Trisilver(I) citrate.

Trisilver(I) citrate, 3Ag(+)·C(6)H(5)O(7) (3-), was obtained by evaporation of a saturated aqueous solution of the raw material that had been obtained from sodium dihydrogen citrate and silver nitrate. It features one formula unit in the asymmetric unit. There is an intra-molecular O-H⋯O hydrogen bond between the OH group and one of the terminal carboxyl-ate groups. Different citrate groups are linked via the three Ag(+) ions, yielding a three-dimensional network with rather irregular [AgO(4)] polyhedra.

Related literature

For the preparation and structure of ammonium disilver(I) citrate monohydrate, see: Sagatys et al. (1993 ▶) and for tetra­ammonium copper(II) bis­(citrate), see: Bott et al. (1991 ▶). For 109Ag solid-state NMR studies on different silver salts, including commercial silver citrate, see: Penner & Li (2004 ▶).

Experimental

Crystal data

3Ag+·C6H5O7 3−

M = 512.71

Orthorhombic,

a = 6.6181 (7) Å

b = 11.8477 (11) Å

c = 22.386 (2) Å

V = 1755.3 (3) Å3

Z = 8

Mo Kα radiation

μ = 6.65 mm−1

T = 299 K

0.12 × 0.05 × 0.02 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.631, T max = 0.876

15238 measured reflections

2008 independent reflections

1493 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.051

S = 1.10

2008 reflections

148 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.21 e Å−3

Δρmin = −1.21 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DIRAX (Duisenberg, 1992 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2007) ▶; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100239X/kp2301sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100239X/kp2301Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

3Ag+·C6H5O73−	F(000) = 1904
Mr = 512.71	Dx = 3.880 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 53 reflections
a = 6.6181 (7) Å	θ = 4.0–20.0°
b = 11.8477 (11) Å	µ = 6.65 mm−1
c = 22.386 (2) Å	T = 299 K
V = 1755.3 (3) Å3	Rod, colourless
Z = 8	0.12 × 0.05 × 0.02 mm

Bruker–Nonius KappaCCD diffractometer	1493 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.055
φ & ω scans	θmax = 27.5°, θmin = 4.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.631, Tmax = 0.876	k = −14→15
15238 measured reflections	l = −29→29
2008 independent 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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.051	w = 1/[σ2(Fo2) + (0.0117P)2 + 5.8189P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max = 0.001
2008 reflections	Δρmax = 1.21 e Å−3
148 parameters	Δρmin = −1.21 e Å−3
1 restraint

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	0.10659 (6)	0.25916 (4)	0.431564 (16)	0.02802 (12)
Ag2	0.27992 (6)	0.15476 (4)	0.296424 (16)	0.03187 (12)
Ag3	0.42015 (6)	0.32800 (4)	0.216249 (16)	0.02955 (12)
C1	0.7295 (7)	0.5962 (4)	0.33652 (19)	0.0165 (10)
C2	0.4709 (7)	0.3885 (4)	0.3454 (2)	0.0181 (11)
C3	0.5610 (7)	0.4467 (4)	0.39995 (19)	0.0168 (10)
C4	0.7567 (7)	0.5110 (4)	0.38916 (18)	0.0155 (10)
C5	0.8155 (7)	0.5769 (4)	0.44573 (19)	0.0160 (10)
C6	1.0229 (7)	0.6305 (4)	0.4444 (2)	0.0176 (11)
O1	0.5862 (5)	0.6651 (3)	0.34287 (14)	0.0244 (8)
O2	0.8489 (5)	0.5926 (3)	0.29317 (14)	0.0240 (8)
O3	0.3092 (5)	0.3355 (3)	0.35141 (15)	0.0317 (9)
O4	0.5631 (5)	0.3974 (3)	0.29684 (14)	0.0307 (9)
O5	0.9113 (5)	0.4296 (3)	0.37668 (14)	0.0186 (7)
O6	1.0678 (5)	0.7019 (3)	0.48333 (15)	0.0296 (9)
O7	1.1480 (5)	0.6006 (3)	0.40461 (15)	0.0272 (8)
H3A	0.4617	0.4990	0.4157	0.020*
H3B	0.5856	0.3900	0.4304	0.020*
H5A	0.7161	0.6359	0.4522	0.019*
H5B	0.8089	0.5260	0.4796	0.019*
H5O	1.012 (5)	0.468 (4)	0.379 (2)	0.028*

	U11	U22	U33	U12	U13	U23
Ag1	0.0264 (2)	0.0362 (3)	0.02149 (19)	0.00746 (19)	0.00281 (17)	−0.00024 (17)
Ag2	0.0284 (2)	0.0484 (3)	0.01882 (19)	−0.0047 (2)	−0.00075 (17)	−0.00654 (19)
Ag3	0.0383 (3)	0.0327 (3)	0.01763 (18)	−0.0018 (2)	−0.00653 (17)	−0.00150 (17)
C1	0.014 (2)	0.020 (3)	0.016 (2)	−0.005 (2)	−0.004 (2)	−0.003 (2)
C2	0.018 (3)	0.014 (3)	0.022 (2)	−0.002 (2)	−0.004 (2)	0.002 (2)
C3	0.014 (2)	0.021 (3)	0.015 (2)	0.001 (2)	0.0015 (19)	−0.0013 (19)
C4	0.015 (2)	0.016 (3)	0.016 (2)	0.003 (2)	0.001 (2)	0.0021 (19)
C5	0.019 (3)	0.015 (3)	0.014 (2)	0.002 (2)	0.0004 (19)	0.0012 (19)
C6	0.017 (3)	0.020 (3)	0.016 (2)	0.002 (2)	−0.004 (2)	0.003 (2)
O1	0.0250 (19)	0.023 (2)	0.0250 (17)	0.0080 (17)	0.0029 (15)	0.0076 (15)
O2	0.0222 (18)	0.034 (2)	0.0162 (16)	0.0004 (16)	0.0039 (15)	0.0037 (15)
O3	0.029 (2)	0.040 (2)	0.0260 (18)	−0.013 (2)	0.0013 (16)	−0.0050 (17)
O4	0.029 (2)	0.044 (2)	0.0188 (17)	−0.0117 (18)	0.0016 (17)	−0.0080 (16)
O5	0.0197 (19)	0.0140 (19)	0.0220 (16)	0.0030 (16)	0.0001 (15)	−0.0033 (14)
O6	0.031 (2)	0.034 (2)	0.0232 (17)	−0.0112 (18)	0.0018 (16)	−0.0115 (16)
O7	0.0223 (19)	0.030 (2)	0.0296 (19)	−0.0022 (17)	0.0038 (16)	−0.0077 (16)

Ag1—O6i	2.275 (3)	C3—C4	1.522 (6)
Ag1—O3	2.416 (3)	C4—O5	1.433 (6)
Ag1—O6ii	2.539 (3)	C4—C5	1.538 (6)
Ag1—O7ii	2.555 (3)	C5—C6	1.513 (7)
Ag2—O2iii	2.300 (3)	C6—O6	1.251 (6)
Ag2—O3	2.477 (4)	C6—O7	1.266 (6)
Ag2—O7ii	2.550 (3)	O1—Ag3vi	2.340 (3)
Ag2—O2ii	2.566 (3)	O2—Ag2vi	2.300 (3)
Ag2—Ag3	2.8801 (6)	O2—Ag2vii	2.566 (3)
Ag2—Ag3iv	3.1563 (7)	O4—Ag3v	2.519 (4)
Ag3—O4	2.197 (3)	O5—Ag3v	2.404 (3)
Ag3—O1iii	2.340 (3)	O6—Ag1i	2.275 (3)
Ag3—O5iv	2.404 (3)	O6—Ag1vii	2.539 (3)
Ag3—O4iv	2.519 (4)	O7—Ag2vii	2.550 (3)
Ag3—Ag2v	3.1563 (7)	O7—Ag1vii	2.555 (3)
C1—O2	1.252 (5)	C3—H3A	0.9700
C1—O1	1.260 (6)	C3—H3B	0.9700
C1—C4	1.562 (6)	C5—H5A	0.9700
C2—O3	1.248 (6)	C5—H5B	0.9700
C2—O4	1.252 (6)	O5—H5O	0.81 (2)
C2—C3	1.523 (6)
O6i—Ag1—O3	145.89 (13)	O4—C2—C3	117.8 (4)
O6i—Ag1—O6ii	95.88 (6)	C4—C3—C2	115.6 (4)
O3—Ag1—O6ii	88.17 (12)	O5—C4—C3	107.6 (4)
O6i—Ag1—O7ii	132.00 (12)	O5—C4—C5	108.8 (4)
O3—Ag1—O7ii	75.34 (12)	C3—C4—C5	109.8 (3)
O6ii—Ag1—O7ii	51.10 (11)	O5—C4—C1	111.7 (3)
O2iii—Ag2—O3	137.63 (12)	C3—C4—C1	110.2 (4)
O2iii—Ag2—O7ii	144.77 (12)	C5—C4—C1	108.8 (4)
O3—Ag2—O7ii	74.39 (11)	C6—C5—C4	115.2 (4)
O2iii—Ag2—O2ii	103.78 (10)	O6—C6—O7	121.6 (4)
O3—Ag2—O2ii	100.80 (12)	O6—C6—C5	119.1 (4)
O7ii—Ag2—O2ii	77.04 (10)	O7—C6—C5	119.4 (4)
O2iii—Ag2—Ag3	78.71 (9)	C1—O1—Ag3vi	119.0 (3)
O3—Ag2—Ag3	70.64 (8)	C1—O2—Ag2vi	115.5 (3)
O7ii—Ag2—Ag3	135.29 (8)	C1—O2—Ag2vii	124.9 (3)
O2ii—Ag2—Ag3	83.01 (8)	Ag2vi—O2—Ag2vii	106.72 (12)
O2iii—Ag2—Ag3iv	81.39 (9)	C2—O3—Ag1	138.1 (3)
O3—Ag2—Ag3iv	62.71 (9)	C2—O3—Ag2	116.7 (3)
O7ii—Ag2—Ag3iv	112.94 (8)	Ag1—O3—Ag2	90.13 (12)
O2ii—Ag2—Ag3iv	155.01 (8)	C2—O4—Ag3	118.2 (3)
Ag3—Ag2—Ag3iv	73.958 (16)	C2—O4—Ag3v	122.1 (3)
O4—Ag3—O1iii	141.33 (13)	Ag3—O4—Ag3v	100.73 (13)
O4—Ag3—O5iv	122.24 (13)	C4—O5—Ag3v	121.5 (2)
O1iii—Ag3—O5iv	85.60 (11)	C6—O6—Ag1i	126.9 (3)
O4—Ag3—O4iv	112.16 (13)	C6—O6—Ag1vii	93.7 (3)
O1iii—Ag3—O4iv	100.76 (12)	Ag1i—O6—Ag1vii	139.37 (15)
O5iv—Ag3—O4iv	73.33 (11)	C6—O7—Ag2vii	136.0 (3)
O4—Ag3—Ag2	83.90 (9)	C6—O7—Ag1vii	92.6 (3)
O1iii—Ag3—Ag2	76.06 (8)	Ag2vii—O7—Ag1vii	85.45 (11)
O5iv—Ag3—Ag2	152.65 (8)	C4—C3—H3A	108.4
O4iv—Ag3—Ag2	90.16 (8)	C2—C3—H3A	108.4
O4—Ag3—Ag2v	89.56 (10)	C4—C3—H3B	108.4
O1iii—Ag3—Ag2v	55.00 (8)	C2—C3—H3B	108.4
O5iv—Ag3—Ag2v	105.44 (8)	H3A—C3—H3B	107.4
O4iv—Ag3—Ag2v	155.43 (9)	C6—C5—H5A	108.5
Ag2—Ag3—Ag2v	80.542 (17)	C4—C5—H5A	108.5
O2—C1—O1	125.8 (4)	C6—C5—H5B	108.5
O2—C1—C4	119.4 (4)	C4—C5—H5B	108.5
O1—C1—C4	114.9 (4)	H5A—C5—H5B	107.5
O3—C2—O4	123.6 (4)	C4—O5—H5O	101 (4)
O3—C2—C3	118.6 (4)	Ag3v—O5—H5O	109 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5O···O7	0.81 (2)	1.90 (3)	2.636 (5)	152 (5)

Table 1

Selected bond lengths (Å)

Ag1—O6i	2.275 (3)
Ag1—O3	2.416 (3)
Ag1—O6ii	2.539 (3)
Ag1—O7ii	2.555 (3)
Ag2—O2iii	2.300 (3)
Ag2—O3	2.477 (4)
Ag2—O7ii	2.550 (3)
Ag2—O2ii	2.566 (3)
Ag3—O4	2.197 (3)
Ag3—O1iii	2.340 (3)
Ag3—O5iv	2.404 (3)
Ag3—O4iv	2.519 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5O⋯O7	0.81 (2)	1.90 (3)	2.636 (5)	152 (5)