A novel hydrolytic stable CoII–organic framework, namely poly[[bis(2-amino-4-sulfonatobenzoato-κO1)tetraaquatris{μ-1,4-bis[(imidazol-1-yl)methyl]benzene-κ2N3:N3′}dicobalt(II)] tetrahydrate], {[Co(C7H5NO5S)(C14H14N4)1.5(H2O)2]·2H2O}n, (1), based on multifunctional 2-amino-5-sulfobenzoic acid (H2asba) and the auxiliary flexible ligand 1,4-bis[(imidazol-1-yl)methyl]benzene (bix), was prepared using the solution evaporation method. The purity of (1) was confirmed by elemental analysis and powder X-ray diffraction (PXRD) analysis. Complex (1) shows a novel 1D→2D interpenetrating network, which is further extended into a 3D supramolecular framework with channels occupied by the lattice water molecules. The 2-amino-4-sulfonatobenzoate (asba2−) ligand adopts a monodentate coordination mode. The bix ligands exhibit gauche–gauche (GG) and trans–trans (TT) conformations. A detailed analysis of the solid-state diffuse-reflectance UV–Vis spectrum reveals that an indirect band gap exists in the complex. The band structure, the total density of states (TDOS) and the partial density of states (PDOS) were calculated using the CASTEP program. The calculated band gap (Eg) matches well with the experimental one. The complex exhibits a reversible dehydration–rehydration behaviour. Interestingly, gas sorption experiments demonstrate that the new fully anhydrous compound obtained by activating complex (1) at 400 K shows selective adsorption of CO2 over N2. Complex (1) retains excellent framework stability in a variety of solvents and manifests distinct solvent-dependent fluorescence properties. Moreover, the complex shows multiresponsive fluorescence sensing for some nitroaromatics in aqueous medium.
Supporting information
CCDC reference: 1482482
Data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXL2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: Mercury (Macrae et al., 2008).
Poly[[bis(2-amino-4-sulfonatobenzoato-
κO1)tetraaquatris{µ-1,4-bis[(imidazol-1-yl)methyl]benzene-
κ2N3:
N3'}dicobalt(II)] tetrahydrate]
top
Crystal data top
[Co(C7H5NO5S)(C14H14N4)1.5(H2O)2]·2H2O | F(000) = 1464 |
Mr = 703.62 | Dx = 1.499 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8248 (10) Å | Cell parameters from 9911 reflections |
b = 21.331 (2) Å | θ = 2.4–27.5° |
c = 13.5460 (15) Å | µ = 0.68 mm−1 |
β = 94.595 (3)° | T = 296 K |
V = 3117.8 (5) Å3 | Block, purple |
Z = 4 | 0.25 × 0.2 × 0.18 mm |
Data collection top
Bruker SMART CCD area detector diffractometer | 5163 reflections with I > 2σ(I) |
phi and ω scans | Rint = 0.048 |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2008) | θmax = 27.6°, θmin = 1.8° |
Tmin = 0.849, Tmax = 0.930 | h = −14→13 |
47170 measured reflections | k = −21→27 |
7197 independent reflections | l = −17→17 |
Refinement top
Refinement on F2 | 12 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0388P)2 + 1.5321P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
7197 reflections | Δρmax = 0.43 e Å−3 |
415 parameters | Δρmin = −0.24 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 | 0.55205 (19) | 0.73516 (10) | 0.11040 (15) | 0.0303 (5) | |
C2 | 0.48663 (18) | 0.68925 (9) | 0.05218 (15) | 0.0280 (5) | |
C3 | 0.54735 (18) | 0.65821 (10) | −0.02082 (15) | 0.0296 (5) | |
H3 | 0.504878 | 0.627755 | −0.059151 | 0.036* | |
C4 | 0.66839 (18) | 0.67152 (10) | −0.03753 (15) | 0.0290 (5) | |
C5 | 0.73010 (19) | 0.71917 (10) | 0.01588 (16) | 0.0340 (5) | |
H5 | 0.810556 | 0.729763 | 0.002905 | 0.041* | |
C6 | 0.67307 (19) | 0.75057 (11) | 0.08742 (17) | 0.0361 (5) | |
H6 | 0.715080 | 0.782884 | 0.121792 | 0.043* | |
C7 | 0.35682 (19) | 0.66993 (10) | 0.06816 (16) | 0.0318 (5) | |
C8 | 0.0135 (2) | 0.80637 (11) | 0.16561 (17) | 0.0382 (5) | |
H8 | −0.053346 | 0.788012 | 0.129082 | 0.046* | |
C9 | 0.1331 (2) | 0.87657 (11) | 0.23801 (18) | 0.0425 (6) | |
H9 | 0.166218 | 0.914533 | 0.261220 | 0.051* | |
C10 | 0.1840 (2) | 0.81947 (10) | 0.25198 (17) | 0.0373 (5) | |
H10 | 0.259307 | 0.811459 | 0.287779 | 0.045* | |
C11 | −0.0705 (2) | 0.91532 (12) | 0.1536 (2) | 0.0477 (6) | |
H11A | −0.087600 | 0.939793 | 0.211264 | 0.057* | |
H11B | −0.146670 | 0.894431 | 0.129579 | 0.057* | |
C12 | −0.03121 (19) | 0.95894 (10) | 0.07418 (16) | 0.0329 (5) | |
C13 | 0.0063 (2) | 0.93627 (10) | −0.01424 (17) | 0.0364 (5) | |
H13 | 0.010981 | 0.893235 | −0.024236 | 0.044* | |
C14 | −0.03677 (19) | 1.02317 (10) | 0.08777 (16) | 0.0353 (5) | |
H14 | −0.061297 | 1.039123 | 0.147038 | 0.042* | |
C15 | 0.3156 (2) | 0.63290 (10) | 0.35967 (16) | 0.0370 (5) | |
H15 | 0.351747 | 0.607246 | 0.314512 | 0.044* | |
C16 | 0.2797 (2) | 0.67932 (10) | 0.49662 (16) | 0.0378 (5) | |
H16 | 0.284282 | 0.692198 | 0.562405 | 0.045* | |
C17 | 0.1961 (2) | 0.69774 (10) | 0.42368 (16) | 0.0364 (5) | |
H17 | 0.132499 | 0.726248 | 0.430993 | 0.044* | |
C18 | 0.4639 (2) | 0.60589 (11) | 0.50453 (17) | 0.0395 (5) | |
H18A | 0.517981 | 0.636768 | 0.538129 | 0.047* | |
H18B | 0.509920 | 0.585465 | 0.455037 | 0.047* | |
C19 | 0.42871 (19) | 0.55762 (10) | 0.57882 (16) | 0.0319 (5) | |
C20 | 0.3270 (2) | 0.51942 (11) | 0.56079 (17) | 0.0405 (6) | |
H20 | 0.275689 | 0.524812 | 0.502998 | 0.049* | |
C21 | 0.29972 (19) | 0.47301 (11) | 0.62737 (18) | 0.0396 (6) | |
H21 | 0.230539 | 0.447678 | 0.613712 | 0.048* | |
C22 | 0.37388 (19) | 0.46413 (10) | 0.71323 (16) | 0.0310 (5) | |
C23 | 0.4757 (2) | 0.50303 (11) | 0.73165 (17) | 0.0419 (6) | |
H23 | 0.526784 | 0.497808 | 0.789586 | 0.050* | |
C24 | 0.5025 (2) | 0.54926 (11) | 0.66578 (17) | 0.0415 (6) | |
H24 | 0.570933 | 0.575056 | 0.679938 | 0.050* | |
C25 | −0.1335 (2) | 0.61945 (10) | 0.19766 (17) | 0.0361 (5) | |
H25 | −0.116281 | 0.589298 | 0.151109 | 0.043* | |
C26 | −0.2320 (2) | 0.67400 (11) | 0.30109 (18) | 0.0422 (6) | |
H26 | −0.293099 | 0.689085 | 0.339401 | 0.051* | |
C27 | −0.1165 (2) | 0.69655 (11) | 0.29819 (17) | 0.0384 (5) | |
H27 | −0.084014 | 0.730402 | 0.334957 | 0.046* | |
C28 | 0.3519 (2) | 0.41377 (11) | 0.78747 (18) | 0.0418 (6) | |
H28A | 0.424028 | 0.386638 | 0.794030 | 0.050* | |
H28B | 0.344183 | 0.433342 | 0.851314 | 0.050* | |
Co1 | 0.13043 (2) | 0.67662 (2) | 0.19342 (2) | 0.02851 (9) | |
N1 | 0.10881 (16) | 0.77464 (8) | 0.20574 (13) | 0.0324 (4) | |
N2 | 0.02332 (17) | 0.86780 (8) | 0.18304 (14) | 0.0370 (4) | |
N3 | 0.21837 (16) | 0.66843 (8) | 0.33721 (13) | 0.0328 (4) | |
N4 | 0.35656 (16) | 0.63793 (8) | 0.45495 (13) | 0.0328 (4) | |
N5 | −0.05354 (16) | 0.66210 (8) | 0.23279 (14) | 0.0348 (4) | |
N6 | −0.24231 (16) | 0.62477 (8) | 0.23702 (14) | 0.0357 (4) | |
N7 | 0.50401 (17) | 0.76515 (9) | 0.18705 (14) | 0.0456 (5) | |
H7A | 0.547282 | 0.792868 | 0.220417 | 0.055* | |
H7B | 0.430322 | 0.756408 | 0.202225 | 0.055* | |
O1 | 0.30963 (13) | 0.69040 (7) | 0.14428 (11) | 0.0377 (4) | |
O2 | 0.30064 (15) | 0.63448 (8) | 0.00598 (14) | 0.0543 (5) | |
O3 | 0.69991 (16) | 0.56416 (8) | −0.12086 (13) | 0.0515 (4) | |
O4 | 0.71524 (16) | 0.65599 (8) | −0.22058 (12) | 0.0509 (4) | |
O5 | 0.87662 (14) | 0.63194 (9) | −0.09371 (14) | 0.0583 (5) | |
O1W | 0.16273 (15) | 0.57782 (8) | 0.17163 (13) | 0.0493 (4) | |
H1WA | 0.107338 | 0.550232 | 0.159124 | 0.074* | |
H1WB | 0.214761 | 0.576771 | 0.128631 | 0.074* | |
O2W | 0.06616 (14) | 0.67859 (8) | 0.03544 (11) | 0.0429 (4) | |
H2WB | 0.002639 | 0.662495 | 0.003686 | 0.064* | |
H2WA | 0.130456 | 0.663475 | 0.012329 | 0.064* | |
O3W | 0.24633 (19) | 0.98955 (9) | 0.45318 (15) | 0.0716 (6) | |
H3WB | 0.271798 | 0.951632 | 0.464202 | 0.107* | |
H3WA | 0.274941 | 1.011154 | 0.504285 | 0.107* | |
O4W | 0.00112 (18) | 0.98599 (8) | 0.37977 (16) | 0.0661 (5) | |
H4WB | −0.041126 | 0.955465 | 0.399566 | 0.099* | |
H4WA | 0.072292 | 0.985644 | 0.412003 | 0.099* | |
S1 | 0.74575 (5) | 0.62794 (3) | −0.12506 (4) | 0.03206 (13) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0277 (11) | 0.0332 (12) | 0.0302 (11) | 0.0015 (9) | 0.0020 (9) | −0.0001 (9) |
C2 | 0.0248 (10) | 0.0314 (11) | 0.0277 (11) | −0.0017 (8) | 0.0013 (8) | 0.0031 (9) |
C3 | 0.0246 (10) | 0.0335 (11) | 0.0301 (11) | −0.0008 (9) | −0.0016 (9) | −0.0006 (9) |
C4 | 0.0264 (10) | 0.0348 (12) | 0.0258 (11) | 0.0010 (9) | 0.0026 (8) | 0.0013 (9) |
C5 | 0.0231 (10) | 0.0410 (13) | 0.0380 (12) | −0.0034 (9) | 0.0034 (9) | −0.0005 (10) |
C6 | 0.0275 (11) | 0.0388 (12) | 0.0419 (13) | −0.0061 (9) | 0.0025 (9) | −0.0084 (10) |
C7 | 0.0261 (11) | 0.0341 (12) | 0.0352 (12) | 0.0002 (9) | 0.0020 (9) | 0.0019 (10) |
C8 | 0.0344 (12) | 0.0371 (13) | 0.0423 (14) | −0.0056 (10) | −0.0022 (10) | 0.0085 (10) |
C9 | 0.0475 (14) | 0.0309 (13) | 0.0487 (15) | −0.0027 (10) | 0.0010 (12) | −0.0014 (11) |
C10 | 0.0347 (12) | 0.0377 (13) | 0.0387 (13) | 0.0001 (10) | −0.0011 (10) | 0.0029 (10) |
C11 | 0.0422 (14) | 0.0455 (14) | 0.0570 (16) | 0.0124 (11) | 0.0133 (12) | 0.0213 (12) |
C12 | 0.0277 (11) | 0.0314 (12) | 0.0392 (13) | 0.0057 (9) | 0.0000 (9) | 0.0099 (10) |
C13 | 0.0386 (12) | 0.0244 (11) | 0.0459 (14) | 0.0037 (9) | 0.0022 (10) | 0.0011 (10) |
C14 | 0.0350 (12) | 0.0387 (13) | 0.0319 (12) | 0.0060 (10) | 0.0013 (9) | −0.0007 (10) |
C15 | 0.0490 (14) | 0.0353 (12) | 0.0277 (12) | 0.0089 (10) | 0.0093 (10) | −0.0004 (10) |
C16 | 0.0490 (14) | 0.0376 (13) | 0.0275 (12) | 0.0034 (11) | 0.0069 (10) | −0.0035 (10) |
C17 | 0.0427 (13) | 0.0331 (12) | 0.0344 (13) | 0.0067 (10) | 0.0095 (10) | −0.0020 (10) |
C18 | 0.0359 (12) | 0.0403 (13) | 0.0417 (13) | 0.0028 (10) | −0.0008 (10) | 0.0096 (11) |
C19 | 0.0303 (11) | 0.0305 (11) | 0.0343 (12) | 0.0010 (9) | −0.0002 (9) | 0.0046 (9) |
C20 | 0.0307 (12) | 0.0450 (14) | 0.0434 (14) | −0.0015 (10) | −0.0123 (10) | 0.0107 (11) |
C21 | 0.0239 (11) | 0.0401 (13) | 0.0533 (15) | −0.0078 (10) | −0.0068 (10) | 0.0075 (11) |
C22 | 0.0265 (11) | 0.0328 (12) | 0.0337 (12) | 0.0006 (9) | 0.0032 (9) | 0.0035 (9) |
C23 | 0.0439 (14) | 0.0453 (14) | 0.0339 (13) | −0.0105 (11) | −0.0131 (10) | 0.0080 (11) |
C24 | 0.0403 (13) | 0.0404 (13) | 0.0419 (14) | −0.0153 (11) | −0.0089 (11) | 0.0042 (11) |
C25 | 0.0375 (13) | 0.0307 (12) | 0.0418 (13) | 0.0006 (10) | 0.0130 (10) | 0.0011 (10) |
C26 | 0.0414 (13) | 0.0427 (14) | 0.0448 (14) | 0.0027 (11) | 0.0182 (11) | −0.0027 (11) |
C27 | 0.0417 (14) | 0.0339 (12) | 0.0411 (13) | −0.0033 (10) | 0.0125 (11) | −0.0047 (10) |
C28 | 0.0360 (13) | 0.0462 (14) | 0.0427 (14) | −0.0066 (10) | 0.0013 (10) | 0.0121 (11) |
Co1 | 0.02796 (16) | 0.02889 (16) | 0.02914 (16) | −0.00229 (12) | 0.00506 (11) | 0.00235 (12) |
N1 | 0.0335 (10) | 0.0298 (10) | 0.0337 (10) | −0.0019 (8) | 0.0013 (8) | 0.0067 (8) |
N2 | 0.0368 (11) | 0.0316 (10) | 0.0429 (11) | 0.0031 (8) | 0.0057 (9) | 0.0129 (8) |
N3 | 0.0397 (10) | 0.0328 (10) | 0.0263 (9) | 0.0067 (8) | 0.0058 (8) | 0.0026 (8) |
N4 | 0.0389 (10) | 0.0305 (10) | 0.0290 (10) | 0.0026 (8) | 0.0025 (8) | 0.0047 (8) |
N5 | 0.0333 (10) | 0.0322 (10) | 0.0403 (11) | −0.0011 (8) | 0.0121 (8) | 0.0012 (8) |
N6 | 0.0330 (10) | 0.0341 (10) | 0.0410 (11) | −0.0046 (8) | 0.0105 (8) | 0.0053 (9) |
N7 | 0.0333 (10) | 0.0582 (13) | 0.0463 (12) | −0.0101 (9) | 0.0100 (9) | −0.0223 (10) |
O1 | 0.0280 (8) | 0.0551 (10) | 0.0309 (8) | −0.0099 (7) | 0.0071 (6) | −0.0019 (7) |
O2 | 0.0339 (9) | 0.0630 (12) | 0.0675 (12) | −0.0162 (8) | 0.0131 (8) | −0.0316 (10) |
O3 | 0.0603 (11) | 0.0376 (10) | 0.0570 (11) | −0.0012 (8) | 0.0075 (9) | −0.0081 (8) |
O4 | 0.0574 (11) | 0.0639 (11) | 0.0324 (9) | 0.0134 (9) | 0.0095 (8) | 0.0045 (8) |
O5 | 0.0243 (8) | 0.0834 (14) | 0.0662 (12) | 0.0087 (8) | −0.0036 (8) | −0.0351 (10) |
O1W | 0.0489 (10) | 0.0413 (10) | 0.0588 (11) | −0.0005 (8) | 0.0118 (8) | −0.0143 (8) |
O2W | 0.0295 (8) | 0.0638 (11) | 0.0352 (9) | −0.0073 (7) | 0.0006 (7) | −0.0076 (8) |
O3W | 0.0850 (15) | 0.0585 (12) | 0.0701 (14) | 0.0075 (11) | −0.0020 (11) | 0.0041 (10) |
O4W | 0.0618 (12) | 0.0419 (10) | 0.0942 (15) | −0.0028 (9) | 0.0038 (11) | 0.0116 (10) |
S1 | 0.0249 (3) | 0.0400 (3) | 0.0310 (3) | 0.0041 (2) | 0.0006 (2) | −0.0046 (2) |
Geometric parameters (Å, º) top
C1—N7 | 1.358 (3) | C18—H18B | 0.9700 |
C1—C6 | 1.409 (3) | C19—C20 | 1.376 (3) |
C1—C2 | 1.412 (3) | C19—C24 | 1.381 (3) |
C2—C3 | 1.397 (3) | C20—C21 | 1.387 (3) |
C2—C7 | 1.497 (3) | C20—H20 | 0.9300 |
C3—C4 | 1.377 (3) | C21—C22 | 1.372 (3) |
C3—H3 | 0.9300 | C21—H21 | 0.9300 |
C4—C5 | 1.388 (3) | C22—C23 | 1.386 (3) |
C4—S1 | 1.769 (2) | C22—C28 | 1.503 (3) |
C5—C6 | 1.365 (3) | C23—C24 | 1.376 (3) |
C5—H5 | 0.9300 | C23—H23 | 0.9300 |
C6—H6 | 0.9300 | C24—H24 | 0.9300 |
C7—O2 | 1.253 (3) | C25—N5 | 1.318 (3) |
C7—O1 | 1.265 (3) | C25—N6 | 1.336 (3) |
C8—N1 | 1.314 (3) | C25—H25 | 0.9300 |
C8—N2 | 1.334 (3) | C26—C27 | 1.344 (3) |
C8—H8 | 0.9300 | C26—N6 | 1.361 (3) |
C9—C10 | 1.344 (3) | C26—H26 | 0.9300 |
C9—N2 | 1.364 (3) | C27—N5 | 1.373 (3) |
C9—H9 | 0.9300 | C27—H27 | 0.9300 |
C10—N1 | 1.374 (3) | C28—N6ii | 1.460 (3) |
C10—H10 | 0.9300 | C28—H28A | 0.9700 |
C11—N2 | 1.467 (3) | C28—H28B | 0.9700 |
C11—C12 | 1.509 (3) | Co1—N3 | 2.1056 (17) |
C11—H11A | 0.9700 | Co1—N1 | 2.1121 (18) |
C11—H11B | 0.9700 | Co1—O1 | 2.1211 (14) |
C12—C13 | 1.382 (3) | Co1—N5 | 2.1251 (17) |
C12—C14 | 1.384 (3) | Co1—O1W | 2.1605 (16) |
C13—C14i | 1.379 (3) | Co1—O2W | 2.1969 (15) |
C13—H13 | 0.9300 | N7—H7A | 0.8599 |
C14—H14 | 0.9300 | N7—H7B | 0.8600 |
C15—N3 | 1.313 (3) | O3—S1 | 1.4510 (17) |
C15—N4 | 1.335 (3) | O4—S1 | 1.4396 (17) |
C15—H15 | 0.9300 | O5—S1 | 1.4485 (16) |
C16—C17 | 1.344 (3) | O1W—H1WA | 0.8474 |
C16—N4 | 1.366 (3) | O1W—H1WB | 0.8424 |
C16—H16 | 0.9300 | O2W—H2WB | 0.8535 |
C17—N3 | 1.366 (3) | O2W—H2WA | 0.8493 |
C17—H17 | 0.9300 | O3W—H3WB | 0.8636 |
C18—N4 | 1.464 (3) | O3W—H3WA | 0.8679 |
C18—C19 | 1.510 (3) | O4W—H4WB | 0.8513 |
C18—H18A | 0.9700 | O4W—H4WA | 0.8546 |
| | | |
N7—C1—C6 | 118.60 (19) | C24—C23—C22 | 121.2 (2) |
N7—C1—C2 | 123.25 (19) | C24—C23—H23 | 119.4 |
C6—C1—C2 | 118.15 (19) | C22—C23—H23 | 119.4 |
C3—C2—C1 | 118.73 (18) | C23—C24—C19 | 120.5 (2) |
C3—C2—C7 | 118.18 (18) | C23—C24—H24 | 119.7 |
C1—C2—C7 | 123.02 (19) | C19—C24—H24 | 119.7 |
C4—C3—C2 | 121.77 (19) | N5—C25—N6 | 111.8 (2) |
C4—C3—H3 | 119.1 | N5—C25—H25 | 124.1 |
C2—C3—H3 | 119.1 | N6—C25—H25 | 124.1 |
C3—C4—C5 | 119.34 (19) | C27—C26—N6 | 106.6 (2) |
C3—C4—S1 | 120.64 (16) | C27—C26—H26 | 126.7 |
C5—C4—S1 | 120.02 (15) | N6—C26—H26 | 126.7 |
C6—C5—C4 | 120.21 (19) | C26—C27—N5 | 109.8 (2) |
C6—C5—H5 | 119.9 | C26—C27—H27 | 125.1 |
C4—C5—H5 | 119.9 | N5—C27—H27 | 125.1 |
C5—C6—C1 | 121.6 (2) | N6ii—C28—C22 | 114.81 (18) |
C5—C6—H6 | 119.2 | N6ii—C28—H28A | 108.6 |
C1—C6—H6 | 119.2 | C22—C28—H28A | 108.6 |
O2—C7—O1 | 123.41 (19) | N6ii—C28—H28B | 108.6 |
O2—C7—C2 | 118.67 (19) | C22—C28—H28B | 108.6 |
O1—C7—C2 | 117.91 (19) | H28A—C28—H28B | 107.5 |
N1—C8—N2 | 112.6 (2) | N3—Co1—N1 | 93.08 (7) |
N1—C8—H8 | 123.7 | N3—Co1—O1 | 86.83 (6) |
N2—C8—H8 | 123.7 | N1—Co1—O1 | 89.86 (6) |
C10—C9—N2 | 106.4 (2) | N3—Co1—N5 | 96.84 (7) |
C10—C9—H9 | 126.8 | N1—Co1—N5 | 90.71 (7) |
N2—C9—H9 | 126.8 | O1—Co1—N5 | 176.25 (6) |
C9—C10—N1 | 110.2 (2) | N3—Co1—O1W | 88.81 (7) |
C9—C10—H10 | 124.9 | N1—Co1—O1W | 175.35 (7) |
N1—C10—H10 | 124.9 | O1—Co1—O1W | 86.00 (6) |
N2—C11—C12 | 113.05 (18) | N5—Co1—O1W | 93.28 (7) |
N2—C11—H11A | 109.0 | N3—Co1—O2W | 170.77 (6) |
C12—C11—H11A | 109.0 | N1—Co1—O2W | 91.70 (6) |
N2—C11—H11B | 109.0 | O1—Co1—O2W | 85.29 (6) |
C12—C11—H11B | 109.0 | N5—Co1—O2W | 90.99 (6) |
H11A—C11—H11B | 107.8 | O1W—Co1—O2W | 85.86 (6) |
C13—C12—C14 | 118.7 (2) | C8—N1—C10 | 104.30 (18) |
C13—C12—C11 | 121.4 (2) | C8—N1—Co1 | 124.42 (15) |
C14—C12—C11 | 119.9 (2) | C10—N1—Co1 | 131.27 (14) |
C14i—C13—C12 | 120.7 (2) | C8—N2—C9 | 106.54 (18) |
C14i—C13—H13 | 119.7 | C8—N2—C11 | 125.9 (2) |
C12—C13—H13 | 119.7 | C9—N2—C11 | 127.4 (2) |
C13i—C14—C12 | 120.6 (2) | C15—N3—C17 | 104.99 (18) |
C13i—C14—H14 | 119.7 | C15—N3—Co1 | 123.84 (14) |
C12—C14—H14 | 119.7 | C17—N3—Co1 | 131.11 (15) |
N3—C15—N4 | 112.06 (19) | C15—N4—C16 | 106.59 (18) |
N3—C15—H15 | 124.0 | C15—N4—C18 | 126.57 (19) |
N4—C15—H15 | 124.0 | C16—N4—C18 | 126.84 (19) |
C17—C16—N4 | 106.35 (19) | C25—N5—C27 | 104.88 (18) |
C17—C16—H16 | 126.8 | C25—N5—Co1 | 127.70 (15) |
N4—C16—H16 | 126.8 | C27—N5—Co1 | 127.39 (15) |
C16—C17—N3 | 110.0 (2) | C25—N6—C26 | 106.88 (18) |
C16—C17—H17 | 125.0 | C25—N6—C28ii | 126.0 (2) |
N3—C17—H17 | 125.0 | C26—N6—C28ii | 127.07 (19) |
N4—C18—C19 | 113.00 (18) | C1—N7—H7A | 120.0 |
N4—C18—H18A | 109.0 | C1—N7—H7B | 120.0 |
C19—C18—H18A | 109.0 | H7A—N7—H7B | 120.0 |
N4—C18—H18B | 109.0 | C7—O1—Co1 | 130.34 (13) |
C19—C18—H18B | 109.0 | Co1—O1W—H1WA | 125.8 |
H18A—C18—H18B | 107.8 | Co1—O1W—H1WB | 104.2 |
C20—C19—C24 | 118.4 (2) | H1WA—O1W—H1WB | 110.2 |
C20—C19—C18 | 121.78 (19) | Co1—O2W—H2WB | 131.5 |
C24—C19—C18 | 119.80 (19) | Co1—O2W—H2WA | 98.4 |
C19—C20—C21 | 121.1 (2) | H2WB—O2W—H2WA | 108.2 |
C19—C20—H20 | 119.5 | H3WB—O3W—H3WA | 105.7 |
C21—C20—H20 | 119.5 | H4WB—O4W—H4WA | 108.5 |
C22—C21—C20 | 120.6 (2) | O4—S1—O5 | 112.80 (11) |
C22—C21—H21 | 119.7 | O4—S1—O3 | 111.74 (11) |
C20—C21—H21 | 119.7 | O5—S1—O3 | 111.92 (11) |
C21—C22—C23 | 118.2 (2) | O4—S1—C4 | 107.29 (10) |
C21—C22—C28 | 123.54 (19) | O5—S1—C4 | 106.07 (10) |
C23—C22—C28 | 118.26 (19) | O3—S1—C4 | 106.53 (10) |
| | | |
N7—C1—C2—C3 | −175.8 (2) | C21—C22—C28—N6ii | −1.6 (3) |
C6—C1—C2—C3 | 4.3 (3) | C23—C22—C28—N6ii | 179.5 (2) |
N7—C1—C2—C7 | 1.1 (3) | N2—C8—N1—C10 | 0.1 (3) |
C6—C1—C2—C7 | −178.74 (19) | N2—C8—N1—Co1 | −178.93 (14) |
C1—C2—C3—C4 | −0.4 (3) | C9—C10—N1—C8 | −0.5 (3) |
C7—C2—C3—C4 | −177.46 (19) | C9—C10—N1—Co1 | 178.44 (16) |
C2—C3—C4—C5 | −3.3 (3) | N1—C8—N2—C9 | 0.3 (3) |
C2—C3—C4—S1 | 175.94 (16) | N1—C8—N2—C11 | −176.2 (2) |
C3—C4—C5—C6 | 3.0 (3) | C10—C9—N2—C8 | −0.6 (3) |
S1—C4—C5—C6 | −176.32 (17) | C10—C9—N2—C11 | 175.8 (2) |
C4—C5—C6—C1 | 1.1 (3) | C12—C11—N2—C8 | −111.5 (3) |
N7—C1—C6—C5 | 175.4 (2) | C12—C11—N2—C9 | 72.8 (3) |
C2—C1—C6—C5 | −4.8 (3) | N4—C15—N3—C17 | −0.1 (3) |
C3—C2—C7—O2 | −11.4 (3) | N4—C15—N3—Co1 | 177.47 (14) |
C1—C2—C7—O2 | 171.6 (2) | C16—C17—N3—C15 | −0.2 (3) |
C3—C2—C7—O1 | 168.48 (19) | C16—C17—N3—Co1 | −177.54 (15) |
C1—C2—C7—O1 | −8.5 (3) | N3—C15—N4—C16 | 0.4 (3) |
N2—C9—C10—N1 | 0.7 (3) | N3—C15—N4—C18 | −178.90 (19) |
N2—C11—C12—C13 | 54.6 (3) | C17—C16—N4—C15 | −0.5 (2) |
N2—C11—C12—C14 | −127.8 (2) | C17—C16—N4—C18 | 178.8 (2) |
C14—C12—C13—C14i | −0.4 (4) | C19—C18—N4—C15 | −111.8 (2) |
C11—C12—C13—C14i | 177.2 (2) | C19—C18—N4—C16 | 69.0 (3) |
C13—C12—C14—C13i | 0.4 (4) | N6—C25—N5—C27 | −0.2 (3) |
C11—C12—C14—C13i | −177.2 (2) | N6—C25—N5—Co1 | −178.30 (14) |
N4—C16—C17—N3 | 0.4 (3) | C26—C27—N5—C25 | 0.1 (3) |
N4—C18—C19—C20 | 39.3 (3) | C26—C27—N5—Co1 | 178.17 (15) |
N4—C18—C19—C24 | −143.4 (2) | N5—C25—N6—C26 | 0.3 (3) |
C24—C19—C20—C21 | −0.9 (4) | N5—C25—N6—C28ii | 178.23 (19) |
C18—C19—C20—C21 | 176.5 (2) | C27—C26—N6—C25 | −0.2 (3) |
C19—C20—C21—C22 | 0.1 (4) | C27—C26—N6—C28ii | −178.1 (2) |
C20—C21—C22—C23 | 0.5 (3) | O2—C7—O1—Co1 | −1.5 (3) |
C20—C21—C22—C28 | −178.4 (2) | C2—C7—O1—Co1 | 178.62 (13) |
C21—C22—C23—C24 | −0.3 (4) | C3—C4—S1—O4 | 85.05 (19) |
C28—C22—C23—C24 | 178.7 (2) | C5—C4—S1—O4 | −95.66 (19) |
C22—C23—C24—C19 | −0.6 (4) | C3—C4—S1—O5 | −154.15 (18) |
C20—C19—C24—C23 | 1.1 (4) | C5—C4—S1—O5 | 25.1 (2) |
C18—C19—C24—C23 | −176.3 (2) | C3—C4—S1—O3 | −34.8 (2) |
N6—C26—C27—N5 | 0.1 (3) | C5—C4—S1—O3 | 144.53 (18) |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4W—H4WB···O5iii | 0.85 | 2.07 | 2.890 (3) | 161 |
C23—H23···O3iv | 0.93 | 2.57 | 3.287 (3) | 134 |
C21—H21···N6ii | 0.93 | 2.54 | 2.880 (3) | 102 |
O3W—H3WA···O3v | 0.87 | 1.94 | 2.796 (3) | 167 |
C28—H28B···O3Wvi | 0.97 | 2.44 | 3.318 (3) | 150 |
C6—H6···O4vi | 0.93 | 2.50 | 3.280 (3) | 141 |
N7—H7A···O4vi | 0.86 | 2.21 | 3.027 (3) | 158 |
O3W—H3WB···O2vi | 0.86 | 1.94 | 2.791 (3) | 168 |
O2W—H2WB···O5vii | 0.85 | 1.93 | 2.772 (2) | 167 |
C25—H25···O4Wviii | 0.93 | 2.58 | 3.391 (3) | 146 |
O1W—H1WA···O4Wviii | 0.85 | 1.85 | 2.696 (2) | 173 |
Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x−1, −y+3/2, z+1/2; (iv) x, y, z+1; (v) −x+1, y+1/2, −z+1/2; (vi) x, −y+3/2, z+1/2; (vii) x−1, y, z; (viii) −x, y−1/2, −z+1/2. |
The fluorescence quenching percentage (QP) (0.075 mM), Stern–Volmer
constants (KSV) and the limits of detection (LOD) for some NACs topNACs | QP (%) | KSV (l mol-1) | LOD (ppm) |
2-MO-5-NP | 46.35 | 1.15 × 104 | 1.38 |
TNP | 78.29 | 4.81 × 104 | 0.37 |
4-NA | 77.07 | 4.48 × 104 | 0.64 |
2-M-4-NA | 79.50 | 5.17 × 104 | 0.57 |
2,6-DC-4-NP | 63.56 | 2.33 × 104 | 0.89 |