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The title complexes, catena-poly[[aqua(1,10-phenanthroline-κ2N,N′)cobalt(II)]-μ-benzene-1,4-dicarboxylato-κ2O1:O4], [Co(C8H4O4)(C12H8N2)(H2O)], (I), and catena-poly[[[(di-2-pyridyl-κN-amine)copper(II)]-μ-benzene-1,4-dicarboxylato-κ4O1,O1′:O4,O4′] hydrate], [Cu(C8H4O4)(C10H9N3)]·H2O, (II), take the form of zigzag chains, with the 1,4-benzenedicarboxylate ion acting as an amphimonodentate ligand in (I) and a bis-bidentate ligand in (II). The CoII ion in (I) is five-coordinate and has a distorted trigonal–bipyramidal geometry. The CuII ion in (II) is in a very distorted octahedral 4+2 environment, with the octahedron elongated along the trans O—Cu—O bonds and with a trans O—Cu—O angle of only 137.22 (8)°.
Supporting information
CCDC references: 187902; 187903
Because the title complexes are insoluble in all common solvents, single
crystals were prepared by a modification of the slow diffusion method.
Typically, a dilute dimethylsulfoxide (DMSO) solution (~0.02 mol dm-3),
containing equimolar quantities of cobalt(II) or copper(II) nitrate, aromatic
amine and H2tpht, was prepared in a small test tube. A dilute solution of
Na2tpht in H2O was then stratified carefully and very slowly in order to
minimize mixing of the solutions. After approximately one week, single
crystals of suitable size were formed near the solution boundary. In the case
of the copper(II) system, two kinds of crystals, one dark-blue and one green,
were obtained. The dark-blue crystals slowly transform to the green phase and,
according to their IR spectra, very probably contain DMSO as an additional
constituent. Due to their instability, these crystals were not characterized
further.
For compound (I), all H atoms were found in difference Fourier maps and refined
isotropically with no constraints. For compound (II), all H atoms were found
in difference Fourier maps and refined isotropically with no constraints.
However, the final geometry of the H2O molecule was not satisfactory.
Because of this, the positions of the water H atoms HW1 and HW2 were
recalculated using the program HYDROGEN (Nardelli, 1999) after the last cycle
of refinement.
Data collection: SMART (Bruker, 1998) for (I); CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: SMART or SAINT? (Siemens, 1996) for (I); CAD-4 Software for (II). Data reduction: SHELXTL (Bruker, 1997) for (I); local modification of MolEN (Fair, 1990) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEX8a (McArdle, 1995; Burnett & Johnson, 1996) for (I); ORTEX7e (McArdle, 1995; Burnett & Johnson, 1996) for (II). Software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1983, 1995) for (I); SHELXL97 and PARST (Nardelli, 1983; Nardelli, 1995) for (II).
(I)
catena-poly-[[aqua(1,10-phenanthroline-
κ2N,
N')cobalt(II)]-µ-benzene- 1,4-dicarboxylato-
κ2O1,
O4]
top
Crystal data top
[Co(C8H4O4)(C12H8N2)(H2O)] | Z = 2 |
Mr = 421.26 | F(000) = 430 |
Triclinic, P1 | Dx = 1.571 Mg m−3 |
a = 9.2688 (17) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.4550 (18) Å | Cell parameters from 954 reflections |
c = 11.349 (2) Å | θ = 3.5–24.2° |
α = 112.462 (3)° | µ = 1.00 mm−1 |
β = 94.924 (2)° | T = 298 K |
γ = 113.908 (2)° | Irregular, brown-purple |
V = 890.6 (3) Å3 | 0.27 × 0.22 × 0.18 mm |
Data collection top
Make? model? CCD area-detector diffractometer | 3128 independent reflections |
Radiation source: fine-focus sealed tube | 2012 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 81.92 pixels mm-1 | θmax = 25.5°, θmin = 3.5° |
ϕ and ω scans | h = −11→10 |
Absorption correction: empirical (using intensity measurements) (XPREP in SHELXTL; Bruker, 1997) | k = −10→12 |
Tmin = 0.736, Tmax = 0.864 | l = −10→13 |
4652 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.060 | All H-atom parameters refined |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0171P)2] where P = (Fo2 + 2Fc2)/3 |
3128 reflections | (Δ/σ)max = 0.002 |
309 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
[Co(C8H4O4)(C12H8N2)(H2O)] | γ = 113.908 (2)° |
Mr = 421.26 | V = 890.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2688 (17) Å | Mo Kα radiation |
b = 10.4550 (18) Å | µ = 1.00 mm−1 |
c = 11.349 (2) Å | T = 298 K |
α = 112.462 (3)° | 0.27 × 0.22 × 0.18 mm |
β = 94.924 (2)° | |
Data collection top
Make? model? CCD area-detector diffractometer | 3128 independent reflections |
Absorption correction: empirical (using intensity measurements) (XPREP in SHELXTL; Bruker, 1997) | 2012 reflections with I > 2σ(I) |
Tmin = 0.736, Tmax = 0.864 | Rint = 0.032 |
4652 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.060 | All H-atom parameters refined |
S = 0.88 | Δρmax = 0.22 e Å−3 |
3128 reflections | Δρmin = −0.25 e Å−3 |
309 parameters | |
Special details top
Experimental. For complex (I), preliminary cell constants were obtained from 180 frames (0.3°
in ω). Final cell parameters were determined in a global refinement of data
obtained after integration of intensities. Data collection nominally covered a
hemisphere of reciprocal space by a combination of five sets of exposures (ω
and ϕ scans). Each exposure of 10 s covered 0.3° in ω. The
crystal-to-detector distance was 6.18 cm. |
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 | |
Co | 0.48616 (5) | 0.89276 (5) | 0.71582 (4) | 0.03683 (15) | |
O1 | 0.6905 (2) | 1.0993 (2) | 0.76184 (17) | 0.0480 (6) | |
O2 | 0.6103 (2) | 1.1559 (2) | 0.94286 (18) | 0.0541 (6) | |
O3 | 0.3173 (2) | 0.9240 (2) | 0.62329 (18) | 0.0449 (5) | |
O4 | 0.1766 (2) | 0.9539 (2) | 0.77342 (19) | 0.0546 (6) | |
OW1 | 0.3172 (3) | 0.7923 (2) | 0.8026 (2) | 0.0444 (6) | |
N1 | 0.5205 (3) | 0.7662 (2) | 0.5357 (2) | 0.0359 (6) | |
N2 | 0.6386 (3) | 0.8084 (2) | 0.7780 (2) | 0.0405 (6) | |
C1 | 0.4644 (4) | 0.7520 (4) | 0.4169 (3) | 0.0439 (8) | |
C2 | 0.5080 (5) | 0.6784 (4) | 0.3062 (3) | 0.0562 (10) | |
C3 | 0.6096 (5) | 0.6167 (4) | 0.3171 (3) | 0.0540 (10) | |
C4 | 0.6720 (4) | 0.6304 (3) | 0.4401 (3) | 0.0423 (8) | |
C5 | 0.7823 (4) | 0.5732 (4) | 0.4635 (4) | 0.0565 (10) | |
C6 | 0.8429 (5) | 0.5955 (4) | 0.5849 (4) | 0.0574 (10) | |
C7 | 0.7984 (4) | 0.6753 (3) | 0.6971 (3) | 0.0474 (8) | |
C8 | 0.8586 (5) | 0.7047 (4) | 0.8276 (4) | 0.0621 (11) | |
C9 | 0.8100 (5) | 0.7826 (4) | 0.9279 (4) | 0.0628 (11) | |
C10 | 0.6993 (4) | 0.8318 (4) | 0.8988 (3) | 0.0523 (10) | |
C11 | 0.6884 (3) | 0.7306 (3) | 0.6780 (3) | 0.0371 (7) | |
C12 | 0.6241 (3) | 0.7078 (3) | 0.5477 (3) | 0.0358 (7) | |
C13 | 0.7102 (3) | 1.1933 (3) | 0.8795 (3) | 0.0355 (7) | |
C14 | 0.8598 (3) | 1.3524 (3) | 0.9413 (2) | 0.0303 (7) | |
C15 | 0.9787 (4) | 1.3873 (3) | 0.8773 (3) | 0.0422 (8) | |
C16 | 0.8823 (4) | 1.4680 (4) | 1.0651 (3) | 0.0428 (9) | |
C17 | 0.2049 (4) | 0.9510 (3) | 0.6664 (3) | 0.0375 (7) | |
C18 | 0.0991 (3) | 0.9771 (3) | 0.5811 (3) | 0.0302 (7) | |
C19 | 0.1137 (4) | 0.9550 (3) | 0.4548 (3) | 0.0349 (8) | |
C20 | 0.0147 (4) | 0.9768 (3) | 0.3747 (3) | 0.0357 (8) | |
HC1 | 0.387 (3) | 0.792 (3) | 0.407 (2) | 0.051 (9)* | |
HC2 | 0.465 (3) | 0.670 (3) | 0.232 (2) | 0.034 (9)* | |
HC3 | 0.636 (3) | 0.566 (3) | 0.242 (3) | 0.054 (9)* | |
HC5 | 0.817 (3) | 0.524 (3) | 0.389 (3) | 0.065 (10)* | |
HC6 | 0.910 (3) | 0.554 (3) | 0.605 (3) | 0.057 (10)* | |
HC8 | 0.931 (3) | 0.671 (3) | 0.839 (3) | 0.054 (10)* | |
HC9 | 0.848 (3) | 0.806 (3) | 1.018 (3) | 0.068 (11)* | |
HC10 | 0.666 (3) | 0.885 (3) | 0.964 (2) | 0.038 (8)* | |
HC15 | 0.962 (3) | 1.304 (3) | 0.791 (2) | 0.048 (8)* | |
HC16 | 0.801 (3) | 1.445 (3) | 1.107 (2) | 0.044 (9)* | |
HC19 | 0.190 (3) | 0.921 (2) | 0.425 (2) | 0.027 (7)* | |
HC20 | 0.025 (3) | 0.966 (2) | 0.289 (2) | 0.031 (7)* | |
HW1 | 0.254 (4) | 0.841 (3) | 0.799 (3) | 0.073 (13)* | |
HW2 | 0.349 (5) | 0.808 (4) | 0.885 (4) | 0.14 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co | 0.0362 (3) | 0.0399 (3) | 0.0377 (2) | 0.0189 (2) | 0.01328 (19) | 0.01953 (19) |
O1 | 0.0480 (14) | 0.0409 (12) | 0.0356 (12) | 0.0146 (11) | 0.0113 (10) | 0.0063 (10) |
O2 | 0.0432 (14) | 0.0591 (14) | 0.0410 (13) | 0.0062 (12) | 0.0119 (11) | 0.0243 (11) |
O3 | 0.0438 (14) | 0.0699 (15) | 0.0464 (12) | 0.0385 (12) | 0.0209 (11) | 0.0365 (11) |
O4 | 0.0592 (15) | 0.0897 (17) | 0.0395 (13) | 0.0488 (14) | 0.0236 (12) | 0.0363 (12) |
OW1 | 0.0468 (15) | 0.0506 (14) | 0.0431 (15) | 0.0230 (12) | 0.0182 (12) | 0.0274 (11) |
N1 | 0.0369 (15) | 0.0365 (15) | 0.0334 (14) | 0.0168 (13) | 0.0071 (12) | 0.0165 (11) |
N2 | 0.0447 (17) | 0.0443 (16) | 0.0333 (15) | 0.0219 (14) | 0.0089 (13) | 0.0180 (12) |
C1 | 0.040 (2) | 0.049 (2) | 0.042 (2) | 0.0208 (18) | 0.0087 (17) | 0.0205 (16) |
C2 | 0.067 (3) | 0.062 (2) | 0.033 (2) | 0.028 (2) | 0.009 (2) | 0.0195 (19) |
C3 | 0.067 (3) | 0.048 (2) | 0.041 (2) | 0.027 (2) | 0.022 (2) | 0.0139 (17) |
C4 | 0.043 (2) | 0.0367 (18) | 0.044 (2) | 0.0171 (17) | 0.0149 (17) | 0.0164 (15) |
C5 | 0.064 (3) | 0.048 (2) | 0.061 (3) | 0.032 (2) | 0.028 (2) | 0.0196 (19) |
C6 | 0.060 (3) | 0.060 (2) | 0.069 (3) | 0.042 (2) | 0.019 (2) | 0.031 (2) |
C7 | 0.046 (2) | 0.049 (2) | 0.054 (2) | 0.0264 (18) | 0.0133 (18) | 0.0249 (17) |
C8 | 0.061 (3) | 0.078 (3) | 0.069 (3) | 0.047 (2) | 0.012 (2) | 0.040 (2) |
C9 | 0.069 (3) | 0.079 (3) | 0.047 (2) | 0.040 (2) | 0.005 (2) | 0.031 (2) |
C10 | 0.064 (3) | 0.058 (2) | 0.041 (2) | 0.034 (2) | 0.016 (2) | 0.0215 (18) |
C11 | 0.0364 (19) | 0.0316 (17) | 0.0452 (19) | 0.0164 (16) | 0.0111 (15) | 0.0193 (14) |
C12 | 0.0352 (19) | 0.0290 (17) | 0.0379 (18) | 0.0112 (15) | 0.0082 (15) | 0.0151 (14) |
C13 | 0.0315 (19) | 0.0435 (19) | 0.0360 (18) | 0.0192 (17) | 0.0050 (15) | 0.0220 (15) |
C14 | 0.0286 (18) | 0.0311 (17) | 0.0295 (16) | 0.0135 (15) | 0.0065 (14) | 0.0133 (13) |
C15 | 0.043 (2) | 0.0347 (19) | 0.0319 (18) | 0.0124 (18) | 0.0139 (16) | 0.0054 (15) |
C16 | 0.043 (2) | 0.045 (2) | 0.0400 (19) | 0.0197 (18) | 0.0248 (18) | 0.0180 (16) |
C17 | 0.035 (2) | 0.0361 (18) | 0.0348 (18) | 0.0159 (16) | 0.0076 (16) | 0.0122 (14) |
C18 | 0.0261 (17) | 0.0317 (16) | 0.0289 (16) | 0.0130 (14) | 0.0039 (13) | 0.0117 (13) |
C19 | 0.0297 (19) | 0.0411 (19) | 0.0365 (19) | 0.0212 (16) | 0.0118 (15) | 0.0150 (14) |
C20 | 0.0353 (19) | 0.0408 (19) | 0.0278 (18) | 0.0174 (16) | 0.0114 (15) | 0.0132 (14) |
Geometric parameters (Å, º) top
Co—O3 | 2.013 (2) | C6—C7 | 1.429 (4) |
Co—O1 | 2.044 (2) | C6—HC6 | 0.95 (3) |
Co—OW1 | 2.061 (2) | C7—C11 | 1.399 (4) |
Co—N1 | 2.102 (2) | C7—C8 | 1.404 (4) |
Co—N2 | 2.142 (2) | C8—C9 | 1.356 (5) |
O1—C13 | 1.261 (3) | C8—HC8 | 0.89 (3) |
O2—C13 | 1.251 (3) | C9—C10 | 1.388 (4) |
O3—C17 | 1.275 (3) | C9—HC9 | 0.95 (3) |
O4—C17 | 1.256 (3) | C10—HC10 | 0.90 (2) |
OW1—HW1 | 0.93 (3) | C11—C12 | 1.436 (4) |
OW1—HW2 | 0.89 (4) | C13—C14 | 1.501 (3) |
N1—C1 | 1.332 (3) | C14—C15 | 1.374 (4) |
N1—C12 | 1.352 (3) | C14—C16 | 1.388 (3) |
N2—C10 | 1.325 (3) | C15—C16i | 1.377 (4) |
N2—C11 | 1.360 (3) | C15—HC15 | 0.98 (2) |
C1—C2 | 1.391 (4) | C16—C15i | 1.377 (4) |
C1—HC1 | 0.98 (3) | C16—HC16 | 0.92 (2) |
C2—C3 | 1.361 (4) | C17—C18 | 1.493 (4) |
C2—HC2 | 0.85 (2) | C18—C20ii | 1.383 (3) |
C3—C4 | 1.396 (4) | C18—C19 | 1.391 (3) |
C3—HC3 | 0.92 (2) | C19—C20 | 1.380 (4) |
C4—C12 | 1.405 (3) | C19—HC19 | 0.95 (2) |
C4—C5 | 1.429 (4) | C20—C18ii | 1.383 (3) |
C5—C6 | 1.336 (4) | C20—HC20 | 0.95 (2) |
C5—HC5 | 0.96 (3) | | |
| | | |
O3—Co—O1 | 99.03 (8) | C8—C7—C6 | 124.8 (3) |
O3—Co—OW1 | 89.2 (1) | C9—C8—C7 | 120.5 (4) |
O1—Co—OW1 | 140.21 (8) | C9—C8—HC8 | 124 (2) |
O3—Co—N1 | 92.54 (9) | C7—C8—HC8 | 116 (2) |
O1—Co—N1 | 94.22 (8) | C8—C9—C10 | 118.7 (4) |
OW1—Co—N1 | 124.44 (8) | C8—C9—HC9 | 123 (2) |
O3—Co—N2 | 167.33 (8) | C10—C9—HC9 | 118 (2) |
O1—Co—N2 | 90.04 (8) | N2—C10—C9 | 123.8 (3) |
OW1—Co—N2 | 89.5 (1) | N2—C10—HC10 | 116 (2) |
N1—Co—N2 | 77.89 (9) | C9—C10—HC10 | 120 (2) |
C13—O1—Co | 106.4 (2) | N2—C11—C7 | 123.4 (3) |
C17—O3—Co | 127.1 (2) | N2—C11—C12 | 116.8 (3) |
Co—OW1—HW1 | 98 (2) | C7—C11—C12 | 119.8 (3) |
Co—OW1—HW2 | 121 (3) | N1—C12—C4 | 122.9 (3) |
HW1—OW1—HW2 | 110 (3) | N1—C12—C11 | 117.2 (3) |
C1—N1—C12 | 118.3 (3) | C4—C12—C11 | 119.9 (3) |
C1—N1—Co | 126.7 (2) | O2—C13—O1 | 121.7 (3) |
C12—N1—Co | 114.7 (2) | O2—C13—C14 | 121.1 (3) |
C10—N2—C11 | 117.2 (3) | O1—C13—C14 | 117.2 (3) |
C10—N2—Co | 129.4 (2) | C15—C14—C16 | 118.2 (3) |
C11—N2—Co | 113.2 (2) | C15—C14—C13 | 121.0 (2) |
N1—C1—C2 | 122.0 (3) | C16—C14—C13 | 120.8 (3) |
N1—C1—HC1 | 119 (2) | C14—C15—C16i | 121.1 (3) |
C2—C1—HC1 | 119 (2) | C14—C15—HC15 | 117 (2) |
C3—C2—C1 | 120.0 (4) | C16i—C15—HC15 | 122 (2) |
C3—C2—HC2 | 122 (2) | C15i—C16—C14 | 120.7 (3) |
C1—C2—HC2 | 117 (2) | C15i—C16—HC16 | 121 (2) |
C2—C3—C4 | 119.7 (3) | C14—C16—HC16 | 118 (2) |
C2—C3—HC3 | 119 (2) | O4—C17—O3 | 124.4 (3) |
C4—C3—HC3 | 121 (2) | O4—C17—C18 | 118.8 (3) |
C3—C4—C12 | 117.1 (3) | O3—C17—C18 | 116.9 (3) |
C3—C4—C5 | 124.4 (3) | C20ii—C18—C19 | 118.7 (3) |
C12—C4—C5 | 118.5 (3) | C20ii—C18—C17 | 121.2 (3) |
C6—C5—C4 | 121.5 (3) | C19—C18—C17 | 120.1 (3) |
C6—C5—HC5 | 121 (2) | C20—C19—C18 | 120.4 (3) |
C4—C5—HC5 | 117 (2) | C20—C19—HC19 | 122 (2) |
C5—C6—C7 | 121.6 (4) | C18—C19—HC19 | 118 (2) |
C5—C6—HC6 | 125 (2) | C19—C20—C18ii | 120.9 (3) |
C7—C6—HC6 | 113 (2) | C19—C20—HC20 | 122 (1) |
C11—C7—C8 | 116.5 (3) | C18ii—C20—HC20 | 118 (1) |
C11—C7—C6 | 118.7 (3) | | |
Symmetry codes: (i) −x+2, −y+3, −z+2; (ii) −x, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—HW1···O4 | 0.93 (4) | 1.70 (4) | 2.608 (4) | 164 (4) |
OW1—HW2···O2iii | 0.88 (5) | 1.82 (5) | 2.696 (3) | 172 (4) |
Symmetry code: (iii) −x+1, −y+2, −z+2. |
(II)
catena-poly-[[[(di-2-pyridyl-
κN-amine)copper(II)]-µ-benzene-1,4-
dicarboxylato-
κ4O1,
O1',
O4,
O4'] hydrate]
top
Crystal data top
[Cu(C8H4O4)(C10H9N3)]·H2O | Z = 2 |
Mr = 416.87 | F(000) = 426 |
Triclinic, P1 | Dx = 1.572 Mg m−3 |
a = 9.009 (4) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 9.289 (3) Å | Cell parameters from 23 reflections |
c = 11.171 (6) Å | θ = 13.2–16.2° |
α = 99.11 (4)° | µ = 1.28 mm−1 |
β = 106.64 (4)° | T = 293 K |
γ = 92.39 (3)° | Prism, green |
V = 880.6 (7) Å3 | 0.31 × 0.18 × 0.08 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.012 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 1.9° |
Graphite monochromator | h = 0→10 |
ω/2θ scans | k = −11→11 |
4069 measured reflections | l = −14→13 |
3746 independent reflections | 2 standard reflections every 1 min |
2814 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0512P)2] where P = (Fo2 + 2Fc2)/3 |
3746 reflections | (Δ/σ)max = 0.001 |
296 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
Crystal data top
[Cu(C8H4O4)(C10H9N3)]·H2O | γ = 92.39 (3)° |
Mr = 416.87 | V = 880.6 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.009 (4) Å | Mo Kα radiation |
b = 9.289 (3) Å | µ = 1.28 mm−1 |
c = 11.171 (6) Å | T = 293 K |
α = 99.11 (4)° | 0.31 × 0.18 × 0.08 mm |
β = 106.64 (4)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.012 |
4069 measured reflections | 2 standard reflections every 1 min |
3746 independent reflections | intensity decay: none |
2814 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.37 e Å−3 |
3746 reflections | Δρmin = −0.51 e Å−3 |
296 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 | |
Cu | 0.58844 (4) | 0.88776 (4) | 0.70282 (3) | 0.03472 (12) | |
O1 | 0.4034 (2) | 0.9937 (2) | 0.69257 (18) | 0.0420 (5) | |
O2 | 0.3712 (2) | 0.8448 (2) | 0.51176 (19) | 0.0502 (5) | |
O3 | 0.4810 (2) | 0.7077 (2) | 0.74281 (18) | 0.0430 (5) | |
O4 | 0.6471 (2) | 0.8310 (2) | 0.91647 (19) | 0.0460 (5) | |
OW1 | 1.2808 (3) | 0.9267 (3) | 0.8948 (3) | 0.0563 (7) | |
N1 | 0.7429 (3) | 0.7659 (2) | 0.6589 (2) | 0.0394 (5) | |
N2 | 0.7433 (2) | 1.0623 (2) | 0.7691 (2) | 0.0333 (5) | |
N3 | 0.9546 (3) | 0.9154 (3) | 0.8053 (2) | 0.0374 (5) | |
C1 | 0.6892 (4) | 0.6389 (4) | 0.5753 (4) | 0.0548 (8) | |
C2 | 0.7804 (5) | 0.5305 (4) | 0.5571 (4) | 0.0722 (12) | |
C3 | 0.9367 (5) | 0.5504 (4) | 0.6294 (4) | 0.0694 (11) | |
C4 | 0.9939 (4) | 0.6780 (3) | 0.7111 (4) | 0.0524 (8) | |
C5 | 0.8943 (3) | 0.7872 (3) | 0.7237 (3) | 0.0365 (6) | |
C6 | 0.8935 (3) | 1.0484 (3) | 0.8213 (2) | 0.0324 (5) | |
C7 | 0.9972 (3) | 1.1676 (3) | 0.8939 (3) | 0.0478 (7) | |
C8 | 0.9437 (4) | 1.3023 (4) | 0.9058 (4) | 0.0681 (11) | |
C9 | 0.7895 (5) | 1.3181 (4) | 0.8493 (4) | 0.0704 (12) | |
C10 | 0.6929 (4) | 1.1967 (3) | 0.7826 (3) | 0.0473 (7) | |
C11 | 0.3198 (3) | 0.9323 (3) | 0.5808 (3) | 0.0368 (6) | |
C12 | 0.1541 (3) | 0.9685 (3) | 0.5393 (2) | 0.0338 (6) | |
C13 | 0.0478 (3) | 0.8786 (3) | 0.4392 (3) | 0.0397 (6) | |
C14 | −0.1054 (3) | 0.9083 (3) | 0.3996 (3) | 0.0408 (7) | |
C15 | 0.5511 (3) | 0.7239 (3) | 0.8600 (3) | 0.0355 (6) | |
C16 | 0.5222 (3) | 0.6086 (3) | 0.9319 (2) | 0.0349 (6) | |
C17 | 0.5959 (4) | 0.6262 (3) | 1.0620 (3) | 0.0456 (7) | |
C18 | 0.4259 (3) | 0.4816 (3) | 0.8709 (3) | 0.0442 (7) | |
HN3 | 1.042 (4) | 0.919 (3) | 0.837 (3) | 0.042 (9)* | |
HC1 | 0.585 (4) | 0.631 (4) | 0.532 (4) | 0.070 (11)* | |
HC2 | 0.748 (4) | 0.447 (4) | 0.510 (3) | 0.059 (10)* | |
HC3 | 0.999 (4) | 0.473 (4) | 0.623 (3) | 0.066 (11)* | |
HC4 | 1.091 (4) | 0.687 (4) | 0.764 (3) | 0.062 (11)* | |
HC7 | 1.091 (4) | 1.154 (3) | 0.929 (3) | 0.049 (9)* | |
HC8 | 1.019 (4) | 1.379 (4) | 0.953 (4) | 0.072 (11)* | |
HC9 | 0.751 (5) | 1.395 (5) | 0.847 (4) | 0.093 (15)* | |
HC10 | 0.573 (4) | 1.206 (4) | 0.747 (3) | 0.065 (10)* | |
HC13 | 0.077 (3) | 0.802 (3) | 0.398 (3) | 0.031 (7)* | |
HC14 | −0.173 (4) | 0.847 (4) | 0.338 (3) | 0.060 (10)* | |
HC17 | 0.658 (3) | 0.711 (3) | 1.101 (3) | 0.044 (8)* | |
HC18 | 0.375 (4) | 0.473 (3) | 0.777 (3) | 0.050 (9)* | |
HW1 | 1.32661 | 0.98780 | 0.96187 | 0.050* | |
HW2 | 1.32149 | 0.94222 | 0.83759 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.02231 (17) | 0.03968 (19) | 0.03831 (19) | −0.00055 (12) | 0.00473 (12) | 0.00449 (13) |
O1 | 0.0245 (9) | 0.0520 (12) | 0.0415 (11) | 0.0029 (8) | 0.0000 (8) | 0.0034 (9) |
O2 | 0.0403 (11) | 0.0690 (14) | 0.0395 (11) | 0.0179 (10) | 0.0079 (9) | 0.0083 (10) |
O3 | 0.0376 (11) | 0.0511 (12) | 0.0373 (11) | −0.0052 (9) | 0.0046 (8) | 0.0139 (9) |
O4 | 0.0427 (12) | 0.0454 (11) | 0.0445 (11) | −0.0098 (9) | 0.0049 (9) | 0.0108 (9) |
OW1 | 0.0347 (12) | 0.0703 (17) | 0.0548 (15) | 0.0033 (12) | 0.0085 (11) | −0.0058 (14) |
N1 | 0.0320 (12) | 0.0371 (12) | 0.0470 (13) | −0.0021 (9) | 0.0130 (10) | 0.0008 (10) |
N2 | 0.0272 (11) | 0.0352 (11) | 0.0365 (12) | 0.0030 (9) | 0.0078 (9) | 0.0065 (9) |
N3 | 0.0226 (12) | 0.0406 (13) | 0.0437 (13) | 0.0043 (10) | 0.0020 (10) | 0.0061 (10) |
C1 | 0.0425 (18) | 0.0507 (18) | 0.063 (2) | −0.0062 (15) | 0.0155 (16) | −0.0088 (15) |
C2 | 0.061 (2) | 0.049 (2) | 0.095 (3) | −0.0088 (17) | 0.027 (2) | −0.024 (2) |
C3 | 0.060 (2) | 0.0441 (19) | 0.107 (3) | 0.0117 (17) | 0.036 (2) | −0.002 (2) |
C4 | 0.0382 (17) | 0.0435 (17) | 0.074 (2) | 0.0084 (13) | 0.0149 (16) | 0.0083 (16) |
C5 | 0.0320 (14) | 0.0355 (14) | 0.0436 (15) | −0.0002 (11) | 0.0124 (12) | 0.0104 (11) |
C6 | 0.0277 (12) | 0.0359 (13) | 0.0317 (13) | 0.0009 (10) | 0.0077 (10) | 0.0034 (10) |
C7 | 0.0301 (15) | 0.0512 (18) | 0.0518 (18) | 0.0003 (13) | 0.0035 (13) | −0.0041 (14) |
C8 | 0.0432 (19) | 0.0423 (18) | 0.097 (3) | −0.0028 (15) | 0.0070 (19) | −0.0224 (18) |
C9 | 0.052 (2) | 0.0374 (18) | 0.107 (3) | 0.0080 (16) | 0.013 (2) | −0.0116 (19) |
C10 | 0.0368 (16) | 0.0394 (16) | 0.063 (2) | 0.0071 (13) | 0.0119 (14) | 0.0056 (14) |
C11 | 0.0299 (14) | 0.0436 (15) | 0.0350 (14) | 0.0033 (11) | 0.0035 (11) | 0.0131 (12) |
C12 | 0.0257 (13) | 0.0410 (14) | 0.0318 (13) | 0.0031 (11) | 0.0024 (10) | 0.0097 (11) |
C13 | 0.0351 (14) | 0.0396 (15) | 0.0389 (15) | 0.0069 (12) | 0.0038 (12) | 0.0037 (12) |
C14 | 0.0318 (14) | 0.0436 (16) | 0.0364 (15) | 0.0001 (12) | −0.0040 (12) | 0.0033 (12) |
C15 | 0.0270 (13) | 0.0379 (14) | 0.0423 (15) | 0.0034 (11) | 0.0100 (11) | 0.0096 (11) |
C16 | 0.0279 (13) | 0.0389 (14) | 0.0357 (14) | 0.0013 (11) | 0.0057 (11) | 0.0072 (11) |
C17 | 0.0448 (17) | 0.0424 (16) | 0.0411 (16) | −0.0114 (13) | 0.0023 (13) | 0.0055 (13) |
C18 | 0.0401 (16) | 0.0527 (17) | 0.0330 (14) | −0.0071 (13) | 0.0009 (12) | 0.0092 (12) |
Geometric parameters (Å, º) top
Cu—N1 | 1.951 (2) | C4—C5 | 1.399 (4) |
Cu—O1 | 1.955 (2) | C4—HC4 | 0.90 (4) |
Cu—N2 | 1.991 (2) | C6—C7 | 1.398 (4) |
Cu—O3 | 2.070 (2) | C7—C8 | 1.359 (5) |
Cu—O2 | 2.412 (2) | C7—HC7 | 0.85 (3) |
Cu—O4 | 2.440 (2) | C8—C9 | 1.377 (5) |
O1—C11 | 1.285 (3) | C8—HC8 | 0.94 (4) |
O2—C11 | 1.228 (3) | C9—C10 | 1.366 (5) |
O3—C15 | 1.261 (3) | C9—HC9 | 0.81 (4) |
O4—C15 | 1.247 (3) | C10—HC10 | 1.05 (4) |
OW1—HW1 | 0.85 | C11—C12 | 1.500 (4) |
OW1—HW2 | 0.85 | C12—C13 | 1.374 (4) |
N1—C5 | 1.338 (4) | C12—C14i | 1.391 (4) |
N1—C1 | 1.357 (4) | C13—C14 | 1.378 (4) |
N2—C6 | 1.332 (3) | C13—HC13 | 0.88 (3) |
N2—C10 | 1.348 (4) | C14—C12i | 1.391 (4) |
N3—C5 | 1.365 (4) | C14—HC14 | 0.88 (3) |
N3—C6 | 1.380 (3) | C15—C16 | 1.493 (4) |
N3—HN3 | 0.76 (3) | C16—C18 | 1.389 (4) |
C1—C2 | 1.353 (5) | C16—C17 | 1.394 (4) |
C1—HC1 | 0.92 (4) | C17—C18ii | 1.382 (4) |
C2—C3 | 1.396 (6) | C17—HC17 | 0.91 (3) |
C2—HC2 | 0.86 (3) | C18—C17ii | 1.382 (4) |
C3—C4 | 1.356 (5) | C18—HC18 | 1.01 (3) |
C3—HC3 | 0.94 (4) | | |
| | | |
N1—Cu—O1 | 162.91 (9) | N3—C5—C4 | 118.4 (3) |
N1—Cu—N2 | 91.8 (1) | N2—C6—N3 | 121.5 (2) |
O1—Cu—N2 | 96.59 (9) | N2—C6—C7 | 121.8 (2) |
N1—Cu—O3 | 89.80 (9) | N3—C6—C7 | 116.7 (2) |
O1—Cu—O3 | 91.12 (9) | C8—C7—C6 | 118.6 (3) |
N2—Cu—O3 | 147.15 (9) | C8—C7—HC7 | 122 (2) |
N1—Cu—O2 | 103.9 (1) | C6—C7—HC7 | 119 (2) |
O1—Cu—O2 | 59.29 (8) | C7—C8—C9 | 119.9 (3) |
N2—Cu—O2 | 127.75 (9) | C7—C8—HC8 | 115 (2) |
O3—Cu—O2 | 83.35 (9) | C9—C8—HC8 | 125 (2) |
N1—Cu—O4 | 93.3 (1) | C10—C9—C8 | 118.8 (3) |
O1—Cu—O4 | 101.57 (9) | C10—C9—HC9 | 115 (3) |
N2—Cu—O4 | 89.67 (9) | C8—C9—HC9 | 126 (3) |
O3—Cu—O4 | 57.48 (8) | N2—C10—C9 | 122.4 (3) |
O2—Cu—O4 | 137.22 (8) | N2—C10—HC10 | 118 (2) |
C11—O1—Cu | 99.0 (2) | C9—C10—HC10 | 119 (2) |
C11—O2—Cu | 79.6 (2) | O2—C11—O1 | 121.8 (2) |
C15—O3—Cu | 98.6 (2) | O2—C11—C12 | 121.0 (2) |
C15—O4—Cu | 81.9 (2) | O1—C11—C12 | 117.1 (2) |
HW1—OW1—HW2 | 108 | O2—C11—Cu | 71.5 (2) |
C5—N1—C1 | 118.6 (3) | O1—C11—Cu | 50.5 (1) |
C5—N1—Cu | 123.0 (2) | C12—C11—Cu | 166.0 (2) |
C1—N1—Cu | 117.2 (2) | C13—C12—C14i | 119.1 (2) |
C6—N2—C10 | 118.5 (2) | C13—C12—C11 | 119.7 (2) |
C6—N2—Cu | 121.2 (2) | C14i—C12—C11 | 121.2 (2) |
C10—N2—Cu | 119.2 (2) | C12—C13—C14 | 121.0 (3) |
C5—N3—C6 | 131.1 (2) | C12—C13—HC13 | 120 (2) |
C5—N3—HN3 | 114 (2) | C14—C13—HC13 | 118 (2) |
C6—N3—HN3 | 114 (2) | C13—C14—C12i | 119.9 (3) |
C2—C1—N1 | 123.1 (3) | C13—C14—HC14 | 120 (2) |
C2—C1—HC1 | 122 (2) | C12i—C14—HC14 | 120 (2) |
N1—C1—HC1 | 115 (2) | O4—C15—O3 | 121.9 (2) |
C1—C2—C3 | 118.0 (3) | O4—C15—C16 | 119.1 (2) |
C1—C2—HC2 | 125 (2) | O3—C15—C16 | 118.9 (2) |
C3—C2—HC2 | 117 (2) | C18—C16—C17 | 119.1 (3) |
C4—C3—C2 | 119.9 (3) | C18—C16—C15 | 121.2 (2) |
C4—C3—HC3 | 121 (2) | C17—C16—C15 | 119.7 (2) |
C2—C3—HC3 | 119 (2) | C18ii—C17—C16 | 120.4 (3) |
C3—C4—C5 | 119.4 (3) | C18ii—C17—HC17 | 122 (2) |
C3—C4—HC4 | 120 (2) | C16—C17—HC17 | 118 (2) |
C5—C4—HC4 | 120 (2) | C17ii—C18—C16 | 120.5 (3) |
N1—C5—N3 | 120.6 (2) | C17ii—C18—HC18 | 123 (2) |
N1—C5—C4 | 120.9 (3) | C16—C18—HC18 | 117 (2) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—HN3···OW1 | 0.76 (3) | 2.06 (3) | 2.812 (4) | 171 (4) |
OW1—HW1···O4iii | 0.85 | 1.95 | 2.743 (4) | 155 |
OW1—HW2···O1iv | 0.85 | 2.07 | 2.920 (4) | 174 |
Symmetry codes: (iii) −x+2, −y+2, −z+2; (iv) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Co(C8H4O4)(C12H8N2)(H2O)] | [Cu(C8H4O4)(C10H9N3)]·H2O |
Mr | 421.26 | 416.87 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 298 | 293 |
a, b, c (Å) | 9.2688 (17), 10.4550 (18), 11.349 (2) | 9.009 (4), 9.289 (3), 11.171 (6) |
α, β, γ (°) | 112.462 (3), 94.924 (2), 113.908 (2) | 99.11 (4), 106.64 (4), 92.39 (3) |
V (Å3) | 890.6 (3) | 880.6 (7) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.00 | 1.28 |
Crystal size (mm) | 0.27 × 0.22 × 0.18 | 0.31 × 0.18 × 0.08 |
|
Data collection |
Diffractometer | Make? model? CCD area-detector diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (XPREP in SHELXTL; Bruker, 1997) | – |
Tmin, Tmax | 0.736, 0.864 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4652, 3128, 2012 | 4069, 3746, 2814 |
Rint | 0.032 | 0.012 |
(sin θ/λ)max (Å−1) | 0.606 | 0.638 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.060, 0.88 | 0.039, 0.100, 1.01 |
No. of reflections | 3128 | 3746 |
No. of parameters | 309 | 296 |
H-atom treatment | All H-atom parameters refined | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.25 | 0.37, −0.51 |
Selected geometric parameters (Å, º) for (I) topCo—O3 | 2.013 (2) | Co—N1 | 2.102 (2) |
Co—O1 | 2.044 (2) | Co—N2 | 2.142 (2) |
Co—OW1 | 2.061 (2) | | |
| | | |
O3—Co—O1 | 99.03 (8) | OW1—Co—N1 | 124.44 (8) |
O3—Co—OW1 | 89.2 (1) | O3—Co—N2 | 167.33 (8) |
O1—Co—OW1 | 140.21 (8) | O1—Co—N2 | 90.04 (8) |
O3—Co—N1 | 92.54 (9) | OW1—Co—N2 | 89.5 (1) |
O1—Co—N1 | 94.22 (8) | N1—Co—N2 | 77.89 (9) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—HW1···O4 | 0.93 (4) | 1.70 (4) | 2.608 (4) | 164 (4) |
OW1—HW2···O2i | 0.88 (5) | 1.82 (5) | 2.696 (3) | 172 (4) |
Symmetry code: (i) −x+1, −y+2, −z+2. |
Selected geometric parameters (Å, º) for (II) topCu—N1 | 1.951 (2) | Cu—O3 | 2.070 (2) |
Cu—O1 | 1.955 (2) | Cu—O2 | 2.412 (2) |
Cu—N2 | 1.991 (2) | Cu—O4 | 2.440 (2) |
| | | |
N1—Cu—O1 | 162.91 (9) | N2—Cu—O2 | 127.75 (9) |
N1—Cu—N2 | 91.8 (1) | O3—Cu—O2 | 83.35 (9) |
O1—Cu—N2 | 96.59 (9) | N1—Cu—O4 | 93.3 (1) |
N1—Cu—O3 | 89.80 (9) | O1—Cu—O4 | 101.57 (9) |
O1—Cu—O3 | 91.12 (9) | N2—Cu—O4 | 89.67 (9) |
N2—Cu—O3 | 147.15 (9) | O3—Cu—O4 | 57.48 (8) |
N1—Cu—O2 | 103.9 (1) | O2—Cu—O4 | 137.22 (8) |
O1—Cu—O2 | 59.29 (8) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—HN3···OW1 | 0.76 (3) | 2.06 (3) | 2.812 (4) | 171 (4) |
OW1—HW1···O4i | 0.85 | 1.95 | 2.743 (4) | 155 |
OW1—HW2···O1ii | 0.85 | 2.07 | 2.920 (4) | 174 |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) x+1, y, z. |
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The dianion of 1,4-benzenedicarboxylic acid (or terephthalic acid, H2tpht), is a potential bis-bidentate and bridging ligand. Although an example of a copper(II) compound containing uncoordinated tpht has been described recently by Huaqiang et al. (1997), in the case of first-row transition metal complexes tpht ions typically act as bis-bidentate (Verdaguer et al., 1984; Deng et al., 1992; Cano et al., 1994; Sun et al., 2001), tridentate (Bakalbassis et al., 1992) or bidentate (Verdaguer et al., 1984; Chaudhuri et al., 1988; Bakalbassis et al., 1991; Cueto et al., 1991; Xanthopoulos et al., 1993; Rogan et al., 2000; Kim et al., 2001; Sun et al., 2001) ligands.
With the exception of rare discrete complexes (Rogan et al., 2000) where tpht is coordinated by only one of its COO groups, tpht complexes are binuclear or polymeric in nature. Interest in such complexes is related to molecular magnetism, a continually growing field of research in modern inorganic chemistry and materials science. It is well documented that two paramagnetic centres could interact through extended bridging ligands. In the case of Cu-tpht complexes, this was initially investigated by Verdaguer et al. (1984), but the magnetic interactions were weak. Very shortly afterwards, some binuclear CuII complexes with unexpectedly strong antiferromagnetic interactions were described (Bakalbassis et al., 1985; Chaudhuri et al., 1988). Hence magnetic properties, together with an orbital interpretation of the magnetic exchange mechanism, were also discussed in many of the papers cited above. Here, two ternary tpht complexes, [Co(H2O)(phen)(tpht)], (I), and [Cu(dipya)(tpht)]·H2O, (II), containing CoII or CuII ions and 1,10-phenanthroline (phen) or 2,2'-dipyridylamine (dipya), are presented. \sch
The structure of complex (I) has recently been solved using low-temperature data collected at 193.2 K (Sun et al., 2001). However, an unusually high S-value (2.52), some duplicated H atoms detected in the corresponding CIF and an inability to locate the water H atoms led us to prepare the same compound by a different procedure and to collect a set of data at room temperature. In addition, for reasons of comparison it was necessary to have both the structures described here studied at the same temperature.
The two reported structures of (I) are found to be essentially identical. The change of temperature caused very small variations of the unit-cell parameters (0.11% for a, -0.74% for b, -0.69% for c and -1.28% for the unit-cell volume). As expected, the atomic displacement parameters have lower values and more isotropic character in the low-temperature data set.
Due to the bridging role of the tpht ions, both (I) and (II) are polymeric and can be described as zigzag chains, with neighbouring diamine ligands trans to each other (Figs. 1 and 2). Very similar chains are found in [Zn(H2O)(phen)(tpht)], which is isostructural with (I), and in [Cu(phen)(tpht)] (Sun et al., 2001), as well as in [Cu(en)(H2O)(tpht)] (en is ethylenediamine; Bakalbassis et al., 1988). In all these complexes, the metal centres are bridged by tpht ions coordinated in an amphimonodentate fashion.
Although the orientation of the chains in (I) and (II) is quite different, being parallel to [211] in (I) and to [111] in (II), the unit-cell volumes (see Crystal data) are very similar; the volume of (I) is slightly larger, due to the bulkier phen ligand. Intrachain Co—Co distances in (I) are alternately 11.063(?) and 11.289(?)Å, while the shortest interchain Co—Co distance is 5.908(?)Å. The corresponding Cu—Cu distances in (II) are 10.706(?), 10.898(?) and 5.153(?)Å, respectively. These values are quite normal for tpht-bridged complexes, therefore both intra- and interchain magnetic interactions might be expected. The shortest intrachain metal-metal distances in [Co(H2O)(phen)(tpht)], [Zn(H2O)(phen)(tpht)] and [Cu(phen)(tpht)] are 11.040(?), 10.853(?) and 11.094(?)Å, respectively (Sun et al., 2001). Please provide nine missing s.u.s
In both complexes, two crystallographically different but chemically identical tpht ions exist. Since the crystallographic inversion centres coincide with the centres of the aromatic rings, only half of each tpht ion belongs to the asymmetric unit. The dihedral angles between the two tpht aromatic rings are almost identical for both compounds, with values of 79.3 (3)° in (I) and 79.0 (3)° in (II).
In (I), the tpht ions do not deviate very much from planarity, with an acute dihedral angle between the C14—C16 aromatic ring and the adjacent COO group of 6.8 (2)°. The corresponding angle for the C18—C20 ring is 7.3 (3)°. In (II), the analogous angles differ more; that for C12—C14 is 17.3 (2)° and that for C16—C18 is only 4.7 (3)°. In two recently published series of tpht complexes (Rogan et al., 2000; Sun et al., 2001), the corresponding angles are relatively small, ranging between 3.5 and 22.3°. Nevertheless, angles up to 51.9° are found in some Cu complexes containing additional triamine ligands (Verdaguer et al., 1984; Bakalbassis et al., 1991). Besides the presence of the four O atoms as potential donor sites, it seems that easy rotation around the Caromatic—Ccarboxylate bonds has a great influence on the coordination of tpht ions and the resulting structures, which cover a wide range from discrete mononuclear complex entities, through binuclear units and chains, up to three-dimensional network structures. According to Kaduk (Kaduk, 2000; Kaduk & Golab, 1999), the completely planar conformation of tpht ions has a minimum energy. However, an increase in the angle of (both) COO groups up to 30° requires an energy increase of less than 20 kJ mol-1. This amount could easily be compensated by more favorable coordination geometries and crystal packing.
The main difference between (I) and (II) is the denticity of the tpht ligands, which are bis-bidentate in (II) and only amphimonodentate in (I). As a result, the coordination polyhedra are also very different. In (I), the Co atom is surrounded by five atoms in a deformed trigonal-bipyramidal arrangement, with atoms O1, N1 and OW1 in the equatorial plane (Table 1). The large O1—Co—OW1 angle could be a consequence of the hydrogen bond mentioned below, with the participation of atoms O2 and OW1. A long Co···O2 contact of 2.653 (3) Å, which is not usually regarded as Co—O bond but which is significantly shorter than the sum of van der Waals radii, should also be mentioned. The dihedral angle between COO groups coordinated to the same Co atom is 80.2 (3)°. No significant variations are observed for the Co—O and Co—N bond distances in (I) and in the previously reported structure (Sun et al., 2001).
In (II), the Cu atoms are in a 4 + 2 environment (Table 3), which, under usual circumstances, should be close to an elongated octahedron. However, to our knowledge, this is the first example of a tpht complex with two COO groups chelating to the same central atom. Due to the constraints imposed by such coordination and the formation of two four-membered rings with O—Cu—O angles less than 60° (Table 3), the coordination polyhedron is highly deformed. For example, the O2—Cu—O4 angle is only 137.22 (8)° (the octahedron is elongated along O2—Cu—O4). In addition, the maximum displacement from the equatorial Cu/N1/N2/O1/O3 plane is 0.611 (2) Å (for atom N2) and the distribution of ligating atoms in the N1/N2/O1/O3 plane is strongly puckered, with an average displacement of 0.426 (2) Å. The coordinated COO groups are almost perpendicular to each other, with a dihedral angle of 88.9 (3)°.
The bond distances and angles within the ligands in (I) and (II) are similar to the values found in the free compounds (H2tpht: Bailey & Brown, 1967; phen: Nishigaki et al., 1978; dipya: Johnson & Jacobson, 1973) and will not be discussed in detail, although there are two points worthy of note. Firstly, the N1/C1—C4 segment of the phen ligand in (I), where, for example, atom C2 deviates from the plane of the ligand by 0.056 (4) Å (ca 13σ), should be mentioned. This could be accounted for by some thermal motion or slight disorder, but this part of the ligand is sandwiched between two other aromatic rings from neighbouring chains, and so van der Waals and/or π interactions cannot be excluded. Secondly, the dihedral angle between the two pyridine rings of dipya in (II) is 14.5 (1)°, which is less than in dipya alone (23°; Johnson & Jacobson, 1973), but within the range of values already found for copper(II) complexes (Poleti et al., 1990).
There are two hydrogen bonds in complex (I) and three in complex (II) (Tables 2 and 4). In (I), the coordinated water molecule is a double hydrogen-bond donor. One of the hydrogen bonds is intramolecular (Fig. 1 and Table 2), while the other connects adjacent chains. In (II), the water of crystallization acts as double hydrogen-bond donor to the carboxylate O atoms, and as a hydrogen-bond acceptor from the amine H atom of dipya (Fig. 2 and Table 4).