A cadmium(II) coordination polymer with a fivefold inter­penetrating diamondoid three-dimensional framework: synthesis, crystal structure, luminescence and photo­catalytic properties

A novel three-dimensional (3D) Cd^II coordination polymer, namely, poly[[μ₂-4,4′-bis­(2-methyl­imidazol-1-yl)-[1,1′-biphen­yl]](μ₂-5-methyl­isophthalato)cadmium(II)], [Cd(C₉H₆O₄)(C₂₀H₁₈N₄)]_n or [Cd(MIP)(4,4′-BMIBP)]_n, (I), was synthesized by the hydro­thermal method using 5-methyl­isophthalic acid (H₂MIP), 4,4′-bis­(2-methyl­imidazol-1-yl)-[1,1′-biphen­yl] (4,4′-BMIBP) and Cd(NO₃)₂·6H₂O, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Compound (I) exhibits a novel fivefold inter­penetrating 3D diamondoid framework. Additionally, it shows fluorescence emission in the solid state and promising photo­catalytic activities for the degradation of methyl­ene blue (MB) in water at room tem­per­ature.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

Poly[[µ₂-4,4'-bis(2-methylimidazol-1-yl)-[1,1'-biphenyl]](µ₂-5-methylisophthalato)cadmium(II)]

Crystal data

[Cd(C9H6O4)(C20H18N4)]	Dx = 1.526 Mg m^−3
Mr = 604.93	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, P212121	Cell parameters from 9858 reflections
a = 14.438 (3) Å	θ = 2.8–26.1°
b = 8.555 (2) Å	µ = 0.87 mm^−1
c = 21.315 (4) Å	T = 293 K
V = 2632.8 (10) Å^3	Block, colorless
Z = 4	0.21 × 0.18 × 0.17 mm
F(000) = 1224

Data collection

Bruker APEXII CCD diffractometer	4412 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 26.0°, θmin = 2.8°
Tmin = 0.664, Tmax = 0.746	h = −17→16
36701 measured reflections	k = −10→10
4952 independent reflections	l = −26→26

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.028P)^2 + 0.9061P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.060	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.39 e Å^−3
4952 reflections	Δρmin = −0.39 e Å^−3
346 parameters	Absolute structure: Flack x determined using 1752 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.012 (8)

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	0.76997 (2)	0.85622 (3)	0.49328 (2)	0.04221 (10)
O3	0.3839 (2)	1.4463 (4)	0.50432 (16)	0.0609 (8)
O2	0.6831 (2)	0.9491 (4)	0.41304 (15)	0.0618 (9)
O4	0.3698 (2)	1.5905 (3)	0.42217 (14)	0.0590 (9)
N2	0.6548 (2)	0.4622 (4)	0.60115 (18)	0.0485 (9)
N3	0.6398 (3)	−0.4639 (4)	0.87442 (18)	0.0506 (9)
O1	0.6420 (2)	1.0429 (4)	0.50271 (17)	0.0669 (9)
C11	0.7264 (3)	0.5540 (5)	0.58515 (19)	0.0463 (10)
N1	0.6984 (3)	0.6654 (4)	0.54809 (19)	0.0587 (10)
C3	0.5196 (3)	1.2578 (4)	0.4450 (2)	0.0401 (9)
H3	0.5158	1.2490	0.4884	0.048*
C4	0.4676 (3)	1.3693 (5)	0.41426 (17)	0.0382 (9)
C8	0.4040 (3)	1.4760 (5)	0.4493 (2)	0.0405 (10)
N4	0.6642 (3)	−0.6708 (4)	0.93137 (19)	0.0581 (10)
C1	0.6373 (3)	1.0435 (5)	0.4452 (2)	0.0451 (10)
C2	0.5769 (3)	1.1596 (5)	0.41186 (18)	0.0404 (9)
C16	0.5983 (3)	0.1887 (5)	0.7286 (2)	0.0504 (11)
H16	0.5585	0.1833	0.7628	0.060*
C23	0.6525 (3)	−0.3319 (5)	0.83427 (18)	0.0439 (10)
C5	0.4729 (3)	1.3790 (5)	0.35004 (19)	0.0473 (10)
H5	0.4378	1.4539	0.3292	0.057*
C24	0.6471 (3)	−0.1867 (5)	0.8600 (2)	0.0462 (11)
H24	0.6414	−0.1745	0.9032	0.055*
C14	0.6557 (3)	0.3264 (4)	0.64043 (19)	0.0450 (10)
C27	0.6998 (3)	−0.5800 (5)	0.8892 (2)	0.0518 (12)
C7	0.5809 (3)	1.1716 (5)	0.3474 (2)	0.0487 (11)
H7	0.6194	1.1044	0.3251	0.058*
C25	0.6501 (3)	−0.0586 (5)	0.82140 (19)	0.0456 (10)
H25	0.6455	0.0405	0.8390	0.055*
C19	0.7127 (3)	0.2053 (5)	0.6267 (2)	0.0546 (12)
H19	0.7505	0.2096	0.5914	0.066*
C18	0.7145 (3)	0.0755 (5)	0.6653 (2)	0.0542 (12)
H18	0.7541	−0.0071	0.6561	0.065*
C17	0.6583 (3)	0.0675 (5)	0.71682 (19)	0.0444 (10)
C20	0.6595 (3)	−0.0721 (5)	0.75843 (19)	0.0433 (10)
C15	0.5963 (3)	0.3185 (5)	0.6900 (2)	0.0538 (12)
H15	0.5550	0.3996	0.6978	0.065*
C12	0.6062 (4)	0.6397 (8)	0.5385 (3)	0.093 (2)
H12	0.5682	0.7003	0.5130	0.112*
C29	0.5636 (4)	−0.4819 (7)	0.9116 (3)	0.0817 (18)
H29	0.5113	−0.4187	0.9126	0.098*
C6	0.5295 (3)	1.2800 (5)	0.3155 (2)	0.0557 (12)
C10	0.8216 (3)	0.5335 (7)	0.6075 (3)	0.0710 (17)
H10A	0.8534	0.4608	0.5808	0.107*
H10B	0.8207	0.4940	0.6496	0.107*
H10C	0.8531	0.6323	0.6067	0.107*
C21	0.6684 (4)	−0.2212 (5)	0.7336 (2)	0.0644 (14)
H21	0.6758	−0.2337	0.6906	0.077*
C13	0.5785 (4)	0.5157 (7)	0.5708 (3)	0.0820 (19)
H13	0.5190	0.4740	0.5724	0.098*
C28	0.5796 (4)	−0.6079 (7)	0.9459 (3)	0.089 (2)
H28	0.5390	−0.6481	0.9757	0.107*
C26	0.7925 (4)	−0.5929 (8)	0.8617 (3)	0.105 (3)
H26A	0.8290	−0.6644	0.8861	0.157*
H26B	0.8216	−0.4920	0.8616	0.157*
H26C	0.7876	−0.6308	0.8194	0.157*
C22	0.6664 (4)	−0.3504 (6)	0.7715 (2)	0.0639 (13)
H22	0.6745	−0.4496	0.7546	0.077*
C9	0.5346 (5)	1.2942 (8)	0.2456 (3)	0.099 (2)
H9A	0.5414	1.4022	0.2342	0.149*
H9B	0.4788	1.2536	0.2273	0.149*
H9C	0.5868	1.2360	0.2303	0.149*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.04896 (17)	0.02868 (14)	0.04900 (16)	−0.00104 (12)	−0.00378 (13)	0.00034 (13)
O3	0.0620 (18)	0.0681 (19)	0.053 (2)	0.0265 (15)	0.0113 (17)	0.0081 (19)
O2	0.072 (2)	0.0473 (19)	0.066 (2)	0.0248 (18)	−0.0011 (17)	−0.0002 (16)
O4	0.079 (2)	0.0407 (18)	0.0573 (18)	0.0243 (16)	0.0026 (16)	0.0051 (14)
N2	0.044 (2)	0.0338 (19)	0.068 (2)	−0.0037 (17)	−0.0050 (18)	0.0072 (17)
N3	0.052 (2)	0.038 (2)	0.061 (2)	0.0016 (18)	0.0073 (19)	0.0085 (18)
O1	0.076 (2)	0.066 (2)	0.059 (2)	0.0308 (16)	−0.0053 (19)	0.008 (2)
C11	0.045 (2)	0.034 (2)	0.060 (2)	−0.001 (2)	−0.007 (2)	0.0045 (19)
N1	0.048 (2)	0.045 (2)	0.083 (3)	−0.0003 (18)	−0.0079 (19)	0.024 (2)
C3	0.040 (2)	0.037 (2)	0.044 (2)	0.0007 (19)	0.0027 (18)	0.0027 (18)
C4	0.037 (2)	0.032 (2)	0.046 (2)	0.0001 (19)	−0.0014 (16)	0.0003 (19)
C8	0.035 (2)	0.038 (2)	0.049 (3)	−0.0043 (19)	−0.0053 (19)	−0.0033 (19)
N4	0.055 (2)	0.044 (2)	0.075 (3)	0.0002 (19)	0.011 (2)	0.020 (2)
C1	0.038 (2)	0.035 (2)	0.062 (3)	−0.0015 (19)	0.001 (2)	0.002 (2)
C2	0.037 (2)	0.032 (2)	0.052 (2)	−0.003 (2)	0.0004 (17)	0.002 (2)
C16	0.051 (3)	0.038 (3)	0.062 (3)	0.002 (2)	0.009 (2)	0.0031 (19)
C23	0.049 (2)	0.035 (2)	0.047 (2)	0.001 (2)	0.0004 (18)	0.0072 (19)
C5	0.053 (2)	0.039 (2)	0.050 (2)	0.008 (2)	−0.0038 (19)	0.008 (2)
C24	0.056 (3)	0.043 (3)	0.040 (2)	0.004 (2)	0.003 (2)	0.0011 (18)
C14	0.052 (2)	0.029 (2)	0.054 (2)	−0.0046 (19)	−0.005 (2)	0.0051 (18)
C27	0.053 (3)	0.036 (2)	0.066 (3)	0.005 (2)	0.010 (2)	0.015 (2)
C7	0.050 (3)	0.041 (3)	0.055 (3)	0.009 (2)	0.003 (2)	−0.004 (2)
C25	0.057 (3)	0.031 (2)	0.049 (3)	0.001 (2)	0.000 (2)	−0.0063 (19)
C19	0.071 (3)	0.040 (2)	0.053 (2)	0.005 (2)	0.017 (3)	0.005 (2)
C18	0.065 (3)	0.035 (2)	0.063 (3)	0.012 (2)	0.019 (2)	0.0052 (19)
C17	0.053 (3)	0.033 (2)	0.048 (2)	−0.001 (2)	−0.001 (2)	−0.0009 (18)
C20	0.052 (2)	0.033 (2)	0.045 (2)	−0.001 (2)	0.001 (2)	−0.0013 (18)
C15	0.046 (3)	0.042 (3)	0.073 (3)	0.005 (2)	0.002 (2)	0.001 (2)
C12	0.053 (3)	0.084 (4)	0.142 (6)	0.005 (3)	−0.016 (3)	0.061 (4)
C29	0.054 (3)	0.075 (4)	0.116 (5)	0.014 (3)	0.025 (3)	0.035 (3)
C6	0.071 (3)	0.051 (3)	0.045 (3)	0.007 (3)	0.001 (2)	0.002 (2)
C10	0.055 (3)	0.057 (3)	0.100 (4)	−0.012 (3)	−0.018 (3)	0.024 (3)
C21	0.113 (4)	0.039 (2)	0.042 (2)	0.000 (3)	0.010 (3)	−0.003 (2)
C13	0.042 (3)	0.077 (4)	0.128 (5)	−0.008 (3)	−0.014 (3)	0.043 (4)
C28	0.064 (4)	0.082 (4)	0.121 (5)	0.011 (3)	0.031 (3)	0.054 (4)
C26	0.079 (4)	0.086 (5)	0.149 (6)	0.032 (3)	0.049 (4)	0.067 (4)
C22	0.104 (4)	0.028 (2)	0.059 (3)	0.003 (3)	0.002 (2)	−0.006 (2)
C9	0.146 (6)	0.102 (5)	0.049 (3)	0.047 (4)	0.012 (3)	0.007 (3)

Geometric parameters (Å, º)

Cd1—N1	2.258 (4)	C23—C22	1.361 (6)
Cd1—O2	2.265 (3)	C5—C6	1.388 (6)
Cd1—N4^i	2.272 (4)	C5—H5	0.9300
Cd1—O4^ii	2.352 (3)	C24—C25	1.371 (6)
Cd1—O3^ii	2.359 (3)	C24—H24	0.9300
Cd1—O1	2.450 (3)	C14—C19	1.355 (6)
Cd1—C1	2.699 (4)	C14—C15	1.362 (6)
Cd1—C8^ii	2.702 (4)	C27—C26	1.465 (7)
O3—C8	1.235 (5)	C7—C6	1.369 (6)
O3—Cd1^iii	2.359 (3)	C7—H7	0.9300
O2—C1	1.249 (5)	C25—C20	1.354 (6)
O4—C8	1.239 (5)	C25—H25	0.9300
O4—Cd1^iii	2.352 (3)	C19—C18	1.383 (6)
N2—C11	1.342 (6)	C19—H19	0.9300
N2—C13	1.357 (6)	C18—C17	1.367 (6)
N2—C14	1.431 (5)	C18—H18	0.9300
N3—C27	1.355 (6)	C17—C20	1.488 (6)
N3—C29	1.364 (6)	C20—C21	1.387 (6)
N3—C23	1.429 (5)	C15—H15	0.9300
O1—C1	1.228 (6)	C12—C13	1.327 (8)
C11—N1	1.301 (5)	C12—H12	0.9300
C11—C10	1.466 (6)	C29—C28	1.322 (8)
N1—C12	1.365 (6)	C29—H29	0.9300
C3—C2	1.375 (6)	C6—C9	1.497 (7)
C3—C4	1.379 (5)	C10—H10A	0.9600
C3—H3	0.9300	C10—H10B	0.9600
C4—C5	1.374 (5)	C10—H10C	0.9600
C4—C8	1.495 (6)	C21—C22	1.369 (6)
C8—Cd1^iii	2.702 (4)	C21—H21	0.9300
N4—C27	1.295 (5)	C13—H13	0.9300
N4—C28	1.371 (6)	C28—H28	0.9300
N4—Cd1^iv	2.272 (4)	C26—H26A	0.9600
C1—C2	1.501 (6)	C26—H26B	0.9600
C2—C7	1.378 (6)	C26—H26C	0.9600
C16—C17	1.375 (6)	C22—H22	0.9300
C16—C15	1.382 (6)	C9—H9A	0.9600
C16—H16	0.9300	C9—H9B	0.9600
C23—C24	1.360 (6)	C9—H9C	0.9600
N1—Cd1—O2	113.02 (13)	C22—C23—N3	121.0 (4)
N1—Cd1—N4^i	89.26 (16)	C4—C5—C6	121.7 (4)
O2—Cd1—N4^i	92.18 (13)	C4—C5—H5	119.2
N1—Cd1—O4^ii	91.37 (13)	C6—C5—H5	119.2
O2—Cd1—O4^ii	148.21 (12)	C23—C24—C25	119.1 (4)
N4^i—Cd1—O4^ii	108.90 (13)	C23—C24—H24	120.5
N1—Cd1—O3^ii	145.67 (13)	C25—C24—H24	120.5
O2—Cd1—O3^ii	98.71 (12)	C19—C14—C15	120.8 (4)
N4^i—Cd1—O3^ii	102.76 (13)	C19—C14—N2	119.9 (4)
O4^ii—Cd1—O3^ii	54.35 (11)	C15—C14—N2	119.2 (4)
N1—Cd1—O1	94.81 (13)	N4—C27—N3	110.3 (4)
O2—Cd1—O1	54.25 (11)	N4—C27—C26	126.5 (4)
N4^i—Cd1—O1	144.91 (13)	N3—C27—C26	123.1 (4)
O4^ii—Cd1—O1	105.83 (12)	C6—C7—C2	121.5 (4)
O3^ii—Cd1—O1	93.28 (12)	C6—C7—H7	119.2
N1—Cd1—C1	107.51 (13)	C2—C7—H7	119.2
O2—Cd1—C1	27.39 (12)	C20—C25—C24	122.0 (4)
N4^i—Cd1—C1	119.39 (14)	C20—C25—H25	119.0
O4^ii—Cd1—C1	127.65 (12)	C24—C25—H25	119.0
O3^ii—Cd1—C1	94.48 (12)	C14—C19—C18	119.8 (4)
O1—Cd1—C1	27.04 (12)	C14—C19—H19	120.1
N1—Cd1—C8^ii	118.50 (14)	C18—C19—H19	120.1
O2—Cd1—C8^ii	123.53 (13)	C17—C18—C19	120.5 (4)
N4^i—Cd1—C8^ii	109.54 (12)	C17—C18—H18	119.8
O4^ii—Cd1—C8^ii	27.28 (11)	C19—C18—H18	119.8
O3^ii—Cd1—C8^ii	27.17 (12)	C18—C17—C16	118.9 (4)
O1—Cd1—C8^ii	99.00 (12)	C18—C17—C20	120.8 (4)
C1—Cd1—C8^ii	111.41 (13)	C16—C17—C20	120.3 (4)
C8—O3—Cd1^iii	92.1 (3)	C25—C20—C21	117.7 (4)
C1—O2—Cd1	96.1 (3)	C25—C20—C17	121.4 (4)
C8—O4—Cd1^iii	92.3 (3)	C21—C20—C17	120.8 (4)
C11—N2—C13	107.9 (4)	C14—C15—C16	119.3 (4)
C11—N2—C14	128.1 (4)	C14—C15—H15	120.4
C13—N2—C14	124.0 (4)	C16—C15—H15	120.4
C27—N3—C29	107.3 (4)	C13—C12—N1	110.2 (5)
C27—N3—C23	129.5 (4)	C13—C12—H12	124.9
C29—N3—C23	122.7 (4)	N1—C12—H12	124.9
C1—O1—Cd1	87.8 (3)	C28—C29—N3	105.8 (5)
N1—C11—N2	110.1 (4)	C28—C29—H29	127.1
N1—C11—C10	125.2 (4)	N3—C29—H29	127.1
N2—C11—C10	124.7 (4)	C7—C6—C5	117.9 (4)
C11—N1—C12	106.0 (4)	C7—C6—C9	121.5 (4)
C11—N1—Cd1	134.5 (3)	C5—C6—C9	120.5 (4)
C12—N1—Cd1	119.0 (3)	C11—C10—H10A	109.5
C2—C3—C4	120.4 (4)	C11—C10—H10B	109.5
C2—C3—H3	119.8	H10A—C10—H10B	109.5
C4—C3—H3	119.8	C11—C10—H10C	109.5
C5—C4—C3	119.0 (4)	H10A—C10—H10C	109.5
C5—C4—C8	119.7 (4)	H10B—C10—H10C	109.5
C3—C4—C8	121.3 (4)	C22—C21—C20	121.0 (4)
O3—C8—O4	120.8 (4)	C22—C21—H21	119.5
O3—C8—C4	119.5 (4)	C20—C21—H21	119.5
O4—C8—C4	119.6 (4)	C12—C13—N2	105.8 (4)
O3—C8—Cd1^iii	60.7 (2)	C12—C13—H13	127.1
O4—C8—Cd1^iii	60.4 (2)	N2—C13—H13	127.1
C4—C8—Cd1^iii	172.1 (3)	C29—C28—N4	110.5 (5)
C27—N4—C28	106.0 (4)	C29—C28—H28	124.8
C27—N4—Cd1^iv	131.0 (3)	N4—C28—H28	124.8
C28—N4—Cd1^iv	121.1 (3)	C27—C26—H26A	109.5
O1—C1—O2	121.1 (4)	C27—C26—H26B	109.5
O1—C1—C2	120.5 (4)	H26A—C26—H26B	109.5
O2—C1—C2	118.4 (4)	C27—C26—H26C	109.5
O1—C1—Cd1	65.1 (2)	H26A—C26—H26C	109.5
O2—C1—Cd1	56.6 (2)	H26B—C26—H26C	109.5
C2—C1—Cd1	170.0 (3)	C23—C22—C21	119.3 (4)
C3—C2—C7	119.5 (4)	C23—C22—H22	120.4
C3—C2—C1	120.7 (4)	C21—C22—H22	120.4
C7—C2—C1	119.8 (4)	C6—C9—H9A	109.5
C17—C16—C15	120.7 (4)	C6—C9—H9B	109.5
C17—C16—H16	119.7	H9A—C9—H9B	109.5
C15—C16—H16	119.7	C6—C9—H9C	109.5
C24—C23—C22	120.7 (4)	H9A—C9—H9C	109.5
C24—C23—N3	118.2 (4)	H9B—C9—H9C	109.5

Symmetry codes: (i) −x+3/2, −y, z−1/2; (ii) x+1/2, −y+5/2, −z+1; (iii) x−1/2, −y+5/2, −z+1; (iv) −x+3/2, −y, z+1/2.