In the title Pb
II coordination polymer, [Pb(C
16H
10O
4)(C
14H
8N
4)(C
3H
7NO)]
n, each Pb
II atom is eight-coordinated by two chelating N atoms from one pyrazino[2,3-
f][1,10]phenanthroline (
L) ligand, one dimethylformamide (DMF) O atom and five carboxylate O atoms from three different 4,4′-ethylenedibenzoate (eedb) ligands. The eedb dianions bridge neighbouring Pb
II centres through four typical Pb—O bonds and one longer Pb—O interaction to form a two-dimensional structure. The C atoms from the
L and eedb ligands form C—H
O hydrogen bonds with the O atoms of eedb and DMF ligands, which further stabilize the structure. The title compound is the first Pb
II coordination polymer incorporating the
L ligand.
Supporting information
CCDC reference: 730076
Pb(NO3)2 (0.166 g, 0.5 mmol), H2eedb (0.133 g, 0.5 mmol) and L
(0.121 g, 0.5 mmol) were dissolved in a mixture of DMF (6 ml) and distilled
water (8 ml). The resulting mixture was stirred for about 1 h at room
temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and
heated at 398 K for 5 d under autogenous pressure. The reaction system was
gradually cooled to room temperature at a rate of 10 K h-1. Pale-yellow
crystals of (I) suitable for single-crystal X-ray diffraction analysis were
collected from the final reaction system by filtration, washed several times
with DMF, and dried in air at ambient temperature (yield 72%, based on
PbII).
Carbon-bound H atoms were positioned geometrically, with C—H = 0.93 Å, and
refined as riding, with Uiso(H) = 1.2Ueq(C). As the
N-heterocycle displays a minor spread of C—C distances, the central
six-carbon ring was refined as a rigid hexagon with sides of 1.39 Å. The DMF
is disordered over two sites with site occupancies 0.5:0.5. The C═O
distances were restrained to 1.25 (1) Å, Ccarbonyl—N to 1.35 (1) Å and
N—Cmethyl to 1.45 (1) Å. Each component was restrained to be nearly
planar. The anisotropic displacement parameters were restrained to be nearly
isotropic. The displacement parameters of the O5/O5' pair were restrained to
be identical. The final difference Fourier map has a large peak at 1 Å from
Pb1 but is otherwise featureless.
Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).
Poly[(
N,
N-dimethylformamide-
κO)(pyrazino[2,3-
f][1,10]phenanthroline-
κ2N8,
N9)(µ
3-ethylene-
4,4'-dibenzoato-
κ5O,O':O':O'',O''')lead(II)]
top
Crystal data top
[Pb(C16H10O4)(C14H8N4)(C3H7NO)] | F(000) = 1520 |
Mr = 778.77 | Dx = 1.818 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5805 reflections |
a = 9.0255 (7) Å | θ = 2.4–25.4° |
b = 25.5628 (19) Å | µ = 5.98 mm−1 |
c = 12.6422 (9) Å | T = 295 K |
β = 102.751 (1)° | Block, yellow |
V = 2844.8 (4) Å3 | 0.23 × 0.20 × 0.18 mm |
Z = 4 | |
Data collection top
Bruker APEX diffractometer | 5224 independent reflections |
Radiation source: fine-focus sealed tube | 4134 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ϕ and ω scans | θmax = 25.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.340, Tmax = 0.412 | k = −12→30 |
14893 measured reflections | l = −15→15 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0399P)2 + 4.4812P] where P = (Fo2 + 2Fc2)/3 |
5224 reflections | (Δ/σ)max = 0.001 |
428 parameters | Δρmax = 1.95 e Å−3 |
72 restraints | Δρmin = −0.92 e Å−3 |
Crystal data top
[Pb(C16H10O4)(C14H8N4)(C3H7NO)] | V = 2844.8 (4) Å3 |
Mr = 778.77 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.0255 (7) Å | µ = 5.98 mm−1 |
b = 25.5628 (19) Å | T = 295 K |
c = 12.6422 (9) Å | 0.23 × 0.20 × 0.18 mm |
β = 102.751 (1)° | |
Data collection top
Bruker APEX diffractometer | 5224 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4134 reflections with I > 2σ(I) |
Tmin = 0.340, Tmax = 0.412 | Rint = 0.046 |
14893 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 72 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.95 e Å−3 |
5224 reflections | Δρmin = −0.92 e Å−3 |
428 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 | Occ. (<1) |
Pb1 | 0.45452 (3) | 0.585997 (9) | 0.483565 (19) | 0.02326 (9) | |
O1 | 0.6637 (5) | 0.52420 (18) | 0.4907 (4) | 0.0301 (11) | |
O2 | 0.6154 (6) | 0.5642 (2) | 0.3318 (4) | 0.0390 (12) | |
O3 | 1.3624 (5) | 0.15296 (17) | −0.0077 (3) | 0.0275 (11) | |
O4 | 1.5564 (5) | 0.17430 (18) | 0.1258 (4) | 0.0311 (11) | |
N1 | 0.5570 (6) | 0.5704 (2) | 0.6895 (4) | 0.0242 (12) | |
N2 | 0.4967 (8) | 0.5918 (2) | 1.0566 (5) | 0.0439 (17) | |
N3 | 0.2946 (6) | 0.6750 (2) | 0.9881 (4) | 0.0322 (14) | |
N4 | 0.3587 (6) | 0.6508 (2) | 0.6228 (4) | 0.0241 (12) | |
C1 | 0.6833 (8) | 0.5301 (3) | 0.3943 (6) | 0.0288 (16) | |
C2 | 0.7903 (7) | 0.4924 (3) | 0.3572 (6) | 0.0288 (16) | |
C3 | 0.7983 (8) | 0.4897 (3) | 0.2501 (7) | 0.0409 (19) | |
H3 | 0.7411 | 0.5123 | 0.1994 | 0.049* | |
C4 | 0.8934 (9) | 0.4528 (3) | 0.2184 (7) | 0.047 (2) | |
H4 | 0.8970 | 0.4499 | 0.1457 | 0.057* | |
C5 | 0.9842 (8) | 0.4197 (3) | 0.2956 (7) | 0.0410 (19) | |
C6 | 0.9773 (8) | 0.4248 (3) | 0.4012 (7) | 0.0399 (19) | |
H6 | 1.0394 | 0.4040 | 0.4531 | 0.048* | |
C7 | 0.8802 (7) | 0.4601 (3) | 0.4332 (7) | 0.0345 (18) | |
H7 | 0.8751 | 0.4622 | 0.5058 | 0.041* | |
C8 | 1.0836 (9) | 0.3772 (3) | 0.2683 (7) | 0.044 (2) | |
H8 | 1.1586 | 0.3639 | 0.3244 | 0.053* | |
C9 | 1.0732 (9) | 0.3577 (3) | 0.1736 (7) | 0.045 (2) | |
H9 | 1.0036 | 0.3722 | 0.1156 | 0.054* | |
C10 | 1.1694 (8) | 0.3124 (3) | 0.1521 (7) | 0.0404 (19) | |
C11 | 1.1249 (8) | 0.2881 (3) | 0.0519 (7) | 0.045 (2) | |
H11 | 1.0396 | 0.3000 | 0.0024 | 0.054* | |
C12 | 1.2076 (8) | 0.2460 (3) | 0.0255 (6) | 0.0376 (18) | |
H12 | 1.1761 | 0.2298 | −0.0417 | 0.045* | |
C13 | 1.3364 (7) | 0.2275 (2) | 0.0974 (5) | 0.0229 (14) | |
C14 | 1.3782 (8) | 0.2521 (3) | 0.1975 (6) | 0.0319 (16) | |
H14 | 1.4638 | 0.2404 | 0.2471 | 0.038* | |
C15 | 1.2958 (8) | 0.2936 (3) | 0.2253 (6) | 0.0356 (18) | |
H15 | 1.3254 | 0.3090 | 0.2934 | 0.043* | |
C16 | 1.4257 (8) | 0.1825 (2) | 0.0710 (5) | 0.0255 (15) | |
C17 | 0.6550 (7) | 0.5318 (3) | 0.7235 (5) | 0.0279 (16) | |
H17 | 0.6986 | 0.5150 | 0.6726 | 0.033* | |
C18 | 0.6962 (7) | 0.5150 (3) | 0.8308 (5) | 0.0301 (16) | |
H18 | 0.7655 | 0.4879 | 0.8510 | 0.036* | |
C19 | 0.6316 (8) | 0.5395 (3) | 0.9054 (6) | 0.0323 (17) | |
H19 | 0.6565 | 0.5288 | 0.9774 | 0.039* | |
C20 | 0.5265 (4) | 0.58133 (14) | 0.8739 (3) | 0.0283 (15) | |
C21 | 0.4915 (4) | 0.59616 (14) | 0.7655 (3) | 0.0221 (14) | |
C27 | 0.3910 (5) | 0.63713 (15) | 0.7316 (2) | 0.0222 (14) | |
C26 | 0.3255 (4) | 0.66328 (13) | 0.8062 (3) | 0.0245 (15) | |
C25 | 0.3605 (5) | 0.64846 (16) | 0.9147 (3) | 0.0286 (16) | |
C22 | 0.4610 (5) | 0.60748 (17) | 0.9485 (2) | 0.0324 (17) | |
C23 | 0.4331 (9) | 0.6176 (3) | 1.1243 (6) | 0.045 (2) | |
H23 | 0.4556 | 0.6082 | 1.1972 | 0.055* | |
C24 | 0.3323 (9) | 0.6588 (3) | 1.0902 (6) | 0.043 (2) | |
H24 | 0.2896 | 0.6757 | 1.1415 | 0.052* | |
C28 | 0.2229 (7) | 0.7054 (2) | 0.7669 (5) | 0.0255 (15) | |
H28 | 0.1765 | 0.7238 | 0.8143 | 0.031* | |
C29 | 0.1937 (7) | 0.7183 (3) | 0.6584 (6) | 0.0304 (16) | |
H29 | 0.1270 | 0.7453 | 0.6315 | 0.037* | |
C30 | 0.2653 (7) | 0.6904 (2) | 0.5904 (6) | 0.0278 (16) | |
H30 | 0.2467 | 0.7001 | 0.5178 | 0.033* | |
O5 | 0.188 (2) | 0.5824 (8) | 0.2910 (14) | 0.067 (2) | 0.33 |
N5 | −0.034 (2) | 0.6263 (6) | 0.2463 (14) | 0.044 (8) | 0.33 |
C31 | 0.0558 (19) | 0.5846 (7) | 0.2381 (17) | 0.061 (8) | 0.33 |
H31 | 0.0171 | 0.5572 | 0.1917 | 0.073* | 0.33 |
C32 | 0.015 (4) | 0.6710 (10) | 0.316 (2) | 0.082 (10) | 0.33 |
H32A | −0.0177 | 0.6667 | 0.3829 | 0.123* | 0.33 |
H32B | −0.0286 | 0.7024 | 0.2806 | 0.123* | 0.33 |
H32C | 0.1237 | 0.6735 | 0.3311 | 0.123* | 0.33 |
C33 | −0.192 (2) | 0.6330 (11) | 0.188 (2) | 0.055 (8) | 0.33 |
H33A | −0.2176 | 0.6063 | 0.1337 | 0.083* | 0.33 |
H33B | −0.2037 | 0.6668 | 0.1537 | 0.083* | 0.33 |
H33C | −0.2574 | 0.6305 | 0.2380 | 0.083* | 0.33 |
O5' | 0.0340 (10) | 0.5715 (3) | 0.0756 (8) | 0.067 (2) | 0.67 |
N5' | −0.0390 (9) | 0.6231 (3) | 0.2045 (10) | 0.041 (3) | 0.67 |
C31' | −0.0554 (12) | 0.6017 (3) | 0.1066 (10) | 0.049 (3) | 0.67 |
H31' | −0.1434 | 0.6103 | 0.0559 | 0.058* | 0.67 |
C32' | 0.0962 (15) | 0.6112 (6) | 0.2885 (10) | 0.062 (4) | 0.67 |
H32D | 0.0664 | 0.5948 | 0.3489 | 0.093* | 0.67 |
H32E | 0.1500 | 0.6430 | 0.3122 | 0.093* | 0.67 |
H32F | 0.1610 | 0.5880 | 0.2596 | 0.093* | 0.67 |
C33' | −0.1524 (16) | 0.6576 (5) | 0.2306 (13) | 0.064 (4) | 0.67 |
H33D | −0.2099 | 0.6732 | 0.1652 | 0.096* | 0.67 |
H33E | −0.1035 | 0.6846 | 0.2787 | 0.096* | 0.67 |
H33F | −0.2192 | 0.6381 | 0.2651 | 0.096* | 0.67 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pb1 | 0.02697 (14) | 0.01988 (14) | 0.02203 (14) | −0.00089 (12) | 0.00348 (9) | −0.00001 (12) |
O1 | 0.034 (3) | 0.031 (3) | 0.026 (3) | 0.003 (2) | 0.005 (2) | 0.001 (2) |
O2 | 0.050 (3) | 0.038 (3) | 0.029 (3) | 0.021 (3) | 0.009 (2) | 0.009 (2) |
O3 | 0.033 (3) | 0.024 (3) | 0.024 (3) | 0.004 (2) | 0.003 (2) | −0.004 (2) |
O4 | 0.027 (3) | 0.029 (3) | 0.034 (3) | 0.005 (2) | −0.001 (2) | −0.006 (2) |
N1 | 0.022 (3) | 0.021 (3) | 0.027 (3) | 0.001 (2) | −0.001 (2) | 0.000 (2) |
N2 | 0.062 (4) | 0.049 (4) | 0.021 (3) | 0.031 (4) | 0.009 (3) | 0.006 (3) |
N3 | 0.038 (3) | 0.032 (3) | 0.025 (3) | 0.005 (3) | 0.001 (3) | −0.004 (3) |
N4 | 0.028 (3) | 0.020 (3) | 0.023 (3) | −0.002 (2) | 0.004 (2) | 0.003 (2) |
C1 | 0.031 (4) | 0.025 (4) | 0.030 (4) | 0.002 (3) | 0.005 (3) | −0.006 (3) |
C2 | 0.025 (3) | 0.027 (4) | 0.035 (4) | −0.004 (3) | 0.007 (3) | −0.004 (3) |
C3 | 0.045 (5) | 0.037 (5) | 0.047 (5) | 0.002 (4) | 0.024 (4) | −0.006 (4) |
C4 | 0.055 (5) | 0.054 (5) | 0.041 (5) | −0.013 (4) | 0.028 (4) | −0.018 (4) |
C5 | 0.032 (4) | 0.028 (4) | 0.065 (6) | −0.005 (3) | 0.014 (4) | −0.002 (4) |
C6 | 0.034 (4) | 0.028 (4) | 0.060 (6) | −0.003 (3) | 0.014 (4) | −0.007 (4) |
C7 | 0.026 (4) | 0.024 (4) | 0.053 (5) | −0.001 (3) | 0.006 (3) | −0.002 (4) |
C8 | 0.039 (5) | 0.044 (5) | 0.048 (5) | −0.010 (4) | 0.007 (4) | −0.003 (4) |
C9 | 0.039 (5) | 0.049 (5) | 0.046 (5) | −0.014 (4) | 0.005 (4) | −0.010 (4) |
C10 | 0.026 (4) | 0.035 (4) | 0.063 (6) | −0.002 (3) | 0.016 (4) | −0.009 (4) |
C11 | 0.031 (4) | 0.041 (5) | 0.058 (5) | 0.008 (4) | 0.000 (4) | −0.008 (4) |
C12 | 0.034 (4) | 0.033 (4) | 0.043 (4) | 0.008 (3) | 0.003 (3) | −0.008 (4) |
C13 | 0.023 (3) | 0.019 (3) | 0.028 (4) | −0.005 (3) | 0.009 (3) | −0.005 (3) |
C14 | 0.027 (4) | 0.035 (4) | 0.035 (4) | −0.010 (3) | 0.009 (3) | −0.002 (3) |
C15 | 0.039 (4) | 0.030 (4) | 0.040 (4) | −0.013 (3) | 0.016 (4) | −0.020 (3) |
C16 | 0.033 (4) | 0.019 (3) | 0.024 (4) | −0.005 (3) | 0.005 (3) | −0.004 (3) |
C17 | 0.030 (4) | 0.028 (4) | 0.023 (4) | 0.002 (3) | 0.000 (3) | −0.007 (3) |
C18 | 0.037 (4) | 0.023 (4) | 0.028 (4) | 0.014 (3) | 0.002 (3) | −0.003 (3) |
C19 | 0.045 (4) | 0.029 (4) | 0.020 (4) | 0.009 (3) | 0.000 (3) | 0.001 (3) |
C20 | 0.037 (4) | 0.024 (4) | 0.021 (3) | 0.004 (3) | −0.001 (3) | −0.002 (3) |
C21 | 0.026 (3) | 0.016 (3) | 0.023 (3) | −0.002 (3) | 0.003 (3) | 0.000 (3) |
C27 | 0.022 (3) | 0.015 (3) | 0.027 (4) | −0.002 (3) | −0.003 (3) | −0.001 (3) |
C26 | 0.024 (3) | 0.017 (3) | 0.033 (4) | −0.004 (3) | 0.007 (3) | −0.003 (3) |
C25 | 0.031 (4) | 0.026 (4) | 0.027 (4) | −0.001 (3) | 0.002 (3) | −0.002 (3) |
C22 | 0.033 (4) | 0.033 (4) | 0.027 (4) | 0.007 (3) | −0.001 (3) | −0.003 (3) |
C23 | 0.064 (5) | 0.046 (5) | 0.025 (4) | 0.024 (4) | 0.006 (4) | −0.001 (4) |
C24 | 0.058 (5) | 0.048 (5) | 0.024 (4) | 0.013 (4) | 0.010 (4) | −0.007 (4) |
C28 | 0.021 (3) | 0.022 (4) | 0.032 (4) | 0.003 (3) | 0.001 (3) | −0.005 (3) |
C29 | 0.025 (4) | 0.023 (4) | 0.042 (4) | 0.001 (3) | 0.003 (3) | 0.004 (3) |
C30 | 0.033 (4) | 0.020 (4) | 0.027 (4) | 0.000 (3) | −0.002 (3) | 0.005 (3) |
O5 | 0.065 (4) | 0.067 (5) | 0.064 (5) | 0.015 (4) | 0.005 (4) | 0.000 (4) |
N5 | 0.041 (11) | 0.046 (11) | 0.040 (11) | −0.002 (8) | 0.001 (8) | 0.007 (8) |
C31 | 0.067 (11) | 0.050 (11) | 0.070 (11) | 0.000 (9) | 0.023 (9) | −0.006 (9) |
C32 | 0.080 (12) | 0.083 (13) | 0.080 (13) | −0.001 (9) | 0.011 (9) | −0.009 (9) |
C33 | 0.056 (11) | 0.054 (11) | 0.054 (11) | 0.007 (9) | 0.011 (8) | 0.005 (8) |
O5' | 0.065 (4) | 0.067 (5) | 0.064 (5) | 0.015 (4) | 0.005 (4) | 0.000 (4) |
N5' | 0.030 (5) | 0.049 (6) | 0.043 (7) | 0.004 (5) | 0.006 (5) | 0.013 (5) |
C31' | 0.042 (6) | 0.042 (6) | 0.061 (7) | 0.013 (5) | 0.012 (5) | −0.006 (5) |
C32' | 0.069 (7) | 0.064 (7) | 0.049 (7) | −0.004 (7) | 0.003 (6) | 0.002 (6) |
C33' | 0.064 (7) | 0.065 (8) | 0.070 (8) | 0.016 (7) | 0.029 (6) | −0.010 (7) |
Geometric parameters (Å, º) top
Pb1—O1 | 2.448 (4) | C14—H14 | 0.9300 |
Pb1—O2 | 2.707 (5) | C15—H15 | 0.9300 |
Pb1—O3i | 2.352 (4) | C16—Pb1iii | 2.839 (7) |
Pb1—O4i | 2.638 (4) | C17—C18 | 1.392 (9) |
Pb1—O1ii | 3.055 (5) | C17—H17 | 0.9300 |
Pb1—O5 | 3.023 (17) | C18—C19 | 1.366 (9) |
Pb1—N1 | 2.594 (5) | C18—H18 | 0.9300 |
Pb1—N4 | 2.695 (5) | C19—C20 | 1.427 (7) |
O1—C1 | 1.278 (8) | C19—H19 | 0.9300 |
O2—C1 | 1.243 (8) | C20—C21 | 1.3900 |
O3—C16 | 1.279 (7) | C20—C22 | 1.3900 |
O3—Pb1iii | 2.352 (4) | C21—C27 | 1.3900 |
O4—C16 | 1.247 (7) | C27—C26 | 1.3900 |
O4—Pb1iii | 2.638 (4) | C26—C25 | 1.3900 |
N1—C17 | 1.331 (8) | C26—C28 | 1.436 (7) |
N1—C21 | 1.399 (6) | C25—C22 | 1.3900 |
N2—C23 | 1.310 (9) | C23—C24 | 1.396 (10) |
N2—C22 | 1.392 (6) | C23—H23 | 0.9300 |
N3—C24 | 1.326 (9) | C24—H24 | 0.9300 |
N3—C25 | 1.386 (6) | C28—C29 | 1.378 (9) |
N4—C30 | 1.324 (8) | C28—H28 | 0.9300 |
N4—C27 | 1.386 (6) | C29—C30 | 1.382 (9) |
C1—C2 | 1.511 (9) | C29—H29 | 0.9300 |
C2—C3 | 1.374 (10) | C30—H30 | 0.9300 |
C2—C7 | 1.385 (9) | O5—C31 | 1.233 (10) |
C3—C4 | 1.393 (10) | N5—C31 | 1.360 (10) |
C3—H3 | 0.9300 | N5—C32 | 1.452 (10) |
C4—C5 | 1.409 (11) | N5—C33 | 1.459 (10) |
C4—H4 | 0.9300 | C31—H31 | 0.9300 |
C5—C6 | 1.356 (11) | C32—H32A | 0.9600 |
C5—C8 | 1.498 (11) | C32—H32B | 0.9600 |
C6—C7 | 1.379 (10) | C32—H32C | 0.9600 |
C6—H6 | 0.9300 | C33—H33A | 0.9600 |
C7—H7 | 0.9300 | C33—H33B | 0.9600 |
C8—C9 | 1.281 (10) | C33—H33C | 0.9600 |
C8—H8 | 0.9300 | O5'—C31' | 1.240 (8) |
C9—C10 | 1.508 (11) | N5'—C31' | 1.332 (16) |
C9—H9 | 0.9300 | N5'—C33' | 1.443 (9) |
C10—C15 | 1.386 (10) | N5'—C32' | 1.462 (9) |
C10—C11 | 1.388 (11) | C31'—H31' | 0.9300 |
C11—C12 | 1.393 (10) | C32'—H32D | 0.9600 |
C11—H11 | 0.9300 | C32'—H32E | 0.9600 |
C12—C13 | 1.390 (9) | C32'—H32F | 0.9600 |
C12—H12 | 0.9300 | C33'—H33D | 0.9600 |
C13—C14 | 1.388 (9) | C33'—H33E | 0.9600 |
C13—C16 | 1.485 (9) | C33'—H33F | 0.9600 |
C14—C15 | 1.386 (9) | | |
| | | |
O3i—Pb1—O1 | 87.19 (16) | C15—C14—C13 | 121.7 (7) |
O3i—Pb1—N1 | 84.09 (15) | C15—C14—H14 | 119.2 |
O1—Pb1—N1 | 76.25 (16) | C13—C14—H14 | 119.2 |
O3i—Pb1—O4i | 52.34 (14) | C14—C15—C10 | 120.3 (7) |
O1—Pb1—O4i | 120.71 (15) | C14—C15—H15 | 119.9 |
N1—Pb1—O4i | 128.44 (15) | C10—C15—H15 | 119.9 |
O3i—Pb1—N4 | 77.60 (15) | O4—C16—O3 | 122.6 (6) |
O1—Pb1—N4 | 136.76 (15) | O4—C16—C13 | 119.9 (6) |
N1—Pb1—N4 | 62.21 (16) | O3—C16—C13 | 117.5 (6) |
O4i—Pb1—N4 | 80.59 (15) | O4—C16—Pb1iii | 68.0 (3) |
O3i—Pb1—O2 | 76.74 (16) | O3—C16—Pb1iii | 55.0 (3) |
O1—Pb1—O2 | 50.46 (14) | C13—C16—Pb1iii | 169.4 (4) |
N1—Pb1—O2 | 123.45 (15) | N1—C17—C18 | 124.0 (6) |
O4i—Pb1—O2 | 76.61 (15) | N1—C17—H17 | 118.0 |
N4—Pb1—O2 | 152.76 (16) | C18—C17—H17 | 118.0 |
O3i—Pb1—O5 | 122.6 (4) | C19—C18—C17 | 117.9 (6) |
O1—Pb1—O5 | 118.7 (4) | C19—C18—H18 | 121.1 |
N1—Pb1—O5 | 148.0 (4) | C17—C18—H18 | 121.1 |
O4i—Pb1—O5 | 70.9 (4) | C18—C19—C20 | 120.7 (6) |
N4—Pb1—O5 | 103.4 (4) | C18—C19—H19 | 119.6 |
O2—Pb1—O5 | 83.0 (4) | C20—C19—H19 | 119.6 |
C16i—Pb1—O5 | 96.3 (4) | C21—C20—C22 | 120.0 |
O3i—Pb1—O1ii | 155.40 (13) | C21—C20—C19 | 118.1 (4) |
O1—Pb1—O1ii | 71.68 (15) | C22—C20—C19 | 121.9 (4) |
N1—Pb1—O1ii | 78.86 (14) | C20—C21—C27 | 120.0 |
O4i—Pb1—O1ii | 150.62 (13) | C20—C21—N1 | 120.7 (3) |
N4—Pb1—O1ii | 109.10 (14) | C27—C21—N1 | 119.3 (3) |
O2—Pb1—O1ii | 98.05 (14) | N4—C27—C26 | 121.6 (3) |
O5—Pb1—O1ii | 79.8 (4) | N4—C27—C21 | 118.4 (3) |
C1—O1—Pb1 | 99.0 (4) | C26—C27—C21 | 120.0 |
C1—O2—Pb1 | 87.7 (4) | C27—C26—C25 | 120.0 |
C16—O3—Pb1iii | 98.5 (4) | C27—C26—C28 | 117.7 (4) |
C16—O4—Pb1iii | 86.0 (4) | C25—C26—C28 | 122.3 (4) |
C17—N1—C21 | 118.6 (5) | N3—C25—C26 | 119.3 (4) |
C17—N1—Pb1 | 120.2 (4) | N3—C25—C22 | 120.7 (4) |
C21—N1—Pb1 | 120.4 (3) | C26—C25—C22 | 120.0 |
C23—N2—C22 | 117.1 (6) | C25—C22—C20 | 120.0 |
C24—N3—C25 | 116.3 (6) | C25—C22—N2 | 120.9 (4) |
C30—N4—C27 | 118.6 (5) | C20—C22—N2 | 119.1 (4) |
C30—N4—Pb1 | 122.9 (4) | N2—C23—C24 | 121.9 (7) |
C27—N4—Pb1 | 117.8 (3) | N2—C23—H23 | 119.1 |
O2—C1—O1 | 122.4 (6) | C24—C23—H23 | 119.1 |
O2—C1—C2 | 120.6 (6) | N3—C24—C23 | 123.1 (7) |
O1—C1—C2 | 116.9 (6) | N3—C24—H24 | 118.4 |
C3—C2—C7 | 120.3 (7) | C23—C24—H24 | 118.4 |
C3—C2—C1 | 120.9 (6) | C29—C28—C26 | 119.4 (6) |
C7—C2—C1 | 118.8 (7) | C29—C28—H28 | 120.3 |
C2—C3—C4 | 119.1 (8) | C26—C28—H28 | 120.3 |
C2—C3—H3 | 120.4 | C28—C29—C30 | 118.9 (6) |
C4—C3—H3 | 120.4 | C28—C29—H29 | 120.6 |
C3—C4—C5 | 120.6 (8) | C30—C29—H29 | 120.6 |
C3—C4—H4 | 119.7 | N4—C30—C29 | 123.8 (6) |
C5—C4—H4 | 119.7 | N4—C30—H30 | 118.1 |
C6—C5—C4 | 118.6 (7) | C29—C30—H30 | 118.1 |
C6—C5—C8 | 117.2 (7) | C31—O5—Pb1 | 159.7 (13) |
C4—C5—C8 | 124.2 (8) | C31—N5—C32 | 124 (2) |
C5—C6—C7 | 121.5 (8) | C31—N5—C33 | 126 (2) |
C5—C6—H6 | 119.3 | C32—N5—C33 | 110.4 (19) |
C7—C6—H6 | 119.3 | O5—C31—N5 | 121 (2) |
C6—C7—C2 | 119.9 (8) | O5—C31—H31 | 119.4 |
C6—C7—H7 | 120.0 | N5—C31—H31 | 119.4 |
C2—C7—H7 | 120.0 | C31'—N5'—C33' | 121.6 (11) |
C9—C8—C5 | 125.0 (8) | C31'—N5'—C32' | 119.5 (10) |
C9—C8—H8 | 117.5 | C33'—N5'—C32' | 118.8 (13) |
C5—C8—H8 | 117.5 | O5'—C31'—N5' | 127.1 (12) |
C8—C9—C10 | 122.7 (8) | O5'—C31'—H31' | 116.5 |
C8—C9—H9 | 118.7 | N5'—C31'—H31' | 116.5 |
C10—C9—H9 | 118.7 | N5'—C32'—H32D | 109.5 |
C15—C10—C11 | 119.0 (7) | N5'—C32'—H32E | 109.5 |
C15—C10—C9 | 124.5 (7) | H32D—C32'—H32E | 109.5 |
C11—C10—C9 | 116.5 (7) | N5'—C32'—H32F | 109.5 |
C10—C11—C12 | 120.1 (7) | H32D—C32'—H32F | 109.5 |
C10—C11—H11 | 119.9 | H32E—C32'—H32F | 109.5 |
C12—C11—H11 | 119.9 | N5'—C33'—H33D | 109.5 |
C13—C12—C11 | 121.3 (7) | N5'—C33'—H33E | 109.5 |
C13—C12—H12 | 119.3 | H33D—C33'—H33E | 109.5 |
C11—C12—H12 | 119.3 | N5'—C33'—H33F | 109.5 |
C14—C13—C12 | 117.6 (6) | H33D—C33'—H33F | 109.5 |
C14—C13—C16 | 120.2 (6) | H33E—C33'—H33F | 109.5 |
C12—C13—C16 | 122.2 (6) | | |
| | | |
O3i—Pb1—O1—C1 | −78.5 (4) | C13—C14—C15—C10 | −1.1 (10) |
N1—Pb1—O1—C1 | −163.1 (4) | C11—C10—C15—C14 | 1.6 (11) |
O4i—Pb1—O1—C1 | −36.3 (4) | C9—C10—C15—C14 | −179.1 (7) |
N4—Pb1—O1—C1 | −147.1 (4) | Pb1iii—O4—C16—O3 | −6.8 (6) |
O2—Pb1—O1—C1 | −3.4 (4) | Pb1iii—O4—C16—C13 | 172.1 (6) |
C16i—Pb1—O1—C1 | −57.7 (4) | Pb1iii—O3—C16—O4 | 7.7 (7) |
O5—Pb1—O1—C1 | 47.4 (6) | Pb1iii—O3—C16—C13 | −171.3 (5) |
O1ii—Pb1—O1—C1 | 114.2 (4) | C14—C13—C16—O4 | −17.0 (9) |
O3i—Pb1—O2—C1 | 100.9 (4) | C12—C13—C16—O4 | 164.4 (6) |
O1—Pb1—O2—C1 | 3.5 (4) | C14—C13—C16—O3 | 162.0 (6) |
N1—Pb1—O2—C1 | 27.3 (5) | C12—C13—C16—O3 | −16.6 (9) |
O4i—Pb1—O2—C1 | 154.8 (4) | C14—C13—C16—Pb1iii | 119 (2) |
N4—Pb1—O2—C1 | 120.9 (4) | C12—C13—C16—Pb1iii | −59 (3) |
C16i—Pb1—O2—C1 | 128.1 (4) | C21—N1—C17—C18 | 0.5 (9) |
O5—Pb1—O2—C1 | −133.2 (5) | Pb1—N1—C17—C18 | −168.8 (5) |
O1ii—Pb1—O2—C1 | −54.6 (4) | N1—C17—C18—C19 | 0.2 (10) |
O3i—Pb1—N1—C17 | −100.2 (5) | C17—C18—C19—C20 | −0.6 (10) |
O1—Pb1—N1—C17 | −11.6 (5) | C18—C19—C20—C21 | 0.3 (8) |
O4i—Pb1—N1—C17 | −130.1 (4) | C18—C19—C20—C22 | −179.0 (5) |
N4—Pb1—N1—C17 | −179.2 (5) | C22—C20—C21—C27 | 0.0 |
O2—Pb1—N1—C17 | −30.3 (5) | C19—C20—C21—C27 | −179.3 (5) |
C16i—Pb1—N1—C17 | −111.9 (5) | C22—C20—C21—N1 | 179.7 (4) |
O5—Pb1—N1—C17 | 111.1 (8) | C19—C20—C21—N1 | 0.5 (5) |
O1ii—Pb1—N1—C17 | 62.0 (5) | C17—N1—C21—C20 | −0.8 (7) |
O3i—Pb1—N1—C21 | 90.7 (4) | Pb1—N1—C21—C20 | 168.4 (2) |
O1—Pb1—N1—C21 | 179.3 (4) | C17—N1—C21—C27 | 178.9 (4) |
O4i—Pb1—N1—C21 | 60.8 (4) | Pb1—N1—C21—C27 | −11.8 (5) |
N4—Pb1—N1—C21 | 11.7 (3) | C30—N4—C27—C26 | 1.3 (7) |
O2—Pb1—N1—C21 | 160.6 (3) | Pb1—N4—C27—C26 | −169.3 (2) |
C16i—Pb1—N1—C21 | 79.0 (4) | C30—N4—C27—C21 | −178.7 (4) |
O5—Pb1—N1—C21 | −58.0 (8) | Pb1—N4—C27—C21 | 10.6 (5) |
O1ii—Pb1—N1—C21 | −107.1 (4) | C20—C21—C27—N4 | −179.9 (4) |
O3i—Pb1—N4—C30 | 88.7 (5) | N1—C21—C27—N4 | 0.3 (5) |
O1—Pb1—N4—C30 | 160.8 (4) | C20—C21—C27—C26 | 0.0 |
N1—Pb1—N4—C30 | 178.5 (5) | N1—C21—C27—C26 | −179.7 (4) |
O4i—Pb1—N4—C30 | 35.4 (5) | N4—C27—C26—C25 | 179.9 (5) |
O2—Pb1—N4—C30 | 68.7 (6) | C21—C27—C26—C25 | 0.0 |
C16i—Pb1—N4—C30 | 61.7 (5) | N4—C27—C26—C28 | −0.3 (5) |
O5—Pb1—N4—C30 | −32.3 (6) | C21—C27—C26—C28 | 179.8 (4) |
O1ii—Pb1—N4—C30 | −116.0 (5) | C24—N3—C25—C26 | 179.8 (5) |
O3i—Pb1—N4—C27 | −101.1 (4) | C24—N3—C25—C22 | −0.4 (8) |
O1—Pb1—N4—C27 | −29.0 (5) | C27—C26—C25—N3 | 179.8 (5) |
N1—Pb1—N4—C27 | −11.3 (3) | C28—C26—C25—N3 | 0.0 (5) |
O4i—Pb1—N4—C27 | −154.4 (4) | C27—C26—C25—C22 | 0.0 |
O2—Pb1—N4—C27 | −121.1 (4) | C28—C26—C25—C22 | −179.8 (5) |
C16i—Pb1—N4—C27 | −128.1 (4) | N3—C25—C22—C20 | −179.8 (5) |
O5—Pb1—N4—C27 | 137.9 (5) | C26—C25—C22—C20 | 0.0 |
O1ii—Pb1—N4—C27 | 54.3 (4) | N3—C25—C22—N2 | 0.7 (6) |
Pb1—O2—C1—O1 | −6.1 (7) | C26—C25—C22—N2 | −179.5 (5) |
Pb1—O2—C1—C2 | 171.9 (6) | C21—C20—C22—C25 | 0.0 |
Pb1—O1—C1—O2 | 6.9 (7) | C19—C20—C22—C25 | 179.2 (5) |
Pb1—O1—C1—C2 | −171.2 (5) | C21—C20—C22—N2 | 179.5 (5) |
O2—C1—C2—C3 | −9.6 (10) | C19—C20—C22—N2 | −1.3 (6) |
O1—C1—C2—C3 | 168.5 (6) | C23—N2—C22—C25 | −0.8 (9) |
O2—C1—C2—C7 | 170.8 (6) | C23—N2—C22—C20 | 179.7 (6) |
O1—C1—C2—C7 | −11.1 (9) | C22—N2—C23—C24 | 0.7 (12) |
C7—C2—C3—C4 | 2.5 (10) | C25—N3—C24—C23 | 0.3 (11) |
C1—C2—C3—C4 | −177.1 (6) | N2—C23—C24—N3 | −0.5 (13) |
C2—C3—C4—C5 | −2.2 (11) | C27—C26—C28—C29 | −0.1 (7) |
C3—C4—C5—C6 | −0.2 (11) | C25—C26—C28—C29 | 179.6 (5) |
C3—C4—C5—C8 | 176.8 (7) | C26—C28—C29—C30 | −0.5 (9) |
C4—C5—C6—C7 | 2.3 (11) | C27—N4—C30—C29 | −2.0 (9) |
C8—C5—C6—C7 | −175.0 (6) | Pb1—N4—C30—C29 | 168.1 (5) |
C5—C6—C7—C2 | −1.9 (11) | C28—C29—C30—N4 | 1.6 (10) |
C3—C2—C7—C6 | −0.5 (10) | O3i—Pb1—O5—C31 | −110 (4) |
C1—C2—C7—C6 | 179.1 (6) | O1—Pb1—O5—C31 | 144 (4) |
C6—C5—C8—C9 | 160.2 (8) | N1—Pb1—O5—C31 | 32 (4) |
C4—C5—C8—C9 | −16.9 (12) | O4i—Pb1—O5—C31 | −101 (4) |
C5—C8—C9—C10 | −175.7 (7) | N4—Pb1—O5—C31 | −26 (4) |
C8—C9—C10—C15 | −12.8 (12) | O2—Pb1—O5—C31 | −179 (5) |
C8—C9—C10—C11 | 166.6 (8) | C16i—Pb1—O5—C31 | −107 (4) |
C15—C10—C11—C12 | −0.8 (12) | O1ii—Pb1—O5—C31 | 81 (4) |
C9—C10—C11—C12 | 179.8 (7) | Pb1—O5—C31—N5 | 51 (4) |
C10—C11—C12—C13 | −0.6 (12) | C32—N5—C31—O5 | −0.1 (3) |
C11—C12—C13—C14 | 1.0 (11) | C33—N5—C31—O5 | −179.9 (3) |
C11—C12—C13—C16 | 179.7 (7) | C33'—N5'—C31'—O5' | −179.7 (4) |
C12—C13—C14—C15 | −0.2 (10) | C32'—N5'—C31'—O5' | −0.3 (4) |
C16—C13—C14—C15 | −178.9 (6) | | |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+2, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O3iv | 0.93 | 2.52 | 3.435 (9) | 168 |
C15—H15···O3iv | 0.93 | 2.65 | 3.567 (8) | 170 |
C17—H17···O1 | 0.93 | 2.26 | 2.968 (8) | 132 |
C18—H18···O5ii | 0.93 | 2.64 | 3.22 (2) | 121 |
C18—H18···O5′ii | 0.93 | 2.39 | 3.309 (11) | 170 |
C23—H23···O2v | 0.93 | 2.27 | 3.090 (9) | 147 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iv) x, −y+1/2, z+1/2; (v) x, y, z+1. |
Experimental details
Crystal data |
Chemical formula | [Pb(C16H10O4)(C14H8N4)(C3H7NO)] |
Mr | 778.77 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 9.0255 (7), 25.5628 (19), 12.6422 (9) |
β (°) | 102.751 (1) |
V (Å3) | 2844.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.98 |
Crystal size (mm) | 0.23 × 0.20 × 0.18 |
|
Data collection |
Diffractometer | Bruker APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.340, 0.412 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14893, 5224, 4134 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.603 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.089, 1.03 |
No. of reflections | 5224 |
No. of parameters | 428 |
No. of restraints | 72 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.95, −0.92 |
Selected geometric parameters (Å, º) topPb1—O1 | 2.448 (4) | Pb1—O1ii | 3.055 (5) |
Pb1—O2 | 2.707 (5) | Pb1—O5 | 3.023 (17) |
Pb1—O3i | 2.352 (4) | Pb1—N1 | 2.594 (5) |
Pb1—O4i | 2.638 (4) | Pb1—N4 | 2.695 (5) |
| | | |
O3i—Pb1—O1 | 87.19 (16) | O3i—Pb1—O5 | 122.6 (4) |
O3i—Pb1—N1 | 84.09 (15) | O1—Pb1—O5 | 118.7 (4) |
O1—Pb1—N1 | 76.25 (16) | N1—Pb1—O5 | 148.0 (4) |
O3i—Pb1—O4i | 52.34 (14) | O4i—Pb1—O5 | 70.9 (4) |
O1—Pb1—O4i | 120.71 (15) | N4—Pb1—O5 | 103.4 (4) |
N1—Pb1—O4i | 128.44 (15) | O2—Pb1—O5 | 83.0 (4) |
O3i—Pb1—N4 | 77.60 (15) | C16i—Pb1—O5 | 96.3 (4) |
O1—Pb1—N4 | 136.76 (15) | O3i—Pb1—O1ii | 155.40 (13) |
N1—Pb1—N4 | 62.21 (16) | O1—Pb1—O1ii | 71.68 (15) |
O4i—Pb1—N4 | 80.59 (15) | N1—Pb1—O1ii | 78.86 (14) |
O3i—Pb1—O2 | 76.74 (16) | O4i—Pb1—O1ii | 150.62 (13) |
O1—Pb1—O2 | 50.46 (14) | N4—Pb1—O1ii | 109.10 (14) |
N1—Pb1—O2 | 123.45 (15) | O2—Pb1—O1ii | 98.05 (14) |
O4i—Pb1—O2 | 76.61 (15) | O5—Pb1—O1ii | 79.8 (4) |
N4—Pb1—O2 | 152.76 (16) | | |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O3iii | 0.93 | 2.52 | 3.435 (9) | 167.9 |
C15—H15···O3iii | 0.93 | 2.65 | 3.567 (8) | 169.9 |
C17—H17···O1 | 0.93 | 2.26 | 2.968 (8) | 132.1 |
C18—H18···O5ii | 0.93 | 2.64 | 3.22 (2) | 121.3 |
C18—H18···O5'ii | 0.93 | 2.39 | 3.309 (11) | 170.4 |
C23—H23···O2iv | 0.93 | 2.27 | 3.090 (9) | 146.5 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z+1/2; (iv) x, y, z+1. |
The rational design and synthesis of metal–organic coordination polymers with novel topological structures have attracted great interest from chemists because of their potential applications as functional solid materials, as well as their fascinating framework structures (Eddaoudi et al., 2001; Hagrman et al., 1999; Noveron et al., 2002; Yang et al., 2008). Until recently, research on coordination polymers has mainly focused on incorporation of s-, d- and even f-block metal ions as the coordination centres, while less consideration has been given to the metals of the p block (Xu et al., 2005). p-Block metal–organic materials may be important in applications such as electroluminescent devices or organic light-emitting diodes (OLEDs), and so have stimulated much interest (Tsuboi & Sifsten, 1991; Singh & Richter, 2004). As far as the intrinsic appeal of PbII is concerned, the presence of a 6s2 outer electron configuration not only leads to interesting topological arrangements, but also plays an important role in the luminescence action of the resulting complex (Deo & Godwin, 2000; Li & Lu, 2000). Lead(II), as a toxic heavy metal, is commonly found in critical life cycles due to its widespread use in numerous industrial applications (Andersen et al., 2006). The possible molecular mechanisms of the toxicity of PbII may affect several different types of protein. Therefore, good knowledge of the coordination properties of PbII, including aspects such as the lone pair of electrons, the coordination number and the coordination geometry, is crucial for understanding the toxicological properties of lead(II).
1,10-Phenanthroline (phen) has been widely used to build supramolecular architectures because of its excellent coordinating ability and large conjugated system that can easily form π–π interactions (Wang et al., 2005; Tong et al., 2000; Zheng et al., 2001). However, far less attention has been given to its derivatives (Yang, Ma et al., 2007; Yang, Li et al., 2007). Pyrazino[2,3-f][1,10]phenanthroline (L) is an important phen derivative. It possesses aromatic systems and is a good candidate for the construction of metal–organic supramolecular architectures (Wang et al., 2007). To the best of our knowledge, coordination polymers constructed from a PbII dicarboxylate ligand and L have not been documented so far (Yang, Ma et al., 2007). Here, we have selected the ethylene-4,4'-dibenzoate dianion (eedb) as an organic linker and L as an N-donor chelating ligand, generating the title new PbII coordination polymer, [Pb(eedb)(L)(DMF)] (DMF is dimethylformamide), (I), the structure of which we now report.
Selected bond lengths and angles for (I) are given in Table 1. As shown in Fig. 1, each PbII atom is eight-coordinated by two N atoms from one L ligand, one DMF O atom, and five carboxylate O atoms from three different eedb ligands (comprising four typical Pb—O bonds and one longer Pb···O interaction). The average Pb—O distance in (I) (Table 1) is comparable with that found in another crystallographically characterized PbII complex, [Pb(bpno)(NO3)2(H2O)]n (bpno is 4,4'-bipyridine N,N'-dioxide; Xu et al., 2005).
As depicted in Fig. 2, the eedb dianions bridge two neighbouring PbII centres, resulting in a one-dimensional chain structure along the b axis. It is noted that the L ligands are extended on both sides of the chains. Clearly, the N-containing chelating L ligand plays an important role in the formation of the chain structure. Two N atoms from the L ligand occupy two coordination positions of the PbII atom, while the remaining coordination positions are available for eedb ligands, allowing the formation of the chain structure. The L ligands from neighbouring chains are well matched [Meaning not clear - please rephrase] with eedb ligands, and adjacent chains are linked through π–π stacking interactions between L and eedb, with a centroid-to-centroid distance of 3.52 (3) Å (face-to-face distance of 3.41 Å), extending the chains into a three-dimensional supramolecular framework in the bc plane (Fig. 3). It is believed that the very strong π–π stacking interactions play an important role in stabilizing the chain structure and the supramolecular architecture. To the best of our knowledge, no other PbII coordination polymer containing the chelating ligand L has been reported so far, although several PbII complexes including phen-like chelating ligands have been reported (Yang, Ma et al., 2007). Finally, C—H···O interactions further stabilize the structure of (I) (Table 2).
It is noteworthy that the structure of (I) is different from that of the related structure [Zn(eedb)(L)(H2O)].0.5DMF (Wang et al., 2008), in which the eedb dianions bridge neighbouring ZnII centres to give a one-dimensional chain structure in the ab plane. In that structure, a three-dimensional supramolecular architecture is formed through two types of π–π interactions between neighbouring chains. One is between the centrosymmetrically related L ligands, and the second is between L and eedb ligands. The structure of (I) is also entirely different from that of the related polymer [Cd2(L)2(1,4-ndc)2] (1,4-ndc is 1,4-naphthalenedicarboxylate; Qiao et al., 2008), in which the 1,4-ndc ligands link the CdII centres to give an interesting six-connected three-dimensional α-Po-related architecture.
The stereochemical activity of the PbII lone pair of electrons is an interesting topic and often discussed. The geometries of PbII complexes can be classified as holo- and hemidirected. Holodirected refers to PbII complexes in which the bonds to the ligand atoms are located throughout the surface of an encompassing sphere, while hemidirected refers to those cases in which the bonds to the ligand atoms are directed through only part of an encompassing sphere (Shimoni-Livny et al., 1998). In compound (I), the central PbII atom is eight-coordinated by two N atoms, one DMF molecule and five carboxylate O atoms. The coordination of the ligands at the opening [Opening of what?] does not leave room for a lone pair of electrons. Therefore, this coordination environment can be considered somewhat holodirected. To date, several PbII coordination polymers with different phen derivatives have been reported (Yang, Li et al., 2007). The PbII coordination geometry of the polymer [Pb(1,4-ndc)(tcpn)2] [tcpn is 2-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)naphthol] is very similar to that observed in (I). In that structure, the PbII atom is also eight-coordinated by four N atoms and four carboxylate O atoms, and the bonds to the ligand atoms are distributed throughout the surface of the encompassing PbII sphere. Therefore, the coordination environment of the PbII atom can also be considered holodirected.