Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006396/ob6124sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006396/ob6124Isup2.hkl |
CCDC reference: 185748
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.007 Å
- R factor = 0.043
- wR factor = 0.093
- Data-to-parameter ratio = 16.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N2 - H2N2 ? PLAT_710 Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 1 N3 -AG1 -N1 -C5 -25.20 1.10 1.555 1.555 1.555 1.555 PLAT_710 Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 2 N3 -AG1 -N1 -C1 156.10 0.80 1.555 1.555 1.555 1.555 PLAT_710 Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 17 N1 -AG1 -N3 -C10 16.20 1.10 1.555 1.555 1.555 1.555 PLAT_710 Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 18 N1 -AG1 -N3 -C6 -171.20 0.80 1.555 1.555 1.555 1.555 PLAT_731 Alert C Bond Calc 0.85(3), Rep 0.849(10) .... 3.00 s.u-Ratio N2 -H2N1 1.555 1.555 PLAT_731 Alert C Bond Calc 0.85(3), Rep 0.852(10) .... 3.00 s.u-Ratio N2 -H2N2 1.555 1.555 PLAT_731 Alert C Bond Calc 0.84(3), Rep 0.840(10) .... 3.00 s.u-Ratio N4 -H4N2 1.555 1.555 PLAT_732 Alert C Angle Calc 110(5), Rep 109.7(17) .... 2.94 s.u-Ratio H2N1 -N2 -H2N2 1.555 1.555 1.555 PLAT_732 Alert C Angle Calc 113(4), Rep 113.2(18) .... 2.22 s.u-Ratio H4N1 -N4 -H4N2 1.555 1.555 1.555 PLAT_735 Alert C D-H Calc 0.85(3), Rep 0.849(10) .... 3.00 s.u-Ratio N2 -H2N1 1.555 1.555 PLAT_736 Alert C H...A Calc 2.22(4), Rep 2.223(17) .... 2.35 s.u-Ratio H2N1 -O3 1.555 4.666
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
12 Alert Level C = Please check
To a solution of AgClO4 (1.0 mmol) in 1:1 (v/v) MeCN/H2O (10 ml), a solution of 2-Clnpy (1.0 mmol) in MeOH (5 ml) was added slowly with stirring for 15 min at 333 K. Colorless block crystals were deposited within five days (90% yield).
The carbon-bound H atoms were generated geometrically and ride on their parent C atoms; Uiso(H) = 1.2Ueq(C). The nitrogen-bound H-atoms were located and the N—H distance was restrained to 0.85 (1) Å.
Data collection: XSCANS (Siemens, 1990); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
[Ag(C5H5ClN2)2]ClO4 | F(000) = 912 |
Mr = 464.44 | Dx = 2.037 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.777 (2) Å | Cell parameters from 25 reflections |
b = 26.904 (8) Å | θ = 7–15° |
c = 7.600 (2) Å | µ = 1.88 mm−1 |
β = 107.72 (1)° | T = 298 K |
V = 1514.7 (7) Å3 | Block, colorless |
Z = 4 | 0.38 × 0.30 × 0.26 mm |
Siemens R3m four-circle diffractometer | 2251 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 27.5°, θmin = 2.8° |
ω scans | h = −10→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −34→0 |
Tmin = 0.494, Tmax = 0.613 | l = 0→9 |
3723 measured reflections | 2 standard reflections every 150 reflections |
3472 independent reflections | intensity decay: none |
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)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0387P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3472 reflections | Δρmax = 0.42 e Å−3 |
216 parameters | Δρmin = −0.43 e Å−3 |
6 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0021 (4) |
[Ag(C5H5ClN2)2]ClO4 | V = 1514.7 (7) Å3 |
Mr = 464.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.777 (2) Å | µ = 1.88 mm−1 |
b = 26.904 (8) Å | T = 298 K |
c = 7.600 (2) Å | 0.38 × 0.30 × 0.26 mm |
β = 107.72 (1)° |
Siemens R3m four-circle diffractometer | 2251 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.024 |
Tmin = 0.494, Tmax = 0.613 | 2 standard reflections every 150 reflections |
3723 measured reflections | intensity decay: none |
3472 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 6 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.42 e Å−3 |
3472 reflections | Δρmin = −0.43 e Å−3 |
216 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 | 0.37799 (5) | 0.347139 (13) | 0.73581 (6) | 0.04964 (15) | |
Cl1 | 0.58803 (16) | 0.24775 (5) | 0.94521 (18) | 0.0552 (3) | |
N1 | 0.2817 (5) | 0.26995 (13) | 0.6987 (5) | 0.0376 (9) | |
N2 | 0.4274 (7) | 0.14677 (16) | 0.8916 (7) | 0.0543 (11) | |
C1 | 0.1211 (6) | 0.25929 (17) | 0.5762 (6) | 0.0421 (11) | |
H1 | 0.0486 | 0.2849 | 0.5117 | 0.051* | |
C2 | 0.0623 (6) | 0.21079 (18) | 0.5449 (7) | 0.0476 (12) | |
H2 | −0.0458 | 0.2037 | 0.4543 | 0.057* | |
C3 | 0.1626 (6) | 0.17327 (17) | 0.6468 (7) | 0.0458 (12) | |
H3 | 0.1202 | 0.1408 | 0.6291 | 0.055* | |
C4 | 0.3270 (6) | 0.18333 (16) | 0.7764 (6) | 0.0400 (10) | |
C5 | 0.3791 (6) | 0.23243 (17) | 0.7916 (6) | 0.0372 (10) | |
Cl2 | 0.71420 (17) | 0.37370 (5) | 1.09506 (18) | 0.0549 (3) | |
N3 | 0.4992 (5) | 0.42085 (13) | 0.8142 (5) | 0.0371 (8) | |
N4 | 0.9015 (6) | 0.4714 (2) | 1.1513 (6) | 0.0539 (11) | |
C6 | 0.4387 (6) | 0.46070 (17) | 0.7083 (6) | 0.0422 (11) | |
H6 | 0.3349 | 0.4580 | 0.6078 | 0.051* | |
C7 | 0.5266 (6) | 0.50549 (18) | 0.7448 (7) | 0.0459 (12) | |
H7 | 0.4819 | 0.5329 | 0.6701 | 0.055* | |
C8 | 0.6797 (6) | 0.50977 (17) | 0.8907 (7) | 0.0451 (12) | |
H8 | 0.7399 | 0.5401 | 0.9139 | 0.054* | |
C9 | 0.7468 (6) | 0.46962 (17) | 1.0051 (6) | 0.0386 (10) | |
C10 | 0.6475 (6) | 0.42570 (16) | 0.9579 (6) | 0.0355 (10) | |
Cl3 | −0.06074 (14) | 0.39819 (4) | 0.61996 (16) | 0.0446 (3) | |
O1 | 0.0491 (5) | 0.40646 (16) | 0.8040 (5) | 0.0762 (12) | |
O2 | 0.0520 (5) | 0.38878 (16) | 0.5066 (5) | 0.0721 (11) | |
O3 | −0.1727 (6) | 0.35651 (17) | 0.6168 (7) | 0.0970 (16) | |
O4 | −0.1670 (6) | 0.44024 (16) | 0.5542 (6) | 0.0949 (15) | |
H2N1 | 0.541 (2) | 0.1483 (17) | 0.942 (8) | 0.09 (2)* | |
H2N2 | 0.397 (6) | 0.1169 (8) | 0.860 (7) | 0.075 (19)* | |
H4N1 | 0.927 (7) | 0.5011 (6) | 1.180 (6) | 0.059 (17)* | |
H4N2 | 0.919 (7) | 0.4525 (12) | 1.243 (4) | 0.07 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0470 (2) | 0.0346 (2) | 0.0599 (3) | −0.00668 (18) | 0.00528 (17) | −0.00435 (19) |
Cl1 | 0.0416 (6) | 0.0548 (7) | 0.0593 (8) | −0.0069 (6) | 0.0004 (6) | 0.0036 (6) |
N1 | 0.036 (2) | 0.0326 (19) | 0.043 (2) | 0.0002 (16) | 0.0101 (17) | 0.0002 (17) |
N2 | 0.058 (3) | 0.035 (3) | 0.068 (3) | 0.010 (2) | 0.016 (2) | 0.008 (2) |
C1 | 0.039 (2) | 0.045 (3) | 0.042 (3) | 0.004 (2) | 0.012 (2) | 0.005 (2) |
C2 | 0.043 (3) | 0.050 (3) | 0.045 (3) | −0.012 (2) | 0.006 (2) | −0.009 (2) |
C3 | 0.049 (3) | 0.031 (2) | 0.057 (3) | −0.008 (2) | 0.016 (2) | −0.007 (2) |
C4 | 0.041 (3) | 0.036 (2) | 0.047 (3) | 0.003 (2) | 0.019 (2) | 0.002 (2) |
C5 | 0.033 (2) | 0.042 (2) | 0.037 (2) | −0.0033 (19) | 0.011 (2) | −0.006 (2) |
Cl2 | 0.0541 (7) | 0.0463 (7) | 0.0550 (8) | 0.0012 (6) | 0.0029 (6) | 0.0035 (6) |
N3 | 0.0336 (19) | 0.037 (2) | 0.040 (2) | −0.0045 (16) | 0.0111 (17) | −0.0088 (17) |
N4 | 0.039 (2) | 0.060 (3) | 0.056 (3) | −0.011 (2) | 0.005 (2) | −0.010 (3) |
C6 | 0.039 (2) | 0.041 (3) | 0.045 (3) | 0.002 (2) | 0.009 (2) | −0.002 (2) |
C7 | 0.045 (3) | 0.043 (3) | 0.053 (3) | 0.001 (2) | 0.019 (2) | 0.000 (2) |
C8 | 0.048 (3) | 0.038 (3) | 0.056 (3) | −0.009 (2) | 0.026 (3) | −0.005 (2) |
C9 | 0.033 (2) | 0.046 (3) | 0.041 (3) | −0.009 (2) | 0.018 (2) | −0.014 (2) |
C10 | 0.037 (2) | 0.037 (2) | 0.036 (2) | 0.0007 (19) | 0.017 (2) | −0.0059 (19) |
Cl3 | 0.0367 (6) | 0.0431 (6) | 0.0457 (7) | 0.0032 (5) | 0.0003 (5) | −0.0034 (5) |
O1 | 0.081 (3) | 0.088 (3) | 0.043 (2) | −0.019 (2) | −0.0057 (19) | −0.004 (2) |
O2 | 0.054 (2) | 0.098 (3) | 0.064 (2) | 0.013 (2) | 0.0170 (19) | −0.018 (2) |
O3 | 0.071 (3) | 0.093 (3) | 0.116 (4) | −0.042 (3) | 0.012 (3) | −0.010 (3) |
O4 | 0.107 (3) | 0.087 (3) | 0.087 (3) | 0.054 (3) | 0.025 (3) | 0.023 (3) |
Ag1—N1 | 2.197 (4) | N3—C10 | 1.332 (5) |
Ag1—N3 | 2.199 (4) | N3—C6 | 1.337 (5) |
Cl1—C5 | 1.737 (4) | N4—C9 | 1.367 (6) |
N1—C5 | 1.329 (5) | N4—H4N1 | 0.837 (10) |
N1—C1 | 1.342 (5) | N4—H4N2 | 0.840 (10) |
N2—C4 | 1.388 (6) | C6—C7 | 1.372 (6) |
N2—H2N1 | 0.849 (10) | C6—H6 | 0.9300 |
N2—H2N2 | 0.852 (10) | C7—C8 | 1.363 (6) |
C1—C2 | 1.379 (6) | C7—H7 | 0.9300 |
C1—H1 | 0.9300 | C8—C9 | 1.385 (6) |
C2—C3 | 1.364 (6) | C8—H8 | 0.9300 |
C2—H2 | 0.9300 | C9—C10 | 1.397 (6) |
C3—C4 | 1.382 (6) | Cl3—O4 | 1.401 (4) |
C3—H3 | 0.9300 | Cl3—O3 | 1.415 (4) |
C4—C5 | 1.376 (6) | Cl3—O1 | 1.417 (4) |
Cl2—C10 | 1.727 (5) | Cl3—O2 | 1.426 (4) |
N1—Ag1—N3 | 171.43 (13) | C9—N4—H4N1 | 109 (3) |
C5—N1—C1 | 117.8 (4) | C9—N4—H4N2 | 122 (4) |
C5—N1—Ag1 | 122.2 (3) | H4N1—N4—H4N2 | 113.2 (18) |
C1—N1—Ag1 | 120.0 (3) | N3—C6—C7 | 121.3 (4) |
C4—N2—H2N1 | 124 (4) | N3—C6—H6 | 119.3 |
C4—N2—H2N2 | 116 (3) | C7—C6—H6 | 119.3 |
H2N1—N2—H2N2 | 109.7 (17) | C8—C7—C6 | 119.8 (5) |
N1—C1—C2 | 120.8 (4) | C8—C7—H7 | 120.1 |
N1—C1—H1 | 119.6 | C6—C7—H7 | 120.1 |
C2—C1—H1 | 119.6 | C7—C8—C9 | 120.9 (4) |
C3—C2—C1 | 120.0 (4) | C7—C8—H8 | 119.5 |
C3—C2—H2 | 120.0 | C9—C8—H8 | 119.5 |
C1—C2—H2 | 120.0 | N4—C9—C8 | 123.6 (4) |
C2—C3—C4 | 120.3 (4) | N4—C9—C10 | 121.3 (5) |
C2—C3—H3 | 119.8 | C8—C9—C10 | 115.2 (4) |
C4—C3—H3 | 119.8 | N3—C10—C9 | 124.5 (4) |
C5—C4—C3 | 115.6 (4) | N3—C10—Cl2 | 116.2 (3) |
C5—C4—N2 | 122.2 (4) | C9—C10—Cl2 | 119.3 (3) |
C3—C4—N2 | 122.1 (4) | O4—Cl3—O3 | 109.9 (3) |
N1—C5—C4 | 125.4 (4) | O4—Cl3—O1 | 109.8 (3) |
N1—C5—Cl1 | 116.2 (3) | O3—Cl3—O1 | 108.9 (3) |
C4—C5—Cl1 | 118.4 (3) | O4—Cl3—O2 | 109.4 (3) |
C10—N3—C6 | 118.3 (4) | O3—Cl3—O2 | 109.7 (3) |
C10—N3—Ag1 | 120.2 (3) | O1—Cl3—O2 | 109.1 (2) |
C6—N3—Ag1 | 121.1 (3) | ||
N3—Ag1—N1—C5 | −25.2 (11) | N1—Ag1—N3—C10 | 16.2 (11) |
N3—Ag1—N1—C1 | 156.1 (8) | N1—Ag1—N3—C6 | −171.2 (8) |
C5—N1—C1—C2 | −1.8 (6) | C10—N3—C6—C7 | 0.4 (7) |
Ag1—N1—C1—C2 | 176.9 (3) | Ag1—N3—C6—C7 | −172.3 (3) |
N1—C1—C2—C3 | 4.0 (7) | N3—C6—C7—C8 | 0.5 (7) |
C1—C2—C3—C4 | −2.7 (7) | C6—C7—C8—C9 | −1.0 (7) |
C2—C3—C4—C5 | −0.5 (7) | C7—C8—C9—N4 | 178.7 (4) |
C2—C3—C4—N2 | 175.5 (5) | C7—C8—C9—C10 | 0.5 (7) |
C1—N1—C5—C4 | −1.7 (7) | C6—N3—C10—C9 | −0.9 (6) |
Ag1—N1—C5—C4 | 179.6 (4) | Ag1—N3—C10—C9 | 171.9 (3) |
C1—N1—C5—Cl1 | 178.7 (3) | C6—N3—C10—Cl2 | 177.5 (3) |
Ag1—N1—C5—Cl1 | 0.0 (5) | Ag1—N3—C10—Cl2 | −9.7 (4) |
C3—C4—C5—N1 | 2.9 (7) | N4—C9—C10—N3 | −177.8 (4) |
N2—C4—C5—N1 | −173.1 (4) | C8—C9—C10—N3 | 0.5 (6) |
C3—C4—C5—Cl1 | −177.6 (3) | N4—C9—C10—Cl2 | 3.9 (6) |
N2—C4—C5—Cl1 | 6.4 (6) | C8—C9—C10—Cl2 | −177.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N1···O3i | 0.85 (1) | 2.22 (2) | 3.061 (6) | 169 (6) |
C3—H3···O1ii | 0.93 | 2.68 | 3.279 (6) | 122 |
C7—H7···O4iii | 0.93 | 2.62 | 3.352 (6) | 135 |
Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C5H5ClN2)2]ClO4 |
Mr | 464.44 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.777 (2), 26.904 (8), 7.600 (2) |
β (°) | 107.72 (1) |
V (Å3) | 1514.7 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.88 |
Crystal size (mm) | 0.38 × 0.30 × 0.26 |
Data collection | |
Diffractometer | Siemens R3m four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.494, 0.613 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3723, 3472, 2251 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.093, 1.01 |
No. of reflections | 3472 |
No. of parameters | 216 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.42, −0.43 |
Computer programs: XSCANS (Siemens, 1990), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N1···O3i | 0.849 (10) | 2.223 (17) | 3.061 (6) | 169 (6) |
C3—H3···O1ii | 0.93 | 2.68 | 3.279 (6) | 121.9 |
C7—H7···O4iii | 0.93 | 2.62 | 3.352 (6) | 135.4 |
Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x, −y+1, −z+1. |
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The synthesis of coordination polymers with large channels or cavities is currently an active field due to their intriguing structural diversity and potential functions as microporous solids for molecular adsorption, ion exchange, and heterogeneous catalysis (Batten et al., 1998; Fujita et al., 1994; Janiak, 1997; Tong Chen et al., 1999; Yaghi et al., 1998). We are interested in the preparation of one-, two- and three-dimensional coordination polymers with potential applications and report here the preparation and crystal structure of [Ag(2-Clnpy)2](ClO4), (I) (2-Clnpy is 3-amino-2-chloropyridine).
The crystal structure of (I) comprises discrete mononuclear [Ag(2-Clnpy)2]+ cations and perchlorate counter-ions. As shown in Fig. 1, each AgI atom is coordinated in a linear geometry to two pyridyl N atoms from two different 2-Clnpy ligands (Table 1). The Ag—N(pyridyl) distances in (I) are comparable to those [2.186 (4)—2.199 (2) Å] found in the silver compounds of bipyridine (Tong et al., 1998; Tong & Chen, 2000; Tong, Chen & Ng, 2000), but are slightly longer than those [2.122 (3) Å] in bis(4-aminopyridine)silver(I) nitrate (Kristiansson, 2000). Adjacent [Ag(2-Clnpy)2]+ cations are interlinked through weak Ag···N(amine) coordination [Ag···N(amine) = 2.762 (5) Å], resulting in a polymeric chain along the c axis direction (Fig. 2). The adjacent chains are further interlinked by perchlorate anions through weak Ag···O2 coordination [Ag···O2 = 2.833 (4) Å] and N2···O3 hydrogen bonds (Table 2). There are also strong interchain π–π interactions between the pyridyl rings of adjacent chains with the staggered face-to-face separation of ca 3.36–3.46 Å. Thus, the structure of (I) provides an interesting three-dimensional supramolecular architecture driven by the extensive supramolecular interactions (Fig. 3).
It should be also noted that non-classical hydrogen-bonding interactions play a role in consolidating the solid-state structure of (I). The perchlorate counter-ions are hydrogen bonded to the adjacent 2-Clnpy ligands (Table 2), which is also observed in other related compounds (Tong, Lee et al., 1999).