Buy article online - an online subscription or single-article purchase is required to access this article.
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.
Supporting information
CCDC reference: 2149877
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(µ
3-benzene-1,3,5-tricarboxylato)bis[µ
3-1,3,5-tris(2-methylimidazol-1-yl)benzene]tricopper(II)] hexahydrate]
top
Crystal data top
[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) Å3 | 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 top
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 top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0012P)2 + 67.658P] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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—C9ii | 1.399 (5) |
C3—N1 | 1.391 (5) | C9—H9 | 0.9300 |
C3—H3 | 0.9300 | Cu1—O1iii | 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—N1iii | 2.011 (3) |
C5—C6i | 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—C9ii | 118.7 (3) |
C2—C1—H1C | 109.5 | C9—C8—C7 | 121.2 (3) |
H1A—C1—H1C | 109.5 | C9ii—C8—C7 | 120.1 (3) |
H1B—C1—H1C | 109.5 | C8—C9—C8v | 121.3 (3) |
N1—C2—N2 | 109.0 (3) | C8—C9—H9 | 119.3 |
N1—C2—C1 | 125.6 (3) | C8v—C9—H9 | 119.3 |
N2—C2—C1 | 125.3 (3) | O1iii—Cu1—O1 | 91.07 (16) |
C4—C3—N1 | 109.1 (3) | O1iii—Cu1—N1 | 93.48 (11) |
C4—C3—H3 | 125.5 | O1—Cu1—N1 | 157.07 (11) |
N1—C3—H3 | 125.5 | O1iii—Cu1—N1iii | 157.07 (11) |
C3—C4—N2 | 106.8 (3) | O1—Cu1—N1iii | 93.47 (11) |
C3—C4—H4 | 126.6 | N1—Cu1—N1iii | 91.04 (16) |
N2—C4—H4 | 126.6 | C2—N1—C3 | 106.7 (3) |
C6—C5—C6i | 120.9 (4) | C2—N1—Cu1 | 126.2 (2) |
C6—C5—N2 | 120.7 (3) | C3—N1—Cu1 | 126.8 (2) |
C6i—C5—N2 | 118.4 (3) | C4—N2—C2 | 108.4 (3) |
C5—C6—C5iv | 119.1 (4) | C4—N2—C5 | 125.4 (3) |
C5—C6—H6 | 120.5 | C2—N2—C5 | 126.0 (3) |
C5iv—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) |
C6i—C5—C6—C5iv | −1.2 (8) | C3—C4—N2—C2 | 0.0 (4) |
N2—C5—C6—C5iv | 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—C9ii | 16.6 (6) | N1—C2—N2—C5 | −176.0 (3) |
O1—C7—C8—C9ii | −162.3 (4) | C1—C2—N2—C5 | 2.4 (6) |
C9ii—C8—C9—C8v | 0.4 (8) | C6—C5—N2—C4 | 131.7 (4) |
C7—C8—C9—C8v | −179.3 (3) | C6i—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) | C6i—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. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.