Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008250/wn6147sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008250/wn6147Isup2.hkl |
CCDC reference: 214570
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.010 Å
- R factor = 0.055
- wR factor = 0.130
- Data-to-parameter ratio = 19.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Ag2O (0.5 mmol, 116 mg) and 4-chlorobenzoic acid (1 mmol, 156 mg) were dissolved in aqueous ammonia (10 ml), stirring for ca 10 min to obtain a clear solution. After the solution had stood in air for two days with ammonia gas escaping, colorless crystals were deposited, collected and washed with water. These crystals were then dried in a vacuum desiccator under drying CaCl2 (yield 66%). Analysis of the title complex (C14H12AgCl2O6) calculated: C 29.87, H 2.15%; found: C 30.05, H 2.18%. A single-crystal of suitable size was used for the X-ray diffraction study.
All H atoms were geometrically fixed with C—H = 0.93 Å and O—H = 0.94–1.00 Å. They were treated as riding atoms with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(O). The maximum and minimum electron-density peaks are located at 1.00 and 1.19 Å from Ag1 and H2W, respectively.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
[Ag2(C7H6ClO3)2(H2O)2] | F(000) = 1088 |
Mr = 562.88 | Dx = 2.139 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 35.978 (5) Å | Cell parameters from 1762 reflections |
b = 4.0535 (6) Å | θ = 3.3–28.3° |
c = 12.3204 (19) Å | µ = 2.57 mm−1 |
β = 103.439 (3)° | T = 293 K |
V = 1747.6 (5) Å3 | Block, colorless |
Z = 4 | 0.40 × 0.20 × 0.20 mm |
Siemens SMART CCD area-detector diffractometer | 2139 independent reflections |
Radiation source: fine-focus sealed tube | 1343 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 3.3° |
ω scans | h = −47→29 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −5→5 |
Tmin = 0.426, Tmax = 0.627 | l = −15→16 |
5101 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0473P)2 + 8.4499P] where P = (Fo2 + 2Fc2)/3 |
2139 reflections | (Δ/σ)max < 0.001 |
109 parameters | Δρmax = 1.09 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
[Ag2(C7H6ClO3)2(H2O)2] | V = 1747.6 (5) Å3 |
Mr = 562.88 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 35.978 (5) Å | µ = 2.57 mm−1 |
b = 4.0535 (6) Å | T = 293 K |
c = 12.3204 (19) Å | 0.40 × 0.20 × 0.20 mm |
β = 103.439 (3)° |
Siemens SMART CCD area-detector diffractometer | 2139 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1343 reflections with I > 2σ(I) |
Tmin = 0.426, Tmax = 0.627 | Rint = 0.031 |
5101 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.09 e Å−3 |
2139 reflections | Δρmin = −0.57 e Å−3 |
109 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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 | 0.008337 (15) | 0.27127 (15) | 0.10458 (4) | 0.0589 (2) | |
Cl1 | 0.23476 (6) | −0.5091 (5) | 0.1096 (2) | 0.0790 (6) | |
O1 | 0.06162 (13) | 0.1284 (14) | 0.0772 (4) | 0.0623 (13) | |
O2 | 0.07161 (16) | −0.0847 (14) | 0.2451 (4) | 0.0734 (16) | |
O1W | −0.04703 (15) | 0.4190 (15) | 0.1140 (4) | 0.0741 (14) | |
H1W | −0.0591 | 0.2198 | 0.1242 | 0.111* | |
H2W | −0.0441 | 0.5983 | 0.1709 | 0.111* | |
C1 | 0.13266 (18) | −0.0794 (17) | 0.0503 (5) | 0.0485 (15) | |
H1 | 0.1170 | 0.0369 | −0.0078 | 0.058* | |
C2 | 0.1682 (2) | −0.1888 (17) | 0.0399 (6) | 0.0533 (17) | |
H2 | 0.1766 | −0.1440 | −0.0246 | 0.064* | |
C3 | 0.19080 (19) | −0.3620 (16) | 0.1246 (6) | 0.0511 (16) | |
C4 | 0.1795 (2) | −0.4225 (17) | 0.2228 (6) | 0.0574 (17) | |
H4 | 0.1954 | −0.5366 | 0.2809 | 0.069* | |
C5 | 0.14458 (19) | −0.3118 (16) | 0.2327 (6) | 0.0505 (16) | |
H5 | 0.1369 | −0.3508 | 0.2985 | 0.061* | |
C6 | 0.12044 (17) | −0.1427 (15) | 0.1467 (5) | 0.0413 (14) | |
C7 | 0.08203 (18) | −0.0275 (15) | 0.1578 (5) | 0.0466 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0505 (3) | 0.0795 (4) | 0.0498 (3) | 0.0078 (3) | 0.0182 (2) | 0.0080 (3) |
Cl1 | 0.0561 (11) | 0.0736 (14) | 0.1169 (17) | 0.0053 (9) | 0.0398 (11) | −0.0058 (12) |
O1 | 0.050 (3) | 0.090 (4) | 0.048 (3) | 0.013 (3) | 0.013 (2) | 0.008 (3) |
O2 | 0.095 (4) | 0.079 (4) | 0.064 (3) | 0.027 (3) | 0.053 (3) | 0.024 (3) |
O1W | 0.078 (4) | 0.077 (4) | 0.073 (4) | −0.006 (3) | 0.031 (3) | −0.005 (3) |
C1 | 0.051 (4) | 0.055 (4) | 0.042 (3) | −0.002 (3) | 0.015 (3) | 0.002 (3) |
C2 | 0.057 (4) | 0.057 (4) | 0.054 (4) | −0.010 (3) | 0.029 (3) | −0.006 (3) |
C3 | 0.053 (4) | 0.040 (3) | 0.066 (4) | −0.006 (3) | 0.025 (3) | −0.009 (3) |
C4 | 0.057 (4) | 0.049 (4) | 0.065 (4) | 0.007 (3) | 0.012 (3) | 0.006 (3) |
C5 | 0.059 (4) | 0.049 (4) | 0.047 (3) | −0.003 (3) | 0.017 (3) | 0.004 (3) |
C6 | 0.045 (3) | 0.041 (3) | 0.040 (3) | −0.006 (3) | 0.014 (3) | −0.003 (3) |
C7 | 0.052 (4) | 0.041 (4) | 0.050 (4) | −0.001 (3) | 0.019 (3) | −0.003 (3) |
Ag1—O1 | 2.103 (5) | C1—H1 | 0.9300 |
Ag1—O1W | 2.109 (5) | C2—C3 | 1.360 (10) |
Ag1—Ag1i | 3.118 (1) | C2—H2 | 0.9300 |
Cl1—C3 | 1.740 (7) | C3—C4 | 1.384 (9) |
O1—C7 | 1.259 (8) | C4—C5 | 1.366 (9) |
O2—C7 | 1.240 (7) | C4—H4 | 0.9300 |
O1W—H1W | 0.9387 | C5—C6 | 1.385 (9) |
O1W—H2W | 0.9981 | C5—H5 | 0.9300 |
C1—C6 | 1.383 (8) | C6—C7 | 1.495 (8) |
C1—C2 | 1.389 (9) | ||
O1—Ag1—O1W | 174.1 (2) | C2—C3—C4 | 121.2 (6) |
O1—Ag1—Ag1i | 92.2 (1) | C2—C3—Cl1 | 119.4 (5) |
O1W—Ag1—Ag1i | 82.8 (2) | C4—C3—Cl1 | 119.4 (6) |
O1—Ag1—Ag1ii | 72.6 (1) | C5—C4—C3 | 118.9 (7) |
O1W—Ag1—Ag1ii | 103.1 (2) | C5—C4—H4 | 120.6 |
Ag1i—Ag1—Ag1ii | 77.76 (3) | C3—C4—H4 | 120.6 |
C7—O1—Ag1 | 113.5 (4) | C4—C5—C6 | 121.4 (6) |
Ag1—O1W—H1W | 103.6 | C4—C5—H5 | 119.3 |
Ag1—O1W—H2W | 107.3 | C6—C5—H5 | 119.3 |
H1W—O1W—H2W | 120.6 | C1—C6—C5 | 118.7 (6) |
C6—C1—C2 | 120.3 (6) | C1—C6—C7 | 120.4 (6) |
C6—C1—H1 | 119.8 | C5—C6—C7 | 120.9 (6) |
C2—C1—H1 | 119.8 | O2—C7—O1 | 122.6 (6) |
C3—C2—C1 | 119.5 (6) | O2—C7—C6 | 119.5 (6) |
C3—C2—H2 | 120.3 | O1—C7—C6 | 117.9 (5) |
C1—C2—H2 | 120.3 | ||
Ag1i—Ag1—O1—C7 | 169.0 (5) | C2—C1—C6—C7 | −179.5 (6) |
Ag1ii—Ag1—O1—C7 | −114.6 (5) | C4—C5—C6—C1 | −1.6 (10) |
C6—C1—C2—C3 | 0.7 (10) | C4—C5—C6—C7 | 179.0 (6) |
C1—C2—C3—C4 | −2.1 (10) | Ag1—O1—C7—O2 | −1.1 (8) |
C1—C2—C3—Cl1 | 178.1 (5) | Ag1—O1—C7—C6 | 179.6 (4) |
C2—C3—C4—C5 | 1.6 (10) | C1—C6—C7—O2 | −179.6 (6) |
Cl1—C3—C4—C5 | −178.6 (5) | C5—C6—C7—O2 | −0.1 (9) |
C3—C4—C5—C6 | 0.3 (10) | C1—C6—C7—O1 | −0.3 (9) |
C2—C1—C6—C5 | 1.0 (10) | C5—C6—C7—O1 | 179.1 (6) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2iii | 0.94 | 2.16 | 2.946 (8) | 141 |
O1W—H2W···O2iv | 1.00 | 2.04 | 2.925 (8) | 146 |
Symmetry codes: (iii) −x, y, −z+1/2; (iv) −x, y+1, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ag2(C7H6ClO3)2(H2O)2] |
Mr | 562.88 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 35.978 (5), 4.0535 (6), 12.3204 (19) |
β (°) | 103.439 (3) |
V (Å3) | 1747.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.57 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.426, 0.627 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5101, 2139, 1343 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.130, 1.09 |
No. of reflections | 2139 |
No. of parameters | 109 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.09, −0.57 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2i | 0.94 | 2.16 | 2.946 (8) | 141 |
O1W—H2W···O2ii | 1.00 | 2.04 | 2.925 (8) | 146 |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, y+1, −z+1/2. |
Ag1···Ag1i | 3.768 (1) |
Ag1···Ag1iii | 3.334 (1) |
Ag1···Ag1iv | 4.054 (1) |
Ag1···O2iv | 3.628 (6) |
Ag1···O1Wi | 3.475 (5) |
Symmetry codes: (i) −x, y, 1/2 − z; (iii) x + 1/2, y + 1/2, z; (iv) x, y + 1, z. |
The study of the structures and properties of d-metal-carboxylates is an important research branch of chemistry. Among different `hot' topics currently being studied, silver(I)–carboxylate complexes have been widely reported (Zhu et al., 1999; Zheng, Tong, Zhu & Chen, 2001; Zheng, Tong, Zhu, Fang & Chen, 2001). In these studies, we have reported and structurally characterized a few silver(I) complexes containing carboxylate anions; some of the complexes have special properties. Recently, we reported the crystal structure of a silver complex with 4-fluorobenzoate, and it was found that this complex has significant antitumor activity (Zhu et al., 2003). We have also prepared an analogous silver(I)-carboxylate complex, viz. the title compound, (I), whose crystal structure is reported here.
In the title complex, the Ag atom is coordinated by two O atoms, one from the water molecule and the other from the benzoate moiety, in a nearly linear geometry, O1—Ag1—O1W being 174.1 (2) Å. The Ag—O bond distances [Ag1—O1 2.103 (5) Å and Ag1—O1W 2.109 (5) Å] are significantly shorter than those in other silver(I) complexes with terephthalate [2.175 (3)–2.191 (2) Å; Zhu et al., 2003]. The benzoate moiety is planar with the carboxylate O atoms deviating by −0.027 (5) Å (O1) and −0.031 (6) Å (O2) from the mean plane.
The asymmetric unit consists of one half of the dimeric complex (Fig. 1), the other half being generated by an inversion center. The dimer is held together by a short Ag···Ag(-x, 1 − y, −z) contact [3.118 (1) Å]. This contact is much shorter than that in the silver(I) complexes with terephthalate [3.489 (7) Å].
In the crystal structure, the molecules are interconnected, in columns parallel to b, by intermolecular O1W—H1W···O2i and O1W—H2W···O2ii hydrogen bonds (Fig. 2; for symmetry codes see Table 2). The molecular columns are further interconnected by intermolecular Ag···Ag and Ag···O short-contacts (Table 3).