Poly[[(μ(2)-acetato-κO,O':O')aqua-bis-(μ(3)-isonicotinato-κO:O':N)samarium(III)silver(I)] perchlorate].

The title compound, {[AgSm(C(6)H(4)NO(2))(2)(CH(3)CO(2))(H(2)O)]ClO(4)}(n), is a three-dimensional heterobimetallic complex constructed from a repeating dimeric unit. Only half of the dimeric moiety is found in the asymmetric unit; the unit cell is completed by crystallographic inversion symmetry. The Sm(III) ion is eight-coordinated by four O atoms of four different isonicotinate ligands, three O atoms of 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 of two different isonicotinate anions, thereby connecting the disamarium units. In addition, the isonicotinate ligands also act as bridging ligands, generating a three-dimensional network. The coordinated water mol-ecules link the carboxyl-ate group and acetate ligands by O-H⋯O hydrogen bonding. Another O-H⋯O hydrogen bond is observed in the crystal structure. The perchlorate ion is disordered over two sites with site-occupancy factors of 0.560 (11) and 0.440 (11), whereas the methyl group of the acetate ligand is disordered over two sites with site-occupancy factors of 0.53 (5) and 0.47 (5).

Related literature

For background to lanthanide–transition metal heterometallic complexes, see: Cheng et al. (2006 ▶); Kuang et al. (2007 ▶); Peng et al. (2008 ▶); Zhu et al. (2009 ▶).

Experimental

Crystal data

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

M = 678.94

Monoclinic,

a = 16.1703 (15) Å

b = 15.1042 (14) Å

c = 7.9858 (7) Å

β = 92.845 (1)°

V = 1948.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 4.19 mm−1

T = 296 K

0.22 × 0.20 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.414, T max = 0.451

9927 measured reflections

3512 independent reflections

2957 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.064

S = 1.07

3512 reflections

320 parameters

158 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.85 e Å−3

Δρmin = −0.59 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811026134/im2297sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811026134/im2297Isup2.hkl

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

[AgSm(C6H4NO2)2(C2H3O2)(H2O)]ClO4	F(000) = 1300
Mr = 678.94	Dx = 2.315 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3844 reflections
a = 16.1703 (15) Å	θ = 2.5–27.3°
b = 15.1042 (14) Å	µ = 4.19 mm−1
c = 7.9858 (7) Å	T = 296 K
β = 92.845 (1)°	Block, yellow
V = 1948.0 (3) Å3	0.22 × 0.20 × 0.19 mm
Z = 4

Bruker APEXII area-detector diffractometer	3512 independent reflections
Radiation source: fine-focus sealed tube	2957 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scan	θmax = 25.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→19
Tmin = 0.414, Tmax = 0.451	k = −17→18
9927 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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0316P)2 + 0.0621P] where P = (Fo2 + 2Fc2)/3
3512 reflections	(Δ/σ)max = 0.001
320 parameters	Δρmax = 0.85 e Å−3
158 restraints	Δρmin = −0.59 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)
Sm1	0.952467 (14)	0.883640 (13)	1.04772 (3)	0.02097 (9)
Ag1	0.52807 (3)	1.23823 (4)	1.39951 (7)	0.06436 (17)
C1	0.8319 (3)	0.7509 (3)	0.7966 (5)	0.0243 (10)
C2	0.7476 (3)	0.7501 (3)	0.8658 (6)	0.0255 (10)
C3	0.7080 (3)	0.6710 (3)	0.8907 (6)	0.0357 (12)
H3	0.7332	0.6178	0.8639	0.043*
C4	0.6304 (3)	0.6710 (3)	0.9558 (7)	0.0465 (14)
H4	0.6042	0.6171	0.9726	0.056*
C5	0.6303 (3)	0.8222 (3)	0.9692 (6)	0.0388 (12)
H5	0.6037	0.8747	0.9948	0.047*
C6	0.7077 (3)	0.8270 (3)	0.9062 (6)	0.0331 (11)
H6	0.7328	0.8816	0.8911	0.040*
C7	0.8665 (3)	1.0831 (3)	1.1375 (7)	0.0367 (12)
C8	0.7883 (3)	1.1243 (3)	1.1940 (6)	0.0310 (11)
C9	0.7177 (3)	1.0739 (3)	1.2021 (7)	0.0414 (13)
H9	0.7186	1.0143	1.1728	0.050*
C10	0.6466 (4)	1.1114 (4)	1.2534 (8)	0.0529 (16)
H10	0.5991	1.0767	1.2566	0.064*
C11	0.7115 (3)	1.2455 (3)	1.2903 (8)	0.0475 (15)
H11	0.7096	1.3048	1.3216	0.057*
C12	0.7843 (3)	1.2127 (3)	1.2376 (7)	0.0431 (14)
H12	0.8304	1.2490	1.2310	0.052*
O1	0.8543 (2)	0.68433 (19)	0.7172 (4)	0.0336 (8)
O2	0.87650 (19)	0.81870 (18)	0.8220 (4)	0.0288 (7)
O3	0.8699 (2)	1.0005 (2)	1.1391 (5)	0.0493 (11)
O4	0.9236 (2)	1.1345 (2)	1.0941 (5)	0.0472 (11)
O5	0.9496 (2)	0.99873 (19)	0.8377 (4)	0.0375 (8)
O6	0.9636 (2)	1.1151 (2)	0.6844 (4)	0.0400 (9)
N1	0.5915 (3)	0.7460 (3)	0.9955 (6)	0.0420 (11)
N2	0.6427 (3)	1.1970 (3)	1.2995 (6)	0.0467 (12)
O1W	0.9949 (3)	0.72899 (19)	1.0725 (4)	0.0411 (9)
H2W	1.012 (3)	0.698 (2)	0.999 (5)	0.062*
H1W	0.974 (3)	0.696 (2)	1.138 (5)	0.062*
C13	0.9284 (3)	1.0421 (3)	0.7094 (6)	0.0305 (11)
C14	0.8508 (14)	1.0157 (19)	0.608 (3)	0.048 (4)	0.47 (5)
H14A	0.8496	0.9525	0.5953	0.071*	0.47 (5)
H14B	0.8506	1.0432	0.5000	0.071*	0.47 (5)
H14C	0.8031	1.0345	0.6656	0.071*	0.47 (5)
C14'	0.8691 (14)	1.0029 (16)	0.577 (3)	0.048 (4)	0.53 (5)
H14D	0.8380	1.0496	0.5221	0.071*	0.53 (5)
H14E	0.8318	0.9631	0.6293	0.071*	0.53 (5)
H14F	0.8997	0.9712	0.4966	0.071*	0.53 (5)
Cl1	0.58196 (10)	0.45830 (10)	0.2449 (2)	0.0586 (4)	0.440 (11)
O7	0.5413 (12)	0.5414 (9)	0.242 (2)	0.091 (8)	0.440 (11)
O8	0.6274 (10)	0.4512 (9)	0.3969 (14)	0.107 (6)	0.440 (11)
O9	0.5293 (9)	0.3894 (8)	0.216 (2)	0.123 (6)	0.440 (11)
O10	0.6425 (9)	0.4616 (9)	0.1148 (18)	0.124 (6)	0.440 (11)
Cl1'	0.58196 (10)	0.45830 (10)	0.2449 (2)	0.0586 (4)	0.560 (11)
O7'	0.5434 (8)	0.5371 (7)	0.201 (2)	0.080 (5)	0.560 (11)
O8'	0.6654 (5)	0.4696 (6)	0.2946 (18)	0.101 (4)	0.560 (11)
O9'	0.5408 (9)	0.4196 (8)	0.3857 (15)	0.139 (6)	0.560 (11)
O10'	0.5760 (8)	0.3951 (8)	0.1174 (13)	0.116 (5)	0.560 (11)

	U11	U22	U33	U12	U13	U23
Sm1	0.02057 (14)	0.01549 (13)	0.02745 (14)	−0.00121 (9)	0.00717 (9)	−0.00001 (9)
Ag1	0.0295 (3)	0.0884 (4)	0.0776 (4)	0.0140 (2)	0.0260 (2)	−0.0008 (3)
C1	0.023 (3)	0.024 (2)	0.026 (2)	−0.0023 (19)	0.0013 (19)	0.0000 (19)
C2	0.023 (3)	0.026 (2)	0.028 (3)	−0.0038 (19)	0.0054 (19)	−0.0029 (19)
C3	0.031 (3)	0.028 (3)	0.049 (3)	−0.004 (2)	0.013 (2)	−0.005 (2)
C4	0.034 (3)	0.041 (3)	0.066 (4)	−0.010 (3)	0.011 (3)	0.002 (3)
C5	0.026 (3)	0.040 (3)	0.051 (3)	0.008 (2)	0.012 (2)	0.002 (2)
C6	0.029 (3)	0.024 (2)	0.047 (3)	0.002 (2)	0.014 (2)	0.001 (2)
C7	0.031 (3)	0.025 (2)	0.056 (3)	0.001 (2)	0.019 (2)	0.002 (2)
C8	0.027 (3)	0.030 (2)	0.037 (3)	0.005 (2)	0.013 (2)	0.003 (2)
C9	0.034 (3)	0.028 (3)	0.063 (4)	−0.005 (2)	0.017 (3)	−0.004 (3)
C10	0.031 (3)	0.047 (3)	0.083 (5)	−0.009 (3)	0.019 (3)	0.005 (3)
C11	0.035 (3)	0.034 (3)	0.075 (4)	0.006 (2)	0.021 (3)	−0.009 (3)
C12	0.029 (3)	0.028 (3)	0.073 (4)	0.000 (2)	0.017 (3)	−0.003 (3)
O1	0.0282 (19)	0.0250 (16)	0.049 (2)	−0.0004 (14)	0.0150 (15)	−0.0096 (15)
O2	0.0237 (18)	0.0259 (16)	0.0371 (19)	−0.0067 (14)	0.0060 (14)	−0.0072 (14)
O3	0.044 (2)	0.0207 (17)	0.086 (3)	0.0039 (16)	0.038 (2)	0.0031 (17)
O4	0.039 (2)	0.0222 (17)	0.083 (3)	0.0019 (15)	0.036 (2)	0.0050 (17)
O5	0.050 (2)	0.0264 (16)	0.0346 (19)	−0.0114 (16)	−0.0101 (16)	0.0089 (15)
O6	0.053 (3)	0.0338 (18)	0.033 (2)	−0.0138 (17)	−0.0029 (16)	0.0100 (15)
N1	0.026 (3)	0.048 (3)	0.054 (3)	−0.004 (2)	0.014 (2)	0.002 (2)
N2	0.028 (3)	0.046 (3)	0.067 (3)	0.011 (2)	0.017 (2)	0.003 (2)
O1W	0.065 (3)	0.0229 (17)	0.037 (2)	0.0084 (18)	0.0223 (19)	0.0043 (15)
C13	0.035 (3)	0.030 (2)	0.026 (3)	−0.005 (2)	0.001 (2)	0.001 (2)
C14	0.047 (6)	0.048 (6)	0.048 (6)	−0.008 (5)	−0.007 (5)	0.003 (4)
C14'	0.047 (6)	0.048 (6)	0.048 (6)	−0.008 (5)	−0.007 (5)	0.003 (4)
Cl1	0.0610 (11)	0.0449 (8)	0.0692 (11)	0.0000 (8)	−0.0030 (8)	−0.0018 (8)
O7	0.097 (11)	0.085 (10)	0.090 (10)	0.023 (8)	0.000 (7)	−0.016 (7)
O8	0.130 (10)	0.104 (8)	0.083 (8)	0.032 (8)	−0.039 (7)	−0.001 (7)
O9	0.129 (10)	0.092 (8)	0.143 (11)	−0.067 (7)	−0.032 (8)	0.025 (7)
O10	0.130 (10)	0.120 (9)	0.125 (10)	0.036 (8)	0.045 (8)	0.001 (7)
Cl1'	0.0610 (11)	0.0449 (8)	0.0692 (11)	0.0000 (8)	−0.0030 (8)	−0.0018 (8)
O7'	0.071 (7)	0.071 (7)	0.100 (8)	0.030 (5)	0.024 (6)	0.043 (6)
O8'	0.065 (6)	0.079 (6)	0.158 (9)	−0.003 (5)	−0.016 (6)	−0.012 (6)
O9'	0.164 (10)	0.131 (8)	0.128 (8)	−0.020 (7)	0.068 (7)	0.039 (7)
O10'	0.127 (9)	0.122 (8)	0.097 (7)	0.022 (7)	−0.017 (6)	−0.058 (6)

Sm1—O2	2.345 (3)	C9—C10	1.364 (7)
Sm1—O3	2.352 (3)	C9—H9	0.9300
Sm1—O4i	2.367 (3)	C10—N2	1.346 (6)
Sm1—O1ii	2.371 (3)	C10—H10	0.9300
Sm1—O5	2.414 (3)	C11—N2	1.337 (7)
Sm1—O1W	2.440 (3)	C11—C12	1.364 (7)
Sm1—O6i	2.476 (3)	C11—H11	0.9300
Sm1—O5i	2.521 (3)	C12—H12	0.9300
Sm1—C13i	2.892 (5)	O1—Sm1iv	2.371 (3)
Sm1—Sm1i	3.9263 (5)	O4—Sm1i	2.367 (3)
Ag1—N2	2.148 (4)	O5—C13	1.249 (5)
Ag1—N1iii	2.149 (4)	O5—Sm1i	2.521 (3)
C1—O1	1.252 (5)	O6—C13	1.262 (5)
C1—O2	1.264 (5)	O6—Sm1i	2.476 (3)
C1—C2	1.495 (6)	N1—Ag1v	2.149 (4)
C2—C3	1.375 (6)	O1W—H2W	0.81 (4)
C2—C6	1.375 (6)	O1W—H1W	0.81 (4)
C3—C4	1.382 (7)	C13—C14	1.511 (10)
C3—H3	0.9300	C13—C14'	1.511 (9)
C4—N1	1.341 (6)	C13—Sm1i	2.892 (5)
C4—H4	0.9300	C14—H14A	0.9600
C5—N1	1.333 (6)	C14—H14B	0.9600
C5—C6	1.373 (6)	C14—H14C	0.9600
C5—H5	0.9300	C14'—H14D	0.9600
C6—H6	0.9300	C14'—H14E	0.9600
C7—O3	1.248 (5)	C14'—H14F	0.9600
C7—O4	1.267 (6)	Cl1—O9	1.357 (9)
C7—C8	1.500 (6)	Cl1—O8	1.391 (9)
C8—C9	1.376 (7)	Cl1—O7	1.417 (10)
C8—C12	1.381 (6)	Cl1—O10	1.464 (9)
O2—Sm1—O3	105.57 (13)	C5—C6—H6	120.4
O2—Sm1—O4i	90.42 (12)	C2—C6—H6	120.4
O3—Sm1—O4i	137.99 (11)	O3—C7—O4	125.7 (4)
O2—Sm1—O1ii	85.29 (11)	O3—C7—C8	116.7 (4)
O3—Sm1—O1ii	75.00 (10)	O4—C7—C8	117.6 (4)
O4i—Sm1—O1ii	146.13 (10)	C9—C8—C12	118.3 (4)
O2—Sm1—O5	77.05 (10)	C9—C8—C7	119.9 (4)
O3—Sm1—O5	71.54 (12)	C12—C8—C7	121.8 (4)
O4i—Sm1—O5	74.83 (12)	C10—C9—C8	119.9 (5)
O1ii—Sm1—O5	135.91 (12)	C10—C9—H9	120.1
O2—Sm1—O1W	78.25 (13)	C8—C9—H9	120.1
O3—Sm1—O1W	148.79 (11)	N2—C10—C9	122.1 (5)
O4i—Sm1—O1W	71.75 (11)	N2—C10—H10	118.9
O1ii—Sm1—O1W	74.48 (11)	C9—C10—H10	118.9
O5—Sm1—O1W	137.85 (11)	N2—C11—C12	123.4 (5)
O2—Sm1—O6i	155.64 (10)	N2—C11—H11	118.3
O3—Sm1—O6i	91.24 (14)	C12—C11—H11	118.3
O4i—Sm1—O6i	88.48 (14)	C11—C12—C8	118.8 (5)
O1ii—Sm1—O6i	82.17 (11)	C11—C12—H12	120.6
O5—Sm1—O6i	125.83 (10)	C8—C12—H12	120.6
O1W—Sm1—O6i	78.31 (12)	C1—O1—Sm1iv	148.9 (3)
O2—Sm1—O5i	150.36 (10)	C1—O2—Sm1	137.3 (3)
O3—Sm1—O5i	73.42 (13)	C7—O3—Sm1	140.5 (3)
O4i—Sm1—O5i	73.96 (12)	C7—O4—Sm1i	134.8 (3)
O1ii—Sm1—O5i	121.62 (11)	C13—O5—Sm1	160.4 (3)
O5—Sm1—O5i	74.62 (12)	C13—O5—Sm1i	94.0 (3)
O1W—Sm1—O5i	118.44 (13)	Sm1—O5—Sm1i	105.38 (12)
O6i—Sm1—O5i	51.22 (10)	C13—O6—Sm1i	95.9 (3)
O2—Sm1—C13i	169.71 (12)	C5—N1—C4	117.6 (4)
O3—Sm1—C13i	82.55 (14)	C5—N1—Ag1v	123.2 (3)
O4i—Sm1—C13i	79.29 (14)	C4—N1—Ag1v	119.2 (3)
O1ii—Sm1—C13i	103.16 (12)	C11—N2—C10	117.5 (4)
O5—Sm1—C13i	100.12 (12)	C11—N2—Ag1	126.6 (4)
O1W—Sm1—C13i	98.16 (14)	C10—N2—Ag1	115.6 (4)
O6i—Sm1—C13i	25.73 (11)	Sm1—O1W—H2W	127 (3)
O5i—Sm1—C13i	25.53 (11)	Sm1—O1W—H1W	121 (3)
O2—Sm1—Sm1i	114.86 (7)	H2W—O1W—H1W	106 (4)
O3—Sm1—Sm1i	67.80 (8)	O5—C13—O6	118.7 (4)
O4i—Sm1—Sm1i	70.22 (7)	O5—C13—C14	119.1 (11)
O1ii—Sm1—Sm1i	141.10 (7)	O6—C13—C14	121.0 (11)
O5—Sm1—Sm1i	38.26 (8)	O5—C13—C14'	120.4 (10)
O1W—Sm1—Sm1i	139.62 (10)	O6—C13—C14'	120.5 (10)
O6i—Sm1—Sm1i	87.58 (7)	C14—C13—C14'	16.7 (16)
O5i—Sm1—Sm1i	36.36 (7)	O5—C13—Sm1i	60.4 (2)
C13i—Sm1—Sm1i	61.87 (9)	O6—C13—Sm1i	58.4 (2)
N2—Ag1—N1iii	166.24 (17)	C14—C13—Sm1i	165.6 (14)
O1—C1—O2	123.7 (4)	C14'—C13—Sm1i	177.6 (12)
O1—C1—C2	118.2 (4)	C13—C14—H14A	109.5
O2—C1—C2	118.1 (4)	C13—C14—H14B	109.5
C3—C2—C6	118.2 (4)	C13—C14—H14C	109.5
C3—C2—C1	120.0 (4)	C13—C14'—H14D	109.5
C6—C2—C1	121.8 (4)	C13—C14'—H14E	109.5
C2—C3—C4	119.6 (4)	H14D—C14'—H14E	109.5
C2—C3—H3	120.2	C13—C14'—H14F	109.5
C4—C3—H3	120.2	H14D—C14'—H14F	109.5
N1—C4—C3	122.2 (5)	H14E—C14'—H14F	109.5
N1—C4—H4	118.9	O9—Cl1—O8	112.8 (7)
C3—C4—H4	118.9	O9—Cl1—O7	113.0 (9)
N1—C5—C6	123.2 (4)	O8—Cl1—O7	108.0 (8)
N1—C5—H5	118.4	O9—Cl1—O10	110.1 (8)
C6—C5—H5	118.4	O8—Cl1—O10	106.2 (8)
C5—C6—C2	119.3 (4)	O7—Cl1—O10	106.5 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O6vi	0.81 (4)	1.98 (4)	2.785 (4)	171 (6)
O1W—H1W···O2ii	0.81 (4)	2.22 (3)	2.921 (5)	146 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯O6i	0.81 (4)	1.98 (4)	2.785 (4)	171 (6)
O1W—H1W⋯O2ii	0.81 (4)	2.22 (3)	2.921 (5)	146 (5)

Symmetry codes: (i) ; (ii) .