Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113023093/lg3119sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113023093/lg3119Isup2.hkl |
CCDC reference: 969450
Coordination polymers have attracted considerable attention in recent years, not only because of their topological and aesthetic features, and interesting physical properties, such as magnetism, but also for numerous other industrial applications, such as in catalysis, gas storage etc. (Shimomura et al., 2009; Kuppler et al., 2009; Farrusseng et al., 2009; Liu et al., 2010). In their syntheses, metal carboxylates, along with ligands with N- and O-donor atoms, have often been used with the aim of constructing coordination polymers with mixed ligands which might have interesting structural features with useful applications. 4,4'-Bipyridine (4,4'-bipy) is a commonly used bridging ligand in the construction of coordination polymers (Lu et al., 1998; Lah & Leban, 2006; Lian et al., 2007; Bo et al., 2008; Li et al., 2009; Zhong et al., 2011) and is known to be used effectively to produce a variety of infinite one-, two- and three-dimensional coordination polymers (Yaghi & Li, 1995; Subramanian & Zaworotko, 1995; MacGillivray et al., 1994; Hagrman et al., 1997; Zheng et al., 1999; Jiang et al., 2005). One feature that makes 4,4'-bipy a good choice in the construction of these compounds is that it is rod-like and linear with exo-bidentate N-donor atoms, which often results in rigid structures. In an attempt to construct coordination polymers with mixed bridging ligands, we carried out a reaction using 4,4'-bipy, 4-nitrophenol and copper(II) acetate. The title coordination polymer, {[Cu(acetate)2(4,4'-bipy)].4-nitrophenol.2H2O}n, (I), was obtained and studied using single-crystal X-ray diffraction analysis.
In separate beakers, 4,4'-bipyridine (104.8 mg, 0.6669 mmol) was dissolved in methanol–acetonitrile–water (10:10:1 v/v/v) and Cu(CH3COO)2 (115.0 mg, 0.6769 mmol) was dissolved in acetonitrile (10 ml). The contents of the two beakers were combined in a 150 ml round-bottomed flask and subjected to ultrasound sonication for 5 min to ensure complete dissolution. The flask was then removed from the sonication bath and the blue solution was refluxed for 24 h. Filtration of the solution followed by slow evaporation of the solvents yielded a small number of blue crystals of (I) after several days.
Crystal data, data collection and structure refinement details are summarized in Table 1. All non-water H atoms were placed in geometrically idealized positions riding on their parent atoms, with C—H = 0.95 Å for aromatic H atoms, C—H = 0.98 Å for methyl groups and O—H = 0.84 Å for the phenol group. Uiso(H) values were set at 1.5Ueq(C) for the methyl H atoms or 1.5Ueq(C) otherwise [These are the same - should they be different?]. For the water molecules, H atoms were located in a difference Fourier map. Their positions were refined with restraints on the O—H distance [0.84 (2) Å] to ensure a reasonable geometry and the Uiso(H) values were refined freely. Four reflections [3 11 2, 658, -684 and 683] were omitted from the final refinement due to large discrepancies between Fobs and Fcalc.
Part of complex (I) is shown in Fig. 1; the asymmetric unit consists of one link of the coordination polymer, [Cu(acetate)3(4,4'-bipy)], a molecule of 4-nitrophenol and two solvent water molecules. The CuII centre has a square-pyramidal environment (τ = 0.030; Addison et al., 1984). Atom Cu1 is coordinated by atoms O1, O3, N2 and N1i in the basal plane of the pyramid, and apically by O3ii [symmetry codes: (i) x, y - 1, z; (ii) -x + 1, -y, -z]. Atom O3, which is a basal atom in the coordination around Cu1, is at the same time an apical ligand in the coordination around Cu1ii. As expected, the apical Cu1—O3ii distance is longer than the basal Cu—O1 and the two Cu—N2 and Cu–N1i bond lengths (see Table 2). The Cu—O and Cu—N bond lengths are comparable with those of complexes with similar coordination geometry (Bian et al. 2003; Xu et al. 2003). The basal geometry is almost square, with the bond angles around the CuII centre very close to orthogonal [ranging between 88.84 (6) and 91.26 (6)°]. The O—C—O angles of the acetate groups are close to 120° (Table 2) and the C—O bond lengths indicate that the mesomeric effect of the acetate groups is less [Than what?], with one of the bonds being significantly shorter than the other. The Cu···Cuii separation within one rung of the ladder [This is the first mention of the ladder. An earlier sentence would help the reader] is 3.4639 (4) Å, forcing the side-by-side bridging 4,4'-bipy ligand into close proximity and a slightly twisted conformation, with a dihedral angle of 15.41 (9)° [or a C4—C3—C6—C10 torsion angle of -15.6 (3)°]. The planes through the acetate groups are almost orthogonal to the planes through the two pyridine rings and have dihedral angles of 85.79 (1) and 88.32 (1)° (through the N2-pyridine ring), and 89.25 (1) and 88.99 (1)° (through the N1-pyridine ring). The 4-nitrophenol molecule lies just out of the planes of the pyridine rings of the 4,4'-bipy ligand along the ladder-like double strands. The dihedral angle between the planes through each of the pyridine rings and that through the 4-nitrophenol ring is 11.14 (7)° for the N1-pyridine ring and 7.82 (6)° for the N2-pyridine ring.
The structure of complex (I) features a prominent ladder-like double-stranded coordination polymer chain extending along the b crystallographic axis (Fig. 2). The chains are composed of two CuII centres that are coordinated by four acetate anions as the horizontal rungs of the ladder and centred on an inversion centre at (1/2, n, 0), with n being an integer. The vertical rails of the ladder are formed by the connecting 4,4'-bipy ligands (double strands). The ladder-like double strands are separated from each other by one unit-cell length along the crystallographic c axis, and in between them the water and 4-nitrophenol molecules are located (Fig. 3). These ladder-like double-stranded coordination polymers are linked by a number of O—H···O and C—H···O hydrogen bonds (Table 3) and form basic motifs that can can be described by three ring motifs, designated R1, R2 and R3 in Fig. 3, described by the graph-set notations (Bernstein et al., 1995) R44(14), R33(12) and R21(7), respectively. Atom O2W is common to R1 and R2, and all three rings connect the different molecules into sheets along the bc plane. Also, between the acetate groups attached to the Cu atoms there is an `intramolecular' interaction described by the graph-set notation S(6), in which atom C14 is the donor and O1 is the acceptor. There are two unique intermolecular π–π interactions in this structure. The first is between the N1-containing ring of 4,4'-bipy and the N2-containing ring of a neighbouring 4,4'-bipy ligand at (-x + 1, -y + 1, -z). The other rings of the two 4,4'-bipy ligands form a self-complementary equivalent contact with a centroid-to-centroid distance of 3.7696 (11) Å. The second is between two neighbouring symmetry-related 4-nitrophenol molecules, i.e. those at (x, y, z) and (-x + 2, -y + 1, -z + 1), with a centroid-to-centroid distance of 3.6151 (14) Å (Fig. 4).
Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).
[Cu(C2H3O2)2(C10H8N2)]·C6H5NO3·2H2O | Z = 2 |
Mr = 512.95 | F(000) = 530 |
Triclinic, P1 | Dx = 1.587 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54184 Å |
a = 8.5997 (5) Å | Cell parameters from 7928 reflections |
b = 11.1264 (6) Å | θ = 3.8–70.1° |
c = 11.6962 (6) Å | µ = 1.96 mm−1 |
α = 85.020 (4)° | T = 173 K |
β = 85.720 (4)° | Block, blue |
γ = 74.647 (5)° | 0.14 × 0.07 × 0.04 mm |
V = 1073.57 (10) Å3 |
Agilent SuperNova Dual diffractometer (Cu at zero) with Atlas detector | 3703 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 70.1°, θmin = 3.8° |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012) | h = −10→10 |
Tmin = 0.771, Tmax = 0.926 | k = −13→13 |
7928 measured reflections | l = −14→14 |
4060 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0514P)2 + 0.3752P] where P = (Fo2 + 2Fc2)/3 |
4060 reflections | (Δ/σ)max = 0.003 |
317 parameters | Δρmax = 0.66 e Å−3 |
4 restraints | Δρmin = −0.56 e Å−3 |
[Cu(C2H3O2)2(C10H8N2)]·C6H5NO3·2H2O | γ = 74.647 (5)° |
Mr = 512.95 | V = 1073.57 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.5997 (5) Å | Cu Kα radiation |
b = 11.1264 (6) Å | µ = 1.96 mm−1 |
c = 11.6962 (6) Å | T = 173 K |
α = 85.020 (4)° | 0.14 × 0.07 × 0.04 mm |
β = 85.720 (4)° |
Agilent SuperNova Dual diffractometer (Cu at zero) with Atlas detector | 4060 independent reflections |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012) | 3703 reflections with I > 2σ(I) |
Tmin = 0.771, Tmax = 0.926 | Rint = 0.025 |
7928 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 4 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.66 e Å−3 |
4060 reflections | Δρmin = −0.56 e Å−3 |
317 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3290 (2) | 0.77888 (18) | 0.07033 (17) | 0.0145 (4) | |
H1 | 0.2724 | 0.8378 | 0.0141 | 0.017* | |
C2 | 0.3252 (2) | 0.65569 (18) | 0.07011 (17) | 0.0139 (4) | |
H2 | 0.2678 | 0.6311 | 0.0139 | 0.017* | |
C3 | 0.4058 (2) | 0.56697 (18) | 0.15264 (16) | 0.0123 (4) | |
C4 | 0.4862 (2) | 0.60964 (18) | 0.23363 (17) | 0.0152 (4) | |
H4 | 0.5406 | 0.5534 | 0.2925 | 0.018* | |
C5 | 0.4860 (2) | 0.73492 (18) | 0.22753 (17) | 0.0159 (4) | |
H5 | 0.5423 | 0.7623 | 0.2827 | 0.019* | |
C6 | 0.4059 (2) | 0.43335 (18) | 0.15306 (16) | 0.0126 (4) | |
C7 | 0.2971 (2) | 0.39649 (18) | 0.09054 (17) | 0.0143 (4) | |
H7 | 0.2201 | 0.4573 | 0.0475 | 0.017* | |
C8 | 0.3011 (2) | 0.27117 (18) | 0.09106 (17) | 0.0154 (4) | |
H8 | 0.2256 | 0.2479 | 0.048 | 0.019* | |
C9 | 0.5124 (2) | 0.21556 (19) | 0.21152 (17) | 0.0152 (4) | |
H9 | 0.5874 | 0.1528 | 0.2543 | 0.018* | |
C10 | 0.5155 (2) | 0.33907 (18) | 0.21498 (16) | 0.0144 (4) | |
H10 | 0.5918 | 0.3597 | 0.2592 | 0.017* | |
C11 | 0.1514 (3) | 0.04433 (18) | 0.28875 (17) | 0.0164 (4) | |
C12 | −0.0214 (3) | 0.0856 (2) | 0.3342 (2) | 0.0276 (5) | |
H12A | −0.0244 | 0.0995 | 0.416 | 0.041* | |
H12B | −0.0764 | 0.0208 | 0.3242 | 0.041* | |
H12C | −0.076 | 0.1635 | 0.2919 | 0.041* | |
C13 | 0.7420 (2) | −0.07518 (17) | 0.13950 (17) | 0.0139 (4) | |
C14 | 0.9128 (2) | −0.1142 (2) | 0.08973 (18) | 0.0179 (4) | |
H14A | 0.9817 | −0.077 | 0.1309 | 0.027* | |
H14B | 0.9159 | −0.0855 | 0.0082 | 0.027* | |
H14C | 0.9521 | −0.2054 | 0.0977 | 0.027* | |
C15 | 0.7709 (3) | 0.4181 (2) | 0.53230 (18) | 0.0198 (4) | |
C16 | 0.8745 (3) | 0.3210 (2) | 0.59573 (18) | 0.0207 (4) | |
H16 | 0.8775 | 0.2366 | 0.5857 | 0.025* | |
C17 | 0.9723 (3) | 0.3483 (2) | 0.67288 (18) | 0.0213 (4) | |
H17 | 1.0435 | 0.283 | 0.7159 | 0.026* | |
C18 | 0.9651 (3) | 0.4723 (2) | 0.68673 (19) | 0.0206 (4) | |
C19 | 0.8663 (3) | 0.5700 (2) | 0.62192 (19) | 0.0211 (4) | |
H19 | 0.8661 | 0.6542 | 0.6305 | 0.025* | |
C20 | 0.7691 (3) | 0.5423 (2) | 0.54517 (19) | 0.0223 (5) | |
H20 | 0.7004 | 0.6079 | 0.5008 | 0.027* | |
N1 | 0.4099 (2) | 0.81902 (15) | 0.14720 (14) | 0.0133 (3) | |
N2 | 0.4076 (2) | 0.18126 (15) | 0.15010 (14) | 0.0130 (3) | |
N3 | 1.0623 (2) | 0.50077 (19) | 0.77231 (17) | 0.0265 (4) | |
O1 | 0.17622 (16) | 0.04564 (12) | 0.18014 (12) | 0.0140 (3) | |
O2 | 0.2636 (2) | 0.01075 (15) | 0.35565 (13) | 0.0254 (3) | |
O1W | 0.3136 (2) | 0.15819 (15) | 0.52155 (14) | 0.0245 (3) | |
O3 | 0.62988 (16) | −0.03629 (12) | 0.06744 (12) | 0.0132 (3) | |
O2W | 0.6227 (2) | 0.17469 (16) | 0.47748 (14) | 0.0259 (4) | |
O4 | 0.71288 (17) | −0.08257 (13) | 0.24466 (12) | 0.0181 (3) | |
O5 | 0.6718 (2) | 0.39693 (15) | 0.45734 (13) | 0.0248 (3) | |
H5A | 0.6524 | 0.3274 | 0.4754 | 0.037* | |
O6 | 1.0695 (2) | 0.60947 (17) | 0.77630 (17) | 0.0370 (4) | |
O7 | 1.1316 (2) | 0.41520 (18) | 0.83938 (16) | 0.0375 (4) | |
Cu1 | 0.40800 (3) | 0.00157 (2) | 0.13693 (2) | 0.01154 (11) | |
H1A | 0.305 (4) | 0.126 (3) | 0.5870 (18) | 0.040 (9)* | |
H1B | 0.293 (4) | 0.113 (3) | 0.477 (2) | 0.040 (9)* | |
H2A | 0.677 (3) | 0.121 (2) | 0.523 (2) | 0.031 (8)* | |
H2B | 0.528 (2) | 0.176 (3) | 0.493 (3) | 0.045 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0164 (9) | 0.0122 (9) | 0.0153 (9) | −0.0040 (8) | −0.0013 (7) | −0.0015 (7) |
C2 | 0.0165 (9) | 0.0123 (9) | 0.0143 (9) | −0.0051 (7) | −0.0015 (7) | −0.0028 (7) |
C3 | 0.0131 (9) | 0.0092 (9) | 0.0148 (9) | −0.0027 (7) | 0.0018 (7) | −0.0042 (7) |
C4 | 0.0196 (10) | 0.0113 (9) | 0.0154 (9) | −0.0043 (8) | −0.0033 (8) | −0.0025 (7) |
C5 | 0.0196 (10) | 0.0138 (9) | 0.0165 (9) | −0.0070 (8) | −0.0026 (8) | −0.0040 (7) |
C6 | 0.0150 (9) | 0.0120 (9) | 0.0111 (9) | −0.0038 (7) | 0.0017 (7) | −0.0037 (7) |
C7 | 0.0177 (9) | 0.0091 (9) | 0.0165 (10) | −0.0027 (7) | −0.0039 (7) | −0.0025 (7) |
C8 | 0.0159 (9) | 0.0120 (9) | 0.0197 (10) | −0.0039 (8) | −0.0042 (8) | −0.0041 (8) |
C9 | 0.0180 (10) | 0.0140 (9) | 0.0137 (9) | −0.0036 (8) | −0.0023 (7) | −0.0029 (7) |
C10 | 0.0188 (10) | 0.0136 (9) | 0.0129 (9) | −0.0063 (8) | −0.0037 (7) | −0.0035 (7) |
C11 | 0.0225 (10) | 0.0111 (9) | 0.0179 (10) | −0.0072 (8) | 0.0005 (8) | −0.0057 (7) |
C12 | 0.0262 (12) | 0.0326 (13) | 0.0267 (12) | −0.0112 (10) | 0.0072 (9) | −0.0127 (10) |
C13 | 0.0187 (10) | 0.0083 (8) | 0.0164 (10) | −0.0060 (7) | −0.0026 (7) | −0.0019 (7) |
C14 | 0.0173 (10) | 0.0210 (10) | 0.0167 (10) | −0.0067 (8) | −0.0030 (8) | −0.0016 (8) |
C15 | 0.0223 (10) | 0.0196 (10) | 0.0160 (10) | −0.0031 (8) | 0.0016 (8) | −0.0024 (8) |
C16 | 0.0267 (11) | 0.0169 (10) | 0.0173 (10) | −0.0039 (9) | 0.0010 (8) | −0.0021 (8) |
C17 | 0.0213 (10) | 0.0217 (11) | 0.0181 (10) | −0.0014 (9) | 0.0000 (8) | 0.0005 (8) |
C18 | 0.0181 (10) | 0.0246 (11) | 0.0186 (10) | −0.0052 (9) | 0.0018 (8) | −0.0028 (8) |
C19 | 0.0234 (11) | 0.0176 (10) | 0.0215 (10) | −0.0049 (9) | 0.0050 (8) | −0.0033 (8) |
C20 | 0.0247 (11) | 0.0197 (11) | 0.0192 (11) | −0.0008 (9) | 0.0001 (8) | 0.0007 (8) |
N1 | 0.0151 (8) | 0.0113 (8) | 0.0148 (8) | −0.0051 (6) | 0.0000 (6) | −0.0031 (6) |
N2 | 0.0158 (8) | 0.0110 (8) | 0.0137 (8) | −0.0049 (6) | −0.0003 (6) | −0.0047 (6) |
N3 | 0.0204 (9) | 0.0317 (11) | 0.0282 (10) | −0.0073 (8) | 0.0012 (8) | −0.0075 (9) |
O1 | 0.0156 (7) | 0.0130 (7) | 0.0142 (7) | −0.0043 (5) | −0.0004 (5) | −0.0039 (5) |
O2 | 0.0287 (8) | 0.0294 (8) | 0.0194 (8) | −0.0079 (7) | −0.0068 (6) | −0.0023 (6) |
O1W | 0.0372 (9) | 0.0208 (8) | 0.0175 (8) | −0.0102 (7) | −0.0031 (7) | −0.0023 (6) |
O3 | 0.0147 (7) | 0.0109 (6) | 0.0150 (7) | −0.0037 (5) | −0.0028 (5) | −0.0034 (5) |
O2W | 0.0290 (9) | 0.0247 (8) | 0.0248 (8) | −0.0075 (7) | −0.0068 (7) | 0.0004 (7) |
O4 | 0.0228 (8) | 0.0178 (7) | 0.0149 (7) | −0.0066 (6) | −0.0021 (6) | −0.0023 (6) |
O5 | 0.0316 (9) | 0.0209 (8) | 0.0214 (8) | −0.0042 (7) | −0.0079 (7) | −0.0007 (6) |
O6 | 0.0383 (10) | 0.0331 (10) | 0.0459 (11) | −0.0172 (8) | −0.0060 (8) | −0.0085 (8) |
O7 | 0.0403 (10) | 0.0390 (10) | 0.0347 (10) | −0.0092 (8) | −0.0172 (8) | −0.0010 (8) |
Cu1 | 0.01398 (17) | 0.00704 (16) | 0.01482 (17) | −0.00394 (11) | −0.00093 (11) | −0.00354 (11) |
C1—N1 | 1.349 (3) | C13—C14 | 1.504 (3) |
C1—C2 | 1.380 (3) | C14—H14A | 0.98 |
C1—H1 | 0.95 | C14—H14B | 0.98 |
C2—C3 | 1.400 (3) | C14—H14C | 0.98 |
C2—H2 | 0.95 | C15—O5 | 1.343 (3) |
C3—C4 | 1.396 (3) | C15—C20 | 1.399 (3) |
C3—C6 | 1.486 (3) | C15—C16 | 1.400 (3) |
C4—C5 | 1.389 (3) | C16—C17 | 1.382 (3) |
C4—H4 | 0.95 | C16—H16 | 0.95 |
C5—N1 | 1.342 (3) | C17—C18 | 1.387 (3) |
C5—H5 | 0.95 | C17—H17 | 0.95 |
C6—C7 | 1.391 (3) | C18—C19 | 1.394 (3) |
C6—C10 | 1.400 (3) | C18—N3 | 1.457 (3) |
C7—C8 | 1.385 (3) | C19—C20 | 1.377 (3) |
C7—H7 | 0.95 | C19—H19 | 0.95 |
C8—N2 | 1.344 (3) | C20—H20 | 0.95 |
C8—H8 | 0.95 | Cu1—N1i | 2.0200 (16) |
C9—N2 | 1.342 (2) | Cu1—N2 | 2.0177 (16) |
C9—C10 | 1.386 (3) | N3—O7 | 1.232 (3) |
C9—H9 | 0.95 | N3—O6 | 1.232 (3) |
C10—H10 | 0.95 | Cu1—O1 | 1.9607 (14) |
C11—O2 | 1.246 (3) | O1W—H1A | 0.823 (18) |
C11—O2 | 1.246 (3) | O1W—H1B | 0.814 (18) |
C11—O1 | 1.272 (2) | Cu1—O3 | 1.9701 (14) |
C11—C12 | 1.505 (3) | Cu1—O3ii | 2.4204 (14) |
C12—H12A | 0.98 | O2W—H2A | 0.829 (17) |
C12—H12B | 0.98 | O2W—H2B | 0.815 (18) |
C12—H12C | 0.98 | O5—H5A | 0.84 |
C13—O4 | 1.237 (2) | Cu1—N1i | 2.0200 (16) |
C13—O3 | 1.290 (2) | Cu1—O3ii | 2.4204 (14) |
N1—C1—C2 | 122.60 (18) | C13—C14—H14C | 109.5 |
N1—C1—H1 | 118.7 | H14A—C14—H14C | 109.5 |
C2—C1—H1 | 118.7 | H14B—C14—H14C | 109.5 |
C1—C2—C3 | 120.06 (18) | O5—C15—C20 | 117.64 (19) |
C1—C2—H2 | 120 | O5—C15—C16 | 122.3 (2) |
C3—C2—H2 | 120 | C20—C15—C16 | 120.0 (2) |
C4—C3—C2 | 117.05 (18) | C17—C16—C15 | 119.9 (2) |
C4—C3—C6 | 121.84 (18) | C17—C16—H16 | 120.1 |
C2—C3—C6 | 121.11 (17) | C15—C16—H16 | 120.1 |
C5—C4—C3 | 119.52 (18) | C16—C17—C18 | 119.1 (2) |
C5—C4—H4 | 120.2 | C16—C17—H17 | 120.4 |
C3—C4—H4 | 120.2 | C18—C17—H17 | 120.4 |
N1—C5—C4 | 122.97 (18) | C17—C18—C19 | 121.8 (2) |
N1—C5—H5 | 118.5 | C17—C18—N3 | 118.9 (2) |
C4—C5—H5 | 118.5 | C19—C18—N3 | 119.2 (2) |
C7—C6—C10 | 117.03 (17) | C20—C19—C18 | 118.7 (2) |
C7—C6—C3 | 121.09 (18) | C20—C19—H19 | 120.6 |
C10—C6—C3 | 121.87 (17) | C18—C19—H19 | 120.6 |
C8—C7—C6 | 119.99 (18) | C19—C20—C15 | 120.3 (2) |
C8—C7—H7 | 120 | C19—C20—H20 | 119.8 |
C6—C7—H7 | 120 | C15—C20—H20 | 119.8 |
N2—C8—C7 | 122.52 (18) | C5—N1—C1 | 117.76 (16) |
N2—C8—H8 | 118.7 | C5—N1—Cu1iii | 123.59 (13) |
C7—C8—H8 | 118.7 | C1—N1—Cu1iii | 118.64 (13) |
N2—C9—C10 | 122.50 (18) | C9—N2—C8 | 118.13 (16) |
N2—C9—H9 | 118.7 | C9—N2—Cu1 | 123.33 (14) |
C10—C9—H9 | 118.7 | C8—N2—Cu1 | 118.49 (13) |
C9—C10—C6 | 119.83 (18) | O7—N3—O6 | 122.6 (2) |
C9—C10—H10 | 120.1 | O7—N3—C18 | 118.40 (19) |
C6—C10—H10 | 120.1 | O6—N3—C18 | 118.9 (2) |
O2—C11—O1 | 122.32 (19) | C11—O1—Cu1 | 111.08 (12) |
O2—C11—O1 | 122.32 (19) | H1A—O1W—H1B | 107 (3) |
O2—C11—C12 | 120.78 (19) | C13—O3—Cu1 | 114.96 (12) |
O2—C11—C12 | 120.78 (19) | C13—O3—Cu1ii | 141.22 (12) |
O1—C11—C12 | 116.90 (18) | Cu1—O3—Cu1ii | 103.70 (6) |
C11—C12—H12A | 109.5 | H2A—O2W—H2B | 107 (3) |
C11—C12—H12B | 109.5 | C15—O5—H5A | 109.5 |
H12A—C12—H12B | 109.5 | O1—Cu1—O3 | 170.61 (6) |
C11—C12—H12C | 109.5 | O1—Cu1—N2 | 88.84 (6) |
H12A—C12—H12C | 109.5 | O3—Cu1—N2 | 91.26 (6) |
H12B—C12—H12C | 109.5 | O1—Cu1—N1i | 89.94 (6) |
O4—C13—O3 | 122.55 (18) | O3—Cu1—N1i | 91.20 (6) |
O4—C13—C14 | 120.64 (17) | N2—Cu1—N1i | 172.21 (7) |
O3—C13—C14 | 116.80 (17) | O1—Cu1—O3ii | 94.31 (5) |
C13—C14—H14A | 109.5 | O3—Cu1—O3ii | 76.30 (6) |
C13—C14—H14B | 109.5 | N2—Cu1—O3ii | 92.12 (6) |
H14A—C14—H14B | 109.5 | N1i—Cu1—O3ii | 95.64 (6) |
N1—C1—C2—C3 | 0.8 (3) | C10—C9—N2—Cu1 | 176.73 (15) |
C1—C2—C3—C4 | 0.8 (3) | C7—C8—N2—C9 | 0.7 (3) |
C1—C2—C3—C6 | −178.97 (18) | C7—C8—N2—Cu1 | −176.86 (15) |
C2—C3—C4—C5 | −1.4 (3) | C17—C18—N3—O7 | −9.1 (3) |
C6—C3—C4—C5 | 178.28 (18) | C19—C18—N3—O7 | 170.3 (2) |
C3—C4—C5—N1 | 0.7 (3) | C17—C18—N3—O6 | 172.3 (2) |
C4—C3—C6—C7 | 164.99 (19) | C19—C18—N3—O6 | −8.3 (3) |
C2—C3—C6—C7 | −15.3 (3) | O2—C11—O1—Cu1 | −4.3 (2) |
C4—C3—C6—C10 | −15.6 (3) | O2—C11—O1—Cu1 | −4.3 (2) |
C2—C3—C6—C10 | 164.08 (19) | C12—C11—O1—Cu1 | 175.63 (14) |
C10—C6—C7—C8 | −0.3 (3) | O1—C11—O2—O2 | 0.00 (11) |
C3—C6—C7—C8 | 179.10 (18) | C12—C11—O2—O2 | 0.00 (8) |
C6—C7—C8—N2 | −0.2 (3) | O4—C13—O3—Cu1 | −3.3 (2) |
N2—C9—C10—C6 | 0.2 (3) | C14—C13—O3—Cu1 | 175.67 (12) |
C7—C6—C10—C9 | 0.3 (3) | O4—C13—O3—Cu1ii | −178.39 (12) |
C3—C6—C10—C9 | −179.11 (18) | C14—C13—O3—Cu1ii | 0.5 (3) |
O5—C15—C16—C17 | −179.1 (2) | C11—O1—Cu1—N2 | −83.93 (13) |
C20—C15—C16—C17 | 1.4 (3) | C11—O1—Cu1—N1i | 88.38 (13) |
C15—C16—C17—C18 | 0.5 (3) | C11—O1—Cu1—O3ii | −175.97 (12) |
C16—C17—C18—C19 | −2.4 (3) | C13—O3—Cu1—N2 | 91.26 (13) |
C16—C17—C18—N3 | 176.92 (19) | Cu1ii—O3—Cu1—N2 | −91.87 (6) |
C17—C18—C19—C20 | 2.4 (3) | C13—O3—Cu1—N1i | −81.35 (13) |
N3—C18—C19—C20 | −176.9 (2) | Cu1ii—O3—Cu1—N1i | 95.52 (6) |
C18—C19—C20—C15 | −0.5 (3) | C13—O3—Cu1—O3ii | −176.87 (15) |
O5—C15—C20—C19 | 179.1 (2) | Cu1ii—O3—Cu1—O3ii | 0 |
C16—C15—C20—C19 | −1.4 (3) | C9—N2—Cu1—O1 | 129.09 (16) |
C4—C5—N1—C1 | 0.8 (3) | C8—N2—Cu1—O1 | −53.47 (15) |
C4—C5—N1—Cu1iii | 179.94 (15) | C9—N2—Cu1—O3 | −60.30 (16) |
C2—C1—N1—C5 | −1.5 (3) | C8—N2—Cu1—O3 | 117.14 (15) |
C2—C1—N1—Cu1iii | 179.28 (15) | C9—N2—Cu1—O3ii | −136.64 (16) |
C10—C9—N2—C8 | −0.7 (3) | C8—N2—Cu1—O3ii | 40.81 (15) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z; (iii) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O4iv | 0.82 (2) | 1.99 (2) | 2.801 (2) | 168 (3) |
O1W—H1B···O2 | 0.81 (2) | 1.97 (2) | 2.774 (2) | 173 (3) |
O2W—H2A···O2iv | 0.83 (2) | 1.95 (2) | 2.746 (2) | 161 (3) |
O2W—H2B···O1W | 0.82 (2) | 1.91 (2) | 2.721 (2) | 173 (3) |
O5—H5A···O2W | 0.84 | 1.78 | 2.605 (2) | 166 |
C4—H4···O5 | 0.95 | 2.59 | 3.542 (3) | 176 |
C10—H10···O5 | 0.95 | 2.56 | 3.406 (2) | 148 |
C14—H14A···O1v | 0.98 | 2.55 | 3.497 (2) | 164 |
Symmetry codes: (iv) −x+1, −y, −z+1; (v) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2H3O2)2(C10H8N2)]·C6H5NO3·2H2O |
Mr | 512.95 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.5997 (5), 11.1264 (6), 11.6962 (6) |
α, β, γ (°) | 85.020 (4), 85.720 (4), 74.647 (5) |
V (Å3) | 1073.57 (10) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 1.96 |
Crystal size (mm) | 0.14 × 0.07 × 0.04 |
Data collection | |
Diffractometer | Agilent SuperNova Dual diffractometer (Cu at zero) with Atlas detector |
Absorption correction | Analytical (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.771, 0.926 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7928, 4060, 3703 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.099, 1.11 |
No. of reflections | 4060 |
No. of parameters | 317 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.66, −0.56 |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 2012).
C11—O2 | 1.246 (3) | Cu1—N2 | 2.0177 (16) |
C11—O1 | 1.272 (2) | Cu1—O1 | 1.9607 (14) |
C13—O4 | 1.237 (2) | Cu1—O3 | 1.9701 (14) |
C13—O3 | 1.290 (2) | Cu1—O3ii | 2.4204 (14) |
Cu1—N1i | 2.0200 (16) | ||
O2—C11—O1 | 122.32 (19) | O3—Cu1—N1i | 91.20 (6) |
O4—C13—O3 | 122.55 (18) | N2—Cu1—N1i | 172.21 (7) |
O1—Cu1—O3 | 170.61 (6) | O1—Cu1—O3ii | 94.31 (5) |
O1—Cu1—N2 | 88.84 (6) | O3—Cu1—O3ii | 76.30 (6) |
O3—Cu1—N2 | 91.26 (6) | N2—Cu1—O3ii | 92.12 (6) |
O1—Cu1—N1i | 89.94 (6) | N1i—Cu1—O3ii | 95.64 (6) |
C11—O1—Cu1—N2 | −83.93 (13) | C13—O3—Cu1—N2 | 91.26 (13) |
C11—O1—Cu1—N1i | 88.38 (13) | Cu1ii—O3—Cu1—N1i | 95.52 (6) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O4iii | 0.823 (18) | 1.991 (19) | 2.801 (2) | 168 (3) |
O1W—H1B···O2 | 0.814 (18) | 1.965 (18) | 2.774 (2) | 173 (3) |
O2W—H2A···O2iii | 0.829 (17) | 1.948 (19) | 2.746 (2) | 161 (3) |
O2W—H2B···O1W | 0.815 (18) | 1.909 (19) | 2.721 (2) | 173 (3) |
O5—H5A···O2W | 0.84 | 1.78 | 2.605 (2) | 166 |
C4—H4···O5 | 0.95 | 2.59 | 3.542 (3) | 176 |
C10—H10···O5 | 0.95 | 2.56 | 3.406 (2) | 148 |
C14—H14A···O1iv | 0.98 | 2.55 | 3.497 (2) | 164 |
Symmetry codes: (iii) −x+1, −y, −z+1; (iv) x+1, y, z. |