Synthesis, crystal structure and photo­catalytic properties of a three-dimensional copper(II) metal–organic framework based on 1,3,5-tris­(2-methyl­imid­azol-1-yl)ben­zene

A three-dimensional metal–organic framework, namely, poly[[bis­(μ₃-ben­zene-1,3,5-tri­carboxyl­ato)bis­[μ₃-1,3,5-tris­(2-methyl­imid­azol-1-yl)ben­zene]­tricop­per(II)] hexa­hydrate], {[Cu₃(C₉H₃O₆)₂(C₁₈H₁₈N₆)₂]·6H₂O}_n or {[Cu(BTC)_2/3(TMIB)_2/3]·2H₂O}_n, (I) [TMIB is 1,3,5-tris­(2-methyl­imid­azol-1-yl)ben­zene and H₃BTC is ben­zene-1,3,5-tri­carb­oxy­lic acid], has been synthesized under solvothermal con­ditions and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction and thermogravimetric analysis (TGA). Com­pound (I) features an unusual three-dimensional (3,4)-connected 2-nodal net with {8³}₄{8⁶}₃ topology. Photocatalytic investigations indicate that (I) affords good photo­catalytic capabilities in the degradation of methyl­ene blue (MB). Furthermore, the possible photo­catalytic mechanism is discussed.

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: publCIF (Westrip, 2010).

Poly[[bis(µ₃-benzene-1,3,5-tricarboxylato)bis[µ₃-1,3,5-tris(2-methylimidazol-1-yl)benzene]tricopper(II)] hexahydrate]

Crystal data

[Cu3(C9H3O6)2(C18H18N6)2]	Mo Kα radiation, λ = 0.71073 Å
Mr = 1241.61	Cell parameters from 9940 reflections
Cubic, Ia3	θ = 3.2–25.6°
a = 22.27 (2) Å	µ = 1.22 mm^−1
V = 11047 (31) Å^3	T = 293 K
Z = 8	Block, blue
F(000) = 5064	0.21 × 0.20 × 0.19 mm
Dx = 1.493 Mg m^−3

Data collection

Bruker APEXII CCD diffractometer	1814 independent reflections
Radiation source: fine-focus sealed-tube	1426 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	Rint = 0.081
φ and ω scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −26→27
Tmin = 0.701, Tmax = 0.746	k = −27→24
48754 measured reflections	l = −24→27

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0012P)^2 + 67.658P] where P = (Fo^2 + 2Fc^2)/3
1814 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.49 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
C1	0.21828 (17)	0.69233 (18)	0.60539 (18)	0.0506 (10)
H1A	0.194212	0.719590	0.582247	0.076*
H1B	0.220536	0.706198	0.646141	0.076*
H1C	0.200425	0.653108	0.604526	0.076*
C2	0.28041 (15)	0.68935 (16)	0.57917 (15)	0.0384 (8)
C3	0.36015 (16)	0.66080 (18)	0.52897 (17)	0.0456 (9)
H3	0.385232	0.639217	0.503509	0.055*
C4	0.37621 (16)	0.71023 (18)	0.56096 (17)	0.0487 (10)
H4	0.413785	0.728449	0.561452	0.058*
C5	0.32433 (16)	0.77704 (16)	0.63512 (16)	0.0426 (9)
C6	0.27919 (17)	0.81988 (16)	0.63216 (16)	0.0448 (9)
H6	0.250764	0.818614	0.601596	0.054*
C7	0.16149 (16)	0.52119 (16)	0.54427 (18)	0.0443 (9)
C8	0.11011 (16)	0.47783 (16)	0.55324 (17)	0.0437 (9)
C9	0.10117 (17)	0.42975 (16)	0.51435 (17)	0.0467 (10)
H9	0.127576	0.423997	0.482513	0.056*
Cu1	0.250000	0.58440 (3)	0.500000	0.03621 (18)
N1	0.30016 (12)	0.64767 (13)	0.54043 (13)	0.0383 (7)
N2	0.32646 (13)	0.72801 (13)	0.59228 (13)	0.0425 (7)
O1	0.18678 (11)	0.52195 (11)	0.49277 (12)	0.0532 (7)
O2	0.17697 (13)	0.55489 (12)	0.58590 (13)	0.0614 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.046 (2)	0.049 (2)	0.056 (2)	−0.0017 (18)	0.0095 (19)	−0.0121 (19)
C2	0.0372 (19)	0.041 (2)	0.0376 (19)	0.0024 (16)	−0.0025 (16)	−0.0018 (16)
C3	0.0325 (19)	0.055 (2)	0.049 (2)	0.0048 (18)	0.0000 (17)	−0.0105 (19)
C4	0.0296 (19)	0.066 (3)	0.050 (2)	−0.0021 (18)	−0.0015 (17)	0.000 (2)
C5	0.045 (2)	0.045 (2)	0.038 (2)	−0.0003 (17)	−0.0014 (17)	−0.0063 (17)
C6	0.047 (2)	0.044 (2)	0.043 (2)	0.0067 (18)	−0.0095 (17)	−0.0045 (17)
C7	0.040 (2)	0.0340 (19)	0.059 (2)	−0.0054 (16)	0.0125 (19)	−0.0094 (18)
C8	0.041 (2)	0.039 (2)	0.051 (2)	−0.0129 (16)	0.0146 (17)	−0.0114 (17)
C9	0.053 (2)	0.042 (2)	0.045 (2)	−0.0138 (17)	0.0214 (18)	−0.0124 (17)
Cu1	0.0332 (3)	0.0343 (3)	0.0411 (3)	0.000	0.0090 (3)	0.000
N1	0.0309 (15)	0.0429 (17)	0.0410 (17)	0.0026 (13)	0.0006 (13)	−0.0042 (14)
N2	0.0380 (17)	0.0462 (18)	0.0434 (17)	0.0031 (14)	−0.0034 (14)	−0.0085 (14)
O1	0.0546 (16)	0.0465 (15)	0.0584 (17)	−0.0187 (12)	0.0229 (14)	−0.0115 (13)
O2	0.0611 (18)	0.0587 (18)	0.0644 (18)	−0.0275 (15)	0.0171 (15)	−0.0196 (15)

Geometric parameters (Å, º)

C1—C2	1.503 (5)	C5—N2	1.451 (4)
C1—H1A	0.9600	C6—H6	0.9300
C1—H1B	0.9600	C7—O2	1.242 (4)
C1—H1C	0.9600	C7—O1	1.278 (4)
C2—N1	1.341 (4)	C7—C8	1.510 (5)
C2—N2	1.371 (5)	C8—C9	1.392 (5)
C3—C4	1.359 (5)	C8—C9^ii	1.399 (5)
C3—N1	1.391 (5)	C9—H9	0.9300
C3—H3	0.9300	Cu1—O1^iii	1.986 (3)
C4—N2	1.368 (5)	Cu1—O1	1.986 (3)
C4—H4	0.9300	Cu1—N1	2.011 (3)
C5—C6	1.388 (5)	Cu1—N1^iii	2.011 (3)
C5—C6^i	1.395 (5)
C2—C1—H1A	109.5	O2—C7—C8	119.9 (3)
C2—C1—H1B	109.5	O1—C7—C8	117.5 (3)
H1A—C1—H1B	109.5	C9—C8—C9^ii	118.7 (3)
C2—C1—H1C	109.5	C9—C8—C7	121.2 (3)
H1A—C1—H1C	109.5	C9^ii—C8—C7	120.1 (3)
H1B—C1—H1C	109.5	C8—C9—C8^v	121.3 (3)
N1—C2—N2	109.0 (3)	C8—C9—H9	119.3
N1—C2—C1	125.6 (3)	C8^v—C9—H9	119.3
N2—C2—C1	125.3 (3)	O1^iii—Cu1—O1	91.07 (16)
C4—C3—N1	109.1 (3)	O1^iii—Cu1—N1	93.48 (11)
C4—C3—H3	125.5	O1—Cu1—N1	157.07 (11)
N1—C3—H3	125.5	O1^iii—Cu1—N1^iii	157.07 (11)
C3—C4—N2	106.8 (3)	O1—Cu1—N1^iii	93.47 (11)
C3—C4—H4	126.6	N1—Cu1—N1^iii	91.04 (16)
N2—C4—H4	126.6	C2—N1—C3	106.7 (3)
C6—C5—C6^i	120.9 (4)	C2—N1—Cu1	126.2 (2)
C6—C5—N2	120.7 (3)	C3—N1—Cu1	126.8 (2)
C6^i—C5—N2	118.4 (3)	C4—N2—C2	108.4 (3)
C5—C6—C5^iv	119.1 (4)	C4—N2—C5	125.4 (3)
C5—C6—H6	120.5	C2—N2—C5	126.0 (3)
C5^iv—C6—H6	120.5	C7—O1—Cu1	104.4 (2)
O2—C7—O1	122.7 (3)
N1—C3—C4—N2	−0.1 (4)	C4—C3—N1—Cu1	173.9 (2)
C6^i—C5—C6—C5^iv	−1.2 (8)	C3—C4—N2—C2	0.0 (4)
N2—C5—C6—C5^iv	177.2 (2)	C3—C4—N2—C5	176.1 (3)
O2—C7—C8—C9	−163.6 (4)	N1—C2—N2—C4	0.1 (4)
O1—C7—C8—C9	17.4 (6)	C1—C2—N2—C4	178.6 (3)
O2—C7—C8—C9^ii	16.6 (6)	N1—C2—N2—C5	−176.0 (3)
O1—C7—C8—C9^ii	−162.3 (4)	C1—C2—N2—C5	2.4 (6)
C9^ii—C8—C9—C8^v	0.4 (8)	C6—C5—N2—C4	131.7 (4)
C7—C8—C9—C8^v	−179.3 (3)	C6^i—C5—N2—C4	−49.8 (5)
N2—C2—N1—C3	−0.1 (4)	C6—C5—N2—C2	−52.8 (5)
C1—C2—N1—C3	−178.6 (3)	C6^i—C5—N2—C2	125.7 (4)
N2—C2—N1—Cu1	−173.9 (2)	O2—C7—O1—Cu1	0.6 (5)
C1—C2—N1—Cu1	7.6 (5)	C8—C7—O1—Cu1	179.5 (3)
C4—C3—N1—C2	0.1 (4)

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