One-dimensional Cu^II coordination polymers containing C_2h-symmetric 1,1':4',1''-terphenyl-3,3'-di­carboxyl­ate linkers

Two new one-dimensional Cu^II coordination polymers (CPs) containing the C_2h-symmetric terphenyl-based di­carboxyl­ate linker 1,1':4',1''-terphenyl-3,3'-di­car­box­yl­ate (3,3'-TPDC), namely catena-poly[[bis­(di­methyl­amine-[kappa]N)copper(II)]-[mu]-1,1':4',1''-terphenyl-3,3'-di­carboxyl­ato-[kappa]⁴O,O':O'':O'''] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂]·H₂O}_n, (I), and catena-poly[[aqua­bis­(di­methyl­amine-[kappa]N)copper(II)]-[mu]-1,1':4',1''-terphenyl-3,3'-di­carboxyl­ato-[kappa]²O³:O^3'] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂(H₂O)]·H₂O}_n, (II), were both obtained from two different methods of preparation: 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 reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X-ray crystallography. The 3,3'-TPDC bridging ligands coordinate the Cu^II ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one-dimensional chains in each case. Both coordination polymers contain two coordinated di­methyl­amine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water mol­ecules are involved in hydrogen bonds between the one-dimensional coordination polymer chains, forming a two-dimensional network in (I) and a three-dimensional network in (II).

S1. Introduction

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 C_2h-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 C_2h) is less symmetric than the more conventionally employed 4,4'-TPDC linker (point group D_2h) (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 D_2h-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 Zn^II 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 Cu^II 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.

S2. Experimental

S2.1. Synthesis and crystallization

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.

S2.2. Refinement

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 U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(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 U_iso(H) = 1.5U_eq(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).

S3. Results and discussion

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 Cu^II 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 Cu^II ion of (I) had a distorted o­cta­hedral geometry. The two 3,3'-TPDC ligands are mutually trans positioned (Fig. 2a). Notably, no Cu^II 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 Cu^II centre (Fig. 2b). The central Cu^II 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 Cu^II ion, like (I). Inter­estingly, the solvent water molecule occupies the area close to the empty space of the sixth-coordination site of the Cu^II 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 Cu^II and Zn^II 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 Cu^II 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 Cd^II coordination polymer having a 3,3'-TPDC ligand (Park et al., 2011). The one-dimensional Cd^II 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 Cd^II 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 Cu^II 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 Cu^II 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).

S4. Conclusions

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 Cu^II 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.

Computing details

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).

Figures

	Fig. 1. Optical micrographs of (a) (I) and (b) (II).
	Fig. 2. The crystal structures of (a) (I) and (b) (II). Displacement ellipsoids are drawn at the 30% probability level. The disordered methyl groups have been omitted, as have all of the H atoms, except for the water and amine H atoms.
	Fig. 3. The hydrogen-bond network of (I). The black dotted lines are hydrogen bonds between the solvent water molecules and the O atoms of 3,3'-TPDC ligands, and the green dotted lines are hydrogen bonds between the coordinated amine H atoms and the solvent water O atoms. All of the H atoms, except for those involved in hydrogen bonds, have been omitted for clarity.
	Fig. 4. The hydrogen-bond networks of (II) (a) along the c axis and (b) along the a axis, and (c) the hydrogen-bonded two-dimensional sheet. The black dotted lines are hydrogen bonds between the solvent water molecules and the uncoordinated O atoms of 3,3'-TPDC ligands, as well as hydrogen bonds between the coordinated water molecules and the uncoordinated O atoms of 3,3'-TPDC ligands. The green dotted lines are hydrogen bonds between the coordinated amine H atoms and solvent water O atoms. All of the H atoms, except for those involved in hydrogen bonds, have been omitted for clarity.

(k09109a) catena-Poly[[bis(dimethylamine-κN)copper(II)]-µ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ⁴O,O':O'':O'''] monohydrate]

Crystal data

[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) Å^3	0.20 × 0.12 × 0.06 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.079	H-atom parameters constrained
wR(F^2) = 0.186	w = 1/[σ^2(Fo^2) + (0.023P)^2 + 2.7226P] where P = (Fo^2 + 2Fc^2)/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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Cu1—O2^i	1.965 (4)	C9—H9	0.9500
Cu1—O2	1.965 (4)	C10—C9^ii	1.397 (8)
Cu1—N1A	2.028 (5)	C10—H10	0.9500
Cu1—N1	2.028 (5)	N1A—C12A	1.447 (15)
Cu1—N1^i	2.028 (5)	N1A—C11A	1.529 (12)
Cu1—N1A^i	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—C10^ii	1.397 (8)
O2^i—Cu1—O2	180.0	C10^ii—C9—C8	120.2 (5)
O2^i—Cu1—N1A	88.72 (17)	C10^ii—C9—H9	119.9
O2—Cu1—N1A	91.28 (17)	C8—C9—H9	119.9
O2^i—Cu1—N1	88.72 (17)	C8—C10—C9^ii	121.4 (5)
O2—Cu1—N1	91.28 (17)	C8—C10—H10	119.3
O2^i—Cu1—N1^i	91.28 (17)	C9^ii—C10—H10	119.3
O2—Cu1—N1^i	88.72 (17)	C12A—N1A—C11A	107.1 (9)
N1—Cu1—N1^i	180.0	C12A—N1A—Cu1	119.2 (6)
O2^i—Cu1—N1A^i	91.28 (17)	C11A—N1A—Cu1	111.9 (6)
O2—Cu1—N1A^i	88.72 (17)	C12A—N1A—H1A	105.9
N1A—Cu1—N1A^i	180.0	C11A—N1A—H1A	105.9
O2^i—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
N1^i—Cu1—O1	89.38 (16)	N1A—C11A—H11F	109.5
N1A^i—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—C10^ii	−1.0 (9)
C2—C3—C4—C5	0.3 (9)	C6—C8—C9—C10^ii	178.5 (5)
C3—C4—C5—C6	0.0 (9)	C9—C8—C10—C9^ii	1.0 (9)
C4—C5—C6—C7	−0.3 (9)	C6—C8—C10—C9^ii	−178.5 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1W^iii	1.00	1.96	2.948 (9)	167
N1—H1···O1W^iv	1.00	1.94	2.912 (9)	164
O1W—H1WA···O1	0.84	1.85	2.689 (9)	180
O1W—H1WB···O1^v	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.

(k09111) catena-Poly[[aquabis(dimethylamine-κN)copper(II)]-µ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ⁴O³:O^3'] monohydrate]

Crystal data

[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) Å^3	Needle, blue
Z = 4	0.20 × 0.10 × 0.04 mm
F(000) = 1060

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.056	H-atom parameters constrained
wR(F^2) = 0.157	w = 1/[σ^2(Fo^2) + (0.0596P)^2 + 5.3006P] where P = (Fo^2 + 2Fc^2)/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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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

Geometric parameters (Å, º)

Cu1—O1	1.975 (3)	C5—C6	1.399 (7)
Cu1—O1^i	1.975 (3)	C5—H5A	0.9500
Cu1—N1^i	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—C10^ii	1.395 (7)
O3—H3O	0.8401	C9—H9	0.9500
N1—C12	1.457 (7)	C10—C9^ii	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—O1^i	173.3 (2)	C3—C4—C5	119.8 (5)
O1—Cu1—N1^i	88.42 (16)	C3—C4—H4A	120.1
O1^i—Cu1—N1^i	91.29 (16)	C5—C4—H4A	120.1
O1—Cu1—N1	91.29 (16)	C4—C5—C6	120.9 (5)
O1^i—Cu1—N1	88.42 (16)	C4—C5—H5A	119.5
N1^i—Cu1—N1	175.1 (2)	C6—C5—H5A	119.5
O1—Cu1—O3	93.35 (11)	C7—C6—C5	118.1 (5)
O1^i—Cu1—O3	93.35 (11)	C7—C6—C8	120.9 (5)
N1^i—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
O1^i—Cu1—O2	127.75 (13)	C6—C7—H7A	119.1
N1^i—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—C10^ii	121.6 (5)
C1—O2—Cu1	66.5 (3)	C8—C9—H9	119.2
Cu1—O3—H3O	132.4	C10^ii—C9—H9	119.2
C12—N1—C11	108.1 (4)	C9^ii—C10—C8	120.1 (5)
C12—N1—Cu1	112.6 (4)	C9^ii—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—C10^ii	−0.3 (10)
C2—C3—C4—C5	−0.7 (8)	C6—C8—C9—C10^ii	177.9 (5)
C3—C4—C5—C6	0.6 (9)	C9—C8—C10—C9^ii	0.3 (10)
C4—C5—C6—C7	−0.6 (8)	C6—C8—C10—C9^ii	−177.9 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2^iii	0.84	2.08	2.827 (4)	149
N1—H1A···O1W	1.00	2.26	3.185 (5)	154
O1W—H1WA···O2^iv	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.