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catena-Poly[[tetraaquabis(1
H-pyrazole-κ
N2)nickel(II)] [[diaquabis(1
H-pyrazole-κ
N2)nickel(II)]-μ-benzene-1,2,4,5-tetracarboxylato-κ
2O1:
O4] tetrahydrate], {[Ni(C
3H
4N
2)
2(H
2O)
4][Ni(C
10H
2O
8)(C
3H
4N
2)
2(H
2O)
2]·4H
2O}
n, (I), and poly[[(μ
4-benzene-1,2,4,5-tetracarboxylato-κ
4O1:
O2:
O4:
O5)octakis(1
H-pyrazole-κ
N2)dicobalt(II)] tetrahydrate], {[Co
2(C
10H
2O
8)(C
3H
4N
2)
8]·4H
2O}
n, (II), are polymeric compounds crystallizing in the space group
P, with two independent metallic cations and one benzene-1,2,4,5-tetracarboxylate (btc) anion, each lying on symmetry centres. Individual coordination polyhedra are regular and the main differences are in the way the btc anion binds [μ
2 in (I) and μ
4 in (II)], promoting a `chain-like' one-dimensional structure in (I) and a `sieve-like' two-dimensional motif in (II).
Supporting information
CCDC references: 742224; 742225
An aqueous solution (30 ml) containing Ni(acetate)2.4H2O (0.2985 g) or
Co(acetate)2.4H2O (0.2988 g) for (I) and (II), respectively, was slowly
added to an aqueous solution (150 ml) containing
benzene-1,2,4,5-tetracarboxylic acid (0.15249 g [5 d.p.s justified?])
and NaOH (0.0903 g). The reaction mixture was heated under reflux for 10 min.
An ethanolic solution (30 ml) of pyrazol (0.2055 g) was added and the
resulting solution was maintained under reflux for 4 h. Single crystals
suitable for X-ray crystallography were grown from the solution by slow
evaporation at room temperature.
C-bound H atoms were constrained geometrically and allowed to ride, with C—H =
0.93–0.97 Å. O-bound H atoms were initially found in a difference
electron-density map and refined with restrained O—H [0.85 (1) Å] and H···H
[1.30 (2) Å] distances until convergence, and then constrained, riding on the
host O atoms in the final cycles. In all cases, Uiso(H) = 1.2 or
1.5Ueq(parent).
For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2002); data reduction: SAINT-NT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008) and PLATON (Spek, 2009).
(I)
catena-Poly[[tetraaquabis(1
H-pyrazole-
κN2)nickel(II)]
[[diaquabis(1
H-pyrazole-
κN2)nickel(II)]-
µ-benzene-1,2,4,5-tetracarboxylato-
κ2O1:
O4]
tetrahydrate]
top
Crystal data top
[Ni(C3H4N2)2(H2O)4][Ni(C10H2O8)(C3H4N2)2(H2O)2]·4H2O | Z = 1 |
Mr = 820.02 | F(000) = 426 |
Triclinic, P1 | Dx = 1.619 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6399 (12) Å | Cell parameters from 5423 reflections |
b = 10.7925 (17) Å | θ = 2.7–26.9° |
c = 11.4616 (19) Å | µ = 1.21 mm−1 |
α = 73.224 (3)° | T = 298 K |
β = 74.613 (2)° | Needle, colourless |
γ = 71.287 (3)° | 0.28 × 0.07 × 0.07 mm |
V = 841.3 (2) Å3 | |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 3650 independent reflections |
Radiation source: fine-focus sealed tube | 2759 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 28.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | h = −9→10 |
Tmin = 0.89, Tmax = 0.92 | k = −13→13 |
7155 measured reflections | l = −15→14 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.067P)2] where P = (Fo2 + 2Fc2)/3 |
3650 reflections | (Δ/σ)max < 0.001 |
229 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
[Ni(C3H4N2)2(H2O)4][Ni(C10H2O8)(C3H4N2)2(H2O)2]·4H2O | γ = 71.287 (3)° |
Mr = 820.02 | V = 841.3 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.6399 (12) Å | Mo Kα radiation |
b = 10.7925 (17) Å | µ = 1.21 mm−1 |
c = 11.4616 (19) Å | T = 298 K |
α = 73.224 (3)° | 0.28 × 0.07 × 0.07 mm |
β = 74.613 (2)° | |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 3650 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | 2759 reflections with I > 2σ(I) |
Tmin = 0.89, Tmax = 0.92 | Rint = 0.030 |
7155 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.58 e Å−3 |
3650 reflections | Δρmin = −0.31 e Å−3 |
229 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.0000 | 0.5000 | 1.0000 | 0.02409 (17) | |
Ni2 | 0.5000 | 0.0000 | 0.5000 | 0.02789 (18) | |
O11 | 0.2245 (3) | 0.7347 (2) | 0.5380 (2) | 0.0400 (6) | |
O21 | −0.0754 (3) | 0.7843 (2) | 0.6323 (2) | 0.0320 (5) | |
O31 | 0.0276 (3) | 0.5108 (2) | 0.81139 (18) | 0.0288 (5) | |
O41 | −0.2319 (3) | 0.4510 (3) | 0.8245 (2) | 0.0403 (6) | |
N12 | 0.2330 (4) | 0.3358 (3) | 1.0064 (2) | 0.0319 (6) | |
N22 | 0.2635 (5) | 0.2457 (3) | 1.1120 (3) | 0.0543 (9) | |
H22 | 0.1867 | 0.2485 | 1.1819 | 0.065* | |
N13 | 0.2921 (4) | 0.0288 (3) | 0.6548 (3) | 0.0370 (7) | |
N23 | 0.2614 (5) | 0.1258 (4) | 0.7161 (3) | 0.0581 (9) | |
H23 | 0.3233 | 0.1854 | 0.6938 | 0.070* | |
C11 | 0.0384 (4) | 0.5966 (3) | 0.5414 (3) | 0.0220 (6) | |
C21 | −0.0456 (4) | 0.5005 (3) | 0.6274 (3) | 0.0233 (6) | |
C31 | −0.0830 (4) | 0.4059 (3) | 0.5836 (3) | 0.0249 (7) | |
H31 | −0.1397 | 0.3422 | 0.6399 | 0.030* | |
C41 | 0.0661 (5) | 0.7128 (3) | 0.5750 (3) | 0.0250 (7) | |
C51 | −0.0885 (4) | 0.4871 (3) | 0.7661 (3) | 0.0251 (7) | |
C12 | 0.4230 (8) | 0.1525 (5) | 1.0979 (5) | 0.0778 (16) | |
H12 | 0.4707 | 0.0806 | 1.1589 | 0.093* | |
C22 | 0.5028 (7) | 0.1819 (5) | 0.9784 (6) | 0.0827 (17) | |
H22A | 0.6182 | 0.1350 | 0.9399 | 0.099* | |
C32 | 0.3795 (6) | 0.2970 (4) | 0.9220 (4) | 0.0555 (11) | |
H32 | 0.3982 | 0.3391 | 0.8383 | 0.067* | |
C13 | 0.1238 (8) | 0.1179 (6) | 0.8154 (5) | 0.0849 (19) | |
H13 | 0.0781 | 0.1746 | 0.8705 | 0.102* | |
C23 | 0.0637 (7) | 0.0118 (7) | 0.8204 (5) | 0.095 (2) | |
H23A | −0.0298 | −0.0200 | 0.8808 | 0.114* | |
C33 | 0.1688 (6) | −0.0419 (4) | 0.7173 (4) | 0.0547 (11) | |
H33 | 0.1545 | −0.1147 | 0.6961 | 0.066* | |
O1W | 0.1654 (3) | 0.6350 (2) | 0.9435 (2) | 0.0365 (6) | |
H1WA | 0.2467 | 0.6303 | 0.8768 | 0.044* | |
H1WB | 0.2246 | 0.6172 | 1.0021 | 0.044* | |
O2W | 0.4087 (3) | 0.2026 (2) | 0.4274 (2) | 0.0373 (6) | |
H2WA | 0.4717 | 0.2562 | 0.3795 | 0.045* | |
H2WB | 0.3067 | 0.2212 | 0.4016 | 0.045* | |
O3W | 0.3164 (3) | −0.0361 (2) | 0.4165 (2) | 0.0379 (6) | |
H3WA | 0.2146 | 0.0261 | 0.4139 | 0.045* | |
H3WB | 0.2884 | −0.1070 | 0.4627 | 0.045* | |
O4W | 0.4509 (3) | 0.5957 (3) | 0.7361 (2) | 0.0466 (7) | |
H4WA | 0.4140 | 0.5547 | 0.6979 | 0.056* | |
H4WB | 0.5494 | 0.5426 | 0.7615 | 0.056* | |
O5W | 0.5589 (4) | 0.6224 (3) | 0.3864 (3) | 0.0593 (8) | |
H5WA | 0.6417 | 0.5908 | 0.4320 | 0.071* | |
H5WB | 0.4519 | 0.6375 | 0.4341 | 0.071* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0281 (3) | 0.0272 (3) | 0.0175 (3) | −0.0075 (2) | −0.0058 (2) | −0.0041 (2) |
Ni2 | 0.0259 (3) | 0.0264 (3) | 0.0301 (3) | −0.0081 (2) | −0.0056 (3) | −0.0027 (2) |
O11 | 0.0377 (14) | 0.0400 (14) | 0.0499 (16) | −0.0185 (11) | −0.0042 (12) | −0.0156 (12) |
O21 | 0.0374 (13) | 0.0254 (12) | 0.0335 (13) | −0.0042 (10) | −0.0073 (11) | −0.0113 (10) |
O31 | 0.0317 (12) | 0.0376 (13) | 0.0196 (11) | −0.0116 (10) | −0.0057 (9) | −0.0068 (9) |
O41 | 0.0384 (14) | 0.0654 (17) | 0.0233 (12) | −0.0293 (13) | −0.0001 (11) | −0.0070 (11) |
N12 | 0.0374 (16) | 0.0318 (15) | 0.0243 (14) | −0.0070 (13) | −0.0069 (12) | −0.0044 (11) |
N22 | 0.070 (2) | 0.0435 (19) | 0.0348 (18) | 0.0023 (18) | −0.0140 (17) | −0.0036 (15) |
N13 | 0.0364 (17) | 0.0377 (16) | 0.0342 (16) | −0.0090 (13) | −0.0044 (13) | −0.0067 (13) |
N23 | 0.059 (2) | 0.055 (2) | 0.053 (2) | −0.0020 (18) | −0.0104 (19) | −0.0162 (18) |
C11 | 0.0224 (15) | 0.0234 (15) | 0.0214 (15) | −0.0056 (12) | −0.0053 (12) | −0.0063 (12) |
C21 | 0.0244 (15) | 0.0260 (16) | 0.0206 (15) | −0.0076 (13) | −0.0063 (12) | −0.0041 (12) |
C31 | 0.0289 (16) | 0.0224 (15) | 0.0226 (16) | −0.0087 (13) | −0.0062 (13) | −0.0003 (12) |
C41 | 0.0320 (17) | 0.0241 (15) | 0.0202 (15) | −0.0082 (14) | −0.0109 (13) | −0.0009 (12) |
C51 | 0.0276 (16) | 0.0256 (16) | 0.0206 (15) | −0.0047 (13) | −0.0062 (13) | −0.0041 (12) |
C12 | 0.074 (4) | 0.059 (3) | 0.078 (4) | 0.022 (3) | −0.031 (3) | −0.011 (3) |
C22 | 0.047 (3) | 0.063 (3) | 0.110 (5) | 0.015 (2) | 0.008 (3) | −0.033 (3) |
C32 | 0.056 (3) | 0.047 (2) | 0.048 (2) | −0.012 (2) | 0.017 (2) | −0.0130 (19) |
C13 | 0.076 (4) | 0.095 (4) | 0.042 (3) | 0.016 (3) | 0.005 (3) | −0.014 (3) |
C23 | 0.046 (3) | 0.139 (6) | 0.053 (3) | −0.017 (3) | 0.017 (2) | 0.017 (4) |
C33 | 0.043 (2) | 0.063 (3) | 0.051 (3) | −0.025 (2) | 0.005 (2) | −0.001 (2) |
O1W | 0.0413 (14) | 0.0418 (14) | 0.0290 (12) | −0.0194 (11) | −0.0079 (11) | −0.0009 (10) |
O2W | 0.0324 (13) | 0.0287 (12) | 0.0474 (15) | −0.0089 (10) | −0.0107 (11) | 0.0006 (11) |
O3W | 0.0338 (13) | 0.0306 (13) | 0.0501 (15) | −0.0085 (10) | −0.0128 (11) | −0.0060 (11) |
O4W | 0.0377 (15) | 0.0589 (17) | 0.0423 (15) | −0.0191 (13) | −0.0103 (12) | −0.0005 (13) |
O5W | 0.0427 (16) | 0.081 (2) | 0.0477 (17) | −0.0036 (15) | −0.0070 (14) | −0.0202 (15) |
Geometric parameters (Å, º) top
Ni1—N12 | 2.070 (3) | C11—C41 | 1.504 (4) |
Ni1—N12i | 2.070 (3) | C21—C31 | 1.391 (4) |
Ni1—O1Wi | 2.083 (2) | C21—C51 | 1.509 (4) |
Ni1—O1W | 2.083 (2) | C31—C11iii | 1.388 (4) |
Ni1—O31 | 2.088 (2) | C31—H31 | 0.9300 |
Ni1—O31i | 2.088 (2) | C12—C22 | 1.334 (7) |
Ni2—O2Wii | 2.059 (2) | C12—H12 | 0.9300 |
Ni2—O2W | 2.059 (2) | C22—C32 | 1.398 (7) |
Ni2—N13 | 2.068 (3) | C22—H22A | 0.9300 |
Ni2—N13ii | 2.068 (3) | C32—H32 | 0.9300 |
Ni2—O3Wii | 2.076 (2) | C13—C23 | 1.345 (9) |
Ni2—O3W | 2.076 (2) | C13—H13 | 0.9300 |
O11—C41 | 1.247 (4) | C23—C33 | 1.404 (7) |
O21—C41 | 1.255 (4) | C23—H23A | 0.9300 |
O31—C51 | 1.260 (4) | C33—H33 | 0.9300 |
O41—C51 | 1.239 (4) | O1W—H1WA | 0.8500 |
N12—C32 | 1.312 (4) | O1W—H1WB | 0.8501 |
N12—N22 | 1.338 (4) | O2W—H2WA | 0.8500 |
N22—C12 | 1.313 (5) | O2W—H2WB | 0.8501 |
N22—H22 | 0.8600 | O3W—H3WA | 0.8499 |
N13—C33 | 1.331 (5) | O3W—H3WB | 0.8499 |
N13—N23 | 1.351 (4) | O4W—H4WA | 0.8500 |
N23—C13 | 1.332 (6) | O4W—H4WB | 0.8501 |
N23—H23 | 0.8600 | O5W—H5WA | 0.8500 |
C11—C31iii | 1.388 (4) | O5W—H5WB | 0.8501 |
C11—C21 | 1.400 (4) | | |
| | | |
N12—Ni1—N12i | 180.0 | C31iii—C11—C41 | 117.0 (3) |
N12—Ni1—O1Wi | 87.54 (10) | C21—C11—C41 | 123.3 (3) |
N12i—Ni1—O1Wi | 92.46 (10) | C31—C21—C11 | 118.3 (3) |
N12—Ni1—O1W | 92.46 (10) | C31—C21—C51 | 117.2 (3) |
N12i—Ni1—O1W | 87.54 (10) | C11—C21—C51 | 124.4 (3) |
O1Wi—Ni1—O1W | 180.0 | C11iii—C31—C21 | 122.2 (3) |
N12—Ni1—O31 | 89.34 (9) | C11iii—C31—H31 | 118.9 |
N12i—Ni1—O31 | 90.66 (9) | C21—C31—H31 | 118.9 |
O1Wi—Ni1—O31 | 93.82 (8) | O11—C41—O21 | 125.3 (3) |
O1W—Ni1—O31 | 86.18 (8) | O11—C41—C11 | 117.5 (3) |
N12—Ni1—O31i | 90.66 (9) | O21—C41—C11 | 117.1 (3) |
N12i—Ni1—O31i | 89.34 (9) | O41—C51—O31 | 126.4 (3) |
O1Wi—Ni1—O31i | 86.18 (8) | O41—C51—C21 | 116.8 (3) |
O1W—Ni1—O31i | 93.82 (8) | O31—C51—C21 | 116.7 (3) |
O31—Ni1—O31i | 180.000 (1) | N22—C12—C22 | 106.1 (4) |
O2Wii—Ni2—O2W | 180.00 (14) | N22—C12—H12 | 126.9 |
O2Wii—Ni2—N13 | 92.62 (10) | C22—C12—H12 | 126.9 |
O2W—Ni2—N13 | 87.38 (10) | C12—C22—C32 | 106.8 (4) |
O2Wii—Ni2—N13ii | 87.38 (10) | C12—C22—H22A | 126.6 |
O2W—Ni2—N13ii | 92.62 (10) | C32—C22—H22A | 126.6 |
N13—Ni2—N13ii | 180.0 | N12—C32—C22 | 108.9 (4) |
O2Wii—Ni2—O3Wii | 89.96 (9) | N12—C32—H32 | 125.5 |
O2W—Ni2—O3Wii | 90.04 (9) | C22—C32—H32 | 125.5 |
N13—Ni2—O3Wii | 89.00 (10) | N23—C13—C23 | 106.6 (5) |
N13ii—Ni2—O3Wii | 91.00 (10) | N23—C13—H13 | 126.7 |
O2Wii—Ni2—O3W | 90.04 (9) | C23—C13—H13 | 126.7 |
O2W—Ni2—O3W | 89.96 (9) | C13—C23—C33 | 107.1 (4) |
N13—Ni2—O3W | 91.00 (10) | C13—C23—H23A | 126.5 |
N13ii—Ni2—O3W | 89.00 (10) | C33—C23—H23A | 126.5 |
O3Wii—Ni2—O3W | 180.0 | N13—C33—C23 | 108.5 (4) |
C51—O31—Ni1 | 124.1 (2) | N13—C33—H33 | 125.8 |
C32—N12—N22 | 105.2 (3) | C23—C33—H33 | 125.8 |
C32—N12—Ni1 | 132.6 (3) | Ni1—O1W—H1WA | 116.9 |
N22—N12—Ni1 | 122.2 (2) | Ni1—O1W—H1WB | 104.9 |
C12—N22—N12 | 112.9 (4) | H1WA—O1W—H1WB | 107.4 |
C12—N22—H22 | 123.5 | Ni2—O2W—H2WA | 129.1 |
N12—N22—H22 | 123.5 | Ni2—O2W—H2WB | 111.1 |
C33—N13—N23 | 105.9 (3) | H2WA—O2W—H2WB | 107.4 |
C33—N13—Ni2 | 129.6 (3) | Ni2—O3W—H3WA | 112.7 |
N23—N13—Ni2 | 124.5 (3) | Ni2—O3W—H3WB | 105.5 |
C13—N23—N13 | 111.8 (4) | H3WA—O3W—H3WB | 107.4 |
C13—N23—H23 | 124.1 | H4WA—O4W—H4WB | 107.4 |
N13—N23—H23 | 124.1 | H5WA—O5W—H5WB | 107.4 |
C31iii—C11—C21 | 119.5 (3) | | |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y, −z+1; (iii) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22···O21i | 0.86 | 2.04 | 2.876 (4) | 162 |
N23—H23···O5Wiv | 0.86 | 2.37 | 3.216 (5) | 168 |
O1W—H1WA···O4W | 0.85 | 1.95 | 2.798 (3) | 172 |
O1W—H1WB···O41i | 0.85 | 1.92 | 2.679 (3) | 148 |
O2W—H2WA···O4Wiv | 0.85 | 1.90 | 2.734 (3) | 165 |
O2W—H2WB···O21iii | 0.85 | 1.93 | 2.759 (3) | 165 |
O3W—H3WA···O21iii | 0.85 | 1.97 | 2.748 (3) | 152 |
O3W—H3WB···O11v | 0.85 | 1.83 | 2.675 (3) | 170 |
O4W—H4WB···O41vi | 0.85 | 1.86 | 2.702 (4) | 171 |
O4W—H4WA···O5Wiv | 0.85 | 2.31 | 3.097 (4) | 154 |
O5W—H5WB···O11 | 0.85 | 2.00 | 2.809 (4) | 159 |
O5W—H5WA···Cg2vii | 0.85 | 2.84 | 3.64 | 156 |
C32—H32···O5Wiv | 0.93 | 2.44 | 3.329 (5) | 161 |
C12—H12···Cg3viii | 0.93 | 2.92 | 3.67 | 140 |
Symmetry codes: (i) −x, −y+1, −z+2; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) x, y−1, z; (vi) x+1, y, z; (vii) x−1, y, z; (viii) x, y+1, z−1. |
(II) poly[[(µ
4-benzene-1,2,4,5-tetracarboxylato-
κ4O1:
O2:
O4:
O5)octakis(1
H-
pyrazole-
κN2)dicobalt(II)] tetrahydrate]
top
Crystal data top
[Co2(C10H2O8)(C3H4N2)8]·4H2O | Z = 1 |
Mr = 984.70 | F(000) = 508 |
Triclinic, P1 | Dx = 1.566 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9122 (18) Å | Cell parameters from 6202 reflections |
b = 11.045 (2) Å | θ = 3.0–27.1° |
c = 11.450 (2) Å | µ = 0.88 mm−1 |
α = 83.381 (3)° | T = 298 K |
β = 74.579 (3)° | Polyhedron, orange |
γ = 74.162 (3)° | 0.42 × 0.30 × 0.14 mm |
V = 1044.1 (3) Å3 | |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 4455 independent reflections |
Radiation source: fine-focus sealed tube | 3228 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ϕ and ω scans | θmax = 27.9°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | h = −11→11 |
Tmin = 0.69, Tmax = 0.89 | k = −14→14 |
8610 measured reflections | l = −14→14 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0566P)2 + 0.3795P] where P = (Fo2 + 2Fc2)/3 |
4455 reflections | (Δ/σ)max < 0.001 |
292 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
Crystal data top
[Co2(C10H2O8)(C3H4N2)8]·4H2O | γ = 74.162 (3)° |
Mr = 984.70 | V = 1044.1 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.9122 (18) Å | Mo Kα radiation |
b = 11.045 (2) Å | µ = 0.88 mm−1 |
c = 11.450 (2) Å | T = 298 K |
α = 83.381 (3)° | 0.42 × 0.30 × 0.14 mm |
β = 74.579 (3)° | |
Data collection top
Bruker SMART? CCD area-detector diffractometer | 4455 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | 3228 reflections with I > 2σ(I) |
Tmin = 0.69, Tmax = 0.89 | Rint = 0.027 |
8610 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.60 e Å−3 |
4455 reflections | Δρmin = −0.55 e Å−3 |
292 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.0000 | 0.5000 | 1.0000 | 0.02710 (17) | |
Co2 | 0.0000 | 1.0000 | 0.5000 | 0.02621 (17) | |
O11 | 0.2707 (3) | 0.3750 (2) | 0.7006 (2) | 0.0423 (6) | |
O21 | 0.0428 (3) | 0.4921 (2) | 0.80832 (19) | 0.0353 (5) | |
O31 | 0.2032 (3) | 0.6802 (2) | 0.6342 (2) | 0.0350 (5) | |
O41 | 0.0655 (3) | 0.80508 (19) | 0.5125 (2) | 0.0390 (6) | |
N12 | 0.1951 (3) | 0.5835 (3) | 0.9758 (3) | 0.0349 (6) | |
N22 | 0.2830 (4) | 0.6137 (3) | 0.8675 (3) | 0.0464 (8) | |
H22 | 0.2638 | 0.6055 | 0.7994 | 0.056* | |
N13 | 0.1551 (3) | 0.3198 (2) | 1.0225 (2) | 0.0331 (6) | |
N23 | 0.2611 (3) | 0.2545 (2) | 0.9311 (2) | 0.0349 (6) | |
H23 | 0.2793 | 0.2821 | 0.8567 | 0.042* | |
N14 | 0.0142 (3) | 1.0120 (2) | 0.6796 (2) | 0.0328 (6) | |
N24 | 0.1158 (3) | 0.9252 (3) | 0.7327 (2) | 0.0354 (7) | |
H24 | 0.1693 | 0.8533 | 0.7034 | 0.043* | |
N15 | 0.2462 (3) | 1.0007 (3) | 0.4309 (2) | 0.0354 (6) | |
N25 | 0.3668 (4) | 0.8991 (3) | 0.3939 (3) | 0.0451 (8) | |
H25 | 0.3552 | 0.8238 | 0.3977 | 0.054* | |
C11 | 0.0685 (3) | 0.4794 (3) | 0.5998 (3) | 0.0241 (6) | |
C21 | 0.0533 (4) | 0.5950 (3) | 0.5347 (3) | 0.0253 (6) | |
C31 | −0.0148 (4) | 0.6129 (3) | 0.4366 (3) | 0.0272 (7) | |
H31 | −0.0248 | 0.6901 | 0.3934 | 0.033* | |
C41 | 0.1338 (4) | 0.4485 (3) | 0.7118 (3) | 0.0283 (7) | |
C51 | 0.1112 (4) | 0.7013 (3) | 0.5640 (3) | 0.0277 (7) | |
C12 | 0.4034 (5) | 0.6577 (4) | 0.8777 (4) | 0.0595 (11) | |
H12 | 0.4796 | 0.6837 | 0.8144 | 0.071* | |
C22 | 0.3939 (5) | 0.6575 (4) | 0.9967 (5) | 0.0611 (12) | |
H22A | 0.4613 | 0.6839 | 1.0323 | 0.073* | |
C32 | 0.2627 (5) | 0.6097 (4) | 1.0560 (3) | 0.0464 (9) | |
H32 | 0.2279 | 0.5980 | 1.1396 | 0.056* | |
C13 | 0.3353 (4) | 0.1412 (3) | 0.9699 (4) | 0.0465 (9) | |
H13 | 0.4130 | 0.0800 | 0.9221 | 0.056* | |
C23 | 0.2776 (5) | 0.1314 (3) | 1.0909 (3) | 0.0493 (10) | |
H23A | 0.3065 | 0.0633 | 1.1434 | 0.059* | |
C33 | 0.1665 (5) | 0.2442 (3) | 1.1198 (3) | 0.0462 (10) | |
H33 | 0.1068 | 0.2649 | 1.1980 | 0.055* | |
C14 | 0.1239 (5) | 0.9637 (4) | 0.8359 (3) | 0.0465 (9) | |
H14 | 0.1870 | 0.9188 | 0.8873 | 0.056* | |
C24 | 0.0229 (5) | 1.0810 (4) | 0.8530 (3) | 0.0468 (9) | |
H24A | 0.0028 | 1.1324 | 0.9172 | 0.056* | |
C34 | −0.0433 (4) | 1.1069 (3) | 0.7536 (3) | 0.0383 (8) | |
H34 | −0.1181 | 1.1811 | 0.7405 | 0.046* | |
C15 | 0.5071 (4) | 0.9298 (4) | 0.3503 (3) | 0.0496 (10) | |
H15 | 0.6066 | 0.8747 | 0.3207 | 0.059* | |
C25 | 0.4772 (5) | 1.0549 (4) | 0.3573 (3) | 0.0501 (10) | |
H25A | 0.5510 | 1.1038 | 0.3329 | 0.060* | |
C35 | 0.3148 (4) | 1.0957 (3) | 0.4081 (3) | 0.0385 (8) | |
H35 | 0.2605 | 1.1791 | 0.4242 | 0.046* | |
O1W | 0.3949 (4) | 0.6402 (3) | 0.3256 (3) | 0.0729 (9) | |
H1WA | 0.4956 | 0.6328 | 0.3109 | 0.088* | |
H1WB | 0.3799 | 0.5667 | 0.3418 | 0.088* | |
O2W | 0.4419 (3) | 0.3811 (3) | 0.4310 (3) | 0.0691 (9) | |
H2WA | 0.5406 | 0.3708 | 0.4292 | 0.083* | |
H2WB | 0.3912 | 0.3777 | 0.5050 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0279 (3) | 0.0266 (3) | 0.0263 (3) | −0.0031 (3) | −0.0099 (3) | −0.0005 (2) |
Co2 | 0.0305 (3) | 0.0227 (3) | 0.0287 (3) | −0.0097 (2) | −0.0111 (3) | 0.0024 (2) |
O11 | 0.0363 (14) | 0.0494 (15) | 0.0349 (13) | 0.0035 (11) | −0.0138 (11) | 0.0000 (11) |
O21 | 0.0396 (13) | 0.0411 (13) | 0.0235 (12) | −0.0060 (11) | −0.0088 (10) | −0.0024 (10) |
O31 | 0.0405 (13) | 0.0338 (12) | 0.0383 (13) | −0.0153 (10) | −0.0186 (11) | 0.0040 (10) |
O41 | 0.0565 (16) | 0.0214 (11) | 0.0454 (14) | −0.0107 (11) | −0.0246 (12) | 0.0037 (10) |
N12 | 0.0341 (16) | 0.0375 (16) | 0.0350 (16) | −0.0112 (13) | −0.0107 (13) | 0.0009 (13) |
N22 | 0.0511 (19) | 0.0524 (19) | 0.0424 (18) | −0.0231 (16) | −0.0166 (15) | 0.0079 (15) |
N13 | 0.0338 (15) | 0.0282 (14) | 0.0325 (15) | −0.0005 (12) | −0.0083 (12) | 0.0003 (12) |
N23 | 0.0369 (16) | 0.0336 (15) | 0.0325 (15) | −0.0024 (12) | −0.0132 (13) | 0.0007 (12) |
N14 | 0.0375 (16) | 0.0327 (15) | 0.0306 (15) | −0.0110 (12) | −0.0115 (13) | 0.0013 (12) |
N24 | 0.0368 (16) | 0.0381 (16) | 0.0332 (16) | −0.0098 (13) | −0.0127 (13) | 0.0019 (12) |
N15 | 0.0337 (15) | 0.0354 (16) | 0.0385 (16) | −0.0102 (13) | −0.0099 (13) | −0.0011 (13) |
N25 | 0.0453 (19) | 0.0369 (17) | 0.053 (2) | −0.0083 (14) | −0.0130 (16) | −0.0055 (14) |
C11 | 0.0252 (16) | 0.0228 (15) | 0.0227 (15) | −0.0035 (12) | −0.0064 (13) | 0.0002 (12) |
C21 | 0.0276 (16) | 0.0237 (15) | 0.0243 (16) | −0.0060 (12) | −0.0056 (13) | −0.0021 (12) |
C31 | 0.0304 (17) | 0.0231 (15) | 0.0275 (17) | −0.0061 (13) | −0.0092 (13) | 0.0046 (12) |
C41 | 0.0330 (18) | 0.0250 (16) | 0.0313 (18) | −0.0114 (14) | −0.0123 (15) | 0.0017 (13) |
C51 | 0.0300 (17) | 0.0248 (16) | 0.0268 (16) | −0.0075 (13) | −0.0044 (14) | 0.0002 (13) |
C12 | 0.048 (2) | 0.060 (3) | 0.077 (3) | −0.026 (2) | −0.019 (2) | 0.012 (2) |
C22 | 0.053 (3) | 0.058 (3) | 0.088 (3) | −0.022 (2) | −0.035 (2) | −0.006 (2) |
C32 | 0.049 (2) | 0.054 (2) | 0.044 (2) | −0.0100 (19) | −0.0244 (19) | −0.0041 (18) |
C13 | 0.042 (2) | 0.037 (2) | 0.052 (2) | 0.0068 (16) | −0.0146 (19) | −0.0035 (17) |
C23 | 0.055 (2) | 0.038 (2) | 0.045 (2) | 0.0012 (18) | −0.0155 (19) | 0.0127 (17) |
C33 | 0.050 (2) | 0.045 (2) | 0.0302 (19) | 0.0033 (18) | −0.0048 (17) | 0.0063 (16) |
C14 | 0.052 (2) | 0.057 (2) | 0.034 (2) | −0.0141 (19) | −0.0181 (18) | 0.0006 (18) |
C24 | 0.059 (3) | 0.052 (2) | 0.034 (2) | −0.021 (2) | −0.0097 (19) | −0.0084 (17) |
C34 | 0.047 (2) | 0.0334 (18) | 0.0336 (19) | −0.0135 (16) | −0.0069 (16) | 0.0010 (15) |
C15 | 0.030 (2) | 0.072 (3) | 0.041 (2) | −0.0063 (19) | −0.0033 (17) | −0.007 (2) |
C25 | 0.040 (2) | 0.063 (3) | 0.051 (2) | −0.025 (2) | −0.0094 (19) | 0.006 (2) |
C35 | 0.036 (2) | 0.0360 (19) | 0.046 (2) | −0.0127 (16) | −0.0125 (17) | 0.0027 (16) |
O1W | 0.0518 (18) | 0.068 (2) | 0.089 (2) | −0.0070 (16) | −0.0088 (17) | −0.0068 (17) |
O2W | 0.0460 (17) | 0.096 (2) | 0.0609 (19) | −0.0130 (16) | −0.0124 (14) | 0.0002 (17) |
Geometric parameters (Å, º) top
Co1—N13 | 2.123 (3) | C11—C31iii | 1.383 (4) |
Co1—N13i | 2.123 (3) | C11—C21 | 1.395 (4) |
Co1—N12i | 2.124 (3) | C11—C41 | 1.512 (4) |
Co1—N12 | 2.124 (3) | C21—C31 | 1.384 (4) |
Co1—O21 | 2.133 (2) | C21—C51 | 1.506 (4) |
Co1—O21i | 2.133 (2) | C31—C11iii | 1.383 (4) |
Co2—O41 | 2.070 (2) | C31—H31 | 0.9300 |
Co2—O41ii | 2.070 (2) | C12—C22 | 1.343 (6) |
Co2—N14ii | 2.114 (3) | C12—H12 | 0.9300 |
Co2—N14 | 2.114 (3) | C22—C32 | 1.393 (6) |
Co2—N15 | 2.127 (3) | C22—H22A | 0.9300 |
Co2—N15ii | 2.127 (3) | C32—H32 | 0.9300 |
O11—C41 | 1.251 (4) | C13—C23 | 1.346 (5) |
O21—C41 | 1.242 (4) | C13—H13 | 0.9300 |
O31—C51 | 1.255 (4) | C23—C33 | 1.375 (5) |
O41—C51 | 1.243 (4) | C23—H23A | 0.9300 |
N12—C32 | 1.319 (4) | C33—H33 | 0.9300 |
N12—N22 | 1.339 (4) | C14—C24 | 1.362 (5) |
N22—C12 | 1.329 (5) | C14—H14 | 0.9300 |
N22—H22 | 0.8600 | C24—C34 | 1.383 (5) |
N13—C33 | 1.322 (4) | C24—H24A | 0.9300 |
N13—N23 | 1.336 (4) | C34—H34 | 0.9300 |
N23—C13 | 1.334 (4) | C15—C25 | 1.342 (5) |
N23—H23 | 0.8600 | C15—H15 | 0.9300 |
N14—C34 | 1.327 (4) | C25—C35 | 1.376 (5) |
N14—N24 | 1.340 (4) | C25—H25A | 0.9300 |
N24—C14 | 1.327 (4) | C35—H35 | 0.9300 |
N24—H24 | 0.8600 | O1W—H1WA | 0.8501 |
N15—C35 | 1.321 (4) | O1W—H1WB | 0.8501 |
N15—N25 | 1.342 (4) | O2W—H2WA | 0.8499 |
N25—C15 | 1.337 (5) | O2W—H2WB | 0.8500 |
N25—H25 | 0.8600 | | |
| | | |
N13—Co1—N13i | 180.00 (15) | N15—N25—H25 | 124.3 |
N13—Co1—N12i | 90.09 (11) | C31iii—C11—C21 | 118.4 (3) |
N13i—Co1—N12i | 89.91 (11) | C31iii—C11—C41 | 116.9 (3) |
N13—Co1—N12 | 89.91 (11) | C21—C11—C41 | 124.6 (3) |
N13i—Co1—N12 | 90.09 (11) | C31—C21—C11 | 118.8 (3) |
N12i—Co1—N12 | 180.00 (12) | C31—C21—C51 | 117.9 (3) |
N13—Co1—O21 | 94.87 (9) | C11—C21—C51 | 123.2 (3) |
N13i—Co1—O21 | 85.13 (9) | C11iii—C31—C21 | 122.7 (3) |
N12i—Co1—O21 | 89.65 (10) | C11iii—C31—H31 | 118.6 |
N12—Co1—O21 | 90.35 (10) | C21—C31—H31 | 118.6 |
N13—Co1—O21i | 85.13 (9) | O21—C41—O11 | 125.7 (3) |
N13i—Co1—O21i | 94.87 (9) | O21—C41—C11 | 117.1 (3) |
N12i—Co1—O21i | 90.35 (10) | O11—C41—C11 | 117.0 (3) |
N12—Co1—O21i | 89.65 (10) | O41—C51—O31 | 124.6 (3) |
O21—Co1—O21i | 180.000 (1) | O41—C51—C21 | 115.8 (3) |
O41—Co2—O41ii | 180.000 (1) | O31—C51—C21 | 119.5 (3) |
O41—Co2—N14ii | 87.97 (9) | N22—C12—C22 | 106.9 (4) |
O41ii—Co2—N14ii | 92.03 (9) | N22—C12—H12 | 126.6 |
O41—Co2—N14 | 92.03 (9) | C22—C12—H12 | 126.6 |
O41ii—Co2—N14 | 87.97 (9) | C12—C22—C32 | 106.0 (4) |
N14ii—Co2—N14 | 180.000 (1) | C12—C22—H22A | 127.0 |
O41—Co2—N15 | 89.73 (10) | C32—C22—H22A | 127.0 |
O41ii—Co2—N15 | 90.27 (10) | N12—C32—C22 | 109.8 (4) |
N14ii—Co2—N15 | 88.63 (10) | N12—C32—H32 | 125.1 |
N14—Co2—N15 | 91.37 (10) | C22—C32—H32 | 125.1 |
O41—Co2—N15ii | 90.27 (10) | N23—C13—C23 | 107.7 (3) |
O41ii—Co2—N15ii | 89.73 (10) | N23—C13—H13 | 126.2 |
N14ii—Co2—N15ii | 91.37 (10) | C23—C13—H13 | 126.2 |
N14—Co2—N15ii | 88.63 (10) | C13—C23—C33 | 104.7 (3) |
N15—Co2—N15ii | 180.000 (1) | C13—C23—H23A | 127.6 |
C41—O21—Co1 | 148.3 (2) | C33—C23—H23A | 127.6 |
C51—O41—Co2 | 153.9 (2) | N13—C33—C23 | 111.6 (3) |
C32—N12—N22 | 105.3 (3) | N13—C33—H33 | 124.2 |
C32—N12—Co1 | 130.4 (3) | C23—C33—H33 | 124.2 |
N22—N12—Co1 | 124.1 (2) | N24—C14—C24 | 107.5 (3) |
C12—N22—N12 | 112.0 (3) | N24—C14—H14 | 126.2 |
C12—N22—H22 | 124.0 | C24—C14—H14 | 126.2 |
N12—N22—H22 | 124.0 | C14—C24—C34 | 104.7 (3) |
C33—N13—N23 | 104.6 (3) | C14—C24—H24A | 127.6 |
C33—N13—Co1 | 131.4 (2) | C34—C24—H24A | 127.6 |
N23—N13—Co1 | 124.0 (2) | N14—C34—C24 | 111.0 (3) |
C13—N23—N13 | 111.4 (3) | N14—C34—H34 | 124.5 |
C13—N23—H23 | 124.3 | C24—C34—H34 | 124.5 |
N13—N23—H23 | 124.3 | N25—C15—C25 | 107.1 (3) |
C34—N14—N24 | 105.0 (3) | N25—C15—H15 | 126.4 |
C34—N14—Co2 | 131.1 (2) | C25—C15—H15 | 126.4 |
N24—N14—Co2 | 122.8 (2) | C15—C25—C35 | 105.7 (4) |
C14—N24—N14 | 111.7 (3) | C15—C25—H25A | 127.1 |
C14—N24—H24 | 124.1 | C35—C25—H25A | 127.1 |
N14—N24—H24 | 124.1 | N15—C35—C25 | 111.0 (3) |
C35—N15—N25 | 104.7 (3) | N15—C35—H35 | 124.5 |
C35—N15—Co2 | 130.1 (2) | C25—C35—H35 | 124.5 |
N25—N15—Co2 | 125.1 (2) | H1WA—O1W—H1WB | 107.4 |
C15—N25—N15 | 111.4 (3) | H2WA—O2W—H2WB | 107.4 |
C15—N25—H25 | 124.3 | | |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22···O31 | 0.86 | 2.12 | 2.907 (4) | 152 |
N23—H23···O11 | 0.86 | 1.96 | 2.806 (4) | 166 |
N24—H24···O31 | 0.86 | 2.07 | 2.878 (4) | 157 |
N25—H25···O1W | 0.86 | 2.18 | 2.978 (4) | 154 |
O1W—H1WA···O11iv | 0.85 | 2.03 | 2.875 (4) | 172 |
O1W—H1WB···O2W | 0.85 | 2.18 | 2.940 (4) | 149 |
O2W—H2WA···O31iv | 0.85 | 2.14 | 2.952 (4) | 160 |
O2W—H2WB···O11 | 0.85 | 2.21 | 3.060 (4) | 176 |
Symmetry code: (iv) −x+1, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Ni(C3H4N2)2(H2O)4][Ni(C10H2O8)(C3H4N2)2(H2O)2]·4H2O | [Co2(C10H2O8)(C3H4N2)8]·4H2O |
Mr | 820.02 | 984.70 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 7.6399 (12), 10.7925 (17), 11.4616 (19) | 8.9122 (18), 11.045 (2), 11.450 (2) |
α, β, γ (°) | 73.224 (3), 74.613 (2), 71.287 (3) | 83.381 (3), 74.579 (3), 74.162 (3) |
V (Å3) | 841.3 (2) | 1044.1 (3) |
Z | 1 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.21 | 0.88 |
Crystal size (mm) | 0.28 × 0.07 × 0.07 | 0.42 × 0.30 × 0.14 |
|
Data collection |
Diffractometer | Bruker SMART? CCD area-detector diffractometer | Bruker SMART? CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-NT; Bruker, 2002) | Multi-scan (SADABS in SAINT-NT; Bruker, 2002) |
Tmin, Tmax | 0.89, 0.92 | 0.69, 0.89 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7155, 3650, 2759 | 8610, 4455, 3228 |
Rint | 0.030 | 0.027 |
(sin θ/λ)max (Å−1) | 0.661 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.125, 1.01 | 0.053, 0.123, 1.04 |
No. of reflections | 3650 | 4455 |
No. of parameters | 229 | 292 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.31 | 0.60, −0.55 |
Selected bond lengths (Å) for (I) topNi1—N12 | 2.070 (3) | Ni2—O2W | 2.059 (2) |
Ni1—O1W | 2.083 (2) | Ni2—N13 | 2.068 (3) |
Ni1—O31 | 2.088 (2) | Ni2—O3W | 2.076 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22···O21i | 0.86 | 2.04 | 2.876 (4) | 162.4 |
N23—H23···O5Wii | 0.86 | 2.37 | 3.216 (5) | 168.4 |
O1W—H1WA···O4W | 0.85 | 1.95 | 2.798 (3) | 172.2 |
O1W—H1WB···O41i | 0.85 | 1.92 | 2.679 (3) | 148.2 |
O2W—H2WA···O4Wii | 0.85 | 1.90 | 2.734 (3) | 164.9 |
O2W—H2WB···O21iii | 0.85 | 1.93 | 2.759 (3) | 164.8 |
O3W—H3WA···O21iii | 0.85 | 1.97 | 2.748 (3) | 151.8 |
O3W—H3WB···O11iv | 0.85 | 1.83 | 2.675 (3) | 170.3 |
O4W—H4WB···O41v | 0.85 | 1.86 | 2.702 (4) | 170.5 |
O4W—H4WA···O5Wii | 0.85 | 2.31 | 3.097 (4) | 154.0 |
O5W—H5WB···O11 | 0.85 | 2.00 | 2.809 (4) | 159.1 |
O5W—H5WA···Cg2vi | 0.85 | 2.84 | 3.64 | 156 |
C32—H32···O5Wii | 0.93 | 2.44 | 3.329 (5) | 160.8 |
C12—H12···Cg3vii | 0.93 | 2.92 | 3.67 | 140 |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) x, y−1, z; (v) x+1, y, z; (vi) x−1, y, z; (vii) x, y+1, z−1. |
Selected bond lengths (Å) for (II) topCo1—N13 | 2.123 (3) | Co2—O41 | 2.070 (2) |
Co1—N12 | 2.124 (3) | Co2—N14 | 2.114 (3) |
Co1—O21 | 2.133 (2) | Co2—N15 | 2.127 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22···O31 | 0.86 | 2.12 | 2.907 (4) | 152.0 |
N23—H23···O11 | 0.86 | 1.96 | 2.806 (4) | 166.1 |
N24—H24···O31 | 0.86 | 2.07 | 2.878 (4) | 156.5 |
N25—H25···O1W | 0.86 | 2.18 | 2.978 (4) | 154.0 |
O1W—H1WA···O11i | 0.85 | 2.03 | 2.875 (4) | 171.9 |
O1W—H1WB···O2W | 0.85 | 2.18 | 2.940 (4) | 148.7 |
O2W—H2WA···O31i | 0.85 | 2.14 | 2.952 (4) | 160.2 |
O2W—H2WB···O11 | 0.85 | 2.21 | 3.060 (4) | 176.2 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
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The study of one-, two- or three-dimensional molecular systems based on carboxylate-bridged metal centres is attractive not only due to their usually interesting structural characteristics (Eddaoudi et al., 2001) but also for their potential applications, viz. in heterogeneous catalysis, medicine or chemical separation, and, on occasion, due to their eventual electronic and/or magnetic properties (Yaghi et al., 1996; Ait-Haddou et al., 2004).
In the synthesis of these systems several factors are of relevance, namely the characteristics of the organic ligands, such as bridging capacity, shape, functionality, flexibility etc. (Tudor et al., 2003; Kooijman et al., 2004), the non-covalent interactions which they might eventually give rise to, viz. hydrogen bonding, π–π interactions etc. (Perron et al., 2004), and, obviously, the nature of the metal ion.
The dramatic effect of this latter factor is apparent in the title complexes, [Ni(btc)(pyr)2(H2O)2]2-.[Ni(pyr)2(H2O)4]2+.4H2O, (I), and Co2(btc)(pyr)8.4H2O, (II) (btc is benzene-1,2,4,5-tetracarboxylate and pyr is pyrazole), where absolute similarity in synthetic procedures, reaction conditions and reactant characteristics (containing closely related, but not identical, metal cations) nevertheless results in different compounds, both at a molecular and at a crystal structure level.
Figs. 1 and 2 show molecular views of (I) and (II), respectively. Tables 1 and 3, in turn, give some selected coordination parameters, and Tables 2 and 4 provide the hydrogen-bonding interactions. Even though both structures are polymeric and crystallize in the triclinic space group P1, with two octahedral metal centres and one btc ligand occupying special positions on non-equivalent symmetry centres, this is basically the only common feature they share.
Compound (I) is ionic, with two well differentiated centrosymmetric substructures, {[Ni(btc)(pyr)(H2O)2]2-}n and n[Ni(pyr)2(H2O)4]2+. The Ni centre in each one of these ionic units displays a rather regular octahedral environment, with mean coordination distances Ni—O = 2.085 (3) and 2.068 (9) Å and Ni—N = 2.070 (3) and 2.068 (3) Å, and extreme values for the cis-coordination angles of 90±3.82 (8) and 90±2.62 (10)° for atoms Ni1 and Ni2, respectively.
In structure (II), instead, both Co centres present one and the same [CoO(btc)2N(pyr)4] coordination but with comparable regularity in the mean coordination distances of Co—O = 2.133 (3) and 2.070 (2) Å and Co—N = 2.070 (3) and 2.120 (7) Å, and extreme values for the cis-coordination angles of 90±4.87 (9) and 90±2.03 (9)° for atoms Co1 and Co2, respectively.
As already stated, in both structures the btc anion lies on a centre of symmetry and, even though it acts as the bridging agent in both cases, it does so in two quite different ways, binding in a µ2-bidentate fashion in the Ni compound and in a µ4-tetradentate way in the Co one. This results in dramatic differences in both structural dimensionality and packing behaviour.
In structure (I), the simple bridging of the [Ni(pyr)2(H2O)4]2+ groups via the (btc)4- anions generates negatively charged chains parallel to [001] containing only one of the two independent Ni atoms, Ni1 (Fig. 3a). Atom Ni2 is involved in the formation of isolated [Ni(pyr)2(H2O)4]2+ cationic groups which form hydrogen-bonded chains perpendicular to the latter [Former?] which balance charges (see discussion below and Fig. 3b).
The larger connectivity of the anion in (II) determines a two-dimensional array with a square grid motif (Fig. 2) presenting the (btc)4- ligands at the corners, interconnecting the two non-equivalent [Co(pyr)4]2+ units located at the edge centres, in a process which involves both atoms Co1 and Co2. The result, presented in Fig. 5, is a neutral tightly bound two-dimensional structure in the form of a `sieve'.
The way in which the polymeric entities interact with each other in each structure is also different, though mediated in both cases by an extremely complex hydrogen-bonding scheme where all the available donors are active [ten water O—H groups, two pyr N—H groups plus two non-conventional pyr C—H groups in (I), and four water O—H groups plus four pyr N—H groups in (II); Tables 3 and 4]. The only exception is atom H5WA in (I), which does not have any possible acceptor to interact with (see Refinement section). The remaining H atoms on atoms O4W and O5W interlink the isolated cationic units having atoms Ni2 as their centres, to define hydrogen-bonded chains running along b (Fig. 3b), almost perpendicular to the covalent chains which run along c, but shifted half a unit-cell translation along a, so that they do not intersect. Figs. 4(a) and 4(b) show views along the c direction, with a c/2 shift in the vertical direction, suggesting the way in which the voids between covalent chains (Fig. 4a) are `filled' by the hydrogen-bonded Ni2 chains (Fig. 4b). Hydrogen bonding between the two types of ionic chains stabilises the structure.
The interplanar interactions in (II) are simpler and are mediated by two solvent water molecules basically interacting with the carboxylate O atoms (Fig. 6). There is, in addition, a π–π bond involving one of the pyr rings [Cg···Cg(1 - x, -y, 1 - z) = 3.74 Å; slippage 26.66°; Cg is the centroid of the N15/N25/C15/C25/C35 ring]
A survey of the 2009 version of the Cambridge Structural Database (CSD; Allen, 2002) shows that no structures have been published previously containing both the btc anion and the pyr ligand. There are, however, quite a few with the closely related L = imidazole (imid) group, differing from pyr in that the two N atoms are not nearest neighbours (positions 1 and 2 in the ring) but next-nearest (positions 1 and 3). In particular, CSD refcode OJOTEM (Cheng et al., 2003), (III), is almost isostructural with (I) in that it presents the equivalent [Ni(L)2(H2O)4(btc)2-]n covalent anionic chain counterbalanced by a perpendicular non-intersecting hydrogen-bonded chain made up of water molecules and [Ni(L)n(H2O)m]2+ cations, the differences being that in OJOTEM L= imid, m = 2 and n = 4, while in (I) L = pyr, m = 4 and n = 2.
This `quasi-isostructurality' between complexes (I) and (III), with an almost identical disposition of equivalent groups, results from the position of the non-coordinated `second' N atom (N22) in the five-membered ring. In structure (I) it occupies site 2, vicinal to the coordinated atom N21 at site 1, a position which forces its H atom (H22) to point inwards within the chain (see Fig. 1), and thus it forms intrachain rather than interchain hydrogen bonds. Its counterpart in OJOTEM, instead, occupies position 3 in the five-membered ring (next-nearest neighbour to the coordinated N atom, the position occupied by atom C12 in Fig. 1), and thus points outwards from the chain in a suitable orientation to act as a donor for strong interchain bonds, which serve to build up hydrogen-bonded two-dimensional structures instead of the basically isolated chains found in (I).
A similar situation arises in (II) where, due to their inward-facing orientation, three out of the four possible N—H groups are forced to make intraplanar hydrogen bonds (Table 4 and Fig. 6) and only the fourth (N25—H25) is involved in the interplanar linkage, via a hydrogen-bonding interaction mediated by atom O1W.
As a final curiosity resulting from this CSD search, it can be mentioned that the [Ni(pyr)2(H2O)4]2+ group in (I) has been reported only once before, its only appearance being in a copper complex (CSD refcode UFIDUI; Wang et al., 2001).