(2-Amino-4,5-dimethyl­benzene­sulfonato-κN)diaqua­silver(I)

The title compound, [Ag(C₈H₁₀NO₃S)(H₂O)₂], shows a T-shaped coordination; the 2-amino-4,5-dimethyl­benzene­sulfonate monoanion binds through the amino group. The mol­ecules are linked together through O—H...O and N—H...O hydrogen bonds into a layer structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.097
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ag1         (1)       0.91
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          7

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

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

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S1. Comment

Metal sulfonates are a class of compounds showing interesting structures and properties (May & Shimizu, 2005; Gao et al., 2005); however, the sulfonate unit itself typically exists as a non-coordinating anion (Liu et al., 2006). Indeed, in a majority of metal complexes with sulfonate counterions, the sulfonate group cannot displace water from the coordination sphere of the metal ion. This feature is also found in the present silver derivative of 2-amino-4,5-dimethylbenzenesulfonic acid.

The silvera tom in (I) is coordinated by the amino group instead; it is also linked to two water molecules in a T–shaped environment (Fig. 1). The molecules are linked through O—H···O and N—H···O hydrogen bonds (Table 2) to form a two-dimensional supramolecular structure (Fig. 2).

Related literature

For studies on metal sulfonates, see: May & Shimizu (2005); Gao et al. (2005); Liu et al. (2006).

S2. Experimental

To a mixture of 2-amino-4,5-dimethylbenzenesulfonic acid (0.5 mmol) and sodium hydroxide 0.5 mmol) in water was added silver nitrate (0.5 mmol). The precipitate that formed was dissolved by ammonium hydroxide. Colorless crystals were obtained from the filtrate after being set aside, away from light, after a week (33% yield).

S3. Refinement

H atoms bonded to N atom were located in a difference map and refined freely, and with U_iso(H) = 1.2U_eq(N). H atoms bonded to C atom were positioned geometrically (C—H = 0.93 Å) and refined as riding, with U_iso(H)=1.2U_eq(carrier). The water H-atoms were located in a difference Fourier map, and were refined with distance restraints of O–H = 0.85 Å; their temperature factors were tied to those of parent atoms by a factor of 1.2.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. (arbitrary spheres for the H atoms).
	Fig. 2. View of the two-dimensional H-bonding structure of (I). H atoms bonded to C atoms have been omitted.

(2-Amino-4,5-dimethylbenzenesulfonato-κN)diaquasilver(I)

Crystal data

[Ag(C8H10NO3S)(H2O)2]	F(000) = 688
Mr = 344.13	Dx = 1.859 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2881 reflections
a = 12.0636 (6) Å	θ = 1.7–28.2°
b = 9.8642 (5) Å	µ = 1.81 mm^−1
c = 10.3509 (6) Å	T = 293 K
β = 93.263 (1)°	Block, colorless
V = 1229.74 (11) Å^3	0.33 × 0.27 × 0.25 mm
Z = 4

Data collection

Bruker APEX CCD area-detector diffractometer	2881 independent reflections
Radiation source: fine-focus sealed tube	2381 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
φ and ω scans	θmax = 28.2°, θmin = 1.7°
Absorption correction: multi-scan (SAINT; Bruker, 1998)	h = −12→16
Tmin = 0.542, Tmax = 0.637	k = −12→10
7355 measured reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0556P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2881 reflections	Δρmax = 0.81 e Å^−3
166 parameters	Δρmin = −0.67 e Å^−3
7 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0241 (14)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7014 (2)	0.5742 (2)	0.2547 (2)	0.0302 (5)
C2	0.5932 (2)	0.5483 (3)	0.2888 (3)	0.0378 (6)
H2	0.5821	0.5069	0.3677	0.045*
C3	0.5019 (2)	0.5827 (3)	0.2082 (3)	0.0414 (7)
C4	0.5188 (2)	0.6492 (3)	0.0924 (3)	0.0408 (6)
C5	0.6275 (2)	0.6730 (3)	0.0580 (3)	0.0386 (6)
H5	0.6386	0.7167	−0.0199	0.046*
C6	0.7194 (2)	0.6339 (3)	0.1355 (2)	0.0311 (5)
C7	0.3854 (3)	0.5482 (5)	0.2461 (4)	0.0643 (10)
H7A	0.3445	0.6304	0.2580	0.096*
H7B	0.3895	0.4974	0.3253	0.096*
H7C	0.3484	0.4951	0.1789	0.096*
C8	0.4235 (3)	0.6948 (4)	0.0021 (4)	0.0580 (9)
H8A	0.4520	0.7349	−0.0738	0.087*
H8B	0.3797	0.7604	0.0450	0.087*
H8C	0.3780	0.6181	−0.0225	0.087*
N1	0.8264 (2)	0.6491 (3)	0.0889 (2)	0.0391 (5)
H2A	0.829 (3)	0.717 (4)	0.040 (4)	0.059*
H1A	0.8871 (19)	0.639 (4)	0.126 (3)	0.059*
O1	0.86923 (19)	0.4162 (2)	0.3114 (2)	0.0460 (5)
O2	0.76622 (16)	0.5008 (2)	0.48734 (17)	0.0433 (5)
O3	0.88482 (17)	0.6513 (2)	0.3724 (2)	0.0467 (5)
S1	0.81314 (5)	0.53146 (7)	0.36498 (6)	0.02929 (17)
Ag1	0.887415 (18)	0.42546 (3)	−0.07922 (2)	0.04829 (14)
O1W	0.8839 (2)	0.2714 (3)	0.0647 (3)	0.0591 (6)
HW11	0.836 (2)	0.210 (3)	0.039 (4)	0.089*
HW12	0.9488 (15)	0.234 (4)	0.073 (4)	0.089*
O2W	0.8922 (2)	0.5559 (3)	−0.2436 (3)	0.0587 (6)
HW21	0.9604 (15)	0.558 (4)	−0.266 (5)	0.088*
HW22	0.872 (3)	0.6373 (18)	−0.226 (4)	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0332 (12)	0.0315 (13)	0.0256 (11)	−0.0003 (10)	0.0005 (9)	−0.0019 (9)
C2	0.0360 (14)	0.0489 (17)	0.0288 (13)	−0.0049 (12)	0.0041 (10)	−0.0018 (11)
C3	0.0324 (13)	0.0505 (18)	0.0413 (15)	−0.0021 (12)	0.0004 (11)	−0.0114 (13)
C4	0.0403 (15)	0.0389 (16)	0.0418 (15)	0.0055 (12)	−0.0088 (11)	−0.0053 (12)
C5	0.0478 (15)	0.0347 (14)	0.0325 (13)	−0.0012 (11)	−0.0036 (11)	0.0061 (11)
C6	0.0348 (12)	0.0298 (13)	0.0287 (12)	−0.0014 (10)	0.0023 (9)	−0.0006 (10)
C7	0.0345 (16)	0.099 (3)	0.059 (2)	−0.0115 (17)	0.0026 (14)	−0.016 (2)
C8	0.0491 (17)	0.053 (2)	0.069 (2)	0.0071 (15)	−0.0193 (15)	0.0019 (17)
N1	0.0382 (12)	0.0436 (15)	0.0363 (12)	−0.0022 (11)	0.0089 (10)	0.0063 (10)
O1	0.0530 (13)	0.0471 (13)	0.0378 (11)	0.0164 (9)	0.0015 (9)	−0.0060 (9)
O2	0.0433 (10)	0.0616 (14)	0.0251 (9)	0.0013 (10)	0.0040 (8)	0.0036 (9)
O3	0.0452 (11)	0.0460 (13)	0.0472 (11)	−0.0137 (9)	−0.0125 (8)	0.0066 (10)
S1	0.0311 (3)	0.0332 (3)	0.0235 (3)	−0.0006 (2)	0.0007 (2)	−0.0003 (2)
Ag1	0.04155 (18)	0.0547 (2)	0.04816 (19)	0.00171 (9)	−0.00134 (11)	0.00677 (10)
O1W	0.0624 (14)	0.0517 (14)	0.0621 (14)	0.0034 (12)	−0.0073 (12)	−0.0065 (12)
O2W	0.0590 (15)	0.0646 (16)	0.0526 (14)	−0.0003 (12)	0.0043 (11)	−0.0009 (12)

Geometric parameters (Å, º)

C1—C2	1.395 (4)	C8—H8A	0.9600
C1—C6	1.396 (4)	C8—H8B	0.9600
C1—S1	1.767 (3)	C8—H8C	0.9600
C2—C3	1.386 (4)	N1—H2A	0.85 (4)
C2—H2	0.9300	N1—H1A	0.814 (19)
C3—C4	1.392 (4)	O1—S1	1.450 (2)
C3—C7	1.519 (4)	O2—S1	1.4484 (18)
C4—C5	1.398 (4)	O3—S1	1.464 (2)
C4—C8	1.509 (4)	Ag1—O1W	2.130 (3)
C5—C6	1.386 (4)	Ag1—O2W	2.136 (3)
C5—H5	0.9300	Ag1—N1	2.930 (3)
C6—N1	1.411 (3)	O1W—HW11	0.87 (3)
C7—H7A	0.9600	O1W—HW12	0.866 (10)
C7—H7B	0.9600	O2W—HW21	0.866 (10)
C7—H7C	0.9600	O2W—HW22	0.864 (10)
C2—C1—C6	119.7 (2)	C4—C8—H8A	109.5
C2—C1—S1	118.9 (2)	C4—C8—H8B	109.5
C6—C1—S1	121.4 (2)	H8A—C8—H8B	109.5
C3—C2—C1	121.8 (3)	C4—C8—H8C	109.5
C3—C2—H2	119.1	H8A—C8—H8C	109.5
C1—C2—H2	119.1	H8B—C8—H8C	109.5
C2—C3—C4	118.9 (3)	C6—N1—H2A	111 (3)
C2—C3—C7	120.4 (3)	C6—N1—H1A	130 (3)
C4—C3—C7	120.7 (3)	H2A—N1—H1A	109 (4)
C3—C4—C5	119.0 (2)	O2—S1—O1	112.63 (13)
C3—C4—C8	122.0 (3)	O2—S1—O3	112.46 (13)
C5—C4—C8	119.0 (3)	O1—S1—O3	111.48 (14)
C6—C5—C4	122.5 (3)	O2—S1—C1	107.04 (12)
C6—C5—H5	118.8	O1—S1—C1	107.20 (12)
C4—C5—H5	118.8	O3—S1—C1	105.53 (12)
C5—C6—C1	118.0 (2)	O1W—Ag1—O2W	171.50 (10)
C5—C6—N1	119.4 (2)	O1W—Ag1—N1	96.09 (9)
C1—C6—N1	122.5 (2)	O2W—Ag1—N1	92.22 (9)
C3—C7—H7A	109.5	Ag1—O1W—HW11	109 (3)
C3—C7—H7B	109.5	Ag1—O1W—HW12	109 (3)
H7A—C7—H7B	109.5	HW11—O1W—HW12	108 (2)
C3—C7—H7C	109.5	Ag1—O2W—HW21	107 (3)
H7A—C7—H7C	109.5	Ag1—O2W—HW22	112 (3)
H7B—C7—H7C	109.5	HW21—O2W—HW22	109 (2)
C6—C1—C2—C3	−1.3 (4)	C4—C5—C6—N1	173.8 (3)
S1—C1—C2—C3	178.3 (2)	C2—C1—C6—C5	3.9 (4)
C1—C2—C3—C4	−2.4 (4)	S1—C1—C6—C5	−175.7 (2)
C1—C2—C3—C7	177.7 (3)	C2—C1—C6—N1	−172.8 (3)
C2—C3—C4—C5	3.3 (4)	S1—C1—C6—N1	7.7 (4)
C7—C3—C4—C5	−176.8 (3)	C2—C1—S1—O2	−11.9 (3)
C2—C3—C4—C8	−177.6 (3)	C6—C1—S1—O2	167.6 (2)
C7—C3—C4—C8	2.4 (5)	C2—C1—S1—O1	109.1 (2)
C3—C4—C5—C6	−0.6 (4)	C6—C1—S1—O1	−71.3 (2)
C8—C4—C5—C6	−179.8 (3)	C2—C1—S1—O3	−131.9 (2)
C4—C5—C6—C1	−3.0 (4)	C6—C1—S1—O3	47.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—HW12···O3^i	0.87 (1)	2.21 (1)	3.067 (3)	170 (4)
O1W—HW11···O2^ii	0.87 (3)	2.29 (2)	3.119 (3)	159 (4)
O2W—HW21···O1^iii	0.87 (1)	2.15 (1)	3.013 (3)	174 (4)
O2W—HW22···O3^iv	0.86 (1)	2.32 (2)	3.131 (3)	157 (4)
N1—H2A···O3^iv	0.85 (4)	2.29 (4)	3.095 (3)	158 (3)

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