Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615017088/yp3102sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615017088/yp3102k09109asup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615017088/yp3102k09111sup5.hkl |
CCDC references: 1424073; 1424072
Metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) are multifunctional nanoporous materials that can be utilized for diverse applications. For instance, MOFs or PCPs can be utilized for gas sorption (Férey, 2008; Czaja et al., 2009; Li et al., 2009; Hwang et al., 2013), heterogeneous catalysis (Fujita et al., 1994; Bhattacharjee et al., 2011; Shultz et al., 2009; Kim et al., 2013), drug delivery (Horcajada et al., 2010; McKinlay et al., 2013; Ma et al., 2013) and precursor materials for porous oxides (Jung et al., 2009; Xu et al., 2012) or carbons [OK?] (Yang et al., 2012; Jeon et al., 2014).
In an attempt to prepare functional MOFs, we recently reported a new C2h-symmetric terphenyl-based dicarboxylate linker, namely 1,1':4',1''-terphenyl-3,3'-dicarboxylate (3,3'-TPDC), and the corresponding Zn–MOF, [Zn(3,3'-TPDC)(DABCO)]·DMF·2H2O, containing 3,3'-TPDC and 1,4-diazabicyclo[2.2.2]octane (DABCO; Gu et al., 2010). The concept behind the design of this new 3,3'-TPDC linker was to lower the symmetry of the bridging ligand in order to develop new topologically interesting functional framework structures. The 3,3'-TPDC (point group C2h) is less symmetric than the more conventionally employed 4,4'-TPDC linker (point group D2h) (Eddaoudi et al., 2002). The resultant Zn–MOF consisted of a three-dimensional-like framework that resulted from the very efficient noncovalent stacking of the two-dimensional layers compared to other MOFs that had a (4,4) grid network structure, which usually contained both the D2h-symmetric dicarboxylate bridging ligand and a N-donor strut linker, i.e. DABCO or 4,4'-bipyridyl (Dybtsev et al., 2004). Therefore, in Zn–MOF, DABCO was coordinated to the ZnII ion via only one N atom instead of the two available. This unprecedented single-coordinated DABCO ligand acted as a very efficient Lewis basic catalytic centre for the nitroaldol (Henry) reaction of 4-nitrobenzaldehyde with various nitroalkanes to produce a series of β-nitro alcohols and for the cyanosilylation of 4-nitrobenzaldehyde with trimethylsilyl cyanide to produce a cyanohydrin (Gu et al., 2011). The exposed N atoms of the DABCO ligands in the Zn–MOF also exhibited an unusually high selectivity for the CO2 adsorption with an exceptionally high heat of adsorption (Gu et al., 2010).
Stimulated by these interesting results, we have attempted to prepare new 3,3'-TPDC-containing MOFs that were derived from other transition metals. For example, the dinuclear Cu2 paddlewheel-based secondary building unit (SBU) (Chui et al., 1999) consisting of the 3,3'-TPDC linker might produce a new Cu–MOF isostructural with the aforementioned Zn–MOF, viz. [Zn(3,3'-TPDC)(DABCO)]. Cu–MOF may also be structurally distinct from the well-known HKUST-1 (Chui et al., 1999), or [Cu3(BTC)2(H2O)3]·xH2O, where BTC is a benzene-1,3,5-tricarboxylate (Dybtsev et al., 2004). We report here on the reaction between Cu(NO3)2·3H2O and 1,1':4',1''-terphenyl-3,3'-dicarboxylic acid (H2TPDC) and the resulting CuII one-dimensional coordination polymers (CPs), namely
containing bridging 3,3'-TPDC ligands, instead of the multidimensional Cu–MOF that contained a dinuclear Cu2 paddlewheel SBU.
A mixture of Cu(NO3)2·3H2O (0.024 g, 0.1 mmol), H2TPDC (0.032 g, 0.1 mmol) and 1,4-diazabicyclo[2.2.2] octane (DABCO; 0.006 g, 0.05 mmol) were dissolved in DMF/H2O (5 ml, 4:1 v/v) in a Teflon-lined high-pressure vessel and heated at 393 K for 6 d. The precipitated solids were filtered off and the clear filtrate was stored at room temperature for several days. Crystals of different colours formed and were separated manually under a microscope after filtration, i.e. violet crystals (10 mg) and blue crystals (1 mg). The violet crystals and blue crystals were directly chosen from the mother solution for X-ray single crystal structure determination. The same reaction in the absence of DABCO also afforded both violet and blue crystals, and they were also investigated by X-ray single crystal structure determination.
Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were refined using a riding model, with methyl C—H = 0.98 Å and aromatic C—H = 0.95 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H atoms or 1.2Ueq(C) for aromatic H atoms. H atoms bonded to water O atoms were placed in calculated positions and refined in a riding-motion approximation, with Uiso(H) = 1.5Ueq(O). The calculated positions were determined by a close examination of sensible hydrogen-bond acceptor atoms which formed acceptable hydrogen-bond geometries. The O—H···O angles are approximately ideal (ca 180°) and the O—H distances were set at 0.84 Å. Although this might not be as precise as refining the H-atom positions, which was not possible, the precision of the O···O distances appear to give a good indication that the hydrogen bonds are present. In (I), disorder of the C11A and C12A methyl groups was modelled over two sets of sites with refined site occupancies of 0.530 (11) and 0.470 (11).
We attempted the preparation of new CPs through the reaction of Cu(NO3)2·3H2O and 1,1':4',1''-terphenyl-3,3'-dicarboxylic acid. First, the reaction was performed in the presence of DABCO as a potential pillar ligand. As mentioned in the Introduction, we anticipated that the Cu2 paddlewheel motif might be formed during the reaction with four 1,1':4',1''-terphenyl-3,3'-dicarboxylate (3,3'-TPDC) ligands and this moiety could behave as an SBU to form either two- or three-dimensional MOF systems with a DABCO pillar. After the hydrothermal reaction, however, the reaction mixture only contained a small amount of very small crystals, which turned out to be metallic Cu0 that was generated from the redox reaction with dimethylformamide (DMF) solvent. DMF has been known to be oxidized into several species in the presence of water under aerobic conditions (Grosjean et al., 2010). Keeping the reaction filtrate in the vial for several days at room temperature produced two different crystalline products. The first form were violet-coloured plate-shaped crystals, (I), and the second form were blue-coloured needle-shaped crystals, (II), as shown in Fig. 1. The violet crystal was a major product. In contrast, only a very small amount of blue crystals were recovered. Both crystals were structurally characterized by single-crystal X-ray diffraction (Table 1).
Based on the single-crystal X-ray diffraction data, the central CuII ion of (I) is coordinated by two carboxylate groups in an asymmetric chelating mode and by two trans-positioned dimethylamine ligands generated by the decomposition of the DMF solvent during the high-temperature reaction (Xiao et al., 2009). The coordination environment around the central CuII ion of (I) had a distorted octahedral geometry. The two 3,3'-TPDC ligands are mutually trans positioned (Fig. 2a). Notably, no CuII paddlewheel SBU was formed in this reaction and the structure was a one-dimensional CP. The solvent water molecules form inter-chain OW—HW···O hydrogen bonds with the O atoms of the 3,3'-TPDC ligands, forming a two-dimensional sheet (Table 2 and Fig. 3). The solvent water molecules also form N—H···OW hydrogen bonds with the amine H atoms (Table 2).
In contrast, the structure of (II) displays a five-coordinate CuII centre (Fig. 2b). The central CuII ion is coordinated by two mutually trans-positioned 3,3'-TPDC in a monodentate bonding mode and one aqua ligand, and two mutually trans-positioned dimethylamine ligands also coordinated to the CuII ion, like (I). Interestingly, the solvent water molecule occupies the area close to the empty space of the sixth-coordination site of the CuII ion of the neighbouring chain and forms two hydrogen bonds with the uncoordinated O atoms of the 3,3'-TPDC ligands, and the coordinated water molecules form inter-chain hydrogen bonds between the uncoordinated O atoms of the 3,3'-TPDC ligand (Table 3). The O atoms of the solvent water molecules also form hydrogen bonds with the coordinated amine H atoms (Table 3 and Fig. 4). These hydrogen-bonded two-dimensional sheets are interconnected by the 3,3-TPDC ligands to form a three-dimensional network.
It is interesting to note that CuII and ZnII ions can both adopt the same dinuclear paddlewheel SBU with four equivalent carboxylate ligands, but we could only obtain two slightly different one-dimensional coordination polymers for the CuII system. We know through this experiment that, even though the synthesis reaction was performed under the same conditions, the one-dimensional coordination polymers formed different structures. The differences in the structures led to the differences in the shape and colour of the crystals. We previously reported a one-dimensional CdII coordination polymer having a 3,3'-TPDC ligand (Park et al., 2011). The one-dimensional CdII polymer, [H2N(CH3)2]2[Cd(3,3'-TPDC)2], contained two chelating carboxylate groups and two monodentate carboxylate groups from four 3,3'-TPDC ligands that were centred around a CdII ion. In contrast, both (I) and (II) show hydrogen bonds that produced two- and three-dimensional networks, respectively.
Although both (I) and (II) are potentially magnetically coupled one-dimensional chain systems, the magnetic interactions between the CuII ions with S = 1/2 through the 3,3'-TPDC ligands can be ignored due to the long Cu···Cu separations [Cu···Cu = 17.63 Å for (I) and 15.80 Å for (II)].
Based on these results, we also tried the same reaction in the absence of the DABCO pillar because DABCO did not incorporate into either (I) or (II). In this case, however, the crude reaction mixture contained more brown metallic Cu0 solids than the reaction with DABCO. Although the role of DABCO is not clearly understood, the absence of DABCO in the reaction mixture may accelerate the reduction of CuII by DMF under our synthetic conditions. We separated the solution by filtration and stored the clear solution in a vial for several days at room temperature. Unlike the previous reaction where DABCO was present, the major product was composed of blue needles, which were also structurally characterized by X-ray crystallography. The crystal structure of the blue needles was the same as that of (II).
Two new one-dimensional coordination polymers were obtained from different preparation methods: one reaction was performed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reaction mixtures provided crystals of different coulour, i.e. violet plates and blue needles. The 3,3'-TPDC ligands coordinate the CuII ions in asymmetric chelating modes in (I) and in monodenate bonding modes in (II), forming one-dimensional chains. Both polymers containe two coordinated dimethylamine ligands in trans positions, and (II) has one aqua ligand. The solvent water molecules form hydrogen bonds between the one-dimensional polymer chains resulting in a two-dimensional network for (I) and a three-dimensional network for (II). Under the same synthetic conditions, two different one-dimensional coordination polymers were formed and the crystals showed different shapes and colours.
For both compounds, data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu(C20H12O4)(C2H7N)2]·H2O | Z = 1 |
Mr = 488.02 | F(000) = 255 |
Triclinic, P1 | Dx = 1.434 Mg m−3 |
a = 5.8806 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.6408 (10) Å | Cell parameters from 5896 reflections |
c = 13.9907 (16) Å | θ = 2.6–27.5° |
α = 103.755 (5)° | µ = 1.00 mm−1 |
β = 91.352 (6)° | T = 150 K |
γ = 111.227 (6)° | Plate, violet |
V = 564.99 (12) Å3 | 0.20 × 0.12 × 0.06 mm |
Nonius KappaCCD diffractometer | 1854 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.078 |
ω scans and ω scans with κ offsets | θmax = 27.6°, θmin = 3.0° |
Absorption correction: multi-scan SORTAV (Blessing 1995) | h = −7→7 |
Tmin = 0.800, Tmax = 0.956 | k = −9→9 |
6138 measured reflections | l = −18→15 |
2573 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.079 | H-atom parameters constrained |
wR(F2) = 0.186 | w = 1/[σ2(Fo2) + (0.023P)2 + 2.7226P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
2573 reflections | Δρmax = 0.53 e Å−3 |
174 parameters | Δρmin = −0.61 e Å−3 |
[Cu(C20H12O4)(C2H7N)2]·H2O | γ = 111.227 (6)° |
Mr = 488.02 | V = 564.99 (12) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.8806 (6) Å | Mo Kα radiation |
b = 7.6408 (10) Å | µ = 1.00 mm−1 |
c = 13.9907 (16) Å | T = 150 K |
α = 103.755 (5)° | 0.20 × 0.12 × 0.06 mm |
β = 91.352 (6)° |
Nonius KappaCCD diffractometer | 2573 independent reflections |
Absorption correction: multi-scan SORTAV (Blessing 1995) | 1854 reflections with I > 2σ(I) |
Tmin = 0.800, Tmax = 0.956 | Rint = 0.078 |
6138 measured reflections |
R[F2 > 2σ(F2)] = 0.079 | 0 restraints |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.53 e Å−3 |
2573 reflections | Δρmin = −0.61 e Å−3 |
174 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.0327 (3) | |
O1 | 0.2419 (7) | 0.2807 (6) | 0.6178 (3) | 0.0455 (11) | |
O2 | 0.6378 (7) | 0.4589 (6) | 0.6182 (3) | 0.0349 (9) | |
C1 | 0.4608 (10) | 0.3535 (8) | 0.6574 (4) | 0.0303 (12) | |
C2 | 0.5258 (9) | 0.3163 (8) | 0.7517 (4) | 0.0299 (12) | |
C3 | 0.7701 (10) | 0.3785 (8) | 0.7917 (4) | 0.0340 (12) | |
H3A | 0.8991 | 0.4412 | 0.7572 | 0.041* | |
C4 | 0.8237 (10) | 0.3485 (9) | 0.8816 (4) | 0.0383 (14) | |
H4A | 0.9903 | 0.3916 | 0.9089 | 0.046* | |
C5 | 0.6386 (10) | 0.2570 (9) | 0.9323 (4) | 0.0383 (13) | |
H5A | 0.6790 | 0.2377 | 0.9941 | 0.046* | |
C6 | 0.3905 (10) | 0.1918 (8) | 0.8937 (4) | 0.0329 (12) | |
C7 | 0.3387 (10) | 0.2235 (8) | 0.8035 (4) | 0.0320 (12) | |
H7A | 0.1723 | 0.1812 | 0.7762 | 0.038* | |
C8 | 0.1908 (10) | 0.0920 (8) | 0.9479 (4) | 0.0340 (12) | |
C9 | 0.1991 (11) | 0.1651 (8) | 1.0509 (4) | 0.0368 (13) | |
H9 | 0.3351 | 0.2772 | 1.0863 | 0.044* | |
C10 | −0.0078 (11) | −0.0731 (8) | 0.8989 (4) | 0.0377 (13) | |
H10 | −0.0143 | −0.1252 | 0.8296 | 0.045* | |
N1A | 0.4505 (8) | 0.7372 (7) | 0.5829 (3) | 0.0341 (11) | 0.470 (11) |
H1A | 0.5438 | 0.8474 | 0.5546 | 0.041* | 0.470 (11) |
C11A | 0.182 (2) | 0.716 (2) | 0.5712 (11) | 0.048 (4) | 0.470 (11) |
H11D | 0.0793 | 0.6029 | 0.5929 | 0.073* | 0.470 (11) |
H11E | 0.1288 | 0.6986 | 0.5015 | 0.073* | 0.470 (11) |
H11F | 0.1657 | 0.8337 | 0.6118 | 0.073* | 0.470 (11) |
C12A | 0.535 (3) | 0.804 (2) | 0.6880 (11) | 0.051 (4) | 0.470 (11) |
H12D | 0.5240 | 0.9305 | 0.7153 | 0.077* | 0.470 (11) |
H12E | 0.7055 | 0.8155 | 0.6985 | 0.077* | 0.470 (11) |
H12F | 0.4313 | 0.7095 | 0.7214 | 0.077* | 0.470 (11) |
N1 | 0.4505 (8) | 0.7372 (7) | 0.5829 (3) | 0.0341 (11) | 0.530 (11) |
H1 | 0.3599 | 0.7788 | 0.5370 | 0.041* | 0.530 (11) |
C11 | 0.312 (3) | 0.720 (2) | 0.6679 (11) | 0.060 (4) | 0.530 (11) |
H11A | 0.4140 | 0.7148 | 0.7228 | 0.090* | 0.530 (11) |
H11B | 0.1635 | 0.6006 | 0.6492 | 0.090* | 0.530 (11) |
H11C | 0.2651 | 0.8328 | 0.6888 | 0.090* | 0.530 (11) |
C12 | 0.698 (2) | 0.8996 (18) | 0.6156 (10) | 0.051 (4) | 0.530 (11) |
H12A | 0.6799 | 1.0105 | 0.6622 | 0.076* | 0.530 (11) |
H12B | 0.7681 | 0.9395 | 0.5578 | 0.076* | 0.530 (11) |
H12C | 0.8073 | 0.8546 | 0.6482 | 0.076* | 0.530 (11) |
O1W | −0.2153 (14) | 0.0763 (12) | 0.5231 (6) | 0.043 (2) | 0.5 |
H1WA | −0.0726 | 0.1405 | 0.5527 | 0.065* | 0.5 |
H1WB | −0.2233 | −0.0267 | 0.4824 | 0.065* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0341 (6) | 0.0339 (6) | 0.0319 (6) | 0.0113 (4) | 0.0056 (4) | 0.0141 (4) |
O1 | 0.033 (2) | 0.057 (3) | 0.048 (3) | 0.012 (2) | 0.0029 (18) | 0.026 (2) |
O2 | 0.037 (2) | 0.041 (2) | 0.033 (2) | 0.0150 (18) | 0.0088 (16) | 0.0214 (18) |
C1 | 0.036 (3) | 0.029 (3) | 0.028 (3) | 0.014 (2) | 0.009 (2) | 0.007 (2) |
C2 | 0.036 (3) | 0.026 (3) | 0.030 (3) | 0.012 (2) | 0.007 (2) | 0.012 (2) |
C3 | 0.032 (3) | 0.035 (3) | 0.038 (3) | 0.012 (2) | 0.005 (2) | 0.017 (3) |
C4 | 0.033 (3) | 0.040 (3) | 0.038 (3) | 0.006 (3) | −0.001 (2) | 0.015 (3) |
C5 | 0.046 (3) | 0.038 (3) | 0.033 (3) | 0.013 (3) | −0.001 (2) | 0.018 (3) |
C6 | 0.038 (3) | 0.027 (3) | 0.032 (3) | 0.009 (2) | 0.006 (2) | 0.011 (2) |
C7 | 0.035 (3) | 0.031 (3) | 0.032 (3) | 0.012 (2) | 0.004 (2) | 0.010 (2) |
C8 | 0.043 (3) | 0.035 (3) | 0.029 (3) | 0.014 (3) | 0.006 (2) | 0.018 (2) |
C9 | 0.047 (3) | 0.028 (3) | 0.032 (3) | 0.007 (3) | 0.003 (2) | 0.012 (3) |
C10 | 0.054 (4) | 0.036 (3) | 0.024 (3) | 0.015 (3) | 0.008 (2) | 0.015 (3) |
N1A | 0.037 (2) | 0.037 (3) | 0.033 (3) | 0.015 (2) | 0.006 (2) | 0.016 (2) |
C11A | 0.027 (7) | 0.054 (9) | 0.053 (9) | 0.009 (6) | 0.005 (6) | 0.007 (7) |
C12A | 0.074 (11) | 0.034 (8) | 0.054 (9) | 0.034 (8) | 0.001 (8) | 0.008 (7) |
N1 | 0.037 (2) | 0.037 (3) | 0.033 (3) | 0.015 (2) | 0.006 (2) | 0.016 (2) |
C11 | 0.075 (11) | 0.049 (9) | 0.064 (10) | 0.026 (8) | 0.035 (8) | 0.023 (7) |
C12 | 0.050 (7) | 0.039 (7) | 0.056 (8) | 0.015 (6) | 0.006 (6) | 0.004 (6) |
O1W | 0.042 (5) | 0.037 (5) | 0.051 (5) | 0.013 (4) | 0.003 (4) | 0.015 (4) |
Cu1—O2i | 1.965 (4) | C9—H9 | 0.9500 |
Cu1—O2 | 1.965 (4) | C10—C9ii | 1.397 (8) |
Cu1—N1A | 2.028 (5) | C10—H10 | 0.9500 |
Cu1—N1 | 2.028 (5) | N1A—C12A | 1.447 (15) |
Cu1—N1i | 2.028 (5) | N1A—C11A | 1.529 (12) |
Cu1—N1Ai | 2.028 (5) | N1A—H1A | 1.0000 |
Cu1—O1 | 2.724 (4) | C11A—H11D | 0.9800 |
O1—C1 | 1.255 (6) | C11A—H11E | 0.9800 |
O2—C1 | 1.289 (6) | C11A—H11F | 0.9800 |
C1—C2 | 1.484 (7) | C12A—H12D | 0.9800 |
C2—C3 | 1.394 (7) | C12A—H12E | 0.9800 |
C2—C7 | 1.398 (7) | C12A—H12F | 0.9800 |
C3—C4 | 1.380 (8) | N1—C11 | 1.463 (13) |
C3—H3A | 0.9500 | N1—C12 | 1.502 (13) |
C4—C5 | 1.377 (8) | N1—H1 | 1.0000 |
C4—H4A | 0.9500 | C11—H11A | 0.9800 |
C5—C6 | 1.406 (8) | C11—H11B | 0.9800 |
C5—H5A | 0.9500 | C11—H11C | 0.9800 |
C6—C7 | 1.388 (8) | C12—H12A | 0.9800 |
C6—C8 | 1.484 (7) | C12—H12B | 0.9800 |
C7—H7A | 0.9500 | C12—H12C | 0.9800 |
C8—C10 | 1.382 (8) | O1W—H1WA | 0.8400 |
C8—C9 | 1.409 (8) | O1W—H1WB | 0.8400 |
C9—C10ii | 1.397 (8) | ||
O2i—Cu1—O2 | 180.0 | C10ii—C9—C8 | 120.2 (5) |
O2i—Cu1—N1A | 88.72 (17) | C10ii—C9—H9 | 119.9 |
O2—Cu1—N1A | 91.28 (17) | C8—C9—H9 | 119.9 |
O2i—Cu1—N1 | 88.72 (17) | C8—C10—C9ii | 121.4 (5) |
O2—Cu1—N1 | 91.28 (17) | C8—C10—H10 | 119.3 |
O2i—Cu1—N1i | 91.28 (17) | C9ii—C10—H10 | 119.3 |
O2—Cu1—N1i | 88.72 (17) | C12A—N1A—C11A | 107.1 (9) |
N1—Cu1—N1i | 180.0 | C12A—N1A—Cu1 | 119.2 (6) |
O2i—Cu1—N1Ai | 91.28 (17) | C11A—N1A—Cu1 | 111.9 (6) |
O2—Cu1—N1Ai | 88.72 (17) | C12A—N1A—H1A | 105.9 |
N1A—Cu1—N1Ai | 180.0 | C11A—N1A—H1A | 105.9 |
O2i—Cu1—O1 | 126.09 (13) | Cu1—N1A—H1A | 105.9 |
O2—Cu1—O1 | 53.91 (13) | N1A—C11A—H11D | 109.5 |
N1A—Cu1—O1 | 90.62 (16) | N1A—C11A—H11E | 109.5 |
N1—Cu1—O1 | 90.62 (16) | H11D—C11A—H11E | 109.5 |
N1i—Cu1—O1 | 89.38 (16) | N1A—C11A—H11F | 109.5 |
N1Ai—Cu1—O1 | 89.38 (16) | H11D—C11A—H11F | 109.5 |
C1—O1—Cu1 | 74.5 (3) | H11E—C11A—H11F | 109.5 |
C1—O2—Cu1 | 108.9 (3) | N1A—C12A—H12D | 109.5 |
O1—C1—O2 | 122.5 (5) | N1A—C12A—H12E | 109.5 |
O1—C1—C2 | 120.2 (5) | H12D—C12A—H12E | 109.5 |
O2—C1—C2 | 117.2 (5) | N1A—C12A—H12F | 109.5 |
C3—C2—C7 | 119.2 (5) | H12D—C12A—H12F | 109.5 |
C3—C2—C1 | 121.3 (5) | H12E—C12A—H12F | 109.5 |
C7—C2—C1 | 119.5 (5) | C11—N1—C12 | 109.6 (9) |
C4—C3—C2 | 119.8 (5) | C11—N1—Cu1 | 119.3 (6) |
C4—C3—H3A | 120.1 | C12—N1—Cu1 | 108.3 (5) |
C2—C3—H3A | 120.1 | C11—N1—H1 | 106.3 |
C5—C4—C3 | 120.7 (5) | C12—N1—H1 | 106.3 |
C5—C4—H4A | 119.6 | Cu1—N1—H1 | 106.3 |
C3—C4—H4A | 119.6 | N1—C11—H11A | 109.5 |
C4—C5—C6 | 120.9 (5) | N1—C11—H11B | 109.5 |
C4—C5—H5A | 119.6 | H11A—C11—H11B | 109.5 |
C6—C5—H5A | 119.6 | N1—C11—H11C | 109.5 |
C7—C6—C5 | 117.8 (5) | H11A—C11—H11C | 109.5 |
C7—C6—C8 | 121.2 (5) | H11B—C11—H11C | 109.5 |
C5—C6—C8 | 120.9 (5) | N1—C12—H12A | 109.5 |
C6—C7—C2 | 121.5 (5) | N1—C12—H12B | 109.5 |
C6—C7—H7A | 119.2 | H12A—C12—H12B | 109.5 |
C2—C7—H7A | 119.2 | N1—C12—H12C | 109.5 |
C10—C8—C9 | 118.4 (5) | H12A—C12—H12C | 109.5 |
C10—C8—C6 | 121.1 (5) | H12B—C12—H12C | 109.5 |
C9—C8—C6 | 120.4 (5) | H1WA—O1W—H1WB | 111.4 |
Cu1—O1—C1—O2 | −3.6 (4) | C4—C5—C6—C8 | 179.6 (5) |
Cu1—O1—C1—C2 | 177.7 (5) | C5—C6—C7—C2 | 0.3 (8) |
Cu1—O2—C1—O1 | 5.1 (6) | C8—C6—C7—C2 | −179.6 (5) |
Cu1—O2—C1—C2 | −176.2 (4) | C3—C2—C7—C6 | 0.0 (8) |
O1—C1—C2—C3 | 173.3 (5) | C1—C2—C7—C6 | −177.7 (5) |
O2—C1—C2—C3 | −5.4 (8) | C7—C6—C8—C10 | 43.8 (8) |
O1—C1—C2—C7 | −9.1 (8) | C5—C6—C8—C10 | −136.0 (6) |
O2—C1—C2—C7 | 172.2 (5) | C7—C6—C8—C9 | −135.7 (6) |
C7—C2—C3—C4 | −0.3 (8) | C5—C6—C8—C9 | 44.4 (8) |
C1—C2—C3—C4 | 177.3 (5) | C10—C8—C9—C10ii | −1.0 (9) |
C2—C3—C4—C5 | 0.3 (9) | C6—C8—C9—C10ii | 178.5 (5) |
C3—C4—C5—C6 | 0.0 (9) | C9—C8—C10—C9ii | 1.0 (9) |
C4—C5—C6—C7 | −0.3 (9) | C6—C8—C10—C9ii | −178.5 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O1Wiii | 1.00 | 1.96 | 2.948 (9) | 167 |
N1—H1···O1Wiv | 1.00 | 1.94 | 2.912 (9) | 164 |
O1W—H1WA···O1 | 0.84 | 1.85 | 2.689 (9) | 180 |
O1W—H1WB···O1v | 0.84 | 2.07 | 2.911 (9) | 180 |
Symmetry codes: (iii) x+1, y+1, z; (iv) −x, −y+1, −z+1; (v) −x, −y, −z+1. |
[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O | Dx = 1.434 Mg m−3 |
Mr = 506.04 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcn | Cell parameters from 9541 reflections |
a = 7.8339 (3) Å | θ = 2.6–27.5° |
b = 11.7791 (3) Å | µ = 0.97 mm−1 |
c = 25.4043 (10) Å | T = 150 K |
V = 2344.21 (14) Å3 | Needle, blue |
Z = 4 | 0.20 × 0.10 × 0.04 mm |
F(000) = 1060 |
Nonius KappaCCD diffractometer | 1131 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.136 |
φ scans and ω scans with κ offsets | θmax = 25.0°, θmin = 3.1° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −9→9 |
Tmin = 0.819, Tmax = 0.969 | k = −12→14 |
16351 measured reflections | l = −26→30 |
2066 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.157 | w = 1/[σ2(Fo2) + (0.0596P)2 + 5.3006P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.003 |
2066 reflections | Δρmax = 1.19 e Å−3 |
153 parameters | Δρmin = −0.54 e Å−3 |
[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O | V = 2344.21 (14) Å3 |
Mr = 506.04 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 7.8339 (3) Å | µ = 0.97 mm−1 |
b = 11.7791 (3) Å | T = 150 K |
c = 25.4043 (10) Å | 0.20 × 0.10 × 0.04 mm |
Nonius KappaCCD diffractometer | 2066 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1131 reflections with I > 2σ(I) |
Tmin = 0.819, Tmax = 0.969 | Rint = 0.136 |
16351 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.19 e Å−3 |
2066 reflections | Δρmin = −0.54 e Å−3 |
153 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 0.22078 (7) | 0.7500 | 0.0238 (3) | |
O1 | 0.3358 (5) | 0.2306 (3) | 0.69121 (13) | 0.0276 (9) | |
O2 | 0.2786 (5) | 0.4156 (3) | 0.70242 (14) | 0.0413 (11) | |
O3 | 0.5000 | 0.0284 (4) | 0.7500 | 0.0338 (13) | |
H3O | 0.4215 | −0.0197 | 0.7468 | 0.051* | |
N1 | 0.3090 (6) | 0.2281 (4) | 0.80337 (16) | 0.0275 (11) | |
H1A | 0.2014 | 0.2114 | 0.7837 | 0.033* | |
C1 | 0.2685 (7) | 0.3260 (5) | 0.6779 (2) | 0.0280 (13) | |
C2 | 0.1673 (7) | 0.3217 (5) | 0.6274 (2) | 0.0277 (13) | |
C3 | 0.0956 (7) | 0.4209 (5) | 0.6068 (2) | 0.0324 (14) | |
H3A | 0.1119 | 0.4910 | 0.6246 | 0.039* | |
C4 | 0.0016 (7) | 0.4185 (4) | 0.5610 (2) | 0.0298 (12) | |
H4A | −0.0475 | 0.4864 | 0.5476 | 0.036* | |
C5 | −0.0211 (7) | 0.3167 (4) | 0.5344 (2) | 0.0294 (14) | |
H5A | −0.0851 | 0.3155 | 0.5026 | 0.035* | |
C6 | 0.0489 (7) | 0.2157 (5) | 0.5537 (2) | 0.0292 (14) | |
C7 | 0.1436 (7) | 0.2205 (4) | 0.6002 (2) | 0.0284 (13) | |
H7A | 0.1932 | 0.1528 | 0.6136 | 0.034* | |
C8 | 0.0210 (7) | 0.1051 (4) | 0.52576 (19) | 0.0260 (13) | |
C9 | 0.0108 (7) | 0.0990 (4) | 0.47145 (19) | 0.0294 (13) | |
H9 | 0.0179 | 0.1669 | 0.4514 | 0.035* | |
C10 | 0.0095 (7) | 0.0043 (4) | 0.55457 (19) | 0.0285 (12) | |
H10 | 0.0155 | 0.0062 | 0.5919 | 0.034* | |
C11 | 0.3163 (9) | 0.1456 (5) | 0.8472 (2) | 0.0512 (18) | |
H11A | 0.2158 | 0.1551 | 0.8697 | 0.077* | |
H11B | 0.4200 | 0.1587 | 0.8679 | 0.077* | |
H11C | 0.3180 | 0.0683 | 0.8329 | 0.077* | |
C12 | 0.2879 (8) | 0.3411 (5) | 0.8258 (2) | 0.0470 (18) | |
H12A | 0.1882 | 0.3418 | 0.8490 | 0.071* | |
H12B | 0.2713 | 0.3963 | 0.7973 | 0.071* | |
H12C | 0.3901 | 0.3613 | 0.8460 | 0.071* | |
O1W | 0.0000 | 0.0953 (4) | 0.7500 | 0.0428 (14) | |
H1WA | −0.0625 | 0.0450 | 0.7634 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0245 (5) | 0.0233 (5) | 0.0235 (5) | 0.000 | −0.0020 (5) | 0.000 |
O1 | 0.029 (2) | 0.028 (2) | 0.025 (2) | 0.0040 (18) | −0.0064 (17) | −0.0035 (17) |
O2 | 0.050 (3) | 0.034 (2) | 0.040 (2) | 0.008 (2) | −0.009 (2) | −0.013 (2) |
O3 | 0.033 (3) | 0.022 (3) | 0.046 (3) | 0.000 | −0.004 (3) | 0.000 |
N1 | 0.024 (3) | 0.029 (2) | 0.029 (3) | 0.003 (2) | −0.003 (2) | −0.003 (2) |
C1 | 0.029 (4) | 0.036 (3) | 0.019 (3) | 0.003 (3) | 0.005 (3) | −0.006 (3) |
C2 | 0.016 (3) | 0.036 (3) | 0.031 (3) | 0.000 (2) | 0.004 (3) | −0.001 (3) |
C3 | 0.034 (4) | 0.033 (3) | 0.031 (3) | −0.004 (3) | 0.005 (3) | −0.003 (3) |
C4 | 0.034 (3) | 0.028 (3) | 0.027 (3) | 0.003 (3) | 0.004 (3) | 0.006 (2) |
C5 | 0.032 (4) | 0.036 (3) | 0.020 (3) | −0.004 (3) | −0.005 (3) | 0.001 (2) |
C6 | 0.036 (4) | 0.034 (3) | 0.018 (3) | 0.000 (3) | 0.002 (2) | −0.004 (2) |
C7 | 0.027 (3) | 0.029 (3) | 0.028 (3) | 0.002 (3) | 0.002 (3) | 0.007 (3) |
C8 | 0.027 (3) | 0.032 (3) | 0.019 (3) | −0.005 (3) | −0.006 (3) | 0.000 (2) |
C9 | 0.032 (3) | 0.030 (3) | 0.026 (3) | 0.000 (3) | −0.002 (3) | 0.005 (2) |
C10 | 0.030 (3) | 0.040 (3) | 0.016 (3) | −0.004 (3) | −0.008 (3) | 0.002 (2) |
C11 | 0.066 (5) | 0.046 (4) | 0.041 (4) | 0.002 (4) | 0.015 (4) | 0.006 (3) |
C12 | 0.049 (5) | 0.046 (4) | 0.046 (4) | 0.009 (3) | 0.007 (3) | −0.002 (3) |
O1W | 0.038 (3) | 0.038 (3) | 0.052 (4) | 0.000 | 0.004 (3) | 0.000 |
Cu1—O1 | 1.975 (3) | C5—C6 | 1.399 (7) |
Cu1—O1i | 1.975 (3) | C5—H5A | 0.9500 |
Cu1—N1i | 2.021 (4) | C6—C7 | 1.395 (7) |
Cu1—N1 | 2.021 (4) | C6—C8 | 1.499 (7) |
Cu1—O3 | 2.266 (5) | C7—H7A | 0.9500 |
Cu1—O2 | 3.120 (4) | C8—C9 | 1.384 (7) |
O1—C1 | 1.287 (6) | C8—C10 | 1.398 (7) |
O2—C1 | 1.228 (6) | C9—C10ii | 1.395 (7) |
O3—H3O | 0.8401 | C9—H9 | 0.9500 |
N1—C12 | 1.457 (7) | C10—C9ii | 1.395 (7) |
N1—C11 | 1.479 (7) | C10—H10 | 0.9500 |
N1—H1A | 1.0000 | C11—H11A | 0.9800 |
C1—C2 | 1.508 (7) | C11—H11B | 0.9800 |
C2—C7 | 1.391 (7) | C11—H11C | 0.9800 |
C2—C3 | 1.399 (7) | C12—H12A | 0.9800 |
C3—C4 | 1.377 (7) | C12—H12B | 0.9800 |
C3—H3A | 0.9500 | C12—H12C | 0.9800 |
C4—C5 | 1.388 (7) | O1W—H1WA | 0.8400 |
C4—H4A | 0.9500 | ||
O1—Cu1—O1i | 173.3 (2) | C3—C4—C5 | 119.8 (5) |
O1—Cu1—N1i | 88.42 (16) | C3—C4—H4A | 120.1 |
O1i—Cu1—N1i | 91.29 (16) | C5—C4—H4A | 120.1 |
O1—Cu1—N1 | 91.29 (16) | C4—C5—C6 | 120.9 (5) |
O1i—Cu1—N1 | 88.42 (16) | C4—C5—H5A | 119.5 |
N1i—Cu1—N1 | 175.1 (2) | C6—C5—H5A | 119.5 |
O1—Cu1—O3 | 93.35 (11) | C7—C6—C5 | 118.1 (5) |
O1i—Cu1—O3 | 93.35 (11) | C7—C6—C8 | 120.9 (5) |
N1i—Cu1—O3 | 92.46 (12) | C5—C6—C8 | 121.0 (5) |
N1—Cu1—O3 | 92.45 (12) | C2—C7—C6 | 121.8 (5) |
O1—Cu1—O2 | 45.72 (12) | C2—C7—H7A | 119.1 |
O1i—Cu1—O2 | 127.75 (13) | C6—C7—H7A | 119.1 |
N1i—Cu1—O2 | 96.90 (14) | C9—C8—C10 | 118.3 (5) |
N1—Cu1—O2 | 79.44 (14) | C9—C8—C6 | 121.7 (4) |
O3—Cu1—O2 | 137.34 (7) | C10—C8—C6 | 119.9 (4) |
C1—O1—Cu1 | 121.1 (3) | C8—C9—C10ii | 121.6 (5) |
C1—O2—Cu1 | 66.5 (3) | C8—C9—H9 | 119.2 |
Cu1—O3—H3O | 132.4 | C10ii—C9—H9 | 119.2 |
C12—N1—C11 | 108.1 (4) | C9ii—C10—C8 | 120.1 (5) |
C12—N1—Cu1 | 112.6 (4) | C9ii—C10—H10 | 120.0 |
C11—N1—Cu1 | 116.6 (4) | C8—C10—H10 | 120.0 |
C12—N1—H1A | 106.3 | N1—C11—H11A | 109.5 |
C11—N1—H1A | 106.3 | N1—C11—H11B | 109.5 |
Cu1—N1—H1A | 106.3 | H11A—C11—H11B | 109.5 |
O2—C1—O1 | 126.2 (5) | N1—C11—H11C | 109.5 |
O2—C1—C2 | 119.6 (5) | H11A—C11—H11C | 109.5 |
O1—C1—C2 | 114.2 (5) | H11B—C11—H11C | 109.5 |
C7—C2—C3 | 118.4 (5) | N1—C12—H12A | 109.5 |
C7—C2—C1 | 121.4 (5) | N1—C12—H12B | 109.5 |
C3—C2—C1 | 120.2 (5) | H12A—C12—H12B | 109.5 |
C4—C3—C2 | 121.0 (5) | N1—C12—H12C | 109.5 |
C4—C3—H3A | 119.5 | H12A—C12—H12C | 109.5 |
C2—C3—H3A | 119.5 | H12B—C12—H12C | 109.5 |
Cu1—O2—C1—O1 | 5.7 (5) | C4—C5—C6—C8 | 178.6 (5) |
Cu1—O2—C1—C2 | −175.2 (6) | C3—C2—C7—C6 | −0.9 (8) |
Cu1—O1—C1—O2 | −9.7 (8) | C1—C2—C7—C6 | 179.4 (5) |
Cu1—O1—C1—C2 | 171.2 (3) | C5—C6—C7—C2 | 0.8 (8) |
O2—C1—C2—C7 | −175.9 (5) | C8—C6—C7—C2 | −178.4 (5) |
O1—C1—C2—C7 | 3.3 (8) | C7—C6—C8—C9 | −146.1 (5) |
O2—C1—C2—C3 | 4.5 (8) | C5—C6—C8—C9 | 34.7 (8) |
O1—C1—C2—C3 | −176.3 (5) | C7—C6—C8—C10 | 32.0 (8) |
C7—C2—C3—C4 | 0.9 (8) | C5—C6—C8—C10 | −147.1 (6) |
C1—C2—C3—C4 | −179.5 (5) | C10—C8—C9—C10ii | −0.3 (10) |
C2—C3—C4—C5 | −0.7 (8) | C6—C8—C9—C10ii | 177.9 (5) |
C3—C4—C5—C6 | 0.6 (9) | C9—C8—C10—C9ii | 0.3 (10) |
C4—C5—C6—C7 | −0.6 (8) | C6—C8—C10—C9ii | −177.9 (5) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O2iii | 0.84 | 2.08 | 2.827 (4) | 149 |
N1—H1A···O1W | 1.00 | 2.26 | 3.185 (5) | 154 |
O1W—H1WA···O2iv | 0.84 | 2.15 | 2.992 (5) | 180 |
Symmetry codes: (iii) −x+1/2, y−1/2, z; (iv) x−1/2, y−1/2, −z+3/2. |
Experimental details
(k09109a) | (k09111) | |
Crystal data | ||
Chemical formula | [Cu(C20H12O4)(C2H7N)2]·H2O | [Cu(C20H12O4)(C2H7N)2(H2O)]·H2O |
Mr | 488.02 | 506.04 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, Pbcn |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 5.8806 (6), 7.6408 (10), 13.9907 (16) | 7.8339 (3), 11.7791 (3), 25.4043 (10) |
α, β, γ (°) | 103.755 (5), 91.352 (6), 111.227 (6) | 90, 90, 90 |
V (Å3) | 564.99 (12) | 2344.21 (14) |
Z | 1 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.00 | 0.97 |
Crystal size (mm) | 0.20 × 0.12 × 0.06 | 0.20 × 0.10 × 0.04 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan SORTAV (Blessing 1995) | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.800, 0.956 | 0.819, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6138, 2573, 1854 | 16351, 2066, 1131 |
Rint | 0.078 | 0.136 |
(sin θ/λ)max (Å−1) | 0.652 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.079, 0.186, 1.09 | 0.056, 0.157, 1.04 |
No. of reflections | 2573 | 2066 |
No. of parameters | 174 | 153 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.61 | 1.19, −0.54 |
Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O1Wi | 1.00 | 1.96 | 2.948 (9) | 167.2 |
N1—H1···O1Wii | 1.00 | 1.94 | 2.912 (9) | 164.4 |
O1W—H1WA···O1 | 0.84 | 1.85 | 2.689 (9) | 179.8 |
O1W—H1WB···O1iii | 0.84 | 2.07 | 2.911 (9) | 179.8 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x, −y+1, −z+1; (iii) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O2i | 0.84 | 2.08 | 2.827 (4) | 148.6 |
N1—H1A···O1W | 1.00 | 2.26 | 3.185 (5) | 154.0 |
O1W—H1WA···O2ii | 0.84 | 2.15 | 2.992 (5) | 179.7 |
Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x−1/2, y−1/2, −z+3/2. |
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