Poly[[μ(2)-acetato-aquadi-μ(3)-isonicotinato-holmium(III)silver(I)] perchlorate].

In the title three-dimensional heterometallic complex, {[AgHo(C(6)H(4)NO(2))(2)(C(2)H(3)O(2))(H(2)O)]ClO(4)}(n), the Ho(III) ion is eight-coordinated by four O atoms from four different isonicotinate ligands, three O atoms from two different acetate ligands and one O atom of a water mol-ecule. The two-coordinate Ag(I) ion is bonded to two N atoms from two different isonicotinate anions. These metal coordination units are connected by bridging isonicotinate and acetate ligands, generating a three-dimensional network. The coordinated water mol-ecules link the carboxyl-ate group of the acetate ligand and the nitrate ligand by O-H⋯O hydrogen bonding. The crystal structure is further stabilized by hydrogen bonds. The perchlorate ion is disordered over two sites with site-occupancy factors 0.539 (12) and 0.461 (12), while the methyl group of the acetate ligand is disordered over two sites with site-occupancy factors 0.51 (4) and 0.49 (4).

Related literature

For the applications of lanthanide–transition metal heterometallic complexes in ion exchange, magnetism, bimetallic catalysis and as luminescent probes, see: Cheng et al. (2006 ▶); Kuang et al. (2007 ▶); Peng et al. (2008 ▶); Zhu et al. (2009 ▶).

Experimental

Crystal data

[AgHo(C6H4NO2)2(C2H3O2)(H2O)]ClO4

M = 693.51

Monoclinic,

a = 16.2158 (10) Å

b = 14.9024 (9) Å

c = 7.9068 (5) Å

β = 91.826 (1)°

V = 1909.7 (2) Å3

Z = 4

Mo Kα radiation

μ = 5.34 mm−1

T = 296 K

0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.357, T max = 0.449

9735 measured reflections

3439 independent reflections

3085 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.054

S = 1.04

3439 reflections

320 parameters

158 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.64 e Å−3

Δρmin = −0.71 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809046601/pv2224sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046601/pv2224Isup2.hkl

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

[AgHo(C6H4NO2)2(C2H3O2)(H2O)]ClO4	F(000) = 1320
Mr = 693.51	Dx = 2.412 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5514 reflections
a = 16.2158 (10) Å	θ = 2.5–27.8°
b = 14.9024 (9) Å	µ = 5.34 mm−1
c = 7.9068 (5) Å	T = 296 K
β = 91.826 (1)°	Block, colorless
V = 1909.7 (2) Å3	0.20 × 0.18 × 0.15 mm
Z = 4

Bruker APEXII area-detector diffractometer	3439 independent reflections
Radiation source: fine-focus sealed tube	3085 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scan	θmax = 25.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→19
Tmin = 0.357, Tmax = 0.449	k = −17→17
9735 measured reflections	l = −7→9

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0229P)2 + 2.5125P] where P = (Fo2 + 2Fc2)/3
3439 reflections	(Δ/σ)max = 0.001
320 parameters	Δρmax = 0.64 e Å−3
158 restraints	Δρmin = −0.71 e Å−3

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	Occ. (<1)
Ho1	0.454984 (11)	0.383812 (12)	0.04996 (2)	0.01844 (7)
Ag1	−0.02677 (3)	0.24033 (4)	0.10033 (7)	0.06287 (16)
C1	−0.3677 (3)	0.0808 (3)	0.3622 (6)	0.0313 (10)
C2	−0.2892 (3)	0.1236 (3)	0.3041 (6)	0.0289 (10)
C3	−0.2191 (3)	0.0720 (3)	0.2964 (7)	0.0410 (12)
H10	−0.2199	0.0117	0.3268	0.049*
C4	−0.1474 (3)	0.1114 (4)	0.2427 (8)	0.0519 (15)
H8	−0.1002	0.0762	0.2380	0.062*
C5	−0.2111 (3)	0.2470 (3)	0.2064 (8)	0.0481 (14)
H7	−0.2086	0.3072	0.1761	0.058*
C6	−0.2852 (3)	0.2128 (3)	0.2588 (7)	0.0409 (12)
H9	−0.3315	0.2493	0.2634	0.049*
C7	0.1336 (3)	0.1719 (4)	−0.0405 (7)	0.0442 (13)
H5	0.1066	0.1176	−0.0251	0.053*
C8	0.2120 (3)	0.1707 (3)	−0.1043 (6)	0.0351 (11)
H4	0.2372	0.1166	−0.1302	0.042*
C9	0.2521 (3)	0.2510 (3)	−0.1289 (5)	0.0230 (9)
C10	0.3375 (2)	0.2510 (3)	−0.1983 (5)	0.0206 (9)
C11	0.2125 (3)	0.3295 (3)	−0.0872 (6)	0.0325 (11)
H3	0.2382	0.3846	−0.1017	0.039*
C12	0.1343 (3)	0.3254 (3)	−0.0238 (6)	0.0376 (12)
H6	0.1080	0.3787	0.0034	0.045*
N1	−0.1427 (2)	0.1969 (3)	0.1974 (6)	0.0458 (11)
N2	0.0950 (2)	0.2480 (3)	0.0001 (5)	0.0394 (10)
O1	−0.4242 (2)	0.1332 (2)	0.4072 (5)	0.0387 (9)
O2	−0.3699 (2)	−0.0029 (2)	0.3616 (4)	0.0397 (8)
O3	0.35906 (18)	0.18441 (19)	−0.2810 (4)	0.0303 (7)
O4	0.38257 (17)	0.31880 (19)	−0.1691 (4)	0.0260 (7)
O5	0.54736 (19)	0.5035 (2)	0.1583 (4)	0.0312 (7)
O6	0.5344 (2)	0.3847 (2)	0.3129 (4)	0.0352 (8)
O1W	0.4985 (2)	0.2318 (2)	0.0763 (4)	0.0353 (8)
H1W	0.478 (3)	0.197 (2)	0.143 (5)	0.053*
H2W	0.516 (3)	0.200 (3)	0.002 (4)	0.053*
C13	0.5691 (3)	0.4589 (3)	0.2876 (5)	0.0272 (10)
C14	0.6256 (13)	0.4991 (15)	0.423 (2)	0.040 (3)	0.49 (4)
H14A	0.5956	0.5074	0.5247	0.060*	0.49 (4)
H14B	0.6457	0.5560	0.3852	0.060*	0.49 (4)
H14C	0.6713	0.4594	0.4455	0.060*	0.49 (4)
C14'	0.6450 (11)	0.4886 (16)	0.388 (3)	0.040 (3)	0.51 (4)
H14D	0.6545	0.4486	0.4821	0.060*	0.51 (4)
H14E	0.6368	0.5484	0.4297	0.060*	0.51 (4)
H14F	0.6918	0.4877	0.3171	0.060*	0.51 (4)
Cl1	0.91931 (10)	0.45924 (11)	0.2560 (2)	0.0625 (4)	0.539 (12)
O7	0.8512 (8)	0.4643 (8)	0.3717 (18)	0.126 (5)	0.539 (12)
O8	0.8847 (9)	0.4462 (8)	0.0955 (12)	0.111 (5)	0.539 (12)
O9	0.9703 (9)	0.3896 (8)	0.300 (2)	0.130 (6)	0.539 (12)
O10	0.9589 (10)	0.5442 (8)	0.259 (2)	0.086 (6)	0.539 (12)
Cl1'	0.91931 (10)	0.45924 (11)	0.2560 (2)	0.0625 (4)	0.461 (12)
O7'	0.8366 (6)	0.4707 (8)	0.210 (2)	0.094 (5)	0.461 (12)
O8'	0.9624 (10)	0.4225 (10)	0.1137 (18)	0.132 (6)	0.461 (12)
O9'	0.9275 (11)	0.3943 (10)	0.3831 (18)	0.131 (7)	0.461 (12)
O10'	0.9581 (11)	0.5392 (9)	0.304 (2)	0.082 (6)	0.461 (12)

	U11	U22	U33	U12	U13	U23
Ho1	0.01607 (11)	0.01592 (11)	0.02369 (12)	−0.00070 (7)	0.00617 (7)	−0.00010 (7)
Ag1	0.0259 (2)	0.0859 (4)	0.0783 (3)	−0.0142 (2)	0.0260 (2)	0.0008 (3)
C1	0.027 (2)	0.023 (2)	0.044 (3)	−0.0049 (19)	0.016 (2)	−0.004 (2)
C2	0.027 (2)	0.027 (2)	0.033 (2)	−0.0057 (19)	0.0118 (19)	−0.0029 (19)
C3	0.027 (3)	0.028 (3)	0.069 (4)	0.002 (2)	0.017 (2)	0.004 (2)
C4	0.027 (3)	0.046 (4)	0.083 (4)	0.000 (2)	0.017 (3)	−0.006 (3)
C5	0.033 (3)	0.034 (3)	0.078 (4)	−0.009 (2)	0.020 (3)	0.008 (3)
C6	0.026 (3)	0.033 (3)	0.064 (4)	−0.001 (2)	0.017 (2)	0.005 (2)
C7	0.032 (3)	0.041 (3)	0.060 (3)	−0.013 (2)	0.014 (2)	0.003 (3)
C8	0.028 (3)	0.028 (3)	0.050 (3)	−0.0040 (19)	0.012 (2)	−0.001 (2)
C9	0.019 (2)	0.027 (2)	0.023 (2)	−0.0016 (17)	0.0029 (17)	−0.0019 (17)
C10	0.018 (2)	0.022 (2)	0.023 (2)	0.0006 (16)	0.0015 (17)	0.0003 (17)
C11	0.025 (2)	0.028 (3)	0.045 (3)	−0.0027 (19)	0.012 (2)	−0.002 (2)
C12	0.028 (3)	0.035 (3)	0.051 (3)	0.005 (2)	0.015 (2)	−0.001 (2)
N1	0.025 (2)	0.046 (3)	0.067 (3)	−0.0090 (19)	0.018 (2)	−0.001 (2)
N2	0.025 (2)	0.047 (3)	0.047 (3)	−0.0028 (18)	0.0136 (18)	−0.001 (2)
O1	0.0304 (18)	0.0221 (17)	0.065 (2)	−0.0017 (13)	0.0281 (17)	−0.0023 (15)
O2	0.0346 (18)	0.0219 (17)	0.064 (2)	−0.0025 (14)	0.0279 (17)	−0.0039 (15)
O3	0.0263 (17)	0.0225 (16)	0.0431 (19)	−0.0017 (13)	0.0144 (14)	−0.0104 (14)
O4	0.0185 (15)	0.0259 (16)	0.0338 (17)	−0.0060 (12)	0.0058 (12)	−0.0054 (13)
O5	0.0382 (18)	0.0269 (17)	0.0279 (16)	−0.0076 (14)	−0.0067 (14)	0.0043 (13)
O6	0.044 (2)	0.0298 (18)	0.0315 (18)	−0.0093 (15)	−0.0022 (15)	0.0102 (14)
O1W	0.049 (2)	0.0215 (16)	0.037 (2)	0.0061 (15)	0.0189 (16)	0.0013 (14)
C13	0.028 (2)	0.029 (2)	0.025 (2)	−0.0030 (19)	−0.0014 (18)	0.0027 (19)
C14	0.039 (6)	0.044 (5)	0.036 (6)	−0.003 (5)	−0.005 (5)	−0.003 (4)
C14'	0.039 (6)	0.044 (5)	0.036 (6)	−0.003 (5)	−0.005 (5)	−0.003 (4)
Cl1	0.0599 (10)	0.0510 (9)	0.0761 (11)	0.0018 (7)	−0.0046 (8)	−0.0019 (8)
O7	0.119 (9)	0.127 (8)	0.133 (9)	−0.027 (7)	0.053 (7)	−0.013 (7)
O8	0.143 (10)	0.114 (8)	0.072 (6)	−0.050 (7)	−0.042 (6)	−0.005 (6)
O9	0.142 (9)	0.098 (7)	0.148 (10)	0.072 (7)	−0.037 (7)	−0.016 (7)
O10	0.077 (8)	0.084 (9)	0.097 (9)	−0.030 (6)	0.007 (6)	−0.010 (6)
Cl1'	0.0599 (10)	0.0510 (9)	0.0761 (11)	0.0018 (7)	−0.0046 (8)	−0.0019 (8)
O7'	0.057 (6)	0.077 (7)	0.145 (10)	0.001 (5)	−0.021 (6)	0.011 (7)
O8'	0.147 (11)	0.131 (9)	0.124 (9)	0.016 (8)	0.068 (8)	−0.035 (7)
O9'	0.143 (11)	0.133 (10)	0.117 (9)	−0.011 (8)	−0.019 (8)	0.065 (8)
O10'	0.069 (9)	0.076 (9)	0.103 (9)	−0.026 (7)	0.022 (7)	−0.045 (7)

Ho1—O4	2.278 (3)	C9—C11	1.380 (6)
Ho1—O2i	2.303 (3)	C9—C10	1.504 (5)
Ho1—O1ii	2.306 (3)	C10—O3	1.245 (5)
Ho1—O3iii	2.318 (3)	C10—O4	1.264 (5)
Ho1—O5iv	2.352 (3)	C11—C12	1.379 (6)
Ho1—O1W	2.380 (3)	C11—H3	0.9300
Ho1—O6	2.410 (3)	C12—N2	1.335 (6)
Ho1—O5	2.465 (3)	C12—H6	0.9300
Ag1—N1	2.152 (4)	O1—Ho1v	2.306 (3)
Ag1—N2	2.154 (4)	O2—Ho1vi	2.303 (3)
C1—O2	1.248 (5)	O3—Ho1vii	2.318 (3)
C1—O1	1.264 (5)	O5—C13	1.260 (5)
C1—C2	1.509 (6)	O5—Ho1iv	2.352 (3)
C2—C3	1.376 (6)	O6—C13	1.259 (5)
C2—C6	1.379 (7)	O1W—H1W	0.82 (4)
C3—C4	1.380 (7)	O1W—H2W	0.81 (4)
C3—H10	0.9300	C13—C14'	1.510 (9)
C4—N1	1.327 (7)	C13—C14	1.511 (9)
C4—H8	0.9300	C14—H14A	0.9600
C5—N1	1.341 (7)	C14—H14B	0.9600
C5—C6	1.380 (6)	C14—H14C	0.9600
C5—H7	0.9300	C14'—H14D	0.9600
C6—H9	0.9300	C14'—H14E	0.9600
C7—N2	1.340 (7)	C14'—H14F	0.9600
C7—C8	1.382 (6)	Cl1—O9	1.364 (8)
C7—H5	0.9300	Cl1—O8	1.385 (8)
C8—C9	1.380 (6)	Cl1—O10	1.419 (9)
C8—H4	0.9300	Cl1—O7	1.458 (8)
O4—Ho1—O2i	104.08 (12)	C2—C6—H9	120.6
O4—Ho1—O1ii	90.36 (11)	C5—C6—H9	120.6
O2i—Ho1—O1ii	139.11 (10)	N2—C7—C8	122.7 (5)
O4—Ho1—O3iii	84.99 (11)	N2—C7—H5	118.7
O2i—Ho1—O3iii	74.14 (10)	C8—C7—H5	118.7
O1ii—Ho1—O3iii	146.11 (10)	C9—C8—C7	119.0 (4)
O4—Ho1—O5iv	76.99 (10)	C9—C8—H4	120.5
O2i—Ho1—O5iv	72.10 (11)	C7—C8—H4	120.5
O1ii—Ho1—O5iv	74.39 (11)	C11—C9—C8	118.4 (4)
O3iii—Ho1—O5iv	136.13 (11)	C11—C9—C10	121.9 (4)
O4—Ho1—O1W	78.79 (12)	C8—C9—C10	119.7 (4)
O2i—Ho1—O1W	148.20 (11)	O3—C10—O4	124.2 (4)
O1ii—Ho1—O1W	71.57 (11)	O3—C10—C9	118.0 (3)
O3iii—Ho1—O1W	74.60 (10)	O4—C10—C9	117.8 (3)
O5iv—Ho1—O1W	137.66 (11)	C12—C11—C9	119.4 (4)
O4—Ho1—O6	155.03 (10)	C12—C11—H3	120.3
O2i—Ho1—O6	92.45 (12)	C9—C11—H3	120.3
O1ii—Ho1—O6	89.10 (12)	N2—C12—C11	122.5 (4)
O3iii—Ho1—O6	81.64 (11)	N2—C12—H6	118.7
O5iv—Ho1—O6	126.62 (10)	C11—C12—H6	118.7
O1W—Ho1—O6	77.37 (12)	C4—N1—C5	117.7 (4)
O4—Ho1—O5	149.88 (10)	C4—N1—Ag1	116.4 (3)
O2i—Ho1—O5	74.19 (11)	C5—N1—Ag1	125.8 (4)
O1ii—Ho1—O5	74.55 (11)	C12—N2—C7	118.0 (4)
O3iii—Ho1—O5	121.89 (11)	C12—N2—Ag1	123.1 (3)
O5iv—Ho1—O5	73.91 (11)	C7—N2—Ag1	118.9 (3)
O1W—Ho1—O5	118.90 (12)	C1—O1—Ho1v	134.8 (3)
O6—Ho1—O5	52.72 (10)	C1—O2—Ho1vi	138.5 (3)
O4—Ho1—C13	170.02 (11)	C10—O3—Ho1vii	149.1 (3)
O2i—Ho1—C13	83.92 (13)	C10—O4—Ho1	139.5 (3)
O1ii—Ho1—C13	79.67 (13)	C13—O5—Ho1iv	160.5 (3)
O3iii—Ho1—C13	103.15 (12)	C13—O5—Ho1	92.9 (2)
O5iv—Ho1—C13	100.29 (11)	Ho1iv—O5—Ho1	106.09 (11)
O1W—Ho1—C13	97.63 (13)	C13—O6—Ho1	95.6 (3)
O6—Ho1—C13	26.34 (11)	Ho1—O1W—H1W	122 (3)
O5—Ho1—C13	26.45 (11)	Ho1—O1W—H2W	127 (3)
O4—Ho1—Ho1iv	114.60 (7)	H1W—O1W—H2W	105 (4)
O2i—Ho1—Ho1iv	68.77 (7)	O6—C13—O5	118.5 (4)
O1ii—Ho1—Ho1iv	70.43 (7)	O6—C13—C14'	122.3 (10)
O3iii—Ho1—Ho1iv	141.14 (7)	O5—C13—C14'	118.3 (10)
O5iv—Ho1—Ho1iv	37.97 (7)	O6—C13—C14	119.9 (10)
O1W—Ho1—Ho1iv	139.55 (8)	O5—C13—C14	120.9 (10)
O6—Ho1—Ho1iv	88.65 (7)	C14'—C13—C14	17.2 (11)
O5—Ho1—Ho1iv	35.94 (7)	O6—C13—Ho1	58.1 (2)
C13—Ho1—Ho1iv	62.34 (9)	O5—C13—Ho1	60.6 (2)
N1—Ag1—N2	165.55 (17)	C14'—C13—Ho1	166.4 (11)
O2—C1—O1	126.7 (4)	C14—C13—Ho1	176.2 (10)
O2—C1—C2	116.5 (4)	C13—C14—H14A	109.5
O1—C1—C2	116.8 (4)	C13—C14—H14B	109.5
C3—C2—C6	118.8 (4)	C13—C14—H14C	109.5
C3—C2—C1	118.9 (4)	C13—C14'—H14D	109.5
C6—C2—C1	122.3 (4)	C13—C14'—H14E	109.5
C2—C3—C4	118.7 (5)	H14D—C14'—H14E	109.5
C2—C3—H10	120.6	C13—C14'—H14F	109.5
C4—C3—H10	120.6	H14D—C14'—H14F	109.5
N1—C4—C3	123.3 (5)	H14E—C14'—H14F	109.5
N1—C4—H8	118.4	O9—Cl1—O8	110.5 (7)
C3—C4—H8	118.4	O9—Cl1—O10	113.8 (8)
N1—C5—C6	122.7 (5)	O8—Cl1—O10	108.2 (8)
N1—C5—H7	118.7	O9—Cl1—O7	110.2 (8)
C6—C5—H7	118.7	O8—Cl1—O7	106.8 (7)
C2—C6—C5	118.9 (5)	O10—Cl1—O7	107.0 (7)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O4iii	0.82 (4)	2.19 (3)	2.898 (4)	145 (4)
O1W—H2W···O6vii	0.81 (4)	1.99 (4)	2.787 (4)	168 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O4i	0.82 (4)	2.19 (3)	2.898 (4)	145 (4)
O1W—H2W⋯O6ii	0.81 (4)	1.99 (4)	2.787 (4)	168 (5)

Symmetry codes: (i) ; (ii) .