Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702329X/at2291sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702329X/at2291Isup2.hkl |
CCDC reference: 650682
An aqueous solution (10 ml) of 2,5-dichloro-4-amino-benzenesulfonic acid (0.121 g, 0.5 mmol) was added to solid Ag2CO3 (0.069 g, 0.25 mmol) and stirred for several minutes until no further CO2 was given off; pyridine (0.0395 g, 0.5 mmol) in methanol (5 ml) was then added and a white precipitate formed. The precipitate was dissolved by dropwise addition of an aqueous solution of NH3 (14 M). Crystals of (I) were obtained by evaporation of the solution for several days at room temperature.
All H atoms on C atoms were positioned geometrically and refined as riding, with C—H = 0.93 ° A and Uiso(H) = 1.2 or 1.5 times Ueq(C). The amino H atoms were located in a difference Fourier map and refined isotropically. The water H atoms were located in a difference Fourier map and refined with Uiso(H) = 1.5Ueq(O).
The structure of the title compound, (I) (Fig. 1), containing a pyridine molecule, three water molecules and 2,5-dichloro-4-amino-benzenesulfonate (L) anion is described. In (I), pyridine and water molecule are coordinated to the metal, resulting in a slightly distorted linear coordination geometry for Ag (Table 1). Atoms Ag1, N1 and O1W are almost linear and the angle of N1—Ag1—O1W is 172.07°. The Ag—Npyrindine and Ag—O1W distances are 2.148 (6)Å and 2.162 (5) Å, respectively; the Ag—Npyrindine distance is similar to the equivalent value in related compound (Li et al., 2006). 2,5-Dichloro-4-amino-benzenesulfonate anion does not coordinate with Ag atom, but acts as counterions..
In (I), the coordination ability of the oxygen atom of guest water molecule is evidently stronger than that of sulfonate group and the latter group does not coordinate to the Ag ion. Adjacent molecules of L are interconnected by strong O—H···O hydrogen-bonding interactions between uncoordinated sulfonate O atoms and uncoordinated water molecules (Table 2). Thus, the compound forms a one-dimensional anions chain through extensive intermolecular hydrogen bonding (Fig. 2).
The related compound, [Ag(HL3)(Pic)2] (HL3 = p-hydroxybenzenesulfonic acid, Pic = β-picoline), has a dimeric structure and each silver cation is coordinated by two nitrogen atoms from two different β-picoline ligands and two oxygen atoms from two HL3 anions with Ag—N distances of 2.168 (3) and 2.163 (3) Å (Li et al., 2006). For related literature, see: Bruker (1997); Sheldrick (1996).
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
[Ag(C5H5N)(H2O)](C6H4Cl2NO3S)·2H2O | F(000) = 480 |
Mr = 482.08 | Dx = 1.835 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3963 reflections |
a = 9.325 (2) Å | θ = 1.7–28.3° |
b = 7.6101 (13) Å | µ = 1.61 mm−1 |
c = 12.3466 (19) Å | T = 294 K |
β = 95.365 (13)° | Block, white |
V = 872.3 (3) Å3 | 0.21 × 0.20 × 0.18 mm |
Z = 2 |
Bruker SMART APEX CCD diffractometer | 3963 independent reflections |
Radiation source: fine-focus sealed tube | 2001 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
phi and ω scans | θmax = 28.3°, θmin = 1.7° |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | h = −12→7 |
Tmin = 0.705, Tmax = 0.75 | k = −10→8 |
6338 measured reflections | l = −16→15 |
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)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0301P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.80 | (Δ/σ)max = 0.001 |
3963 reflections | Δρmax = 0.41 e Å−3 |
232 parameters | Δρmin = −0.38 e Å−3 |
13 restraints | Absolute structure: Flack (1983), 1632 Freidel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.06 (4) |
[Ag(C5H5N)(H2O)](C6H4Cl2NO3S)·2H2O | V = 872.3 (3) Å3 |
Mr = 482.08 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.325 (2) Å | µ = 1.61 mm−1 |
b = 7.6101 (13) Å | T = 294 K |
c = 12.3466 (19) Å | 0.21 × 0.20 × 0.18 mm |
β = 95.365 (13)° |
Bruker SMART APEX CCD diffractometer | 3963 independent reflections |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | 2001 reflections with I > 2σ(I) |
Tmin = 0.705, Tmax = 0.75 | Rint = 0.066 |
6338 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | Δρmax = 0.41 e Å−3 |
S = 0.80 | Δρmin = −0.38 e Å−3 |
3963 reflections | Absolute structure: Flack (1983), 1632 Freidel pairs |
232 parameters | Absolute structure parameter: −0.06 (4) |
13 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 | ||
Ag1 | 0.14273 (6) | 0.76552 (8) | 0.76877 (5) | 0.0596 (2) | |
C1 | 0.6240 (7) | 0.2943 (9) | 0.8378 (4) | 0.0313 (15) | |
C2 | 0.5928 (7) | 0.4023 (8) | 0.9251 (5) | 0.0312 (16) | |
C3 | 0.4540 (8) | 0.4444 (8) | 0.9427 (5) | 0.0338 (16) | |
H3 | 0.4378 | 0.5136 | 1.0025 | 0.041* | |
C4 | 0.3366 (7) | 0.3871 (8) | 0.8744 (5) | 0.0311 (16) | |
C5 | 0.3702 (6) | 0.2774 (10) | 0.7844 (4) | 0.0354 (15) | |
C6 | 0.5080 (6) | 0.2342 (9) | 0.7697 (5) | 0.0319 (16) | |
H6 | 0.5253 | 0.1615 | 0.7118 | 0.038* | |
C7 | 0.4620 (8) | 0.7543 (13) | 0.7271 (5) | 0.0561 (18) | |
H7 | 0.4749 | 0.8099 | 0.7944 | 0.067* | |
C8 | 0.5811 (9) | 0.7031 (12) | 0.6767 (8) | 0.075 (3) | |
H8 | 0.6731 | 0.7213 | 0.7108 | 0.090* | |
C9 | 0.5637 (11) | 0.6263 (13) | 0.5774 (8) | 0.077 (3) | |
H9 | 0.6433 | 0.5953 | 0.5414 | 0.092* | |
C10 | 0.4290 (11) | 0.5955 (13) | 0.5315 (7) | 0.075 (3) | |
H10 | 0.4143 | 0.5386 | 0.4647 | 0.090* | |
C11 | 0.3146 (10) | 0.6493 (12) | 0.5847 (6) | 0.069 (3) | |
H11 | 0.2222 | 0.6313 | 0.5513 | 0.083* | |
N1 | 0.1990 (7) | 0.4291 (8) | 0.8898 (6) | 0.0493 (17) | |
N2 | 0.3290 (6) | 0.7260 (8) | 0.6816 (4) | 0.0474 (16) | |
O1 | 0.8803 (5) | 0.3887 (6) | 0.7913 (4) | 0.0484 (13) | |
O2 | 0.7831 (5) | 0.1100 (6) | 0.7236 (4) | 0.0512 (14) | |
O3 | 0.8638 (5) | 0.1433 (6) | 0.9135 (4) | 0.0504 (14) | |
O1W | −0.0366 (6) | 0.7715 (10) | 0.8677 (4) | 0.0765 (15) | |
O2W | 0.9509 (9) | −0.0802 (8) | 0.5812 (5) | 0.0661 (19) | |
O3W | 0.9266 (11) | 0.5599 (7) | 0.5930 (6) | 0.076 (2) | |
S1 | 0.80197 (17) | 0.2296 (2) | 0.81471 (13) | 0.0344 (4) | |
Cl1 | 0.7303 (2) | 0.4896 (2) | 1.01407 (15) | 0.0508 (5) | |
Cl2 | 0.2283 (2) | 0.1997 (2) | 0.69835 (16) | 0.0566 (6) | |
H1A | −0.010 (7) | 0.759 (12) | 0.945 (3) | 0.085* | |
H1B | −0.107 (7) | 0.680 (9) | 0.867 (6) | 0.085* | |
H2A | 0.909 (8) | −0.178 (7) | 0.586 (5) | 0.085* | |
H2B | 0.981 (10) | −0.055 (10) | 0.641 (4) | 0.085* | |
H1N | 0.123 (7) | 0.383 (10) | 0.858 (6) | 0.085* | |
H3A | 0.963 (10) | 0.506 (10) | 0.543 (5) | 0.085* | |
H3B | 0.902 (10) | 0.494 (9) | 0.633 (5) | 0.085* | |
H2N | 0.173 (8) | 0.472 (11) | 0.943 (5) | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0553 (4) | 0.0648 (4) | 0.0599 (4) | 0.0080 (4) | 0.0108 (3) | 0.0016 (4) |
C1 | 0.041 (4) | 0.027 (4) | 0.027 (3) | −0.005 (3) | 0.006 (3) | 0.005 (3) |
C2 | 0.031 (4) | 0.029 (4) | 0.033 (4) | 0.002 (3) | −0.001 (3) | 0.001 (3) |
C3 | 0.046 (5) | 0.028 (4) | 0.028 (4) | 0.005 (3) | 0.005 (3) | −0.005 (3) |
C4 | 0.029 (4) | 0.029 (4) | 0.038 (4) | 0.003 (3) | 0.014 (3) | 0.011 (3) |
C5 | 0.034 (4) | 0.032 (3) | 0.039 (3) | 0.008 (4) | 0.000 (3) | −0.002 (4) |
C6 | 0.035 (4) | 0.032 (4) | 0.030 (3) | −0.002 (4) | 0.007 (3) | 0.001 (3) |
C7 | 0.052 (5) | 0.062 (5) | 0.052 (4) | −0.003 (6) | −0.002 (4) | 0.002 (6) |
C8 | 0.049 (6) | 0.089 (9) | 0.086 (7) | −0.004 (6) | −0.004 (5) | 0.014 (6) |
C9 | 0.066 (7) | 0.095 (7) | 0.074 (7) | −0.002 (6) | 0.033 (6) | 0.000 (6) |
C10 | 0.079 (8) | 0.093 (7) | 0.057 (6) | −0.014 (6) | 0.024 (6) | −0.015 (5) |
C11 | 0.059 (6) | 0.100 (7) | 0.046 (5) | −0.003 (5) | −0.002 (5) | −0.007 (5) |
N1 | 0.038 (4) | 0.048 (4) | 0.062 (5) | 0.012 (3) | 0.004 (3) | −0.005 (3) |
N2 | 0.051 (4) | 0.048 (4) | 0.043 (3) | 0.001 (3) | 0.003 (3) | 0.001 (3) |
O1 | 0.040 (3) | 0.045 (3) | 0.061 (3) | −0.011 (3) | 0.011 (3) | 0.004 (3) |
O2 | 0.042 (3) | 0.058 (3) | 0.054 (3) | 0.008 (3) | 0.008 (3) | −0.030 (3) |
O3 | 0.053 (3) | 0.046 (3) | 0.051 (3) | 0.025 (3) | −0.001 (3) | 0.011 (2) |
O1W | 0.078 (4) | 0.073 (4) | 0.080 (3) | −0.002 (5) | 0.020 (3) | 0.001 (5) |
O2W | 0.083 (5) | 0.063 (4) | 0.057 (4) | 0.002 (4) | 0.026 (4) | 0.000 (3) |
O3W | 0.114 (7) | 0.054 (4) | 0.064 (5) | 0.014 (4) | 0.037 (4) | 0.004 (3) |
S1 | 0.0331 (9) | 0.0353 (11) | 0.0355 (9) | 0.0011 (8) | 0.0070 (7) | −0.0034 (8) |
Cl1 | 0.0497 (13) | 0.0557 (12) | 0.0460 (11) | 0.0030 (10) | −0.0013 (9) | −0.0191 (9) |
Cl2 | 0.0391 (11) | 0.0650 (14) | 0.0631 (12) | −0.0029 (10) | −0.0087 (10) | −0.0129 (10) |
Ag1—N2 | 2.148 (6) | C8—H8 | 0.9300 |
Ag1—O1W | 2.162 (5) | C9—C10 | 1.349 (12) |
C1—C6 | 1.384 (8) | C9—H9 | 0.9300 |
C1—C2 | 1.408 (8) | C10—C11 | 1.367 (11) |
C1—S1 | 1.779 (6) | C10—H10 | 0.9300 |
C2—C3 | 1.371 (9) | C11—N2 | 1.327 (9) |
C2—Cl1 | 1.740 (7) | C11—H11 | 0.9300 |
C3—C4 | 1.388 (9) | N1—H1N | 0.85 (4) |
C3—H3 | 0.9300 | N1—H2N | 0.79 (4) |
C4—N1 | 1.353 (8) | O1—S1 | 1.457 (5) |
C4—C5 | 1.447 (9) | O2—S1 | 1.445 (4) |
C5—C6 | 1.355 (8) | O3—S1 | 1.456 (4) |
C5—Cl2 | 1.722 (6) | O1W—H1A | 0.97 (4) |
C6—H6 | 0.9300 | O1W—H1B | 0.96 (4) |
C7—N2 | 1.330 (8) | O2W—H2A | 0.85 (4) |
C7—C8 | 1.380 (10) | O2W—H2B | 0.79 (4) |
C7—H7 | 0.9300 | O3W—H3A | 0.84 (4) |
C8—C9 | 1.355 (11) | O3W—H3B | 0.76 (4) |
N2—Ag1—O1W | 172.1 (3) | C10—C9—H9 | 120.5 |
C6—C1—C2 | 116.9 (6) | C8—C9—H9 | 120.5 |
C6—C1—S1 | 119.9 (5) | C9—C10—C11 | 118.9 (9) |
C2—C1—S1 | 123.1 (5) | C9—C10—H10 | 120.5 |
C3—C2—C1 | 121.6 (6) | C11—C10—H10 | 120.5 |
C3—C2—Cl1 | 117.5 (5) | N2—C11—C10 | 123.2 (8) |
C1—C2—Cl1 | 120.9 (5) | N2—C11—H11 | 118.4 |
C2—C3—C4 | 122.2 (6) | C10—C11—H11 | 118.4 |
C2—C3—H3 | 118.9 | C4—N1—H1N | 126 (5) |
C4—C3—H3 | 118.9 | C4—N1—H2N | 125 (6) |
N1—C4—C3 | 123.0 (6) | H1N—N1—H2N | 105 (5) |
N1—C4—C5 | 121.4 (6) | C11—N2—C7 | 117.6 (7) |
C3—C4—C5 | 115.7 (6) | C11—N2—Ag1 | 119.7 (6) |
C6—C5—C4 | 121.3 (6) | C7—N2—Ag1 | 122.1 (5) |
C6—C5—Cl2 | 121.1 (5) | Ag1—O1W—H1A | 115 (4) |
C4—C5—Cl2 | 117.6 (5) | Ag1—O1W—H1B | 123 (5) |
C5—C6—C1 | 122.4 (6) | H1A—O1W—H1B | 93 (4) |
C5—C6—H6 | 118.8 | H2A—O2W—H2B | 106 (5) |
C1—C6—H6 | 118.8 | H3A—O3W—H3B | 109 (5) |
N2—C7—C8 | 121.5 (8) | O2—S1—O3 | 112.2 (3) |
N2—C7—H7 | 119.3 | O2—S1—O1 | 113.3 (3) |
C8—C7—H7 | 119.3 | O3—S1—O1 | 112.0 (3) |
C9—C8—C7 | 119.8 (8) | O2—S1—C1 | 104.5 (3) |
C9—C8—H8 | 120.1 | O3—S1—C1 | 107.0 (3) |
C7—C8—H8 | 120.1 | O1—S1—C1 | 107.1 (3) |
C10—C9—C8 | 118.9 (9) | ||
C6—C1—C2—C3 | 0.8 (9) | S1—C1—C6—C5 | 179.1 (6) |
S1—C1—C2—C3 | −177.6 (5) | N2—C7—C8—C9 | 1.8 (14) |
C6—C1—C2—Cl1 | −178.5 (5) | C7—C8—C9—C10 | −2.5 (14) |
S1—C1—C2—Cl1 | 3.2 (8) | C8—C9—C10—C11 | 2.7 (14) |
C1—C2—C3—C4 | −1.7 (10) | C9—C10—C11—N2 | −2.2 (14) |
Cl1—C2—C3—C4 | 177.6 (5) | C10—C11—N2—C7 | 1.5 (13) |
C2—C3—C4—N1 | −179.1 (7) | C10—C11—N2—Ag1 | −169.8 (7) |
C2—C3—C4—C5 | 1.1 (9) | C8—C7—N2—C11 | −1.2 (12) |
N1—C4—C5—C6 | −179.4 (7) | C8—C7—N2—Ag1 | 169.8 (7) |
C3—C4—C5—C6 | 0.3 (10) | C6—C1—S1—O2 | −2.8 (6) |
N1—C4—C5—Cl2 | −0.8 (9) | C2—C1—S1—O2 | 175.5 (5) |
C3—C4—C5—Cl2 | 179.0 (5) | C6—C1—S1—O3 | −122.0 (5) |
C4—C5—C6—C1 | −1.2 (11) | C2—C1—S1—O3 | 56.3 (6) |
Cl2—C5—C6—C1 | −179.8 (5) | C6—C1—S1—O1 | 117.7 (5) |
C2—C1—C6—C5 | 0.7 (9) | C2—C1—S1—O1 | −64.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H2B···O2 | 0.79 (4) | 2.53 (10) | 2.855 (8) | 106 (8) |
O2W—H2A···O3Wi | 0.85 (4) | 2.00 (6) | 2.753 (8) | 147 (8) |
O3W—H3B···O1 | 0.76 (4) | 2.14 (5) | 2.842 (8) | 155 (9) |
O3W—H3A···O2Wii | 0.84 (4) | 1.92 (4) | 2.744 (7) | 171 (8) |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C5H5N)(H2O)](C6H4Cl2NO3S)·2H2O |
Mr | 482.08 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 294 |
a, b, c (Å) | 9.325 (2), 7.6101 (13), 12.3466 (19) |
β (°) | 95.365 (13) |
V (Å3) | 872.3 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.61 |
Crystal size (mm) | 0.21 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Empirical (using intensity measurements) SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.705, 0.75 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6338, 3963, 2001 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.093, 0.80 |
No. of reflections | 3963 |
No. of parameters | 232 |
No. of restraints | 13 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.41, −0.38 |
Absolute structure | Flack (1983), 1632 Freidel pairs |
Absolute structure parameter | −0.06 (4) |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H2B···O2 | 0.79 (4) | 2.53 (10) | 2.855 (8) | 106 (8) |
O2W—H2A···O3Wi | 0.85 (4) | 2.00 (6) | 2.753 (8) | 147 (8) |
O3W—H3B···O1 | 0.76 (4) | 2.14 (5) | 2.842 (8) | 155 (9) |
O3W—H3A···O2Wii | 0.84 (4) | 1.92 (4) | 2.744 (7) | 171 (8) |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, y+1/2, −z+1. |
The structure of the title compound, (I) (Fig. 1), containing a pyridine molecule, three water molecules and 2,5-dichloro-4-amino-benzenesulfonate (L) anion is described. In (I), pyridine and water molecule are coordinated to the metal, resulting in a slightly distorted linear coordination geometry for Ag (Table 1). Atoms Ag1, N1 and O1W are almost linear and the angle of N1—Ag1—O1W is 172.07°. The Ag—Npyrindine and Ag—O1W distances are 2.148 (6)Å and 2.162 (5) Å, respectively; the Ag—Npyrindine distance is similar to the equivalent value in related compound (Li et al., 2006). 2,5-Dichloro-4-amino-benzenesulfonate anion does not coordinate with Ag atom, but acts as counterions..
In (I), the coordination ability of the oxygen atom of guest water molecule is evidently stronger than that of sulfonate group and the latter group does not coordinate to the Ag ion. Adjacent molecules of L are interconnected by strong O—H···O hydrogen-bonding interactions between uncoordinated sulfonate O atoms and uncoordinated water molecules (Table 2). Thus, the compound forms a one-dimensional anions chain through extensive intermolecular hydrogen bonding (Fig. 2).