A novel (3,6)-connected Cd^II coordination polymer based on an ether-linked tri­carboxyl­ate ligand: synthesis, topology and luminescence sensing properties in aqueous solution

A novel three-dimensional coordination polymer, namely, poly[[diaquabis(μ-4,4′-bi­pyridine)­bis­{μ₃-5-[(2-carb­oxy­phen­oxy)meth­yl]isophthalato}tri­cadmium(III)] di­methyl­formamide monosolvate 2.5-hydrate], {[Cd₃(C₁₆H₉O₇)₂(C₁₀H₈N₂)₂(H₂O)₂]·2C₃H₇NO·5H₂O}_n, was obtained by the reaction of ether-linked 5-[(2-carb­oxy­phen­oxy)meth­yl]isophthalic acid (H₃L) with Cd^II salts in the presence of 4,4′-bi­pyridine (bpy) under solvothermal conditions. In this com­plex, the Cd^II centres are connected by the carboxyl­ate ligands to form two-dimensional wave-like layers, which are pillared by bpy ligands and extended into a rare three-dimensional (3,6)-connected sqc27 framework. The com­plex demonstrated good water stability and strong luminescence emissions. It not only possesses excellent luminescence sensing activities toward Fe³⁺ and Cr₂O₇²⁻ in aqueous solution, but can also distinguish between Cr₂O₇²⁻ and CrO₄²⁻ by luminescence. Furthermore, it could be simply and quickly re­­gener­­ated at least five times. A study of the sensing mechanism indicated that luminescence quenching may be related to the energy com­petition between the com­plex and sensing analytes.

Computing details

Data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2008); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

Poly[[diaqiabis(µ-4,4'-bipyridine)bis{µ₃-5-[(2-carboxyphenoxy)methyl]isophthalato}tricadmium(III)] dimethylformamide monosolvate 2.5-hydrate]

Crystal data

[Cd3(C16H9O7)2(C10H8N2)2(H2O)2]·2C3H7NO·5H2O	F(000) = 1300
Mr = 1548.35	Dx = 1.623 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.2511 (14) Å	Cell parameters from 2165 reflections
b = 11.6120 (11) Å	θ = 2.3–22.0°
c = 20.2609 (18) Å	µ = 1.08 mm^−1
β = 124.020 (5)°	T = 298 K
V = 3169.0 (5) Å^3	Crystal, colour
Z = 2	0.21 × 0.20 × 0.06 mm

Data collection

Bruker SMART-1000 CCD area detector diffractometer	3051 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.110
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 25.0°, θmin = 2.4°
Tmin = 0.95, Tmax = 1	h = −15→19
14901 measured reflections	k = −13→13
5552 independent reflections	l = −24→23

Refinement

Refinement on F^2	918 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.179	w = 1/[σ^2(Fo^2) + (0.072P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
5552 reflections	Δρmax = 1.93 e Å^−3
339 parameters	Δρmin = −1.56 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.59630 (4)	1.00061 (5)	0.61645 (3)	0.0334 (2)
Cd2	1.000000	1.14470 (12)	0.250000	0.0813 (4)
N1	0.5884 (5)	0.8038 (6)	0.6066 (4)	0.0435 (16)
N2	0.5926 (5)	0.1988 (5)	0.6124 (4)	0.0414 (16)
O1	0.7101 (4)	1.0104 (4)	0.5846 (3)	0.0437 (13)
O2	0.5731 (4)	0.9937 (4)	0.4684 (3)	0.0468 (14)
O3	0.5966 (4)	1.0016 (5)	0.2299 (3)	0.0476 (14)
O4	0.7405 (4)	1.0192 (5)	0.2505 (3)	0.0614 (17)
O5	1.0120 (4)	1.1630 (6)	0.4980 (3)	0.0621 (16)
O6	1.0125 (5)	1.1411 (7)	0.3683 (3)	0.0760 (18)
O7	1.1116 (5)	1.2511 (7)	0.3598 (4)	0.088 (2)
O8	0.8856 (5)	1.0086 (6)	0.2240 (4)	0.089 (3)
H8C	0.855332	1.014912	0.247091	0.107*
H8D	0.841982	1.002034	0.174331	0.107*
C1	0.6644 (6)	1.0097 (7)	0.5117 (4)	0.0384 (17)
C2	0.7201 (6)	1.0322 (7)	0.4749 (5)	0.0443 (19)
C3	0.6772 (6)	1.0175 (7)	0.3961 (4)	0.0427 (18)
H3	0.611264	0.994268	0.363550	0.051*
C4	0.7328 (6)	1.0374 (8)	0.3632 (4)	0.0425 (18)
C5	0.8303 (6)	1.0762 (7)	0.4125 (4)	0.0487 (19)
H5	0.867025	1.091062	0.391065	0.058*
C6	0.8722 (6)	1.0925 (7)	0.4914 (5)	0.0487 (19)
C7	0.8168 (6)	1.0718 (8)	0.5223 (5)	0.0454 (18)
H7	0.844916	1.084789	0.576135	0.054*
C8	0.6865 (7)	1.0164 (8)	0.2753 (5)	0.051 (2)
C9	0.9758 (6)	1.1379 (9)	0.5452 (5)	0.056 (2)
H9A	0.975664	1.206881	0.572098	0.067*
H9B	1.017635	1.080784	0.585108	0.067*
C10	1.1036 (7)	1.2133 (9)	0.5356 (5)	0.060 (2)
C11	1.1371 (6)	1.2377 (9)	0.4861 (5)	0.059 (2)
C12	1.2288 (7)	1.2890 (9)	0.5215 (5)	0.070 (2)
H12A	1.253706	1.307050	0.491122	0.084*
C13	1.2853 (7)	1.3144 (9)	0.6037 (6)	0.076 (3)
H13	1.346668	1.350206	0.627011	0.091*
C14	1.2509 (7)	1.2871 (9)	0.6484 (6)	0.070 (3)
H14	1.289555	1.302900	0.702684	0.084*
C15	1.1609 (7)	1.2369 (9)	0.6159 (5)	0.062 (2)
H15	1.137972	1.218596	0.647592	0.075*
C16	1.0826 (7)	1.2094 (10)	0.4008 (5)	0.065 (2)
C17	0.5128 (6)	0.7433 (7)	0.5962 (5)	0.053 (2)
H17	0.458059	0.782731	0.588162	0.064*
C18	0.5114 (7)	0.6263 (8)	0.5967 (6)	0.061 (2)
H18	0.455613	0.587870	0.587315	0.074*
C19	0.5914 (6)	0.5646 (8)	0.6107 (5)	0.0463 (18)
C20	0.6686 (7)	0.6282 (8)	0.6204 (6)	0.060 (2)
H20	0.723613	0.591133	0.627329	0.073*
C21	0.6650 (7)	0.7436 (8)	0.6200 (5)	0.058 (2)
H21	0.720267	0.783839	0.629768	0.070*
C22	0.5127 (7)	0.3771 (8)	0.5961 (6)	0.066 (2)
H22	0.455163	0.415358	0.582984	0.079*
C23	0.5155 (7)	0.2582 (8)	0.5987 (6)	0.065 (2)
H23	0.460763	0.218543	0.590452	0.078*
C24	0.6696 (7)	0.2598 (8)	0.6289 (6)	0.067 (3)
H24	0.726873	0.220357	0.642443	0.081*
C25	0.6717 (7)	0.3756 (8)	0.6276 (6)	0.068 (2)
H25	0.728053	0.412770	0.637139	0.082*
C26	0.5932 (6)	0.4386 (7)	0.6126 (5)	0.0431 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0399 (4)	0.0382 (3)	0.0341 (3)	−0.0011 (3)	0.0281 (3)	0.0009 (3)
Cd2	0.0691 (8)	0.1322 (11)	0.0598 (6)	0.000	0.0467 (6)	0.000
N1	0.050 (4)	0.040 (4)	0.053 (3)	−0.001 (3)	0.037 (3)	0.000 (3)
N2	0.052 (4)	0.032 (3)	0.058 (4)	−0.004 (3)	0.042 (3)	−0.001 (3)
O1	0.043 (3)	0.065 (3)	0.035 (2)	−0.002 (2)	0.029 (2)	0.001 (3)
O2	0.027 (3)	0.069 (4)	0.056 (3)	0.000 (3)	0.030 (2)	0.005 (3)
O3	0.038 (3)	0.085 (4)	0.028 (2)	−0.009 (3)	0.023 (2)	−0.010 (3)
O4	0.049 (3)	0.115 (5)	0.045 (3)	−0.005 (3)	0.041 (3)	−0.007 (3)
O5	0.049 (3)	0.100 (4)	0.050 (3)	−0.025 (3)	0.036 (3)	−0.007 (3)
O6	0.068 (4)	0.125 (5)	0.048 (3)	−0.035 (4)	0.041 (3)	−0.015 (3)
O7	0.089 (4)	0.133 (5)	0.063 (4)	−0.029 (4)	0.055 (3)	−0.011 (4)
O8	0.059 (4)	0.162 (8)	0.065 (4)	−0.001 (4)	0.047 (4)	0.000 (4)
C1	0.047 (4)	0.049 (4)	0.037 (3)	0.002 (3)	0.034 (3)	0.003 (3)
C2	0.043 (4)	0.060 (4)	0.043 (3)	−0.002 (3)	0.032 (3)	0.001 (3)
C3	0.038 (4)	0.073 (5)	0.033 (3)	−0.005 (3)	0.029 (3)	−0.001 (3)
C4	0.041 (4)	0.070 (4)	0.033 (3)	−0.002 (3)	0.031 (3)	−0.004 (3)
C5	0.048 (4)	0.072 (5)	0.043 (4)	−0.011 (3)	0.035 (3)	−0.005 (4)
C6	0.045 (4)	0.070 (5)	0.039 (4)	−0.009 (3)	0.028 (3)	−0.003 (4)
C7	0.042 (4)	0.072 (5)	0.035 (3)	−0.009 (3)	0.030 (3)	−0.003 (3)
C8	0.047 (4)	0.083 (5)	0.033 (4)	−0.003 (4)	0.029 (3)	0.000 (4)
C9	0.053 (4)	0.086 (5)	0.038 (4)	−0.011 (4)	0.030 (3)	0.005 (4)
C10	0.049 (4)	0.087 (5)	0.055 (4)	−0.011 (4)	0.036 (3)	−0.008 (4)
C11	0.051 (4)	0.091 (5)	0.052 (4)	−0.019 (4)	0.040 (3)	−0.010 (4)
C12	0.060 (5)	0.101 (5)	0.066 (4)	−0.019 (4)	0.045 (4)	−0.009 (4)
C13	0.054 (5)	0.109 (6)	0.071 (5)	−0.027 (5)	0.039 (4)	−0.013 (5)
C14	0.054 (5)	0.099 (6)	0.059 (5)	−0.023 (4)	0.033 (4)	−0.014 (5)
C15	0.058 (5)	0.091 (6)	0.052 (4)	−0.017 (4)	0.039 (4)	−0.006 (4)
C16	0.056 (5)	0.105 (6)	0.056 (4)	−0.009 (4)	0.045 (4)	−0.003 (4)
C17	0.055 (5)	0.039 (4)	0.080 (5)	−0.004 (4)	0.046 (4)	0.002 (4)
C18	0.059 (5)	0.045 (4)	0.095 (5)	−0.002 (4)	0.052 (4)	0.002 (4)
C19	0.059 (4)	0.041 (4)	0.064 (4)	0.000 (4)	0.050 (3)	−0.001 (4)
C20	0.058 (5)	0.045 (5)	0.093 (5)	0.001 (4)	0.051 (4)	0.004 (4)
C21	0.053 (4)	0.049 (5)	0.078 (5)	−0.004 (4)	0.040 (4)	0.004 (4)
C22	0.063 (5)	0.049 (5)	0.104 (5)	0.005 (4)	0.057 (4)	−0.001 (4)
C23	0.066 (5)	0.047 (5)	0.104 (6)	−0.002 (4)	0.061 (4)	0.000 (5)
C24	0.057 (5)	0.042 (5)	0.104 (6)	0.001 (4)	0.046 (4)	0.005 (5)
C25	0.062 (5)	0.042 (5)	0.104 (5)	−0.004 (4)	0.049 (4)	0.000 (4)
C26	0.056 (4)	0.033 (4)	0.065 (4)	−0.005 (4)	0.048 (3)	−0.003 (4)

Geometric parameters (Å, º)

Cd1—O1	2.277 (5)	C5—C6	1.355 (10)
Cd1—O2^i	2.289 (5)	C5—H5	0.9300
Cd1—N1	2.291 (7)	C6—C7	1.375 (10)
Cd1—O3^ii	2.297 (5)	C6—C9	1.499 (10)
Cd1—N2^iii	2.303 (6)	C7—H7	0.9300
Cd1—O4^ii	2.408 (6)	C9—H9A	0.9700
Cd1—C8^ii	2.695 (8)	C9—H9B	0.9700
Cd2—O8	2.267 (7)	C10—C15	1.376 (11)
Cd2—O8^iv	2.267 (7)	C10—C11	1.413 (11)
Cd2—O6	2.289 (6)	C11—C12	1.376 (11)
Cd2—O6^iv	2.289 (6)	C11—C16	1.472 (12)
Cd2—O7^iv	2.291 (6)	C12—C13	1.412 (12)
Cd2—O7	2.291 (7)	C12—H12A	0.9300
Cd2—C16^iv	2.667 (9)	C13—C14	1.341 (12)
N1—C21	1.317 (10)	C13—H13	0.9300
N1—C17	1.326 (10)	C14—C15	1.355 (11)
N2—C24	1.307 (10)	C14—H14	0.9300
N2—C23	1.317 (10)	C15—H15	0.9300
O1—C1	1.226 (9)	C17—C18	1.359 (11)
O2—C1	1.245 (9)	C17—H17	0.9300
O3—C8	1.228 (10)	C18—C19	1.367 (11)
O4—C8	1.229 (10)	C18—H18	0.9300
O5—C10	1.367 (9)	C19—C20	1.372 (11)
O5—C9	1.404 (9)	C19—C26	1.463 (11)
O6—C16	1.233 (10)	C20—C21	1.342 (12)
O7—C16	1.259 (10)	C20—H20	0.9300
O8—H8C	0.8500	C21—H21	0.9300
O8—H8D	0.8500	C22—C26	1.358 (11)
C1—C2	1.483 (10)	C22—C23	1.381 (12)
C2—C3	1.350 (11)	C22—H22	0.9300
C2—C7	1.384 (10)	C23—H23	0.9300
C3—C4	1.409 (10)	C24—C25	1.346 (12)
C3—H3	0.9300	C24—H24	0.9300
C4—C5	1.393 (10)	C25—C26	1.349 (11)
C4—C8	1.516 (11)	C25—H25	0.9300
O1—Cd1—O2^i	127.68 (19)	C6—C5—H5	119.6
O1—Cd1—N1	92.3 (2)	C4—C5—H5	119.6
O2^i—Cd1—N1	88.7 (2)	C5—C6—C7	119.2 (8)
O1—Cd1—O3^ii	137.51 (18)	C5—C6—C9	121.7 (8)
O2^i—Cd1—O3^ii	94.6 (2)	C7—C6—C9	119.0 (7)
N1—Cd1—O3^ii	92.5 (2)	C6—C7—C2	121.4 (7)
O1—Cd1—N2^iii	87.1 (2)	C6—C7—H7	119.3
O2^i—Cd1—N2^iii	87.0 (2)	C2—C7—H7	119.3
N1—Cd1—N2^iii	174.1 (2)	O3—C8—O4	121.3 (7)
O3^ii—Cd1—N2^iii	91.9 (2)	O3—C8—C4	120.1 (7)
O1—Cd1—O4^ii	83.86 (18)	O4—C8—C4	118.5 (8)
O2^i—Cd1—O4^ii	148.4 (2)	O3—C8—Cd1^vi	58.1 (4)
N1—Cd1—O4^ii	88.6 (2)	O4—C8—Cd1^vi	63.3 (4)
O3^ii—Cd1—O4^ii	54.10 (18)	C4—C8—Cd1^vi	174.4 (6)
N2^iii—Cd1—O4^ii	97.2 (2)	O5—C9—C6	107.8 (6)
O1—Cd1—C8^ii	110.9 (2)	O5—C9—H9A	110.1
O2^i—Cd1—C8^ii	121.4 (2)	C6—C9—H9A	110.1
N1—Cd1—C8^ii	89.8 (3)	O5—C9—H9B	110.1
O3^ii—Cd1—C8^ii	27.0 (2)	C6—C9—H9B	110.1
N2^iii—Cd1—C8^ii	95.9 (2)	H9A—C9—H9B	108.5
O4^ii—Cd1—C8^ii	27.1 (2)	O5—C10—C15	123.3 (8)
O8—Cd2—O8^iv	91.6 (4)	O5—C10—C11	115.0 (7)
O8—Cd2—O6	79.1 (2)	C15—C10—C11	121.6 (9)
O8^iv—Cd2—O6	99.4 (3)	C12—C11—C10	116.9 (8)
O8—Cd2—O6^iv	99.4 (3)	C12—C11—C16	118.3 (8)
O8^iv—Cd2—O6^iv	79.1 (2)	C10—C11—C16	124.8 (8)
O6—Cd2—O6^iv	177.9 (4)	C11—C12—C13	120.3 (9)
O8—Cd2—O7^iv	92.8 (3)	C11—C12—H12A	119.8
O8^iv—Cd2—O7^iv	134.6 (2)	C13—C12—H12A	119.8
O6—Cd2—O7^iv	125.8 (3)	C14—C13—C12	120.4 (9)
O6^iv—Cd2—O7^iv	55.6 (2)	C14—C13—H13	119.8
O8—Cd2—O7	134.6 (2)	C12—C13—H13	119.8
O8^iv—Cd2—O7	92.8 (3)	C13—C14—C15	121.2 (9)
O6—Cd2—O7	55.6 (2)	C13—C14—H14	119.4
O6^iv—Cd2—O7	125.8 (3)	C15—C14—H14	119.4
O7^iv—Cd2—O7	114.7 (4)	C14—C15—C10	119.6 (9)
O8—Cd2—C16^iv	96.2 (3)	C14—C15—H15	120.2
O8^iv—Cd2—C16^iv	106.5 (3)	C10—C15—H15	120.2
O6—Cd2—C16^iv	153.8 (3)	O6—C16—O7	118.0 (9)
O6^iv—Cd2—C16^iv	27.5 (2)	O6—C16—C11	122.7 (8)
O7^iv—Cd2—C16^iv	28.1 (2)	O7—C16—C11	119.2 (9)
O7—Cd2—C16^iv	125.3 (3)	N1—C17—C18	123.1 (8)
C21—N1—C17	115.9 (8)	N1—C17—H17	118.5
C21—N1—Cd1	120.7 (6)	C18—C17—H17	118.5
C17—N1—Cd1	123.0 (6)	C17—C18—C19	120.6 (9)
C24—N2—C23	115.6 (8)	C17—C18—H18	119.7
C24—N2—Cd1^v	122.0 (6)	C19—C18—H18	119.7
C23—N2—Cd1^v	122.2 (6)	C18—C19—C20	115.7 (9)
C1—O1—Cd1	107.5 (5)	C18—C19—C26	122.2 (8)
C1—O2—Cd1^i	169.5 (5)	C20—C19—C26	122.0 (8)
C8—O3—Cd1^vi	94.9 (5)	C21—C20—C19	120.3 (9)
C8—O4—Cd1^vi	89.5 (5)	C21—C20—H20	119.9
C10—O5—C9	116.7 (6)	C19—C20—H20	119.9
C16—O6—Cd2	93.6 (5)	N1—C21—C20	124.3 (9)
C16—O7—Cd2	92.8 (6)	N1—C21—H21	117.8
Cd2—O8—H8C	117.6	C20—C21—H21	117.8
Cd2—O8—H8D	111.7	C26—C22—C23	120.7 (9)
H8C—O8—H8D	107.7	C26—C22—H22	119.7
O1—C1—O2	122.0 (7)	C23—C22—H22	119.7
O1—C1—C2	118.4 (7)	N2—C23—C22	122.6 (9)
O2—C1—C2	119.6 (7)	N2—C23—H23	118.7
C3—C2—C7	119.8 (8)	C22—C23—H23	118.7
C3—C2—C1	121.1 (7)	N2—C24—C25	124.5 (9)
C7—C2—C1	119.1 (7)	N2—C24—H24	117.7
C2—C3—C4	119.7 (8)	C25—C24—H24	117.7
C2—C3—H3	120.2	C24—C25—C26	121.1 (9)
C4—C3—H3	120.2	C24—C25—H25	119.5
C5—C4—C3	119.1 (7)	C26—C25—H25	119.5
C5—C4—C8	120.8 (7)	C25—C26—C22	115.4 (9)
C3—C4—C8	120.1 (7)	C25—C26—C19	123.5 (8)
C6—C5—C4	120.7 (8)	C22—C26—C19	121.1 (8)

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