Poly­[di-μ-aqua-bis­(μ₈-3-carboxyl­ato-4-hydroxy­benzene­sulfonato)tetrasilver(I)]

In the polymeric title compound, [Ag₄(C₇H₄O₆S)₂(H₂O)₂]_n, the 3-carboxyl­ato-4-hydroxy­benzene­sulfonate anion uses its hydroxy (–OH) unit to bind to an Ag atom and its sulfonyl (–SO₃) unit to bind to five Ag atoms; it uses its carboxyl­ate (–CO₂) group to bridge an Ag—Ag [Ag—Ag = 2.7778 (8) Å] unit. The bonding mode gives rise to a three-dimensional network structure that is consolidated by hydrogen bonds involving the coordinated water mol­ecules. The four Ag atoms in the asymmetric unit all lie on special positions of site symmetry 2.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.026
• wR factor = 0.068
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.94
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.23 Ratio
PLAT731_ALERT_1_B Bond    Calc     0.86(5), Rep   0.850(10) ......       5.00 su-Rat
              O1W  -H1W2    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.86(5), Rep   0.850(10) ......       5.00 su-Rat
              O1W  -H2#     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.86(5), Rep   0.850(10) ......       5.00 su-Rat
              O1W  -H2#     1.555   1.555

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           27.50
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total               2158
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         2309
           Completeness (_total/calc)             93.46%
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.94
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT128_ALERT_4_C Non-standard setting of Space group P2/c    ....    P2/n
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        Ag2
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O6   -H6O     1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      110(5), Rep   109.8(18) ......       2.78 su-Rat
              H1W1 -O1W  -H1W2    1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc     -4.5(7), Rep     -4.6(3) ......       2.33 su-Rat
              O4  -AG4 -O4  -C7     2.754   1.555   1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O6   -H6O     1.555   1.555

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

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

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Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); 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.

Poly[tetrasilver(I)-di-µ-aqua-bis[µ₈-3-carboxylato-4- hydroxybenzenesulfonato]

Crystal data

[Ag4(C7H4O6S)2(H2O)2]	F(000) = 856
Mr = 899.94	Dx = 2.980 Mg m^−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 9456 reflections
a = 7.493 (2) Å	θ = 3.0–27.5°
b = 16.237 (3) Å	µ = 4.13 mm^−1
c = 8.253 (2) Å	T = 295 K
β = 92.91 (3)°	Block, colorless
V = 1002.8 (3) Å^3	0.32 × 0.25 × 0.17 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	2158 independent reflections
Radiation source: fine-focus sealed tube	2015 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→9
Tmin = 0.294, Tmax = 0.495	k = −21→21
8593 measured reflections	l = −10→10

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0367P)^2 + 2.4683P] where P = (Fo^2 + 2Fc^2)/3
2158 reflections	(Δ/σ)max = 0.001
168 parameters	Δρmax = 0.91 e Å^−3
4 restraints	Δρmin = −1.25 e Å^−3

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

	x	y	z	Uiso*/Ueq
Ag1	0.7500	0.49393 (2)	0.7500	0.0325 (1)
Ag2	0.7500	0.48836 (3)	0.2500	0.0475 (2)
Ag3	1.2500	0.92255 (2)	−0.2500	0.0402 (1)
Ag4	1.2500	0.75147 (2)	−0.2500	0.0322 (1)
S1	0.9283 (1)	0.63097 (5)	0.5065 (1)	0.0203 (2)
O1	0.7488 (3)	0.6163 (2)	0.5588 (4)	0.0357 (6)
O2	0.9751 (4)	0.5767 (1)	0.3742 (3)	0.0292 (5)
O3	1.0610 (4)	0.6291 (2)	0.6421 (3)	0.0317 (6)
O4	1.1192 (4)	0.7661 (2)	−0.0274 (3)	0.0346 (6)
O5	1.1124 (4)	0.9033 (2)	−0.0077 (3)	0.0335 (6)
O6	0.9917 (4)	0.9681 (2)	0.2517 (3)	0.0370 (7)
O1w	0.6103 (4)	0.4246 (2)	0.5116 (3)	0.0329 (6)
C1	1.0182 (4)	0.8221 (2)	0.2120 (4)	0.0205 (6)
C2	0.9976 (4)	0.7432 (2)	0.2756 (4)	0.0213 (6)
C3	0.9362 (4)	0.7322 (2)	0.4285 (4)	0.0198 (6)
C4	0.8915 (5)	0.8001 (2)	0.5229 (4)	0.0256 (7)
C5	0.9107 (5)	0.8786 (2)	0.4620 (4)	0.0279 (7)
C6	0.9745 (5)	0.8898 (2)	0.3073 (4)	0.0237 (6)
C7	1.0880 (5)	0.8311 (2)	0.0461 (4)	0.0239 (7)
H6o	1.019 (8)	0.963 (4)	0.153 (3)	0.07 (2)*
H1w1	0.498 (2)	0.417 (3)	0.506 (7)	0.07 (2)*
H1w2	0.663 (6)	0.383 (3)	0.47 (1)	0.11 (3)*
H2	1.0257	0.6975	0.2138	0.026*
H4	0.8492	0.7924	0.6258	0.031*
H5	0.8812	0.9240	0.5239	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0399 (2)	0.0321 (2)	0.0255 (2)	0.000	0.0022 (2)	0.000
Ag2	0.0474 (3)	0.0303 (2)	0.0622 (3)	0.000	−0.0225 (2)	0.000
Ag3	0.0611 (3)	0.02319 (19)	0.0393 (2)	0.000	0.0307 (2)	0.000
Ag4	0.0518 (3)	0.02488 (19)	0.0213 (2)	0.000	0.0149 (2)	0.000
S1	0.0226 (4)	0.0198 (4)	0.0187 (4)	−0.0036 (3)	0.0014 (3)	0.0027 (3)
O1	0.027 (1)	0.039 (1)	0.042 (2)	−0.008 (1)	0.011 (1)	0.009 (1)
O2	0.041 (1)	0.021 (1)	0.027 (1)	−0.002 (1)	0.004 (1)	−0.002 (1)
O3	0.041 (2)	0.026 (1)	0.027 (1)	−0.002 (1)	−0.010 (1)	0.005 (1)
O4	0.055 (2)	0.027 (1)	0.024 (1)	−0.002 (1)	0.018 (1)	−0.002 (1)
O5	0.050 (2)	0.024 (1)	0.029 (1)	0.003 (1)	0.018 (1)	0.008 (1)
O6	0.062 (2)	0.019 (1)	0.031 (2)	0.007 (1)	0.017 (1)	0.004 (1)
O1w	0.027 (1)	0.039 (2)	0.033 (1)	0.004 (1)	0.002 (1)	−0.006 (1)
C1	0.024 (2)	0.021 (1)	0.016 (1)	0.002 (1)	0.003 (1)	0.002 (1)
C2	0.025 (2)	0.019 (1)	0.020 (2)	0.002 (1)	0.004 (1)	0.000 (1)
C3	0.022 (2)	0.020 (1)	0.018 (2)	−0.001 (1)	0.001 (1)	0.003 (1)
C4	0.028 (2)	0.031 (2)	0.019 (2)	0.001 (1)	0.009 (1)	0.001 (1)
C5	0.037 (2)	0.023 (2)	0.024 (2)	0.006 (1)	0.010 (2)	−0.003 (1)
C6	0.029 (2)	0.019 (1)	0.024 (2)	0.003 (1)	0.006 (1)	0.002 (1)
C7	0.025 (2)	0.028 (2)	0.020 (2)	0.001 (1)	0.005 (1)	0.001 (1)

Geometric parameters (Å, º)

Ag1—O1	2.537 (3)	S1—O1	1.453 (3)
Ag1—O1^i	2.537 (3)	S1—O3	1.459 (3)
Ag1—O2^ii	2.612 (3)	S1—O2	1.459 (3)
Ag1—O2^iii	2.612 (3)	S1—C3	1.767 (3)
Ag1—O1w	2.455 (3)	O4—C7	1.246 (4)
Ag1—O1w^i	2.455 (3)	O5—C7	1.270 (4)
Ag2—O2	2.404 (3)	O6—C6	1.360 (4)
Ag2—O2^iv	2.404 (3)	C1—C2	1.396 (4)
Ag2—O3^ii	2.512 (3)	C1—C6	1.400 (4)
Ag2—O3^v	2.512 (3)	C1—C7	1.497 (4)
Ag2—O1w	2.657 (3)	C2—C3	1.377 (4)
Ag2—O1w^iv	2.657 (3)	C3—C4	1.401 (4)
Ag3—O5	2.317 (2)	C4—C5	1.380 (5)
Ag3—O5^vi	2.317 (2)	C5—C6	1.397 (5)
Ag3—O6^vii	2.536 (3)	O6—H6o	0.85 (1)
Ag3—O6^viii	2.536 (3)	O1w—H1w1	0.85 (1)
Ag4—O3^ix	2.573 (3)	O1w—H1w2	0.85 (1)
Ag4—O3^x	2.573 (3)	C2—H2	0.93
Ag4—O4	2.139 (3)	C4—H4	0.93
Ag4—O4^vi	2.139 (3)	C5—H5	0.93
Ag3—Ag4	2.7778 (8)
O1—Ag1—O1^i	76.9 (1)	O1—S1—O2	112.6 (2)
O1—Ag1—O2^ii	94.5 (1)	O3—S1—O2	112.4 (2)
O1—Ag1—O2^iii	127.6 (1)	O1—S1—C3	108.0 (2)
O1—Ag1—O1w	82.7 (1)	O3—S1—C3	105.4 (2)
O1—Ag1—O1w^i	147.8 (1)	O2—S1—C3	106.0 (2)
O1^i—Ag1—O2^ii	127.6 (1)	S1—O1—Ag1	109.8 (2)
O1^i—Ag1—O2^iii	94.5 (1)	S1—O2—Ag2	119.3 (2)
O1^i—Ag1—O1w	147.8 (1)	S1—O3—Ag2^ii	129.6 (2)
O1^i—Ag1—O1w^i	82.7 (1)	S1—O3—Ag4^xi	126.2 (2)
O2^ii—Ag1—O2^iii	127.9 (1)	Ag2^ii—O3—Ag4^xi	100.0 (1)
O2^ii—Ag1—O1w	78.3 (1)	Ag1—O1w—Ag2	107.6 (1)
O2^ii—Ag1—O1w^i	78.5 (1)	C7—O4—Ag4	128.2 (2)
O2^iii—Ag1—O1w	78.5 (1)	C7—O5—Ag3	120.3 (2)
O2^iii—Ag1—O1w^i	78.3 (1)	C6—O6—Ag3^vii	125.2 (2)
O1w—Ag1—O1w^i	125.4 (1)	C2—C1—C6	118.4 (3)
O2—Ag2—O2^iv	106.7 (1)	C2—C1—C7	118.9 (3)
O2—Ag2—O3^ii	86.1 (1)	C6—C1—C7	122.6 (3)
O2—Ag2—O3^v	167.2 (1)	C3—C2—C1	120.8 (3)
O2—Ag2—O1w	100.6 (1)	C2—C3—C4	120.5 (3)
O2—Ag2—O1w^iv	106.4 (1)	C2—C3—S1	118.3 (2)
O2^iv—Ag2—O3^ii	167.2 (1)	C4—C3—S1	121.1 (2)
O2^iv—Ag2—O3^v	86.1 (1)	C5—C4—C3	119.5 (3)
O2^iv—Ag2—O1w	106.4 (1)	C4—C5—C6	120.0 (3)
O2^iv—Ag2—O1w^iv	100.6 (1)	O6—C6—C5	118.2 (3)
O3^ii—Ag2—O3^v	81.2 (1)	O6—C6—C1	121.0 (3)
O3^ii—Ag2—O1w	69.8 (1)	C5—C6—C1	120.7 (3)
O3^ii—Ag2—O1w^iv	75.8 (1)	O4—C7—O5	125.3 (3)
O3^v—Ag2—O1w	75.8 (1)	O4—C7—C1	116.4 (3)
O3^v—Ag2—O1w^iv	69.8 (1)	O5—C7—C1	118.2 (3)
O1w—Ag2—O1w^iv	134.1 (1)	C6—O6—H6o	105 (4)
O5—Ag3—O5^vi	164.5 (1)	Ag3^vii—O6—H6o	106 (4)
O5—Ag3—O6^vii	75.5 (1)	Ag1—O1w—H1w1	119 (4)
O5—Ag3—O6^viii	116.0 (1)	Ag2—O1w—H1w1	116 (4)
O5^vi—Ag3—O6^vii	116.0 (1)	Ag1—O1w—H1w2	118 (5)
O5^vi—Ag3—O6^viii	75.5 (1)	Ag2—O1w—H1w2	79 (5)
O6^vii—Ag3—O6^viii	91.1 (1)	H1w1—O1w—H1w2	109.8 (18)
O3^ix—Ag4—O3^x	78.9 (1)	C3—C2—H2	119.6
O3^ix—Ag4—O4	96.6 (1)	C1—C2—H2	119.6
O3^ix—Ag4—O4^vi	93.3 (1)	C5—C4—H4	120.3
O3^x—Ag4—O4	93.3 (1)	C3—C4—H4	120.3
O3^x—Ag4—O4^vi	96.6 (1)	C4—C5—H5	120.0
O4—Ag4—O4^vi	167.2 (1)	C6—C5—H5	120.0
O1—S1—O3	112.0 (2)
O5^vi—Ag3—Ag4—O4	−179.2 (1)	O6^viii—Ag3—O5—C7	−133.9 (3)
O5—Ag3—Ag4—O4	0.8 (1)	O6^vii—Ag3—O5—C7	142.0 (3)
O6^viii—Ag3—Ag4—O4	119.9 (1)	Ag4—Ag3—O5—C7	2.1 (3)
O6^vii—Ag3—Ag4—O4	−60.1 (1)	O1w^i—Ag1—O1w—Ag2	−128.6 (1)
O5^vi—Ag3—Ag4—O4^vi	0.8 (1)	O1^i—Ag1—O1w—Ag2	84.9 (2)
O5—Ag3—Ag4—O4^vi	−179.2 (1)	O1—Ag1—O1w—Ag2	34.1 (1)
O6^viii—Ag3—Ag4—O4^vi	−60.1 (1)	O2^iii—Ag1—O1w—Ag2	164.9 (1)
O6^vii—Ag3—Ag4—O4^vi	119.9 (1)	O2^ii—Ag1—O1w—Ag2	−62.1 (1)
O5^vi—Ag3—Ag4—O3^ix	−86.6 (1)	O2—Ag2—O1w—Ag1	5.6 (1)
O5—Ag3—Ag4—O3^ix	93.4 (1)	O2^iv—Ag2—O1w—Ag1	−105.5 (1)
O6^viii—Ag3—Ag4—O3^ix	−147.5 (1)	O3^v—Ag2—O1w—Ag1	173.1 (1)
O6^vii—Ag3—Ag4—O3^ix	32.5 (1)	O3^ii—Ag2—O1w—Ag1	87.4 (1)
O5^vi—Ag3—Ag4—O3^x	93.4 (1)	O1w^iv—Ag2—O1w—Ag1	131.1 (1)
O5—Ag3—Ag4—O3^x	−86.6 (1)	C6—C1—C2—C3	−0.1 (5)
O6^viii—Ag3—Ag4—O3^x	32.5 (1)	C7—C1—C2—C3	179.1 (3)
O6^vii—Ag3—Ag4—O3^x	−147.5 (1)	C1—C2—C3—C4	0.6 (5)
O3—S1—O1—Ag1	−46.5 (2)	C1—C2—C3—S1	−175.7 (3)
O2—S1—O1—Ag1	81.4 (2)	O1—S1—C3—C2	−127.0 (3)
C3—S1—O1—Ag1	−162.0 (1)	O3—S1—C3—C2	113.2 (3)
O1w—Ag1—O1—S1	−105.2 (2)	O2—S1—C3—C2	−6.2 (3)
O1w^i—Ag1—O1—S1	47.8 (3)	O1—S1—C3—C4	56.7 (3)
O1^i—Ag1—O1—S1	100.0 (2)	O3—S1—C3—C4	−63.1 (3)
O2^iii—Ag1—O1—S1	−174.5 (1)	O2—S1—C3—C4	177.6 (3)
O2^ii—Ag1—O1—S1	−27.6 (2)	C2—C3—C4—C5	−0.5 (5)
O1—S1—O2—Ag2	6.8 (2)	S1—C3—C4—C5	175.6 (3)
O3—S1—O2—Ag2	134.4 (2)	C3—C4—C5—C6	0.0 (5)
C3—S1—O2—Ag2	−111.0 (2)	Ag3^vii—O6—C6—C5	−50.9 (4)
O2^iv—Ag2—O2—S1	63.6 (1)	Ag3^vii—O6—C6—C1	128.6 (3)
O3^v—Ag2—O2—S1	−119.1 (4)	C4—C5—C6—O6	−180.0 (3)
O3^ii—Ag2—O2—S1	−115.8 (2)	C4—C5—C6—C1	0.5 (6)
O1w^iv—Ag2—O2—S1	170.3 (2)	C2—C1—C6—O6	−179.9 (3)
O1w—Ag2—O2—S1	−47.3 (2)	C7—C1—C6—O6	0.9 (5)
O1—S1—O3—Ag2^ii	93.7 (2)	C2—C1—C6—C5	−0.4 (5)
O2—S1—O3—Ag2^ii	−34.2 (2)	C7—C1—C6—C5	−179.6 (3)
C3—S1—O3—Ag2^ii	−149.2 (2)	Ag4—O4—C7—O5	8.0 (6)
O1—S1—O3—Ag4^xi	−114.0 (2)	Ag4—O4—C7—C1	−171.3 (2)
O2—S1—O3—Ag4^xi	118.1 (2)	Ag3—O5—C7—O4	−6.3 (5)
C3—S1—O3—Ag4^xi	3.1 (2)	Ag3—O5—C7—C1	173.0 (2)
O4^vi—Ag4—O4—C7	−4.6 (3)	C2—C1—C7—O4	1.9 (5)
O3^ix—Ag4—O4—C7	−144.9 (3)	C6—C1—C7—O4	−178.9 (3)
O3^x—Ag4—O4—C7	136.0 (3)	C2—C1—C7—O5	−177.4 (3)
Ag3—Ag4—O4—C7	−4.6 (3)	C6—C1—C7—O5	1.8 (5)
O5^vi—Ag3—O5—C7	2.1 (3)

Symmetry codes: (i) −x+3/2, y, −z+3/2; (ii) −x+2, −y+1, −z+1; (iii) x−1/2, −y+1, z+1/2; (iv) −x+3/2, y, −z+1/2; (v) x−1/2, −y+1, z−1/2; (vi) −x+5/2, y, −z−1/2; (vii) −x+2, −y+2, −z; (viii) x+1/2, −y+2, z−1/2; (ix) x, y, z−1; (x) −x+5/2, y, −z+1/2; (xi) x, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6o···O5	0.85 (1)	1.81 (3)	2.589 (4)	151 (6)
O1w—H1w1···O1^xii	0.85 (1)	1.97 (2)	2.803 (4)	165 (5)
O1w—H1w2···O3^ii	0.85 (1)	2.33 (5)	2.959 (4)	131 (5)
O1w—H1w2···O4^iii	0.85 (1)	2.44 (5)	3.114 (4)	137 (6)

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