Poly[[di-μ(3)-nicotinato-μ(3)-oxalato-samarium(III)silver(I)] dihydrate].

In the title three-dimensional heterometallic complex, {[AgSm(C(6)H(4)NO(2))(2)(C(2)O(4))]·2H(2)O}(n), the Sm(III) ion is eight-coordinated by four O atoms from four different nicotinate ligands and four O atoms from two different oxalate ligands. The three-coordinate Ag(I) ion is bonded to two N atoms from two different nicotinate anions and one O atom from an oxalate anion. These metal coordination units are connected by bridging nicotinate and oxalate ligands, generating a three-dimensional network. The uncoordinated water mol-ecules link the carboxyl-ate groups via O-H⋯O hydrogen bonding. The crystal structure is further stabilized by hydrogen bonds between the water mol-ecules.

Related literature

For theapplications of lanthanide–transition metal heterometallic complexes with bridging multifunctional organic ligands, see: Cheng et al. (2006 ▶); Kuang et al. (2007 ▶); Luo et al. (2007 ▶); Peng et al. (2008 ▶).

Experimental

Crystal data

[AgSm(C6H4NO2)2(C2O4)]·2H2O

M = 626.49

Monoclinic,

a = 9.7145 (9) Å

b = 22.3444 (15) Å

c = 9.1726 (6) Å

β = 117.295 (1)°

V = 1769.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 4.45 mm−1

T = 296 K

0.23 × 0.20 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.374, T max = 0.429

8972 measured reflections

3171 independent reflections

2995 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.052

S = 1.12

3171 reflections

254 parameters

H-atom parameters constrained

Δρmax = 0.84 e Å−3

Δρmin = −0.65 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: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809032115/pv2185sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032115/pv2185Isup2.hkl

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

[AgSm(C6H4NO2)2(C2O4)]·2H2O	F(000) = 1196
Mr = 626.49	Dx = 2.352 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6346 reflections
a = 9.7145 (9) Å	θ = 2.4–27.8°
b = 22.3444 (15) Å	µ = 4.45 mm−1
c = 9.1726 (6) Å	T = 296 K
β = 117.295 (1)°	Block, colorless
V = 1769.4 (2) Å3	0.23 × 0.20 × 0.19 mm
Z = 4

Bruker APEXII area-detector diffractometer	3171 independent reflections
Radiation source: fine-focus sealed tube	2995 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 25.2°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→11
Tmin = 0.374, Tmax = 0.429	k = −26→26
8972 measured reflections	l = −10→10

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023	H-atom parameters constrained
wR(F2) = 0.052	w = 1/[σ2(Fo2) + (0.0174P)2 + 1.7329P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max = 0.002
3171 reflections	Δρmax = 0.84 e Å−3
254 parameters	Δρmin = −0.65 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00351 (16)

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
Sm1	0.85715 (2)	0.991315 (8)	0.11767 (2)	0.01683 (8)
Ag2	0.82067 (4)	0.852371 (14)	0.48309 (5)	0.04794 (12)
O1	0.8835 (3)	0.94402 (11)	0.3695 (3)	0.0275 (6)
N1	0.6254 (4)	0.88411 (15)	0.5163 (4)	0.0346 (8)
C4	0.3834 (4)	0.93617 (16)	0.4147 (4)	0.0231 (8)
C3	0.4789 (5)	0.88129 (19)	0.6648 (5)	0.0368 (10)
H3	0.4696	0.8681	0.7560	0.044*
C1	0.5154 (4)	0.91951 (17)	0.4047 (5)	0.0291 (9)
H1	0.5291	0.9334	0.3166	0.035*
C2	0.6042 (5)	0.86566 (19)	0.6441 (5)	0.0382 (10)
H2	0.6788	0.8410	0.7221	0.046*
C6	0.2586 (4)	0.97226 (16)	0.2811 (4)	0.0222 (8)
C5	0.3662 (5)	0.91690 (17)	0.5490 (4)	0.0293 (9)
H5	0.2795	0.9279	0.5608	0.035*
O3	0.2900 (3)	0.99674 (11)	0.1769 (3)	0.0284 (6)
O2	0.1309 (3)	0.97383 (13)	0.2834 (3)	0.0313 (6)
N2	0.9619 (4)	0.78296 (14)	0.4537 (4)	0.0332 (8)
C7	0.9364 (4)	0.72618 (16)	0.4792 (5)	0.0287 (8)
H7	0.8605	0.7184	0.5117	0.034*
C9	1.1309 (5)	0.6899 (2)	0.4136 (5)	0.0390 (10)
H9	1.1876	0.6589	0.3994	0.047*
C8	1.0722 (5)	0.79305 (19)	0.4069 (5)	0.0408 (10)
H8	1.0903	0.8322	0.3859	0.049*
O7	0.6156 (3)	0.93618 (11)	0.0496 (3)	0.0253 (6)
C10	1.0169 (4)	0.67816 (16)	0.4599 (4)	0.0239 (8)
C12	1.1588 (5)	0.7483 (2)	0.3889 (6)	0.0490 (12)
H12	1.2365	0.7573	0.3600	0.059*
C13	0.9793 (4)	0.96697 (16)	0.5028 (4)	0.0207 (7)
O8	1.0418 (3)	0.94114 (11)	0.6386 (3)	0.0255 (6)
O6	0.3580 (3)	0.94430 (11)	−0.0787 (3)	0.0280 (6)
O1W	0.6113 (6)	0.69616 (19)	0.5607 (5)	0.0925 (14)
H1W	0.6115	0.6576	0.5630	0.139*
H2W	0.5551	0.7081	0.6053	0.139*
O2W	0.4884 (7)	0.7331 (2)	0.7801 (6)	0.1179 (19)
H3W	0.4044	0.7508	0.7119	0.177*
H4W	0.5226	0.7525	0.8720	0.177*
C11	0.9771 (4)	0.61643 (15)	0.4922 (4)	0.0236 (8)
O4	0.8882 (3)	0.61157 (11)	0.5557 (3)	0.0322 (6)
O5	1.0350 (3)	0.57246 (12)	0.4552 (3)	0.0353 (7)
C14	0.4919 (4)	0.96531 (16)	−0.0083 (4)	0.0216 (8)

	U11	U22	U33	U12	U13	U23
Sm1	0.01410 (11)	0.01776 (12)	0.01771 (11)	0.00069 (7)	0.00649 (8)	0.00163 (7)
Ag2	0.0358 (2)	0.02335 (18)	0.0903 (3)	0.00795 (13)	0.0338 (2)	0.00929 (16)
O1	0.0327 (16)	0.0290 (14)	0.0187 (12)	−0.0129 (12)	0.0100 (12)	−0.0031 (10)
N1	0.0243 (18)	0.0306 (19)	0.046 (2)	0.0061 (14)	0.0134 (16)	0.0060 (15)
C4	0.021 (2)	0.026 (2)	0.0181 (17)	−0.0007 (15)	0.0052 (15)	0.0010 (14)
C3	0.044 (3)	0.042 (3)	0.024 (2)	0.010 (2)	0.0148 (19)	0.0092 (17)
C1	0.023 (2)	0.032 (2)	0.032 (2)	0.0064 (16)	0.0126 (17)	0.0080 (17)
C2	0.032 (3)	0.037 (2)	0.034 (2)	0.0069 (19)	0.005 (2)	0.0100 (18)
C6	0.0167 (19)	0.0244 (19)	0.0190 (17)	0.0007 (15)	0.0027 (15)	−0.0008 (14)
C5	0.026 (2)	0.035 (2)	0.027 (2)	0.0038 (17)	0.0124 (17)	0.0024 (17)
O3	0.0231 (15)	0.0376 (16)	0.0205 (13)	0.0005 (11)	0.0066 (11)	0.0056 (11)
O2	0.0161 (14)	0.0495 (17)	0.0254 (14)	0.0082 (12)	0.0070 (11)	0.0042 (12)
N2	0.0314 (19)	0.0210 (17)	0.048 (2)	0.0001 (14)	0.0188 (16)	0.0057 (15)
C7	0.024 (2)	0.023 (2)	0.041 (2)	0.0007 (16)	0.0171 (18)	0.0021 (16)
C9	0.036 (3)	0.037 (3)	0.053 (3)	0.0067 (19)	0.029 (2)	0.005 (2)
C8	0.044 (3)	0.031 (2)	0.053 (3)	−0.0032 (19)	0.026 (2)	0.010 (2)
O7	0.0179 (14)	0.0232 (13)	0.0326 (14)	0.0020 (11)	0.0097 (11)	0.0017 (11)
C10	0.022 (2)	0.0234 (19)	0.0251 (18)	0.0017 (15)	0.0098 (16)	−0.0018 (15)
C12	0.041 (3)	0.051 (3)	0.071 (3)	−0.002 (2)	0.040 (3)	0.011 (2)
C13	0.0181 (19)	0.0234 (19)	0.0239 (19)	0.0007 (14)	0.0126 (16)	0.0006 (14)
O8	0.0291 (15)	0.0218 (13)	0.0221 (13)	0.0012 (11)	0.0088 (11)	0.0022 (10)
O6	0.0179 (14)	0.0271 (14)	0.0371 (15)	−0.0011 (11)	0.0109 (12)	−0.0066 (11)
O1W	0.120 (4)	0.060 (3)	0.108 (3)	0.008 (3)	0.062 (3)	−0.012 (2)
O2W	0.147 (5)	0.100 (4)	0.106 (4)	0.027 (4)	0.056 (4)	0.012 (3)
C11	0.024 (2)	0.0162 (18)	0.0233 (18)	0.0018 (14)	0.0045 (16)	−0.0033 (14)
O4	0.0308 (16)	0.0235 (14)	0.0488 (17)	−0.0014 (11)	0.0239 (14)	0.0039 (12)
O5	0.0417 (18)	0.0265 (15)	0.0296 (14)	0.0111 (12)	0.0092 (13)	−0.0050 (11)
C14	0.021 (2)	0.025 (2)	0.0208 (18)	−0.0003 (15)	0.0115 (16)	−0.0035 (14)

Sm1—O5i	2.340 (3)	N2—C7	1.334 (5)
Sm1—O2ii	2.414 (2)	N2—C8	1.342 (5)
Sm1—O4iii	2.420 (3)	C7—C10	1.386 (5)
Sm1—O3iv	2.424 (2)	C7—H7	0.9300
Sm1—O6iv	2.425 (2)	C9—C12	1.372 (6)
Sm1—O1	2.444 (2)	C9—C10	1.381 (5)
Sm1—O7	2.464 (2)	C9—H9	0.9300
Sm1—O8v	2.496 (2)	C8—C12	1.366 (6)
Ag2—N2	2.168 (3)	C8—H8	0.9300
Ag2—N1	2.174 (3)	O7—C14	1.251 (4)
Ag2—O1	2.497 (2)	C10—C11	1.498 (5)
O1—C13	1.257 (4)	C12—H12	0.9300
N1—C2	1.344 (5)	C13—O8	1.249 (4)
N1—C1	1.346 (5)	C13—C13v	1.537 (7)
C4—C1	1.378 (5)	O8—Sm1v	2.496 (2)
C4—C5	1.385 (5)	O6—C14	1.249 (4)
C4—C6	1.504 (5)	O6—Sm1iv	2.425 (2)
C3—C2	1.361 (6)	O1W—H1W	0.8624
C3—C5	1.376 (5)	O1W—H2W	0.8612
C3—H3	0.9300	O2W—H3W	0.8629
C1—H1	0.9300	O2W—H4W	0.8667
C2—H2	0.9300	C11—O4	1.249 (4)
C6—O2	1.251 (4)	C11—O5	1.253 (4)
C6—O3	1.254 (4)	O4—Sm1vii	2.420 (3)
C5—H5	0.9300	O5—Sm1viii	2.340 (3)
O3—Sm1iv	2.424 (2)	C14—C14iv	1.559 (7)
O2—Sm1vi	2.414 (2)
O5i—Sm1—O2ii	78.29 (10)	N1—C2—C3	123.2 (4)
O5i—Sm1—O4iii	123.28 (10)	N1—C2—H2	118.4
O2ii—Sm1—O4iii	76.96 (9)	C3—C2—H2	118.4
O5i—Sm1—O3iv	73.05 (9)	O2—C6—O3	126.2 (3)
O2ii—Sm1—O3iv	129.50 (9)	O2—C6—C4	115.9 (3)
O4iii—Sm1—O3iv	85.19 (9)	O3—C6—C4	117.9 (3)
O5i—Sm1—O6iv	88.09 (10)	C3—C5—C4	119.2 (4)
O2ii—Sm1—O6iv	144.58 (9)	C3—C5—H5	120.4
O4iii—Sm1—O6iv	136.12 (9)	C4—C5—H5	120.4
O3iv—Sm1—O6iv	75.08 (9)	C6—O3—Sm1iv	132.3 (2)
O5i—Sm1—O1	137.60 (8)	C6—O2—Sm1vi	143.9 (2)
O2ii—Sm1—O1	74.16 (9)	C7—N2—C8	117.1 (4)
O4iii—Sm1—O1	80.84 (9)	C7—N2—Ag2	118.6 (3)
O3iv—Sm1—O1	148.63 (9)	C8—N2—Ag2	124.2 (3)
O6iv—Sm1—O1	96.06 (9)	N2—C7—C10	123.6 (4)
O5i—Sm1—O7	144.52 (9)	N2—C7—H7	118.2
O2ii—Sm1—O7	136.44 (9)	C10—C7—H7	118.2
O4iii—Sm1—O7	70.86 (9)	C12—C9—C10	118.5 (4)
O3iv—Sm1—O7	76.49 (9)	C12—C9—H9	120.7
O6iv—Sm1—O7	66.61 (8)	C10—C9—H9	120.7
O1—Sm1—O7	72.42 (8)	N2—C8—C12	122.8 (4)
O5i—Sm1—O8v	75.15 (9)	N2—C8—H8	118.6
O2ii—Sm1—O8v	70.51 (9)	C12—C8—H8	118.6
O4iii—Sm1—O8v	138.13 (9)	C14—O7—Sm1	117.7 (2)
O3iv—Sm1—O8v	136.13 (8)	C9—C10—C7	118.1 (4)
O6iv—Sm1—O8v	74.44 (8)	C9—C10—C11	123.5 (3)
O1—Sm1—O8v	65.62 (8)	C7—C10—C11	118.4 (3)
O7—Sm1—O8v	117.85 (8)	C8—C12—C9	119.8 (4)
N2—Ag2—N1	153.35 (12)	C8—C12—H12	120.1
N2—Ag2—O1	104.18 (11)	C9—C12—H12	120.1
N1—Ag2—O1	100.77 (11)	O8—C13—O1	125.9 (3)
C13—O1—Sm1	116.9 (2)	O8—C13—C13v	117.5 (4)
C13—O1—Ag2	98.2 (2)	O1—C13—C13v	116.6 (4)
Sm1—O1—Ag2	144.02 (10)	C13—O8—Sm1v	115.2 (2)
C2—N1—C1	117.2 (4)	C14—O6—Sm1iv	118.5 (2)
C2—N1—Ag2	120.9 (3)	H1W—O1W—H2W	106.9
C1—N1—Ag2	121.7 (3)	H3W—O2W—H4W	106.8
C1—C4—C5	118.1 (3)	O4—C11—O5	123.4 (3)
C1—C4—C6	121.2 (3)	O4—C11—C10	118.0 (3)
C5—C4—C6	120.7 (3)	O5—C11—C10	118.7 (3)
C2—C3—C5	119.1 (4)	C11—O4—Sm1vii	112.3 (2)
C2—C3—H3	120.5	C11—O5—Sm1viii	179.0 (3)
C5—C3—H3	120.5	O6—C14—O7	126.5 (3)
N1—C1—C4	123.1 (4)	O6—C14—C14iv	117.3 (4)
N1—C1—H1	118.4	O7—C14—C14iv	116.2 (4)
C4—C1—H1	118.4

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O7vii	0.86	2.10	2.960 (5)	175
O1W—H2W···O2W	0.86	2.06	2.892 (7)	161
O2W—H4W···O1Wvii	0.87	1.92	2.780 (7)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O7i	0.86	2.10	2.960 (5)	175
O1W—H2W⋯O2W	0.86	2.06	2.892 (7)	161
O2W—H4W⋯O1Wi	0.87	1.92	2.780 (7)	171

Symmetry code: (i) .