The title one-dimensional chain nickel(II)-disulfide complex, [Ni(C14H8O4S2)(C5H5N)2(H2O)]n, has each NiII cation coordinated by two N atoms from two pyridine ligands, three carboxylate O atoms from two different dithiodibenzoate ligands and one O atom from a coordinated water molecule, in a distorted octahedral coordination geometry. Each dithiodibenzoate ion links two NiII cations through its carboxylate O atoms, making the structure polymeric. Hydrogen-bond interactions between two shoulder-to-shoulder chains lead to the formation of a ladder-like structure.
Supporting information
CCDC reference: 251292
A mixture of Ni(NO3)2·6H2O (0.2 mmol) with 2,2'-H2dtdb (0.2 mmol) and pyridine (0.4 mmol) in the molar ratio 1:1:4 dissolved in water(10 ml) was sealed in a stainless-steel reactor with a Teflon liner and heated at 383 K for 2 d. A quantity of green block crystals of (I) was obtained after cooling the solution to room temperature. The yield of (I) is ca 65%, based on dtdb.
H atoms on C atoms were generated geometrically and allowed to ride on their respective parent atoms, with C—H = 0.95 Å Please check added text and with Uiso = 1.2Ueq(C). Water H atoms were located in difference maps and refined freely.
Data collection: SMART (Siemens, 1994); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
catena-poly[[aquadipyridinenickel(II)]-µ-2,2'-dithiodibenzoato-
κ3O,
O':
O'']
top
Crystal data top
[Ni(C14H8O4S2)(C5H5N)2(H2O)] | F(000) = 1112 |
Mr = 539.25 | Dx = 1.482 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.925 (3) Å | Cell parameters from 5535 reflections |
b = 15.099 (3) Å | θ = 1.6–27.5° |
c = 12.581 (3) Å | µ = 1.01 mm−1 |
β = 114.00 (3)° | T = 293 K |
V = 2416.5 (11) Å3 | Prism, green |
Z = 4 | 0.26 × 0.20 × 0.18 mm |
Data collection top
Siemens SMART CCD area-detector diffractometer | 5535 independent reflections |
Radiation source: fine-focus sealed tube | 4673 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 8.192 pixels mm-1 | θmax = 27.5°, θmin = 1.6° |
ω scans | h = −18→16 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −19→0 |
Tmin = 0.784, Tmax = 0.833 | l = 0→16 |
5535 measured reflections | |
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) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0509P)2] where P = (Fo2 + 2Fc2)/3 |
5535 reflections | (Δ/σ)max = 0.001 |
315 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
Crystal data top
[Ni(C14H8O4S2)(C5H5N)2(H2O)] | V = 2416.5 (11) Å3 |
Mr = 539.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.925 (3) Å | µ = 1.01 mm−1 |
b = 15.099 (3) Å | T = 293 K |
c = 12.581 (3) Å | 0.26 × 0.20 × 0.18 mm |
β = 114.00 (3)° | |
Data collection top
Siemens SMART CCD area-detector diffractometer | 5535 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 4673 reflections with I > 2σ(I) |
Tmin = 0.784, Tmax = 0.833 | Rint = 0.000 |
5535 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.43 e Å−3 |
5535 reflections | Δρmin = −0.43 e Å−3 |
315 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.310763 (15) | 0.545321 (13) | 0.337064 (15) | 0.02778 (7) | |
S1 | 0.34865 (4) | 0.48680 (3) | 0.72865 (3) | 0.03882 (11) | |
S2 | 0.34706 (3) | 0.48577 (3) | 0.89089 (3) | 0.03878 (11) | |
O1 | 0.35858 (8) | 0.49645 (7) | 0.51243 (9) | 0.0317 (2) | |
O2 | 0.24018 (8) | 0.42843 (8) | 0.36270 (9) | 0.0329 (2) | |
O3 | 0.23655 (9) | 0.55062 (8) | 1.16170 (9) | 0.0383 (3) | |
O4 | 0.35868 (9) | 0.50460 (10) | 1.10235 (9) | 0.0446 (3) | |
O5 | 0.43190 (10) | 0.46810 (9) | 0.32881 (12) | 0.0358 (3) | |
N1 | 0.18751 (11) | 0.62022 (10) | 0.35226 (13) | 0.0396 (3) | |
N2 | 0.39798 (11) | 0.65947 (9) | 0.36060 (11) | 0.0365 (3) | |
C1 | 0.29389 (12) | 0.43317 (10) | 0.47049 (12) | 0.0280 (3) | |
C2 | 0.27896 (12) | 0.36492 (11) | 0.54828 (13) | 0.0312 (3) | |
C3 | 0.23973 (15) | 0.28299 (11) | 0.49957 (15) | 0.0412 (4) | |
H3A | 0.2219 | 0.2735 | 0.4191 | 0.049* | |
C4 | 0.22617 (17) | 0.21507 (12) | 0.56592 (18) | 0.0504 (5) | |
H4A | 0.2005 | 0.1591 | 0.5318 | 0.060* | |
C5 | 0.25042 (17) | 0.22956 (13) | 0.68237 (18) | 0.0518 (5) | |
H5B | 0.2425 | 0.1830 | 0.7290 | 0.062* | |
C6 | 0.28601 (15) | 0.31125 (13) | 0.73124 (16) | 0.0452 (4) | |
H6A | 0.2999 | 0.3209 | 0.8108 | 0.054* | |
C7 | 0.30197 (12) | 0.37981 (11) | 0.66640 (13) | 0.0331 (3) | |
C8 | 0.21369 (13) | 0.51239 (11) | 0.86541 (13) | 0.0325 (3) | |
C9 | 0.13389 (14) | 0.51484 (13) | 0.75260 (14) | 0.0440 (4) | |
H9A | 0.1504 | 0.5031 | 0.6877 | 0.053* | |
C10 | 0.03184 (15) | 0.53414 (14) | 0.73507 (16) | 0.0508 (5) | |
H10A | −0.0209 | 0.5363 | 0.6580 | 0.061* | |
C11 | 0.00473 (15) | 0.55043 (14) | 0.82722 (17) | 0.0498 (5) | |
H11A | −0.0662 | 0.5621 | 0.8143 | 0.060* | |
C12 | 0.08334 (14) | 0.54948 (12) | 0.93924 (15) | 0.0414 (4) | |
H12A | 0.0657 | 0.5621 | 1.0031 | 0.050* | |
C13 | 0.18730 (12) | 0.53040 (10) | 0.96011 (13) | 0.0309 (3) | |
C14 | 0.26771 (12) | 0.52800 (10) | 1.08404 (13) | 0.0298 (3) | |
C15 | 0.12065 (18) | 0.66475 (16) | 0.2611 (2) | 0.0635 (6) | |
H15A | 0.1298 | 0.6631 | 0.1903 | 0.076* | |
C16 | 0.0383 (2) | 0.7134 (2) | 0.2656 (3) | 0.0941 (10) | |
H16A | −0.0078 | 0.7447 | 0.1989 | 0.113* | |
C17 | 0.0236 (2) | 0.7162 (2) | 0.3660 (3) | 0.0952 (10) | |
H17A | −0.0330 | 0.7489 | 0.3703 | 0.114* | |
C18 | 0.0916 (3) | 0.6713 (2) | 0.4600 (3) | 0.0893 (9) | |
H18A | 0.0834 | 0.6719 | 0.5314 | 0.107* | |
C19 | 0.17262 (19) | 0.62487 (16) | 0.4499 (2) | 0.0614 (6) | |
H19A | 0.2205 | 0.5945 | 0.5164 | 0.074* | |
C20 | 0.42270 (18) | 0.70668 (15) | 0.45765 (16) | 0.0582 (6) | |
H20A | 0.4043 | 0.6839 | 0.5172 | 0.070* | |
C21 | 0.4736 (2) | 0.78675 (16) | 0.47544 (19) | 0.0668 (6) | |
H21A | 0.4896 | 0.8184 | 0.5458 | 0.080* | |
C22 | 0.50099 (16) | 0.82030 (13) | 0.39099 (17) | 0.0504 (5) | |
H22A | 0.5347 | 0.8763 | 0.4006 | 0.061* | |
C23 | 0.47898 (16) | 0.77182 (13) | 0.29287 (17) | 0.0529 (5) | |
H23A | 0.4987 | 0.7927 | 0.2334 | 0.063* | |
C24 | 0.42769 (16) | 0.69209 (13) | 0.28075 (16) | 0.0490 (5) | |
H24B | 0.4128 | 0.6588 | 0.2118 | 0.059* | |
H5A | 0.4258 (17) | 0.4740 (14) | 0.268 (2) | 0.046 (6)* | |
H5C | 0.489 (2) | 0.4813 (16) | 0.368 (2) | 0.068 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.02987 (12) | 0.03325 (12) | 0.02115 (11) | −0.00044 (8) | 0.01132 (8) | 0.00012 (7) |
S1 | 0.0449 (2) | 0.0507 (3) | 0.0254 (2) | −0.00992 (19) | 0.01903 (18) | −0.00540 (17) |
S2 | 0.0344 (2) | 0.0608 (3) | 0.02169 (19) | 0.00148 (19) | 0.01190 (16) | −0.00187 (18) |
O1 | 0.0329 (6) | 0.0385 (6) | 0.0223 (5) | −0.0053 (5) | 0.0100 (4) | −0.0007 (4) |
O2 | 0.0353 (6) | 0.0391 (6) | 0.0219 (5) | −0.0030 (5) | 0.0093 (4) | −0.0009 (4) |
O3 | 0.0374 (6) | 0.0561 (8) | 0.0220 (5) | 0.0075 (5) | 0.0126 (5) | 0.0007 (5) |
O4 | 0.0356 (6) | 0.0733 (9) | 0.0227 (6) | 0.0125 (6) | 0.0098 (5) | −0.0030 (6) |
O5 | 0.0321 (7) | 0.0494 (7) | 0.0260 (6) | 0.0034 (5) | 0.0119 (5) | 0.0013 (5) |
N1 | 0.0394 (8) | 0.0389 (8) | 0.0429 (8) | 0.0047 (6) | 0.0192 (6) | −0.0018 (6) |
N2 | 0.0406 (8) | 0.0370 (7) | 0.0326 (7) | −0.0045 (6) | 0.0156 (6) | −0.0009 (6) |
C1 | 0.0287 (7) | 0.0342 (8) | 0.0237 (7) | 0.0028 (6) | 0.0132 (6) | −0.0005 (6) |
C2 | 0.0328 (8) | 0.0349 (8) | 0.0286 (8) | 0.0019 (6) | 0.0152 (6) | 0.0028 (6) |
C3 | 0.0530 (10) | 0.0379 (9) | 0.0377 (9) | −0.0011 (8) | 0.0235 (8) | −0.0027 (7) |
C4 | 0.0653 (12) | 0.0330 (9) | 0.0588 (12) | −0.0035 (9) | 0.0314 (10) | 0.0001 (8) |
C5 | 0.0640 (12) | 0.0445 (11) | 0.0554 (12) | 0.0020 (9) | 0.0329 (10) | 0.0155 (9) |
C6 | 0.0534 (10) | 0.0527 (11) | 0.0344 (9) | 0.0000 (9) | 0.0231 (8) | 0.0082 (8) |
C7 | 0.0329 (8) | 0.0400 (9) | 0.0286 (8) | 0.0005 (7) | 0.0146 (6) | 0.0026 (6) |
C8 | 0.0332 (8) | 0.0385 (8) | 0.0241 (7) | −0.0011 (7) | 0.0099 (6) | 0.0012 (6) |
C9 | 0.0423 (10) | 0.0626 (12) | 0.0223 (8) | −0.0009 (9) | 0.0081 (7) | −0.0027 (8) |
C10 | 0.0386 (10) | 0.0701 (14) | 0.0296 (9) | −0.0010 (9) | −0.0005 (7) | −0.0016 (8) |
C11 | 0.0300 (8) | 0.0691 (13) | 0.0424 (10) | 0.0034 (8) | 0.0065 (7) | −0.0026 (9) |
C12 | 0.0358 (9) | 0.0537 (11) | 0.0345 (9) | 0.0007 (8) | 0.0141 (7) | −0.0010 (8) |
C13 | 0.0331 (8) | 0.0347 (8) | 0.0231 (7) | −0.0020 (6) | 0.0097 (6) | 0.0007 (6) |
C14 | 0.0341 (8) | 0.0324 (8) | 0.0226 (7) | 0.0000 (6) | 0.0113 (6) | 0.0011 (6) |
C15 | 0.0632 (13) | 0.0653 (14) | 0.0574 (13) | 0.0243 (11) | 0.0198 (10) | 0.0035 (10) |
C16 | 0.0775 (17) | 0.093 (2) | 0.098 (2) | 0.0485 (16) | 0.0215 (15) | 0.0041 (17) |
C17 | 0.0818 (19) | 0.086 (2) | 0.138 (3) | 0.0324 (17) | 0.065 (2) | −0.006 (2) |
C18 | 0.109 (2) | 0.086 (2) | 0.110 (2) | 0.0305 (18) | 0.083 (2) | 0.0031 (17) |
C19 | 0.0733 (14) | 0.0649 (14) | 0.0590 (13) | 0.0201 (12) | 0.0402 (11) | 0.0035 (11) |
C20 | 0.0787 (14) | 0.0620 (13) | 0.0363 (10) | −0.0272 (11) | 0.0257 (10) | −0.0065 (9) |
C21 | 0.0899 (17) | 0.0658 (14) | 0.0480 (12) | −0.0344 (13) | 0.0313 (11) | −0.0204 (11) |
C22 | 0.0555 (12) | 0.0400 (10) | 0.0538 (12) | −0.0129 (9) | 0.0201 (9) | −0.0026 (8) |
C23 | 0.0636 (12) | 0.0508 (11) | 0.0498 (11) | −0.0128 (10) | 0.0290 (10) | 0.0033 (9) |
C24 | 0.0626 (12) | 0.0495 (11) | 0.0423 (10) | −0.0152 (9) | 0.0289 (9) | −0.0091 (8) |
Geometric parameters (Å, º) top
Ni1—O3i | 2.0216 (13) | C6—C7 | 1.391 (2) |
Ni1—N2 | 2.0594 (14) | C6—H6A | 0.9500 |
Ni1—O5 | 2.0877 (13) | C8—C9 | 1.403 (2) |
Ni1—O2 | 2.1079 (12) | C8—C13 | 1.409 (2) |
Ni1—N1 | 2.1279 (14) | C9—C10 | 1.378 (3) |
Ni1—O1 | 2.1588 (11) | C9—H9A | 0.9500 |
Ni1—C1 | 2.4620 (15) | C10—C11 | 1.380 (3) |
S1—C7 | 1.7976 (18) | C10—H10A | 0.9500 |
S1—S2 | 2.0502 (7) | C11—C12 | 1.389 (3) |
S2—C8 | 1.7970 (17) | C11—H11A | 0.9500 |
O1—C1 | 1.2713 (19) | C12—C13 | 1.392 (2) |
O2—C1 | 1.2564 (18) | C12—H12A | 0.9500 |
O3—C14 | 1.2668 (19) | C13—C14 | 1.505 (2) |
O3—Ni1ii | 2.0216 (13) | C15—C16 | 1.382 (3) |
O4—C14 | 1.243 (2) | C15—H15A | 0.9500 |
O5—O4i | 2.6642 (19) | C16—C17 | 1.360 (4) |
O5—O1iii | 2.837 (2) | C16—H16A | 0.9500 |
O5—H5A | 0.74 (2) | C17—C18 | 1.359 (4) |
O5—H5C | 0.78 (3) | C17—H17A | 0.9500 |
N1—C19 | 1.328 (2) | C18—C19 | 1.378 (3) |
N1—C15 | 1.329 (3) | C18—H18A | 0.9500 |
N2—C24 | 1.327 (2) | C19—H19A | 0.9500 |
N2—C20 | 1.332 (2) | C20—C21 | 1.373 (3) |
C1—C2 | 1.493 (2) | C20—H20A | 0.9500 |
C2—C3 | 1.390 (2) | C21—C22 | 1.364 (3) |
C2—C7 | 1.405 (2) | C21—H21A | 0.9500 |
C3—C4 | 1.383 (2) | C22—C23 | 1.359 (3) |
C3—H3A | 0.9500 | C22—H22A | 0.9500 |
C4—C5 | 1.380 (3) | C23—C24 | 1.376 (3) |
C4—H4A | 0.9500 | C23—H23A | 0.9500 |
C5—C6 | 1.377 (3) | C24—H24B | 0.9500 |
C5—H5B | 0.9500 | | |
| | | |
O3i—Ni1—N2 | 97.68 (6) | C4—C5—H5B | 119.9 |
O3i—Ni1—O5 | 91.87 (6) | C5—C6—C7 | 121.27 (17) |
N2—Ni1—O5 | 91.92 (6) | C5—C6—H6A | 119.4 |
O3i—Ni1—O2 | 97.87 (5) | C7—C6—H6A | 119.4 |
N2—Ni1—O2 | 164.42 (5) | C6—C7—C2 | 118.62 (16) |
O5—Ni1—O2 | 88.65 (5) | C6—C7—S1 | 121.95 (13) |
O3i—Ni1—N1 | 90.23 (6) | C2—C7—S1 | 119.42 (12) |
N2—Ni1—N1 | 89.56 (6) | C9—C8—C13 | 118.61 (15) |
O5—Ni1—N1 | 177.25 (5) | C9—C8—S2 | 121.48 (13) |
O2—Ni1—N1 | 89.31 (5) | C13—C8—S2 | 119.90 (12) |
O3i—Ni1—O1 | 159.57 (5) | C10—C9—C8 | 120.57 (17) |
N2—Ni1—O1 | 102.73 (5) | C10—C9—H9A | 119.7 |
O5—Ni1—O1 | 86.58 (5) | C8—C9—H9A | 119.7 |
O2—Ni1—O1 | 61.75 (4) | C9—C10—C11 | 121.35 (17) |
N1—Ni1—O1 | 90.84 (5) | C9—C10—H10A | 119.3 |
O3i—Ni1—C1 | 128.54 (5) | C11—C10—H10A | 119.3 |
N2—Ni1—C1 | 133.78 (5) | C10—C11—C12 | 118.60 (18) |
O5—Ni1—C1 | 87.30 (5) | C10—C11—H11A | 120.7 |
O2—Ni1—C1 | 30.69 (5) | C12—C11—H11A | 120.7 |
N1—Ni1—C1 | 90.01 (6) | C11—C12—C13 | 121.56 (17) |
O1—Ni1—C1 | 31.06 (5) | C11—C12—H12A | 119.2 |
C7—S1—S2 | 106.17 (6) | C13—C12—H12A | 119.2 |
C8—S2—S1 | 104.46 (6) | C12—C13—C8 | 119.29 (14) |
C1—O1—Ni1 | 87.75 (9) | C12—C13—C14 | 118.61 (14) |
C1—O2—Ni1 | 90.43 (9) | C8—C13—C14 | 122.09 (14) |
C14—O3—Ni1ii | 130.36 (11) | O4—C14—O3 | 125.22 (14) |
Ni1—O5—O4i | 88.40 (6) | O4—C14—C13 | 118.13 (14) |
Ni1—O5—O1iii | 118.69 (6) | O3—C14—C13 | 116.65 (14) |
O4i—O5—O1iii | 123.40 (6) | N1—C15—C16 | 122.4 (2) |
Ni1—O5—H5A | 103.2 (17) | N1—C15—H15A | 118.8 |
O4i—O5—H5A | 15.5 (17) | C16—C15—H15A | 118.8 |
O1iii—O5—H5A | 111.0 (17) | C17—C16—C15 | 119.7 (3) |
Ni1—O5—H5C | 117.8 (19) | C17—C16—H16A | 120.1 |
O4i—O5—H5C | 118.6 (19) | C15—C16—H16A | 120.1 |
O1iii—O5—H5C | 5.4 (18) | C18—C17—C16 | 118.5 (2) |
H5A—O5—H5C | 107 (2) | C18—C17—H17A | 120.7 |
C19—N1—C15 | 116.94 (18) | C16—C17—H17A | 120.7 |
C19—N1—Ni1 | 123.11 (13) | C17—C18—C19 | 118.7 (3) |
C15—N1—Ni1 | 119.95 (13) | C17—C18—H18A | 120.6 |
C24—N2—C20 | 116.82 (16) | C19—C18—H18A | 120.6 |
C24—N2—Ni1 | 123.30 (12) | N1—C19—C18 | 123.7 (2) |
C20—N2—Ni1 | 119.80 (12) | N1—C19—H19A | 118.2 |
O2—C1—O1 | 120.07 (14) | C18—C19—H19A | 118.2 |
O2—C1—C2 | 119.19 (14) | N2—C20—C21 | 122.98 (19) |
O1—C1—C2 | 120.72 (13) | N2—C20—H20A | 118.5 |
O2—C1—Ni1 | 58.89 (8) | C21—C20—H20A | 118.5 |
O1—C1—Ni1 | 61.18 (8) | C22—C21—C20 | 119.30 (19) |
C2—C1—Ni1 | 177.65 (11) | C22—C21—H21A | 120.4 |
C3—C2—C7 | 119.24 (15) | C20—C21—H21A | 120.4 |
C3—C2—C1 | 117.38 (14) | C23—C22—C21 | 118.45 (18) |
C7—C2—C1 | 123.37 (14) | C23—C22—H22A | 120.8 |
C4—C3—C2 | 121.30 (16) | C21—C22—H22A | 120.8 |
C4—C3—H3A | 119.4 | C22—C23—C24 | 119.15 (18) |
C2—C3—H3A | 119.4 | C22—C23—H23A | 120.4 |
C5—C4—C3 | 119.24 (18) | C24—C23—H23A | 120.4 |
C5—C4—H4A | 120.4 | N2—C24—C23 | 123.26 (18) |
C3—C4—H4A | 120.4 | N2—C24—H24B | 118.4 |
C6—C5—C4 | 120.26 (17) | C23—C24—H24B | 118.4 |
C6—C5—H5B | 119.9 | | |
Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1; (iii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O4i | 0.74 (2) | 1.96 (2) | 2.6642 (19) | 159 (2) |
O5—H5C···O1iii | 0.78 (3) | 2.06 (3) | 2.837 (2) | 173 (3) |
Symmetry codes: (i) x, y, z−1; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Ni(C14H8O4S2)(C5H5N)2(H2O)] |
Mr | 539.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.925 (3), 15.099 (3), 12.581 (3) |
β (°) | 114.00 (3) |
V (Å3) | 2416.5 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.01 |
Crystal size (mm) | 0.26 × 0.20 × 0.18 |
|
Data collection |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.784, 0.833 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5535, 5535, 4673 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.082, 1.07 |
No. of reflections | 5535 |
No. of parameters | 315 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.43 |
Selected geometric parameters (Å, º) topNi1—O3i | 2.0216 (13) | Ni1—O1 | 2.1588 (11) |
Ni1—N2 | 2.0594 (14) | S1—C7 | 1.7976 (18) |
Ni1—O5 | 2.0877 (13) | S1—S2 | 2.0502 (7) |
Ni1—O2 | 2.1079 (12) | S2—C8 | 1.7970 (17) |
Ni1—N1 | 2.1279 (14) | | |
| | | |
O3i—Ni1—N2 | 97.68 (6) | O2—Ni1—N1 | 89.31 (5) |
O3i—Ni1—O5 | 91.87 (6) | O3i—Ni1—O1 | 159.57 (5) |
N2—Ni1—O5 | 91.92 (6) | N2—Ni1—O1 | 102.73 (5) |
O3i—Ni1—O2 | 97.87 (5) | O5—Ni1—O1 | 86.58 (5) |
N2—Ni1—O2 | 164.42 (5) | O2—Ni1—O1 | 61.75 (4) |
O5—Ni1—O2 | 88.65 (5) | N1—Ni1—O1 | 90.84 (5) |
O3i—Ni1—N1 | 90.23 (6) | C7—S1—S2 | 106.17 (6) |
N2—Ni1—N1 | 89.56 (6) | C8—S2—S1 | 104.46 (6) |
O5—Ni1—N1 | 177.25 (5) | | |
Symmetry code: (i) x, y, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O4i | 0.74 (2) | 1.96 (2) | 2.6642 (19) | 159 (2) |
O5—H5C···O1ii | 0.78 (3) | 2.06 (3) | 2.837 (2) | 173 (3) |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1. |
The rational design of coordination polymers has attracted much attention, due to the potential applications of these materials, which range from gas storage and ion exchange to heterogeneous catalysis (Moulton & Zaworotko, 2001; Janiak, 2003). The construction of metal-organic frameworks can be achieved via two kinds of interaction, i.e. coordinate covalent bonds and weaker intermolecular forces. Weaker noncovalent interactions, such as hydrogen bonds or π–π interactions, are important for the packing of one-dimensional chains, two-dimensional nets and three-dimensional open frameworks. Furthermore, the selection or design of suitable ligands containing certain features, such as flexibility and versatile binding modes, is crucial for the construction of specific supramolecular architectures. This concept has been demonstrated by a great variety of structural topologies of discrete supramolecular complexes or infinite supramolecular arrays (Leininger et al., 2000; Janiak, 2003).
Against this background, we chose 2,2'-dithiodibenzoic acid (2,2'-H2dtdb) as an organic ligand for study, based on the following considerations. Firstly, the twisted binding site passing through the centre of the S—S bond makes the ligand flexible. Secondly, the carboxylate binding groups, coupled with the different coordination modes of 2,2'-dtdb, should allow the fabrication of different coordination polymer topologies. Finally, the ligand has a strong capability of forming hydrogen bonds, which play an important role in the assembly of supramolecular compounds. Thus we prepared the title compound, (I), by the hydrothermal reaction of an NiII salt with the ligand and pyridine in the molar ratio 1:1:4 at 383 K for 2 d. \sch
The present crystallographic analysis reveals that (I) is a one-dimensional ladder-like coordination polymer. As shown in Fig. 1, each NiII cation is coordinated by two N atoms from two pyridine ligands, three carboxylate O atoms from two different dithiodibenzoate ligands and one O atom from a coordinated water molecule. One N atom (N2) and three O atoms (O1, O2 and O3A) form the equatorial plane, while the axial positions are occupied by one N atom (N1) and one O atom (O5), with an N1—Ni1—O5 bond angle of 177.25 (5)°. Thus, the coordination environment around the NiII centre can be best described as having a distorted octahedral geometry. The NiII cation is approximately coplanar with the coordination atoms in the equatorial plane, with a slight deviation of 0.001 Å. The Ni—N and Ni—O distances are in the ranges 2.0594 (14)–2.1279 (14) and 2.0216 (13)–2.1588 (11) Å, respectively (Table 1), which are typical values for Ni—N and Ni—O coordination distances (Kongshaug & Fgellvag, 2003).
The two carboxylate groups of each dtdb ligand adopt different coordination modes, namley monodentate and chelating-bidentate. As a result, the O1—C1—O2 angle [120.07 (13)°] is about 5° smaller than that of O3—C14—O4 [125.22 (14)°]. The dihedral angle between the two phenyl rings is 96.7 (5)°, which is close to that in the analogous Co-dtdb complex (Ganesh et al., 1990).
Each dithiodibenzoate anion links two NiII cations through its carboxylate O atoms, making the structure polymeric. The Ni···Ni distance bridged by dtdb is 12.581 (8) Å. Furthermore, hydrogen-bond interactions between two shoulder-to-shoulder chains lead to the formation of a ladder-like structure (Fig. 2). The hydrogen-bond distances of O5—H5A···O4(x, y, z − 1) and O5—H5C···O1(1 − x, 1 − y, 1 − z) are 2.664 (19) and 2.837 (2) Å, respectively. A bimetallic six-membered hydrogen-bonded ring is thus formed, with an Ni···Ni distance of 5.374 (8) Å.
The bimetallic unit can be viewed as the basic building block of the structure, and these are joined together through sharing the NiII apices with dtdb ligands to give the final one-dimensional polymer, which consists of rectangular grids with dimensions of 12.6 × 5.4 Å, based on the metal-to-metal distances. Therefore, the presence of hydrogen bonds in (I) plays an important role in the formation of the final ladder-like coordination polymer, which is notably different from other ladder-like structures based on coordinate covalent bonds (Liu et al., 2004).