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The two isomorphous title structures, formulated as {[Co(C
10H
4O
8)(C
12H
10N
2)(H
2O)
2]·C
12H
10N
2}
n, (I), and {[Co(C
10H
4O
8)(C
12H
12N
2)(H
2O)
2]·C
12H
12N
2}
n, (II), respectively, are reported. They crystallize in the space group
P with only one formula unit in the asymmetric unit, so that the organic ligands lie about inversion centres and the Co atom lies on an inversion centre. The Co atoms are octahedrally coordinated by a carboxylate O atom from 2,5-dicarboxybenzene-1,4-dicarboxylate (H
2btc), one N atom from 1,2-di-4-pyridylethene (
L) in (I) or from 1,2-di-4-pyridylethane (
L) in (II), and one coordinated water molecule, plus their inversion-related species. This particular coordination results in a two-dimensional array, with an elemental unit in the shape of a parallelogram having the Co
II cations at the corners, linked in one direction by
L bridges and in the opposite direction by H
2btc groups. The
L solvent molecules act as pillars between parallel planes, linking them by strong hydrogen bonds where the H atoms lie midway between the formal donor/acceptor atoms in a `shared' mode. Comparison is made with structures presenting the same structural motif, strongly suggesting that the two-dimensional arrangement reported here might be a very stable robust building block for molecular engineering purposes.
Supporting information
CCDC references: 718107; 718108
An aqueous solution (50 ml) containing CoII acetate tetrahydrate (0.33 mmol)
was added to an aqueous solution (50 ml) containg 1,2,4,5-benzene
tetracarboxylic acid (0.33 mmol) and NaOH (1.33 mmol). The mixture was heated
under reflux for 20 min. An ethanolic solution (20 ml) containing the ligand
[0.33 mmol; bpe1 for (I), bpe2 for (II)] was added slowly and the final
solution was maintained under reflux for 4 h. Single crystals adequate for
X-ray diffraction studies were obtained by slow concentration of the
solutions.
All H atoms were originally found in a difference Fourier map, but they were
treated differently. H atoms bonded to C atoms were repositioned at their
expected locations and allowed to ride, with C—H = 0.93–0.97 Å and
Uiso(H) = 1.2 or 1.5Ueq(C). Water H atoms were refined with
O—H restrained to 0.85 (1) Å but free Uiso(H). Finally, atom
H33A, which forms a very strong O—H···N bond that forces it to lie
essentially midway between the two atoms in a `shared' mode, was refined
freely.
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).
(I) poly[[diaqua-µ-2,5-dicarboxybenzene-1,4-dicarboxylato-
µ-1,2-di-4-pyridylethene-cobalt(II)] 1,2-di-4-pyridylethene solvate]
top
Crystal data top
[Co(C10H4O8)(C12H10N2)(H2O)2]·C12H10N2 | Z = 1 |
Mr = 711.53 | F(000) = 367 |
Triclinic, P1 | Dx = 1.562 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0283 (2) Å | Cell parameters from 6054 reflections |
b = 9.6152 (2) Å | θ = 2.2–27.8° |
c = 10.1064 (3) Å | µ = 0.64 mm−1 |
α = 93.1051 (14)° | T = 150 K |
β = 113.8441 (13)° | Polyhedron, pink |
γ = 106.2234 (14)° | 0.55 × 0.42 × 0.23 mm |
V = 756.41 (3) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3331 independent reflections |
Radiation source: fine-focus sealed tube | 3132 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
CCD rotation images, thin slices scans | θmax = 27.8°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | h = −11→11 |
Tmin = 0.70, Tmax = 0.86 | k = −12→11 |
12370 measured reflections | l = −12→12 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0432P)2 + 0.4048P] where P = (Fo2 + 2Fc2)/3 |
3331 reflections | (Δ/σ)max < 0.001 |
235 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
[Co(C10H4O8)(C12H10N2)(H2O)2]·C12H10N2 | γ = 106.2234 (14)° |
Mr = 711.53 | V = 756.41 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.0283 (2) Å | Mo Kα radiation |
b = 9.6152 (2) Å | µ = 0.64 mm−1 |
c = 10.1064 (3) Å | T = 150 K |
α = 93.1051 (14)° | 0.55 × 0.42 × 0.23 mm |
β = 113.8441 (13)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3331 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | 3132 reflections with I > 2σ(I) |
Tmin = 0.70, Tmax = 0.86 | Rint = 0.017 |
12370 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.38 e Å−3 |
3331 reflections | Δρmin = −0.25 e Å−3 |
235 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 | 1.0000 | 0.5000 | 0.5000 | 0.01298 (9) | |
N11 | 1.01957 (16) | 0.65228 (13) | 0.67162 (13) | 0.0167 (2) | |
C11 | 1.03383 (19) | 0.61342 (16) | 0.80048 (16) | 0.0192 (3) | |
H11 | 1.0383 | 0.5174 | 0.8141 | 0.023* | |
C21 | 1.0424 (2) | 0.70658 (17) | 0.91461 (16) | 0.0201 (3) | |
H21 | 1.0567 | 0.6758 | 1.0055 | 0.024* | |
C31 | 1.02991 (19) | 0.84579 (16) | 0.89522 (16) | 0.0180 (3) | |
C41 | 1.0187 (2) | 0.88780 (16) | 0.76216 (16) | 0.0190 (3) | |
H41 | 1.0136 | 0.9830 | 0.7453 | 0.023* | |
C51 | 1.01496 (19) | 0.78910 (16) | 0.65568 (16) | 0.0191 (3) | |
H51 | 1.0088 | 0.8195 | 0.5662 | 0.023* | |
C61 | 1.0239 (2) | 0.94025 (17) | 1.01034 (16) | 0.0199 (3) | |
H61 | 1.0560 | 0.9150 | 1.1052 | 0.024* | |
N12 | 0.62629 (16) | 0.59521 (14) | 0.84960 (14) | 0.0199 (3) | |
C12 | 0.5584 (2) | 0.68283 (18) | 0.76311 (18) | 0.0270 (3) | |
H12 | 0.5330 | 0.6643 | 0.6617 | 0.032* | |
C22 | 0.5238 (2) | 0.79944 (18) | 0.81624 (18) | 0.0279 (4) | |
H22 | 0.4767 | 0.8604 | 0.7521 | 0.034* | |
C32 | 0.55852 (19) | 0.82723 (17) | 0.96460 (17) | 0.0208 (3) | |
C42 | 0.6294 (2) | 0.73470 (18) | 1.05249 (17) | 0.0257 (3) | |
H42 | 0.6558 | 0.7500 | 1.1543 | 0.031* | |
C52 | 0.6615 (2) | 0.62079 (18) | 0.99221 (18) | 0.0245 (3) | |
H52 | 0.7101 | 0.5587 | 1.0539 | 0.029* | |
C62 | 0.5236 (2) | 0.94623 (18) | 1.03210 (18) | 0.0240 (3) | |
H62 | 0.5360 | 0.9462 | 1.1300 | 0.029* | |
C13 | 0.65820 (18) | 0.11433 (15) | 0.55886 (15) | 0.0143 (3) | |
C23 | 0.51484 (18) | 0.14047 (15) | 0.56273 (15) | 0.0151 (3) | |
C33 | 0.35838 (18) | 0.02575 (15) | 0.50243 (15) | 0.0158 (3) | |
H33 | 0.2603 | 0.0436 | 0.5032 | 0.019* | |
C43 | 0.82592 (18) | 0.23614 (15) | 0.60063 (15) | 0.0151 (3) | |
C53 | 0.52051 (18) | 0.28671 (16) | 0.63096 (16) | 0.0172 (3) | |
O13 | 0.81410 (13) | 0.34150 (11) | 0.53333 (11) | 0.0168 (2) | |
O23 | 0.96182 (13) | 0.21851 (12) | 0.68884 (12) | 0.0217 (2) | |
O33 | 0.65657 (14) | 0.35861 (12) | 0.74754 (12) | 0.0219 (2) | |
H33A | 0.642 (4) | 0.485 (3) | 0.799 (3) | 0.077 (9)* | |
O43 | 0.39350 (15) | 0.32596 (13) | 0.57317 (14) | 0.0306 (3) | |
O1W | 1.19427 (14) | 0.43673 (12) | 0.66059 (12) | 0.0178 (2) | |
H1WB | 1.258 (3) | 0.410 (3) | 0.635 (3) | 0.041 (6)* | |
H1WA | 1.136 (3) | 0.361 (3) | 0.675 (2) | 0.036 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.01582 (14) | 0.01038 (14) | 0.01430 (14) | 0.00455 (10) | 0.00801 (11) | 0.00171 (10) |
N11 | 0.0200 (6) | 0.0139 (6) | 0.0185 (6) | 0.0065 (5) | 0.0101 (5) | 0.0017 (5) |
C11 | 0.0248 (7) | 0.0162 (7) | 0.0204 (7) | 0.0090 (6) | 0.0119 (6) | 0.0045 (6) |
C21 | 0.0274 (8) | 0.0199 (7) | 0.0179 (7) | 0.0105 (6) | 0.0124 (6) | 0.0055 (6) |
C31 | 0.0201 (7) | 0.0173 (7) | 0.0180 (7) | 0.0070 (6) | 0.0093 (6) | 0.0015 (5) |
C41 | 0.0263 (7) | 0.0139 (7) | 0.0205 (7) | 0.0085 (6) | 0.0124 (6) | 0.0037 (5) |
C51 | 0.0259 (7) | 0.0171 (7) | 0.0184 (7) | 0.0085 (6) | 0.0125 (6) | 0.0044 (6) |
C61 | 0.0254 (7) | 0.0190 (7) | 0.0169 (7) | 0.0076 (6) | 0.0108 (6) | 0.0019 (5) |
N12 | 0.0213 (6) | 0.0162 (6) | 0.0207 (6) | 0.0064 (5) | 0.0084 (5) | −0.0012 (5) |
C12 | 0.0394 (9) | 0.0225 (8) | 0.0199 (7) | 0.0134 (7) | 0.0119 (7) | 0.0016 (6) |
C22 | 0.0404 (9) | 0.0216 (8) | 0.0229 (8) | 0.0178 (7) | 0.0099 (7) | 0.0051 (6) |
C32 | 0.0211 (7) | 0.0173 (7) | 0.0227 (7) | 0.0071 (6) | 0.0083 (6) | 0.0007 (6) |
C42 | 0.0356 (9) | 0.0256 (8) | 0.0190 (7) | 0.0157 (7) | 0.0113 (7) | 0.0025 (6) |
C52 | 0.0299 (8) | 0.0223 (8) | 0.0229 (8) | 0.0139 (7) | 0.0097 (6) | 0.0041 (6) |
C62 | 0.0298 (8) | 0.0224 (8) | 0.0215 (7) | 0.0122 (6) | 0.0109 (6) | 0.0018 (6) |
C13 | 0.0168 (6) | 0.0128 (6) | 0.0147 (6) | 0.0050 (5) | 0.0080 (5) | 0.0030 (5) |
C23 | 0.0189 (7) | 0.0117 (6) | 0.0165 (6) | 0.0054 (5) | 0.0094 (5) | 0.0031 (5) |
C33 | 0.0170 (7) | 0.0146 (7) | 0.0196 (7) | 0.0065 (5) | 0.0108 (6) | 0.0037 (5) |
C43 | 0.0183 (7) | 0.0128 (6) | 0.0158 (6) | 0.0044 (5) | 0.0099 (5) | 0.0001 (5) |
C53 | 0.0204 (7) | 0.0134 (7) | 0.0226 (7) | 0.0056 (5) | 0.0143 (6) | 0.0028 (5) |
O13 | 0.0173 (5) | 0.0137 (5) | 0.0208 (5) | 0.0044 (4) | 0.0098 (4) | 0.0047 (4) |
O23 | 0.0175 (5) | 0.0200 (5) | 0.0259 (6) | 0.0056 (4) | 0.0075 (4) | 0.0092 (4) |
O33 | 0.0237 (5) | 0.0176 (5) | 0.0219 (5) | 0.0081 (4) | 0.0076 (4) | −0.0028 (4) |
O43 | 0.0242 (6) | 0.0244 (6) | 0.0384 (7) | 0.0133 (5) | 0.0071 (5) | −0.0067 (5) |
O1W | 0.0187 (5) | 0.0162 (5) | 0.0216 (5) | 0.0069 (4) | 0.0109 (4) | 0.0050 (4) |
Geometric parameters (Å, º) top
Co1—O13 | 2.0824 (10) | C22—C32 | 1.396 (2) |
Co1—O13i | 2.0824 (10) | C22—H22 | 0.9500 |
Co1—O1Wi | 2.1171 (11) | C32—C42 | 1.391 (2) |
Co1—O1W | 2.1171 (11) | C32—C62 | 1.471 (2) |
Co1—N11 | 2.1251 (12) | C42—C52 | 1.379 (2) |
Co1—N11i | 2.1251 (12) | C42—H42 | 0.9500 |
N11—C11 | 1.3403 (19) | C52—H52 | 0.9500 |
N11—C51 | 1.3440 (19) | C62—C62iii | 1.330 (3) |
C11—C21 | 1.384 (2) | C62—H62 | 0.9500 |
C11—H11 | 0.9500 | C13—C33iv | 1.3936 (19) |
C21—C31 | 1.392 (2) | C13—C23 | 1.4006 (19) |
C21—H21 | 0.9500 | C13—C43 | 1.5105 (19) |
C31—C41 | 1.398 (2) | C23—C33 | 1.394 (2) |
C31—C61 | 1.465 (2) | C23—C53 | 1.5105 (19) |
C41—C51 | 1.379 (2) | C33—C13iv | 1.3936 (19) |
C41—H41 | 0.9500 | C33—H33 | 0.9500 |
C51—H51 | 0.9500 | C43—O13 | 1.2557 (17) |
C61—C61ii | 1.334 (3) | C43—O23 | 1.2558 (18) |
C61—H61 | 0.9500 | C53—O43 | 1.2340 (19) |
N12—C12 | 1.336 (2) | C53—O33 | 1.2814 (18) |
N12—C52 | 1.336 (2) | O33—H33A | 1.35 (3) |
N12—H33A | 1.22 (3) | O1W—H1WB | 0.81 (3) |
C12—C22 | 1.382 (2) | O1W—H1WA | 0.83 (2) |
C12—H12 | 0.9500 | | |
| | | |
O13—Co1—O13i | 180.00 (5) | N12—C12—C22 | 122.19 (15) |
O13—Co1—O1Wi | 89.99 (4) | N12—C12—H12 | 118.9 |
O13i—Co1—O1Wi | 90.01 (4) | C22—C12—H12 | 118.9 |
O13—Co1—O1W | 90.01 (4) | C12—C22—C32 | 119.67 (15) |
O13i—Co1—O1W | 89.99 (4) | C12—C22—H22 | 120.2 |
O1Wi—Co1—O1W | 180.0 | C32—C22—H22 | 120.2 |
O13—Co1—N11 | 88.87 (4) | C42—C32—C22 | 117.08 (14) |
O13i—Co1—N11 | 91.13 (4) | C42—C32—C62 | 118.69 (14) |
O1Wi—Co1—N11 | 91.65 (4) | C22—C32—C62 | 124.24 (14) |
O1W—Co1—N11 | 88.35 (4) | C52—C42—C32 | 120.15 (15) |
O13—Co1—N11i | 91.13 (4) | C52—C42—H42 | 119.9 |
O13i—Co1—N11i | 88.87 (4) | C32—C42—H42 | 119.9 |
O1Wi—Co1—N11i | 88.35 (4) | N12—C52—C42 | 121.93 (15) |
O1W—Co1—N11i | 91.65 (4) | N12—C52—H52 | 119.0 |
N11—Co1—N11i | 180.0 | C42—C52—H52 | 119.0 |
C11—N11—C51 | 117.22 (12) | C62iii—C62—C32 | 125.63 (19) |
C11—N11—Co1 | 120.58 (10) | C62iii—C62—H62 | 117.2 |
C51—N11—Co1 | 122.19 (10) | C32—C62—H62 | 117.2 |
N11—C11—C21 | 123.09 (14) | C33iv—C13—C23 | 119.33 (13) |
N11—C11—H11 | 118.5 | C33iv—C13—C43 | 117.50 (12) |
C21—C11—H11 | 118.5 | C23—C13—C43 | 122.71 (12) |
C11—C21—C31 | 119.47 (14) | C33—C23—C13 | 118.83 (13) |
C11—C21—H21 | 120.3 | C33—C23—C53 | 117.70 (12) |
C31—C21—H21 | 120.3 | C13—C23—C53 | 123.47 (13) |
C21—C31—C41 | 117.52 (13) | C13iv—C33—C23 | 121.83 (13) |
C21—C31—C61 | 119.91 (13) | C13iv—C33—H33 | 119.1 |
C41—C31—C61 | 122.54 (13) | C23—C33—H33 | 119.1 |
C51—C41—C31 | 119.05 (14) | O13—C43—O23 | 126.62 (13) |
C51—C41—H41 | 120.5 | O13—C43—C13 | 114.91 (12) |
C31—C41—H41 | 120.5 | O23—C43—C13 | 118.26 (12) |
N11—C51—C41 | 123.55 (14) | O43—C53—O33 | 125.13 (13) |
N11—C51—H51 | 118.2 | O43—C53—C23 | 118.05 (13) |
C41—C51—H51 | 118.2 | O33—C53—C23 | 116.80 (12) |
C61ii—C61—C31 | 123.80 (18) | C43—O13—Co1 | 130.15 (9) |
C61ii—C61—H61 | 118.1 | C53—O33—H33A | 110.3 (13) |
C31—C61—H61 | 118.1 | Co1—O1W—H1WB | 117.5 (17) |
C12—N12—C52 | 118.97 (13) | Co1—O1W—H1WA | 100.8 (15) |
C12—N12—H33A | 121.5 (14) | H1WB—O1W—H1WA | 105 (2) |
C52—N12—H33A | 119.2 (14) | | |
| | | |
O13—Co1—N11—C11 | 47.47 (11) | C62—C32—C42—C52 | 179.10 (16) |
O13i—Co1—N11—C11 | −132.53 (11) | C12—N12—C52—C42 | 0.2 (2) |
O1Wi—Co1—N11—C11 | 137.42 (11) | C32—C42—C52—N12 | −0.1 (3) |
O1W—Co1—N11—C11 | −42.58 (11) | C42—C32—C62—C62iii | 171.3 (2) |
O13—Co1—N11—C51 | −131.22 (12) | C22—C32—C62—C62iii | −9.2 (3) |
O13i—Co1—N11—C51 | 48.78 (12) | C33iv—C13—C23—C33 | −1.2 (2) |
O1Wi—Co1—N11—C51 | −41.26 (12) | C43—C13—C23—C33 | 170.81 (13) |
O1W—Co1—N11—C51 | 138.74 (12) | C33iv—C13—C23—C53 | 177.99 (13) |
C51—N11—C11—C21 | 0.5 (2) | C43—C13—C23—C53 | −10.0 (2) |
Co1—N11—C11—C21 | −178.23 (11) | C13—C23—C33—C13iv | 1.2 (2) |
N11—C11—C21—C31 | 2.3 (2) | C53—C23—C33—C13iv | −178.01 (13) |
C11—C21—C31—C41 | −3.5 (2) | C33iv—C13—C43—O13 | 118.33 (14) |
C11—C21—C31—C61 | 174.74 (14) | C23—C13—C43—O13 | −53.78 (18) |
C21—C31—C41—C51 | 2.0 (2) | C33iv—C13—C43—O23 | −56.73 (18) |
C61—C31—C41—C51 | −176.16 (14) | C23—C13—C43—O23 | 131.16 (15) |
C11—N11—C51—C41 | −2.1 (2) | C33—C23—C53—O43 | −35.65 (19) |
Co1—N11—C51—C41 | 176.61 (11) | C13—C23—C53—O43 | 145.19 (15) |
C31—C41—C51—N11 | 0.8 (2) | C33—C23—C53—O33 | 142.57 (14) |
C21—C31—C61—C61ii | −165.20 (19) | C13—C23—C53—O33 | −36.6 (2) |
C41—C31—C61—C61ii | 12.9 (3) | O23—C43—O13—Co1 | 15.1 (2) |
C52—N12—C12—C22 | 0.2 (3) | C13—C43—O13—Co1 | −159.49 (9) |
N12—C12—C22—C32 | −0.7 (3) | O1Wi—Co1—O13—C43 | 167.20 (12) |
C12—C22—C32—C42 | 0.8 (3) | O1W—Co1—O13—C43 | −12.80 (12) |
C12—C22—C32—C62 | −178.72 (16) | N11—Co1—O13—C43 | −101.15 (12) |
C22—C32—C42—C52 | −0.4 (2) | N11i—Co1—O13—C43 | 78.85 (12) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+2, −z+2; (iii) −x+1, −y+2, −z+2; (iv) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O33—H33A···N12 | 1.35 (3) | 1.22 (3) | 2.5759 (16) | 177 (3) |
O1W—H1WB···O43v | 0.81 (3) | 1.92 (3) | 2.7210 (16) | 174 (2) |
O1W—H1WA···O23 | 0.83 (2) | 1.83 (2) | 2.6414 (16) | 165 (2) |
Symmetry code: (v) x+1, y, z. |
(II) poly[[diaqua-µ-2,5-dicarboxybenzene-1,4-dicarboxylato-
µ-1,2-di-4-pyridylethene-cobalt(II)] 1,2-di-4-pyridylethane solvate]
top
Crystal data top
[Co(C10H4O8)(C12H12N2)(H2O)2]·C12H12N2 | Z = 1 |
Mr = 715.57 | F(000) = 371 |
Triclinic, P1 | Dx = 1.544 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0933 (4) Å | Cell parameters from 6988 reflections |
b = 9.5887 (5) Å | θ = 2.2–27.7° |
c = 10.0058 (5) Å | µ = 0.63 mm−1 |
α = 92.2999 (7)° | T = 150 K |
β = 111.9705 (6)° | Polyhedron, yellow |
γ = 105.6443 (7)° | 0.29 × 0.21 × 0.18 mm |
V = 769.33 (7) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3442 independent reflections |
Radiation source: fine-focus sealed tube | 3363 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
CCD rotation images, thin slices scans | θmax = 27.9°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | h = −11→11 |
Tmin = 0.84, Tmax = 0.89 | k = −12→12 |
16531 measured reflections | l = −12→13 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0432P)2 + 0.4048P] where P = (Fo2 + 2Fc2)/3 |
3442 reflections | (Δ/σ)max < 0.001 |
235 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
[Co(C10H4O8)(C12H12N2)(H2O)2]·C12H12N2 | γ = 105.6443 (7)° |
Mr = 715.57 | V = 769.33 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.0933 (4) Å | Mo Kα radiation |
b = 9.5887 (5) Å | µ = 0.63 mm−1 |
c = 10.0058 (5) Å | T = 150 K |
α = 92.2999 (7)° | 0.29 × 0.21 × 0.18 mm |
β = 111.9705 (6)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3442 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | 3363 reflections with I > 2σ(I) |
Tmin = 0.84, Tmax = 0.89 | Rint = 0.015 |
16531 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.43 e Å−3 |
3442 reflections | Δρmin = −0.27 e Å−3 |
235 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 | 1.0000 | 0.5000 | 0.5000 | 0.01268 (8) | |
N11 | 1.00772 (14) | 0.64830 (12) | 0.66911 (12) | 0.0166 (2) | |
C11 | 1.01890 (18) | 0.60773 (15) | 0.79794 (15) | 0.0206 (3) | |
H11 | 1.0145 | 0.5091 | 0.8099 | 0.025* | |
C21 | 1.03664 (18) | 0.70288 (15) | 0.91484 (15) | 0.0221 (3) | |
H21 | 1.0469 | 0.6699 | 1.0052 | 0.026* | |
C31 | 1.03933 (18) | 0.84696 (15) | 0.89905 (15) | 0.0205 (3) | |
C41 | 1.02532 (19) | 0.88863 (15) | 0.76420 (15) | 0.0228 (3) | |
H41 | 1.0255 | 0.9856 | 0.7480 | 0.027* | |
C51 | 1.01111 (18) | 0.78745 (15) | 0.65403 (15) | 0.0199 (3) | |
H51 | 1.0034 | 0.8180 | 0.5631 | 0.024* | |
C61 | 1.0565 (2) | 0.95237 (17) | 1.02381 (15) | 0.0267 (3) | |
H61A | 1.1736 | 1.0161 | 1.0712 | 0.032* | |
H61B | 1.0303 | 0.8960 | 1.0971 | 0.032* | |
N12 | 0.61075 (15) | 0.58527 (13) | 0.84643 (13) | 0.0207 (2) | |
C12 | 0.52451 (19) | 0.66391 (16) | 0.76178 (16) | 0.0248 (3) | |
H12 | 0.4868 | 0.6408 | 0.6589 | 0.030* | |
C22 | 0.4878 (2) | 0.77847 (16) | 0.81846 (16) | 0.0276 (3) | |
H22 | 0.4253 | 0.8319 | 0.7549 | 0.033* | |
C32 | 0.54274 (17) | 0.81441 (15) | 0.96850 (15) | 0.0207 (3) | |
C42 | 0.6322 (2) | 0.73079 (16) | 1.05508 (15) | 0.0251 (3) | |
H42 | 0.6719 | 0.7515 | 1.1583 | 0.030* | |
C52 | 0.6632 (2) | 0.61772 (16) | 0.99128 (16) | 0.0257 (3) | |
H52 | 0.7237 | 0.5612 | 1.0521 | 0.031* | |
C62 | 0.5060 (2) | 0.93506 (16) | 1.04066 (16) | 0.0266 (3) | |
H62A | 0.5948 | 0.9711 | 1.1400 | 0.032* | |
H62B | 0.3996 | 0.8928 | 1.0511 | 0.032* | |
C13 | 0.65325 (16) | 0.11282 (13) | 0.55581 (13) | 0.0145 (2) | |
C23 | 0.51056 (16) | 0.13905 (13) | 0.56013 (14) | 0.0154 (2) | |
C33 | 0.35951 (16) | 0.02621 (14) | 0.50310 (14) | 0.0159 (2) | |
H33 | 0.2625 | 0.0447 | 0.5045 | 0.019* | |
C43 | 0.81693 (16) | 0.23255 (13) | 0.59562 (13) | 0.0149 (2) | |
C53 | 0.51163 (17) | 0.28302 (14) | 0.62758 (15) | 0.0176 (3) | |
O13 | 0.80913 (11) | 0.34027 (10) | 0.52823 (10) | 0.01647 (19) | |
O23 | 0.94715 (12) | 0.21110 (11) | 0.68265 (11) | 0.0219 (2) | |
O33 | 0.64417 (12) | 0.35290 (11) | 0.74026 (11) | 0.0221 (2) | |
H33A | 0.636 (3) | 0.468 (3) | 0.791 (3) | 0.076 (9)* | |
O43 | 0.38682 (13) | 0.32279 (12) | 0.57544 (13) | 0.0301 (3) | |
O1W | 1.17975 (12) | 0.42847 (11) | 0.65954 (10) | 0.01734 (19) | |
H1WB | 1.248 (3) | 0.402 (2) | 0.632 (2) | 0.035 (5)* | |
H1WA | 1.124 (3) | 0.356 (2) | 0.672 (2) | 0.033 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.01498 (13) | 0.01026 (12) | 0.01364 (13) | 0.00431 (9) | 0.00641 (9) | 0.00109 (8) |
N11 | 0.0194 (5) | 0.0141 (5) | 0.0178 (5) | 0.0058 (4) | 0.0087 (4) | 0.0009 (4) |
C11 | 0.0279 (7) | 0.0162 (6) | 0.0208 (6) | 0.0085 (5) | 0.0120 (5) | 0.0035 (5) |
C21 | 0.0317 (7) | 0.0220 (7) | 0.0177 (6) | 0.0113 (6) | 0.0132 (6) | 0.0051 (5) |
C31 | 0.0266 (7) | 0.0206 (6) | 0.0175 (6) | 0.0114 (5) | 0.0096 (5) | 0.0009 (5) |
C41 | 0.0356 (8) | 0.0169 (6) | 0.0201 (6) | 0.0131 (6) | 0.0121 (6) | 0.0030 (5) |
C51 | 0.0290 (7) | 0.0179 (6) | 0.0171 (6) | 0.0110 (5) | 0.0110 (5) | 0.0038 (5) |
C61 | 0.0409 (9) | 0.0274 (7) | 0.0168 (6) | 0.0195 (7) | 0.0110 (6) | 0.0002 (5) |
N12 | 0.0225 (6) | 0.0166 (5) | 0.0225 (6) | 0.0066 (4) | 0.0085 (5) | −0.0013 (4) |
C12 | 0.0333 (8) | 0.0197 (7) | 0.0198 (6) | 0.0096 (6) | 0.0084 (6) | −0.0006 (5) |
C22 | 0.0375 (8) | 0.0223 (7) | 0.0214 (7) | 0.0167 (6) | 0.0051 (6) | 0.0016 (5) |
C32 | 0.0242 (7) | 0.0157 (6) | 0.0222 (7) | 0.0080 (5) | 0.0082 (5) | −0.0002 (5) |
C42 | 0.0343 (8) | 0.0244 (7) | 0.0177 (6) | 0.0153 (6) | 0.0077 (6) | 0.0013 (5) |
C52 | 0.0324 (8) | 0.0238 (7) | 0.0223 (7) | 0.0167 (6) | 0.0068 (6) | 0.0021 (5) |
C62 | 0.0398 (8) | 0.0210 (7) | 0.0240 (7) | 0.0175 (6) | 0.0128 (6) | 0.0018 (6) |
C13 | 0.0168 (6) | 0.0129 (5) | 0.0149 (5) | 0.0044 (5) | 0.0075 (5) | 0.0023 (4) |
C23 | 0.0186 (6) | 0.0126 (5) | 0.0170 (6) | 0.0056 (5) | 0.0088 (5) | 0.0023 (4) |
C33 | 0.0173 (6) | 0.0145 (6) | 0.0194 (6) | 0.0062 (5) | 0.0099 (5) | 0.0030 (5) |
C43 | 0.0174 (6) | 0.0131 (5) | 0.0157 (6) | 0.0045 (5) | 0.0088 (5) | 0.0003 (4) |
C53 | 0.0207 (6) | 0.0134 (6) | 0.0227 (6) | 0.0050 (5) | 0.0132 (5) | 0.0017 (5) |
O13 | 0.0165 (4) | 0.0138 (4) | 0.0196 (4) | 0.0043 (3) | 0.0079 (4) | 0.0040 (3) |
O23 | 0.0170 (4) | 0.0202 (5) | 0.0262 (5) | 0.0047 (4) | 0.0061 (4) | 0.0095 (4) |
O33 | 0.0230 (5) | 0.0180 (5) | 0.0234 (5) | 0.0079 (4) | 0.0068 (4) | −0.0039 (4) |
O43 | 0.0233 (5) | 0.0238 (5) | 0.0390 (6) | 0.0124 (4) | 0.0058 (5) | −0.0080 (4) |
O1W | 0.0171 (4) | 0.0155 (4) | 0.0204 (5) | 0.0058 (4) | 0.0079 (4) | 0.0035 (4) |
Geometric parameters (Å, º) top
Co1—O13 | 2.0990 (9) | C22—C32 | 1.388 (2) |
Co1—O13i | 2.0991 (9) | C22—H22 | 0.9500 |
Co1—O1Wi | 2.1049 (9) | C32—C42 | 1.3910 (19) |
Co1—O1W | 2.1049 (9) | C32—C62 | 1.5142 (18) |
Co1—N11 | 2.1341 (11) | C42—C52 | 1.3811 (19) |
Co1—N11i | 2.1341 (11) | C42—H42 | 0.9500 |
N11—C11 | 1.3368 (17) | C52—H52 | 0.9500 |
N11—C51 | 1.3422 (17) | C62—C62iii | 1.521 (3) |
C11—C21 | 1.3857 (19) | C62—H62A | 0.9900 |
C11—H11 | 0.9500 | C62—H62B | 0.9900 |
C21—C31 | 1.3916 (19) | C13—C33iv | 1.3930 (17) |
C21—H21 | 0.9500 | C13—C23 | 1.4020 (17) |
C31—C41 | 1.3923 (19) | C13—C43 | 1.5133 (17) |
C31—C61 | 1.5074 (18) | C23—C33 | 1.3948 (18) |
C41—C51 | 1.3831 (18) | C23—C53 | 1.5082 (17) |
C41—H41 | 0.9500 | C33—C13iv | 1.3930 (17) |
C51—H51 | 0.9500 | C33—H33 | 0.9500 |
C61—C61ii | 1.514 (3) | C43—O23 | 1.2557 (16) |
C61—H61A | 0.9900 | C43—O13 | 1.2594 (15) |
C61—H61B | 0.9900 | C53—O43 | 1.2297 (17) |
N12—C12 | 1.3320 (19) | C53—O33 | 1.2883 (17) |
N12—C52 | 1.3384 (19) | O33—H33A | 1.23 (3) |
N12—H33A | 1.34 (3) | O1W—H1WB | 0.85 (2) |
C12—C22 | 1.389 (2) | O1W—H1WA | 0.79 (2) |
C12—H12 | 0.9500 | | |
| | | |
O13—Co1—O13i | 180.00 (4) | N12—C12—C22 | 122.38 (13) |
O13—Co1—O1Wi | 89.85 (4) | N12—C12—H12 | 118.8 |
O13i—Co1—O1Wi | 90.15 (4) | C22—C12—H12 | 118.8 |
O13—Co1—O1W | 90.15 (4) | C32—C22—C12 | 119.64 (13) |
O13i—Co1—O1W | 89.85 (4) | C32—C22—H22 | 120.2 |
O1Wi—Co1—O1W | 180.0 | C12—C22—H22 | 120.2 |
O13—Co1—N11 | 89.34 (4) | C22—C32—C42 | 117.15 (12) |
O13i—Co1—N11 | 90.66 (4) | C22—C32—C62 | 123.61 (13) |
O1Wi—Co1—N11 | 91.35 (4) | C42—C32—C62 | 119.21 (13) |
O1W—Co1—N11 | 88.65 (4) | C52—C42—C32 | 120.14 (13) |
O13—Co1—N11i | 90.66 (4) | C52—C42—H42 | 119.9 |
O13i—Co1—N11i | 89.34 (4) | C32—C42—H42 | 119.9 |
O1Wi—Co1—N11i | 88.65 (4) | N12—C52—C42 | 122.03 (13) |
O1W—Co1—N11i | 91.35 (4) | N12—C52—H52 | 119.0 |
N11—Co1—N11i | 180.000 (1) | C42—C52—H52 | 119.0 |
C11—N11—C51 | 117.35 (11) | C32—C62—C62iii | 114.79 (15) |
C11—N11—Co1 | 120.74 (9) | C32—C62—H62A | 108.6 |
C51—N11—Co1 | 121.81 (9) | C62iii—C62—H62A | 108.6 |
N11—C11—C21 | 123.04 (12) | C32—C62—H62B | 108.6 |
N11—C11—H11 | 118.5 | C62iii—C62—H62B | 108.6 |
C21—C11—H11 | 118.5 | H62A—C62—H62B | 107.5 |
C11—C21—C31 | 119.62 (12) | C33iv—C13—C23 | 118.93 (11) |
C11—C21—H21 | 120.2 | C33iv—C13—C43 | 117.48 (11) |
C31—C21—H21 | 120.2 | C23—C13—C43 | 123.18 (11) |
C21—C31—C41 | 117.31 (12) | C33—C23—C13 | 119.16 (11) |
C21—C31—C61 | 120.77 (12) | C33—C23—C53 | 117.40 (11) |
C41—C31—C61 | 121.92 (12) | C13—C23—C53 | 123.41 (11) |
C51—C41—C31 | 119.36 (12) | C13iv—C33—C23 | 121.90 (12) |
C51—C41—H41 | 120.3 | C13iv—C33—H33 | 119.1 |
C31—C41—H41 | 120.3 | C23—C33—H33 | 119.1 |
N11—C51—C41 | 123.29 (12) | O23—C43—O13 | 126.34 (12) |
N11—C51—H51 | 118.4 | O23—C43—C13 | 117.96 (11) |
C41—C51—H51 | 118.4 | O13—C43—C13 | 115.47 (11) |
C31—C61—C61ii | 112.98 (15) | O43—C53—O33 | 125.00 (12) |
C31—C61—H61A | 109.0 | O43—C53—C23 | 118.74 (12) |
C61ii—C61—H61A | 109.0 | O33—C53—C23 | 116.21 (11) |
C31—C61—H61B | 109.0 | C43—O13—Co1 | 129.42 (8) |
C61ii—C61—H61B | 109.0 | C53—O33—H33A | 112.8 (13) |
H61A—C61—H61B | 107.8 | Co1—O1W—H1WB | 116.0 (14) |
C12—N12—C52 | 118.67 (12) | Co1—O1W—H1WA | 101.5 (15) |
C12—N12—H33A | 122.1 (12) | H1WB—O1W—H1WA | 105 (2) |
C52—N12—H33A | 119.1 (12) | | |
| | | |
O13—Co1—N11—C11 | 50.41 (11) | C62—C32—C42—C52 | 178.30 (15) |
O13i—Co1—N11—C11 | −129.59 (11) | C12—N12—C52—C42 | −0.7 (2) |
O1Wi—Co1—N11—C11 | 140.24 (11) | C32—C42—C52—N12 | 0.5 (3) |
O1W—Co1—N11—C11 | −39.76 (11) | C22—C32—C62—C62iii | −32.6 (3) |
O13—Co1—N11—C51 | −133.41 (11) | C42—C32—C62—C62iii | 149.39 (18) |
O13i—Co1—N11—C51 | 46.59 (11) | C33iv—C13—C23—C33 | −1.1 (2) |
O1Wi—Co1—N11—C51 | −43.58 (11) | C43—C13—C23—C33 | 171.44 (12) |
O1W—Co1—N11—C51 | 136.42 (11) | C33iv—C13—C23—C53 | 177.10 (12) |
C51—N11—C11—C21 | −1.2 (2) | C43—C13—C23—C53 | −10.34 (19) |
Co1—N11—C11—C21 | 175.12 (11) | C13—C23—C33—C13iv | 1.2 (2) |
N11—C11—C21—C31 | 1.6 (2) | C53—C23—C33—C13iv | −177.18 (12) |
C11—C21—C31—C41 | −0.6 (2) | C33iv—C13—C43—O23 | −56.23 (16) |
C11—C21—C31—C61 | 179.29 (14) | C23—C13—C43—O23 | 131.12 (13) |
C21—C31—C41—C51 | −0.6 (2) | C33iv—C13—C43—O13 | 118.61 (13) |
C61—C31—C41—C51 | 179.54 (14) | C23—C13—C43—O13 | −54.04 (17) |
C11—N11—C51—C41 | 0.0 (2) | C33—C23—C53—O43 | −33.79 (18) |
Co1—N11—C51—C41 | −176.34 (11) | C13—C23—C53—O43 | 147.96 (14) |
C31—C41—C51—N11 | 0.9 (2) | C33—C23—C53—O33 | 143.98 (12) |
C21—C31—C61—C61ii | −138.30 (18) | C13—C23—C53—O33 | −34.27 (18) |
C41—C31—C61—C61ii | 41.6 (3) | O23—C43—O13—Co1 | 13.17 (19) |
C52—N12—C12—C22 | 0.2 (2) | C13—C43—O13—Co1 | −161.17 (8) |
N12—C12—C22—C32 | 0.4 (2) | O1Wi—Co1—O13—C43 | 168.07 (11) |
C12—C22—C32—C42 | −0.6 (2) | O1W—Co1—O13—C43 | −11.93 (11) |
C12—C22—C32—C62 | −178.65 (15) | N11—Co1—O13—C43 | −100.58 (11) |
C22—C32—C42—C52 | 0.1 (2) | N11i—Co1—O13—C43 | 79.42 (11) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+2, −z+2; (iii) −x+1, −y+2, −z+2; (iv) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O33—H33A···N12 | 1.23 (3) | 1.34 (3) | 2.5695 (15) | 174 (3) |
O1W—H1WB···O43v | 0.85 (2) | 1.87 (2) | 2.7252 (14) | 174 (2) |
O1W—H1WA···O23 | 0.79 (2) | 1.86 (2) | 2.6265 (14) | 164 (2) |
Symmetry code: (v) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Co(C10H4O8)(C12H10N2)(H2O)2]·C12H10N2 | [Co(C10H4O8)(C12H12N2)(H2O)2]·C12H12N2 |
Mr | 711.53 | 715.57 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 9.0283 (2), 9.6152 (2), 10.1064 (3) | 9.0933 (4), 9.5887 (5), 10.0058 (5) |
α, β, γ (°) | 93.1051 (14), 113.8441 (13), 106.2234 (14) | 92.2999 (7), 111.9705 (6), 105.6443 (7) |
V (Å3) | 756.41 (3) | 769.33 (7) |
Z | 1 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.64 | 0.63 |
Crystal size (mm) | 0.55 × 0.42 × 0.23 | 0.29 × 0.21 × 0.18 |
|
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 | 0.70, 0.86 | 0.84, 0.89 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12370, 3331, 3132 | 16531, 3442, 3363 |
Rint | 0.017 | 0.015 |
(sin θ/λ)max (Å−1) | 0.657 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.078, 1.04 | 0.028, 0.076, 1.05 |
No. of reflections | 3331 | 3442 |
No. of parameters | 235 | 235 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.25 | 0.43, −0.27 |
Selected geometric parameters (Å, º) for (I) topCo1—O13 | 2.0824 (10) | Co1—N11 | 2.1251 (12) |
Co1—O1W | 2.1171 (11) | | |
| | | |
O13—Co1—O1W | 90.01 (4) | O1W—Co1—N11 | 88.35 (4) |
O13—Co1—N11 | 88.87 (4) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O33—H33A···N12 | 1.35 (3) | 1.22 (3) | 2.5759 (16) | 177 (3) |
O1W—H1WB···O43i | 0.81 (3) | 1.92 (3) | 2.7210 (16) | 174 (2) |
O1W—H1WA···O23 | 0.83 (2) | 1.83 (2) | 2.6414 (16) | 165 (2) |
Symmetry code: (i) x+1, y, z. |
Selected geometric parameters (Å, º) for (II) topCo1—O13 | 2.0990 (9) | Co1—N11 | 2.1341 (11) |
Co1—O1W | 2.1049 (9) | | |
| | | |
O13—Co1—O1W | 90.15 (4) | O1W—Co1—N11 | 88.65 (4) |
O13—Co1—N11 | 89.34 (4) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O33—H33A···N12 | 1.23 (3) | 1.34 (3) | 2.5695 (15) | 174 (3) |
O1W—H1WB···O43i | 0.85 (2) | 1.87 (2) | 2.7252 (14) | 174 (2) |
O1W—H1WA···O23 | 0.79 (2) | 1.86 (2) | 2.6265 (14) | 164 (2) |
Symmetry code: (i) x+1, y, z. |
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The ab initio design of supramolecular materials starting from molecular building blocks is an active research field in molecular engineering. In particular, great effort is currently dedicated to the assembly of metal ions and organic ligands in polymeric complexes (Moulton & Zaworotko, 2001; Janiak, 2003), in a process which can in principle be understood as one where the `interactive' information carried by the ligands is to be `decoded' by the metal ions through the `algorithm' determined by their coordination capabilities (Lehn, 1995). This process can lead to the formation of reproducible primary structures, which can in turn be used as secondary building units in the construction of even more complex structures, and the usefulness of these relies heavily on their stability. If one such structure is shown to be robust enough to survive almost unchanged in a number of compounds where it is subject to a diversity of interaction environments, it can then be considered an interesting target for crystal engineering. We report here a structural investigation of the two title isomorphous cobalt complexes, (I) and (II), characterized by one such seemingly robust structural motif.
The title compounds are formulated as [Co(H2btc)(L)(H2O)2].L, where (H4btc) is benzyl tetracarboxylic acid, C10H6O8, in both structures, and L, the ligand differentiating them, is 1,2-bis(4-pyridyl)ethene, C10H10N2 (bpe1), in (I) and 1,2-bis(4-pyridyl)ethane, C10H12N2 (bpe2), in (II). For the sake of simplicity, we shall only discuss the (I) isologue as representative of both, commenting on the corresponding differences when significant.
Fig. 1 shows a molecular view of (I), while Tables 1 and 3 present some selected coordination parameters and Tables 2 and 4 the main hydrogen-bonding interactions for (I) and (II), respectively.
Compound (I) crystallizes in the triclinic space group P1 with only one formula unit per unit cell. Thus, the organic ligands lie about inversion centres and the Co atom lies on an inversion centre. The CoII cation has an octahedral coordination, provided by a carboxylate O atom from (H2btc), an N atom from (bpe1) and one coordinated water molecule, plus their inversion-related species. The O atoms define the square equatorial plane, with a tight Co—O span [2.0824 (10)–2.1171 (11) Å for (I) and 2.0819 (10)–2.0919 (9) Å for (II)], while the N atoms occupy the apical positions, with Co—N = 2.1251 (12) Å in (I) and 2.1316 (11) Å in (II). The angles are also quite regular, with departures from ideal values of less than 1.8° in (I) and 2.4° in (II).
The organic ligands are regular and show no unusual features. The only obvious difference between the two structures is due to the double/single bond character of the mid C—C' bonds in bpe1 and bpe2 and, correspondingly, the number of H atoms attached. The coordinated bpe1 and H2btc ligands act in a similar bridging mode, the former through its two N atoms and the latter via two opposite carboxylate O atoms, binding in its most outstretched fashion. The result is a two-dimensional array (Fig. 2) with an elemental unit presenting a parallelogram shape with the CoII cations at the corners, linked in one direction (horizontally in Fig. 2) by the bpe1 bridges and in the opposite one (vertically in Fig. 2) by H2btc groups. For clarity, Fig. 2 has been drawn in a `channelling' view, along the crystallographic b axis. However, the two-dimensional structures are not parallel to the projection plane but run in a slanted manner, parallel to the (111) planes instead. This particular view was chosen to make the mesh-like structure more clearly visible, as well as to make obvious the linking role of the bpe1 solvate molecule, which runs from top to bottom in Fig. 2 and acts as an acceptor of two extremely strong hydrogen bonds (see below for details) to carboxylate O—H groups in two adjacent planes (above and below the solvate), thus configuring a very tight hydrogen-bonded three-dimensional structure. Fig. 3 shows a lateral view of that presented in Fig. 2, showing the planes sideways (bold horizontal lines), connected by the interleaved bpe1 ligands, shown as weak quasi-vertical lines.
A completely analogous two-dimensional motif has recently been reported in poly[[diaquacobalt(II)]-µ-2,5-dicarboxybenzene-1,4-dicarboxylato-µ-di-4- pyridylethene (Xing & Li, 2006), [Co(H2btc)(L)(H2O)2], (III), which uses the same ligands disposed in a topologically similar way but does not have the additional L solvate ligand as in (I). This results in a comparable two-dimensional structure characterized by a unit mesh motif of 13.681 (1) × 11.420 (1) Å, 106.7 (1)°, compared with 13.578 (1) × 11.296 (1) Å, 101.5 (1)°, for (I) and 13.567 (1) × 11.201 (1) Å, 109.9 (1)°, for (II). This metric conservation suggests that the two-dimensional structure might be considered a robust building layer, in particular when other parameters in the corresponding structures are significantly different. There is nothing occupying the interplanar space in (III) and neighbouring planes are simply linked by strong hydrogen bonds mediated by the coordinated water molecules. This leads to an extremely short interplanar spacing of 3.18 (1) Å. In compounds (I) and (II), the planes are supported by slanting L molecules [the N···N axes subtend to the plane normals angles of 66.1 (1)° in (I) and 65.88 (1) in (II)], leading to interplanar spacings of 5.118 (1) and 5.052 (1) Å, respectively. This suggests that the planes might `sandwich' a variety of different molecules in a pre-designed fashion and so be a potentially useful tool for use in molecular engineering.
The hydrogen bond linking atoms O33 and N12 deserves some attention. In both (I) and (II) it presents the same delocalized character, with the H atom `shared' by both eventual donor/acceptor atoms. Difference map plots show these H atoms with prolate spheroid shapes in both cases, and free refinement of the low-temperature data takes atom H33A quite close to the midpoint between atoms O33 (the expected donor) and N12 (the expected acceptor). In the case of (I), the H atom lies even slightly nearer to N12 (Table 3). These hydrogen bonds might be considered a measure of the strength of the interaction and, accordingly, of the stability of the three-dimensional structure derived from it.
In order to assess how common this kind of D—H—A interaction could be, we looked for comparable cases in the Cambridge Structural Database (CSD, Version?; Allen, 2002) where the D—H···A hydrogen bond could be described as a hard D—H—A synthon with the H atom simultaneously bound to both neighbours. Very often (about 50% of the situations found), the whole group appears to be riding on a special position (inversion centre or twofold axis), thus forcing D and A to be of the same species with the bridging H atom appearing midway, on the special position. The most frequent case is that in which D = A = O (337 cases), followed by D = A = N (28 cases). However, the case with D = O and A = N (reported here) appears just twice, and in one of the occurrences, bis(1,2-bis(4-pyridyl)ethene (2R,3R)-tartaric acid (2R,3R)-tartrate (Farrell et al., 2002), the N atom corresponds to the bpe1 ligand, as in (I) reported here. The other case is 4-methylpyridine pentachlorophenol (Steiner et al., 2001).
In addition to the short O···H···N hydrogen bonds found in both (I) and (II), there are strong hydrogen bonds (H···O = 1.86–1.92 Å) involving the water H atoms and the uncoordinated H2btc carboxylate O atoms which, being internal to the two-dimensional structures, contribute even further to their overall stability (Fig. 1 and Tables 2 and 4).