Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101002888/sk1453sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101002888/sk1453Isup2.hkl |
CCDC reference: 164626
The title compound was synthesized by mixing successively the methanol solution of Pb(NO3)2 (0.03 g, 0.1 mmol), bpe (0.02 g, 0.1 mmol), and KNCS (0.02 g, 0.2 mmol) at room temperature. Colorless crystals were obtained by slow evaporation of the solution.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids with numbering scheme. | |
Fig. 2. Packing diagram viewed down the a axis. |
[Pb(NCS)2(C12H12N2)] | F(000) = 476 |
Mr = 507.59 | Dx = 2.023 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6335 (1) Å | Cell parameters from 5094 reflections |
b = 5.6309 (1) Å | θ = 2.0–28.2° |
c = 14.8578 (2) Å | µ = 10.37 mm−1 |
β = 121.091 (1)° | T = 293 K |
V = 833.48 (2) Å3 | Prism, colourless |
Z = 2 | 0.42 × 0.28 × 0.22 mm |
Siemens SMART CCD area detector diffractometer | 3678 independent reflections |
Radiation source: fine-focus sealed tube | 3398 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.2°, θmin = 2.0° |
ω scans | h = −15→15 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −7→3 |
Tmin = 0.042, Tmax = 0.102 | l = −19→18 |
5572 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.089 | (Δ/σ)max = 0.001 |
S = 0.92 | Δρmax = 1.38 e Å−3 |
3678 reflections | Δρmin = −1.64 e Å−3 |
203 parameters | Extinction correction: SHELXTL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.0199 (10) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack, H. D. (1983), Acta Cryst. A39, 876-881 |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.006 (9) |
[Pb(NCS)2(C12H12N2)] | V = 833.48 (2) Å3 |
Mr = 507.59 | Z = 2 |
Monoclinic, Pc | Mo Kα radiation |
a = 11.6335 (1) Å | µ = 10.37 mm−1 |
b = 5.6309 (1) Å | T = 293 K |
c = 14.8578 (2) Å | 0.42 × 0.28 × 0.22 mm |
β = 121.091 (1)° |
Siemens SMART CCD area detector diffractometer | 3678 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3398 reflections with I > 2σ(I) |
Tmin = 0.042, Tmax = 0.102 | Rint = 0.050 |
5572 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.089 | Δρmax = 1.38 e Å−3 |
S = 0.92 | Δρmin = −1.64 e Å−3 |
3678 reflections | Absolute structure: Flack, H. D. (1983), Acta Cryst. A39, 876-881 |
203 parameters | Absolute structure parameter: 0.006 (9) |
2 restraints |
Experimental. he data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Coverage of the unique set is over 98.3% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible |
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 | ||
Pb | 1.00026 (7) | 0.59744 (4) | 0.25149 (6) | 0.03240 (12) | |
S1 | 0.7742 (4) | 1.3377 (9) | 0.2804 (4) | 0.0528 (10) | |
S2 | 1.2239 (4) | 1.3226 (10) | 0.2282 (4) | 0.0612 (12) | |
N1 | 0.8497 (9) | 0.9230 (16) | 0.2216 (9) | 0.053 (2) | |
N2 | 1.0960 (12) | 0.8898 (16) | 0.1902 (10) | 0.055 (2) | |
N3 | 0.8194 (7) | 0.5060 (16) | 0.0599 (5) | 0.0358 (16) | |
N4 | 0.1747 (9) | −0.1568 (17) | −0.5732 (6) | 0.048 (2) | |
C1 | 0.8185 (11) | 1.0955 (16) | 0.2469 (9) | 0.033 (2) | |
C2 | 1.1533 (12) | 1.070 (2) | 0.2083 (10) | 0.039 (3) | |
C3 | 0.8415 (11) | 0.317 (2) | 0.0169 (7) | 0.049 (2) | |
H3A | 0.9288 | 0.2603 | 0.0462 | 0.07 (4)* | |
C4 | 0.7387 (14) | 0.200 (3) | −0.0699 (10) | 0.045 (3) | |
H4B | 0.7566 | 0.0631 | −0.0955 | 0.10 (6)* | |
C5 | 0.6077 (9) | 0.292 (2) | −0.1190 (7) | 0.039 (2) | |
C6 | 0.5907 (10) | 0.487 (2) | −0.0753 (8) | 0.048 (2) | |
H6A | 0.5054 | 0.5527 | −0.1051 | 0.12 (7)* | |
C7 | 0.6965 (11) | 0.5943 (19) | 0.0126 (9) | 0.047 (3) | |
H7A | 0.6805 | 0.7321 | 0.0389 | 0.04 (3)* | |
C8 | 0.4961 (14) | 0.170 (3) | −0.2150 (10) | 0.053 (4) | |
H8A | 0.4116 | 0.2036 | −0.2194 | 0.05 (3)* | |
H8B | 0.5105 | 0.0000 | −0.2071 | 0.08 (5)* | |
C9 | 0.4861 (13) | 0.246 (2) | −0.3148 (8) | 0.049 (3) | |
H9A | 0.4678 | 0.4151 | −0.3245 | 0.09 (6)* | |
H9B | 0.5716 | 0.2183 | −0.3097 | 0.06 (4)* | |
C10 | 0.3775 (10) | 0.115 (2) | −0.4089 (7) | 0.044 (2) | |
C11 | 0.2417 (16) | 0.174 (3) | −0.4558 (12) | 0.052 (4) | |
H11A | 0.2158 | 0.3087 | −0.4343 | 0.06 (4)* | |
C12 | 0.1449 (11) | 0.028 (3) | −0.5359 (9) | 0.054 (3) | |
H12A | 0.0548 | 0.0651 | −0.5638 | 0.05 (4)* | |
C13 | 0.3028 (12) | −0.215 (2) | −0.5290 (9) | 0.052 (3) | |
H13A | 0.3254 | −0.3482 | −0.5536 | 0.04 (3)* | |
C14 | 0.4048 (12) | −0.085 (2) | −0.4478 (9) | 0.056 (3) | |
H14A | 0.4934 | −0.1341 | −0.4189 | 0.06 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pb | 0.03174 (15) | 0.02993 (15) | 0.02920 (16) | −0.0068 (2) | 0.01124 (11) | −0.0074 (2) |
S1 | 0.063 (3) | 0.0359 (17) | 0.079 (3) | 0.0086 (17) | 0.050 (2) | −0.0003 (19) |
S2 | 0.049 (2) | 0.042 (2) | 0.092 (3) | −0.0073 (18) | 0.035 (2) | −0.008 (2) |
N1 | 0.039 (5) | 0.046 (5) | 0.064 (6) | 0.006 (3) | 0.019 (5) | −0.015 (4) |
N2 | 0.068 (6) | 0.041 (5) | 0.071 (7) | −0.005 (4) | 0.047 (6) | 0.002 (4) |
N3 | 0.033 (4) | 0.044 (4) | 0.022 (3) | −0.005 (3) | 0.008 (3) | −0.009 (3) |
N4 | 0.048 (5) | 0.052 (5) | 0.029 (4) | −0.013 (4) | 0.010 (4) | −0.017 (4) |
C1 | 0.036 (5) | 0.033 (5) | 0.031 (6) | −0.004 (4) | 0.019 (5) | −0.002 (4) |
C2 | 0.039 (6) | 0.046 (6) | 0.032 (6) | 0.007 (4) | 0.017 (5) | 0.001 (4) |
C3 | 0.042 (5) | 0.062 (6) | 0.029 (4) | 0.003 (5) | 0.008 (4) | −0.007 (5) |
C4 | 0.047 (6) | 0.041 (7) | 0.034 (6) | 0.002 (5) | 0.013 (5) | −0.004 (5) |
C5 | 0.037 (5) | 0.045 (5) | 0.030 (4) | −0.011 (4) | 0.012 (4) | 0.002 (4) |
C6 | 0.031 (4) | 0.058 (6) | 0.041 (5) | −0.006 (5) | 0.008 (4) | −0.008 (5) |
C7 | 0.038 (5) | 0.050 (7) | 0.039 (5) | 0.002 (4) | 0.010 (4) | −0.011 (4) |
C8 | 0.055 (7) | 0.059 (7) | 0.038 (6) | −0.026 (6) | 0.018 (6) | −0.010 (5) |
C9 | 0.049 (7) | 0.061 (8) | 0.026 (5) | −0.028 (6) | 0.012 (5) | −0.014 (5) |
C10 | 0.036 (5) | 0.062 (7) | 0.023 (4) | −0.014 (4) | 0.007 (4) | −0.008 (4) |
C11 | 0.051 (7) | 0.056 (7) | 0.040 (7) | −0.010 (6) | 0.016 (6) | −0.023 (6) |
C12 | 0.034 (5) | 0.070 (7) | 0.041 (5) | −0.010 (5) | 0.008 (4) | −0.007 (6) |
C13 | 0.054 (6) | 0.041 (6) | 0.050 (6) | 0.001 (5) | 0.018 (5) | −0.014 (5) |
C14 | 0.044 (6) | 0.066 (8) | 0.043 (6) | 0.004 (5) | 0.012 (5) | −0.013 (5) |
Pb—N2 | 2.415 (9) | C5—C8 | 1.508 (14) |
Pb—N1 | 2.413 (9) | C6—C7 | 1.387 (14) |
Pb—N3 | 2.570 (7) | C6—H6A | 0.9300 |
Pb—N4i | 2.713 (8) | C7—H7A | 0.9300 |
S1—C1 | 1.625 (11) | C8—C9 | 1.488 (16) |
S2—C2 | 1.591 (14) | C8—H8A | 0.9700 |
N1—C1 | 1.165 (12) | C8—H8B | 0.9701 |
N2—C2 | 1.167 (15) | C9—C10 | 1.508 (13) |
N3—C3 | 1.336 (15) | C9—H9A | 0.9701 |
N3—C7 | 1.322 (13) | C9—H9B | 0.9699 |
N4—C12 | 1.308 (16) | C10—C14 | 1.375 (16) |
N4—C13 | 1.323 (15) | C10—C11 | 1.40 (2) |
N4—Pbii | 2.713 (8) | C11—C12 | 1.406 (17) |
C3—C4 | 1.389 (17) | C11—H11A | 0.9300 |
C3—H3A | 0.9300 | C12—H12A | 0.9300 |
C4—C5 | 1.404 (17) | C13—C14 | 1.386 (15) |
C4—H4B | 0.9300 | C13—H13A | 0.9300 |
C5—C6 | 1.343 (17) | C14—H14A | 0.9301 |
N2—Pb—N1 | 81.1 (3) | N3—C7—H7A | 119.1 |
N2—Pb—N3 | 89.6 (4) | C6—C7—H7A | 119.1 |
N1—Pb—N3 | 81.2 (3) | C9—C8—C5 | 113.5 (10) |
N2—Pb—N4i | 75.7 (4) | C9—C8—H8A | 108.8 |
N1—Pb—N4i | 84.3 (3) | C5—C8—H8A | 108.9 |
N3—Pb—N4i | 160.7 (3) | C9—C8—H8B | 108.9 |
C1—N1—Pb | 153.1 (9) | C5—C8—H8B | 108.8 |
C2—N2—Pb | 145.7 (10) | H8A—C8—H8B | 107.7 |
C3—N3—C7 | 117.9 (8) | C8—C9—C10 | 112.4 (9) |
C3—N3—Pb | 116.1 (6) | C8—C9—H9A | 109.1 |
C7—N3—Pb | 123.8 (7) | C10—C9—H9A | 109.2 |
C12—N4—C13 | 117.7 (9) | C8—C9—H9B | 109.1 |
C12—N4—Pbii | 125.6 (7) | C10—C9—H9B | 109.1 |
C13—N4—Pbii | 116.3 (7) | H9A—C9—H9B | 107.9 |
N1—C1—S1 | 179.2 (11) | C14—C10—C11 | 115.7 (10) |
N2—C2—S2 | 176.9 (12) | C14—C10—C9 | 121.7 (11) |
N3—C3—C4 | 122.3 (11) | C11—C10—C9 | 122.3 (12) |
N3—C3—H3A | 118.8 | C12—C11—C10 | 119.1 (14) |
C4—C3—H3A | 118.9 | C12—C11—H11A | 120.5 |
C5—C4—C3 | 119.5 (12) | C10—C11—H11A | 120.4 |
C5—C4—H4B | 120.2 | N4—C12—C11 | 123.6 (12) |
C3—C4—H4B | 120.2 | N4—C12—H12A | 118.3 |
C4—C5—C6 | 116.1 (9) | C11—C12—H12A | 118.2 |
C4—C5—C8 | 119.9 (12) | N4—C13—C14 | 122.7 (12) |
C6—C5—C8 | 124.0 (10) | N4—C13—H13A | 118.7 |
C5—C6—C7 | 122.1 (10) | C14—C13—H13A | 118.6 |
C5—C6—H6A | 118.9 | C10—C14—C13 | 121.2 (11) |
C7—C6—H6A | 119.0 | C10—C14—H14A | 119.3 |
N3—C7—C6 | 121.8 (10) | C13—C14—H14A | 119.5 |
N2—Pb—N1—C1 | −86 (2) | C3—N3—C7—C6 | 4.1 (17) |
N3—Pb—N1—C1 | −177 (2) | Pb—N3—C7—C6 | −158.6 (9) |
N4i—Pb—N1—C1 | −10 (2) | C5—C6—C7—N3 | −1.8 (19) |
N1—Pb—N2—C2 | 67.1 (17) | C4—C5—C8—C9 | −84.9 (15) |
N3—Pb—N2—C2 | 148.2 (18) | C6—C5—C8—C9 | 95.1 (14) |
N4i—Pb—N2—C2 | −19.3 (17) | C5—C8—C9—C10 | 177.7 (13) |
N2—Pb—N3—C3 | 98.1 (8) | C8—C9—C10—C14 | −94.9 (14) |
N1—Pb—N3—C3 | 179.2 (8) | C8—C9—C10—C11 | 78.8 (17) |
N4i—Pb—N3—C3 | 137.4 (10) | C14—C10—C11—C12 | 1 (2) |
N2—Pb—N3—C7 | −99.0 (9) | C9—C10—C11—C12 | −173.1 (13) |
N1—Pb—N3—C7 | −17.9 (9) | C13—N4—C12—C11 | 4 (2) |
N4i—Pb—N3—C7 | −59.6 (13) | Pbii—N4—C12—C11 | −168.7 (12) |
C7—N3—C3—C4 | −5.3 (18) | C10—C11—C12—N4 | −3 (2) |
Pb—N3—C3—C4 | 158.7 (10) | C12—N4—C13—C14 | −1.7 (19) |
N3—C3—C4—C5 | 4 (2) | Pbii—N4—C13—C14 | 171.3 (10) |
C3—C4—C5—C6 | −1.7 (18) | C11—C10—C14—C13 | 0.7 (19) |
C3—C4—C5—C8 | 178.3 (12) | C9—C10—C14—C13 | 174.8 (12) |
C4—C5—C6—C7 | 0.6 (18) | N4—C13—C14—C10 | 0 (2) |
C8—C5—C6—C7 | −179.4 (11) |
Symmetry codes: (i) x+1, y+1, z+1; (ii) x−1, y−1, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Pb(NCS)2(C12H12N2)] |
Mr | 507.59 |
Crystal system, space group | Monoclinic, Pc |
Temperature (K) | 293 |
a, b, c (Å) | 11.6335 (1), 5.6309 (1), 14.8578 (2) |
β (°) | 121.091 (1) |
V (Å3) | 833.48 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 10.37 |
Crystal size (mm) | 0.42 × 0.28 × 0.22 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.042, 0.102 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5572, 3678, 3398 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.089, 0.92 |
No. of reflections | 3678 |
No. of parameters | 203 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.38, −1.64 |
Absolute structure | Flack, H. D. (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | 0.006 (9) |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
Pb—N2 | 2.415 (9) | Pb—N3 | 2.570 (7) |
Pb—N1 | 2.413 (9) | Pb—N4i | 2.713 (8) |
N2—Pb—N1 | 81.1 (3) | N3—Pb—N4i | 160.7 (3) |
N2—Pb—N3 | 89.6 (4) | C1—N1—Pb | 153.1 (9) |
N1—Pb—N3 | 81.2 (3) | C2—N2—Pb | 145.7 (10) |
N2—Pb—N4i | 75.7 (4) | N1—C1—S1 | 179.2 (11) |
N1—Pb—N4i | 84.3 (3) | N2—C2—S2 | 176.9 (12) |
Symmetry code: (i) x+1, y+1, z+1. |
The study of coordination polymers in modern supramolecular chemistry has spawned tremendous interest in the role of multifunctional bridging ligands in determining the final type or topology of the self-assembled product. Among these basic building blocks, 4,4'-bipyridine and its derivatives have been widely employed for their appropriate rigidity and capacity in the construction of solid-state architecture, mostly with linear chain structures (Fujita & Kwon, 1994; Witherly & Blake, 1997; Losier & Zaworotko, 1996; Hennigar et al., 1997; Lu et al., 1997). The main effort in this field have been devoted to their reactions with transition metals with different coordination numbers and preferences. However, there are few reports on bivalent main group metal polymers such as PbII polymers with these spacers. We report here the self assembly of a two-dimensional polymer with PbII, (I). \sch
The PbII adopts a distorted octahedral geometry. The bpe acts as a bridge between two PbII centers to result in the formation of a linear Pb-pbe-Pb chain. The terminal S atoms of the NCS- ligands make short contacts with the PbII atom of the neighbouring polymeric chain to form an infinite two-dimensional polymeric structure (Fig. 2).
Its octahedral coordination is defined by four N atoms and two S atoms: two N atoms belong to NCS- anions [Pb—N1 = 2.413 (9), Pb—N2 = 2.415 (9) Å], two other N atoms belong to the bpe units [Pb—N3 = 2.570 (7), Pb—N4i= 2.713 (8) Å] and two S atoms [Pb—S1ii = 3.226 (6), Pb—S2ii = 3.196 (6) Å]. The equatorial plane consists of N1, N2, S1ii and S2ii atoms whereas the axial atoms are N3 and N4i. [Symmetry codes: (i) 1 + x, 1 + y, 1 + z; (ii) x, -1 + y, z].
The N3—Pb—N4i angle is 160.7 (3)°, smaller than those found in the related transition metal assemblies exhibiting M-anti-bpe-M bridges (Hong & Do, 1998; Hernandez et al., 1999, 2000; Fujita et al., 1994). The chain exhibits slight zigzag characteristics. The terminal NCS- groups is almost linear with N—C—S angles of 176.9 (1) and 179.2 (1)°, respectively. The connections between the PbII atom and two NCS- groups are bent with the Pb—N—C angles of 145.7 (1) and 153.1 (9)°, respectively. It can be deduced that the bivalent main group metals exhibiting different coordination preferences influence the crystal packing and final structure of self-assembled product.