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The title two-dimensional hydrogen-bonded coordination compounds, [Cu(C
8H
5O
4)
2(C
4H
6N
2)
2], (I), and [Cu(C
8H
7O
2)
2(C
4H
6N
2)
2]·H
2O, (II), have been synthesized and structurally characterized. The molecule of complex (I) lies across an inversion centre, and the Cu
2+ ion is coordinated by two N atoms from two 4-methyl-1
H-imidazole (4-MeIM) molecules and two O atoms from two 3-carboxybenzoate (HBDC
−) anions in a square-planar geometry. Adjacent molecules are linked through intermolecular N—H
O and O—H
O hydrogen bonds into a two-dimensional sheet with (4,4) topology. In the asymmetric part of the unit cell of (II) there are two symmetry-independent molecules, in which each Cu
2+ ion is also coordinated by two N atoms from two 4-MeIM molecules and two O atoms from two 3-methylbenzoate (3-MeBC
−) anions in a square-planar coordination. Two neutral complex molecules are held together
via N—H
O(carboxylate) hydrogen bonds to generate a dimeric pair, which is further linked
via discrete water molecules into a two-dimensional network with the Schläfli symbol (4
3)
2(4
6,6
6,8
3). In both compounds, as well as the strong intermolecular hydrogen bonds, π–π interactions also stabilize the crystal stacking.
Supporting information
CCDC references: 733209; 733210
CuCl2.2H2O (0.17 g, 1.0 mmol) was slowly added to an aqueous solution (15 ml) of H2BDC (0.16 g, 1.0 mmol) and NaOH (0.04 g, 1.0 mmol) and the mixture
was refluxed for 30 min. An ethanol solution (10 ml) containing 4-MeIM (0.08 g, 1.0 mmol) was then added slowly with continuous stirring. The resulting
solution was refluxed for 3 h, filtered and left to stand for crystallization.
After 10 d, blue crystals of (I) suitable for single-crystal X-ray diffraction
were obtained.
Compound (II) was synthesized similarly to compound (I), but the H2BDC was
replaced with 3-MeBC (0.14 g, 1.0 mmol). After 4 d, blue crystals of (II) were
obtained.
For both compounds, H atoms bonded to N atoms, carboxyl O atoms and water O
atoms were located in difference maps and refined isotropically, with
distances restrained to N—H = 0.86 (3) Å, O—H = 0.82 (3) Å and H···H =
1.34 (3) Å. All remaining H atoms were positioned geometrically, with C—H =
0.93 Å (aromatic) or 0.96 Å (methyl), and refined as riding, with
Uiso(H) = 1.2Ueq(C) (aromatic) or 1.5Ueq(C)
(methyl).
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and TOPOS (Blatov et al., 2000); software used to prepare material for publication: PLATON (Spek, 2003).
(I) bis(3-carboxybenzoato-
κO)bis(4-methyl-1
H-imidazole-
κN3)copper(II)
top
Crystal data top
[Cu(C8H5O4)2(C4H6N2)2] | Z = 1 |
Mr = 558.01 | F(000) = 287 |
Triclinic, P1 | Dx = 1.572 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3188 (6) Å | Cell parameters from 2266 reflections |
b = 8.5847 (7) Å | θ = 2.5–28.0° |
c = 10.1033 (8) Å | µ = 0.99 mm−1 |
α = 96.487 (1)° | T = 292 K |
β = 98.756 (2)° | Block, blue |
γ = 107.620 (1)° | 0.23 × 0.20 × 0.15 mm |
V = 589.37 (8) Å3 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2290 independent reflections |
Radiation source: sealed tube | 2155 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.011 |
0.3° wide ω exposures scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→8 |
Tmin = 0.805, Tmax = 0.866 | k = −9→10 |
3304 measured reflections | l = −9→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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0266P)2 + 0.4865P] where P = (Fo2 + 2Fc2)/3 |
2290 reflections | (Δ/σ)max < 0.001 |
178 parameters | Δρmax = 0.33 e Å−3 |
14 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
[Cu(C8H5O4)2(C4H6N2)2] | γ = 107.620 (1)° |
Mr = 558.01 | V = 589.37 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.3188 (6) Å | Mo Kα radiation |
b = 8.5847 (7) Å | µ = 0.99 mm−1 |
c = 10.1033 (8) Å | T = 292 K |
α = 96.487 (1)° | 0.23 × 0.20 × 0.15 mm |
β = 98.756 (2)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2290 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2155 reflections with I > 2σ(I) |
Tmin = 0.805, Tmax = 0.866 | Rint = 0.011 |
3304 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | 14 restraints |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.33 e Å−3 |
2290 reflections | Δρmin = −0.26 e Å−3 |
178 parameters | |
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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.5000 | 1.0000 | 0.5000 | 0.02581 (12) | |
N1 | 0.2441 (3) | 0.9069 (2) | 0.55176 (17) | 0.0302 (4) | |
N2 | −0.0108 (3) | 0.8966 (2) | 0.6415 (2) | 0.0367 (4) | |
H2A | −0.081 (4) | 0.929 (3) | 0.684 (3) | 0.0404 (8)* | |
O1 | 0.4157 (2) | 0.83152 (17) | 0.33760 (14) | 0.0314 (3) | |
O2 | 0.3075 (2) | 1.00692 (18) | 0.22997 (16) | 0.0379 (4) | |
O3 | 0.2011 (3) | 0.1880 (2) | −0.08798 (18) | 0.0574 (5) | |
O4 | 0.2902 (3) | 0.2760 (2) | 0.13449 (18) | 0.0481 (4) | |
H4 | 0.297 (4) | 0.184 (3) | 0.141 (3) | 0.0465 (14)* | |
C1 | 0.1736 (3) | 0.9837 (3) | 0.6417 (2) | 0.0338 (5) | |
H1A | 0.2432 | 1.0848 | 0.6975 | 0.041* | |
C2 | −0.0662 (3) | 0.7544 (3) | 0.5469 (2) | 0.0354 (5) | |
C3 | 0.0940 (3) | 0.7624 (3) | 0.4924 (2) | 0.0334 (5) | |
H3A | 0.1017 | 0.6826 | 0.4251 | 0.040* | |
C4 | −0.2662 (4) | 0.6312 (4) | 0.5187 (3) | 0.0523 (7) | |
H4A | −0.3012 | 0.6020 | 0.6025 | 0.078* | |
H4B | −0.2689 | 0.5337 | 0.4605 | 0.078* | |
H4C | −0.3576 | 0.6782 | 0.4747 | 0.078* | |
C5 | 0.2944 (3) | 0.7491 (2) | 0.1030 (2) | 0.0262 (4) | |
C6 | 0.2939 (3) | 0.5892 (3) | 0.1132 (2) | 0.0285 (4) | |
H6A | 0.3243 | 0.5617 | 0.1984 | 0.034* | |
C7 | 0.2487 (3) | 0.4698 (3) | −0.0020 (2) | 0.0303 (4) | |
C8 | 0.2087 (4) | 0.5132 (3) | −0.1287 (2) | 0.0394 (5) | |
H8A | 0.1797 | 0.4345 | −0.2067 | 0.047* | |
C9 | 0.2117 (4) | 0.6726 (3) | −0.1393 (2) | 0.0453 (6) | |
H9A | 0.1867 | 0.7012 | −0.2247 | 0.054* | |
C10 | 0.2515 (4) | 0.7905 (3) | −0.0241 (2) | 0.0360 (5) | |
H10A | 0.2495 | 0.8969 | −0.0320 | 0.043* | |
C11 | 0.3406 (3) | 0.8732 (2) | 0.2306 (2) | 0.0267 (4) | |
C12 | 0.2436 (3) | 0.2968 (3) | 0.0079 (2) | 0.0353 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0347 (2) | 0.02360 (19) | 0.01970 (18) | 0.01288 (14) | 0.00338 (14) | −0.00096 (13) |
N1 | 0.0375 (10) | 0.0305 (9) | 0.0239 (9) | 0.0144 (8) | 0.0054 (7) | 0.0017 (7) |
N2 | 0.0409 (8) | 0.0391 (8) | 0.0374 (8) | 0.0199 (7) | 0.0136 (7) | 0.0085 (7) |
O1 | 0.0439 (9) | 0.0271 (7) | 0.0225 (7) | 0.0141 (6) | 0.0034 (6) | −0.0014 (6) |
O2 | 0.0561 (10) | 0.0265 (8) | 0.0372 (9) | 0.0214 (7) | 0.0120 (7) | 0.0038 (6) |
O3 | 0.0985 (16) | 0.0334 (9) | 0.0396 (10) | 0.0259 (10) | 0.0126 (10) | −0.0074 (8) |
O4 | 0.0816 (12) | 0.0302 (8) | 0.0382 (9) | 0.0269 (8) | 0.0106 (8) | 0.0064 (7) |
C1 | 0.0450 (13) | 0.0332 (11) | 0.0276 (11) | 0.0188 (10) | 0.0091 (9) | 0.0038 (9) |
C2 | 0.0392 (12) | 0.0368 (12) | 0.0335 (11) | 0.0157 (10) | 0.0061 (9) | 0.0112 (9) |
C3 | 0.0391 (12) | 0.0317 (11) | 0.0286 (11) | 0.0131 (9) | 0.0030 (9) | 0.0020 (9) |
C4 | 0.0427 (15) | 0.0534 (16) | 0.0576 (17) | 0.0087 (12) | 0.0103 (12) | 0.0149 (13) |
C5 | 0.0298 (10) | 0.0241 (10) | 0.0249 (10) | 0.0100 (8) | 0.0049 (8) | 0.0017 (8) |
C6 | 0.0375 (11) | 0.0277 (10) | 0.0218 (10) | 0.0138 (9) | 0.0047 (8) | 0.0035 (8) |
C7 | 0.0362 (11) | 0.0267 (10) | 0.0276 (10) | 0.0118 (9) | 0.0053 (9) | 0.0001 (8) |
C8 | 0.0558 (15) | 0.0379 (12) | 0.0224 (10) | 0.0179 (11) | 0.0023 (10) | −0.0034 (9) |
C9 | 0.0699 (17) | 0.0450 (14) | 0.0223 (11) | 0.0245 (13) | 0.0005 (11) | 0.0066 (10) |
C10 | 0.0496 (14) | 0.0310 (11) | 0.0302 (11) | 0.0182 (10) | 0.0042 (10) | 0.0075 (9) |
C11 | 0.0308 (10) | 0.0236 (10) | 0.0260 (10) | 0.0089 (8) | 0.0080 (8) | 0.0016 (8) |
C12 | 0.0456 (13) | 0.0291 (11) | 0.0333 (12) | 0.0148 (10) | 0.0114 (10) | 0.0009 (9) |
Geometric parameters (Å, º) top
Cu1—O1i | 1.9442 (13) | C3—H3A | 0.9300 |
Cu1—O1 | 1.9442 (13) | C4—H4A | 0.9600 |
Cu1—N1 | 1.9763 (18) | C4—H4B | 0.9600 |
Cu1—N1i | 1.9763 (18) | C4—H4C | 0.9600 |
N1—C1 | 1.319 (3) | C5—C6 | 1.387 (3) |
N1—C3 | 1.382 (3) | C5—C10 | 1.387 (3) |
N2—C1 | 1.330 (3) | C5—C11 | 1.500 (3) |
N2—C2 | 1.374 (3) | C6—C7 | 1.387 (3) |
N2—H2A | 0.81 (2) | C6—H6A | 0.9300 |
O1—C11 | 1.274 (2) | C7—C8 | 1.387 (3) |
O2—C11 | 1.243 (2) | C7—C12 | 1.490 (3) |
O3—C12 | 1.199 (3) | C8—C9 | 1.378 (3) |
O4—C12 | 1.319 (3) | C8—H8A | 0.9300 |
O4—H4 | 0.82 (2) | C9—C10 | 1.384 (3) |
C1—H1A | 0.9300 | C9—H9A | 0.9300 |
C2—C3 | 1.356 (3) | C10—H10A | 0.9300 |
C2—C4 | 1.487 (3) | | |
| | | |
O1i—Cu1—O1 | 180.000 (1) | H4A—C4—H4C | 109.5 |
O1i—Cu1—N1 | 90.05 (7) | H4B—C4—H4C | 109.5 |
O1—Cu1—N1 | 89.95 (7) | C6—C5—C10 | 119.53 (19) |
O1i—Cu1—N1i | 89.95 (7) | C6—C5—C11 | 118.92 (18) |
O1—Cu1—N1i | 90.05 (7) | C10—C5—C11 | 121.55 (18) |
N1—Cu1—N1i | 180.0 | C5—C6—C7 | 120.80 (19) |
C1—N1—C3 | 105.68 (19) | C5—C6—H6A | 119.6 |
C1—N1—Cu1 | 125.31 (16) | C7—C6—H6A | 119.6 |
C3—N1—Cu1 | 128.54 (14) | C8—C7—C6 | 119.16 (19) |
C1—N2—C2 | 108.99 (19) | C8—C7—C12 | 119.58 (19) |
C1—N2—H2A | 124.4 (19) | C6—C7—C12 | 121.25 (19) |
C2—N2—H2A | 126.3 (19) | C9—C8—C7 | 120.2 (2) |
C11—O1—Cu1 | 115.63 (12) | C9—C8—H8A | 119.9 |
C12—O4—H4 | 114 (2) | C7—C8—H8A | 119.9 |
N1—C1—N2 | 110.6 (2) | C8—C9—C10 | 120.6 (2) |
N1—C1—H1A | 124.7 | C8—C9—H9A | 119.7 |
N2—C1—H1A | 124.7 | C10—C9—H9A | 119.7 |
C3—C2—N2 | 104.8 (2) | C9—C10—C5 | 119.6 (2) |
C3—C2—C4 | 132.5 (2) | C9—C10—H10A | 120.2 |
N2—C2—C4 | 122.7 (2) | C5—C10—H10A | 120.2 |
C2—C3—N1 | 109.9 (2) | O2—C11—O1 | 123.23 (18) |
C2—C3—H3A | 125.0 | O2—C11—C5 | 121.51 (18) |
N1—C3—H3A | 125.0 | O1—C11—C5 | 115.26 (17) |
C2—C4—H4A | 109.5 | O3—C12—O4 | 123.5 (2) |
C2—C4—H4B | 109.5 | O3—C12—C7 | 124.0 (2) |
H4A—C4—H4B | 109.5 | O4—C12—C7 | 112.47 (18) |
C2—C4—H4C | 109.5 | | |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2ii | 0.81 (2) | 2.16 (2) | 2.965 (3) | 170 (2) |
O4—H4···O2iii | 0.82 (2) | 1.86 (2) | 2.632 (2) | 156 (3) |
Symmetry codes: (ii) −x, −y+2, −z+1; (iii) x, y−1, z. |
(II) bis(3-methylbenzoato-
κN)bis(4-methyl-1
H-imidazole-
κN3)copper(II) monohydrate
top
Crystal data top
[Cu(C8H7O2)2(C4H6N2)2]·H2O | F(000) = 2152 |
Mr = 516.04 | Dx = 1.377 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3676 reflections |
a = 14.3860 (2) Å | θ = 2.3–22.0° |
b = 15.2620 (4) Å | µ = 0.92 mm−1 |
c = 24.6922 (5) Å | T = 292 K |
β = 113.288 (2)° | Block, blue |
V = 4979.71 (18) Å3 | 0.28 × 0.25 × 0.20 mm |
Z = 8 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 9780 independent reflections |
Radiation source: sealed tube | 5859 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
0.3° wide ω exposures scans | θmax = 26.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −17→17 |
Tmin = 0.783, Tmax = 0.838 | k = −18→18 |
27494 measured reflections | l = −12→30 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | w = 1/[σ2(Fo2) + (0.046P)2] where P = (Fo2 + 2Fc2)/3 |
9780 reflections | (Δ/σ)max = 0.003 |
653 parameters | Δρmax = 0.50 e Å−3 |
38 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
[Cu(C8H7O2)2(C4H6N2)2]·H2O | V = 4979.71 (18) Å3 |
Mr = 516.04 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.3860 (2) Å | µ = 0.92 mm−1 |
b = 15.2620 (4) Å | T = 292 K |
c = 24.6922 (5) Å | 0.28 × 0.25 × 0.20 mm |
β = 113.288 (2)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 9780 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5859 reflections with I > 2σ(I) |
Tmin = 0.783, Tmax = 0.838 | Rint = 0.048 |
27494 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 38 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.50 e Å−3 |
9780 reflections | Δρmin = −0.28 e Å−3 |
653 parameters | |
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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.01541 (3) | 0.48340 (2) | 0.250539 (15) | 0.04663 (12) | |
Cu2 | 0.47403 (3) | 0.24525 (2) | 0.259132 (15) | 0.04463 (12) | |
O1 | 0.05721 (16) | 0.60261 (14) | 0.32491 (9) | 0.0644 (6) | |
O2 | 0.05913 (15) | 0.45999 (14) | 0.33727 (9) | 0.0541 (5) | |
O3 | −0.02634 (14) | 0.51213 (13) | 0.16714 (8) | 0.0507 (5) | |
O4 | −0.01921 (15) | 0.36976 (14) | 0.14832 (9) | 0.0615 (6) | |
O5 | 0.50141 (14) | 0.35576 (14) | 0.35324 (9) | 0.0603 (6) | |
O6 | 0.51484 (14) | 0.21236 (14) | 0.34233 (8) | 0.0504 (5) | |
O7 | 0.43313 (15) | 0.28299 (14) | 0.17636 (9) | 0.0531 (5) | |
O8 | 0.43613 (17) | 0.13910 (15) | 0.16738 (10) | 0.0714 (7) | |
O1W | 0.63066 (19) | 0.47523 (17) | 0.32971 (12) | 0.0730 (7) | |
H1WA | 0.5886 (18) | 0.4392 (16) | 0.3288 (13) | 0.0750 (9)* | |
H1WB | 0.609 (2) | 0.5241 (10) | 0.3315 (13) | 0.0750 (9)* | |
N1 | −0.12886 (18) | 0.47597 (16) | 0.23917 (11) | 0.0495 (6) | |
N2 | −0.2644 (2) | 0.47562 (18) | 0.25915 (14) | 0.0566 (7) | |
H2 | −0.295 (2) | 0.475 (2) | 0.2820 (11) | 0.068 (11)* | |
N3 | 0.15883 (17) | 0.48069 (16) | 0.26013 (11) | 0.0484 (6) | |
N4 | 0.3190 (2) | 0.44839 (17) | 0.29268 (12) | 0.0545 (7) | |
H4 | 0.3709 (13) | 0.4173 (14) | 0.3104 (11) | 0.0525 (9)* | |
N5 | 0.32926 (17) | 0.24047 (15) | 0.24777 (11) | 0.0456 (6) | |
N6 | 0.1678 (2) | 0.27165 (18) | 0.21464 (12) | 0.0563 (7) | |
H6A | 0.1136 (13) | 0.2975 (17) | 0.1940 (11) | 0.056 (10)* | |
N7 | 0.61906 (18) | 0.25282 (15) | 0.27226 (11) | 0.0470 (6) | |
N8 | 0.7564 (2) | 0.25719 (18) | 0.25403 (13) | 0.0543 (7) | |
H8 | 0.794 (2) | 0.262 (2) | 0.2350 (14) | 0.092 (14)* | |
C1 | 0.0729 (2) | 0.5375 (2) | 0.35786 (14) | 0.0492 (8) | |
C2 | 0.1054 (2) | 0.5496 (2) | 0.42318 (13) | 0.0478 (8) | |
C3 | 0.1095 (2) | 0.4797 (2) | 0.45979 (14) | 0.0519 (8) | |
H3 | 0.0933 | 0.4239 | 0.4437 | 0.062* | |
C4 | 0.1374 (2) | 0.4910 (2) | 0.52023 (15) | 0.0549 (9) | |
C5 | 0.1629 (2) | 0.5742 (2) | 0.54252 (15) | 0.0645 (10) | |
H5 | 0.1825 | 0.5831 | 0.5828 | 0.077* | |
C6 | 0.1604 (3) | 0.6441 (2) | 0.50745 (16) | 0.0744 (11) | |
H6 | 0.1787 | 0.6995 | 0.5240 | 0.089* | |
C7 | 0.1306 (2) | 0.6326 (2) | 0.44711 (14) | 0.0618 (9) | |
H7 | 0.1275 | 0.6803 | 0.4230 | 0.074* | |
C8 | 0.1378 (3) | 0.4155 (2) | 0.55880 (14) | 0.0706 (10) | |
H8A | 0.1955 | 0.4198 | 0.5956 | 0.106* | |
H8B | 0.1411 | 0.3616 | 0.5395 | 0.106* | |
H8C | 0.0770 | 0.4164 | 0.5661 | 0.106* | |
C9 | −0.0392 (2) | 0.4476 (2) | 0.13210 (14) | 0.0458 (8) | |
C10 | −0.0829 (2) | 0.4702 (2) | 0.06751 (13) | 0.0455 (7) | |
C11 | −0.0808 (2) | 0.5561 (2) | 0.04899 (13) | 0.0513 (8) | |
H11 | −0.0526 | 0.5996 | 0.0771 | 0.062* | |
C12 | −0.1193 (2) | 0.5786 (2) | −0.01013 (15) | 0.0604 (9) | |
C13 | −0.1632 (3) | 0.5145 (3) | −0.05112 (16) | 0.0750 (11) | |
H13 | −0.1899 | 0.5285 | −0.0910 | 0.090* | |
C14 | −0.1684 (3) | 0.4293 (3) | −0.03392 (17) | 0.0809 (12) | |
H14 | −0.1997 | 0.3868 | −0.0623 | 0.097* | |
C15 | −0.1271 (2) | 0.4063 (2) | 0.02546 (15) | 0.0657 (10) | |
H15 | −0.1293 | 0.3485 | 0.0368 | 0.079* | |
C16 | −0.1132 (3) | 0.6721 (2) | −0.02862 (16) | 0.0898 (13) | |
H16A | −0.0619 | 0.6766 | −0.0442 | 0.135* | |
H16B | −0.0966 | 0.7101 | 0.0049 | 0.135* | |
H16C | −0.1774 | 0.6891 | −0.0583 | 0.135* | |
C17 | −0.1632 (2) | 0.4750 (2) | 0.28140 (15) | 0.0562 (8) | |
H17 | −0.1224 | 0.4740 | 0.3215 | 0.067* | |
C18 | −0.2989 (2) | 0.4760 (2) | 0.19946 (15) | 0.0523 (8) | |
C19 | −0.2153 (2) | 0.4761 (2) | 0.18759 (14) | 0.0544 (8) | |
H19 | −0.2155 | 0.4761 | 0.1499 | 0.065* | |
C20 | −0.4093 (2) | 0.4777 (2) | 0.16067 (16) | 0.0758 (11) | |
H20A | −0.4376 | 0.5328 | 0.1651 | 0.114* | |
H20B | −0.4430 | 0.4310 | 0.1717 | 0.114* | |
H20C | −0.4181 | 0.4702 | 0.1203 | 0.114* | |
C21 | 0.2346 (2) | 0.4421 (2) | 0.30223 (13) | 0.0537 (8) | |
H21 | 0.2298 | 0.4140 | 0.3345 | 0.064* | |
C22 | 0.2990 (2) | 0.49339 (19) | 0.24162 (14) | 0.0510 (8) | |
C23 | 0.1987 (2) | 0.5131 (2) | 0.22183 (14) | 0.0527 (8) | |
H23 | 0.1624 | 0.5439 | 0.1874 | 0.063* | |
C24 | 0.3755 (2) | 0.5113 (2) | 0.21629 (16) | 0.0707 (10) | |
H24A | 0.3962 | 0.4571 | 0.2048 | 0.106* | |
H24B | 0.4332 | 0.5398 | 0.2453 | 0.106* | |
H24C | 0.3463 | 0.5486 | 0.1824 | 0.106* | |
C25 | 0.5237 (2) | 0.2802 (2) | 0.37427 (14) | 0.0479 (8) | |
C26 | 0.5643 (2) | 0.2662 (2) | 0.43961 (13) | 0.0494 (8) | |
C27 | 0.5757 (2) | 0.3368 (2) | 0.47743 (15) | 0.0622 (9) | |
H27 | 0.5568 | 0.3925 | 0.4616 | 0.075* | |
C28 | 0.6151 (2) | 0.3258 (3) | 0.53865 (17) | 0.0699 (10) | |
C29 | 0.6433 (3) | 0.2424 (3) | 0.56000 (17) | 0.0854 (13) | |
H29 | 0.6706 | 0.2333 | 0.6005 | 0.102* | |
C30 | 0.6324 (3) | 0.1726 (3) | 0.52343 (17) | 0.0822 (12) | |
H30 | 0.6517 | 0.1170 | 0.5393 | 0.099* | |
C31 | 0.5934 (2) | 0.1837 (2) | 0.46336 (14) | 0.0621 (9) | |
H31 | 0.5865 | 0.1358 | 0.4387 | 0.074* | |
C32 | 0.6273 (3) | 0.4023 (3) | 0.57857 (18) | 0.1162 (17) | |
H32A | 0.5845 | 0.3948 | 0.5998 | 0.174* | |
H32B | 0.6087 | 0.4551 | 0.5556 | 0.174* | |
H32C | 0.6966 | 0.4063 | 0.6060 | 0.174* | |
C33 | 0.4205 (2) | 0.2129 (2) | 0.14528 (13) | 0.0491 (8) | |
C34 | 0.3869 (2) | 0.2244 (2) | 0.08004 (14) | 0.0550 (9) | |
C35 | 0.3823 (2) | 0.3067 (3) | 0.05616 (15) | 0.0645 (10) | |
H35 | 0.3993 | 0.3554 | 0.0808 | 0.077* | |
C36 | 0.3519 (3) | 0.3182 (3) | −0.00569 (19) | 0.0796 (12) | |
C37 | 0.3258 (3) | 0.2429 (4) | −0.03957 (19) | 0.0926 (15) | |
H37 | 0.3049 | 0.2483 | −0.0802 | 0.111* | |
C38 | 0.3290 (3) | 0.1617 (4) | −0.0168 (2) | 0.0995 (15) | |
H38 | 0.3101 | 0.1131 | −0.0415 | 0.119* | |
C39 | 0.3607 (3) | 0.1518 (3) | 0.04327 (16) | 0.0757 (11) | |
H39 | 0.3645 | 0.0961 | 0.0593 | 0.091* | |
C40 | 0.3512 (3) | 0.4061 (3) | −0.03010 (19) | 0.1225 (18) | |
H40A | 0.4076 | 0.4119 | −0.0413 | 0.184* | |
H40B | 0.3562 | 0.4494 | −0.0009 | 0.184* | |
H40C | 0.2893 | 0.4144 | −0.0641 | 0.184* | |
C41 | 0.2897 (2) | 0.21060 (19) | 0.28695 (13) | 0.0486 (8) | |
H41 | 0.3265 | 0.1816 | 0.3221 | 0.058* | |
C42 | 0.1899 (2) | 0.22929 (19) | 0.26720 (14) | 0.0482 (8) | |
C43 | 0.2523 (2) | 0.2770 (2) | 0.20483 (14) | 0.0543 (8) | |
H43 | 0.2564 | 0.3032 | 0.1718 | 0.065* | |
C44 | 0.1144 (2) | 0.2147 (2) | 0.29388 (14) | 0.0674 (10) | |
H44A | 0.0966 | 0.2698 | 0.3058 | 0.101* | |
H44B | 0.1431 | 0.1771 | 0.3276 | 0.101* | |
H44C | 0.0549 | 0.1877 | 0.2653 | 0.101* | |
C45 | 0.7048 (2) | 0.2509 (2) | 0.32460 (14) | 0.0543 (8) | |
H45 | 0.7040 | 0.2480 | 0.3620 | 0.065* | |
C46 | 0.7889 (2) | 0.25386 (19) | 0.31367 (15) | 0.0517 (8) | |
C47 | 0.6559 (2) | 0.2568 (2) | 0.23110 (14) | 0.0547 (8) | |
H47 | 0.6163 | 0.2591 | 0.1909 | 0.066* | |
C48 | 0.8994 (2) | 0.2526 (2) | 0.35311 (15) | 0.0746 (11) | |
H48A | 0.9071 | 0.2470 | 0.3934 | 0.112* | |
H48B | 0.9304 | 0.3061 | 0.3483 | 0.112* | |
H48C | 0.9313 | 0.2038 | 0.3428 | 0.112* | |
O2W | 0.86386 (19) | 0.25847 (16) | 0.18570 (12) | 0.0709 (7) | |
H2WA | 0.9047 (18) | 0.2948 (16) | 0.1851 (13) | 0.0739 (9)* | |
H2WB | 0.881 (2) | 0.2088 (10) | 0.1817 (13) | 0.0738 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0457 (2) | 0.0539 (2) | 0.0372 (2) | 0.00492 (18) | 0.01310 (18) | −0.00106 (18) |
Cu2 | 0.0445 (2) | 0.0517 (2) | 0.0348 (2) | 0.00415 (17) | 0.01262 (17) | 0.00448 (17) |
O1 | 0.0812 (16) | 0.0574 (15) | 0.0469 (15) | −0.0020 (12) | 0.0170 (12) | 0.0035 (11) |
O2 | 0.0609 (14) | 0.0565 (14) | 0.0432 (13) | −0.0012 (11) | 0.0187 (11) | −0.0030 (10) |
O3 | 0.0480 (12) | 0.0628 (14) | 0.0384 (13) | 0.0073 (10) | 0.0140 (10) | 0.0023 (11) |
O4 | 0.0570 (13) | 0.0565 (15) | 0.0685 (16) | 0.0081 (11) | 0.0223 (12) | 0.0147 (12) |
O5 | 0.0470 (12) | 0.0647 (15) | 0.0611 (15) | 0.0045 (11) | 0.0127 (11) | 0.0167 (12) |
O6 | 0.0473 (12) | 0.0661 (15) | 0.0359 (12) | 0.0065 (10) | 0.0146 (10) | 0.0080 (11) |
O7 | 0.0558 (13) | 0.0594 (14) | 0.0399 (13) | −0.0008 (11) | 0.0143 (10) | 0.0036 (11) |
O8 | 0.0859 (17) | 0.0620 (16) | 0.0591 (16) | −0.0032 (13) | 0.0209 (13) | 0.0079 (12) |
O1W | 0.0734 (9) | 0.0733 (9) | 0.0762 (9) | 0.0003 (6) | 0.0337 (8) | 0.0006 (7) |
N1 | 0.0504 (15) | 0.0572 (16) | 0.0428 (17) | 0.0043 (12) | 0.0205 (13) | −0.0004 (13) |
N2 | 0.0541 (18) | 0.0609 (18) | 0.064 (2) | −0.0013 (14) | 0.0327 (17) | −0.0044 (15) |
N3 | 0.0454 (14) | 0.0527 (15) | 0.0404 (16) | 0.0103 (12) | 0.0098 (13) | 0.0011 (12) |
N4 | 0.0506 (10) | 0.0535 (10) | 0.0549 (10) | 0.0049 (8) | 0.0159 (9) | −0.0014 (8) |
N5 | 0.0404 (14) | 0.0530 (16) | 0.0389 (15) | 0.0035 (11) | 0.0107 (12) | 0.0029 (12) |
N6 | 0.0382 (16) | 0.0696 (19) | 0.0498 (19) | 0.0089 (14) | 0.0052 (15) | 0.0024 (15) |
N7 | 0.0456 (15) | 0.0555 (16) | 0.0394 (15) | 0.0036 (12) | 0.0164 (13) | 0.0034 (12) |
N8 | 0.0490 (17) | 0.0641 (19) | 0.0549 (19) | 0.0037 (14) | 0.0259 (16) | 0.0021 (14) |
C1 | 0.0411 (18) | 0.061 (2) | 0.043 (2) | 0.0007 (16) | 0.0138 (15) | −0.0067 (17) |
C2 | 0.0409 (17) | 0.062 (2) | 0.042 (2) | −0.0023 (15) | 0.0176 (15) | −0.0036 (16) |
C3 | 0.0447 (18) | 0.059 (2) | 0.050 (2) | 0.0037 (15) | 0.0163 (16) | −0.0052 (17) |
C4 | 0.0465 (19) | 0.071 (2) | 0.048 (2) | 0.0059 (16) | 0.0202 (16) | 0.0002 (17) |
C5 | 0.070 (2) | 0.078 (3) | 0.042 (2) | −0.007 (2) | 0.0176 (18) | −0.0086 (19) |
C6 | 0.094 (3) | 0.072 (3) | 0.054 (3) | −0.022 (2) | 0.026 (2) | −0.016 (2) |
C7 | 0.072 (2) | 0.065 (2) | 0.045 (2) | −0.0123 (18) | 0.0202 (18) | −0.0058 (17) |
C8 | 0.076 (2) | 0.081 (3) | 0.061 (2) | 0.013 (2) | 0.033 (2) | 0.013 (2) |
C9 | 0.0297 (16) | 0.060 (2) | 0.048 (2) | 0.0010 (15) | 0.0158 (14) | 0.0034 (17) |
C10 | 0.0345 (15) | 0.060 (2) | 0.0413 (19) | −0.0021 (14) | 0.0141 (14) | −0.0038 (16) |
C11 | 0.0501 (19) | 0.054 (2) | 0.044 (2) | 0.0002 (15) | 0.0117 (15) | 0.0032 (16) |
C12 | 0.051 (2) | 0.078 (3) | 0.050 (2) | 0.0011 (18) | 0.0161 (17) | 0.0112 (19) |
C13 | 0.070 (2) | 0.104 (3) | 0.042 (2) | 0.001 (2) | 0.0121 (19) | 0.005 (2) |
C14 | 0.082 (3) | 0.099 (3) | 0.050 (3) | −0.019 (2) | 0.014 (2) | −0.028 (2) |
C15 | 0.067 (2) | 0.067 (2) | 0.059 (3) | −0.0091 (18) | 0.0204 (19) | −0.0130 (19) |
C16 | 0.083 (3) | 0.099 (3) | 0.077 (3) | 0.006 (2) | 0.020 (2) | 0.036 (2) |
C17 | 0.053 (2) | 0.064 (2) | 0.052 (2) | 0.0030 (16) | 0.0211 (17) | −0.0012 (17) |
C18 | 0.0502 (19) | 0.0514 (19) | 0.057 (2) | 0.0026 (15) | 0.0233 (17) | 0.0025 (16) |
C19 | 0.0519 (19) | 0.064 (2) | 0.044 (2) | 0.0069 (16) | 0.0160 (17) | 0.0026 (16) |
C20 | 0.048 (2) | 0.094 (3) | 0.081 (3) | −0.0019 (19) | 0.021 (2) | 0.004 (2) |
C21 | 0.056 (2) | 0.056 (2) | 0.044 (2) | 0.0067 (16) | 0.0146 (17) | −0.0007 (16) |
C22 | 0.0461 (18) | 0.0474 (19) | 0.056 (2) | −0.0010 (15) | 0.0162 (16) | −0.0065 (15) |
C23 | 0.0480 (19) | 0.055 (2) | 0.051 (2) | 0.0038 (15) | 0.0154 (16) | 0.0023 (16) |
C24 | 0.0480 (19) | 0.078 (3) | 0.086 (3) | −0.0030 (17) | 0.026 (2) | 0.000 (2) |
C25 | 0.0292 (16) | 0.062 (2) | 0.051 (2) | 0.0042 (15) | 0.0147 (15) | 0.0103 (18) |
C26 | 0.0371 (17) | 0.074 (2) | 0.0379 (19) | −0.0005 (15) | 0.0160 (14) | 0.0023 (17) |
C27 | 0.050 (2) | 0.076 (3) | 0.060 (3) | −0.0038 (17) | 0.0214 (18) | −0.007 (2) |
C28 | 0.050 (2) | 0.105 (3) | 0.056 (3) | −0.015 (2) | 0.0219 (19) | −0.021 (2) |
C29 | 0.069 (3) | 0.143 (4) | 0.041 (2) | −0.006 (3) | 0.018 (2) | −0.006 (3) |
C30 | 0.089 (3) | 0.103 (3) | 0.049 (3) | 0.017 (2) | 0.022 (2) | 0.023 (2) |
C31 | 0.063 (2) | 0.074 (3) | 0.046 (2) | 0.0060 (18) | 0.0184 (17) | 0.0099 (18) |
C32 | 0.113 (4) | 0.152 (5) | 0.092 (4) | −0.032 (3) | 0.050 (3) | −0.056 (3) |
C33 | 0.0369 (17) | 0.070 (2) | 0.0377 (19) | −0.0022 (16) | 0.0115 (14) | 0.0056 (18) |
C34 | 0.0383 (18) | 0.086 (3) | 0.041 (2) | −0.0048 (17) | 0.0163 (15) | 0.0001 (19) |
C35 | 0.0423 (19) | 0.094 (3) | 0.053 (2) | −0.0015 (18) | 0.0147 (17) | 0.012 (2) |
C36 | 0.050 (2) | 0.123 (4) | 0.067 (3) | 0.003 (2) | 0.025 (2) | 0.033 (3) |
C37 | 0.062 (3) | 0.161 (5) | 0.053 (3) | −0.004 (3) | 0.022 (2) | 0.014 (3) |
C38 | 0.090 (3) | 0.142 (5) | 0.072 (3) | −0.022 (3) | 0.037 (3) | −0.032 (3) |
C39 | 0.065 (2) | 0.116 (3) | 0.048 (2) | −0.014 (2) | 0.0228 (19) | −0.019 (2) |
C40 | 0.104 (3) | 0.164 (5) | 0.105 (4) | 0.037 (3) | 0.047 (3) | 0.078 (4) |
C41 | 0.0467 (18) | 0.054 (2) | 0.0411 (19) | 0.0007 (15) | 0.0128 (15) | 0.0057 (15) |
C42 | 0.0417 (18) | 0.053 (2) | 0.047 (2) | −0.0043 (14) | 0.0146 (16) | −0.0042 (15) |
C43 | 0.050 (2) | 0.066 (2) | 0.042 (2) | 0.0062 (16) | 0.0125 (17) | 0.0034 (16) |
C44 | 0.0482 (19) | 0.082 (3) | 0.070 (3) | −0.0064 (18) | 0.0213 (18) | −0.0019 (19) |
C45 | 0.0477 (19) | 0.072 (2) | 0.0410 (19) | 0.0058 (16) | 0.0154 (16) | 0.0077 (16) |
C46 | 0.0460 (19) | 0.055 (2) | 0.055 (2) | 0.0079 (15) | 0.0198 (17) | 0.0057 (16) |
C47 | 0.051 (2) | 0.068 (2) | 0.045 (2) | 0.0013 (16) | 0.0197 (17) | 0.0014 (16) |
C48 | 0.045 (2) | 0.100 (3) | 0.073 (3) | 0.0140 (18) | 0.0175 (19) | 0.009 (2) |
O2W | 0.0727 (9) | 0.0731 (9) | 0.0731 (9) | −0.0004 (6) | 0.0352 (8) | 0.0000 (7) |
Geometric parameters (Å, º) top
Cu1—N1 | 1.985 (2) | C15—H15 | 0.9300 |
Cu1—N3 | 1.982 (2) | C16—H16A | 0.9600 |
Cu1—O3 | 1.9534 (19) | C16—H16B | 0.9600 |
Cu2—N5 | 1.990 (2) | C16—H16C | 0.9600 |
Cu2—N7 | 1.984 (2) | C17—H17 | 0.9300 |
Cu1—O2 | 2.011 (2) | C18—C19 | 1.346 (4) |
Cu2—O6 | 1.9654 (19) | C18—C20 | 1.496 (4) |
Cu2—O7 | 1.9759 (19) | C19—H19 | 0.9300 |
O1—C1 | 1.247 (3) | C20—H20A | 0.9600 |
O2—C1 | 1.272 (3) | C20—H20B | 0.9600 |
O3—C9 | 1.275 (3) | C20—H20C | 0.9600 |
O4—C9 | 1.251 (3) | C21—H21 | 0.9300 |
O5—C25 | 1.253 (3) | C22—C23 | 1.361 (4) |
O6—C25 | 1.277 (4) | C22—C24 | 1.491 (4) |
O7—C33 | 1.287 (4) | C23—H23 | 0.9300 |
O8—C33 | 1.233 (3) | C24—H24A | 0.9600 |
O1W—H1WA | 0.81 (3) | C24—H24B | 0.9600 |
O1W—H1WB | 0.816 (10) | C24—H24C | 0.9600 |
N1—C17 | 1.319 (4) | C25—C26 | 1.498 (4) |
N1—C19 | 1.384 (3) | C26—C31 | 1.383 (4) |
N2—C17 | 1.337 (4) | C26—C27 | 1.392 (4) |
N2—C18 | 1.356 (4) | C27—C28 | 1.399 (4) |
N2—H2 | 0.84 (3) | C27—H27 | 0.9300 |
N3—C21 | 1.311 (3) | C28—C29 | 1.377 (5) |
N3—C23 | 1.377 (4) | C28—C32 | 1.493 (5) |
N4—C21 | 1.329 (4) | C29—C30 | 1.365 (5) |
N4—C22 | 1.363 (4) | C29—H29 | 0.9300 |
N4—H4 | 0.846 (10) | C30—C31 | 1.373 (4) |
N5—C43 | 1.316 (3) | C30—H30 | 0.9300 |
N5—C41 | 1.380 (4) | C31—H31 | 0.9300 |
N6—C43 | 1.333 (4) | C32—H32A | 0.9600 |
N6—C42 | 1.370 (4) | C32—H32B | 0.9600 |
N6—H6A | 0.842 (10) | C32—H32C | 0.9600 |
N7—C47 | 1.321 (4) | C33—C34 | 1.498 (4) |
N7—C45 | 1.390 (3) | C34—C35 | 1.378 (4) |
N8—C47 | 1.328 (4) | C34—C39 | 1.387 (4) |
N8—C46 | 1.359 (4) | C35—C36 | 1.423 (5) |
N8—H8 | 0.85 (3) | C35—H35 | 0.9300 |
C1—C2 | 1.502 (4) | C36—C37 | 1.383 (6) |
C2—C3 | 1.384 (4) | C36—C40 | 1.469 (5) |
C2—C7 | 1.384 (4) | C37—C38 | 1.353 (6) |
C3—C4 | 1.395 (4) | C37—H37 | 0.9300 |
C3—H3 | 0.9300 | C38—C39 | 1.378 (5) |
C4—C5 | 1.374 (4) | C38—H38 | 0.9300 |
C4—C8 | 1.495 (4) | C39—H39 | 0.9300 |
C5—C6 | 1.366 (4) | C40—H40A | 0.9600 |
C5—H5 | 0.9300 | C40—H40B | 0.9600 |
C6—C7 | 1.389 (4) | C40—H40C | 0.9600 |
C6—H6 | 0.9300 | C41—C42 | 1.352 (4) |
C7—H7 | 0.9300 | C41—H41 | 0.9300 |
C8—H8A | 0.9600 | C42—C44 | 1.493 (4) |
C8—H8B | 0.9600 | C43—H43 | 0.9300 |
C8—H8C | 0.9600 | C44—H44A | 0.9600 |
C9—C10 | 1.505 (4) | C44—H44B | 0.9600 |
C10—C15 | 1.383 (4) | C44—H44C | 0.9600 |
C10—C11 | 1.392 (4) | C45—C46 | 1.340 (4) |
C11—C12 | 1.384 (4) | C45—H45 | 0.9300 |
C11—H11 | 0.9300 | C46—C48 | 1.500 (4) |
C12—C13 | 1.370 (5) | C47—H47 | 0.9300 |
C12—C16 | 1.512 (4) | C48—H48A | 0.9600 |
C13—C14 | 1.379 (5) | C48—H48B | 0.9600 |
C13—H13 | 0.9300 | C48—H48C | 0.9600 |
C14—C15 | 1.392 (4) | O2W—H2WA | 0.81 (3) |
C14—H14 | 0.9300 | O2W—H2WB | 0.815 (10) |
| | | |
O3—Cu1—N1 | 89.73 (9) | C18—C20—H20B | 109.5 |
O3—Cu1—N3 | 90.14 (9) | H20A—C20—H20B | 109.5 |
O2—Cu1—O3 | 177.26 (9) | C18—C20—H20C | 109.5 |
N1—Cu1—N3 | 175.37 (10) | H20A—C20—H20C | 109.5 |
N1—Cu1—O2 | 90.56 (9) | H20B—C20—H20C | 109.5 |
N3—Cu1—O2 | 89.80 (9) | N3—C21—N4 | 111.0 (3) |
O6—Cu2—O7 | 177.84 (9) | N3—C21—H21 | 124.5 |
O6—Cu2—N5 | 90.08 (9) | N4—C21—H21 | 124.5 |
O6—Cu2—N7 | 89.07 (9) | C23—C22—N4 | 104.5 (3) |
O7—Cu2—N5 | 89.87 (9) | C23—C22—C24 | 131.5 (3) |
O7—Cu2—N7 | 90.91 (9) | N4—C22—C24 | 124.0 (3) |
N5—Cu2—N7 | 178.27 (10) | C22—C23—N3 | 110.1 (3) |
C1—O2—Cu1 | 101.20 (19) | C22—C23—H23 | 124.9 |
C9—O3—Cu1 | 116.35 (19) | N3—C23—H23 | 124.9 |
C25—O6—Cu2 | 110.73 (19) | C22—C24—H24A | 109.5 |
C33—O7—Cu2 | 106.77 (19) | C22—C24—H24B | 109.5 |
H1WA—O1W—H1WB | 109 (3) | H24A—C24—H24B | 109.5 |
C17—N1—C19 | 104.3 (3) | C22—C24—H24C | 109.5 |
C17—N1—Cu1 | 125.9 (2) | H24A—C24—H24C | 109.5 |
C19—N1—Cu1 | 129.7 (2) | H24B—C24—H24C | 109.5 |
C17—N2—C18 | 108.5 (3) | O5—C25—O6 | 122.9 (3) |
C17—N2—H2 | 120 (2) | O5—C25—C26 | 120.3 (3) |
C18—N2—H2 | 131 (2) | O6—C25—C26 | 116.8 (3) |
C21—N3—C23 | 105.4 (3) | C31—C26—C27 | 119.0 (3) |
C21—N3—Cu1 | 127.1 (2) | C31—C26—C25 | 120.7 (3) |
C23—N3—Cu1 | 127.4 (2) | C27—C26—C25 | 120.3 (3) |
C21—N4—C22 | 109.1 (3) | C26—C27—C28 | 121.5 (3) |
C21—N4—H4 | 123.3 (19) | C26—C27—H27 | 119.3 |
C22—N4—H4 | 126 (2) | C28—C27—H27 | 119.3 |
C43—N5—C41 | 104.8 (3) | C29—C28—C27 | 117.2 (4) |
C43—N5—Cu2 | 126.7 (2) | C29—C28—C32 | 122.1 (4) |
C41—N5—Cu2 | 127.8 (2) | C27—C28—C32 | 120.8 (4) |
C43—N6—C42 | 108.3 (2) | C30—C29—C28 | 122.0 (4) |
C43—N6—H6A | 124 (2) | C30—C29—H29 | 119.0 |
C42—N6—H6A | 127 (2) | C28—C29—H29 | 119.0 |
C47—N7—C45 | 103.7 (3) | C29—C30—C31 | 120.6 (4) |
C47—N7—Cu2 | 126.4 (2) | C29—C30—H30 | 119.7 |
C45—N7—Cu2 | 129.8 (2) | C31—C30—H30 | 119.7 |
C47—N8—C46 | 108.2 (3) | C30—C31—C26 | 119.8 (3) |
C47—N8—H8 | 126 (3) | C30—C31—H31 | 120.1 |
C46—N8—H8 | 126 (3) | C26—C31—H31 | 120.1 |
O1—C1—O2 | 121.4 (3) | C28—C32—H32A | 109.5 |
O1—C1—C2 | 120.1 (3) | C28—C32—H32B | 109.5 |
O2—C1—C2 | 118.5 (3) | H32A—C32—H32B | 109.5 |
C3—C2—C7 | 119.3 (3) | C28—C32—H32C | 109.5 |
C3—C2—C1 | 121.4 (3) | H32A—C32—H32C | 109.5 |
C7—C2—C1 | 119.3 (3) | H32B—C32—H32C | 109.5 |
C2—C3—C4 | 121.6 (3) | O8—C33—O7 | 122.5 (3) |
C2—C3—H3 | 119.2 | O8—C33—C34 | 120.5 (3) |
C4—C3—H3 | 119.2 | O7—C33—C34 | 117.0 (3) |
C5—C4—C3 | 117.5 (3) | C35—C34—C39 | 119.6 (3) |
C5—C4—C8 | 121.6 (3) | C35—C34—C33 | 120.5 (3) |
C3—C4—C8 | 120.9 (3) | C39—C34—C33 | 119.9 (3) |
C6—C5—C4 | 122.1 (3) | C34—C35—C36 | 120.9 (4) |
C6—C5—H5 | 118.9 | C34—C35—H35 | 119.5 |
C4—C5—H5 | 118.9 | C36—C35—H35 | 119.5 |
C5—C6—C7 | 120.0 (3) | C37—C36—C35 | 116.2 (4) |
C5—C6—H6 | 120.0 | C37—C36—C40 | 123.7 (4) |
C7—C6—H6 | 120.0 | C35—C36—C40 | 120.2 (5) |
C2—C7—C6 | 119.4 (3) | C38—C37—C36 | 123.6 (4) |
C2—C7—H7 | 120.3 | C38—C37—H37 | 118.2 |
C6—C7—H7 | 120.3 | C36—C37—H37 | 118.2 |
C4—C8—H8A | 109.5 | C37—C38—C39 | 119.4 (4) |
C4—C8—H8B | 109.5 | C37—C38—H38 | 120.3 |
H8A—C8—H8B | 109.5 | C39—C38—H38 | 120.3 |
C4—C8—H8C | 109.5 | C38—C39—C34 | 120.4 (4) |
H8A—C8—H8C | 109.5 | C38—C39—H39 | 119.8 |
H8B—C8—H8C | 109.5 | C34—C39—H39 | 119.8 |
O4—C9—O3 | 124.3 (3) | C36—C40—H40A | 109.5 |
O4—C9—C10 | 120.3 (3) | C36—C40—H40B | 109.5 |
O3—C9—C10 | 115.5 (3) | H40A—C40—H40B | 109.5 |
C15—C10—C11 | 118.7 (3) | C36—C40—H40C | 109.5 |
C15—C10—C9 | 120.6 (3) | H40A—C40—H40C | 109.5 |
C11—C10—C9 | 120.6 (3) | H40B—C40—H40C | 109.5 |
C12—C11—C10 | 121.9 (3) | C42—C41—N5 | 110.6 (3) |
C12—C11—H11 | 119.1 | C42—C41—H41 | 124.7 |
C10—C11—H11 | 119.1 | N5—C41—H41 | 124.7 |
C13—C12—C11 | 118.5 (3) | C41—C42—N6 | 104.9 (3) |
C13—C12—C16 | 121.1 (3) | C41—C42—C44 | 131.6 (3) |
C11—C12—C16 | 120.4 (3) | N6—C42—C44 | 123.5 (3) |
C12—C13—C14 | 120.8 (3) | N5—C43—N6 | 111.4 (3) |
C12—C13—H13 | 119.6 | N5—C43—H43 | 124.3 |
C14—C13—H13 | 119.6 | N6—C43—H43 | 124.3 |
C13—C14—C15 | 120.6 (3) | C42—C44—H44A | 109.5 |
C13—C14—H14 | 119.7 | C42—C44—H44B | 109.5 |
C15—C14—H14 | 119.7 | H44A—C44—H44B | 109.5 |
C10—C15—C14 | 119.4 (3) | C42—C44—H44C | 109.5 |
C10—C15—H15 | 120.3 | H44A—C44—H44C | 109.5 |
C14—C15—H15 | 120.3 | H44B—C44—H44C | 109.5 |
C12—C16—H16A | 109.5 | C46—C45—N7 | 110.6 (3) |
C12—C16—H16B | 109.5 | C46—C45—H45 | 124.7 |
H16A—C16—H16B | 109.5 | N7—C45—H45 | 124.7 |
C12—C16—H16C | 109.5 | C45—C46—N8 | 105.6 (3) |
H16A—C16—H16C | 109.5 | C45—C46—C48 | 132.7 (3) |
H16B—C16—H16C | 109.5 | N8—C46—C48 | 121.7 (3) |
N1—C17—N2 | 111.3 (3) | N7—C47—N8 | 111.9 (3) |
N1—C17—H17 | 124.4 | N7—C47—H47 | 124.0 |
N2—C17—H17 | 124.4 | N8—C47—H47 | 124.0 |
C19—C18—N2 | 105.2 (3) | C46—C48—H48A | 109.5 |
C19—C18—C20 | 132.4 (3) | C46—C48—H48B | 109.5 |
N2—C18—C20 | 122.3 (3) | H48A—C48—H48B | 109.5 |
C18—C19—N1 | 110.8 (3) | C46—C48—H48C | 109.5 |
C18—C19—H19 | 124.6 | H48A—C48—H48C | 109.5 |
N1—C19—H19 | 124.6 | H48B—C48—H48C | 109.5 |
C18—C20—H20A | 109.5 | H2WA—O2W—H2WB | 112 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O5 | 0.81 (3) | 2.04 (3) | 2.824 (3) | 163 (3) |
O1W—H1WB···O8i | 0.81 (3) | 1.88 (1) | 2.690 (3) | 176 (3) |
N2—H2···O1Wii | 0.84 (3) | 1.88 (3) | 2.719 (4) | 177 (3) |
N4—H4···O5 | 0.85 (1) | 1.99 (1) | 2.832 (3) | 174 (3) |
N6—H6A···O4 | 0.84 (1) | 2.11 (1) | 2.946 (3) | 175 (3) |
N8—H8···O2W | 0.85 (3) | 1.86 (3) | 2.701 (4) | 171 (4) |
O2W—H2WA···O4iii | 0.81 (3) | 2.03 (2) | 2.792 (3) | 156 (3) |
O2W—H2WB···O1iv | 0.82 (1) | 1.89 (1) | 2.693 (3) | 170 (3) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1, y, z; (iii) x+1, y, z; (iv) −x+1, y−1/2, −z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Cu(C8H5O4)2(C4H6N2)2] | [Cu(C8H7O2)2(C4H6N2)2]·H2O |
Mr | 558.01 | 516.04 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 292 | 292 |
a, b, c (Å) | 7.3188 (6), 8.5847 (7), 10.1033 (8) | 14.3860 (2), 15.2620 (4), 24.6922 (5) |
α, β, γ (°) | 96.487 (1), 98.756 (2), 107.620 (1) | 90, 113.288 (2), 90 |
V (Å3) | 589.37 (8) | 4979.71 (18) |
Z | 1 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.99 | 0.92 |
Crystal size (mm) | 0.23 × 0.20 × 0.15 | 0.28 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.805, 0.866 | 0.783, 0.838 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3304, 2290, 2155 | 27494, 9780, 5859 |
Rint | 0.011 | 0.048 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.069, 1.00 | 0.047, 0.108, 0.98 |
No. of reflections | 2290 | 9780 |
No. of parameters | 178 | 653 |
No. of restraints | 14 | 38 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.26 | 0.50, −0.28 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.81 (2) | 2.16 (2) | 2.965 (3) | 170 (2) |
O4—H4···O2ii | 0.82 (2) | 1.86 (2) | 2.632 (2) | 156 (3) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z. |
Selected geometric parameters (Å, º) for (II) topCu1—N1 | 1.985 (2) | Cu2—N7 | 1.984 (2) |
Cu1—N3 | 1.982 (2) | Cu1—O2 | 2.011 (2) |
Cu1—O3 | 1.9534 (19) | Cu2—O6 | 1.9654 (19) |
Cu2—N5 | 1.990 (2) | Cu2—O7 | 1.9759 (19) |
| | | |
O3—Cu1—N1 | 89.73 (9) | O6—Cu2—O7 | 177.84 (9) |
O3—Cu1—N3 | 90.14 (9) | O6—Cu2—N5 | 90.08 (9) |
O2—Cu1—O3 | 177.26 (9) | O6—Cu2—N7 | 89.07 (9) |
N1—Cu1—N3 | 175.37 (10) | O7—Cu2—N5 | 89.87 (9) |
N1—Cu1—O2 | 90.56 (9) | O7—Cu2—N7 | 90.91 (9) |
N3—Cu1—O2 | 89.80 (9) | N5—Cu2—N7 | 178.27 (10) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O5 | 0.81 (3) | 2.04 (3) | 2.824 (3) | 163 (3) |
O1W—H1WB···O8i | 0.81 (3) | 1.876 (11) | 2.690 (3) | 176 (3) |
N2—H2···O1Wii | 0.84 (3) | 1.88 (3) | 2.719 (4) | 177 (3) |
N4—H4···O5 | 0.846 (10) | 1.989 (11) | 2.832 (3) | 174 (3) |
N6—H6A···O4 | 0.842 (10) | 2.106 (11) | 2.946 (3) | 175 (3) |
N8—H8···O2W | 0.85 (3) | 1.86 (3) | 2.701 (4) | 171 (4) |
O2W—H2WA···O4iii | 0.81 (3) | 2.028 (16) | 2.792 (3) | 156 (3) |
O2W—H2WB···O1iv | 0.815 (10) | 1.887 (12) | 2.693 (3) | 170 (3) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1, y, z; (iii) x+1, y, z; (iv) −x+1, y−1/2, −z+1/2. |
Geometry of π–π stacking interactions (°, Å) for compounds (I) and (II) topCgi···Cgj | Cg···Cg | α | β | γ | Cgi_perp | Cgj_perp |
(I) | | | | | | |
Cg3···Cg3i | 3.4184 (15) | 0.00 | 18.98 | 18.98 | 3.233 | 3.233 |
Cg4···Cg4ii | 3.7528 (16) | 0.00 | 19.58 | 19.58 | 3.536 | 3.536 |
(II) | | | | | | |
Cg1···Cg8iii | 3.8847 (18) | 2.28 | 29.80 | 31.95 | 3.296 | 3.371 |
Cg2···Cg7 | 3.5422 (18) | 2.15 | 24.27 | 22.27 | 3.278 | 3.229 |
Cg4···Cg4iv | 3.733 (2) | 0.00 | 14.46 | 14.46 | 3.615 | 3.615 |
Cg7···Cg2 | 3.5421 (18) | 2.17 | 22.28 | 24.27 | 3.229 | 3.278 |
Cg8···Cg1v | 3.8848 (18) | 2.28 | 31.95 | 29.80 | 3.371 | 3.296 |
Cg9···Cg10vi | 3.783 (2) | 5.05 | 14.72 | 14.53 | 3.662 | 3.659 |
Cg10···Cg9vii | 3.783 (2) | 5.05 | 14.53 | 14.72 | 3.659 | 3.662 |
In (I), Cg3 and Cg4 are the centroids of the N1/C1/N2/C2–C3 and C5–C10 rings,
respectively. In (II), Cg1, Cg2, Cg4, Cg7, Cg8, Cg9 and Cg10 are the centroids
of the rings N1/C17/N2/C18/C19, N3/C21/N4/C22/C23, C10–C15, N5/C41/C42/N6/C43,
N7/C45/C46/N8/C47, C26–C30 and C34–C39, respectively.
Cg···Cg is the distance between ring centroids i and j.
α is the dihedral angle between planes i and j.
β is the angle between Cgi-->Cgj and the normal to the plane i.
γ is the angle between Cgi-->Cgj and the normal to the plane j.
Cgi_perp is the perpendicular distance of Cgi from ring j.
Cgj_perp is the perpendicular distance of Cgj from ring i.
Symmetry codes: (i) -x, -y + 2, -z + 1; (ii) -x, -y + 1, -z;
(iii) -1 + x, y, z; (iv) -x, 1 - y, -z; (v) 1 + x, y, z;
(vi) x, 1/2 - y, 1/2 + z; (vii) x, 1/2 - y, -1/2 + z. |
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Hydrogen bonds having good directionality and flexibility and suitable strength are very important and have been widely studied in physics, chemistry and biology (Beatty, 2003). To our knowledge, most reported work has mainly been concentrated on organic crystal engineering (Rambaran et al., 2009; Koshima et al., 2005; Childs & Hardcastle, 2007; Aakeröy et al., 2007). It is well known that crystal engineering with coordination bonds is a popular research area because of the stable coordination bonds and versatile coordination modes of metal ions, especially transition metals. However, transition metal coordination compounds assembled by hydrogen-bonding interactions have been less well studied (Liu et al., 2007; Beatty, 2001; Larsson & Öhrström, 2003; Aakeröy et al., 1998, 2004). Therefore, our focus is on arranging transition metal cationic centres through hydrogen bonds, attempting to construct structures with interesting dimensions and topologies. Here, we present the two title two-dimensional hydrogen-bonded coordination networks, (I) and (II).
The molecular structure for (I) is shown in Fig. 1. The Cu2+ ion is coordinated by two 4-methyl-1H-imidazole (4-MeIM) molecules and two 3-carboxybenzoate (HBDC-) anions and is located on an inversion centre, giving an approximate square-planar arrangement [Cu1—O = 1.9451 (14) Å and Cu1—N = 1.9761 (19) Å]. Each 4-MeIM molecule and HBDC- anion binds to the metal centre through one N atom and one O atom. Obviously, the HBDC- anion coordinates as a monodentate ligand to the Cu2+ ion. The other carboxyl group does not lose its H atom, so each [Cu(4-MeIM)2(HBDC)2] molecular unit simultaneously possesses two N—H donors and two O—H donors.
Adjacent 4-MeIM molecules in (I) are linked by two pairs of N2—H2A···O2 hydrogen bonds into a one-dimensional chain along the [100] direction. Similarly, adjacent 4-MeIM units are held together through two sets of O4—H4···O2 hydrogen bonds, forming a one-dimensional chain substructure along the [010] direction. This combination of [100] and [010] chains results in a two-dimensional sheet parallel to the (001) plane (Fig. 2, Table 1), and thus each [Cu(4-MeIM)2(HBDC)2] unit interacts with four neighbouring units through hydrogen-bonding contacts. Therefore, each [Cu(4-MeIM)2(HBDC)2] unit can be considered as a four-connected node, generating a (4,4) net (Öhrström & Larsson, 2005) with dimensions of 7.319 × 8.585 Å (Fig. 3). The connectivity for each node is four, corresponding to four four-membered circuits. Connections between adjacent units are further reinforced by π–π interactions, with distances between the ring centroids of 3.4178 (17) and 3.7520 (18) Å [For which rings?], respectively (Table 2). These two rings are strictly parallel.
When H2BDC in (I) is replaced with 3-methylbenzoate (3-HMeBC), compound (II) is produced wherein an analogous two-dimensional hydrogen-bonded structure on the (001) plane is formed. Compound (II) crystallizes in the monoclinic P21/c space group with two symmetry-independent molecules in the asymmetric unit, which is thus composed of two Cu2+ ions, four 4-MeIM molecules, four 3-MeBC- anions and two isolated water molecules. Each Cu2+ centre is coordinated by two N atoms and two O atoms in a square-planar arrangement with an identical coordination environment to that in (I) [Cu—O and Cu—N distances in the ranges 1.9534 (19)–2.011 (2) and 1.982 (2)–1.990 (2) Å, respectively].
In the structure of (II), two neutral [Cu(4-MeIM)2(3-MeBC)2] molecules are held together via N4—H4···O5 and N6—H6A···O4 hydrogen bonds, leading to a dimeric pair, which links two discrete water molecules O1W and O2W through O1W–H1WA···O5 and N8—H8···O2W hydrogen bonds to form the asymmetric unit (Fig. 4). In fact, each [Cu(4-MeIM)2(3-MeBC)2]2 dimeric pair interacts with six surrounding water molecules, while each water molecule bridges three dimeric units to form a two-dimensional (001) sheet (Fig. 5). In addition, there are complex strong π–π interactions to stabilize the crystal stacking (Table 2). If the dimeric pairs and water molecules are considered as six- and three-connected nodes, respectively, compound (II) can be simplified as a two-dimensional (43)2(46, 66, 83) net (Öhrström & Larsson, 2005) (Fig. 6) and the connectivities are 3 and 6. For each three-connected node, there are three four-membered circuits; for each three-connected node, there are six four-membered, six six-membered and three eight-membered circuits simultaneously, with stoichiometry coefficients of 2:1.
We conclude that 4-MeIM coordinates to the Cu2+ ion as a monodentate ligand because the steric hindrance of the methyl group leads the N—H donor to interact with other hydrogen-bond acceptors via hydrogen bonds, while H2BDC and 3-MeBC carboxylate ligands not only have strong coordination abilities but also are good hydrogen-bond acceptors. The successful combination of their metal-coordinating ability and hydrogen-bonding function results in two two-dimensional frameworks. Thus, a rational change of the substituent group in the organic ligand can construct similar hydrogen-bonded networks with different topologies.