5-[(Imidazol-1-yl)methyl]benzene-1,3-dicarboxylic acid (H2L) was synthesized and the dimethylformamide- and dimethylacetamide-solvated structures of its adducts with CuII, namely catena-poly[[copper(II)-bis[μ-3-carboxy-5-[(imidazol-1-yl)methyl]benzoato]] dimethylformamide disolvate], {[Cu(C12H9N2O4)2]·2C3H7NO}n, (I), and catena-poly[[copper(II)-bis[μ-3-carboxy-5-[(imidazol-1-yl)methyl]benzoato]] dimethylacetamide disolvate], {[Cu(C12H9N2O4)2]·2C4H9NO}n, (II), the formation of which are associated with mono-deprotonation of H2L. The two structures are isomorphous and isometric. They consist of one-dimensional coordination polymers of the organic ligand with CuII in a 2:1 ratio, [Cu(μ-HL)2]n, crystallizing as the dimethylformamide (DMF) or dimethylacetamide (DMA) disolvates. The CuII cations are characterized by a coordination number of six, being located on centres of crystallographic inversion. In the polymeric chains, each CuII cation is linked to four neighbouring HL− ligands, and the organic ligand is coordinated via Cu—O and Cu—N bonds to two CuII cations. In the corresponding crystal structures of (I) and (II), the coordination chains, aligned parallel to the c axis, are further interlinked by strong hydrogen bonds between the noncoordinated carboxy groups in one array and the coordinated carboxylate groups of neighbouring chains. Molecules of DMF and DMA (disordered) are accommodated at the interface between adjacent polymeric assemblies. This report provides the first structural evidence for the formation of coordination polymers with H2L via multiple metal–ligand bonds through both carboxylate and imidazole groups.
Supporting information
CCDC references: 934595; 934596
For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2012 (Sheldrick, 2008).
(I)
catena-poly[[copper(II)-bis[µ-3-carboxy-5-[(imidazol-1-yl)methyl]benzoato]] dimethylformamide disolvate]
top
Crystal data top
[Cu(C12H9N2O4)2]·2C3H7NO | F(000) = 726 |
Mr = 700.17 | Dx = 1.475 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5555 (1) Å | Cell parameters from 3437 reflections |
b = 21.9603 (5) Å | θ = 2.8–27.8° |
c = 9.8497 (2) Å | µ = 0.76 mm−1 |
β = 105.2590 (9)° | T = 110 K |
V = 1576.66 (5) Å3 | Prism, green |
Z = 2 | 0.30 × 0.25 × 0.25 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3689 independent reflections |
Radiation source: sealed X-ray tube | 2639 reflections with I > 2σ(I) |
Detector resolution: 12.8 pixels mm-1 | Rint = 0.050 |
1° φ and ω scans | θmax = 27.8°, θmin = 2.8° |
Absorption correction: multi-scan (Blessing, 1995) | h = −9→9 |
Tmin = 0.804, Tmax = 0.833 | k = −28→28 |
12428 measured reflections | l = −12→12 |
Refinement top
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0892P)2 + 0.9016P], where P = (Fo2 + 2Fc2)/3 |
3689 reflections | (Δ/σ)max = 0.003 |
217 parameters | Δρmax = 0.89 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 1.0000 | 0.0000 | 1.0000 | 0.01997 (17) | |
O2 | 0.8865 (3) | 0.01891 (9) | 0.7991 (2) | 0.0219 (4) | |
O3 | 1.0407 (3) | 0.10340 (9) | 0.8724 (2) | 0.0265 (5) | |
C4 | 0.9250 (4) | 0.07429 (13) | 0.7813 (3) | 0.0211 (6) | |
C5 | 0.8188 (4) | 0.10403 (13) | 0.6471 (3) | 0.0223 (6) | |
C6 | 0.8110 (4) | 0.16732 (13) | 0.6368 (3) | 0.0225 (6) | |
H6 | 0.8764 | 0.1915 | 0.7136 | 0.027* | |
C7 | 0.7084 (4) | 0.19521 (13) | 0.5149 (3) | 0.0238 (6) | |
C8 | 0.7049 (4) | 0.26335 (14) | 0.5099 (3) | 0.0274 (7) | |
O9 | 0.7652 (3) | 0.29491 (10) | 0.6109 (2) | 0.0361 (6) | |
O10 | 0.6367 (4) | 0.28468 (11) | 0.3815 (2) | 0.0452 (6) | |
H10 | 0.6062 | 0.3213 | 0.3859 | 0.068* | |
C11 | 0.6091 (4) | 0.16024 (14) | 0.4024 (3) | 0.0240 (6) | |
H11 | 0.5391 | 0.1795 | 0.3191 | 0.029* | |
C12 | 0.6132 (4) | 0.09634 (14) | 0.4127 (3) | 0.0229 (6) | |
C13 | 0.7189 (4) | 0.06904 (14) | 0.5341 (3) | 0.0225 (6) | |
H13 | 0.7234 | 0.0259 | 0.5407 | 0.027* | |
C14 | 0.5056 (4) | 0.05795 (15) | 0.2918 (3) | 0.0248 (6) | |
H14A | 0.4991 | 0.0156 | 0.3247 | 0.030* | |
H14B | 0.3788 | 0.0738 | 0.2599 | 0.030* | |
N15 | 0.5888 (3) | 0.05786 (11) | 0.1726 (2) | 0.0221 (5) | |
C16 | 0.7474 (4) | 0.03079 (14) | 0.1726 (3) | 0.0251 (6) | |
H16 | 0.8234 | 0.0099 | 0.2509 | 0.030* | |
N17 | 0.7851 (3) | 0.03691 (11) | 0.0488 (2) | 0.0228 (5) | |
C18 | 0.6374 (4) | 0.06878 (16) | −0.0345 (3) | 0.0318 (7) | |
H18 | 0.6227 | 0.0796 | −0.1302 | 0.038* | |
C19 | 0.5170 (4) | 0.08215 (16) | 0.0423 (3) | 0.0313 (7) | |
H19 | 0.4052 | 0.1040 | 0.0114 | 0.038* | |
O20 | 0.2857 (5) | 0.07385 (14) | 0.6088 (3) | 0.0649 (9) | |
C21 | 0.2918 (6) | 0.1295 (2) | 0.6124 (5) | 0.0593 (12) | |
H21 | 0.3629 | 0.1481 | 0.6962 | 0.071* | |
N22 | 0.2068 (4) | 0.16587 (16) | 0.5085 (4) | 0.0501 (9) | |
C23 | 0.2170 (7) | 0.2311 (2) | 0.5154 (8) | 0.088 (2) | |
H23A | 0.2934 | 0.2435 | 0.6079 | 0.132* | |
H23B | 0.0934 | 0.2480 | 0.5012 | 0.132* | |
H23C | 0.2713 | 0.2463 | 0.4419 | 0.132* | |
C24 | 0.0989 (6) | 0.1401 (3) | 0.3784 (6) | 0.0689 (14) | |
H24A | 0.1138 | 0.0958 | 0.3810 | 0.103* | |
H24B | 0.1402 | 0.1568 | 0.2997 | 0.103* | |
H24C | −0.0307 | 0.1503 | 0.3662 | 0.103* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0217 (3) | 0.0189 (3) | 0.0178 (3) | 0.00116 (18) | 0.00244 (18) | 0.00131 (19) |
O2 | 0.0246 (10) | 0.0196 (10) | 0.0201 (10) | 0.0016 (8) | 0.0033 (8) | 0.0029 (8) |
O3 | 0.0288 (10) | 0.0209 (10) | 0.0248 (11) | −0.0021 (8) | −0.0017 (9) | 0.0008 (9) |
C4 | 0.0221 (13) | 0.0200 (14) | 0.0211 (14) | 0.0025 (11) | 0.0058 (11) | 0.0003 (11) |
C5 | 0.0224 (14) | 0.0229 (15) | 0.0206 (14) | 0.0025 (11) | 0.0038 (11) | 0.0033 (12) |
C6 | 0.0221 (14) | 0.0217 (15) | 0.0217 (14) | −0.0008 (11) | 0.0020 (11) | −0.0006 (12) |
C7 | 0.0250 (14) | 0.0195 (15) | 0.0256 (15) | 0.0009 (11) | 0.0044 (12) | −0.0004 (12) |
C8 | 0.0292 (15) | 0.0222 (16) | 0.0267 (16) | 0.0018 (12) | −0.0001 (13) | 0.0013 (12) |
O9 | 0.0477 (13) | 0.0226 (12) | 0.0291 (12) | 0.0001 (10) | −0.0057 (10) | −0.0011 (10) |
O10 | 0.0688 (17) | 0.0216 (12) | 0.0320 (13) | 0.0061 (12) | −0.0099 (12) | 0.0014 (10) |
C11 | 0.0235 (14) | 0.0242 (15) | 0.0223 (14) | 0.0018 (11) | 0.0026 (11) | 0.0011 (12) |
C12 | 0.0211 (13) | 0.0252 (15) | 0.0225 (14) | 0.0000 (11) | 0.0059 (11) | −0.0010 (12) |
C13 | 0.0230 (13) | 0.0222 (15) | 0.0225 (14) | 0.0004 (11) | 0.0062 (11) | 0.0022 (12) |
C14 | 0.0219 (14) | 0.0312 (16) | 0.0211 (14) | −0.0017 (12) | 0.0054 (12) | −0.0012 (12) |
N15 | 0.0224 (11) | 0.0232 (12) | 0.0193 (12) | −0.0004 (9) | 0.0029 (9) | −0.0026 (9) |
C16 | 0.0251 (14) | 0.0268 (16) | 0.0218 (15) | 0.0026 (12) | 0.0031 (12) | 0.0006 (12) |
N17 | 0.0242 (12) | 0.0230 (13) | 0.0192 (12) | 0.0005 (10) | 0.0024 (10) | 0.0015 (10) |
C18 | 0.0317 (16) | 0.0380 (19) | 0.0255 (16) | 0.0092 (14) | 0.0073 (13) | 0.0074 (14) |
C19 | 0.0314 (16) | 0.0329 (18) | 0.0273 (15) | 0.0089 (13) | 0.0037 (13) | 0.0021 (13) |
O20 | 0.092 (2) | 0.0385 (17) | 0.081 (2) | 0.0115 (16) | 0.0520 (19) | 0.0138 (16) |
C21 | 0.065 (3) | 0.056 (3) | 0.066 (3) | 0.010 (2) | 0.035 (2) | 0.009 (2) |
N22 | 0.0426 (17) | 0.046 (2) | 0.070 (2) | 0.0083 (15) | 0.0291 (17) | 0.0170 (18) |
C23 | 0.074 (3) | 0.041 (3) | 0.168 (6) | 0.009 (2) | 0.066 (4) | 0.022 (3) |
C24 | 0.053 (3) | 0.084 (4) | 0.079 (3) | 0.012 (2) | 0.033 (3) | 0.018 (3) |
Geometric parameters (Å, º) top
Cu1—O2i | 1.9828 (19) | C14—N15 | 1.470 (4) |
Cu1—O2 | 1.9828 (19) | C14—H14A | 0.9900 |
Cu1—N17ii | 1.983 (2) | C14—H14B | 0.9900 |
Cu1—N17iii | 1.983 (2) | N15—C16 | 1.338 (4) |
Cu1—O3 | 2.652 (2) | N15—C19 | 1.364 (4) |
Cu1—O3i | 2.652 (2) | C16—N17 | 1.330 (4) |
O2—C4 | 1.273 (3) | C16—H16 | 0.9500 |
O3—C4 | 1.251 (3) | N17—C18 | 1.388 (4) |
C4—C5 | 1.503 (4) | N17—Cu1iv | 1.983 (2) |
C5—C6 | 1.394 (4) | C18—C19 | 1.359 (4) |
C5—C13 | 1.399 (4) | C18—H18 | 0.9500 |
C6—C7 | 1.388 (4) | C19—H19 | 0.9500 |
C6—H6 | 0.9500 | O20—C21 | 1.224 (5) |
C7—C11 | 1.394 (4) | C21—N22 | 1.323 (6) |
C7—C8 | 1.497 (4) | C21—H21 | 0.9500 |
C8—O9 | 1.200 (4) | N22—C23 | 1.435 (6) |
C8—O10 | 1.319 (4) | N22—C24 | 1.441 (6) |
O10—H10 | 0.8400 | C23—H23A | 0.9800 |
C11—C12 | 1.407 (4) | C23—H23B | 0.9800 |
C11—H11 | 0.9500 | C23—H23C | 0.9800 |
C12—C13 | 1.387 (4) | C24—H24A | 0.9800 |
C12—C14 | 1.510 (4) | C24—H24B | 0.9800 |
C13—H13 | 0.9500 | C24—H24C | 0.9800 |
| | | |
O2i—Cu1—O2 | 180.00 (11) | C12—C14—H14B | 109.2 |
O2i—Cu1—N17ii | 89.40 (9) | H14A—C14—H14B | 107.9 |
O2—Cu1—N17ii | 90.60 (9) | C16—N15—C19 | 107.9 (2) |
O2i—Cu1—N17iii | 90.60 (9) | C16—N15—C14 | 124.9 (2) |
O2—Cu1—N17iii | 89.40 (9) | C19—N15—C14 | 127.1 (2) |
N17ii—Cu1—N17iii | 180.0 | N17—C16—N15 | 111.3 (3) |
C4—O2—Cu1 | 106.43 (17) | N17—C16—H16 | 124.3 |
O3—C4—O2 | 122.1 (3) | N15—C16—H16 | 124.3 |
O3—C4—C5 | 121.3 (3) | C16—N17—C18 | 105.1 (2) |
O2—C4—C5 | 116.6 (2) | C16—N17—Cu1iv | 124.6 (2) |
C6—C5—C13 | 119.1 (3) | C18—N17—Cu1iv | 130.2 (2) |
C6—C5—C4 | 120.0 (3) | C19—C18—N17 | 109.4 (3) |
C13—C5—C4 | 120.8 (3) | C19—C18—H18 | 125.3 |
C7—C6—C5 | 120.4 (3) | N17—C18—H18 | 125.3 |
C7—C6—H6 | 119.8 | C18—C19—N15 | 106.3 (3) |
C5—C6—H6 | 119.8 | C18—C19—H19 | 126.8 |
C6—C7—C11 | 120.4 (3) | N15—C19—H19 | 126.8 |
C6—C7—C8 | 118.1 (3) | O20—C21—N22 | 125.0 (5) |
C11—C7—C8 | 121.5 (3) | O20—C21—H21 | 117.5 |
O9—C8—O10 | 123.8 (3) | N22—C21—H21 | 117.5 |
O9—C8—C7 | 123.4 (3) | C21—N22—C23 | 123.8 (5) |
O10—C8—C7 | 112.7 (3) | C21—N22—C24 | 119.8 (4) |
C8—O10—H10 | 109.5 | C23—N22—C24 | 116.4 (4) |
C7—C11—C12 | 119.7 (3) | N22—C23—H23A | 109.5 |
C7—C11—H11 | 120.2 | N22—C23—H23B | 109.5 |
C12—C11—H11 | 120.2 | H23A—C23—H23B | 109.5 |
C13—C12—C11 | 119.4 (3) | N22—C23—H23C | 109.5 |
C13—C12—C14 | 120.5 (3) | H23A—C23—H23C | 109.5 |
C11—C12—C14 | 120.2 (3) | H23B—C23—H23C | 109.5 |
C12—C13—C5 | 121.1 (3) | N22—C24—H24A | 109.5 |
C12—C13—H13 | 119.5 | N22—C24—H24B | 109.5 |
C5—C13—H13 | 119.5 | H24A—C24—H24B | 109.5 |
N15—C14—C12 | 112.1 (2) | N22—C24—H24C | 109.5 |
N15—C14—H14A | 109.2 | H24A—C24—H24C | 109.5 |
C12—C14—H14A | 109.2 | H24B—C24—H24C | 109.5 |
N15—C14—H14B | 109.2 | | |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, −y, −z+1; (iii) x, y, z+1; (iv) x, y, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10···O3v | 0.84 | 1.72 | 2.557 (3) | 173 |
Symmetry code: (v) x−1/2, −y+1/2, z−1/2. |
(II)
catena-poly[[copper(II)-bis[µ-3-carboxy-5-[(imidazol-1-yl)methyl]benzoato]] dimethylacetamide disolvate]
top
Crystal data top
[Cu(C12H9N2O4)2]·2C4H9NO | F(000) = 758 |
Mr = 728.22 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7557 (2) Å | Cell parameters from 3589 reflections |
b = 21.9826 (4) Å | θ = 2.8–27.8° |
c = 9.8160 (3) Å | µ = 0.74 mm−1 |
β = 102.9198 (9)° | T = 110 K |
V = 1631.17 (7) Å3 | Prism, green |
Z = 2 | 0.35 × 0.25 × 0.15 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3856 independent reflections |
Radiation source: fine-focussealed tube | 2759 reflections with I > 2σ(I) |
Detector resolution: 12.8 pixels mm-1 | Rint = 0.051 |
1° φ and ω scans | θmax = 27.8°, θmin = 2.8° |
Absorption correction: multi-scan (Blessing, 1995) | h = −10→10 |
Tmin = 0.737, Tmax = 0.897 | k = −28→28 |
13044 measured reflections | l = −12→12 |
Refinement top
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0666P)2 + 0.7243P], where P = (Fo2 + 2Fc2)/3 |
3856 reflections | (Δ/σ)max = 0.019 |
224 parameters | Δρmax = 0.45 e Å−3 |
1 restraint | Δρmin = −0.43 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 | Occ. (<1) |
Cu1 | 1.0000 | 0.0000 | 1.0000 | 0.02180 (15) | |
O2 | 0.8896 (2) | 0.01963 (7) | 0.80335 (17) | 0.0238 (4) | |
O3 | 1.0298 (2) | 0.10518 (7) | 0.87420 (19) | 0.0290 (4) | |
C4 | 0.9232 (3) | 0.07523 (10) | 0.7846 (3) | 0.0233 (5) | |
C5 | 0.8213 (3) | 0.10380 (10) | 0.6512 (3) | 0.0228 (5) | |
C6 | 0.8126 (3) | 0.16662 (11) | 0.6372 (3) | 0.0256 (5) | |
H6 | 0.8811 | 0.1918 | 0.7077 | 0.031* | |
C7 | 0.7035 (3) | 0.19281 (11) | 0.5198 (3) | 0.0251 (5) | |
C8 | 0.6935 (4) | 0.26077 (11) | 0.5131 (3) | 0.0280 (6) | |
O9 | 0.7857 (3) | 0.29380 (8) | 0.5971 (2) | 0.0402 (5) | |
O10 | 0.5731 (3) | 0.28024 (8) | 0.4062 (2) | 0.0445 (6) | |
H10 | 0.5673 | 0.3184 | 0.4090 | 0.067* | |
C11 | 0.6058 (3) | 0.15605 (11) | 0.4137 (3) | 0.0247 (5) | |
H11 | 0.5312 | 0.1741 | 0.3339 | 0.030* | |
C12 | 0.6184 (3) | 0.09252 (11) | 0.4255 (3) | 0.0237 (5) | |
C13 | 0.7262 (3) | 0.06708 (11) | 0.5443 (3) | 0.0244 (5) | |
H13 | 0.7353 | 0.0241 | 0.5528 | 0.029* | |
C14 | 0.5177 (3) | 0.05198 (11) | 0.3112 (3) | 0.0268 (6) | |
H14A | 0.5166 | 0.0100 | 0.3472 | 0.032* | |
H14B | 0.3937 | 0.0662 | 0.2831 | 0.032* | |
N15 | 0.5968 (3) | 0.05183 (9) | 0.1882 (2) | 0.0249 (5) | |
C16 | 0.7446 (3) | 0.02185 (12) | 0.1787 (3) | 0.0286 (6) | |
H16 | 0.8097 | −0.0039 | 0.2497 | 0.034* | |
N17 | 0.7882 (3) | 0.03271 (9) | 0.0578 (2) | 0.0250 (5) | |
C18 | 0.6573 (4) | 0.07157 (14) | −0.0133 (3) | 0.0420 (7) | |
H18 | 0.6508 | 0.0873 | −0.1045 | 0.050* | |
C19 | 0.5407 (4) | 0.08363 (13) | 0.0671 (3) | 0.0393 (7) | |
H19 | 0.4396 | 0.1092 | 0.0438 | 0.047* | |
O20 | 0.2637 (9) | 0.0770 (3) | 0.5737 (7) | 0.053 (2)* | 0.5 |
C21 | 0.3333 (12) | 0.1585 (4) | 0.6889 (9) | 0.056 (2)* | 0.5 |
H21A | 0.3105 | 0.1378 | 0.7715 | 0.084* | 0.5 |
H21B | 0.2924 | 0.2007 | 0.6875 | 0.084* | 0.5 |
H21C | 0.4605 | 0.1579 | 0.6922 | 0.084* | 0.5 |
C22 | 0.2389 (8) | 0.1273 (3) | 0.5631 (7) | 0.0293 (13)* | 0.5 |
N23 | 0.1612 (6) | 0.1601 (2) | 0.4477 (5) | 0.0340 (11)* | 0.5 |
C24 | 0.0641 (12) | 0.1288 (4) | 0.3219 (10) | 0.045 (2)* | 0.5 |
H24A | 0.0565 | 0.0853 | 0.3416 | 0.068* | 0.5 |
H24B | 0.1263 | 0.1344 | 0.2462 | 0.068* | 0.5 |
H24C | −0.0553 | 0.1459 | 0.2937 | 0.068* | 0.5 |
C25 | 0.1624 (9) | 0.2266 (3) | 0.4381 (8) | 0.0429 (15)* | 0.5 |
H25A | 0.0558 | 0.2430 | 0.4627 | 0.064* | 0.5 |
H25B | 0.1646 | 0.2387 | 0.3424 | 0.064* | 0.5 |
H25C | 0.2675 | 0.2427 | 0.5028 | 0.064* | 0.5 |
O28 | 0.2206 (8) | 0.0701 (2) | 0.5518 (6) | 0.0377 (15)* | 0.5 |
C27 | 0.1988 (10) | 0.1242 (3) | 0.5056 (8) | 0.0425 (17)* | 0.5 |
C26 | 0.0858 (14) | 0.1268 (4) | 0.3636 (11) | 0.057 (3)* | 0.5 |
H26A | 0.0803 | 0.0864 | 0.3204 | 0.085* | 0.5 |
H26B | 0.1354 | 0.1560 | 0.3073 | 0.085* | 0.5 |
H26C | −0.0336 | 0.1397 | 0.3685 | 0.085* | 0.5 |
N29 | 0.2419 (8) | 0.1766 (3) | 0.5720 (6) | 0.0561 (15)* | 0.5 |
C30 | 0.3559 (14) | 0.1755 (5) | 0.7143 (7) | 0.074 (3)* | 0.5 |
H30A | 0.2904 | 0.1917 | 0.7807 | 0.110* | 0.5 |
H30B | 0.4613 | 0.2004 | 0.7167 | 0.110* | 0.5 |
H30C | 0.3919 | 0.1335 | 0.7398 | 0.110* | 0.5 |
C31 | 0.1893 (11) | 0.2358 (3) | 0.5194 (9) | 0.0565 (19)* | 0.5 |
H31A | 0.1415 | 0.2583 | 0.5888 | 0.085* | 0.5 |
H31B | 0.0982 | 0.2322 | 0.4327 | 0.085* | 0.5 |
H31C | 0.2918 | 0.2575 | 0.5006 | 0.085* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0270 (3) | 0.0187 (2) | 0.0180 (2) | 0.00284 (16) | 0.00143 (17) | 0.00190 (16) |
O2 | 0.0303 (10) | 0.0178 (8) | 0.0215 (9) | 0.0009 (7) | 0.0020 (8) | 0.0011 (7) |
O3 | 0.0337 (10) | 0.0218 (9) | 0.0271 (10) | −0.0010 (7) | −0.0029 (8) | 0.0021 (7) |
C4 | 0.0258 (13) | 0.0216 (12) | 0.0224 (13) | 0.0033 (9) | 0.0051 (11) | 0.0008 (10) |
C5 | 0.0247 (13) | 0.0217 (12) | 0.0216 (13) | 0.0027 (9) | 0.0041 (10) | 0.0036 (9) |
C6 | 0.0266 (14) | 0.0247 (13) | 0.0240 (13) | 0.0008 (10) | 0.0027 (11) | −0.0009 (10) |
C7 | 0.0270 (14) | 0.0214 (12) | 0.0265 (14) | 0.0032 (9) | 0.0049 (11) | 0.0016 (10) |
C8 | 0.0309 (14) | 0.0247 (13) | 0.0274 (14) | 0.0028 (10) | 0.0043 (12) | 0.0034 (10) |
O9 | 0.0487 (13) | 0.0232 (9) | 0.0397 (12) | −0.0016 (8) | −0.0094 (10) | −0.0006 (8) |
O10 | 0.0553 (14) | 0.0203 (9) | 0.0452 (13) | 0.0024 (9) | −0.0159 (10) | 0.0039 (8) |
C11 | 0.0258 (14) | 0.0247 (12) | 0.0228 (13) | 0.0009 (10) | 0.0040 (11) | 0.0031 (10) |
C12 | 0.0248 (13) | 0.0241 (12) | 0.0224 (13) | 0.0000 (9) | 0.0061 (10) | 0.0013 (10) |
C13 | 0.0261 (13) | 0.0197 (12) | 0.0276 (14) | 0.0009 (9) | 0.0062 (11) | 0.0005 (10) |
C14 | 0.0277 (14) | 0.0275 (13) | 0.0243 (14) | −0.0017 (10) | 0.0042 (11) | 0.0008 (10) |
N15 | 0.0277 (11) | 0.0245 (11) | 0.0215 (11) | 0.0021 (8) | 0.0032 (9) | −0.0015 (8) |
C16 | 0.0309 (15) | 0.0245 (12) | 0.0280 (15) | 0.0012 (10) | 0.0016 (12) | −0.0001 (11) |
N17 | 0.0292 (12) | 0.0230 (11) | 0.0209 (11) | 0.0058 (8) | 0.0018 (9) | 0.0018 (8) |
C18 | 0.0492 (19) | 0.0497 (18) | 0.0281 (16) | 0.0196 (14) | 0.0106 (14) | 0.0132 (13) |
C19 | 0.0417 (18) | 0.0452 (17) | 0.0306 (16) | 0.0198 (13) | 0.0071 (14) | 0.0101 (13) |
Geometric parameters (Å, º) top
Cu1—O2 | 1.9764 (16) | C18—H18 | 0.9500 |
Cu1—O2i | 1.9765 (16) | C19—H19 | 0.9500 |
Cu1—N17ii | 1.989 (2) | O20—C22 | 1.123 (8) |
Cu1—N17iii | 1.989 (2) | C21—C22 | 1.458 (11) |
O2—C4 | 1.272 (3) | C21—H21A | 0.9800 |
O3—C4 | 1.252 (3) | C21—H21B | 0.9800 |
C4—C5 | 1.506 (3) | C21—H21C | 0.9800 |
C5—C6 | 1.388 (3) | C22—N23 | 1.364 (8) |
C5—C13 | 1.397 (3) | N23—C25 | 1.466 (8) |
C6—C7 | 1.393 (3) | N23—C24 | 1.465 (10) |
C6—H6 | 0.9500 | C24—H24A | 0.9800 |
C7—C11 | 1.399 (3) | C24—H24B | 0.9800 |
C7—C8 | 1.497 (3) | C24—H24C | 0.9800 |
C8—O9 | 1.206 (3) | C25—H25A | 0.9800 |
C8—O10 | 1.311 (3) | C25—H25B | 0.9800 |
O10—H10 | 0.8400 | C25—H25C | 0.9800 |
C11—C12 | 1.403 (3) | O28—C27 | 1.270 (9) |
C11—H11 | 0.9500 | C27—N29 | 1.329 (9) |
C12—C13 | 1.391 (3) | C27—C26 | 1.473 (12) |
C12—C14 | 1.507 (3) | C26—H26A | 0.9800 |
C13—H13 | 0.9500 | C26—H26B | 0.9800 |
C14—N15 | 1.471 (3) | C26—H26C | 0.9800 |
C14—H14A | 0.9900 | N29—C30 | 1.477 (2) |
C14—H14B | 0.9900 | N29—C31 | 1.425 (9) |
N15—C16 | 1.343 (3) | C30—H30A | 0.9800 |
N15—C19 | 1.363 (3) | C30—H30B | 0.9800 |
C16—N17 | 1.326 (3) | C30—H30C | 0.9800 |
C16—H16 | 0.9500 | C31—H31A | 0.9800 |
N17—C18 | 1.389 (3) | C31—H31B | 0.9800 |
N17—Cu1iv | 1.989 (2) | C31—H31C | 0.9800 |
C18—C19 | 1.353 (4) | | |
| | | |
O2—Cu1—O2i | 180.0 | C18—C19—H19 | 126.8 |
O2—Cu1—N17ii | 90.30 (8) | N15—C19—H19 | 126.8 |
O2i—Cu1—N17ii | 89.71 (8) | C22—C21—H21A | 109.5 |
O2—Cu1—N17iii | 89.70 (8) | C22—C21—H21B | 109.5 |
O2i—Cu1—N17iii | 90.29 (8) | H21A—C21—H21B | 109.5 |
N17ii—Cu1—N17iii | 180.0 | C22—C21—H21C | 109.5 |
C4—O2—Cu1 | 107.06 (15) | H21A—C21—H21C | 109.5 |
O3—C4—O2 | 121.9 (2) | H21B—C21—H21C | 109.5 |
O3—C4—C5 | 121.8 (2) | O20—C22—N23 | 129.2 (7) |
O2—C4—C5 | 116.2 (2) | O20—C22—C21 | 109.9 (7) |
C6—C5—C13 | 119.6 (2) | N23—C22—C21 | 120.0 (6) |
C6—C5—C4 | 120.4 (2) | C22—N23—C25 | 124.9 (5) |
C13—C5—C4 | 119.9 (2) | C22—N23—C24 | 120.0 (6) |
C5—C6—C7 | 120.0 (2) | C25—N23—C24 | 115.0 (5) |
C5—C6—H6 | 120.0 | N23—C24—H24A | 109.5 |
C7—C6—H6 | 120.0 | N23—C24—H24B | 109.5 |
C6—C7—C11 | 120.3 (2) | H24A—C24—H24B | 109.5 |
C6—C7—C8 | 117.7 (2) | N23—C24—H24C | 109.5 |
C11—C7—C8 | 122.0 (2) | H24A—C24—H24C | 109.5 |
O9—C8—O10 | 123.9 (2) | H24B—C24—H24C | 109.5 |
O9—C8—C7 | 123.6 (2) | N23—C25—H25A | 109.5 |
O10—C8—C7 | 112.5 (2) | N23—C25—H25B | 109.5 |
C8—O10—H10 | 109.5 | H25A—C25—H25B | 109.5 |
C7—C11—C12 | 119.8 (2) | N23—C25—H25C | 109.5 |
C7—C11—H11 | 120.1 | H25A—C25—H25C | 109.5 |
C12—C11—H11 | 120.1 | H25B—C25—H25C | 109.5 |
C13—C12—C11 | 119.1 (2) | O28—C27—N29 | 129.6 (8) |
C13—C12—C14 | 120.1 (2) | O28—C27—C26 | 112.2 (7) |
C11—C12—C14 | 120.8 (2) | N29—C27—C26 | 117.5 (7) |
C12—C13—C5 | 121.0 (2) | C27—C26—H26A | 109.5 |
C12—C13—H13 | 119.5 | C27—C26—H26B | 109.5 |
C5—C13—H13 | 119.5 | H26A—C26—H26B | 109.5 |
N15—C14—C12 | 111.8 (2) | C27—C26—H26C | 109.5 |
N15—C14—H14A | 109.3 | H26A—C26—H26C | 109.5 |
C12—C14—H14A | 109.3 | H26B—C26—H26C | 109.5 |
N15—C14—H14B | 109.3 | C27—N29—C30 | 118.7 (7) |
C12—C14—H14B | 109.3 | C27—N29—C31 | 126.4 (6) |
H14A—C14—H14B | 107.9 | C30—N29—C31 | 114.9 (7) |
C16—N15—C19 | 107.6 (2) | N29—C30—H30A | 109.5 |
C16—N15—C14 | 125.2 (2) | N29—C30—H30B | 109.5 |
C19—N15—C14 | 127.1 (2) | H30A—C30—H30B | 109.5 |
N17—C16—N15 | 111.4 (2) | N29—C30—H30C | 109.5 |
N17—C16—H16 | 124.3 | H30A—C30—H30C | 109.5 |
N15—C16—H16 | 124.3 | H30B—C30—H30C | 109.5 |
C16—N17—C18 | 104.9 (2) | N29—C31—H31A | 109.5 |
C16—N17—Cu1iv | 125.61 (17) | N29—C31—H31B | 109.5 |
C18—N17—Cu1iv | 129.50 (18) | H31A—C31—H31B | 109.5 |
C19—C18—N17 | 109.6 (2) | N29—C31—H31C | 109.5 |
C19—C18—H18 | 125.2 | H31A—C31—H31C | 109.5 |
N17—C18—H18 | 125.2 | H31B—C31—H31C | 109.5 |
C18—C19—N15 | 106.4 (2) | | |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, −y, −z+1; (iii) x, y, z+1; (iv) x, y, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10···O3v | 0.84 | 1.73 | 2.551 (2) | 166 |
Symmetry code: (v) x−1/2, −y+1/2, z−1/2. |