | C25—C24—H24 | 119.4 |
Ag—N4—H4 | 107.5 | C24—C25—H25 | 120.2 |
C21—N4—H4 | 107.5 | C26—C25—H25 | 120.2 |
C20—N4—H4 | 107.5 | C25—C26—H26 | 119.4 |
N1—C1—H1A | 108.9 | C27—C26—H26 | 119.4 |
N1—C1—H1B | 108.9 | C22—C27—H27 | 120.5 |
C2—C1—H1A | 108.9 | C26—C27—H27 | 120.5 |
Experimental details
Crystal data | |
Chemical formula | [Ag(C27H36N4)]ClO4 |
Mr | 623.92 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 296 |
a, b, c (Å) | 16.0287 (11), 9.6132 (7), 20.2697 (15) |
β (°) | 110.906 (1) |
V (Å3) | 2917.7 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.82 |
Crystal size (mm) | 0.5 × 0.4 × 0.4 |
Data collection | |
Diffractometer | Siemens SMART Query CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9303, 5264, 4068 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.090, 0.99 |
No. of reflections | 5264 |
No. of parameters | 334 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.31 |
Absolute structure | Flack (1983), 1637 Friedel pairs |
Absolute structure parameter | 0.02 (3) |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXTL (Siemens, 1996), SHELXTL.
Ag—N4 | 2.353 (3) | Ag—N3 | 2.362 (3) |
Ag—N2 | 2.350 (3) | Ag—N1 | 2.507 (5) |
N4—Ag—N2 | 111.22 (13) | N4—Ag—N1 | 75.34 (14) |
N4—Ag—N3 | 114.19 (13) | N2—Ag—N1 | 75.27 (14) |
N2—Ag—N3 | 115.53 (13) | N3—Ag—N1 | 74.79 (13) |
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Tripodal complexes with transition metals have been widely investigated. Most of the ligands used in this area were tren, the tripodal tetraamine N(CH2CH2NH2)3, and its derivatives (Zipp et al., 1974). Many cage complexes, such as dimetallic complexes with bis(tren) cryptands, have also been reported (Amendola et al., 2001). Acyclic ionophores with aromatic end groups, so-called podands, sometimes form unusual pseudo-cyclic complexes with alkali or soft metal ions via intramolecular π–π interactions between two aromatic end groups (Weber & Saenger, 1979). However, tripodal pseudo-cage complexes formed by π–π interactions between aromatic end groups have not yet been reported. As part of our continuing studies (Lee et al., 1995; Chung et al., 1997) involving such multipodal ligands and their pseudo-cyclic complexes, the present ligand was chosen with this aspect in mind. Herein, we report our result in this area, with the crystal structure of {tris[2-(benzylamino)ethyl]amine-κ4N}silver(I) perchlorate, [Ag(bz3tren)]ClO4, (I). \sch
As shown in Fig. 1, the Ag atom in (I) is coordinated to the bridgehead N atom, Nbr, and to three secondary amino N atoms (N2, N3 and N4). Upon complexation, the tren unit becomes quite rigid and maintains the endo conformation, with the Nbr atom displaced 0.387 (6) Å towards the Ag atom above the triangular plane through atoms C1, C10 and C19. The N1—C—C—N torsion angles are in the range 61.1 (6)–62.5 (6)°, suggesting gauche conformations. The Ag atom is displaced by 0.604 (3) Å out of the trigonal plane described by the three secondary amines, in the direction away from the Nbr atom. The Ag—Nbr bond [2.507 (5) Å] is at the upper end of the range for Ag—Nbr (Ferguson et al., 1989; Adam et al., 1995), and is significantly longer than other the Ag—N bonds in (I) [2.350 (3)–2.362 (3) Å]. Selected geometric parameters and the hydrogen-bonding geometry are listed in Tables 1 and 2, respectively.
The potential threefold symmetry of the complex cation in (I) is broken by the non-coordinating ClO4- ion and the three less well aligned aromatic end groups. The three aromatic rings are essentially planar and lie nearly perpendicular to each other, with dihedral angles of 73.1 (2), 67.0 (2) and 65.7 (2)°, respectively. This permits weak edge-to-face π–π interactions between aromatic end groups, with distances from atom C9 to the centroid of the neighbouring C22—C27 ring of 3.856 (8) Å, from atom C14 to the centroid of the neighbouring C4—C9 ring of 3.962 (8) Å and from atom C23 to the centroid of the neighbouring C13—C18 ring of 3.989 (8) Å.
The principle distortion of the coordination sphere arises from the shift of the Ag atom out of the trigonal plane. The shortest Ag···Carene distance is 3.383 (6) Å, well outside the normal Ag···π interaction range (2.47–2.76 Å; Munakata et al., 1998). The shift of the Ag atom towards the aromatic end groups, and the elongation of the Ag—Nbr bond, which is about 0.15 Å longer than the Ag—N bond, may reflect, at least in part, the presence of an additional long range Ag···arene interaction (Galka & Gade, 1999).
The π–π interactions between the benzylic end groups, and the partial contribution of weak Ag···arene interactions, allow little room for anion or solvent, which usually coordinates to a metal centre to give the five-coordinate geometry normally observed in tripodal ligands of similar structure.