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Acta Cryst. (2007). E63, m1680    [ doi:10.1107/S160053680702329X ]

Aquapyridinesilver(I) 4-amino-2,5-dichlorobenzenesulfonate dihydrate

S.-P. Shangguan, Y.-J. Li and H. Wu

Abstract top

The title compound, [Ag(C5H5N)(H2O)](C6H4Cl2NO3S)·2H2O, has a mononuclear structure in which the Ag+ cation is two-coordinated by one N atom from a pyridine molecule and one O atom from a water molecule. The 4-amino-2,5-dichlorobenzenesulfonate anion does not coordinate to the Ag atom, but acts as a counterion. Intermolecular O-H...O hydrogen bonds link the ions and water molecules.

Comment top

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).

Related literature top

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).

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. One-dimensional chain of (I), formed through hydrogen-bonding (dashed lines) interactions.The atoms not involved in hydrogen bonding have been omitted.
Aquapyridinesilver(I) 4-amino-2,5-dichlorobenzenesulfonate dihydrate top
Crystal data top
[Ag(C5H5N)(H2O)](C6H4Cl2NO3S)·2H2OF(000) = 480
Mr = 482.08Dx = 1.835 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 3963 reflections
a = 9.325 (2) Åθ = 1.7–28.3°
b = 7.6101 (13) ŵ = 1.61 mm−1
c = 12.3466 (19) ÅT = 294 K
β = 95.365 (13)°Block, white
V = 872.3 (3) Å30.21 × 0.20 × 0.18 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer		3963 independent reflections
Radiation source: fine-focus sealed tube2001 reflections with I > 2σ(I)
graphiteRint = 0.066
phi and ω scansθmax = 28.3°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements)
SADABS (Sheldrick, 1996)		h = −12→7
Tmin = 0.705, Tmax = 0.75k = −10→8
6338 measured reflectionsl = −16→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H 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 reflectionsΔρmax = 0.41 e Å−3
232 parametersΔρmin = −0.38 e Å−3
13 restraintsAbsolute structure: Flack (1983), 1632 Freidel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.06 (4)
Crystal data top
[Ag(C5H5N)(H2O)](C6H4Cl2NO3S)·2H2OV = 872.3 (3) Å3
Mr = 482.08Z = 2
Monoclinic, P21Mo Kα radiation
a = 9.325 (2) ŵ = 1.61 mm−1
b = 7.6101 (13) ÅT = 294 K
c = 12.3466 (19) Å0.21 × 0.20 × 0.18 mm
β = 95.365 (13)°
Data collection top
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 = 0.75Rint = 0.066
6338 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093Δρmax = 0.41 e Å−3
S = 0.80Δρmin = −0.38 e Å−3
3963 reflectionsAbsolute structure: Flack (1983), 1632 Freidel pairs
232 parametersFlack parameter: −0.06 (4)
13 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.14273 (6)0.76552 (8)0.76877 (5)0.0596 (2)
C10.6240 (7)0.2943 (9)0.8378 (4)0.0313 (15)
C20.5928 (7)0.4023 (8)0.9251 (5)0.0312 (16)
C30.4540 (8)0.4444 (8)0.9427 (5)0.0338 (16)
H30.43780.51361.00250.041*
C40.3366 (7)0.3871 (8)0.8744 (5)0.0311 (16)
C50.3702 (6)0.2774 (10)0.7844 (4)0.0354 (15)
C60.5080 (6)0.2342 (9)0.7697 (5)0.0319 (16)
H60.52530.16150.71180.038*
C70.4620 (8)0.7543 (13)0.7271 (5)0.0561 (18)
H70.47490.80990.79440.067*
C80.5811 (9)0.7031 (12)0.6767 (8)0.075 (3)
H80.67310.72130.71080.090*
C90.5637 (11)0.6263 (13)0.5774 (8)0.077 (3)
H90.64330.59530.54140.092*
C100.4290 (11)0.5955 (13)0.5315 (7)0.075 (3)
H100.41430.53860.46470.090*
C110.3146 (10)0.6493 (12)0.5847 (6)0.069 (3)
H110.22220.63130.55130.083*
N10.1990 (7)0.4291 (8)0.8898 (6)0.0493 (17)
N20.3290 (6)0.7260 (8)0.6816 (4)0.0474 (16)
O10.8803 (5)0.3887 (6)0.7913 (4)0.0484 (13)
O20.7831 (5)0.1100 (6)0.7236 (4)0.0512 (14)
O30.8638 (5)0.1433 (6)0.9135 (4)0.0504 (14)
O1W−0.0366 (6)0.7715 (10)0.8677 (4)0.0765 (15)
O2W0.9509 (9)−0.0802 (8)0.5812 (5)0.0661 (19)
O3W0.9266 (11)0.5599 (7)0.5930 (6)0.076 (2)
S10.80197 (17)0.2296 (2)0.81471 (13)0.0344 (4)
Cl10.7303 (2)0.4896 (2)1.01407 (15)0.0508 (5)
Cl20.2283 (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*
H2A0.909 (8)−0.178 (7)0.586 (5)0.085*
H2B0.981 (10)−0.055 (10)0.641 (4)0.085*
H1N0.123 (7)0.383 (10)0.858 (6)0.085*
H3A0.963 (10)0.506 (10)0.543 (5)0.085*
H3B0.902 (10)0.494 (9)0.633 (5)0.085*
H2N0.173 (8)0.472 (11)0.943 (5)0.085*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0553 (4)0.0648 (4)0.0599 (4)0.0080 (4)0.0108 (3)0.0016 (4)
C10.041 (4)0.027 (4)0.027 (3)−0.005 (3)0.006 (3)0.005 (3)
C20.031 (4)0.029 (4)0.033 (4)0.002 (3)−0.001 (3)0.001 (3)
C30.046 (5)0.028 (4)0.028 (4)0.005 (3)0.005 (3)−0.005 (3)
C40.029 (4)0.029 (4)0.038 (4)0.003 (3)0.014 (3)0.011 (3)
C50.034 (4)0.032 (3)0.039 (3)0.008 (4)0.000 (3)−0.002 (4)
C60.035 (4)0.032 (4)0.030 (3)−0.002 (4)0.007 (3)0.001 (3)
C70.052 (5)0.062 (5)0.052 (4)−0.003 (6)−0.002 (4)0.002 (6)
C80.049 (6)0.089 (9)0.086 (7)−0.004 (6)−0.004 (5)0.014 (6)
C90.066 (7)0.095 (7)0.074 (7)−0.002 (6)0.033 (6)0.000 (6)
C100.079 (8)0.093 (7)0.057 (6)−0.014 (6)0.024 (6)−0.015 (5)
C110.059 (6)0.100 (7)0.046 (5)−0.003 (5)−0.002 (5)−0.007 (5)
N10.038 (4)0.048 (4)0.062 (5)0.012 (3)0.004 (3)−0.005 (3)
N20.051 (4)0.048 (4)0.043 (3)0.001 (3)0.003 (3)0.001 (3)
O10.040 (3)0.045 (3)0.061 (3)−0.011 (3)0.011 (3)0.004 (3)
O20.042 (3)0.058 (3)0.054 (3)0.008 (3)0.008 (3)−0.030 (3)
O30.053 (3)0.046 (3)0.051 (3)0.025 (3)−0.001 (3)0.011 (2)
O1W0.078 (4)0.073 (4)0.080 (3)−0.002 (5)0.020 (3)0.001 (5)
O2W0.083 (5)0.063 (4)0.057 (4)0.002 (4)0.026 (4)0.000 (3)
O3W0.114 (7)0.054 (4)0.064 (5)0.014 (4)0.037 (4)0.004 (3)
S10.0331 (9)0.0353 (11)0.0355 (9)0.0011 (8)0.0070 (7)−0.0034 (8)
Cl10.0497 (13)0.0557 (12)0.0460 (11)0.0030 (10)−0.0013 (9)−0.0191 (9)
Cl20.0391 (11)0.0650 (14)0.0631 (12)−0.0029 (10)−0.0087 (10)−0.0129 (10)
Geometric parameters (Å, °) top
Ag1—N22.148 (6)C8—H80.9300
Ag1—O1W2.162 (5)C9—C101.349 (12)
C1—C61.384 (8)C9—H90.9300
C1—C21.408 (8)C10—C111.367 (11)
C1—S11.779 (6)C10—H100.9300
C2—C31.371 (9)C11—N21.327 (9)
C2—Cl11.740 (7)C11—H110.9300
C3—C41.388 (9)N1—H1N0.85 (4)
C3—H30.9300N1—H2N0.79 (4)
C4—N11.353 (8)O1—S11.457 (5)
C4—C51.447 (9)O2—S11.445 (4)
C5—C61.355 (8)O3—S11.456 (4)
C5—Cl21.722 (6)O1W—H1A0.97 (4)
C6—H60.9300O1W—H1B0.96 (4)
C7—N21.330 (8)O2W—H2A0.85 (4)
C7—C81.380 (10)O2W—H2B0.79 (4)
C7—H70.9300O3W—H3A0.84 (4)
C8—C91.355 (11)O3W—H3B0.76 (4)
N2—Ag1—O1W172.1 (3)C10—C9—H9120.5
C6—C1—C2116.9 (6)C8—C9—H9120.5
C6—C1—S1119.9 (5)C9—C10—C11118.9 (9)
C2—C1—S1123.1 (5)C9—C10—H10120.5
C3—C2—C1121.6 (6)C11—C10—H10120.5
C3—C2—Cl1117.5 (5)N2—C11—C10123.2 (8)
C1—C2—Cl1120.9 (5)N2—C11—H11118.4
C2—C3—C4122.2 (6)C10—C11—H11118.4
C2—C3—H3118.9C4—N1—H1N126 (5)
C4—C3—H3118.9C4—N1—H2N125 (6)
N1—C4—C3123.0 (6)H1N—N1—H2N105 (5)
N1—C4—C5121.4 (6)C11—N2—C7117.6 (7)
C3—C4—C5115.7 (6)C11—N2—Ag1119.7 (6)
C6—C5—C4121.3 (6)C7—N2—Ag1122.1 (5)
C6—C5—Cl2121.1 (5)Ag1—O1W—H1A115 (4)
C4—C5—Cl2117.6 (5)Ag1—O1W—H1B123 (5)
C5—C6—C1122.4 (6)H1A—O1W—H1B93 (4)
C5—C6—H6118.8H2A—O2W—H2B106 (5)
C1—C6—H6118.8H3A—O3W—H3B109 (5)
N2—C7—C8121.5 (8)O2—S1—O3112.2 (3)
N2—C7—H7119.3O2—S1—O1113.3 (3)
C8—C7—H7119.3O3—S1—O1112.0 (3)
C9—C8—C7119.8 (8)O2—S1—C1104.5 (3)
C9—C8—H8120.1O3—S1—C1107.0 (3)
C7—C8—H8120.1O1—S1—C1107.1 (3)
C10—C9—C8118.9 (9)
C6—C1—C2—C30.8 (9)S1—C1—C6—C5179.1 (6)
S1—C1—C2—C3−177.6 (5)N2—C7—C8—C91.8 (14)
C6—C1—C2—Cl1−178.5 (5)C7—C8—C9—C10−2.5 (14)
S1—C1—C2—Cl13.2 (8)C8—C9—C10—C112.7 (14)
C1—C2—C3—C4−1.7 (10)C9—C10—C11—N2−2.2 (14)
Cl1—C2—C3—C4177.6 (5)C10—C11—N2—C71.5 (13)
C2—C3—C4—N1−179.1 (7)C10—C11—N2—Ag1−169.8 (7)
C2—C3—C4—C51.1 (9)C8—C7—N2—C11−1.2 (12)
N1—C4—C5—C6−179.4 (7)C8—C7—N2—Ag1169.8 (7)
C3—C4—C5—C60.3 (10)C6—C1—S1—O2−2.8 (6)
N1—C4—C5—Cl2−0.8 (9)C2—C1—S1—O2175.5 (5)
C3—C4—C5—Cl2179.0 (5)C6—C1—S1—O3−122.0 (5)
C4—C5—C6—C1−1.2 (11)C2—C1—S1—O356.3 (6)
Cl2—C5—C6—C1−179.8 (5)C6—C1—S1—O1117.7 (5)
C2—C1—C6—C50.7 (9)C2—C1—S1—O1−64.0 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2W—H2B···O20.79 (4)2.53 (10)2.855 (8)106 (8)
O2W—H2A···O3Wi0.85 (4)2.00 (6)2.753 (8)147 (8)
O3W—H3B···O10.76 (4)2.14 (5)2.842 (8)155 (9)
O3W—H3A···O2Wii0.84 (4)1.92 (4)2.744 (7)171 (8)
Symmetry codes: (i) x, y−1, z; (ii) −x+2, y+1/2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Ag1—N22.148 (6)Ag1—O1W2.162 (5)
N2—Ag1—O1W172.1 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2W—H2B···O20.79 (4)2.53 (10)2.855 (8)106 (8)
O2W—H2A···O3Wi0.85 (4)2.00 (6)2.753 (8)147 (8)
O3W—H3B···O10.76 (4)2.14 (5)2.842 (8)155 (9)
O3W—H3A···O2Wii0.84 (4)1.92 (4)2.744 (7)171 (8)
Symmetry codes: (i) x, y−1, z; (ii) −x+2, y+1/2, −z+1.
references
References top

Bruker (1997). SMART. Version 5.622. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1999). SAINT. Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Li, F.-F., Ma, J.-F., Song, S.-Y., Yang, J., Jia, H.-Q. & Hu, N.-H. (2006). Cryst. Growth Des. 6, 209–215.

Sheldrick, G. M. (1990). SHELXTL-Plus. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.