Poly[[aqua­bis(μ3-isonicotinato-κ3O:O′:N)tris­(μ2-isonicotinato-κ3O,O′:N)(nitrato-κO)bis­(μ4-oxalato-κ6O1,O2:O2:O1′,O2′:O1′)dierbium(III)tetra­silver(I)] tetra­hydrate]

Wen, Y.-M.; Feng, T.-J.; He, L.-X.

doi:10.1107/S160053680901842X

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages m676-m677

doi:10.1107/S160053680901842X

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Poly[[aquabis(μ₃-isonicotinato-κ³O:O′:N)tris(μ₂-isonicotinato-κ³O,O′:N)(nitrato-κO)bis(μ₄-oxalato-κ⁶O¹,O²:O²:O^1′,O^2′:O^1′)dierbium(III)tetrasilver(I)] tetrahydrate]

Yan-Mei Wen,^a ^* Tian-Jun Feng ^b and Li-Xin He ^c

^aCollege of Science, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China, ^bCollege of Mathematics, Physics and Software Engineering, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China, and ^cSchool of Pharmacy, Guangdong Phamaceutical University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: wenym75@126.com

(Received 15 April 2009; accepted 15 May 2009; online 23 May 2009)

In the title coordination polymer, {[Ag₄Er₂(C₆H₄NO₂)₅(C₂O₄)₂(NO₃)(H₂O)]·4H₂O}_n, each Er^III atom is coordinated in a bicapped trigonal–prismatic coordination geometry by three O atoms from two isonicotinate (IN) ligands, four O atoms from two oxalate ligands and one O atom from either a nitrate ion or a water molecule, both of which are half-occupied over the same site. One Ag^I atom has a Y-shaped geometry defined by one N atom from one IN ligand, one O atom from another IN ligand and one O atom from an oxalate ligand. The other Ag^I atom is coordinated by two IN ligands and one O atom from an oxalate ligand. One of the IN ligands is disordered over an inversion center and forms a bridge between two centrosymmetric Ag^I ions. Due to the disorder, this IN ligand coordinates to the Ag atom through either the pyridyl N or the carboxylate O atoms. The IN and oxalate ligands link the Er and Ag atoms into a three-dimensional coordination framework. O—H⋯O and C—H⋯O hydrogen bonds are observed in the crystal structure.

Related literature

For general background to coordination polymers and open framework materials, see: Barbour (2006 ); Kepert (2006 ); Kong et al. (2008 ); Rao et al. (2004 ); Zhang et al. (2005 ). For background to isonicotinate complexes, see: Gheorghe et al. (2002 ).

Experimental

Crystal data

[Ag₄Er₂(C₆H₄NO₂)₅(C₂O₄)₂(NO₃)(H₂O)]·4H₂O
M_r = 1704.64
Triclinic, $[P \overline 1]$
a = 8.8561 (8) Å
b = 11.6428 (8) Å
c = 11.9597 (9) Å
α = 76.940 (1)°
β = 76.612 (1)°
γ = 76.035 (1)°
V = 1145.14 (16) Å³
Z = 1
Mo Kα radiation
μ = 5.40 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.224, T_max = 0.336
5823 measured reflections
4043 independent reflections
3265 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.128
S = 1.06
4043 reflections
377 parameters
95 restraints
H-atom parameters constrained
Δρ_max = 1.57 e Å⁻³
Δρ_min = −1.32 e Å⁻³

Table 1
Selected bond lengths (Å)

Er1—O7	2.254 (7)
Er1—O11	2.339 (8)
Er1—O2ⁱ	2.364 (7)
Er1—O4ⁱⁱ	2.369 (7)
Er1—O3	2.371 (6)
Er1—O1	2.382 (6)
Er1—O5ⁱⁱⁱ	2.400 (6)
Er1—O6ⁱⁱⁱ	2.423 (7)
Ag1—N1	2.231 (8)
Ag1—O8	2.263 (7)
Ag1—O1	2.417 (7)
Ag2—N5	2.122 (9)
Ag2—N2	2.199 (8)
Ag2—O9^iv	2.521 (9)
Ag2—O10^iv	2.492 (9)
Symmetry codes: (i) -x+2, -y+2, -z+2; (ii) -x+1, -y+2, -z+2; (iii) x-1, y, z+1; (iv) -x, -y, -z+3.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O14—H14A⋯O9^v	0.84	2.39	2.81 (3)	111
O14—H14B⋯O12^vi	0.84	1.99	2.62 (3)	131
O16—H16A⋯O11^vii	0.84	1.95	2.773 (12)	170
O16—H16B⋯O5^viii	0.84	2.06	2.862 (12)	158
C6—H6⋯O2	0.93	2.53	3.371 (12)	151
C11—H11⋯O5ⁱⁱⁱ	0.93	2.42	3.315 (8)	162
C12—H12⋯O14^ix	0.93	2.56	3.441 (2)	158
Symmetry codes: (iii) x-1, y, z+1; (v) -x, -y, -z+2; (vi) -x+1, -y+1, -z+2; (vii) -x+2, -y+1, -z+2; (viii) -x+2, -y+1, -z+1; (ix) x, y, z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901842X/hy2195sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901842X/hy2195Isup2.hkl

checkCIF report

Comment top

The design and construction of transition-lanthanide metal complexes have gained great recognition over the last decade because of their intriguing network topologies and potential applications, and due to their magnetic properties, their capacity for gas storage, as luminescent materials, and so on (Barbour, 2006; Kepert, 2006; Kong et al., 2008; Rao et al., 2004; Zhang et al., 2005). Isonicotinic acid is a multifunctional bridging ligand possessing of oxygen and nitrogen donors, which can thus be utilized to construct lanthanide-transition heterometallic complexes via the carboxyl oxygen atoms binding to lanthanides and nitrogen atoms bonding to transition metal ions such as Ag^I or Cu^I ions (Gheorghe et al., 2002). On the basis of above considerations, we chose nicotinic acid, mixed 4 d–4f metal ions and nitric acid as our building blocks. A new three-dimensional 4 d–4f coordination framework resulted from the hydrothermal treatment of Er₂O₃, AgNO₃, oxalic acid, isonicotinic acid and nitric acid in water.

As depicted in Fig. 1, the asymmetric unit of the title compound contains one Er^III atom, two Ag^I atoms, two and a half IN ligands, two half oxalate anions, each on an inversion center, a half-occupied nitrate ion, a half-occupied coordinated water molecule and two uncoordinated water molecules. The Er^III atom is eight-coordinated in a bicapped trigonal prism coordination geometry by three O atoms from two IN ligands, four O atoms from two oxalate ligands and one O atom from either a nitrate ion or a water molecule, both of which are half-occupied over the same site (Table 1). The Ag1 atom is located in a Y-shaped configuration, defined by one N atom from one IN ligand, one O atom from another IN ligand and one O atom from one oxalate ligand. One of the IN ligands is disordered on an inversion center halfway between two Ag2 atoms and forms a bridge between the two Ag2 atoms. Due to the inversion disorder of this IN ligand, Ag2 is thus coordinated either to two N atoms or to a pyridyl N and two carboxylate O atoms from two IN ligands. In the crystal structure, a zigzag Er–oxalate–Ag chain is formed via the oxalate ligand. The chains are linked by pillared IN ligands to form a two-dimensional layer. The layers are further interconnected by Ag₂(IN)₃ units to form a three-dimensional coordination framework. The supramolecular structure are further stabilized by O—H···O and C—H···O hydrogen bonds involving the carboxylate groups, uncoordinated water molecules and disordered nitrate ions (Table 2; Fig. 2).

Related literature top

For general background to coordination polymers and open framework materials, see: Barbour (2006); Kepert (2006); Kong et al. (2008); Rao et al. (2004); Zhang et al. (2005). For background to isonicotinate complexes, see: Gheorghe et al. (2002).

Experimental top

A mixture of Er₂O₃ (0.192 g, 0.5 mmol), AgNO₃ (0.169 g, 1 mmol), isonicotinic acid (0.123 g, 1 mmol), oxalic acid (0.09 g, 1 mmol), HNO₃ (0.12 ml) and H₂O (10 ml) was placed in a 23 ml Teflon-lined reactor, which was heated to 433 K for 3 d and then cooled to room temperature at a rate of 10 K h^-1. The pale-purple crystals obtained were washed with water and dried in air (yield 46% based on Er).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound, with the symmetry-related atoms to complete the Er coordination. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 2 - x, 2 - y, 2 - z; (ii) 1 - x, 2 - y, 2 - z; (iii) -1 + x, y, 1 + z; (iv) -x, -y, 3 - z.]
	Fig. 2. A packing view of the title compound. Hydrogen bonds are shown as dashed lines.

Poly[[aquabis(µ₃-isonicotinato-κ³O:O':N)tris(µ₂- isonicotinato-κ³O,O':N)(nitrato-κO)bis(µ₄- oxalato-κ⁶O¹,O²:O²:O^1',O^2': O^1')dierbium(III)tetrasilver(I)] tetrahydrate] top

Crystal data top

[Ag₄Er₂(C₆H₄NO₂)₅(C₂O₄)₂(NO₃)(H₂O)]·4H₂O	Z = 1
M_r = 1704.64	F(000) = 808
Triclinic, P1	D_x = 2.472 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8561 (8) Å	Cell parameters from 2895 reflections
b = 11.6428 (8) Å	θ = 2.4–27.9°
c = 11.9597 (9) Å	µ = 5.40 mm⁻¹
α = 76.940 (1)°	T = 296 K
β = 76.612 (1)°	Block, colorless
γ = 76.035 (1)°	0.30 × 0.25 × 0.21 mm
V = 1145.14 (16) Å³

Data collection top

Bruker APEXII CCD diffractometer	4043 independent reflections
Radiation source: fine-focus sealed tube	3265 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.224, T_max = 0.336	k = −9→13
5823 measured reflections	l = −12→14

Refinement top

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0536P)² + 8.9026P] where P = (F_o² + 2F_c²)/3
4043 reflections	(Δ/σ)_max = 0.001
377 parameters	Δρ_max = 1.57 e Å⁻³
95 restraints	Δρ_min = −1.32 e Å⁻³

Crystal data top

[Ag₄Er₂(C₆H₄NO₂)₅(C₂O₄)₂(NO₃)(H₂O)]·4H₂O	γ = 76.035 (1)°
M_r = 1704.64	V = 1145.14 (16) Å³
Triclinic, P1	Z = 1
a = 8.8561 (8) Å	Mo Kα radiation
b = 11.6428 (8) Å	µ = 5.40 mm⁻¹
c = 11.9597 (9) Å	T = 296 K
α = 76.940 (1)°	0.30 × 0.25 × 0.21 mm
β = 76.612 (1)°

Data collection top

Bruker APEXII CCD diffractometer	4043 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3265 reflections with I > 2σ(I)
T_min = 0.224, T_max = 0.336	R_int = 0.028
5823 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	95 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.06	Δρ_max = 1.57 e Å⁻³
4043 reflections	Δρ_min = −1.32 e Å⁻³
377 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Er1	0.75631 (5)	0.84475 (4)	1.13533 (4)	0.02560 (13)
Ag1	1.03061 (11)	0.73575 (8)	0.83111 (8)	0.0482 (3)
Ag2	0.34657 (11)	0.20986 (8)	1.22733 (8)	0.0471 (2)
C1	1.0226 (11)	0.9620 (8)	0.9516 (8)	0.027 (2)
C2	0.4797 (11)	1.0449 (8)	1.0425 (8)	0.027 (2)
C3	1.5447 (11)	0.8125 (8)	0.3439 (9)	0.029 (2)
C4	1.4291 (12)	0.7896 (9)	0.4583 (9)	0.034 (3)
C5	1.4180 (12)	0.8533 (8)	0.5437 (9)	0.034 (3)
H5	1.4845	0.9070	0.5338	0.041*
C6	1.3046 (12)	0.8368 (8)	0.6469 (9)	0.035 (3)
H6	1.2931	0.8834	0.7031	0.042*
C7	1.2262 (14)	0.6927 (10)	0.5844 (10)	0.046 (3)
H7	1.1616	0.6370	0.5969	0.056*
C8	1.3334 (13)	0.7052 (10)	0.4786 (10)	0.044 (3)
H8	1.3407	0.6585	0.4232	0.053*
C9	0.8121 (10)	0.5945 (8)	1.0183 (9)	0.029 (2)
C10	0.7093 (11)	0.5019 (8)	1.0682 (9)	0.030 (2)
C11	0.5937 (12)	0.5111 (9)	1.1686 (10)	0.042 (3)
H11	0.5839	0.5735	1.2082	0.050*
C12	0.4945 (13)	0.4316 (9)	1.2108 (10)	0.040 (3)
H12	0.4167	0.4421	1.2769	0.048*
C13	0.6205 (13)	0.3255 (10)	1.0633 (10)	0.043 (3)
H13	0.6291	0.2613	1.0264	0.052*
C14	0.7232 (13)	0.4003 (9)	1.0175 (10)	0.039 (3)
H14	0.8023	0.3851	0.9532	0.046*
N1	1.2105 (10)	0.7535 (8)	0.6665 (8)	0.038 (2)
N2	0.5076 (10)	0.3372 (7)	1.1577 (7)	0.032 (2)
O1	0.9558 (8)	0.8752 (6)	0.9658 (6)	0.0322 (17)
O2	1.1251 (8)	0.9947 (6)	0.8621 (6)	0.0335 (17)
O3	0.5567 (8)	1.0219 (5)	1.1240 (6)	0.0308 (16)
O4	0.3750 (8)	1.1387 (6)	1.0208 (6)	0.0323 (16)
O5	1.5301 (8)	0.7718 (6)	0.2569 (6)	0.0358 (18)
O6	1.6484 (8)	0.8716 (7)	0.3354 (6)	0.0425 (19)
O7	0.8188 (8)	0.6624 (6)	1.0829 (6)	0.0359 (18)
O8	0.8790 (8)	0.5966 (6)	0.9143 (6)	0.0387 (18)
O11	0.9834 (9)	0.7560 (8)	1.2154 (8)	0.057 (2)
H11A	1.0281	0.7809	1.2572	0.085*	0.50
H11B	0.9946	0.6776	1.2434	0.085*	0.50
N3	0.995 (4)	0.651 (2)	1.281 (2)	0.085 (8)	0.50
O12	0.860 (3)	0.612 (2)	1.318 (2)	0.088 (7)	0.50
O13	1.125 (3)	0.595 (3)	1.313 (3)	0.133 (12)	0.50
O14	0.209 (2)	0.3871 (14)	0.4571 (16)	0.063 (5)	0.50
H14A	0.1251	0.3651	0.4575	0.095*	0.50
H14B	0.1868	0.4304	0.5088	0.095*	0.50
O15	1.035 (3)	0.5205 (17)	1.2890 (18)	0.078 (6)	0.50
H15A	1.0173	0.4989	1.2315	0.117*	0.50
H15B	1.1234	0.4801	1.3018	0.117*	0.50
O16	0.7488 (11)	0.1435 (8)	0.8439 (9)	0.080 (3)
H16A	0.8223	0.1814	0.8284	0.120*
H16B	0.6798	0.1831	0.8045	0.120*
N5	0.1892 (14)	0.1154 (11)	1.3561 (10)	0.037 (4)	0.50
C15	0.1322 (18)	0.0286 (12)	1.3241 (10)	0.042 (5)	0.50
H15	0.1631	0.0135	1.2482	0.051*	0.50
C16	0.029 (2)	−0.0355 (13)	1.4057 (13)	0.049 (5)	0.50
H16	−0.0092	−0.0935	1.3843	0.058*	0.50
C17	−0.0173 (19)	−0.0129 (14)	1.5192 (12)	0.035 (4)	0.50
C18	0.0398 (18)	0.0739 (14)	1.5512 (9)	0.039 (4)	0.50
H18	0.0088	0.0890	1.6271	0.047*	0.50
C19	0.1430 (16)	0.1380 (11)	1.4696 (11)	0.042 (5)	0.50
H19	0.1812	0.1960	1.4910	0.050*	0.50
C20	−0.136 (3)	−0.087 (2)	1.607 (3)	0.048 (5)	0.50
O9	−0.180 (3)	−0.162 (2)	1.5730 (17)	0.095 (7)	0.50
O10	−0.170 (2)	−0.0606 (18)	1.7064 (16)	0.070 (6)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Er1	0.0229 (2)	0.0283 (2)	0.0268 (2)	−0.01183 (17)	0.00013 (17)	−0.00509 (17)
Ag1	0.0470 (5)	0.0600 (6)	0.0354 (5)	−0.0242 (4)	0.0112 (4)	−0.0090 (4)
Ag2	0.0507 (5)	0.0476 (5)	0.0445 (5)	−0.0299 (4)	0.0100 (4)	−0.0089 (4)
C1	0.023 (5)	0.032 (5)	0.026 (5)	−0.009 (4)	0.002 (4)	−0.005 (4)
C2	0.026 (5)	0.027 (5)	0.027 (5)	−0.008 (4)	0.001 (4)	−0.004 (4)
C3	0.031 (5)	0.021 (5)	0.033 (6)	−0.006 (4)	−0.005 (4)	−0.003 (4)
C4	0.029 (5)	0.036 (6)	0.032 (6)	−0.004 (4)	0.002 (4)	−0.007 (5)
C5	0.043 (6)	0.023 (5)	0.035 (6)	−0.019 (4)	0.007 (5)	−0.002 (4)
C6	0.046 (6)	0.021 (5)	0.038 (6)	−0.010 (4)	−0.006 (5)	−0.004 (4)
C7	0.053 (7)	0.046 (6)	0.040 (7)	−0.032 (5)	0.014 (5)	−0.010 (5)
C8	0.049 (6)	0.042 (6)	0.044 (7)	−0.027 (5)	0.015 (5)	−0.019 (5)
C9	0.016 (4)	0.026 (5)	0.043 (6)	−0.009 (4)	−0.014 (4)	0.012 (4)
C10	0.030 (5)	0.028 (5)	0.035 (6)	−0.013 (4)	−0.012 (4)	0.003 (4)
C11	0.043 (6)	0.031 (5)	0.056 (7)	−0.021 (5)	0.013 (5)	−0.027 (5)
C12	0.047 (6)	0.037 (6)	0.040 (6)	−0.022 (5)	0.005 (5)	−0.015 (5)
C13	0.055 (7)	0.035 (6)	0.042 (7)	−0.026 (5)	0.002 (6)	−0.007 (5)
C14	0.042 (6)	0.035 (6)	0.038 (6)	−0.017 (5)	0.006 (5)	−0.010 (5)
N1	0.036 (5)	0.043 (5)	0.031 (5)	−0.016 (4)	0.009 (4)	−0.004 (4)
N2	0.042 (5)	0.021 (4)	0.036 (5)	−0.016 (4)	−0.002 (4)	−0.001 (3)
O1	0.034 (4)	0.025 (3)	0.036 (4)	−0.018 (3)	0.008 (3)	−0.005 (3)
O2	0.037 (4)	0.036 (4)	0.034 (4)	−0.023 (3)	0.003 (3)	−0.013 (3)
O3	0.033 (4)	0.024 (3)	0.039 (4)	−0.002 (3)	−0.011 (3)	−0.012 (3)
O4	0.031 (4)	0.037 (4)	0.032 (4)	−0.001 (3)	−0.009 (3)	−0.016 (3)
O5	0.036 (4)	0.032 (4)	0.039 (4)	−0.017 (3)	0.001 (3)	−0.004 (3)
O6	0.039 (4)	0.058 (5)	0.036 (4)	−0.034 (4)	0.006 (3)	−0.006 (3)
O7	0.038 (4)	0.022 (3)	0.049 (5)	−0.014 (3)	−0.005 (3)	−0.004 (3)
O8	0.041 (4)	0.035 (4)	0.042 (5)	−0.020 (3)	−0.001 (4)	−0.004 (3)
O11	0.052 (5)	0.055 (5)	0.068 (6)	−0.011 (4)	−0.033 (4)	0.001 (4)
N3	0.12 (2)	0.081 (17)	0.087 (18)	−0.060 (16)	−0.025 (17)	−0.036 (14)
O12	0.099 (15)	0.086 (14)	0.102 (17)	−0.043 (13)	−0.028 (13)	−0.030 (12)
O13	0.099 (19)	0.12 (2)	0.14 (2)	−0.004 (17)	−0.052 (18)	0.058 (18)
O14	0.054 (10)	0.040 (9)	0.082 (13)	−0.013 (8)	−0.005 (10)	0.015 (9)
O15	0.121 (17)	0.054 (11)	0.080 (14)	−0.036 (12)	−0.042 (13)	−0.010 (10)
O16	0.068 (6)	0.064 (6)	0.117 (9)	−0.029 (5)	−0.044 (6)	0.010 (6)
N5	0.041 (10)	0.028 (9)	0.043 (8)	−0.021 (7)	0.005 (8)	−0.003 (7)
C15	0.053 (12)	0.037 (11)	0.041 (10)	−0.017 (9)	−0.015 (8)	0.000 (8)
C16	0.055 (12)	0.039 (11)	0.062 (9)	−0.029 (9)	−0.007 (9)	−0.014 (8)
C17	0.020 (8)	0.029 (9)	0.057 (8)	−0.009 (6)	−0.009 (7)	−0.003 (7)
C18	0.032 (10)	0.043 (10)	0.042 (9)	−0.019 (7)	0.003 (8)	−0.007 (7)
C19	0.049 (12)	0.029 (10)	0.049 (10)	−0.025 (8)	0.002 (10)	−0.007 (8)
C20	0.026 (10)	0.029 (10)	0.075 (10)	−0.006 (7)	−0.011 (9)	0.018 (8)
O9	0.090 (13)	0.125 (15)	0.088 (14)	−0.089 (12)	0.001 (13)	0.001 (11)
O10	0.053 (11)	0.068 (13)	0.072 (10)	−0.016 (10)	0.005 (10)	0.011 (9)

Geometric parameters (Å, º) top

Er1—O7	2.254 (7)	C10—C11	1.392 (14)
Er1—O11	2.339 (8)	C10—C14	1.415 (15)
Er1—O2ⁱ	2.364 (7)	C11—C12	1.365 (14)
Er1—O4ⁱⁱ	2.369 (7)	C11—H11	0.9300
Er1—O3	2.371 (6)	C12—N2	1.357 (13)
Er1—O1	2.382 (6)	C12—H12	0.9300
Er1—O5ⁱⁱⁱ	2.400 (6)	C13—N2	1.332 (13)
Er1—O6ⁱⁱⁱ	2.423 (7)	C13—C14	1.350 (14)
Ag1—N1	2.231 (8)	C13—H13	0.9300
Ag1—O8	2.263 (7)	C14—H14	0.9300
Ag1—O1	2.417 (7)	O2—Er1ⁱ	2.364 (7)
Ag2—N5	2.122 (9)	O4—Er1ⁱⁱ	2.369 (7)
Ag2—N2	2.199 (8)	O5—Er1^v	2.400 (6)
Ag2—O9^iv	2.521 (9)	O6—Er1^v	2.423 (7)
Ag2—O10^iv	2.492 (9)	O11—N3	1.28 (3)
C1—O1	1.251 (11)	O11—H11A	0.8385
C1—O2	1.283 (11)	O11—H11B	0.8880
C1—C1ⁱ	1.536 (19)	N3—O13	1.28 (4)
C2—O3	1.260 (12)	N3—O12	1.32 (3)
C2—O4	1.270 (11)	O14—H14A	0.8385
C2—C2ⁱⁱ	1.545 (19)	O14—H14B	0.8436
C3—O6	1.248 (12)	O15—H15A	0.8402
C3—O5	1.280 (12)	O15—H15B	0.8410
C3—C4	1.519 (13)	O16—H16A	0.8365
C3—Er1^v	2.762 (10)	O16—H16B	0.8405
C4—C5	1.365 (15)	N5—C15	1.3900
C4—C8	1.394 (14)	N5—C19	1.3900
C5—C6	1.407 (14)	C15—C16	1.3900
C5—H5	0.9300	C15—H15	0.9300
C6—N1	1.374 (13)	C16—C17	1.3900
C6—H6	0.9300	C16—H16	0.9300
C7—N1	1.299 (14)	C17—C18	1.3900
C7—C8	1.396 (15)	C17—C20	1.57 (3)
C7—H7	0.9300	C18—C19	1.3900
C8—H8	0.9300	C18—H18	0.9300
C9—O7	1.243 (12)	C19—H19	0.9300
C9—O8	1.246 (12)	C20—O9	1.22 (3)
C9—C10	1.509 (13)	C20—O10	1.24 (3)

O7—Er1—O11	78.4 (3)	C14—C10—C9	123.0 (9)
O7—Er1—O2ⁱ	140.7 (2)	C12—C11—C10	122.1 (10)
O11—Er1—O2ⁱ	74.3 (3)	C12—C11—H11	118.9
O7—Er1—O4ⁱⁱ	73.3 (2)	C10—C11—H11	118.9
O11—Er1—O4ⁱⁱ	146.0 (3)	N2—C12—C11	121.0 (10)
O2ⁱ—Er1—O4ⁱⁱ	118.2 (2)	N2—C12—H12	119.5
O7—Er1—O3	139.7 (2)	C11—C12—H12	119.5
O11—Er1—O3	141.7 (3)	N2—C13—C14	124.5 (10)
O2ⁱ—Er1—O3	73.1 (2)	N2—C13—H13	117.7
O4ⁱⁱ—Er1—O3	69.5 (2)	C14—C13—H13	117.7
O7—Er1—O1	78.8 (2)	C13—C14—C10	119.4 (10)
O11—Er1—O1	79.9 (3)	C13—C14—H14	120.3
O2ⁱ—Er1—O1	69.1 (2)	C10—C14—H14	120.3
O4ⁱⁱ—Er1—O1	76.4 (2)	C7—N1—C6	117.5 (9)
O3—Er1—O1	106.1 (2)	C7—N1—Ag1	123.2 (7)
O7—Er1—O5ⁱⁱⁱ	83.7 (2)	C6—N1—Ag1	119.2 (7)
O11—Er1—O5ⁱⁱⁱ	110.4 (3)	C13—N2—C12	117.6 (9)
O2ⁱ—Er1—O5ⁱⁱⁱ	132.3 (2)	C13—N2—Ag2	122.1 (7)
O4ⁱⁱ—Er1—O5ⁱⁱⁱ	85.0 (2)	C12—N2—Ag2	120.4 (7)
O3—Er1—O5ⁱⁱⁱ	78.5 (2)	C1—O1—Er1	118.2 (6)
O1—Er1—O5ⁱⁱⁱ	157.4 (2)	C1—O1—Ag1	121.9 (6)
O7—Er1—O6ⁱⁱⁱ	122.2 (2)	Er1—O1—Ag1	119.9 (3)
O11—Er1—O6ⁱⁱⁱ	81.4 (3)	C1—O2—Er1ⁱ	118.2 (6)
O2ⁱ—Er1—O6ⁱⁱⁱ	81.1 (2)	C2—O3—Er1	117.8 (6)
O4ⁱⁱ—Er1—O6ⁱⁱⁱ	130.0 (2)	C2—O4—Er1ⁱⁱ	118.2 (6)
O3—Er1—O6ⁱⁱⁱ	74.3 (2)	C3—O5—Er1^v	92.1 (6)
O1—Er1—O6ⁱⁱⁱ	148.1 (2)	C3—O6—Er1^v	91.9 (6)
O5ⁱⁱⁱ—Er1—O6ⁱⁱⁱ	54.4 (2)	C9—O7—Er1	150.9 (6)
N1—Ag1—O8	132.0 (3)	C9—O8—Ag1	118.1 (6)
N1—Ag1—O1	124.5 (3)	N3—O11—Er1	120.6 (14)
O8—Ag1—O1	103.6 (2)	N3—O11—H11A	91.9
N5—Ag2—N2	156.4 (4)	Er1—O11—H11A	130.9
O1—C1—O2	125.7 (9)	Er1—O11—H11B	115.6
O1—C1—C1ⁱ	117.7 (10)	H11A—O11—H11B	103.8
O2—C1—C1ⁱ	116.6 (10)	O13—N3—O11	121 (3)
O3—C2—O4	125.6 (9)	O13—N3—O12	123 (3)
O3—C2—C2ⁱⁱ	117.8 (10)	O11—N3—O12	115 (3)
O4—C2—C2ⁱⁱ	116.5 (11)	O13—N3—H11B	120.8
O6—C3—O5	121.5 (9)	O12—N3—H11B	110.8
O6—C3—C4	120.3 (9)	N3—O13—H15B	100.2
O5—C3—C4	118.2 (9)	H14A—O14—H14B	106.6
O6—C3—Er1^v	61.3 (5)	H15A—O15—H15B	106.7
O5—C3—Er1^v	60.3 (5)	H16A—O16—H16B	107.4
C4—C3—Er1^v	177.8 (7)	C15—N5—C19	120.0
C5—C4—C8	118.8 (9)	C15—N5—Ag2	118.0 (7)
C5—C4—C3	119.4 (9)	C19—N5—Ag2	122.0 (7)
C8—C4—C3	121.8 (10)	N5—C15—C16	120.0
C4—C5—C6	119.2 (10)	N5—C15—H15	120.0
C4—C5—H5	120.4	C16—C15—H15	120.0
C6—C5—H5	120.4	C15—C16—C17	120.0
N1—C6—C5	121.6 (10)	C15—C16—H16	120.0
N1—C6—H6	119.2	C17—C16—H16	120.0
C5—C6—H6	119.2	C18—C17—C16	120.0
N1—C7—C8	124.5 (10)	C18—C17—C20	122.1 (15)
N1—C7—H7	117.8	C16—C17—C20	117.9 (15)
C8—C7—H7	117.8	C17—C18—C19	120.0
C4—C8—C7	118.2 (10)	C17—C18—H18	120.0
C4—C8—H8	120.9	C19—C18—H18	120.0
C7—C8—H8	120.9	C18—C19—N5	120.0
O7—C9—O8	126.5 (9)	C18—C19—H19	120.0
O7—C9—C10	117.7 (9)	N5—C19—H19	120.0
O8—C9—C10	115.7 (9)	O9—C20—O10	128 (2)
C11—C10—C14	115.3 (9)	O9—C20—C17	118 (2)
C11—C10—C9	121.7 (9)	O10—C20—C17	113 (2)

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+2, −z+2; (iii) x−1, y, z+1; (iv) −x, −y, −z+3; (v) x+1, y, z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O14—H14A···O9^vi	0.84	2.39	2.81 (3)	111
O14—H14B···O12^vii	0.84	1.99	2.62 (3)	131
O16—H16A···O11^viii	0.84	1.95	2.773 (12)	170
O16—H16B···O5^ix	0.84	2.06	2.862 (12)	158
C6—H6···O2	0.93	2.53	3.371 (12)	151
C11—H11···O5ⁱⁱⁱ	0.93	2.42	3.315 (8)	162
C12—H12···O14^x	0.93	2.56	3.441 (2)	158

Symmetry codes: (iii) x−1, y, z+1; (vi) −x, −y, −z+2; (vii) −x+1, −y+1, −z+2; (viii) −x+2, −y+1, −z+2; (ix) −x+2, −y+1, −z+1; (x) x, y, z+1.

Experimental details

Crystal data
Chemical formula	[Ag₄Er₂(C₆H₄NO₂)₅(C₂O₄)₂(NO₃)(H₂O)]·4H₂O
M_r	1704.64
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.8561 (8), 11.6428 (8), 11.9597 (9)
α, β, γ (°)	76.940 (1), 76.612 (1), 76.035 (1)
V (Å³)	1145.14 (16)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	5.40
Crystal size (mm)	0.30 × 0.25 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.224, 0.336
No. of measured, independent and observed [I > 2σ(I)] reflections	5823, 4043, 3265
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.128, 1.06
No. of reflections	4043
No. of parameters	377
No. of restraints	95
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.57, −1.32

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Er1—O7	2.254 (7)	Ag1—N1	2.231 (8)
Er1—O11	2.339 (8)	Ag1—O8	2.263 (7)
Er1—O2ⁱ	2.364 (7)	Ag1—O1	2.417 (7)
Er1—O4ⁱⁱ	2.369 (7)	Ag2—N5	2.122 (9)
Er1—O3	2.371 (6)	Ag2—N2	2.199 (8)
Er1—O1	2.382 (6)	Ag2—O9^iv	2.521 (9)
Er1—O5ⁱⁱⁱ	2.400 (6)	Ag2—O10^iv	2.492 (9)
Er1—O6ⁱⁱⁱ	2.423 (7)

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+2, −z+2; (iii) x−1, y, z+1; (iv) −x, −y, −z+3.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O14—H14A···O9^v	0.84	2.39	2.81 (3)	111
O14—H14B···O12^vi	0.84	1.99	2.62 (3)	131
O16—H16A···O11^vii	0.84	1.95	2.773 (12)	170
O16—H16B···O5^viii	0.84	2.06	2.862 (12)	158
C6—H6···O2	0.93	2.53	3.371 (12)	151
C11—H11···O5ⁱⁱⁱ	0.93	2.42	3.315 (8)	162
C12—H12···O14^ix	0.93	2.56	3.441 (2)	158

Symmetry codes: (iii) x−1, y, z+1; (v) −x, −y, −z+2; (vi) −x+1, −y+1, −z+2; (vii) −x+2, −y+1, −z+2; (viii) −x+2, −y+1, −z+1; (ix) x, y, z+1.

Acknowledgements

The authors kindly acknowledge Guangdong Ocean University for supporting this work.

References

Barbour, L. J. (2006). Chem. Commun. pp. 1163–1168. Web of Science CrossRef Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gheorghe, R., Andruh, M., Muller, A. & Schmidtmann, M. (2002). Inorg. Chem. 41, 5314–5316. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kepert, C. J. (2006). Chem. Commun. pp. 695–700. Web of Science CrossRef Google Scholar
Kong, X. J., Ren, Y. P., Chen, W. X., Long, L. S., Zheng, Z. P., Huang, R. B. & Zheng, L. S. (2008). Angew. Chem. Int. Ed. 47, 2398–2401. Web of Science CSD CrossRef CAS Google Scholar
Rao, C. N. R., Natarajan, S. & Vaidhyanthan, R. (2004). Angew. Chem. Int. Ed. 43, 1466–1496. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, M. B., Zhang, J., Zheng, S. T. & Yang, G. Y. (2005). Angew. Chem. Int. Ed. 44, 1385–1388. Web of Science CSD CrossRef CAS Google Scholar

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