Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031625/bt2419sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031625/bt2419Isup2.hkl |
CCDC reference: 657534
A mixture of Zn(NO3)2 (0.145 g, 0.5 mmol), Na2CO3 (0.05 g, 0.5 mmol), terephthalate (0.08 g, 0.5 mmol), 1,3-di-4-pyridylpropane (0.09 g, 0.5 mmol) and H2O (10 ml) was sealed in a 25 ml stainless-steel reactor with a Teflon-lined stainless steel reactor and was heated at 393 K for 3 d. On completion of the reaction, the reactor was cooled slowly to room temperature and the mixture was filtered, giving colorless single crystals suitable for X-ray analysis.
All H atoms were placed at calculated positions, and refined with isotropic displacement parameters, using a riding model [C—H 0.93Å and Uiso(H) = 1.2Ueq(C)].
Ligands containing O– or N-donors can bind metal centers. Thus, they serve as building blocks to construct supramolecular architectures. Herein we report the structure of [Zn(tp)(bpp)]n (tp = terephthalate, bpp = 1,3-di-4-pyridylpropane).
As shown in Figure 1, the asymmetric unit of the title compound is composed of a four-coordinate Zn(II)center, a tp ligand and a bpp ligand, in which each Zinc center is coordinated in a distorted tetrahedral geometry to two tp ligands and two bpp ligands through two carboxylate groups and two nitrogen donors. An isostructural compound Cd(tp)(bpp) has been reported (Dai et al., 2004).
For related literature, see: Dai et al. (2004).
Data collection: SMART (Siemens, 1996a); cell refinement: SAINT (Siemens, 1996a); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996b); software used to prepare material for publication: SHELXTL.
[Zn(C8H4O4)(C13H14N2)] | F(000) = 1760 |
Mr = 427.74 | Dx = 1.497 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | θ = 2.1–25.0° |
a = 11.7563 (4) Å | µ = 1.32 mm−1 |
b = 16.3925 (5) Å | T = 273 K |
c = 19.7019 (7) Å | Prism, colorless |
V = 3796.9 (2) Å3 | 0.20 × 0.14 × 0.10 mm |
Z = 8 |
Siemens SMART 1K CCD area-detector diffractometer | 3350 independent reflections |
Radiation source: fine-focus sealed tube | 2358 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
φ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.800, Tmax = 0.850 | k = −19→19 |
28979 measured reflections | l = −22→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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0511P)2] where P = (Fo2 + 2Fc2)/3 |
3350 reflections | (Δ/σ)max = 0.001 |
253 parameters | Δρmax = 0.79 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[Zn(C8H4O4)(C13H14N2)] | V = 3796.9 (2) Å3 |
Mr = 427.74 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.7563 (4) Å | µ = 1.32 mm−1 |
b = 16.3925 (5) Å | T = 273 K |
c = 19.7019 (7) Å | 0.20 × 0.14 × 0.10 mm |
Siemens SMART 1K CCD area-detector diffractometer | 3350 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2358 reflections with I > 2σ(I) |
Tmin = 0.800, Tmax = 0.850 | Rint = 0.084 |
28979 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.79 e Å−3 |
3350 reflections | Δρmin = −0.48 e Å−3 |
253 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. |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.03302 (3) | 0.11133 (2) | 0.628053 (18) | 0.02148 (13) | |
O1 | 0.13272 (19) | 0.23097 (12) | 0.56729 (11) | 0.0316 (6) | |
O2 | −0.01621 (18) | 0.15596 (12) | 0.53795 (11) | 0.0292 (5) | |
O3 | 0.0110 (2) | 0.32360 (13) | 0.20996 (12) | 0.0348 (6) | |
O4 | 0.1115 (3) | 0.42520 (19) | 0.25268 (15) | 0.0705 (10) | |
N1 | 0.1814 (2) | 0.04851 (14) | 0.60977 (13) | 0.0215 (6) | |
N2 | 0.9127 (2) | 0.01958 (15) | 0.63451 (13) | 0.0232 (6) | |
C1 | 0.0592 (3) | 0.24763 (17) | 0.45592 (17) | 0.0220 (7) | |
C2 | −0.0246 (3) | 0.22873 (18) | 0.40925 (17) | 0.0255 (7) | |
H2A | −0.0842 | 0.1945 | 0.4217 | 0.031* | |
C3 | −0.0204 (3) | 0.26049 (18) | 0.34390 (18) | 0.0288 (8) | |
H3A | −0.0761 | 0.2464 | 0.3125 | 0.035* | |
C4 | 0.0664 (3) | 0.31303 (19) | 0.32547 (17) | 0.0285 (8) | |
C5 | 0.1504 (3) | 0.3327 (2) | 0.37208 (18) | 0.0309 (8) | |
H5A | 0.2086 | 0.3682 | 0.3600 | 0.037* | |
C6 | 0.1473 (3) | 0.29935 (18) | 0.43646 (17) | 0.0264 (8) | |
H6A | 0.2048 | 0.3116 | 0.4672 | 0.032* | |
C7 | 0.0599 (3) | 0.21031 (18) | 0.52526 (17) | 0.0259 (8) | |
C8 | 0.0673 (3) | 0.3545 (2) | 0.2571 (2) | 0.0440 (10) | |
C9 | 0.1854 (3) | −0.03344 (18) | 0.60805 (18) | 0.0295 (8) | |
H9A | 0.1177 | −0.0623 | 0.6123 | 0.035* | |
C10 | 0.2853 (3) | −0.07658 (19) | 0.60027 (19) | 0.0317 (9) | |
H10A | 0.2839 | −0.1333 | 0.5988 | 0.038* | |
C11 | 0.3881 (3) | −0.03531 (18) | 0.59467 (17) | 0.0238 (7) | |
C12 | 0.3835 (3) | 0.04878 (18) | 0.59680 (18) | 0.0288 (8) | |
H12A | 0.4501 | 0.0790 | 0.5928 | 0.035* | |
C13 | 0.2810 (3) | 0.08814 (19) | 0.60476 (18) | 0.0297 (8) | |
H13A | 0.2807 | 0.1448 | 0.6068 | 0.036* | |
C14 | 0.5000 (2) | −0.07953 (19) | 0.58788 (18) | 0.0281 (8) | |
H14A | 0.5587 | −0.0406 | 0.5757 | 0.034* | |
H14B | 0.4943 | −0.1190 | 0.5514 | 0.034* | |
C15 | 0.5349 (3) | −0.12322 (18) | 0.65255 (19) | 0.0298 (8) | |
H15A | 0.4779 | −0.1639 | 0.6636 | 0.036* | |
H15B | 0.5372 | −0.0841 | 0.6895 | 0.036* | |
C16 | 0.6511 (3) | −0.16502 (19) | 0.6468 (2) | 0.0342 (9) | |
H16A | 0.6632 | −0.1994 | 0.6863 | 0.041* | |
H16B | 0.6521 | −0.1996 | 0.6069 | 0.041* | |
C17 | 0.7464 (3) | −0.10311 (19) | 0.64198 (17) | 0.0267 (8) | |
C18 | 0.7910 (3) | −0.0679 (2) | 0.69933 (18) | 0.0340 (9) | |
H18A | 0.7660 | −0.0847 | 0.7418 | 0.041* | |
C19 | 0.8727 (3) | −0.0077 (2) | 0.69445 (18) | 0.0327 (8) | |
H19A | 0.9012 | 0.0151 | 0.7342 | 0.039* | |
C20 | 0.7884 (3) | −0.07596 (18) | 0.58023 (18) | 0.0287 (8) | |
H20A | 0.7619 | −0.0988 | 0.5400 | 0.034* | |
C21 | 0.8697 (3) | −0.01512 (18) | 0.57826 (17) | 0.0255 (8) | |
H21A | 0.8957 | 0.0026 | 0.5362 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0232 (2) | 0.0222 (2) | 0.0190 (2) | 0.00177 (16) | −0.00028 (17) | −0.00100 (16) |
O1 | 0.0448 (15) | 0.0261 (12) | 0.0240 (14) | 0.0051 (11) | −0.0072 (12) | 0.0018 (11) |
O2 | 0.0345 (13) | 0.0268 (11) | 0.0262 (14) | 0.0001 (11) | 0.0032 (11) | 0.0076 (11) |
O3 | 0.0539 (16) | 0.0316 (12) | 0.0189 (13) | −0.0003 (11) | −0.0016 (12) | 0.0017 (11) |
O4 | 0.085 (2) | 0.0718 (19) | 0.055 (2) | −0.0278 (18) | −0.0141 (18) | 0.0243 (17) |
N1 | 0.0203 (14) | 0.0214 (13) | 0.0228 (16) | −0.0028 (11) | 0.0007 (12) | −0.0019 (12) |
N2 | 0.0205 (14) | 0.0287 (14) | 0.0205 (16) | 0.0023 (12) | 0.0001 (12) | 0.0017 (13) |
C1 | 0.0280 (19) | 0.0168 (15) | 0.0214 (18) | 0.0058 (13) | 0.0034 (15) | −0.0008 (13) |
C2 | 0.0313 (19) | 0.0207 (15) | 0.0245 (19) | −0.0027 (14) | 0.0012 (16) | 0.0009 (15) |
C3 | 0.038 (2) | 0.0252 (17) | 0.0232 (19) | 0.0006 (16) | −0.0050 (17) | −0.0031 (15) |
C4 | 0.033 (2) | 0.0289 (18) | 0.023 (2) | 0.0028 (15) | 0.0037 (16) | 0.0044 (15) |
C5 | 0.0260 (18) | 0.0377 (19) | 0.029 (2) | −0.0033 (15) | 0.0033 (16) | 0.0079 (17) |
C6 | 0.0237 (18) | 0.0296 (17) | 0.026 (2) | 0.0025 (14) | −0.0024 (15) | 0.0000 (16) |
C7 | 0.033 (2) | 0.0210 (16) | 0.0234 (19) | 0.0119 (15) | 0.0032 (16) | −0.0009 (15) |
C8 | 0.052 (3) | 0.045 (2) | 0.035 (3) | −0.006 (2) | −0.002 (2) | 0.011 (2) |
C9 | 0.0195 (17) | 0.0247 (17) | 0.044 (2) | −0.0044 (14) | 0.0008 (16) | −0.0018 (16) |
C10 | 0.0233 (19) | 0.0201 (16) | 0.052 (2) | −0.0008 (14) | 0.0017 (17) | −0.0055 (17) |
C11 | 0.0230 (18) | 0.0279 (17) | 0.0203 (18) | −0.0016 (14) | 0.0000 (15) | −0.0023 (15) |
C12 | 0.0206 (18) | 0.0265 (17) | 0.039 (2) | −0.0057 (14) | 0.0010 (16) | 0.0011 (17) |
C13 | 0.029 (2) | 0.0210 (16) | 0.039 (2) | −0.0021 (15) | −0.0015 (16) | −0.0024 (15) |
C14 | 0.0195 (18) | 0.0287 (17) | 0.036 (2) | −0.0005 (14) | 0.0030 (15) | −0.0086 (16) |
C15 | 0.0194 (17) | 0.0265 (17) | 0.044 (2) | 0.0004 (14) | 0.0048 (16) | −0.0012 (16) |
C16 | 0.0244 (19) | 0.0278 (18) | 0.050 (3) | −0.0006 (15) | 0.0047 (17) | 0.0024 (17) |
C17 | 0.0197 (17) | 0.0250 (16) | 0.035 (2) | 0.0071 (14) | 0.0026 (15) | 0.0022 (16) |
C18 | 0.030 (2) | 0.045 (2) | 0.026 (2) | −0.0064 (17) | 0.0025 (17) | 0.0096 (17) |
C19 | 0.032 (2) | 0.045 (2) | 0.021 (2) | −0.0058 (17) | −0.0010 (16) | 0.0012 (17) |
C20 | 0.0231 (18) | 0.0309 (18) | 0.032 (2) | 0.0004 (15) | −0.0003 (16) | −0.0087 (16) |
C21 | 0.0244 (18) | 0.0331 (18) | 0.0191 (19) | 0.0000 (15) | 0.0031 (15) | −0.0018 (15) |
Zn1—O3i | 1.952 (2) | C9—C10 | 1.380 (4) |
Zn1—O2 | 2.005 (2) | C9—H9A | 0.9300 |
Zn1—N1 | 2.058 (2) | C10—C11 | 1.389 (4) |
Zn1—N2ii | 2.068 (3) | C10—H10A | 0.9300 |
O1—C7 | 1.239 (4) | C11—C12 | 1.380 (4) |
O2—C7 | 1.287 (4) | C11—C14 | 1.508 (4) |
O3—C8 | 1.248 (4) | C12—C13 | 1.375 (4) |
O3—Zn1iii | 1.952 (2) | C12—H12A | 0.9300 |
O4—C8 | 1.273 (4) | C13—H13A | 0.9300 |
N1—C13 | 1.342 (4) | C14—C15 | 1.518 (5) |
N1—C9 | 1.345 (4) | C14—H14A | 0.9700 |
N2—C21 | 1.345 (4) | C14—H14B | 0.9700 |
N2—C19 | 1.348 (4) | C15—C16 | 1.533 (4) |
N2—Zn1iv | 2.068 (3) | C15—H15A | 0.9700 |
C1—C2 | 1.382 (4) | C15—H15B | 0.9700 |
C1—C6 | 1.392 (4) | C16—C17 | 1.515 (4) |
C1—C7 | 1.497 (4) | C16—H16A | 0.9700 |
C2—C3 | 1.390 (5) | C16—H16B | 0.9700 |
C2—H2A | 0.9300 | C17—C18 | 1.373 (5) |
C3—C4 | 1.384 (4) | C17—C20 | 1.386 (5) |
C3—H3A | 0.9300 | C18—C19 | 1.380 (4) |
C4—C5 | 1.386 (5) | C18—H18A | 0.9300 |
C4—C8 | 1.509 (5) | C19—H19A | 0.9300 |
C5—C6 | 1.382 (4) | C20—C21 | 1.381 (4) |
C5—H5A | 0.9300 | C20—H20A | 0.9300 |
C6—H6A | 0.9300 | C21—H21A | 0.9300 |
O3i—Zn1—O2 | 119.62 (9) | C11—C10—H10A | 120.0 |
O3i—Zn1—N1 | 122.05 (10) | C12—C11—C10 | 116.7 (3) |
O2—Zn1—N1 | 105.80 (9) | C12—C11—C14 | 121.1 (3) |
O3i—Zn1—N2ii | 104.82 (10) | C10—C11—C14 | 122.1 (3) |
O2—Zn1—N2ii | 97.03 (10) | C13—C12—C11 | 120.4 (3) |
N1—Zn1—N2ii | 103.10 (9) | C13—C12—H12A | 119.8 |
C7—O2—Zn1 | 102.9 (2) | C11—C12—H12A | 119.8 |
C8—O3—Zn1iii | 108.9 (2) | N1—C13—C12 | 123.0 (3) |
C13—N1—C9 | 116.8 (3) | N1—C13—H13A | 118.5 |
C13—N1—Zn1 | 120.7 (2) | C12—C13—H13A | 118.5 |
C9—N1—Zn1 | 122.2 (2) | C11—C14—C15 | 112.8 (3) |
C21—N2—C19 | 116.8 (3) | C11—C14—H14A | 109.0 |
C21—N2—Zn1iv | 120.9 (2) | C15—C14—H14A | 109.0 |
C19—N2—Zn1iv | 122.3 (2) | C11—C14—H14B | 109.0 |
C2—C1—C6 | 118.9 (3) | C15—C14—H14B | 109.0 |
C2—C1—C7 | 121.3 (3) | H14A—C14—H14B | 107.8 |
C6—C1—C7 | 119.7 (3) | C14—C15—C16 | 113.0 (3) |
C1—C2—C3 | 120.5 (3) | C14—C15—H15A | 109.0 |
C1—C2—H2A | 119.8 | C16—C15—H15A | 109.0 |
C3—C2—H2A | 119.8 | C14—C15—H15B | 109.0 |
C4—C3—C2 | 120.1 (3) | C16—C15—H15B | 109.0 |
C4—C3—H3A | 119.9 | H15A—C15—H15B | 107.8 |
C2—C3—H3A | 119.9 | C17—C16—C15 | 111.4 (3) |
C3—C4—C5 | 119.7 (3) | C17—C16—H16A | 109.4 |
C3—C4—C8 | 121.3 (3) | C15—C16—H16A | 109.4 |
C5—C4—C8 | 118.8 (3) | C17—C16—H16B | 109.4 |
C6—C5—C4 | 119.8 (3) | C15—C16—H16B | 109.4 |
C6—C5—H5A | 120.1 | H16A—C16—H16B | 108.0 |
C4—C5—H5A | 120.1 | C18—C17—C20 | 116.8 (3) |
C5—C6—C1 | 120.9 (3) | C18—C17—C16 | 120.8 (3) |
C5—C6—H6A | 119.6 | C20—C17—C16 | 122.3 (3) |
C1—C6—H6A | 119.6 | C17—C18—C19 | 120.6 (3) |
O1—C7—O2 | 122.7 (3) | C17—C18—H18A | 119.7 |
O1—C7—C1 | 120.1 (3) | C19—C18—H18A | 119.7 |
O2—C7—C1 | 117.2 (3) | N2—C19—C18 | 122.8 (3) |
O3—C8—O4 | 122.4 (4) | N2—C19—H19A | 118.6 |
O3—C8—C4 | 118.5 (3) | C18—C19—H19A | 118.6 |
O4—C8—C4 | 118.3 (4) | C21—C20—C17 | 120.2 (3) |
N1—C9—C10 | 123.0 (3) | C21—C20—H20A | 119.9 |
N1—C9—H9A | 118.5 | C17—C20—H20A | 119.9 |
C10—C9—H9A | 118.5 | N2—C21—C20 | 122.8 (3) |
C9—C10—C11 | 120.0 (3) | N2—C21—H21A | 118.6 |
C9—C10—H10A | 120.0 | C20—C21—H21A | 118.6 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x−1, y, z; (iii) x, −y+1/2, z−1/2; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C8H4O4)(C13H14N2)] |
Mr | 427.74 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 273 |
a, b, c (Å) | 11.7563 (4), 16.3925 (5), 19.7019 (7) |
V (Å3) | 3796.9 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.20 × 0.14 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART 1K CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.800, 0.850 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28979, 3350, 2358 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.096, 0.94 |
No. of reflections | 3350 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.79, −0.48 |
Computer programs: SMART (Siemens, 1996a), SAINT (Siemens, 1996a), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996b), SHELXTL.
Zn1—O3i | 1.952 (2) | Zn1—N1 | 2.058 (2) |
Zn1—O2 | 2.005 (2) | Zn1—N2ii | 2.068 (3) |
O3i—Zn1—O2 | 119.62 (9) | O2—Zn1—N2ii | 97.03 (10) |
O3i—Zn1—N1 | 122.05 (10) | N1—Zn1—N2ii | 103.10 (9) |
O2—Zn1—N1 | 105.80 (9) | C7—O2—Zn1 | 102.9 (2) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x−1, y, z. |
Ligands containing O– or N-donors can bind metal centers. Thus, they serve as building blocks to construct supramolecular architectures. Herein we report the structure of [Zn(tp)(bpp)]n (tp = terephthalate, bpp = 1,3-di-4-pyridylpropane).
As shown in Figure 1, the asymmetric unit of the title compound is composed of a four-coordinate Zn(II)center, a tp ligand and a bpp ligand, in which each Zinc center is coordinated in a distorted tetrahedral geometry to two tp ligands and two bpp ligands through two carboxylate groups and two nitrogen donors. An isostructural compound Cd(tp)(bpp) has been reported (Dai et al., 2004).