catena-Poly[diammonium [diaqua­bis(pyridine-2,4-dicarboxyl­ato-κ2N,O2)cuprate(II)] [[diaqua­copper(II)]-μ-pyridine-2,4-dicarboxyl­ato-κ3N,O2:O2′-[tetra­aqua­cadmium(II)]-μ-pyridine-2,4-dicarboxyl­ato-κ3O2:N,O2′] hexa­hydrate]

Wang, G.-H.; Li, Z.-G.; Jia, H.-Q.; Hu, N.-H.; Xu, J.-W.

doi:10.1107/S1600536809046911

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages m1568-m1569

doi:10.1107/S1600536809046911

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catena-Poly[diammonium [diaquabis(pyridine-2,4-dicarboxylato-κ²N,O²)cuprate(II)] [[diaquacopper(II)]-μ-pyridine-2,4-dicarboxylato-κ³N,O²:O^2′-[tetraaquacadmium(II)]-μ-pyridine-2,4-dicarboxylato-κ³O²:N,O^2′] hexahydrate]

Guan-Hua Wang,^a,^b Zhi-Gang Li,^a,^b Heng-Qing Jia,^a Ning-Hai Hu ^a ^* and Jing-Wei Xu ^a

^aThe State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China, and ^bGraduate School, Chinese Academy of Sciences, Beijing 100039, People's Republic of China
^*Correspondence e-mail: hunh@ciac.jl.cn

(Received 21 October 2009; accepted 6 November 2009; online 14 November 2009)

The title mixed-metal complex, {(NH₄)₂[Cu(C₇H₃NO₄)₂(H₂O)₂][CdCu(C₇H₃NO₄)₂(H₂O)₆]·6H₂O}_n, contains one octahedrally coordinated Cd^II center and two octahedrally coordinated Cu^II centers, each lying on an inversion center. The two Cu^II atoms are each coordinated by two O atoms and two N atoms from two 2,4-pydc (2,4-H₂pydc = pyridine-2,4-dicarboxylic acid) ligands in the equatorial plane and two water molecules at the axial sites, thus producing two crystallographically independent [Cu(2,4-pydc)₂(H₂O)₂]²⁻ metalloligands. One metalloligand exists as a discrete anion and the other connects the Cd(H₂O)₄ units, forming a neutral chain. O—H⋯O and N—H⋯O hydrogen bonds connects the polymeric chains, complex anions, ammonium cations and uncoordinated water molecules into a three-dimensional supramolecular network.

Related literature

For general background to coordination polymers, see: Caneschi et al. (2001 ); Dong et al. (2000 ); Evans & Lin (2002 ); Kitagawa et al. (1999 , 2004 , 2006 ). For related structures, see: Li et al. (2008 ); Noro et al. (2002a ,b ); Wang et al. (2009 ).

Experimental

Crystal data

(NH₄)₂[Cu(C₇H₃NO₄)₂(H₂O)₂][CdCu(C₇H₃NO₄)₂(H₂O)₆]·6H₂O
M_r = 1188.20
Triclinic, $[P \overline 1]$
a = 10.4520 (19) Å
b = 10.5252 (19) Å
c = 10.6733 (19) Å
α = 102.869 (2)°
β = 103.536 (2)°
γ = 94.834 (2)°
V = 1101.3 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.54 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.720, T_max = 0.785
6205 measured reflections
4212 independent reflections
3869 reflections with I > 2σ(I)
R_int = 0.011

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.073
S = 1.05
4212 reflections
361 parameters
31 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O7ⁱ	0.94 (2)	1.80 (1)	2.739 (2)	171 (2)
O1W—H1B⋯O4ⁱⁱ	0.95 (2)	1.82 (1)	2.769 (2)	177 (3)
O2W—H2A⋯O3ⁱⁱ	0.95 (1)	1.72 (1)	2.657 (3)	168 (2)
O2W—H2B⋯O8ⁱⁱⁱ	0.95 (1)	1.77 (1)	2.722 (2)	177 (2)
O3W—H3A⋯O6W^iv	0.94 (1)	1.84 (1)	2.781 (3)	172 (3)
O3W—H3B⋯O7^iv	0.94 (1)	1.84 (1)	2.776 (3)	172 (3)
O4W—H4A⋯O3W^v	0.95 (1)	1.89 (1)	2.827 (3)	169 (2)
O4W—H4B⋯O4ⁱ	0.95 (1)	1.80 (1)	2.752 (3)	176 (2)
O5W—H5A⋯O4W^vi	0.95 (1)	2.10 (1)	3.048 (3)	170 (3)
O5W—H5B⋯O3	0.96 (1)	1.93 (1)	2.882 (3)	171 (3)
O6W—H6A⋯O6	0.95 (1)	1.79 (1)	2.742 (3)	173 (3)
O6W—H6B⋯O2W^vii	0.96 (3)	2.14 (2)	2.991 (3)	147 (2)
O7W—H7A⋯O2	0.95 (3)	2.09 (3)	3.009 (3)	163 (3)
O7W—H7B⋯O5W	0.95 (3)	1.93 (3)	2.861 (3)	165 (4)
N3—H31⋯O7W^viii	0.98 (2)	1.90 (2)	2.867 (3)	174 (2)
N3—H32⋯O8	0.99 (2)	1.92 (1)	2.886 (3)	164 (2)
N3—H33⋯O5W^ix	0.99 (1)	2.53 (2)	3.208 (4)	126 (2)
N3—H33⋯O5^x	0.99 (1)	2.30 (2)	3.131 (3)	140 (2)
N3—H33⋯O6^x	0.99 (1)	2.19 (2)	2.888 (3)	126 (2)
N3—H34⋯O8^xi	0.99 (2)	2.34 (1)	3.277 (3)	157 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y, z+1; (iii) x-1, y-1, z; (iv) x, y-1, z; (v) x, y+1, z+1; (vi) x, y-1, z-1; (vii) x, y+1, z; (viii) -x+1, -y, -z+1; (ix) x+1, y+1, z+1; (x) x+1, y, z; (xi) -x+2, -y+1, -z+1.

Data collection: SMART (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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809046911/bg2303sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046911/bg2303Isup2.hkl

checkCIF report

Comment top

Coordination polymers constructed from metal ions and bridging ligands have been of great interest owing to their structural diversities and fascinating properties (Caneschi et al., 2001; Evans & Lin, 2002; Kitagawa et al., 1999, 2004). In recent years, the design and synthesis of mixed-metal coordination polymers have received much attention because such heterometallic materials might exhibit interesting physical properties, resulting from interactions between two neighboring metal centers connected by a suitable linker (Dong et al., 2000; Kitagawa et al., 2006). Noro et al. (2002a, b) have prepared mixed-metal coordination polymers by using the Et₃NH salt of a metalloligand, [Cu(2,4-pydc)₂]^2- (2,4-H₂pydc = pyridine-2,4-dicarboxylic acid). We prepared recently a mixed-metal complex with a metalloligand [Cu(2,5-pydc)₂]^2- by a simplified synthetic method (Wang et al., 2009). As a continuation of our work, we report here the synthesis and structure of the title compound.

The asymmetric unit of the title compound contains one six-coordinated Cd^II atom and two six-coordinated Cu^II atoms, each lying on an inversion center, two 2,4-pydc ligands, one ammonium ion, four coordinated water molecules and three uncoordinated water molecules (Fig. 1). Both Cu1 and Cu2 atoms have an axially elongated octahedral coordination geometry, defined by two O atoms and two N atoms from two 2,4-pydc ligands in the equatorial plane and two water molecules at the axial sites, thus producing two crystallographically independent [Cu(2,4-pydc)₂(H₂O)₂]^2- metalloligands. In each metalloligand, the equatorial plane consists of trans N donors and trans O donors. The Cd^II ions coordinated by four water molecules are linked by the Cu1-metalloligands, via the bidentate-bridging 2-carboxylate groups, into a one-dimensional polymeric chain along the [100] direction (Fig. 2). The shortest Cu···Cd distance is 5.226 (1) Å. The 2,4-pydc ligand binds Cu1 and Cd1 atoms in a µ₂-(κ³N,O²:O^2') mode with the 4-carboxylate group uncoordinated (Li et al., 2008). The Cu2-metalloligand acts as a discrete divalent anion and does not interact with a second metal ion. The 2,4-pydc ligand in the Cu2-metalloligand adopts a (κ²N,O²) chelating mode with the 4-carboxylate group remaining idle. Extensive O—H···O and N—H···O hydrogen bonds (Table 1) assemble the various components into a supramolecular network (Fig. 3).

Related literature top

For general background to coordination polymers, see: Caneschi et al. (2001); Dong et al. (2000); Evans & Lin (2002); Kitagawa et al. (1999, 2004, 2006). For related structures, see: Li et al. (2008); Noro et al. (2002a,b); Wang et al. (2009).

Experimental top

An aqueous solution (20 ml) of Cu(NO₃)₂.3H₂O (0.125 g, 0.3 mmol) and a suspension of 2,4-H₂pydc (0.083 g, 0.3 mmol) in ethanol (10 ml) were mixed and refluxed for 24 h until a clear solution was obtained. To this solution, an aqueous solution (5 ml) of CdCl₂ (0.055 g, 0.5 mmol) was added. Aqueous NH₃ (25%, 0.06 ml) was then slowly added to the reaction mixture. The resulting solution was filtered off. Blue block crystals were obtained by allowing the filtrate to stand at room temperature for several days.

Computing details top

Data collection: SMART (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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound, together with symmetry-related atoms to complete the Cd1, Cu1 and Cu2 coordination. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) 1 - x, -y, 1 - z; (ii) 1 - x, 1 - y, 2 - z; (iii) -x, -y, 1 - z.]
	Fig. 2. The one-dimensional chain in the title compound. H atoms have been omitted for clarity.
	Fig. 3. The crystal packing of the title compound. Dashed lines denote hydrogen bonds.

catena-Poly[diammonium [diaquabis(pyridine-2,4-dicarboxylato-κ²N,O²)cuprate(II)] [[diaquacopper(II)]-µ-pyridine-2,4-dicarboxylato- κ³N,O²:O^2'-[tetraaquacadmium(II)]- µ-pyridine-2,4-dicarboxylato-κ³O²:N,O^2'] hexahydrate] top

Crystal data top

(NH₄)₂[Cu(C₇H₃NO₄)₂(H₂O)₂][CdCu(C₇H₃NO₄)₂(H₂O)₆]·6H₂O	Z = 1
M_r = 1188.20	F(000) = 604
Triclinic, P1	D_x = 1.792 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.4520 (19) Å	Cell parameters from 4140 reflections
b = 10.5252 (19) Å	θ = 2.5–26.1°
c = 10.6733 (19) Å	µ = 1.54 mm⁻¹
α = 102.869 (2)°	T = 293 K
β = 103.536 (2)°	Block, blue
γ = 94.834 (2)°	0.22 × 0.20 × 0.16 mm
V = 1101.3 (3) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	4212 independent reflections
Radiation source: fine-focus sealed tube	3869 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.011
ϕ and ω scans	θ_max = 26.1°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→8
T_min = 0.720, T_max = 0.785	k = −12→12
6205 measured reflections	l = −11→13

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0412P)² + 0.7186P] where P = (F_o² + 2F_c²)/3
4212 reflections	(Δ/σ)_max = 0.004
361 parameters	Δρ_max = 0.67 e Å⁻³
31 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

(NH₄)₂[Cu(C₇H₃NO₄)₂(H₂O)₂][CdCu(C₇H₃NO₄)₂(H₂O)₆]·6H₂O	γ = 94.834 (2)°
M_r = 1188.20	V = 1101.3 (3) Å³
Triclinic, P1	Z = 1
a = 10.4520 (19) Å	Mo Kα radiation
b = 10.5252 (19) Å	µ = 1.54 mm⁻¹
c = 10.6733 (19) Å	T = 293 K
α = 102.869 (2)°	0.22 × 0.20 × 0.16 mm
β = 103.536 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	4212 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3869 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.785	R_int = 0.011
6205 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	31 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.67 e Å⁻³
4212 reflections	Δρ_min = −0.41 e Å⁻³
361 parameters

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

	x	y	z	U_iso*/U_eq
Cd1	0.0000	0.0000	0.5000	0.02604 (8)
Cu1	0.5000	0.0000	0.5000	0.02460 (10)
Cu2	0.5000	0.5000	1.0000	0.03268 (11)
N1	0.44406 (17)	0.04440 (17)	0.32615 (17)	0.0221 (4)
N2	0.60608 (19)	0.56353 (19)	0.88835 (18)	0.0282 (4)
O1	0.30942 (15)	−0.02363 (16)	0.48585 (15)	0.0281 (3)
O2	0.11497 (15)	−0.03483 (18)	0.34073 (16)	0.0342 (4)
O3	0.1713 (2)	−0.0467 (2)	−0.13119 (19)	0.0591 (6)
O4	0.30140 (19)	0.1332 (2)	−0.12763 (17)	0.0439 (5)
O5	0.35050 (16)	0.49779 (19)	0.84955 (17)	0.0369 (4)
O6	0.30210 (18)	0.5639 (2)	0.6633 (2)	0.0490 (5)
O7	0.71230 (17)	0.72200 (19)	0.51106 (18)	0.0391 (4)
O8	0.89977 (16)	0.65182 (18)	0.59992 (18)	0.0366 (4)
C1	0.2382 (2)	−0.0169 (2)	0.3746 (2)	0.0239 (4)
C2	0.3115 (2)	0.0180 (2)	0.2780 (2)	0.0227 (4)
C3	0.2475 (2)	0.0220 (2)	0.1505 (2)	0.0269 (5)
H3	0.1557	0.0001	0.1186	0.032*
C4	0.3247 (2)	0.0598 (2)	0.0707 (2)	0.0267 (5)
C5	0.2599 (2)	0.0495 (3)	−0.0752 (2)	0.0327 (5)
C6	0.4603 (2)	0.0970 (2)	0.1247 (2)	0.0262 (5)
H6	0.5124	0.1301	0.0763	0.031*
C7	0.5176 (2)	0.0845 (2)	0.2518 (2)	0.0255 (4)
H7	0.6094	0.1046	0.2858	0.031*
C8	0.7820 (2)	0.6710 (2)	0.5938 (2)	0.0280 (5)
C9	0.7192 (2)	0.6332 (2)	0.6975 (2)	0.0270 (5)
C10	0.7977 (2)	0.6251 (3)	0.8193 (2)	0.0337 (5)
H10	0.8898	0.6421	0.8379	0.040*
C11	0.7380 (2)	0.5914 (3)	0.9128 (2)	0.0340 (5)
H11	0.7913	0.5882	0.9948	0.041*
C12	0.5292 (2)	0.5726 (2)	0.7720 (2)	0.0261 (5)
C13	0.5820 (2)	0.6079 (2)	0.6751 (2)	0.0258 (4)
H13	0.5262	0.6147	0.5958	0.031*
C14	0.3820 (2)	0.5433 (2)	0.7580 (2)	0.0305 (5)
O1W	0.14804 (16)	0.17674 (17)	0.64065 (16)	0.0324 (4)
H1A	0.202 (2)	0.205 (3)	0.590 (2)	0.039*
H1B	0.201 (2)	0.159 (3)	0.7184 (16)	0.039*
O2W	0.08911 (16)	−0.15033 (17)	0.60774 (17)	0.0323 (4)
H2A	0.121 (2)	−0.102 (2)	0.6985 (13)	0.039*
H2B	0.023 (2)	−0.2214 (18)	0.603 (2)	0.039*
O3W	0.46396 (19)	−0.24026 (19)	0.37308 (18)	0.0397 (4)
H3A	0.3913 (16)	−0.275 (3)	0.399 (3)	0.048*
H3B	0.5449 (13)	−0.261 (3)	0.419 (3)	0.048*
O4W	0.4544 (2)	0.7280 (2)	1.10086 (19)	0.0445 (4)
H4A	0.447 (3)	0.731 (3)	1.1887 (15)	0.053*
H4B	0.5379 (17)	0.775 (3)	1.106 (3)	0.053*
O5W	0.1659 (2)	−0.2927 (2)	−0.0551 (2)	0.0585 (6)
H5A	0.2575 (14)	−0.294 (3)	−0.016 (3)	0.070*
H5B	0.158 (3)	−0.213 (2)	−0.084 (3)	0.070*
O6W	0.2430 (2)	0.6784 (2)	0.4538 (2)	0.0459 (5)
H6A	0.260 (3)	0.632 (2)	0.522 (2)	0.055*
H6B	0.210 (3)	0.7573 (18)	0.488 (3)	0.055*
O7W	0.0227 (3)	−0.2976 (3)	0.1422 (3)	0.0668 (7)
H7A	0.033 (3)	−0.2138 (19)	0.202 (3)	0.080*
H7B	0.083 (3)	−0.297 (3)	0.088 (3)	0.080*
N3	1.0503 (2)	0.4588 (2)	0.6944 (3)	0.0482 (6)
H31	1.020 (2)	0.406 (2)	0.749 (2)	0.058*
H32	0.9847 (18)	0.5165 (19)	0.666 (2)	0.058*
H33	1.1357 (14)	0.5156 (19)	0.745 (2)	0.058*
H34	1.065 (2)	0.4011 (19)	0.6132 (15)	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02452 (13)	0.03503 (14)	0.02213 (13)	0.00417 (9)	0.00922 (9)	0.01115 (9)
Cu1	0.02026 (19)	0.0393 (2)	0.01908 (19)	0.00659 (15)	0.00640 (15)	0.01509 (16)
Cu2	0.0253 (2)	0.0519 (3)	0.0262 (2)	−0.00001 (18)	0.00792 (17)	0.02147 (19)
N1	0.0217 (9)	0.0281 (9)	0.0180 (8)	0.0046 (7)	0.0060 (7)	0.0077 (7)
N2	0.0284 (10)	0.0354 (10)	0.0239 (9)	0.0021 (8)	0.0081 (8)	0.0132 (8)
O1	0.0248 (8)	0.0418 (9)	0.0230 (8)	0.0056 (7)	0.0091 (6)	0.0158 (7)
O2	0.0214 (8)	0.0579 (11)	0.0241 (8)	0.0019 (7)	0.0082 (7)	0.0113 (8)
O3	0.0686 (15)	0.0667 (14)	0.0275 (10)	−0.0263 (12)	−0.0090 (10)	0.0183 (9)
O4	0.0468 (11)	0.0582 (12)	0.0280 (9)	−0.0027 (9)	0.0038 (8)	0.0235 (9)
O5	0.0264 (9)	0.0565 (11)	0.0323 (9)	−0.0003 (8)	0.0089 (7)	0.0214 (8)
O6	0.0295 (9)	0.0816 (15)	0.0422 (11)	0.0023 (9)	0.0037 (8)	0.0367 (11)
O7	0.0360 (9)	0.0528 (11)	0.0423 (10)	0.0131 (8)	0.0178 (8)	0.0298 (9)
O8	0.0295 (9)	0.0450 (10)	0.0460 (10)	0.0076 (7)	0.0177 (8)	0.0241 (8)
C1	0.0238 (11)	0.0291 (11)	0.0201 (10)	0.0040 (8)	0.0076 (8)	0.0068 (8)
C2	0.0219 (10)	0.0292 (11)	0.0199 (10)	0.0055 (8)	0.0077 (8)	0.0087 (8)
C3	0.0220 (11)	0.0375 (12)	0.0216 (11)	0.0040 (9)	0.0047 (9)	0.0096 (9)
C4	0.0305 (12)	0.0319 (12)	0.0191 (10)	0.0054 (9)	0.0063 (9)	0.0089 (9)
C5	0.0345 (13)	0.0440 (14)	0.0214 (11)	0.0053 (11)	0.0069 (10)	0.0124 (10)
C6	0.0290 (11)	0.0314 (11)	0.0213 (10)	0.0021 (9)	0.0110 (9)	0.0092 (9)
C7	0.0231 (11)	0.0322 (12)	0.0236 (11)	0.0030 (9)	0.0088 (9)	0.0095 (9)
C8	0.0308 (12)	0.0278 (11)	0.0310 (12)	0.0035 (9)	0.0139 (10)	0.0129 (9)
C9	0.0305 (12)	0.0263 (11)	0.0285 (11)	0.0041 (9)	0.0127 (9)	0.0104 (9)
C10	0.0257 (12)	0.0453 (14)	0.0328 (12)	0.0026 (10)	0.0090 (10)	0.0149 (11)
C11	0.0263 (12)	0.0498 (15)	0.0291 (12)	0.0031 (10)	0.0058 (10)	0.0190 (11)
C12	0.0277 (11)	0.0267 (11)	0.0263 (11)	0.0037 (9)	0.0092 (9)	0.0091 (9)
C13	0.0280 (11)	0.0299 (11)	0.0223 (10)	0.0035 (9)	0.0085 (9)	0.0104 (9)
C14	0.0280 (12)	0.0377 (13)	0.0274 (12)	0.0017 (10)	0.0076 (10)	0.0123 (10)
O1W	0.0271 (8)	0.0448 (10)	0.0260 (8)	−0.0001 (7)	0.0065 (7)	0.0126 (7)
O2W	0.0289 (9)	0.0393 (9)	0.0310 (9)	0.0019 (7)	0.0074 (7)	0.0150 (7)
O3W	0.0398 (10)	0.0460 (11)	0.0390 (10)	0.0101 (8)	0.0139 (8)	0.0168 (8)
O4W	0.0488 (12)	0.0475 (11)	0.0367 (10)	−0.0018 (9)	0.0118 (9)	0.0120 (9)
O5W	0.0555 (13)	0.0568 (13)	0.0681 (15)	0.0083 (11)	0.0205 (12)	0.0208 (11)
O6W	0.0532 (12)	0.0450 (11)	0.0466 (11)	0.0098 (9)	0.0174 (9)	0.0205 (9)
O7W	0.0744 (17)	0.0650 (15)	0.0564 (15)	−0.0103 (13)	0.0218 (13)	0.0085 (12)
N3	0.0302 (12)	0.0545 (15)	0.0682 (17)	0.0102 (10)	0.0157 (11)	0.0277 (13)

Geometric parameters (Å, º) top

Cd1—O2	2.2850 (16)	C3—H3	0.9300
Cd1—O2ⁱ	2.2850 (16)	C4—C6	1.384 (3)
Cd1—O1W	2.3004 (17)	C4—C5	1.521 (3)
Cd1—O2Wⁱ	2.2915 (17)	C6—C7	1.389 (3)
Cd1—O2W	2.2915 (17)	C6—H6	0.9300
Cd1—O1Wⁱ	2.3004 (17)	C7—H7	0.9300
Cu1—O1ⁱⁱ	1.9523 (15)	C8—C9	1.519 (3)
Cu1—O1	1.9523 (15)	C9—C13	1.390 (3)
Cu1—N1	1.9819 (17)	C9—C10	1.389 (3)
Cu1—N1ⁱⁱ	1.9819 (17)	C10—C11	1.386 (3)
Cu1—O3Wⁱⁱ	2.539 (2)	C10—H10	0.9300
Cu1—O3W	2.539 (2)	C11—H11	0.9300
Cu2—O5	1.9553 (17)	C12—C13	1.385 (3)
Cu2—O5ⁱⁱⁱ	1.9553 (17)	C12—C14	1.509 (3)
Cu2—N2	1.9862 (18)	C13—H13	0.9300
Cu2—N2ⁱⁱⁱ	1.9862 (18)	O1W—H1A	0.94 (2)
Cu2—O4Wⁱⁱⁱ	2.535 (2)	O1W—H1B	0.95 (2)
Cu2—O4W	2.535 (2)	O2W—H2A	0.95 (1)
N1—C7	1.334 (3)	O2W—H2B	0.95 (1)
N1—C2	1.342 (3)	O3W—H3A	0.94 (1)
N2—C11	1.336 (3)	O3W—H3B	0.94 (1)
N2—C12	1.340 (3)	O4W—H4A	0.95 (1)
O1—C1	1.266 (3)	O4W—H4B	0.95 (1)
O2—C1	1.239 (3)	O5W—H5A	0.95 (1)
O3—C5	1.246 (3)	O5W—H5B	0.96 (1)
O4—C5	1.244 (3)	O6W—H6A	0.95 (1)
O5—C14	1.275 (3)	O6W—H6B	0.96 (3)
O6—C14	1.224 (3)	O7W—H7A	0.95 (3)
O7—C8	1.255 (3)	O7W—H7B	0.95 (3)
O8—C8	1.253 (3)	N3—H31	0.98 (2)
C1—C2	1.509 (3)	N3—H32	0.99 (2)
C2—C3	1.379 (3)	N3—H33	0.99 (1)
C3—C4	1.397 (3)	N3—H34	0.99 (2)

O2—Cd1—O2ⁱ	180.00 (6)	N1—C2—C3	122.80 (19)
O2—Cd1—O2Wⁱ	84.25 (6)	N1—C2—C1	114.40 (18)
O2ⁱ—Cd1—O2Wⁱ	95.75 (6)	C3—C2—C1	122.80 (19)
O2—Cd1—O2W	95.75 (6)	C2—C3—C4	118.1 (2)
O2ⁱ—Cd1—O2W	84.25 (6)	C2—C3—H3	121.0
O2Wⁱ—Cd1—O2W	180.0	C4—C3—H3	121.0
O2—Cd1—O1W	95.40 (6)	C6—C4—C3	118.78 (19)
O2ⁱ—Cd1—O1W	84.60 (6)	C6—C4—C5	121.7 (2)
O2Wⁱ—Cd1—O1W	85.58 (6)	C3—C4—C5	119.4 (2)
O2W—Cd1—O1W	94.42 (6)	O4—C5—O3	126.5 (2)
O2—Cd1—O1Wⁱ	84.60 (6)	O4—C5—C4	118.3 (2)
O2ⁱ—Cd1—O1Wⁱ	95.40 (6)	O3—C5—C4	115.1 (2)
O2Wⁱ—Cd1—O1Wⁱ	94.43 (6)	C4—C6—C7	119.3 (2)
O2W—Cd1—O1Wⁱ	85.57 (6)	C4—C6—H6	120.3
O1W—Cd1—O1Wⁱ	179.999 (1)	C7—C6—H6	120.3
O1ⁱⁱ—Cu1—O1	180.0	N1—C7—C6	121.5 (2)
O1ⁱⁱ—Cu1—N1	96.26 (7)	N1—C7—H7	119.2
O1—Cu1—N1	83.74 (7)	C6—C7—H7	119.2
O1ⁱⁱ—Cu1—N1ⁱⁱ	83.74 (7)	O8—C8—O7	125.5 (2)
O1—Cu1—N1ⁱⁱ	96.26 (7)	O8—C8—C9	117.5 (2)
N1—Cu1—N1ⁱⁱ	180.0	O7—C8—C9	117.0 (2)
O1ⁱⁱ—Cu1—O3Wⁱⁱ	85.99 (6)	C13—C9—C10	117.8 (2)
O1—Cu1—O3Wⁱⁱ	94.01 (6)	C13—C9—C8	121.3 (2)
N1—Cu1—O3Wⁱⁱ	92.15 (7)	C10—C9—C8	120.8 (2)
N1ⁱⁱ—Cu1—O3Wⁱⁱ	87.85 (7)	C11—C10—C9	119.8 (2)
O1ⁱⁱ—Cu1—O3W	94.01 (6)	C11—C10—H10	120.1
O1—Cu1—O3W	85.99 (6)	C9—C10—H10	120.1
N1—Cu1—O3W	87.85 (7)	N2—C11—C10	121.8 (2)
N1ⁱⁱ—Cu1—O3W	92.15 (7)	N2—C11—H11	119.1
O3Wⁱⁱ—Cu1—O3W	180.00 (4)	C10—C11—H11	119.1
O5—Cu2—O5ⁱⁱⁱ	180.0	N2—C12—C13	122.2 (2)
O5—Cu2—N2	83.06 (7)	N2—C12—C14	114.18 (19)
O5ⁱⁱⁱ—Cu2—N2	96.94 (7)	C13—C12—C14	123.7 (2)
O5—Cu2—N2ⁱⁱⁱ	96.95 (7)	C12—C13—C9	119.4 (2)
O5ⁱⁱⁱ—Cu2—N2ⁱⁱⁱ	83.05 (7)	C12—C13—H13	120.3
N2—Cu2—N2ⁱⁱⁱ	179.998 (1)	C9—C13—H13	120.3
O5—Cu2—O4Wⁱⁱⁱ	94.09 (7)	O6—C14—O5	124.6 (2)
O5ⁱⁱⁱ—Cu2—O4Wⁱⁱⁱ	85.91 (7)	O6—C14—C12	119.9 (2)
N2—Cu2—O4Wⁱⁱⁱ	86.13 (7)	O5—C14—C12	115.49 (19)
N2ⁱⁱⁱ—Cu2—O4Wⁱⁱⁱ	93.87 (7)	Cd1—O1W—H1A	106.3 (16)
O5—Cu2—O4W	85.91 (7)	Cd1—O1W—H1B	114.8 (16)
O5ⁱⁱⁱ—Cu2—O4W	94.09 (7)	H1A—O1W—H1B	110 (1)
N2—Cu2—O4W	93.87 (7)	Cd1—O2W—H2A	104.0 (16)
N2ⁱⁱⁱ—Cu2—O4W	86.13 (7)	Cd1—O2W—H2B	112.0 (16)
O4Wⁱⁱⁱ—Cu2—O4W	180.0	H2A—O2W—H2B	108 (1)
C7—N1—C2	119.16 (18)	H3A—O3W—H3B	112 (1)
C7—N1—Cu1	129.85 (15)	H4A—O4W—H4B	109 (3)
C2—N1—Cu1	110.76 (13)	H5A—O5W—H5B	108 (3)
C11—N2—C12	119.09 (19)	H6A—O6W—H6B	108 (1)
C11—N2—Cu2	128.85 (15)	H7A—O7W—H7B	110 (3)
C12—N2—Cu2	112.00 (15)	H31—N3—H32	112 (1)
C1—O1—Cu1	113.79 (13)	H31—N3—H33	110 (1)
C1—O2—Cd1	119.57 (14)	H32—N3—H33	108 (1)
C14—O5—Cu2	114.67 (15)	H31—N3—H34	111 (1)
O2—C1—O1	125.21 (19)	H32—N3—H34	108 (1)
O2—C1—C2	118.48 (18)	H33—N3—H34	108 (1)
O1—C1—C2	116.30 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O7^iv	0.94 (2)	1.80 (1)	2.739 (2)	171 (2)
O1W—H1B···O4^v	0.95 (2)	1.82 (1)	2.769 (2)	177 (3)
O2W—H2A···O3^v	0.95 (1)	1.72 (1)	2.657 (3)	168 (2)
O2W—H2B···O8^vi	0.95 (1)	1.77 (1)	2.722 (2)	177 (2)
O3W—H3A···O6W^vii	0.94 (1)	1.84 (1)	2.781 (3)	172 (3)
O3W—H3B···O7^vii	0.94 (1)	1.84 (1)	2.776 (3)	172 (3)
O4W—H4A···O3W^viii	0.95 (1)	1.89 (1)	2.827 (3)	169 (2)
O4W—H4B···O4^iv	0.95 (1)	1.80 (1)	2.752 (3)	176 (2)
O5W—H5A···O4W^ix	0.95 (1)	2.10 (1)	3.048 (3)	170 (3)
O5W—H5B···O3	0.96 (1)	1.93 (1)	2.882 (3)	171 (3)
O6W—H6A···O6	0.95 (1)	1.79 (1)	2.742 (3)	173 (3)
O6W—H6B···O2W^x	0.96 (3)	2.14 (2)	2.991 (3)	147 (2)
O7W—H7A···O2	0.95 (3)	2.09 (3)	3.009 (3)	163 (3)
O7W—H7B···O5W	0.95 (3)	1.93 (3)	2.861 (3)	165 (4)
N3—H31···O7Wⁱⁱ	0.98 (2)	1.90 (2)	2.867 (3)	174 (2)
N3—H32···O8	0.99 (2)	1.92 (1)	2.886 (3)	164 (2)
N3—H33···O5W^xi	0.99 (1)	2.53 (2)	3.208 (4)	126 (2)
N3—H33···O5^xii	0.99 (1)	2.30 (2)	3.131 (3)	140 (2)
N3—H33···O6^xii	0.99 (1)	2.19 (2)	2.888 (3)	126 (2)
N3—H34···O8^xiii	0.99 (2)	2.34 (1)	3.277 (3)	157 (2)

Symmetry codes: (ii) −x+1, −y, −z+1; (iv) −x+1, −y+1, −z+1; (v) x, y, z+1; (vi) x−1, y−1, z; (vii) x, y−1, z; (viii) x, y+1, z+1; (ix) x, y−1, z−1; (x) x, y+1, z; (xi) x+1, y+1, z+1; (xii) x+1, y, z; (xiii) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	(NH₄)₂[Cu(C₇H₃NO₄)₂(H₂O)₂][CdCu(C₇H₃NO₄)₂(H₂O)₆]·6H₂O
M_r	1188.20
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.4520 (19), 10.5252 (19), 10.6733 (19)
α, β, γ (°)	102.869 (2), 103.536 (2), 94.834 (2)
V (Å³)	1101.3 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.54
Crystal size (mm)	0.22 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.720, 0.785
No. of measured, independent and observed [I > 2σ(I)] reflections	6205, 4212, 3869
R_int	0.011
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.073, 1.05
No. of reflections	4212
No. of parameters	361
No. of restraints	31
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.41

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O7ⁱ	0.94 (2)	1.80 (1)	2.739 (2)	171 (2)
O1W—H1B···O4ⁱⁱ	0.95 (2)	1.82 (1)	2.769 (2)	177 (3)
O2W—H2A···O3ⁱⁱ	0.95 (1)	1.72 (1)	2.657 (3)	168 (2)
O2W—H2B···O8ⁱⁱⁱ	0.95 (1)	1.77 (1)	2.722 (2)	177 (2)
O3W—H3A···O6W^iv	0.94 (1)	1.84 (1)	2.781 (3)	172 (3)
O3W—H3B···O7^iv	0.94 (1)	1.84 (1)	2.776 (3)	172 (3)
O4W—H4A···O3W^v	0.95 (1)	1.89 (1)	2.827 (3)	169 (2)
O4W—H4B···O4ⁱ	0.95 (1)	1.80 (1)	2.752 (3)	176 (2)
O5W—H5A···O4W^vi	0.95 (1)	2.10 (1)	3.048 (3)	170 (3)
O5W—H5B···O3	0.96 (1)	1.93 (1)	2.882 (3)	171 (3)
O6W—H6A···O6	0.95 (1)	1.79 (1)	2.742 (3)	173 (3)
O6W—H6B···O2W^vii	0.96 (3)	2.14 (2)	2.991 (3)	147 (2)
O7W—H7A···O2	0.95 (3)	2.09 (3)	3.009 (3)	163 (3)
O7W—H7B···O5W	0.95 (3)	1.93 (3)	2.861 (3)	165 (4)
N3—H31···O7W^viii	0.98 (2)	1.90 (2)	2.867 (3)	174 (2)
N3—H32···O8	0.99 (2)	1.92 (1)	2.886 (3)	164 (2)
N3—H33···O5W^ix	0.99 (1)	2.53 (2)	3.208 (4)	126 (2)
N3—H33···O5^x	0.99 (1)	2.30 (2)	3.131 (3)	140 (2)
N3—H33···O6^x	0.99 (1)	2.19 (2)	2.888 (3)	126 (2)
N3—H34···O8^xi	0.99 (2)	2.34 (1)	3.277 (3)	157 (2)

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

Acknowledgements

The authors thank the Changchun Institute of Applied Chemistry for supporting this work.

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