Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112048937/sk3461sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112048937/sk3461Isup2.hkl |
CCDC reference: 925250
A mixture containing Cu(OAc)2.H2O (19.9 mg, 0.10 mmol), HL (14.5 mg, 0.10 mmol), phthalic acid (16.8 mg, 0.10 mmol) and ????? [Text missing] (10 ml) was sealed in a Teflon-lined stainless steel vessel (20 ml), which was heated at 413 K for 3 d and then cooled to room temperature at a rate of 5 K h-1. Blue block-shaped crystals of (I) suitable for X-ray analysis were obtained in 60% yield. Analysis, calculated for (I): C 49.74, H 2.78, N 14.50%; found: C 49.61, H 2.84, N 14.59%.
Although all H atoms were visible in difference maps, they were subsequently placed in geometrically calculated positions, with C—H = 0.93 Å, and included in the final refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg et al., 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Fig. 1. A view of the local coordination of the CuII cations in (I), showing
the atom-numbering scheme. Displacement ellipsoids are drawn at the 30%
probability level. [Symmetry codes: (i) x, -y + 3/2, z +
1/2; (ii) x + 1, -y + 3/2, z + 1/2.] Fig. 2. A perspective view of the two-dimensional layered framework parallel to the (010) plane. Dashed lines indicate π–π interactions [Added text OK?]. Fig. 3. The three-dimensional structure of (I) formed through π–π stacking interactions (dashed lines; L linkers are shown as simple rods for clarity). |
[Cu2(C8H4O4)(C8H6N3)2] | F(000) = 1168 |
Mr = 579.51 | Dx = 1.732 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4370 reflections |
a = 7.752 (2) Å | θ = 2.5–28.4° |
b = 20.566 (7) Å | µ = 1.96 mm−1 |
c = 14.141 (4) Å | T = 296 K |
β = 99.639 (6)° | Block, blue |
V = 2222.7 (12) Å3 | 0.28 × 0.22 × 0.20 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 4813 independent reflections |
Radiation source: fine-focus sealed tube | 3469 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 27.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −9→9 |
Tmin = 0.610, Tmax = 0.695 | k = −26→25 |
12705 measured reflections | l = −13→18 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0287P)2 + 1.8398P] where P = (Fo2 + 2Fc2)/3 |
4813 reflections | (Δ/σ)max = 0.001 |
325 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[Cu2(C8H4O4)(C8H6N3)2] | V = 2222.7 (12) Å3 |
Mr = 579.51 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.752 (2) Å | µ = 1.96 mm−1 |
b = 20.566 (7) Å | T = 296 K |
c = 14.141 (4) Å | 0.28 × 0.22 × 0.20 mm |
β = 99.639 (6)° |
Bruker APEXII CCD area-detector diffractometer | 4813 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3469 reflections with I > 2σ(I) |
Tmin = 0.610, Tmax = 0.695 | Rint = 0.024 |
12705 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.38 e Å−3 |
4813 reflections | Δρmin = −0.36 e Å−3 |
325 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 | ||
Cu1 | 0.76108 (4) | 0.759298 (16) | 0.57840 (2) | 0.02923 (10) | |
Cu2 | 1.05463 (4) | 0.805560 (16) | 0.82856 (2) | 0.02947 (10) | |
O1 | 0.6334 (2) | 0.68530 (9) | 0.51198 (14) | 0.0315 (4) | |
O2 | 0.8618 (3) | 0.68147 (11) | 0.43756 (18) | 0.0504 (6) | |
O3 | 0.3944 (3) | 0.67498 (10) | 0.30964 (14) | 0.0379 (5) | |
O4 | 0.2065 (2) | 0.62158 (9) | 0.38407 (15) | 0.0353 (5) | |
N1 | 0.6539 (3) | 0.82191 (11) | 0.47260 (17) | 0.0340 (6) | |
N2 | 0.8424 (3) | 0.84219 (11) | 0.64051 (17) | 0.0316 (5) | |
N3 | 0.9415 (3) | 0.86178 (11) | 0.72439 (17) | 0.0338 (6) | |
N4 | 1.1584 (3) | 0.74380 (11) | 0.93560 (17) | 0.0299 (5) | |
N5 | 0.9626 (3) | 0.72221 (11) | 0.76932 (16) | 0.0299 (5) | |
N6 | 0.8685 (3) | 0.70246 (11) | 0.68402 (17) | 0.0336 (6) | |
C1 | 0.5582 (4) | 0.80677 (16) | 0.3870 (2) | 0.0415 (8) | |
H1 | 0.5422 | 0.7632 | 0.3701 | 0.050* | |
C2 | 0.4833 (5) | 0.85353 (17) | 0.3237 (2) | 0.0485 (9) | |
H2 | 0.4170 | 0.8415 | 0.2653 | 0.058* | |
C3 | 0.5071 (5) | 0.91833 (17) | 0.3474 (2) | 0.0501 (9) | |
H3 | 0.4570 | 0.9505 | 0.3054 | 0.060* | |
C4 | 0.6069 (5) | 0.93459 (16) | 0.4347 (2) | 0.0450 (8) | |
H4 | 0.6257 | 0.9779 | 0.4521 | 0.054* | |
C5 | 0.6783 (4) | 0.88528 (14) | 0.4958 (2) | 0.0349 (7) | |
C6 | 0.7846 (4) | 0.89583 (14) | 0.5904 (2) | 0.0352 (7) | |
C7 | 0.8445 (5) | 0.95050 (15) | 0.6410 (2) | 0.0475 (9) | |
H7 | 0.8239 | 0.9937 | 0.6231 | 0.057* | |
C8 | 0.9427 (4) | 0.92699 (14) | 0.7249 (2) | 0.0441 (8) | |
H8 | 1.0010 | 0.9526 | 0.7743 | 0.053* | |
C9 | 1.2500 (4) | 0.76037 (16) | 1.0207 (2) | 0.0384 (7) | |
H9 | 1.2807 | 0.8038 | 1.0319 | 0.046* | |
C10 | 1.3011 (4) | 0.71566 (17) | 1.0928 (2) | 0.0464 (8) | |
H10 | 1.3664 | 0.7285 | 1.1511 | 0.056* | |
C11 | 1.2530 (4) | 0.65144 (17) | 1.0764 (2) | 0.0468 (8) | |
H11 | 1.2849 | 0.6203 | 1.1238 | 0.056* | |
C12 | 1.1568 (4) | 0.63395 (15) | 0.9889 (2) | 0.0417 (8) | |
H12 | 1.1231 | 0.5909 | 0.9768 | 0.050* | |
C13 | 1.1113 (4) | 0.68106 (14) | 0.9196 (2) | 0.0322 (7) | |
C14 | 1.0087 (4) | 0.66960 (14) | 0.8242 (2) | 0.0323 (7) | |
C15 | 0.9430 (5) | 0.61432 (15) | 0.7750 (2) | 0.0481 (9) | |
H15 | 0.9545 | 0.5714 | 0.7959 | 0.058* | |
C16 | 0.8565 (5) | 0.63704 (14) | 0.6877 (2) | 0.0461 (8) | |
H16 | 0.7985 | 0.6110 | 0.6387 | 0.055* | |
C17 | 0.6653 (4) | 0.59072 (13) | 0.42102 (19) | 0.0278 (6) | |
C18 | 0.7891 (4) | 0.54115 (16) | 0.4341 (2) | 0.0395 (7) | |
H18 | 0.9065 | 0.5512 | 0.4538 | 0.047* | |
C19 | 0.7391 (4) | 0.47669 (15) | 0.4179 (2) | 0.0414 (8) | |
H19 | 0.8224 | 0.4438 | 0.4273 | 0.050* | |
C20 | 0.5647 (4) | 0.46185 (14) | 0.3878 (2) | 0.0380 (7) | |
H20 | 0.5300 | 0.4187 | 0.3788 | 0.046* | |
C21 | 0.4416 (4) | 0.51109 (14) | 0.3710 (2) | 0.0333 (7) | |
H21 | 0.3250 | 0.5007 | 0.3491 | 0.040* | |
C22 | 0.4901 (3) | 0.57597 (13) | 0.38658 (18) | 0.0264 (6) | |
C23 | 0.7249 (4) | 0.65767 (14) | 0.4558 (2) | 0.0301 (6) | |
C24 | 0.3562 (4) | 0.62900 (13) | 0.35832 (19) | 0.0283 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03229 (19) | 0.02369 (18) | 0.0296 (2) | −0.00350 (14) | −0.00082 (15) | 0.00080 (14) |
Cu2 | 0.03007 (19) | 0.02453 (18) | 0.0315 (2) | −0.00157 (14) | −0.00162 (14) | −0.00052 (14) |
O1 | 0.0322 (11) | 0.0287 (11) | 0.0322 (11) | −0.0028 (8) | 0.0019 (9) | −0.0031 (8) |
O2 | 0.0377 (13) | 0.0532 (15) | 0.0639 (16) | −0.0163 (11) | 0.0188 (12) | −0.0109 (12) |
O3 | 0.0422 (12) | 0.0364 (12) | 0.0325 (11) | 0.0004 (10) | −0.0010 (9) | 0.0087 (9) |
O4 | 0.0281 (11) | 0.0312 (11) | 0.0447 (13) | 0.0025 (9) | 0.0004 (9) | 0.0028 (9) |
N1 | 0.0370 (14) | 0.0314 (14) | 0.0323 (14) | −0.0059 (11) | 0.0018 (11) | 0.0033 (10) |
N2 | 0.0365 (14) | 0.0239 (12) | 0.0316 (13) | −0.0022 (10) | −0.0029 (11) | 0.0030 (10) |
N3 | 0.0396 (14) | 0.0258 (13) | 0.0330 (14) | −0.0044 (11) | −0.0021 (11) | −0.0015 (10) |
N4 | 0.0281 (12) | 0.0304 (13) | 0.0306 (13) | 0.0012 (10) | 0.0036 (10) | 0.0001 (10) |
N5 | 0.0345 (13) | 0.0266 (12) | 0.0261 (12) | −0.0001 (10) | −0.0027 (10) | −0.0002 (10) |
N6 | 0.0384 (14) | 0.0255 (13) | 0.0333 (14) | −0.0034 (10) | −0.0042 (11) | −0.0002 (10) |
C1 | 0.0478 (19) | 0.0381 (17) | 0.0349 (18) | −0.0093 (15) | −0.0039 (15) | 0.0025 (14) |
C2 | 0.055 (2) | 0.051 (2) | 0.0353 (18) | −0.0070 (17) | −0.0038 (16) | 0.0071 (16) |
C3 | 0.061 (2) | 0.046 (2) | 0.0396 (19) | 0.0061 (17) | 0.0001 (17) | 0.0161 (16) |
C4 | 0.061 (2) | 0.0333 (17) | 0.0375 (19) | 0.0025 (16) | 0.0005 (16) | 0.0056 (14) |
C5 | 0.0382 (17) | 0.0314 (16) | 0.0339 (17) | −0.0004 (13) | 0.0025 (13) | 0.0046 (13) |
C6 | 0.0443 (18) | 0.0258 (15) | 0.0338 (17) | 0.0004 (13) | 0.0015 (14) | 0.0035 (12) |
C7 | 0.065 (2) | 0.0227 (15) | 0.049 (2) | 0.0000 (15) | −0.0071 (17) | 0.0023 (14) |
C8 | 0.059 (2) | 0.0260 (16) | 0.0424 (19) | −0.0042 (15) | −0.0064 (16) | −0.0035 (14) |
C9 | 0.0391 (17) | 0.0421 (18) | 0.0320 (17) | 0.0000 (14) | 0.0001 (14) | −0.0028 (14) |
C10 | 0.049 (2) | 0.059 (2) | 0.0296 (17) | −0.0013 (17) | −0.0006 (15) | 0.0011 (15) |
C11 | 0.055 (2) | 0.051 (2) | 0.0331 (18) | 0.0074 (17) | 0.0031 (16) | 0.0113 (16) |
C12 | 0.053 (2) | 0.0320 (17) | 0.0392 (18) | 0.0043 (15) | 0.0057 (16) | 0.0056 (14) |
C13 | 0.0301 (15) | 0.0344 (17) | 0.0320 (16) | 0.0054 (12) | 0.0051 (13) | 0.0006 (12) |
C14 | 0.0384 (17) | 0.0253 (15) | 0.0319 (16) | 0.0038 (12) | 0.0022 (13) | 0.0031 (12) |
C15 | 0.066 (2) | 0.0237 (16) | 0.048 (2) | 0.0012 (15) | −0.0094 (17) | 0.0031 (14) |
C16 | 0.061 (2) | 0.0261 (16) | 0.0441 (19) | −0.0055 (15) | −0.0105 (17) | −0.0023 (14) |
C17 | 0.0287 (14) | 0.0296 (15) | 0.0242 (14) | 0.0003 (12) | 0.0019 (12) | −0.0014 (11) |
C18 | 0.0285 (16) | 0.0446 (19) | 0.0433 (19) | 0.0046 (14) | −0.0002 (14) | −0.0032 (15) |
C19 | 0.0426 (18) | 0.0346 (17) | 0.0451 (19) | 0.0131 (14) | 0.0019 (15) | −0.0021 (14) |
C20 | 0.0513 (19) | 0.0269 (16) | 0.0338 (17) | 0.0028 (14) | 0.0013 (15) | −0.0047 (13) |
C21 | 0.0337 (16) | 0.0326 (16) | 0.0309 (16) | −0.0022 (13) | −0.0027 (13) | −0.0065 (12) |
C22 | 0.0276 (14) | 0.0302 (15) | 0.0200 (14) | 0.0011 (11) | −0.0003 (11) | −0.0018 (11) |
C23 | 0.0272 (15) | 0.0318 (16) | 0.0289 (15) | −0.0016 (12) | −0.0020 (12) | 0.0010 (12) |
C24 | 0.0316 (15) | 0.0271 (15) | 0.0224 (14) | 0.0006 (12) | −0.0068 (12) | −0.0040 (11) |
Cu1—O1 | 1.9663 (19) | C4—H4 | 0.9300 |
Cu1—N6 | 1.968 (2) | C5—C6 | 1.465 (4) |
Cu1—N2 | 1.972 (2) | C6—C7 | 1.372 (4) |
Cu1—N1 | 2.042 (2) | C7—C8 | 1.385 (4) |
Cu2—N3 | 1.960 (2) | C7—H7 | 0.9300 |
Cu2—O4i | 1.984 (2) | C8—H8 | 0.9300 |
Cu2—N5 | 1.987 (2) | C9—C10 | 1.381 (4) |
Cu2—N4 | 2.036 (2) | C9—H9 | 0.9300 |
Cu2—O2ii | 2.335 (2) | C10—C11 | 1.381 (5) |
O1—C23 | 1.283 (3) | C10—H10 | 0.9300 |
O2—C23 | 1.234 (3) | C11—C12 | 1.381 (5) |
O2—Cu2iii | 2.335 (2) | C11—H11 | 0.9300 |
O3—C24 | 1.235 (3) | C12—C13 | 1.381 (4) |
O4—C24 | 1.283 (3) | C12—H12 | 0.9300 |
O4—Cu2iv | 1.984 (2) | C13—C14 | 1.466 (4) |
N1—C1 | 1.346 (4) | C14—C15 | 1.385 (4) |
N1—C5 | 1.350 (4) | C15—C16 | 1.383 (4) |
N2—C6 | 1.347 (4) | C15—H15 | 0.9300 |
N2—N3 | 1.362 (3) | C16—H16 | 0.9300 |
N3—C8 | 1.341 (4) | C17—C18 | 1.391 (4) |
N4—C9 | 1.335 (4) | C17—C22 | 1.397 (4) |
N4—C13 | 1.350 (4) | C17—C23 | 1.508 (4) |
N5—C14 | 1.345 (3) | C18—C19 | 1.389 (4) |
N5—N6 | 1.363 (3) | C18—H18 | 0.9300 |
N6—C16 | 1.350 (4) | C19—C20 | 1.381 (4) |
C1—C2 | 1.374 (4) | C19—H19 | 0.9300 |
C1—H1 | 0.9300 | C20—C21 | 1.385 (4) |
C2—C3 | 1.379 (5) | C20—H20 | 0.9300 |
C2—H2 | 0.9300 | C21—C22 | 1.394 (4) |
C3—C4 | 1.384 (5) | C21—H21 | 0.9300 |
C3—H3 | 0.9300 | C22—C24 | 1.512 (4) |
C4—C5 | 1.386 (4) | ||
O1—Cu1—N6 | 91.03 (9) | C6—C7—C8 | 104.5 (3) |
O1—Cu1—N2 | 168.38 (9) | C6—C7—H7 | 127.7 |
N6—Cu1—N2 | 96.45 (10) | C8—C7—H7 | 127.7 |
O1—Cu1—N1 | 91.58 (9) | N3—C8—C7 | 110.0 (3) |
N6—Cu1—N1 | 177.34 (10) | N3—C8—H8 | 125.0 |
N2—Cu1—N1 | 80.89 (10) | C7—C8—H8 | 125.0 |
N3—Cu2—O4i | 90.75 (9) | N4—C9—C10 | 122.6 (3) |
N3—Cu2—N5 | 96.21 (10) | N4—C9—H9 | 118.7 |
O4i—Cu2—N5 | 164.89 (9) | C10—C9—H9 | 118.7 |
N3—Cu2—N4 | 176.46 (10) | C9—C10—C11 | 118.5 (3) |
O4i—Cu2—N4 | 92.44 (9) | C9—C10—H10 | 120.8 |
N5—Cu2—N4 | 81.05 (10) | C11—C10—H10 | 120.8 |
N3—Cu2—O2ii | 99.98 (10) | C12—C11—C10 | 119.3 (3) |
O4i—Cu2—O2ii | 93.18 (9) | C12—C11—H11 | 120.4 |
N5—Cu2—O2ii | 98.78 (9) | C10—C11—H11 | 120.4 |
N4—Cu2—O2ii | 78.31 (9) | C11—C12—C13 | 119.2 (3) |
C23—O1—Cu1 | 110.63 (17) | C11—C12—H12 | 120.4 |
C23—O2—Cu2iii | 148.3 (2) | C13—C12—H12 | 120.4 |
C24—O4—Cu2iv | 107.64 (17) | N4—C13—C12 | 121.5 (3) |
C1—N1—C5 | 118.4 (3) | N4—C13—C14 | 113.5 (2) |
C1—N1—Cu1 | 127.5 (2) | C12—C13—C14 | 125.1 (3) |
C5—N1—Cu1 | 114.1 (2) | N5—C14—C15 | 109.3 (3) |
C6—N2—N3 | 107.8 (2) | N5—C14—C13 | 116.9 (3) |
C6—N2—Cu1 | 114.85 (19) | C15—C14—C13 | 133.8 (3) |
N3—N2—Cu1 | 137.33 (18) | C16—C15—C14 | 104.7 (3) |
C8—N3—N2 | 107.6 (2) | C16—C15—H15 | 127.6 |
C8—N3—Cu2 | 125.7 (2) | C14—C15—H15 | 127.6 |
N2—N3—Cu2 | 126.60 (17) | N6—C16—C15 | 110.2 (3) |
C9—N4—C13 | 118.9 (3) | N6—C16—H16 | 124.9 |
C9—N4—Cu2 | 126.5 (2) | C15—C16—H16 | 124.9 |
C13—N4—Cu2 | 114.18 (19) | C18—C17—C22 | 119.7 (3) |
C14—N5—N6 | 108.8 (2) | C18—C17—C23 | 117.3 (3) |
C14—N5—Cu2 | 114.13 (19) | C22—C17—C23 | 122.6 (2) |
N6—N5—Cu2 | 137.00 (18) | C19—C18—C17 | 120.7 (3) |
C16—N6—N5 | 107.0 (2) | C19—C18—H18 | 119.7 |
C16—N6—Cu1 | 126.7 (2) | C17—C18—H18 | 119.7 |
N5—N6—Cu1 | 126.18 (18) | C20—C19—C18 | 119.6 (3) |
N1—C1—C2 | 122.2 (3) | C20—C19—H19 | 120.2 |
N1—C1—H1 | 118.9 | C18—C19—H19 | 120.2 |
C2—C1—H1 | 118.9 | C19—C20—C21 | 120.1 (3) |
C1—C2—C3 | 119.6 (3) | C19—C20—H20 | 119.9 |
C1—C2—H2 | 120.2 | C21—C20—H20 | 119.9 |
C3—C2—H2 | 120.2 | C20—C21—C22 | 120.9 (3) |
C2—C3—C4 | 118.8 (3) | C20—C21—H21 | 119.6 |
C2—C3—H3 | 120.6 | C22—C21—H21 | 119.6 |
C4—C3—H3 | 120.6 | C21—C22—C17 | 118.9 (3) |
C3—C4—C5 | 119.0 (3) | C21—C22—C24 | 119.6 (2) |
C3—C4—H4 | 120.5 | C17—C22—C24 | 121.3 (2) |
C5—C4—H4 | 120.5 | O2—C23—O1 | 122.5 (3) |
N1—C5—C4 | 122.0 (3) | O2—C23—C17 | 121.4 (3) |
N1—C5—C6 | 113.5 (3) | O1—C23—C17 | 115.8 (2) |
C4—C5—C6 | 124.5 (3) | O3—C24—O4 | 124.2 (3) |
N2—C6—C7 | 110.0 (3) | O3—C24—C22 | 118.8 (3) |
N2—C6—C5 | 116.5 (3) | O4—C24—C22 | 116.9 (2) |
C7—C6—C5 | 133.5 (3) | ||
N6—Cu1—O1—C23 | −89.56 (19) | Cu1—N2—C6—C5 | −3.0 (4) |
N2—Cu1—O1—C23 | 140.2 (4) | N1—C5—C6—N2 | −0.1 (4) |
N1—Cu1—O1—C23 | 90.93 (19) | C4—C5—C6—N2 | 179.5 (3) |
O1—Cu1—N1—C1 | −9.3 (3) | N1—C5—C6—C7 | 178.2 (4) |
N2—Cu1—N1—C1 | 179.6 (3) | C4—C5—C6—C7 | −2.2 (6) |
O1—Cu1—N1—C5 | 167.5 (2) | N2—C6—C7—C8 | 0.2 (4) |
N2—Cu1—N1—C5 | −3.6 (2) | C5—C6—C7—C8 | −178.2 (4) |
O1—Cu1—N2—C6 | −46.6 (6) | N2—N3—C8—C7 | −0.1 (4) |
N6—Cu1—N2—C6 | −176.4 (2) | Cu2—N3—C8—C7 | −177.9 (2) |
N1—Cu1—N2—C6 | 3.6 (2) | C6—C7—C8—N3 | 0.0 (4) |
O1—Cu1—N2—N3 | 131.4 (4) | C13—N4—C9—C10 | 1.0 (5) |
N6—Cu1—N2—N3 | 1.6 (3) | Cu2—N4—C9—C10 | 173.5 (2) |
N1—Cu1—N2—N3 | −178.5 (3) | N4—C9—C10—C11 | −1.0 (5) |
C6—N2—N3—C8 | 0.3 (3) | C9—C10—C11—C12 | 0.4 (5) |
Cu1—N2—N3—C8 | −177.8 (2) | C10—C11—C12—C13 | 0.1 (5) |
C6—N2—N3—Cu2 | 177.9 (2) | C9—N4—C13—C12 | −0.5 (4) |
Cu1—N2—N3—Cu2 | −0.1 (4) | Cu2—N4—C13—C12 | −173.8 (2) |
O4i—Cu2—N3—C8 | −18.9 (3) | C9—N4—C13—C14 | 178.9 (3) |
N5—Cu2—N3—C8 | 174.5 (3) | Cu2—N4—C13—C14 | 5.6 (3) |
O2ii—Cu2—N3—C8 | 74.5 (3) | C11—C12—C13—N4 | −0.1 (5) |
O4i—Cu2—N3—N2 | 163.8 (2) | C11—C12—C13—C14 | −179.4 (3) |
N5—Cu2—N3—N2 | −2.7 (2) | N6—N5—C14—C15 | −0.5 (3) |
O2ii—Cu2—N3—N2 | −102.8 (2) | Cu2—N5—C14—C15 | −178.0 (2) |
O4i—Cu2—N4—C9 | 17.5 (2) | N6—N5—C14—C13 | −179.9 (2) |
N5—Cu2—N4—C9 | −176.2 (3) | Cu2—N5—C14—C13 | 2.6 (3) |
O2ii—Cu2—N4—C9 | −75.2 (2) | N4—C13—C14—N5 | −5.5 (4) |
O4i—Cu2—N4—C13 | −169.7 (2) | C12—C13—C14—N5 | 173.9 (3) |
N5—Cu2—N4—C13 | −3.4 (2) | N4—C13—C14—C15 | 175.3 (3) |
O2ii—Cu2—N4—C13 | 97.6 (2) | C12—C13—C14—C15 | −5.4 (6) |
N3—Cu2—N5—C14 | −177.4 (2) | N5—C14—C15—C16 | 0.3 (4) |
O4i—Cu2—N5—C14 | 65.7 (4) | C13—C14—C15—C16 | 179.7 (3) |
N4—Cu2—N5—C14 | 0.4 (2) | N5—N6—C16—C15 | −0.2 (4) |
O2ii—Cu2—N5—C14 | −76.2 (2) | Cu1—N6—C16—C15 | −177.4 (2) |
N3—Cu2—N5—N6 | 6.1 (3) | C14—C15—C16—N6 | −0.1 (4) |
O4i—Cu2—N5—N6 | −110.9 (4) | C22—C17—C18—C19 | −3.3 (5) |
N4—Cu2—N5—N6 | −176.2 (3) | C23—C17—C18—C19 | 169.9 (3) |
O2ii—Cu2—N5—N6 | 107.2 (3) | C17—C18—C19—C20 | 0.5 (5) |
C14—N5—N6—C16 | 0.4 (3) | C18—C19—C20—C21 | 2.0 (5) |
Cu2—N5—N6—C16 | 177.1 (2) | C19—C20—C21—C22 | −1.7 (5) |
C14—N5—N6—Cu1 | 177.7 (2) | C20—C21—C22—C17 | −1.0 (4) |
Cu2—N5—N6—Cu1 | −5.7 (4) | C20—C21—C22—C24 | 173.9 (3) |
O1—Cu1—N6—C16 | 6.7 (3) | C18—C17—C22—C21 | 3.5 (4) |
N2—Cu1—N6—C16 | 177.8 (3) | C23—C17—C22—C21 | −169.3 (3) |
O1—Cu1—N6—N5 | −170.0 (2) | C18—C17—C22—C24 | −171.4 (3) |
N2—Cu1—N6—N5 | 1.1 (2) | C23—C17—C22—C24 | 15.8 (4) |
C5—N1—C1—C2 | −0.9 (5) | Cu2iii—O2—C23—O1 | −149.6 (3) |
Cu1—N1—C1—C2 | 175.8 (3) | Cu2iii—O2—C23—C17 | 36.8 (6) |
N1—C1—C2—C3 | 0.5 (5) | Cu1—O1—C23—O2 | −9.6 (3) |
C1—C2—C3—C4 | 0.2 (6) | Cu1—O1—C23—C17 | 164.29 (18) |
C2—C3—C4—C5 | −0.5 (5) | C18—C17—C23—O2 | 46.8 (4) |
C1—N1—C5—C4 | 0.5 (5) | C22—C17—C23—O2 | −140.2 (3) |
Cu1—N1—C5—C4 | −176.6 (3) | C18—C17—C23—O1 | −127.2 (3) |
C1—N1—C5—C6 | −179.9 (3) | C22—C17—C23—O1 | 45.8 (4) |
Cu1—N1—C5—C6 | 3.0 (3) | Cu2iv—O4—C24—O3 | 1.6 (3) |
C3—C4—C5—N1 | 0.2 (5) | Cu2iv—O4—C24—C22 | −175.63 (18) |
C3—C4—C5—C6 | −179.3 (3) | C21—C22—C24—O3 | −130.1 (3) |
N3—N2—C6—C7 | −0.3 (4) | C17—C22—C24—O3 | 44.7 (4) |
Cu1—N2—C6—C7 | 178.3 (2) | C21—C22—C24—O4 | 47.3 (4) |
N3—N2—C6—C5 | 178.4 (3) | C17—C22—C24—O4 | −137.9 (3) |
Symmetry codes: (i) x+1, −y+3/2, z+1/2; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2; (iv) x−1, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C8H4O4)(C8H6N3)2] |
Mr | 579.51 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 7.752 (2), 20.566 (7), 14.141 (4) |
β (°) | 99.639 (6) |
V (Å3) | 2222.7 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.96 |
Crystal size (mm) | 0.28 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.610, 0.695 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12705, 4813, 3469 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.079, 1.07 |
No. of reflections | 4813 |
No. of parameters | 325 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.36 |
Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg et al., 2005), SHELXTL (Sheldrick, 2008).
Cu1—O1 | 1.9663 (19) | Cu2—O4i | 1.984 (2) |
Cu1—N6 | 1.968 (2) | Cu2—N5 | 1.987 (2) |
Cu1—N2 | 1.972 (2) | Cu2—N4 | 2.036 (2) |
Cu1—N1 | 2.042 (2) | Cu2—O2ii | 2.335 (2) |
Cu2—N3 | 1.960 (2) | ||
O1—Cu1—N6 | 91.03 (9) | O4i—Cu2—N5 | 164.89 (9) |
O1—Cu1—N2 | 168.38 (9) | N3—Cu2—N4 | 176.46 (10) |
N6—Cu1—N2 | 96.45 (10) | O4i—Cu2—N4 | 92.44 (9) |
O1—Cu1—N1 | 91.58 (9) | N5—Cu2—N4 | 81.05 (10) |
N6—Cu1—N1 | 177.34 (10) | N3—Cu2—O2ii | 99.98 (10) |
N2—Cu1—N1 | 80.89 (10) | O4i—Cu2—O2ii | 93.18 (9) |
N3—Cu2—O4i | 90.75 (9) | N5—Cu2—O2ii | 98.78 (9) |
N3—Cu2—N5 | 96.21 (10) | N4—Cu2—O2ii | 78.31 (9) |
Symmetry codes: (i) x+1, −y+3/2, z+1/2; (ii) x, −y+3/2, z+1/2. |
The rapid development in crystal engineering of metal-directed supramolecular architectures assembled by means of coordinative forces, and other weak cooperative interactions such as hydrogen bonding and aromatic stacking, continues to attract considerable interest in the design of new crystalline materials (Ye et al., 2005). As is widely known, the assembly of such materials can be influenced significantly by the reaction temperature, metal–ligand ratio, anion type, acidity and even the solvent, leading to the formation of a variety of interesting coordination complexes (Du et al., 2006). In this regard, further exploration and appropriate experimental results may guide chemists from spontaneous assembly to the controllable preparation of metallosupramolecular systems. With regard to the organic ligands suitable for designing new metal–organic supramolecular structures, dicarboxylates such as the rigid aromatic phthalate, isophthalate and terephthalate anions have been widely utilized (Ye et al., 2005).
N-Donor building blocks, such as the traditionally employed 2-(1H-pyrazol-3-yl)pyridine, have been extensively studied in coordination chemistry. 2-(1H-Pyrazol-3-yl)pyridine (HL), first reported by Tisler et al. (1980), is a multifunctional ligand having several coordination modes. For a long time, HL was considered as a simple bidentate chelating ligand (Sugiyarto & Goodwin, 1988) similar to 2,2-bipyridine. However, in 1997, Ward and co-workers (Jones et al., 1997) observed another coordination mode, where it acted as a terdentate bridging ligand via deprotonation of the pyrazole NH group and coordination of the pyrazole N atom to a second metal ion. The coordination chemistry of HL as a terdentate bridging ligand with CuII cations has been studied by several researchers to date (Jeffery et al., 1997; Mann et al., 1999; Chandrasekhar et al., 2005; Hu et al., 2006), but to the best of our knowledge, only three structurally related CuII complexes with deprotonation of HL and aromatic acids have been reported (Hu et al., 2006). As a systematic investigation of the coordination chemistry of HL with CuII, we report here the preparation and structural characterization of the title novel CuII complex, (I).
The structure of (I) is a two-dimensional layer constructed by the dicarboxylate ligands linking binuclear Cu2(L)2 units with pyrazolate bridges. As shown in Fig. 1, there are two independent CuII cations (Cu1 and Cu2) in the asymmetric unit. Atom Cu1 is four-coordinated by three N atoms of two distinct L ligands and one carboxylate O atom from a phthalate dianion to form a distorted square[-planar?] geometry, with angles around the CuII centre ranging from 80.89 (10) to 96.45 (10)° (Table 1). Atom Cu2 has a distorted square-pyramidal coordination geometry with three N atoms from two distinct L ligands and two O atoms from different carboxylate groups. Two L ligands bridge the two CuII centres to form an approximately planar Cu2(L)2 binuclear unit. Within this binuclear unit, the Cu1···Cu2 distance is 3.988 (1) Å and the two planar Cu2(L)2 units are further bridged by bidentate (O1 and O2) and monodentate (O4) phthalate O atoms to form a two-dimensional layer parallel to the (010) plane. It should be noted that the phthalate dianions adopt two kinds of coordination mode in this two-dimensional pattern.
Within the two-dimensional layer, neighbouring parallel aromatic rings of L are 3.686 (2) and 3.898 (2) Å apart, indicating the presence of centroid-to-centroid π–π stacking interactions that further stabilize the crystal structure (Fig. 2). The benzene rings, located on both sides of the coordination layers, show strong interlayer π–π stacking interactions (Fig. 3); the centroid-to-centroid distances here are 3.674 (2) Å. These π–π interactions extend the two-dimensional layer network into a three-dimensional framework.
The structure of (I) thus shows that the assembly of this complex is directed by the stereochemical preference of the CuII cations: fulfilling this requirement necessitates deprotonation of the pyrazole groups to form a planar binuclear Cu2(L)2 unit.