Di-μ-aqua-bis­[(2-amino-4,5-dimethyl­benzene­sulfonato-κN)aqua­silver(I)]

In the title compound, [Ag₂(C₈H₁₀NO₃S)₂(H₂O)₄], each Ag^I atom is coordinated by three water mol­ecules and one N atom from a 2-amino-4,5-dimethyl­benzene­sulfonate ligand in a severely distorted tetra­hedral geometry. The two Ag^I atoms are bridged by two water mol­ecules, forming a centrosymmetric binuclear complex. The distance of 3.615 (9) Å between the two Ag^I atoms suggests that there are no Ag...Ag inter­action within the binuclear mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.031
• wR factor = 0.074
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.16 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ag1    -   O1W     ..       7.41 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ag1    -   O2W     ..       9.78 su

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound shows a binuclear structure (Fig. 1). Each Ag^I atom is coordinated by three water molecules with Ag—O_bridge distance larger than that of Ag—O_terminal (Table 1), but both in the range of normal Ag—O distance. The Ag^I atom has a seriously distorted tetrahedral coodination geometry. The two Ag^I atoms are bridged by two water molecules, forming a binuclear structure. The Ag···Ag distance is 3.615 (9) Å, indicating no metal–metal interaction within the binuclear molecule. The molecular geometry of the title compound has been changed largely when compared with a related compound (Li et al., 2007). Adjacent molecules are connected by O—H···O and N—H···O hydrogen bonds (Table2), forming a two-dimensional supramolecular structure (Fig.2).

Related literature

The related compound, [Ag(C₈H₁₀NO₃S)(H₂O)₂], has a mononuclear structure (Li et al., 2007).

S2. Experimental

An aqueous solution (10 ml) of 2-amino-4,5-dimethylbenzenesulfonic acid (0.101 g, 0.5 mmol) was added to solid Ag₂CO₃ (0.069 g, 0.25 mmol) with stirring for several minutes until no further CO₂ was given off. The precipitate was dissolved by dropwise addition of an aqueous solution of NH₃ (14 M). Then a solution of β-picoline (0.039 g, 0.5 mmol) in CH₃OH (8 ml) was added with stirring for 30 min. Crystals of the title compound were obtained by evaporation of the solution for several days at room temperature. β-Picoline did not react with the silversulfonate.

S3. Refinement

H atoms bonded to C atoms were positioned geometrically and refined as riding, with C—H = 0.93Å and U_iso(H) = 1.2U_eq(C) for aromatic, and C—H = 0.96Å and U_iso(H) = 1.5U_eq(C) for methyl groups. H atoms bonded to N atom and water molecules were located in a difference map and refined isotropically.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x, 1 - y, 1 - z.]
	Fig. 2. Two-dimensional supramolecular structure of the title compound, formed through hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonds have been omitted.

Di-µ-aqua-bis[(2-amino-4,5-dimethylbenzenesulfonato-κN)aquasilver(I)]

Crystal data

[Ag2(C8H10NO3S)2(H2O)4]	F(000) = 688
Mr = 688.26	Dx = 1.909 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2822 reflections
a = 12.5391 (11) Å	θ = 1.7–28.3°
b = 8.7406 (7) Å	µ = 1.86 mm^−1
c = 11.3861 (10) Å	T = 292 K
β = 106.319 (1)°	Plate, colorless
V = 1197.63 (18) Å^3	0.35 × 0.25 × 0.18 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer	2822 independent reflections
Radiation source: fine-focus sealed tube	2077 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
ϕ and ω scans	θmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −14→16
Tmin = 0.515, Tmax = 0.715	k = −10→11
7202 measured reflections	l = −13→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	w = 1/[σ^2(Fo^2) + (0.0359P)^2] where P = (Fo^2 + 2Fc^2)/3
2822 reflections	(Δ/σ)max < 0.001
170 parameters	Δρmax = 0.73 e Å^−3
6 restraints	Δρmin = −0.55 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ag1	0.09929 (2)	0.40908 (3)	0.62723 (2)	0.05391 (11)
C1	0.27697 (19)	0.0783 (3)	0.6403 (2)	0.0286 (5)
C2	0.3878 (2)	0.0391 (3)	0.6914 (2)	0.0336 (6)
H2	0.4056	−0.0315	0.7551	0.040*
C3	0.4731 (2)	0.1015 (3)	0.6508 (3)	0.0358 (6)
C4	0.4451 (2)	0.2062 (3)	0.5542 (2)	0.0345 (6)
C5	0.3339 (2)	0.2459 (3)	0.5042 (2)	0.0341 (6)
H5	0.3158	0.3166	0.4406	0.041*
C6	0.24956 (19)	0.1846 (3)	0.5454 (2)	0.0285 (5)
C7	0.5317 (2)	0.2733 (4)	0.5006 (3)	0.0453 (7)
H7A	0.4973	0.3451	0.4375	0.068*
H7B	0.5659	0.1930	0.4665	0.068*
H7C	0.5872	0.3247	0.5637	0.068*
C8	0.5921 (2)	0.0541 (4)	0.7108 (3)	0.0501 (8)
H8A	0.6243	0.0148	0.6497	0.075*
H8B	0.5935	−0.0236	0.7707	0.075*
H8C	0.6339	0.1412	0.7498	0.075*
N1	0.13838 (19)	0.2376 (3)	0.4950 (2)	0.0345 (5)
O1	0.12030 (16)	0.1204 (2)	0.74406 (18)	0.0406 (4)
O2	0.09741 (15)	−0.0815 (2)	0.59466 (19)	0.0458 (5)
O3	0.22979 (15)	−0.1105 (2)	0.79442 (19)	0.0477 (5)
O1W	−0.1147 (2)	0.3633 (3)	0.5210 (2)	0.0572 (6)
O2W	0.1232 (2)	0.5614 (3)	0.7848 (2)	0.0672 (7)
S1	0.17342 (5)	−0.00523 (7)	0.69825 (6)	0.02996 (15)
H1N	0.088 (3)	0.177 (4)	0.486 (3)	0.076 (13)*
H1A	−0.125 (2)	0.278 (3)	0.486 (3)	0.047 (9)*
H1B	−0.152 (3)	0.364 (4)	0.564 (3)	0.063 (12)*
H2N	0.128 (2)	0.287 (3)	0.419 (3)	0.038 (7)*
H2B	0.159 (3)	0.648 (4)	0.770 (3)	0.057 (10)*
H2A	0.052 (3)	0.559 (6)	0.805 (4)	0.120 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.06478 (19)	0.04141 (16)	0.06053 (19)	0.00582 (11)	0.02579 (14)	−0.00630 (11)
C1	0.0268 (13)	0.0302 (13)	0.0298 (13)	−0.0002 (10)	0.0095 (10)	−0.0024 (10)
C2	0.0321 (14)	0.0371 (14)	0.0321 (14)	0.0013 (11)	0.0096 (11)	0.0015 (11)
C3	0.0269 (13)	0.0420 (15)	0.0390 (15)	−0.0012 (11)	0.0100 (11)	−0.0081 (12)
C4	0.0339 (13)	0.0384 (14)	0.0337 (14)	−0.0094 (11)	0.0138 (11)	−0.0067 (12)
C5	0.0385 (14)	0.0358 (14)	0.0287 (13)	−0.0044 (11)	0.0103 (11)	0.0009 (11)
C6	0.0290 (12)	0.0296 (13)	0.0271 (12)	−0.0013 (10)	0.0078 (10)	−0.0047 (10)
C7	0.0377 (15)	0.0569 (19)	0.0459 (17)	−0.0137 (13)	0.0190 (13)	−0.0043 (14)
C8	0.0289 (14)	0.063 (2)	0.058 (2)	0.0013 (14)	0.0118 (14)	0.0009 (16)
N1	0.0323 (12)	0.0355 (13)	0.0355 (13)	0.0021 (10)	0.0091 (10)	0.0045 (10)
O1	0.0416 (11)	0.0412 (11)	0.0460 (11)	0.0032 (8)	0.0237 (9)	−0.0013 (9)
O2	0.0371 (11)	0.0474 (13)	0.0513 (12)	−0.0114 (8)	0.0097 (9)	−0.0092 (9)
O3	0.0358 (11)	0.0527 (13)	0.0562 (13)	0.0038 (8)	0.0153 (10)	0.0243 (10)
O1W	0.0778 (17)	0.0461 (14)	0.0578 (15)	−0.0058 (12)	0.0354 (14)	−0.0052 (12)
O2W	0.0702 (17)	0.0601 (15)	0.0814 (19)	−0.0123 (13)	0.0378 (14)	−0.0108 (13)
S1	0.0259 (3)	0.0309 (3)	0.0338 (3)	−0.0009 (2)	0.0096 (3)	0.0024 (3)

Geometric parameters (Å, º)

Ag1—O2W	2.186 (3)	C7—H7A	0.9600
Ag1—N1	2.273 (2)	C7—H7B	0.9600
Ag1—O1W	2.645 (3)	C7—H7C	0.9600
Ag1—O1W^i	2.651 (4)	C8—H8A	0.9600
C1—C2	1.391 (3)	C8—H8B	0.9600
C1—C6	1.394 (3)	C8—H8C	0.9600
C1—S1	1.771 (2)	N1—H1N	0.81 (3)
C2—C3	1.390 (4)	N1—H2N	0.95 (3)
C2—H2	0.9300	O1—S1	1.4551 (19)
C3—C4	1.398 (4)	O2—S1	1.453 (2)
C3—C8	1.513 (4)	O3—S1	1.4524 (19)
C4—C5	1.394 (4)	O1W—H1A	0.84 (3)
C4—C7	1.506 (3)	O1W—H1B	0.76 (3)
C5—C6	1.380 (3)	O2W—H2B	0.92 (3)
C5—H5	0.9300	O2W—H2A	0.98 (4)
C6—N1	1.427 (3)
O2W—Ag1—N1	160.00 (9)	H7A—C7—H7B	109.5
O1W—Ag1—O1W^i	93.92 (8)	C4—C7—H7C	109.5
O1W—Ag1—O2W	110.79 (9)	H7A—C7—H7C	109.5
O1W—Ag1—N1	88.69 (8)	H7B—C7—H7C	109.5
O2W—Ag1—O1W^i	92.74 (8)	C3—C8—H8A	109.5
N1—Ag1—O1W^i	90.30 (8)	C3—C8—H8B	109.5
C2—C1—C6	119.3 (2)	H8A—C8—H8B	109.5
C2—C1—S1	119.59 (19)	C3—C8—H8C	109.5
C6—C1—S1	121.14 (18)	H8A—C8—H8C	109.5
C3—C2—C1	122.4 (2)	H8B—C8—H8C	109.5
C3—C2—H2	118.8	C6—N1—Ag1	108.40 (16)
C1—C2—H2	118.8	C6—N1—H1N	118 (3)
C2—C3—C4	118.1 (2)	Ag1—N1—H1N	102 (3)
C2—C3—C8	119.7 (3)	C6—N1—H2N	112.8 (15)
C4—C3—C8	122.1 (2)	Ag1—N1—H2N	107.7 (16)
C5—C4—C3	119.1 (2)	H1N—N1—H2N	106 (3)
C5—C4—C7	119.4 (2)	H1A—O1W—H1B	106 (3)
C3—C4—C7	121.5 (2)	Ag1—O2W—H2B	108 (2)
C6—C5—C4	122.6 (2)	Ag1—O2W—H2A	105 (3)
C6—C5—H5	118.7	H2B—O2W—H2A	125 (4)
C4—C5—H5	118.7	O3—S1—O2	112.99 (12)
C5—C6—C1	118.5 (2)	O3—S1—O1	112.48 (12)
C5—C6—N1	119.5 (2)	O2—S1—O1	112.04 (12)
C1—C6—N1	121.9 (2)	O3—S1—C1	106.83 (11)
C4—C7—H7A	109.5	O2—S1—C1	105.61 (12)
C4—C7—H7B	109.5	O1—S1—C1	106.26 (11)
C6—C1—C2—C3	−0.4 (4)	S1—C1—C6—C5	179.91 (18)
S1—C1—C2—C3	−179.4 (2)	C2—C1—C6—N1	−175.5 (2)
C1—C2—C3—C4	−0.7 (4)	S1—C1—C6—N1	3.5 (3)
C1—C2—C3—C8	179.8 (2)	C5—C6—N1—Ag1	−99.9 (2)
C2—C3—C4—C5	1.2 (4)	C1—C6—N1—Ag1	76.5 (2)
C8—C3—C4—C5	−179.3 (2)	O2W—Ag1—N1—C6	7.0 (4)
C2—C3—C4—C7	−177.0 (2)	C2—C1—S1—O3	−1.5 (2)
C8—C3—C4—C7	2.5 (4)	C6—C1—S1—O3	179.50 (19)
C3—C4—C5—C6	−0.8 (4)	C2—C1—S1—O2	−122.0 (2)
C7—C4—C5—C6	177.5 (2)	C6—C1—S1—O2	59.0 (2)
C4—C5—C6—C1	−0.3 (4)	C2—C1—S1—O1	118.8 (2)
C4—C5—C6—N1	176.2 (2)	C6—C1—S1—O1	−60.2 (2)
C2—C1—C6—C5	0.9 (4)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2^ii	0.84 (3)	2.02 (3)	2.830 (3)	161 (3)
O1W—H1B···O3^iii	0.76 (3)	2.12 (3)	2.874 (3)	169 (4)
O2W—H2A···O1^iii	0.98 (4)	2.14 (4)	3.022 (3)	148 (4)
O2W—H2B···O3^iv	0.92 (3)	2.28 (3)	3.154 (3)	159 (3)
N1—H1N···O2^ii	0.81 (3)	2.40 (3)	3.154 (3)	156 (4)
N1—H2N···O1^v	0.95 (3)	2.12 (3)	3.065 (3)	172 (2)

Symmetry codes: (ii) −x, −y, −z+1; (iii) −x, y+1/2, −z+3/2; (iv) x, y+1, z; (v) x, −y+1/2, z−1/2.