A new two-dimensional cadmium(II) coordination polymer based on the asymmetric di­carb­oxy­lic acid homophthalic acid: synthesis, structure and properties

A new coordination polymer poly[[μ₂-4,4′-bis­(2-methyl­imidazol-1-yl)biphenyl-κ²N³:N^3′]bis­[μ₃-2-(2-carboxyl­atophen­yl)acetato-κ⁵O,O′:O′,O′′:O′′]dicadmium(II)], [Cd(C₉H₆O₄)(C₂₀H₁₈N₄)_0.5]_n or [Cd(HMPH)(4,4′-BMIBP)_0.5]_n [H₂HMPH is homophthalic acid and 4,4′-BMIBP is 4,4′-bis­(2-methyl­imidazol-1-yl)biphen­yl], (I), was synthesized by the solvothermal method and was structurally char­­acterized by means of single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Coordination polymer (I) exhibits a two-dimensional layer based on one-dimensional [Cd(HMPH)]_n chains. Remarkably, photocatalytic degradation experiments on methyl­ene blue (MB) indicated that (I) exhibits an obvious degradation effect. Moreover, an investigation of the luminescence properties of (I) revealed that it could be considered as a potential highly selective luminescence sensor for nitro­furan­toin (NFT).

Computing details

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

Poly[[µ₂-4,4'-bis(2-methylimidazol-1-yl)biphenyl-κ²N³:N^3']bis[µ₃-2-(2-carboxylatophenyl)acetato-κ⁵O,O':O',O'':O'']dicadmium(II)],

Crystal data

[Cd(C9H6O4)(C20H18N4)0.5]	F(000) = 892
Mr = 447.74	Dx = 1.709 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.5769 (3) Å	Cell parameters from 9822 reflections
b = 7.5529 (4) Å	θ = 3.2–27.6°
c = 18.5933 (3) Å	µ = 1.28 mm^−1
β = 99.863 (2)°	T = 293 K
V = 1740.11 (11) Å^3	Block, colorless
Z = 4	0.13 × 0.11 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	3423 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.027
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 27.6°, θmin = 3.2°
Tmin = 0.697, Tmax = 0.746	h = −16→16
31753 measured reflections	k = −9→9
3997 independent reflections	l = −24→24

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.058	w = 1/[σ^2(Fo^2) + (0.0181P)^2 + 1.925P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.003
3997 reflections	Δρmax = 0.65 e Å^−3
236 parameters	Δρmin = −0.72 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	0.53581 (2)	0.23915 (2)	0.52137 (2)	0.02534 (6)
O1	0.61095 (13)	0.5560 (2)	0.51288 (9)	0.0334 (4)
O2	0.61807 (16)	0.3461 (2)	0.43169 (10)	0.0442 (5)
O3	0.39567 (12)	0.0352 (2)	0.49439 (10)	0.0341 (4)
O4	0.74333 (16)	1.1154 (3)	0.56097 (13)	0.0608 (6)
N1	0.55144 (16)	0.2769 (2)	0.64193 (10)	0.0289 (4)
N2	0.55280 (17)	0.2323 (3)	0.75855 (10)	0.0321 (4)
C1	0.64231 (19)	0.4983 (3)	0.45590 (13)	0.0308 (5)
C2	0.70932 (18)	0.6132 (3)	0.41515 (12)	0.0271 (5)
C3	0.7119 (2)	0.5657 (3)	0.34299 (13)	0.0362 (5)
H3	0.6708	0.4703	0.3225	0.043*
C4	0.7741 (2)	0.6575 (4)	0.30159 (14)	0.0435 (6)
H4	0.7735	0.6266	0.2531	0.052*
C5	0.8374 (2)	0.7957 (4)	0.33259 (15)	0.0445 (6)
H5	0.8813	0.8563	0.3054	0.053*
C6	0.8357 (2)	0.8440 (3)	0.40375 (15)	0.0391 (6)
H6	0.8790	0.9373	0.4240	0.047*
C7	0.77096 (18)	0.7571 (3)	0.44637 (12)	0.0277 (5)
C8	0.77736 (19)	0.8219 (3)	0.52393 (13)	0.0324 (5)
H8A	0.7576	0.7256	0.5536	0.039*
H8B	0.8515	0.8541	0.5431	0.039*
C9	0.70553 (19)	0.9788 (3)	0.53128 (12)	0.0304 (5)
C10	0.4805 (3)	−0.0156 (4)	0.67494 (15)	0.0550 (8)
H10A	0.4170	−0.0061	0.6383	0.082*
H10B	0.4617	−0.0649	0.7186	0.082*
H10C	0.5321	−0.0911	0.6576	0.082*
C11	0.52814 (19)	0.1623 (3)	0.69086 (12)	0.0296 (5)
C12	0.5920 (2)	0.4252 (3)	0.68000 (13)	0.0422 (6)
H12	0.6153	0.5270	0.6592	0.051*
C13	0.5929 (3)	0.4011 (4)	0.75185 (14)	0.0470 (7)
H13	0.6157	0.4813	0.7893	0.056*
C14	0.53384 (19)	0.1550 (3)	0.82596 (12)	0.0298 (5)
C15	0.4569 (2)	0.2301 (3)	0.86091 (13)	0.0359 (5)
H15	0.4142	0.3223	0.8390	0.043*
C16	0.4433 (2)	0.1683 (3)	0.92859 (13)	0.0341 (5)
H16	0.3914	0.2202	0.9519	0.041*
C17	0.5933 (2)	0.0127 (3)	0.85649 (12)	0.0336 (5)
H17	0.6428	−0.0414	0.8318	0.040*
C18	0.5790 (2)	−0.0496 (3)	0.92435 (12)	0.0323 (5)
H18	0.6191	−0.1463	0.9447	0.039*
C19	0.50564 (18)	0.0302 (3)	0.96263 (11)	0.0254 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.03552 (10)	0.02047 (8)	0.02193 (9)	0.00076 (6)	0.01034 (6)	0.00050 (6)
O1	0.0393 (9)	0.0354 (9)	0.0289 (9)	0.0045 (7)	0.0153 (7)	0.0076 (7)
O2	0.0639 (12)	0.0260 (9)	0.0497 (11)	−0.0072 (8)	0.0294 (10)	−0.0007 (8)
O3	0.0261 (8)	0.0232 (8)	0.0521 (11)	0.0027 (6)	0.0042 (8)	−0.0012 (7)
O4	0.0452 (12)	0.0452 (12)	0.0880 (16)	−0.0029 (9)	0.0003 (11)	−0.0300 (11)
N1	0.0381 (11)	0.0292 (10)	0.0202 (9)	−0.0023 (8)	0.0074 (8)	0.0009 (7)
N2	0.0458 (12)	0.0325 (10)	0.0183 (9)	−0.0068 (9)	0.0059 (8)	0.0014 (7)
C1	0.0335 (12)	0.0271 (11)	0.0329 (12)	0.0050 (9)	0.0092 (10)	0.0095 (9)
C2	0.0292 (11)	0.0252 (10)	0.0293 (12)	0.0042 (9)	0.0119 (9)	0.0038 (9)
C3	0.0423 (14)	0.0359 (13)	0.0330 (13)	−0.0011 (11)	0.0137 (11)	−0.0016 (10)
C4	0.0523 (16)	0.0515 (16)	0.0305 (13)	0.0043 (13)	0.0183 (12)	0.0032 (12)
C5	0.0493 (16)	0.0456 (15)	0.0438 (15)	−0.0006 (12)	0.0230 (13)	0.0124 (12)
C6	0.0413 (14)	0.0325 (13)	0.0458 (15)	−0.0027 (11)	0.0145 (12)	0.0044 (11)
C7	0.0265 (11)	0.0275 (11)	0.0303 (11)	0.0072 (9)	0.0083 (9)	0.0049 (9)
C8	0.0301 (12)	0.0347 (12)	0.0312 (12)	0.0056 (10)	0.0019 (10)	0.0007 (10)
C9	0.0352 (13)	0.0293 (11)	0.0277 (11)	0.0007 (10)	0.0079 (10)	−0.0002 (9)
C10	0.097 (2)	0.0412 (15)	0.0274 (13)	−0.0259 (16)	0.0125 (15)	−0.0002 (11)
C11	0.0384 (13)	0.0308 (11)	0.0201 (11)	−0.0008 (10)	0.0065 (9)	0.0026 (9)
C12	0.0654 (18)	0.0328 (13)	0.0295 (13)	−0.0145 (12)	0.0112 (12)	0.0028 (10)
C13	0.077 (2)	0.0360 (14)	0.0287 (13)	−0.0178 (14)	0.0109 (13)	−0.0021 (11)
C14	0.0398 (13)	0.0321 (12)	0.0170 (10)	−0.0071 (10)	0.0035 (9)	0.0009 (9)
C15	0.0420 (14)	0.0403 (13)	0.0245 (11)	0.0067 (11)	0.0034 (10)	0.0088 (10)
C16	0.0364 (13)	0.0419 (13)	0.0247 (12)	0.0074 (11)	0.0077 (10)	0.0061 (10)
C17	0.0430 (14)	0.0360 (13)	0.0233 (11)	0.0010 (11)	0.0103 (10)	−0.0015 (9)
C18	0.0440 (14)	0.0298 (11)	0.0235 (11)	0.0026 (10)	0.0070 (10)	0.0036 (9)
C19	0.0293 (11)	0.0268 (10)	0.0197 (10)	−0.0062 (9)	0.0028 (9)	0.0005 (8)

Geometric parameters (Å, º)

Cd1—N1	2.2346 (18)	C6—C7	1.394 (3)
Cd1—O2	2.2571 (17)	C6—H6	0.9300
Cd1—O3^i	2.2826 (15)	C7—C8	1.512 (3)
Cd1—O3	2.3296 (16)	C8—C9	1.511 (3)
Cd1—O1^ii	2.4093 (16)	C8—H8A	0.9700
Cd1—O1	2.5875 (17)	C8—H8B	0.9700
O1—C1	1.269 (3)	C9—O3^ii	1.285 (3)
O1—Cd1^ii	2.4093 (16)	C10—C11	1.480 (3)
O2—C1	1.253 (3)	C10—H10A	0.9600
O3—C9^ii	1.285 (3)	C10—H10B	0.9600
O3—Cd1^i	2.2826 (15)	C10—H10C	0.9600
O4—C9	1.227 (3)	C12—C13	1.347 (3)
N1—C11	1.324 (3)	C12—H12	0.9300
N1—C12	1.376 (3)	C13—H13	0.9300
N2—C11	1.351 (3)	C14—C17	1.375 (3)
N2—C13	1.384 (3)	C14—C15	1.377 (3)
N2—C14	1.439 (3)	C15—C16	1.380 (3)
C1—C2	1.502 (3)	C15—H15	0.9300
C2—C3	1.395 (3)	C16—C19	1.391 (3)
C2—C7	1.402 (3)	C16—H16	0.9300
C3—C4	1.375 (4)	C17—C18	1.387 (3)
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.377 (4)	C18—C19	1.395 (3)
C4—H4	0.9300	C18—H18	0.9300
C5—C6	1.376 (4)	C19—C19^iii	1.492 (4)
C5—H5	0.9300
N1—Cd1—O2	136.28 (7)	C6—C7—C2	117.7 (2)
N1—Cd1—O3^i	105.93 (7)	C6—C7—C8	116.7 (2)
O2—Cd1—O3^i	89.95 (6)	C2—C7—C8	125.5 (2)
N1—Cd1—O3	103.51 (7)	C9—C8—C7	113.91 (19)
O2—Cd1—O3	120.20 (7)	C9—C8—H8A	108.8
O3^i—Cd1—O3	70.15 (6)	C7—C8—H8A	108.8
N1—Cd1—O1^ii	96.61 (6)	C9—C8—H8B	108.8
O2—Cd1—O1^ii	90.13 (6)	C7—C8—H8B	108.8
O3^i—Cd1—O1^ii	146.95 (6)	H8A—C8—H8B	107.7
O3—Cd1—O1^ii	81.41 (6)	O4—C9—O3^ii	121.3 (2)
N1—Cd1—O1	88.45 (6)	O4—C9—C8	120.6 (2)
O2—Cd1—O1	53.53 (6)	O3^ii—C9—C8	118.1 (2)
O3^i—Cd1—O1	133.00 (5)	C11—C10—H10A	109.5
O3—Cd1—O1	150.34 (6)	C11—C10—H10B	109.5
O1^ii—Cd1—O1	70.19 (6)	H10A—C10—H10B	109.5
C1—O1—Cd1^ii	109.46 (14)	C11—C10—H10C	109.5
C1—O1—Cd1	84.41 (13)	H10A—C10—H10C	109.5
Cd1^ii—O1—Cd1	109.80 (6)	H10B—C10—H10C	109.5
C1—O2—Cd1	100.19 (15)	N1—C11—N2	110.0 (2)
C9^ii—O3—Cd1^i	104.42 (14)	N1—C11—C10	125.8 (2)
C9^ii—O3—Cd1	143.07 (15)	N2—C11—C10	124.2 (2)
Cd1^i—O3—Cd1	109.85 (6)	C13—C12—N1	109.8 (2)
C11—N1—C12	106.54 (19)	C13—C12—H12	125.1
C11—N1—Cd1	127.88 (15)	N1—C12—H12	125.1
C12—N1—Cd1	125.53 (15)	C12—C13—N2	105.8 (2)
C11—N2—C13	107.79 (19)	C12—C13—H13	127.1
C11—N2—C14	127.3 (2)	N2—C13—H13	127.1
C13—N2—C14	124.7 (2)	C17—C14—C15	120.2 (2)
O2—C1—O1	121.6 (2)	C17—C14—N2	121.1 (2)
O2—C1—C2	118.1 (2)	C15—C14—N2	118.6 (2)
O1—C1—C2	120.3 (2)	C14—C15—C16	119.9 (2)
C3—C2—C7	119.7 (2)	C14—C15—H15	120.1
C3—C2—C1	116.4 (2)	C16—C15—H15	120.1
C7—C2—C1	123.9 (2)	C15—C16—C19	121.4 (2)
C4—C3—C2	121.2 (2)	C15—C16—H16	119.3
C4—C3—H3	119.4	C19—C16—H16	119.3
C2—C3—H3	119.4	C14—C17—C18	119.7 (2)
C3—C4—C5	119.4 (2)	C14—C17—H17	120.2
C3—C4—H4	120.3	C18—C17—H17	120.2
C5—C4—H4	120.3	C17—C18—C19	121.2 (2)
C6—C5—C4	120.0 (2)	C17—C18—H18	119.4
C6—C5—H5	120.0	C19—C18—H18	119.4
C4—C5—H5	120.0	C16—C19—C18	117.5 (2)
C5—C6—C7	121.9 (2)	C16—C19—C19^iii	121.1 (3)
C5—C6—H6	119.0	C18—C19—C19^iii	121.3 (3)
C7—C6—H6	119.0
Cd1—O2—C1—O1	−6.1 (3)	Cd1—N1—C11—N2	177.50 (15)
Cd1—O2—C1—C2	174.45 (17)	C12—N1—C11—C10	178.9 (3)
Cd1^ii—O1—C1—O2	−103.8 (2)	Cd1—N1—C11—C10	−3.4 (4)
Cd1—O1—C1—O2	5.2 (2)	C13—N2—C11—N1	0.6 (3)
Cd1^ii—O1—C1—C2	75.6 (2)	C14—N2—C11—N1	176.0 (2)
Cd1—O1—C1—C2	−175.3 (2)	C13—N2—C11—C10	−178.5 (3)
O2—C1—C2—C3	19.0 (3)	C14—N2—C11—C10	−3.1 (4)
O1—C1—C2—C3	−160.5 (2)	C11—N1—C12—C13	−0.3 (3)
O2—C1—C2—C7	−158.3 (2)	Cd1—N1—C12—C13	−178.1 (2)
O1—C1—C2—C7	22.2 (3)	N1—C12—C13—N2	0.7 (3)
C7—C2—C3—C4	0.1 (4)	C11—N2—C13—C12	−0.8 (3)
C1—C2—C3—C4	−177.4 (2)	C14—N2—C13—C12	−176.3 (2)
C2—C3—C4—C5	1.9 (4)	C11—N2—C14—C17	71.8 (3)
C3—C4—C5—C6	−1.8 (4)	C13—N2—C14—C17	−113.6 (3)
C4—C5—C6—C7	−0.2 (4)	C11—N2—C14—C15	−110.4 (3)
C5—C6—C7—C2	2.1 (4)	C13—N2—C14—C15	64.3 (3)
C5—C6—C7—C8	179.4 (2)	C17—C14—C15—C16	3.4 (4)
C3—C2—C7—C6	−2.0 (3)	N2—C14—C15—C16	−174.5 (2)
C1—C2—C7—C6	175.2 (2)	C14—C15—C16—C19	−0.3 (4)
C3—C2—C7—C8	−179.1 (2)	C15—C14—C17—C18	−3.0 (4)
C1—C2—C7—C8	−1.8 (3)	N2—C14—C17—C18	174.8 (2)
C6—C7—C8—C9	84.1 (3)	C14—C17—C18—C19	−0.4 (4)
C2—C7—C8—C9	−98.8 (3)	C15—C16—C19—C18	−3.0 (4)
C7—C8—C9—O4	−124.7 (3)	C15—C16—C19—C19^iii	177.0 (3)
C7—C8—C9—O3^ii	55.3 (3)	C17—C18—C19—C16	3.3 (3)
C12—N1—C11—N2	−0.2 (3)	C17—C18—C19—C19^iii	−176.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1	0.97	2.27	2.882 (3)	121