Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111043551/gg3260sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111043551/gg3260Isup2.hkl |
CCDC reference: 855956
An aqueous solution (50 ml) of cobalt(II) acetate (0,164 g, 6.6 mmol) was added to a solution of benzene-1,2,4,5-tetracarboxylic acid (0.168 g, 6.6 mmol) and 4,4-trimethylenedipyridine (0.130 g, 6.6 mmol) in a mixture of ethanol–water (250 ml), which had previously been stirred under reflux for 30 min. The reaction mixture was heated under reflux for 2 h. Single crystals adequate for X-ray diffraction studies were obtained by slow evaporation at room temperature. All reagents and solvents were commercially available and used without additional purification. Elemental analysis was performed with a Carlo–Erba 1108 analyser. Analysis required: C 51.39, H 4.97, N 6.09, O 29.00, Co 8.55%; found: C 51.8, H 4.9, N 6.0, O 28.8, Co 8.6%.
All H atoms were clearly visible in difference Fourier maps. They were, however, treated differently. C—H hydrogens were repositioned at their expected locations, and allowed to ride with respect to both coordinates (C—H = 0.93 and 0.99 Å) and isotropic displacement parameters [Uiso(H) = 1.2Ueq(host)]. Those attached to O and N atoms were refined freely. As already stated, the three bpp groups evolve around different twofold axes; in units 2 and 4 the symmetry element passes through the central C atom, and thus the molecules have genuine C2 symmetry, while unit 3 is so only on average, disordered around the symmetry element. This disorder takes place in such a way as to have the two lateral bpy groups reasonably well defined, while linked by a disordered propane group split into two separate components of equal occupancy.
Data collection: SMART (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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
(C13H16N2)[Co(C10H3O8)(C13H14N2)(H2O)2]·5H2O | F(000) = 1436 |
Mr = 1379.05 | Dx = 1.499 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 8234 reflections |
a = 18.068 (4) Å | θ = 2.1–27.0° |
b = 9.346 (2) Å | µ = 0.63 mm−1 |
c = 18.209 (4) Å | T = 150 K |
β = 96.421 (6)° | Blocks, pink |
V = 3055.5 (12) Å3 | 0.36 × 0.35 × 0.17 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 6749 independent reflections |
Radiation source: fine-focus sealed tube | 5280 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
CCD rotation images, thin slices scans | θmax = 27.9°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | h = −22→23 |
Tmin = 0.79, Tmax = 0.89 | k = −11→11 |
24669 measured reflections | l = −23→23 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0636P)2 + 1.2623P] where P = (Fo2 + 2Fc2)/3 |
6749 reflections | (Δ/σ)max < 0.001 |
477 parameters | Δρmax = 0.86 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
(C13H16N2)[Co(C10H3O8)(C13H14N2)(H2O)2]·5H2O | V = 3055.5 (12) Å3 |
Mr = 1379.05 | Z = 2 |
Monoclinic, P2/n | Mo Kα radiation |
a = 18.068 (4) Å | µ = 0.63 mm−1 |
b = 9.346 (2) Å | T = 150 K |
c = 18.209 (4) Å | 0.36 × 0.35 × 0.17 mm |
β = 96.421 (6)° |
Bruker SMART CCD area-detector diffractometer | 6749 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002) | 5280 reflections with I > 2σ(I) |
Tmin = 0.79, Tmax = 0.89 | Rint = 0.029 |
24669 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.86 e Å−3 |
6749 reflections | Δρmin = −0.46 e Å−3 |
477 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Co1 | 0.5000 | 0.5000 | 0.5000 | 0.01704 (11) | |
Co2 | 0.5000 | 0.5000 | 1.0000 | 0.01864 (11) | |
C11 | 0.48876 (11) | 0.9303 (2) | 0.80253 (11) | 0.0179 (4) | |
C21 | 0.51798 (12) | 0.9948 (2) | 0.74278 (11) | 0.0189 (4) | |
H21 | 0.5147 | 1.0958 | 0.7373 | 0.023* | |
C31 | 0.55188 (11) | 0.9152 (2) | 0.69085 (11) | 0.0180 (4) | |
C41 | 0.55714 (10) | 0.7659 (2) | 0.69914 (10) | 0.0169 (4) | |
C51 | 0.53088 (11) | 0.7028 (2) | 0.76060 (10) | 0.0182 (4) | |
H51 | 0.5371 | 0.6027 | 0.7679 | 0.022* | |
C61 | 0.49583 (10) | 0.7817 (2) | 0.81157 (10) | 0.0170 (4) | |
C71 | 0.45052 (11) | 1.0234 (2) | 0.85379 (11) | 0.0188 (4) | |
C81 | 0.58081 (11) | 0.9933 (2) | 0.62667 (12) | 0.0204 (4) | |
C91 | 0.57758 (11) | 0.6627 (2) | 0.64005 (10) | 0.0167 (4) | |
C101 | 0.46370 (11) | 0.6936 (2) | 0.87045 (11) | 0.0180 (4) | |
O11 | 0.43006 (9) | 0.95596 (17) | 0.91189 (9) | 0.0275 (4) | |
H11O | 0.412 (2) | 1.019 (4) | 0.940 (2) | 0.072 (11)* | |
O21 | 0.43995 (10) | 1.15004 (16) | 0.84260 (8) | 0.0303 (4) | |
O31 | 0.55778 (10) | 1.11596 (17) | 0.61300 (10) | 0.0386 (4) | |
O41 | 0.62654 (8) | 0.92567 (16) | 0.59127 (8) | 0.0261 (3) | |
O51 | 0.52941 (8) | 0.65433 (15) | 0.58418 (7) | 0.0205 (3) | |
O61 | 0.63449 (8) | 0.58587 (15) | 0.65347 (8) | 0.0231 (3) | |
O71 | 0.40241 (8) | 0.63738 (16) | 0.85238 (8) | 0.0252 (3) | |
O81 | 0.50545 (8) | 0.67515 (15) | 0.93073 (7) | 0.0211 (3) | |
N12 | 0.42304 (10) | 0.40110 (19) | 0.56384 (9) | 0.0219 (4) | |
C12 | 0.35708 (12) | 0.3509 (2) | 0.53401 (12) | 0.0267 (5) | |
H12 | 0.3418 | 0.3702 | 0.4834 | 0.032* | |
C22 | 0.30992 (13) | 0.2720 (3) | 0.57354 (12) | 0.0295 (5) | |
H22 | 0.2631 | 0.2401 | 0.5504 | 0.035* | |
C32 | 0.33181 (12) | 0.2400 (2) | 0.64724 (12) | 0.0249 (5) | |
C42 | 0.39948 (12) | 0.2965 (2) | 0.67882 (12) | 0.0245 (5) | |
H42 | 0.4155 | 0.2810 | 0.7297 | 0.029* | |
C52 | 0.44278 (12) | 0.3745 (2) | 0.63604 (11) | 0.0244 (5) | |
H52 | 0.4888 | 0.4115 | 0.6585 | 0.029* | |
C62 | 0.28542 (13) | 0.1503 (2) | 0.69342 (13) | 0.0285 (5) | |
H62A | 0.3172 | 0.0760 | 0.7197 | 0.034* | |
H62B | 0.2457 | 0.1016 | 0.6608 | 0.034* | |
C72 | 0.2500 | 0.2426 (3) | 0.7500 | 0.0264 (7) | |
H72 | 0.2116 | 0.3049 | 0.7233 | 0.032* | |
N13 | 0.58874 (10) | 0.4057 (2) | 0.94744 (10) | 0.0267 (4) | |
C13 | 0.64402 (14) | 0.4857 (3) | 0.92498 (15) | 0.0394 (6) | |
H13 | 0.6470 | 0.5838 | 0.9387 | 0.047* | |
C23 | 0.69665 (16) | 0.4311 (4) | 0.88271 (16) | 0.0536 (8) | |
H23 | 0.7349 | 0.4913 | 0.8684 | 0.064* | |
C33 | 0.69341 (17) | 0.2887 (4) | 0.86127 (15) | 0.0578 (9) | |
C43 | 0.63620 (16) | 0.2066 (3) | 0.88507 (14) | 0.0476 (7) | |
H43 | 0.6313 | 0.1087 | 0.8713 | 0.057* | |
C53 | 0.58662 (14) | 0.2673 (3) | 0.92862 (13) | 0.0333 (5) | |
H53 | 0.5495 | 0.2082 | 0.9459 | 0.040* | |
C63A | 0.7470 (5) | 0.1788 (8) | 0.8258 (4) | 0.068 (2) | 0.50 |
H63A | 0.7824 | 0.1360 | 0.8651 | 0.082* | 0.50 |
H63B | 0.7172 | 0.1007 | 0.8005 | 0.082* | 0.50 |
C73A | 0.7900 (4) | 0.2585 (8) | 0.7702 (3) | 0.066 (2) | 0.50 |
H64C | 0.8430 | 0.2835 | 0.7836 | 0.079* | 0.50 |
H64D | 0.7706 | 0.2594 | 0.7171 | 0.079* | 0.50 |
C63B | 0.7545 (3) | 0.2613 (8) | 0.8086 (3) | 0.0466 (15) | 0.50 |
H63C | 0.7951 | 0.2572 | 0.8499 | 0.056* | 0.50 |
H63D | 0.7404 | 0.1595 | 0.8011 | 0.056* | 0.50 |
N14 | 0.33837 (10) | 0.91781 (19) | 0.51918 (10) | 0.0225 (4) | |
H14N | 0.3508 (16) | 0.977 (3) | 0.4789 (16) | 0.049 (8)* | |
C14 | 0.26605 (12) | 0.8888 (2) | 0.52268 (12) | 0.0272 (5) | |
H14 | 0.2293 | 0.9314 | 0.4881 | 0.033* | |
C24 | 0.24461 (12) | 0.7982 (2) | 0.57579 (12) | 0.0261 (5) | |
H24 | 0.1933 | 0.7778 | 0.5776 | 0.031* | |
C34 | 0.29807 (11) | 0.7362 (2) | 0.62699 (11) | 0.0196 (4) | |
C44 | 0.37223 (12) | 0.7688 (3) | 0.62167 (12) | 0.0280 (5) | |
H44 | 0.4102 | 0.7291 | 0.6560 | 0.034* | |
C54 | 0.39095 (12) | 0.8588 (3) | 0.56664 (12) | 0.0286 (5) | |
H54 | 0.4419 | 0.8788 | 0.5626 | 0.034* | |
C64 | 0.27622 (11) | 0.6424 (2) | 0.68812 (11) | 0.0211 (4) | |
H64A | 0.3194 | 0.5836 | 0.7081 | 0.025* | |
H64B | 0.2357 | 0.5770 | 0.6683 | 0.025* | |
C74 | 0.2500 | 0.7334 (3) | 0.7500 | 0.0195 (6) | |
H74 | 0.2086 | 0.7958 | 0.7291 | 0.023* | |
O1W | 0.58851 (9) | 0.37203 (18) | 0.55185 (8) | 0.0225 (3) | |
H1WA | 0.5811 (15) | 0.289 (3) | 0.5697 (15) | 0.042 (8)* | |
H1WB | 0.6096 (17) | 0.423 (4) | 0.5848 (18) | 0.052 (9)* | |
O2W | 0.41393 (9) | 0.39625 (19) | 0.92896 (9) | 0.0249 (3) | |
H2WA | 0.4003 (19) | 0.463 (4) | 0.8990 (19) | 0.060 (10)* | |
H2WB | 0.4199 (18) | 0.328 (4) | 0.9049 (18) | 0.055 (10)* | |
O3W | 0.89175 (11) | 0.88639 (18) | 0.52078 (9) | 0.0314 (4) | |
H3WA | 0.9245 (17) | 0.822 (3) | 0.5367 (16) | 0.049 (9)* | |
H3WB | 0.8595 (18) | 0.876 (3) | 0.5461 (17) | 0.054 (10)* | |
O4W | 0.77770 (12) | 0.8425 (3) | 0.61098 (14) | 0.0554 (6) | |
H4WA | 0.781 (2) | 0.821 (4) | 0.653 (2) | 0.083 (14)* | |
H4WB | 0.7302 (19) | 0.860 (3) | 0.6073 (17) | 0.054 (9)* | |
O5W | 0.7500 | 0.7177 (3) | 0.7500 | 0.0312 (5) | |
H5W | 0.7834 (17) | 0.672 (3) | 0.7726 (18) | 0.058 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0193 (2) | 0.0179 (2) | 0.0144 (2) | −0.00045 (15) | 0.00410 (15) | 0.00164 (14) |
Co2 | 0.0219 (2) | 0.0172 (2) | 0.0168 (2) | −0.00188 (15) | 0.00214 (15) | 0.00409 (14) |
C11 | 0.0192 (9) | 0.0179 (10) | 0.0168 (9) | 0.0009 (8) | 0.0026 (8) | −0.0003 (7) |
C21 | 0.0218 (10) | 0.0162 (10) | 0.0186 (10) | −0.0014 (8) | 0.0015 (8) | 0.0021 (7) |
C31 | 0.0184 (9) | 0.0188 (10) | 0.0170 (9) | −0.0010 (8) | 0.0027 (8) | 0.0036 (8) |
C41 | 0.0157 (9) | 0.0189 (10) | 0.0157 (9) | 0.0006 (8) | 0.0005 (7) | −0.0004 (7) |
C51 | 0.0214 (10) | 0.0152 (10) | 0.0181 (10) | 0.0003 (8) | 0.0024 (8) | 0.0018 (7) |
C61 | 0.0170 (9) | 0.0195 (10) | 0.0144 (9) | −0.0008 (8) | 0.0012 (7) | 0.0017 (7) |
C71 | 0.0213 (10) | 0.0209 (10) | 0.0140 (9) | 0.0006 (8) | 0.0008 (8) | −0.0010 (8) |
C81 | 0.0196 (10) | 0.0203 (11) | 0.0218 (10) | −0.0012 (8) | 0.0052 (8) | 0.0031 (8) |
C91 | 0.0198 (9) | 0.0155 (9) | 0.0157 (9) | −0.0020 (8) | 0.0057 (8) | 0.0029 (7) |
C101 | 0.0210 (10) | 0.0151 (9) | 0.0186 (10) | 0.0037 (8) | 0.0055 (8) | 0.0003 (7) |
O11 | 0.0394 (9) | 0.0209 (8) | 0.0254 (8) | 0.0044 (7) | 0.0176 (7) | 0.0011 (6) |
O21 | 0.0520 (10) | 0.0187 (8) | 0.0218 (8) | 0.0080 (7) | 0.0111 (7) | 0.0013 (6) |
O31 | 0.0505 (10) | 0.0255 (9) | 0.0450 (10) | 0.0105 (8) | 0.0283 (9) | 0.0171 (8) |
O41 | 0.0281 (8) | 0.0271 (8) | 0.0255 (8) | 0.0034 (6) | 0.0133 (6) | 0.0065 (6) |
O51 | 0.0229 (7) | 0.0208 (7) | 0.0180 (7) | 0.0008 (6) | 0.0033 (6) | −0.0005 (5) |
O61 | 0.0227 (7) | 0.0245 (8) | 0.0219 (7) | 0.0055 (6) | 0.0019 (6) | −0.0006 (6) |
O71 | 0.0216 (7) | 0.0277 (8) | 0.0261 (8) | −0.0027 (6) | 0.0016 (6) | 0.0088 (6) |
O81 | 0.0260 (7) | 0.0200 (7) | 0.0171 (7) | −0.0024 (6) | 0.0011 (6) | 0.0042 (5) |
N12 | 0.0253 (9) | 0.0231 (9) | 0.0181 (8) | −0.0005 (7) | 0.0064 (7) | 0.0009 (7) |
C12 | 0.0288 (11) | 0.0328 (12) | 0.0193 (10) | −0.0015 (10) | 0.0056 (9) | 0.0017 (9) |
C22 | 0.0311 (12) | 0.0336 (13) | 0.0250 (11) | −0.0075 (10) | 0.0079 (9) | −0.0042 (9) |
C32 | 0.0320 (11) | 0.0202 (11) | 0.0251 (11) | 0.0011 (9) | 0.0150 (9) | −0.0017 (8) |
C42 | 0.0288 (11) | 0.0270 (11) | 0.0189 (10) | 0.0048 (9) | 0.0080 (9) | 0.0049 (8) |
C52 | 0.0249 (10) | 0.0293 (12) | 0.0193 (10) | 0.0018 (9) | 0.0036 (8) | 0.0000 (8) |
C62 | 0.0369 (12) | 0.0237 (11) | 0.0284 (12) | −0.0044 (10) | 0.0187 (10) | −0.0030 (9) |
C72 | 0.0292 (16) | 0.0241 (16) | 0.0285 (16) | 0.000 | 0.0152 (13) | 0.000 |
N13 | 0.0281 (9) | 0.0255 (10) | 0.0271 (10) | 0.0034 (8) | 0.0062 (8) | 0.0061 (8) |
C13 | 0.0340 (13) | 0.0371 (14) | 0.0494 (16) | 0.0049 (11) | 0.0147 (12) | 0.0168 (12) |
C23 | 0.0417 (15) | 0.080 (2) | 0.0425 (16) | 0.0169 (15) | 0.0209 (13) | 0.0290 (16) |
C33 | 0.0521 (18) | 0.100 (3) | 0.0218 (13) | 0.0366 (18) | 0.0056 (12) | −0.0020 (15) |
C43 | 0.0513 (17) | 0.0554 (18) | 0.0323 (14) | 0.0236 (14) | −0.0121 (13) | −0.0171 (13) |
C53 | 0.0361 (13) | 0.0318 (13) | 0.0301 (12) | 0.0058 (10) | −0.0047 (10) | 0.0002 (10) |
C63A | 0.117 (7) | 0.044 (4) | 0.055 (4) | −0.006 (4) | 0.062 (4) | 0.009 (3) |
C73A | 0.077 (4) | 0.094 (5) | 0.034 (3) | −0.012 (4) | 0.039 (3) | 0.011 (3) |
C63B | 0.046 (3) | 0.062 (4) | 0.035 (3) | −0.009 (3) | 0.018 (3) | −0.020 (3) |
N14 | 0.0255 (9) | 0.0244 (10) | 0.0189 (9) | 0.0012 (7) | 0.0081 (7) | 0.0032 (7) |
C14 | 0.0220 (10) | 0.0336 (12) | 0.0261 (11) | 0.0032 (9) | 0.0025 (9) | 0.0066 (9) |
C24 | 0.0187 (10) | 0.0336 (12) | 0.0263 (11) | −0.0016 (9) | 0.0034 (9) | 0.0043 (9) |
C34 | 0.0234 (10) | 0.0205 (10) | 0.0160 (9) | 0.0024 (8) | 0.0068 (8) | −0.0032 (8) |
C44 | 0.0205 (10) | 0.0415 (14) | 0.0220 (11) | 0.0029 (10) | 0.0023 (9) | 0.0073 (9) |
C54 | 0.0182 (10) | 0.0406 (14) | 0.0275 (12) | −0.0001 (9) | 0.0048 (9) | 0.0057 (10) |
C64 | 0.0236 (10) | 0.0219 (10) | 0.0189 (10) | 0.0022 (8) | 0.0074 (8) | 0.0012 (8) |
C74 | 0.0205 (14) | 0.0210 (14) | 0.0173 (13) | 0.000 | 0.0043 (11) | 0.000 |
O1W | 0.0275 (8) | 0.0188 (8) | 0.0216 (8) | −0.0001 (6) | 0.0039 (6) | 0.0028 (6) |
O2W | 0.0322 (8) | 0.0190 (8) | 0.0229 (8) | −0.0018 (7) | 0.0005 (7) | 0.0025 (7) |
O3W | 0.0370 (9) | 0.0306 (9) | 0.0292 (9) | 0.0103 (8) | 0.0151 (8) | 0.0116 (7) |
O4W | 0.0320 (11) | 0.0792 (16) | 0.0588 (14) | 0.0182 (10) | 0.0219 (10) | 0.0417 (12) |
O5W | 0.0289 (13) | 0.0325 (13) | 0.0303 (13) | 0.000 | −0.0045 (11) | 0.000 |
Co1—N12 | 2.1215 (17) | C72—H72 | 0.9899 |
Co1—N12i | 2.1215 (17) | N13—C53 | 1.337 (3) |
Co1—O51 | 2.1285 (14) | N13—C13 | 1.347 (3) |
Co1—O51i | 2.1285 (14) | C13—C23 | 1.386 (4) |
Co1—O1Wi | 2.1312 (15) | C13—H13 | 0.9500 |
Co1—O1W | 2.1312 (15) | C23—C33 | 1.386 (5) |
Co2—O81 | 2.0755 (14) | C23—H23 | 0.9500 |
Co2—O81ii | 2.0755 (14) | C33—C43 | 1.395 (5) |
Co2—O2W | 2.1406 (16) | C33—C63B | 1.563 (6) |
Co2—O2Wii | 2.1406 (16) | C33—C63A | 1.597 (8) |
Co2—N13 | 2.1463 (19) | C43—C53 | 1.383 (4) |
Co2—N13ii | 2.1463 (19) | C43—H43 | 0.9500 |
C11—C21 | 1.398 (3) | C53—H53 | 0.9500 |
C11—C61 | 1.403 (3) | C63A—C73A | 1.536 (8) |
C11—C71 | 1.500 (3) | C63A—H63A | 0.9900 |
C21—C31 | 1.397 (3) | C63A—H63B | 0.9900 |
C21—H21 | 0.9500 | C73A—C63Biv | 1.565 (9) |
C31—C41 | 1.406 (3) | C63B—C33 | 1.563 (8) |
C31—C81 | 1.519 (3) | C73A—H64C | 0.9900 |
C41—C51 | 1.394 (3) | C73A—H64D | 0.9900 |
C41—C91 | 1.521 (3) | C63B—H63C | 0.9900 |
C51—C61 | 1.392 (3) | C63B—H63D | 0.9900 |
C51—H51 | 0.9500 | N14—C54 | 1.330 (3) |
C61—C101 | 1.518 (3) | N14—C14 | 1.343 (3) |
C71—O21 | 1.212 (2) | N14—H14N | 0.96 (3) |
C71—O11 | 1.319 (2) | C14—C24 | 1.374 (3) |
C81—O31 | 1.235 (2) | C14—H14 | 0.9500 |
C81—O41 | 1.272 (3) | C24—C34 | 1.392 (3) |
C91—O61 | 1.256 (2) | C24—H24 | 0.9500 |
C91—O51 | 1.265 (2) | C34—C44 | 1.388 (3) |
C101—O71 | 1.237 (2) | C34—C64 | 1.503 (3) |
C101—O81 | 1.272 (2) | C44—C54 | 1.379 (3) |
O11—H11O | 0.87 (4) | C44—H44 | 0.9500 |
N12—C12 | 1.338 (3) | C54—H54 | 0.9500 |
N12—C52 | 1.346 (3) | C64—C74 | 1.529 (3) |
C12—C22 | 1.388 (3) | C64—H64A | 0.9900 |
C12—H12 | 0.9500 | C64—H64B | 0.9900 |
C22—C32 | 1.388 (3) | C74—C64iii | 1.529 (3) |
C22—H22 | 0.9500 | C74—H74 | 0.9901 |
C32—C42 | 1.395 (3) | O1W—H1WA | 0.86 (3) |
C32—C62 | 1.507 (3) | O1W—H1WB | 0.82 (3) |
C42—C52 | 1.374 (3) | O2W—H2WA | 0.85 (4) |
C42—H42 | 0.9500 | O2W—H2WB | 0.78 (3) |
C52—H52 | 0.9500 | O3W—H3WA | 0.87 (3) |
C62—C72 | 1.537 (3) | O3W—H3WB | 0.79 (3) |
C62—H62A | 0.9900 | O4W—H4WA | 0.79 (4) |
C62—H62B | 0.9900 | O4W—H4WB | 0.87 (3) |
C72—C62iii | 1.537 (3) | O5W—H5W | 0.81 (3) |
N12—Co1—N12i | 180.0 | C22—C32—C62 | 122.9 (2) |
N12—Co1—O51 | 91.53 (6) | C42—C32—C62 | 119.8 (2) |
N12i—Co1—O51 | 88.47 (6) | C52—C42—C32 | 119.7 (2) |
N12—Co1—O51i | 88.47 (6) | C52—C42—H42 | 120.2 |
N12i—Co1—O51i | 91.53 (6) | C32—C42—H42 | 120.2 |
O51—Co1—O51i | 180.0 | N12—C52—C42 | 123.1 (2) |
N12—Co1—O1Wi | 88.96 (6) | N12—C52—H52 | 118.4 |
N12i—Co1—O1Wi | 91.04 (6) | C42—C52—H52 | 118.4 |
O51—Co1—O1Wi | 93.06 (6) | C32—C62—C72 | 111.18 (19) |
O51i—Co1—O1Wi | 86.94 (6) | C32—C62—H62A | 109.4 |
N12—Co1—O1W | 91.04 (6) | C72—C62—H62A | 109.4 |
N12i—Co1—O1W | 88.96 (6) | C32—C62—H62B | 109.4 |
O51—Co1—O1W | 86.94 (6) | C72—C62—H62B | 109.4 |
O51i—Co1—O1W | 93.06 (6) | H62A—C62—H62B | 108.0 |
O1Wi—Co1—O1W | 180.00 (8) | C62—C72—C62iii | 111.7 (3) |
O81—Co2—O81ii | 180.000 (1) | C62—C72—H72 | 108.8 |
O81—Co2—O2W | 94.05 (6) | C62iii—C72—H72 | 109.7 |
O81ii—Co2—O2W | 85.95 (6) | C53—N13—C13 | 117.4 (2) |
O81—Co2—O2Wii | 85.95 (6) | C53—N13—Co2 | 120.65 (16) |
O81ii—Co2—O2Wii | 94.05 (6) | C13—N13—Co2 | 121.58 (16) |
O2W—Co2—O2Wii | 180.000 (1) | N13—C13—C23 | 122.8 (3) |
O81—Co2—N13 | 87.95 (6) | N13—C13—H13 | 118.6 |
O81ii—Co2—N13 | 92.05 (6) | C23—C13—H13 | 118.6 |
O2W—Co2—N13 | 94.19 (7) | C13—C23—C33 | 120.0 (3) |
O2Wii—Co2—N13 | 85.81 (7) | C13—C23—H23 | 120.0 |
O81—Co2—N13ii | 92.05 (6) | C33—C23—H23 | 120.0 |
O81ii—Co2—N13ii | 87.95 (6) | C23—C33—C43 | 116.8 (3) |
O2W—Co2—N13ii | 85.81 (7) | C23—C33—C63B | 108.7 (4) |
O2Wii—Co2—N13ii | 94.19 (7) | C43—C33—C63B | 134.4 (4) |
C21—C11—C61 | 118.75 (18) | C23—C33—C63A | 136.3 (4) |
C21—C11—C71 | 118.32 (18) | C43—C33—C63A | 106.0 (4) |
C61—C11—C71 | 122.93 (17) | C53—C43—C33 | 120.2 (3) |
C31—C21—C11 | 121.97 (18) | C53—C43—H43 | 119.9 |
C31—C21—H21 | 119.0 | C33—C43—H43 | 119.9 |
C11—C21—H21 | 119.0 | N13—C53—C43 | 122.8 (3) |
C21—C31—C41 | 119.03 (18) | N13—C53—H53 | 118.6 |
C21—C31—C81 | 118.66 (17) | C43—C53—H53 | 118.6 |
C41—C31—C81 | 122.31 (18) | C54—N14—C14 | 120.89 (19) |
C51—C41—C31 | 118.74 (18) | C54—N14—H14N | 121.4 (18) |
C51—C41—C91 | 115.54 (17) | C14—N14—H14N | 117.5 (18) |
C31—C41—C91 | 124.92 (17) | N14—C14—C24 | 120.7 (2) |
C61—C51—C41 | 122.18 (18) | N14—C14—H14 | 119.7 |
C61—C51—H51 | 118.9 | C24—C14—H14 | 119.7 |
C41—C51—H51 | 118.9 | C14—C24—C34 | 119.9 (2) |
C51—C61—C11 | 119.22 (18) | C14—C24—H24 | 120.0 |
C51—C61—C101 | 114.99 (17) | C34—C24—H24 | 120.0 |
C11—C61—C101 | 125.66 (17) | C44—C34—C24 | 117.70 (19) |
O21—C71—O11 | 123.24 (19) | C44—C34—C64 | 121.01 (18) |
O21—C71—C11 | 122.45 (18) | C24—C34—C64 | 121.23 (18) |
O11—C71—C11 | 114.31 (17) | C54—C44—C34 | 120.1 (2) |
O31—C81—O41 | 125.62 (19) | C54—C44—H44 | 119.9 |
O31—C81—C31 | 117.62 (18) | C34—C44—H44 | 119.9 |
O41—C81—C31 | 116.76 (17) | N14—C54—C44 | 120.6 (2) |
O61—C91—O51 | 126.58 (18) | N14—C54—H54 | 119.7 |
O61—C91—C41 | 118.90 (17) | C44—C54—H54 | 119.7 |
O51—C91—C41 | 114.11 (17) | C34—C64—C74 | 110.51 (17) |
O71—C101—O81 | 126.78 (18) | C34—C64—H64A | 109.5 |
O71—C101—C61 | 116.39 (17) | C74—C64—H64A | 109.5 |
O81—C101—C61 | 116.52 (17) | C34—C64—H64B | 109.5 |
C71—O11—H11O | 108 (2) | C74—C64—H64B | 109.5 |
C91—O51—Co1 | 135.64 (13) | H64A—C64—H64B | 108.1 |
C101—O81—Co2 | 124.58 (13) | C64—C74—C64iii | 112.4 (2) |
C12—N12—C52 | 117.30 (18) | C64—C74—H74 | 109.1 |
C12—N12—Co1 | 122.60 (14) | C64iii—C74—H74 | 109.1 |
C52—N12—Co1 | 119.81 (14) | Co1—O1W—H1WA | 122.3 (19) |
N12—C12—C22 | 123.1 (2) | Co1—O1W—H1WB | 105 (2) |
N12—C12—H12 | 118.4 | H1WA—O1W—H1WB | 109 (3) |
C22—C12—H12 | 118.4 | Co2—O2W—H2WA | 101 (2) |
C12—C22—C32 | 119.4 (2) | Co2—O2W—H2WB | 125 (2) |
C12—C22—H22 | 120.3 | H2WA—O2W—H2WB | 106 (3) |
C32—C22—H22 | 120.3 | H3WA—O3W—H3WB | 104 (3) |
C22—C32—C42 | 117.3 (2) | H4WA—O4W—H4WB | 95 (3) |
C61—C11—C21—C31 | 1.9 (3) | O1W—Co1—N12—C12 | −132.00 (17) |
C71—C11—C21—C31 | −177.49 (18) | O51—Co1—N12—C52 | −45.38 (16) |
C11—C21—C31—C41 | −0.4 (3) | O51i—Co1—N12—C52 | 134.62 (16) |
C11—C21—C31—C81 | 178.78 (18) | O1Wi—Co1—N12—C52 | −138.41 (16) |
C21—C31—C41—C51 | −2.5 (3) | O1W—Co1—N12—C52 | 41.59 (16) |
C81—C31—C41—C51 | 178.44 (18) | C52—N12—C12—C22 | −1.2 (3) |
C21—C31—C41—C91 | 166.84 (18) | Co1—N12—C12—C22 | 172.53 (17) |
C81—C31—C41—C91 | −12.3 (3) | N12—C12—C22—C32 | −1.3 (4) |
C31—C41—C51—C61 | 3.8 (3) | C12—C22—C32—C42 | 3.3 (3) |
C91—C41—C51—C61 | −166.48 (17) | C12—C22—C32—C62 | −177.6 (2) |
C41—C51—C61—C11 | −2.2 (3) | C22—C32—C42—C52 | −2.9 (3) |
C41—C51—C61—C101 | 173.89 (17) | C62—C32—C42—C52 | 178.0 (2) |
C21—C11—C61—C51 | −0.7 (3) | C12—N12—C52—C42 | 1.6 (3) |
C71—C11—C61—C51 | 178.74 (18) | Co1—N12—C52—C42 | −172.28 (16) |
C21—C11—C61—C101 | −176.33 (18) | C32—C42—C52—N12 | 0.4 (3) |
C71—C11—C61—C101 | 3.1 (3) | C22—C32—C62—C72 | −107.5 (2) |
C21—C11—C71—O21 | 4.8 (3) | C42—C32—C62—C72 | 71.5 (2) |
C61—C11—C71—O21 | −174.6 (2) | C32—C62—C72—C62iii | −169.6 (2) |
C21—C11—C71—O11 | −174.72 (18) | O81—Co2—N13—C53 | −136.85 (17) |
C61—C11—C71—O11 | 5.9 (3) | O81ii—Co2—N13—C53 | 43.15 (17) |
C21—C31—C81—O31 | −17.1 (3) | O2W—Co2—N13—C53 | −42.94 (17) |
C41—C31—C81—O31 | 162.0 (2) | O2Wii—Co2—N13—C53 | 137.06 (17) |
C21—C31—C81—O41 | 163.35 (19) | O81—Co2—N13—C13 | 35.79 (19) |
C41—C31—C81—O41 | −17.5 (3) | O81ii—Co2—N13—C13 | −144.21 (19) |
C51—C41—C91—O61 | −70.7 (2) | O2W—Co2—N13—C13 | 129.71 (19) |
C31—C41—C91—O61 | 119.7 (2) | O2Wii—Co2—N13—C13 | −50.29 (19) |
C51—C41—C91—O51 | 102.5 (2) | C53—N13—C13—C23 | 1.3 (4) |
C31—C41—C91—O51 | −67.1 (2) | Co2—N13—C13—C23 | −171.6 (2) |
C51—C61—C101—O71 | −80.8 (2) | N13—C13—C23—C33 | 0.5 (4) |
C11—C61—C101—O71 | 95.0 (2) | C13—C23—C33—C43 | −0.8 (4) |
C51—C61—C101—O81 | 93.2 (2) | C13—C23—C33—C63B | 174.8 (3) |
C11—C61—C101—O81 | −91.0 (2) | C13—C23—C33—C63A | −167.8 (5) |
O61—C91—O51—Co1 | 15.8 (3) | C23—C33—C43—C53 | −0.7 (4) |
C41—C91—O51—Co1 | −156.75 (13) | C13—N13—C53—C43 | −2.9 (3) |
N12—Co1—O51—C91 | 90.11 (18) | Co2—N13—C53—C43 | 170.02 (18) |
N12i—Co1—O51—C91 | −89.89 (18) | C33—C43—C53—N13 | 2.7 (4) |
O1Wi—Co1—O51—C91 | 179.15 (18) | C54—N14—C14—C24 | 0.5 (3) |
O1W—Co1—O51—C91 | −0.85 (18) | N14—C14—C24—C34 | 0.4 (3) |
O71—C101—O81—Co2 | 21.1 (3) | C14—C24—C34—C44 | −0.4 (3) |
C61—C101—O81—Co2 | −152.18 (13) | C14—C24—C34—C64 | 176.9 (2) |
O2W—Co2—O81—C101 | 2.34 (16) | C24—C34—C44—C54 | −0.6 (3) |
O2Wii—Co2—O81—C101 | −177.66 (16) | C64—C34—C44—C54 | −177.8 (2) |
N13—Co2—O81—C101 | 96.39 (16) | C14—N14—C54—C44 | −1.5 (3) |
N13ii—Co2—O81—C101 | −83.61 (16) | C34—C44—C54—N14 | 1.5 (4) |
O51—Co1—N12—C12 | 141.03 (17) | C44—C34—C64—C74 | 99.3 (2) |
O51i—Co1—N12—C12 | −38.97 (17) | C24—C34—C64—C74 | −77.8 (2) |
O1Wi—Co1—N12—C12 | 48.00 (17) | C34—C64—C74—C64iii | 177.37 (19) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) −x+1/2, y, −z+3/2; (iv) −x+3/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11O···O3Wv | 0.87 (4) | 1.79 (4) | 2.625 (2) | 161 (3) |
N14—H14N···O41vi | 0.96 (3) | 1.66 (3) | 2.621 (2) | 178 (3) |
O1W—H1WA···O31vii | 0.86 (3) | 1.87 (3) | 2.723 (2) | 175 (3) |
O1W—H1WB···O61 | 0.82 (3) | 1.99 (3) | 2.786 (2) | 162 (3) |
O2W—H2WA···O71 | 0.85 (4) | 1.84 (4) | 2.646 (2) | 158 (3) |
O2W—H2WB···O21vii | 0.78 (3) | 2.07 (4) | 2.855 (2) | 178 (3) |
O3W—H3WA···O81iv | 0.87 (3) | 1.91 (3) | 2.786 (2) | 178 (3) |
O3W—H3WB···O4W | 0.79 (3) | 2.02 (3) | 2.805 (3) | 178 (3) |
O4W—H4WA···O5W | 0.79 (4) | 2.14 (4) | 2.882 (2) | 157 (4) |
O4W—H4WB···O41 | 0.87 (3) | 1.96 (3) | 2.824 (3) | 172 (3) |
O5W—H5W···O61iv | 0.81 (3) | 2.05 (3) | 2.8535 (19) | 169 (3) |
Symmetry codes: (iv) −x+3/2, y, −z+3/2; (v) x−1/2, −y+2, z+1/2; (vi) −x+1, −y+2, −z+1; (vii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | (C13H16N2)[Co(C10H3O8)(C13H14N2)(H2O)2]·5H2O |
Mr | 1379.05 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 150 |
a, b, c (Å) | 18.068 (4), 9.346 (2), 18.209 (4) |
β (°) | 96.421 (6) |
V (Å3) | 3055.5 (12) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.63 |
Crystal size (mm) | 0.36 × 0.35 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-NT; Bruker, 2002) |
Tmin, Tmax | 0.79, 0.89 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24669, 6749, 5280 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.115, 1.03 |
No. of reflections | 6749 |
No. of parameters | 477 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.86, −0.46 |
Computer programs: SMART (Bruker, 2001), SAINT-NT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11O···O3Wi | 0.87 (4) | 1.79 (4) | 2.625 (2) | 161 (3) |
N14—H14N···O41ii | 0.96 (3) | 1.66 (3) | 2.621 (2) | 178 (3) |
O1W—H1WA···O31iii | 0.86 (3) | 1.87 (3) | 2.723 (2) | 175 (3) |
O1W—H1WB···O61 | 0.82 (3) | 1.99 (3) | 2.786 (2) | 162 (3) |
O2W—H2WA···O71 | 0.85 (4) | 1.84 (4) | 2.646 (2) | 158 (3) |
O2W—H2WB···O21iii | 0.78 (3) | 2.07 (4) | 2.855 (2) | 178 (3) |
O3W—H3WA···O81iv | 0.87 (3) | 1.91 (3) | 2.786 (2) | 178 (3) |
O3W—H3WB···O4W | 0.79 (3) | 2.02 (3) | 2.805 (3) | 178 (3) |
O4W—H4WA···O5W | 0.79 (4) | 2.14 (4) | 2.882 (2) | 157 (4) |
O4W—H4WB···O41 | 0.87 (3) | 1.96 (3) | 2.824 (3) | 172 (3) |
O5W—H5W···O61iv | 0.81 (3) | 2.05 (3) | 2.8535 (19) | 169 (3) |
Symmetry codes: (i) x−1/2, −y+2, z+1/2; (ii) −x+1, −y+2, −z+1; (iii) x, y−1, z; (iv) −x+3/2, y, −z+3/2. |
Multidentate ligands are basic in the design of metal–organic coordination polymers, not only because they can produce unexpected structural motifs (Archer, 2001), but also because the resulting compounds may contain some interesting properties with potential applications as functional materials (Kitagawa et al., 2004; Kondo et al., 1997; Fujita et al., 1994; Yoghi et al., 2001). Some of the properties analysed in these ligands are flexibility and multidenticity, which when adequately combined in the same compound often lead to intriguing structural topologies. 1,3-Bis(4-pyridyl)propane (bpp) is an excellent example of the first group. The ligand, an analogue of 4,4'-bipyridine, possesses variable flexibility and functionality owing to the introduction of three methylene groups between the two pyridine (py) rings (Zhang et al., 2010; Carlucci et al., 1997; Plater et al., 2000). Its binding diversity is limited, since it can present only two possible coordination modes, viz. either through its two pyridine N atoms [by far the most frequent one, accounting for an overwhelming 95% of the reported cases in the CSD (Cambridge Structural Database) (Allen, 2002)], or just through one of them. But even within this almost unique µ2-mode the flexibility allowed by the central (saturated) bridge allows for at least two different conformations, very clearly differentiated by their internal N···N distance: (a) bridging, covering more than 90% of the entries in the CSD and the ligand displaying a fully stretched geometry, reflected in an N···N range of 7.5–10.5 Å and (b) chelating, with the ligand heavily bent onto itself. Even if this second group is in the minority, there is a clear bimodal distribution of N···N distances within the group: a subgroup falling into an N···N range of 5.5–6.5 Å, displaying a rather `twisted' chelating geometry with no direct interaction between offset py groups, and the conformation with an N···N range of 3.8–4.2 Å, which could be termed face-to-face chelating with a clear π–π interaction between stacking py groups.
On the other hand, benzene-1,2,4,5-tetracarboxylic acid (H4btc) is an outstanding representative of multidentate ligands with eight possible active sites available for coordination and/or hydrogen bonding (Chu et al., 2001; Rochon Fernande & Massarweh, 2000; Bok et al., 2005). In addition, the rotational degree of freedom of its four carboxyate groups gives the ligand an astonishing variety of binding modes, in a surprising mixture of bridging and chelation. It was clear then that the simultaneous presence of these two ingredients in a single complex should in principle give rise to interesting (and at the same time unpredictable) crystal structures, and therefore we decided to investigate the system. We report herein our first successful result, the cobalt(II) title polymeric complex formulated as {(H2bpp)[Co(Hbtc)(bpp)(H2O)2]2.5H2O}n, (I).
Fig. 1 presents the asymmetric unit of (I), which consists of two independent metal ions residing on two different centres of symmetry, two halves of coordinated bpp ligands, two coordinated water molecules and one singly protonated Hbtc. The halving of both coordinated bpp ligands takes place by way of two different twofold rotation axes: in unit 2 (as defined by its trailing number in Fig. 1) the axis bisects the central propane C atom, and thus defines a true symmetry for the ligand, while in unit 3 (after its trailing number in Fig. 1) this is just an `average symmetry' built up around a disordered central propane group (in broken lines in Fig. 1) (see Refinement for details). The independent set is completed by half of a doubly protonated H2bpp2+ cation (hereafter unit 4) also split through the central propane atoms by the same twofold axis halving unit 2, and two and a half water solvates. Fig. 1 presents the minimum formula unit having chemical sense, formulated as (H2bpp)[Co(Hbtc)(bpp)(H2O)2]2.5H2O; in this figure, the effect of the symmetry operations involved (1 on Co1, Co2, a twofold rotation through C72, C74 and O5W, on one side and C73'' on the other) is apparent. Both CoII cations present similar CoN2O4 octahedral environments, with the same ligands: one N from bpp, one O from Hbtec and one aqua molecule, plus their symmetry-related counterparts. The octahedra are quite regular and display similar mean Co—O/N distances [with ranges from 2.1215 (14) to 2.1463 (19) Å], apart from Co2—O81 = 2.0755 (14) Å. The maximum angular deviations from 90° for cis coordination angles are also larger for Co2 [3.06 (6) and 4.18 (7)°, respectively]. All three ligands (one Hbtc and two bpp) act in a similar µ2-bridging mode: the two bpp ones in the usual role as a spacer, through the two outermost N atoms; the Hbtc3- anion, binding laterally through two, noncontiguous carboxylates and `offering' the opposite side for hydrogen bonding. This µ2,κO,O' mode in Hnbtc (n = 0–4) is found rather infrequently in the literature: a search of the CSD (Version 5.3; Allen, 2002) showed 309 complexes having the group as a ligand, with only four of them presenting this binding mode. On the other hand, the µ2,κN,N' mode in bpp is by far the most most common: 379 cases out of 403 complexes (CSD) exhibit this mode. The averaging effect of resonance in the C—O distances in the non-protonated carboxylates is uneven, though clear, with percentage C—O bond differences of 0.4, 2.6 and 2.8%, as compared with 8.0% for the protonated one.
The crystal structure can be described as an anionic two-dimensional mesh characterized by a [Co(H2O)2(bpp)(Hbtc)]2-2 motif, with interspersed (H2bpp)2+ cations and water molecules providing for charge balance and structure stabilization. The grid consists of two independent types of [Co(H2O)2]2+ nodes (lying on inversion centres), interconnected along the [101] direction by two independent sets of bridging bpp ligands. One set is formed by the genuinely symmetric moieties, while those in the second set are formed by the disordered ones. These chains do not mix cobalt centres nor bpp ligands and thus contain only Co1/bpp2 and Co2/bpp3 units, respectively; metal cations in contiguous chains are laterally bridged by Hbtc3- anions, to form new, transversal chains of alternating Co1/Co2 cations (Fig. 2; A···A). The elemental motive [motif?] of the resulting grid is a higlhy distorted parallelogram (Fig. 2), with intermetal distances of 13.5242 (18) Å along [101] (the bpp direction) and 9.105 (2) Å along [100] (the Hbtc one); distortion is best assessed by the large internal angle of 138.42 (16)°.
These two-dimensional structures have a profuse hydrogen-bonding interaction with each other. Fig. 3 presents a simplified packing view where intra/inter-grid hydrogen bonds (not mediated by unbound anions or water solvates) are shown. In particular, there are two interactions internal to the coordination polyhedra (entries 1–2 in Table 1) defining two R(6) rings labelled as `a' and `b' in Fig. 3. Adjacent two-dimensional structures, in turn, interact directly along the [100] direction through the hydrogen bonds involving the remaining H atoms of the two aqua (Table 1), to form three different connecting loops [`c', R44(20); `d' and `e', R22(18)]. In addition to these interactions there are a large number of strong O—H···O, N—H···O hydrogen bonds, mediated by the 1,3-bis(4-pyridinium) propane anion and the solvation water molecules (Table 1), and some weaker non-conventional C—H···O and C—H···Cg bonds which give a strong three-dimensional coherence to the structure of (I).
In order to compare the structure of (I) with some related analogues we searched the CSD (Allen, 2002) and found another compound constructed from the same constituent components as (I), viz. catena[(OH2)(btc)2(bpp)Co5], (II) (Jia et al., 2007). As analysed for (I), a general scheme of cobalt nodes interlinked by btc and bpp ligands, but which, irrespective of these basic similarities in components and general architecture, displays an absolutely different structure, with (II) being definitely three-dimensional. In the structure of (II) the btc acts in an extremely complex µ8 mode with all its available O atoms engaged in coordination, and defining on its own the three-dimensional structural cage. The bpp ligands, in turn, even if bound to the metal centres play only a secondary role, folded into a nearly circular shape [N···N: 5.628 (2) Å] and filling the voids within the `elementary cells' defined by the btc groups which build up the grid.
This contrasts with (I), where the `first rank' structural building blocks can be shown to be the parallel [1,0,1] chains defined by the [fully stretched, N···N: 9.346 (2) Å] bpps, and where the Hbtc units appear to act as `second rank' interchain µ2 connectors, to form the (010) two-dimensional structures (Fig. 2) and, via hydrogen bonding, promote the interactions between planes (Fig. 3).
There are many possible reasons for the varying behaviour of the btc and bpp (synthesis conditions, ligand ratio etc.) and their analysis exceeds the scope of this report; the examples given, however, clearly show the versatility with which both ligands can adapt in different circumstances.