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Reactions of 2-(hydroxymethyl)pyridine (Hhmp) with PbCl
2 and Pb(NO
3)
2 at room temperature led to the formation of two novel compounds, namely tetrakis[
3-(pyridin-2-yl)methanolato]-
tetrahedro-tetrakis[chloridolead(II)], [Pb
4(C
6H
6NO)
4Cl
4], (I), and poly[(
2-nitrato)[
2-(pyridin-2-yl)methanolato]lead(II)], [Pb(C
6H
6NO)(NO
3)]
n, (II). Compound (I) exhibits a tetranuclear Pb
4O
4 cubane structure, which is connected through
-
stacking interactions between the pyridine groups of the (pyridin-2-yl)methanolate (hmp
-) ligands and through C-H
Cl interactions to form an interesting threefold diamondoid network. Compound (II) possesses two-dimensional (4,4)-sql topology based on a Pb
2O
2 unit, which is further extended into a three-dimensional supramolecular network through
-
stacking interactions between adjacent pyridine rings and through C-H
O interactions between the pyridine C atoms of the hmp
- ligands and the nitrate anions.
Supporting information
CCDC references: 695068; 695069
For both compounds, data collection: SMART (Bruker, 2006); cell refinement: SMART (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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).
(I) Tetrakis[µ
3-(pyridin-2-yl)methanolato]-
tetrahedro-tetrakis[chloridolead(II)]
top
Crystal data top
[Pb4(C6H6NO)4Cl4] | Dx = 2.968 Mg m−3 |
Mr = 1403.03 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 2590 reflections |
Hall symbol: -I 4ad | θ = 2.7–27.9° |
a = 15.373 (3) Å | µ = 21.76 mm−1 |
c = 13.287 (2) Å | T = 298 K |
V = 3140.2 (9) Å3 | Block, colourless |
Z = 4 | 0.22 × 0.16 × 0.14 mm |
F(000) = 2496 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1374 independent reflections |
Radiation source: fine-focus sealed tube | 1111 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
φ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2006) | h = −18→15 |
Tmin = 0.087, Tmax = 0.151 | k = −18→11 |
5724 measured reflections | l = −13→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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0179P)2 + 15.1275P] where P = (Fo2 + 2Fc2)/3 |
1374 reflections | (Δ/σ)max = 0.001 |
91 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −1.09 e Å−3 |
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 | |
Pb1 | 0.082587 (19) | 0.15495 (2) | 1.01747 (2) | 0.02877 (13) | |
Cl1 | 0.25474 (16) | 0.1803 (3) | 1.0781 (2) | 0.0868 (11) | |
O1 | 0.0748 (3) | 0.3044 (3) | 1.0454 (4) | 0.0294 (13) | |
N1 | 0.1143 (4) | 0.2488 (4) | 0.8570 (5) | 0.0314 (16) | |
C1 | 0.1333 (6) | 0.3577 (6) | 0.9861 (6) | 0.043 (2) | |
H1A | 0.1906 | 0.3562 | 1.0166 | 0.051* | |
H1B | 0.1130 | 0.4174 | 0.9880 | 0.051* | |
C2 | 0.1407 (5) | 0.3302 (5) | 0.8800 (6) | 0.0271 (18) | |
C3 | 0.1749 (5) | 0.3846 (6) | 0.8075 (6) | 0.037 (2) | |
H3 | 0.1937 | 0.4403 | 0.8242 | 0.044* | |
C4 | 0.1808 (6) | 0.3546 (6) | 0.7095 (6) | 0.046 (2) | |
H4 | 0.2039 | 0.3901 | 0.6596 | 0.055* | |
C5 | 0.1525 (5) | 0.2729 (6) | 0.6861 (6) | 0.040 (2) | |
H5 | 0.1555 | 0.2523 | 0.6204 | 0.048* | |
C6 | 0.1200 (6) | 0.2225 (6) | 0.7610 (6) | 0.040 (2) | |
H6 | 0.1008 | 0.1669 | 0.7449 | 0.047* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pb1 | 0.0318 (2) | 0.0293 (2) | 0.02518 (18) | 0.00448 (14) | 0.00250 (13) | −0.00316 (13) |
Cl1 | 0.0322 (14) | 0.181 (4) | 0.0474 (16) | 0.0112 (18) | 0.0063 (12) | 0.0237 (19) |
O1 | 0.033 (3) | 0.028 (3) | 0.027 (3) | −0.008 (2) | 0.007 (2) | 0.000 (2) |
N1 | 0.034 (4) | 0.032 (4) | 0.029 (4) | −0.002 (3) | −0.002 (3) | 0.002 (3) |
C1 | 0.044 (6) | 0.043 (6) | 0.041 (5) | −0.021 (4) | 0.011 (4) | −0.003 (4) |
C2 | 0.024 (4) | 0.028 (5) | 0.030 (4) | 0.002 (4) | 0.000 (3) | 0.000 (4) |
C3 | 0.028 (5) | 0.042 (5) | 0.041 (5) | 0.003 (4) | 0.003 (4) | 0.013 (4) |
C4 | 0.048 (6) | 0.057 (7) | 0.033 (5) | 0.011 (5) | 0.015 (4) | 0.022 (5) |
C5 | 0.050 (6) | 0.044 (6) | 0.026 (5) | 0.008 (5) | 0.000 (4) | 0.000 (4) |
C6 | 0.059 (6) | 0.036 (5) | 0.024 (4) | 0.003 (5) | −0.005 (4) | −0.002 (4) |
Geometric parameters (Å, º) top
Pb1—O1 | 2.330 (5) | C1—H1A | 0.9700 |
Pb1—O1i | 2.527 (5) | C1—H1B | 0.9700 |
Pb1—O1ii | 2.544 (5) | C2—C3 | 1.379 (11) |
Pb1—N1 | 2.620 (6) | C3—C4 | 1.385 (12) |
Pb1—Cl1 | 2.794 (3) | C3—H3 | 0.9300 |
O1—C1 | 1.450 (10) | C4—C5 | 1.364 (12) |
O1—Pb1i | 2.527 (5) | C4—H4 | 0.9300 |
O1—Pb1iii | 2.544 (5) | C5—C6 | 1.357 (11) |
N1—C6 | 1.342 (9) | C5—H5 | 0.9300 |
N1—C2 | 1.351 (10) | C6—H6 | 0.9300 |
C1—C2 | 1.476 (11) | | |
| | | |
O1—Pb1—O1i | 71.5 (2) | O1—C1—H1A | 108.8 |
O1—Pb1—O1ii | 73.45 (18) | C2—C1—H1A | 108.8 |
O1i—Pb1—O1ii | 70.30 (18) | O1—C1—H1B | 108.8 |
O1—Pb1—N1 | 66.17 (19) | C2—C1—H1B | 108.8 |
O1i—Pb1—N1 | 99.27 (18) | H1A—C1—H1B | 107.7 |
O1ii—Pb1—N1 | 139.46 (18) | N1—C2—C3 | 121.3 (7) |
O1—Pb1—Cl1 | 82.26 (15) | N1—C2—C1 | 117.2 (7) |
O1i—Pb1—Cl1 | 146.16 (14) | C3—C2—C1 | 121.5 (8) |
O1ii—Pb1—Cl1 | 82.12 (13) | C2—C3—C4 | 118.6 (8) |
N1—Pb1—Cl1 | 88.94 (15) | C2—C3—H3 | 120.7 |
C1—O1—Pb1 | 116.1 (5) | C4—C3—H3 | 120.7 |
C1—O1—Pb1i | 112.0 (5) | C5—C4—C3 | 120.1 (8) |
Pb1—O1—Pb1i | 105.65 (19) | C5—C4—H4 | 120.0 |
C1—O1—Pb1iii | 111.1 (5) | C3—C4—H4 | 120.0 |
Pb1—O1—Pb1iii | 108.5 (2) | C6—C5—C4 | 118.4 (8) |
Pb1i—O1—Pb1iii | 102.61 (17) | C6—C5—H5 | 120.8 |
C6—N1—C2 | 118.3 (7) | C4—C5—H5 | 120.8 |
C6—N1—Pb1 | 128.4 (5) | N1—C6—C5 | 123.4 (8) |
C2—N1—Pb1 | 112.5 (5) | N1—C6—H6 | 118.3 |
O1—C1—C2 | 113.9 (7) | C5—C6—H6 | 118.3 |
Symmetry codes: (i) −x, −y+1/2, z; (ii) y−1/4, −x+1/4, −z+9/4; (iii) −y+1/4, x+1/4, −z+9/4. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···Cl1iv | 0.93 | 2.77 | 3.550 (9) | 142 |
Symmetry code: (iv) −y+1/4, x−1/4, z−1/4. |
(II) Poly[(µ
2-nitrato)[µ
2-(pyridin-2-yl)methanolato]lead(II)]
top
Crystal data top
[Pb(C6H6NO)(NO3)] | F(000) = 680 |
Mr = 377.32 | Dx = 2.883 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2331 reflections |
a = 10.0543 (15) Å | θ = 2.4–28.1° |
b = 10.3292 (16) Å | µ = 19.39 mm−1 |
c = 8.3716 (9) Å | T = 298 K |
β = 91.388 (2)° | Block, yellow |
V = 869.2 (2) Å3 | 0.28 × 0.23 × 0.22 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1518 independent reflections |
Radiation source: fine-focus sealed tube | 1252 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
φ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2006) | h = −11→11 |
Tmin = 0.074, Tmax = 0.100 | k = −11→12 |
3802 measured reflections | l = −9→4 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0351P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
1518 reflections | Δρmax = 1.59 e Å−3 |
119 parameters | Δρmin = −1.80 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0049 (4) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | |
Pb1 | 0.93927 (3) | −0.05917 (3) | 0.20092 (4) | 0.0301 (2) | |
O1 | 0.8952 (7) | 0.0696 (6) | −0.0113 (8) | 0.0403 (18) | |
O2 | 1.0286 (9) | 0.1634 (7) | 0.3088 (11) | 0.070 (3) | |
O3 | 1.1890 (9) | 0.2372 (8) | 0.4475 (12) | 0.079 (3) | |
O4 | 1.1623 (8) | 0.0280 (8) | 0.4271 (11) | 0.063 (2) | |
N1 | 0.6985 (9) | 0.0298 (8) | 0.1954 (9) | 0.036 (2) | |
N2 | 1.1300 (9) | 0.1414 (10) | 0.3974 (10) | 0.045 (2) | |
C1 | 0.7879 (11) | 0.1593 (10) | −0.0178 (14) | 0.048 (3) | |
H1A | 0.7566 | 0.1682 | −0.1278 | 0.057* | |
H1B | 0.8197 | 0.2433 | 0.0180 | 0.057* | |
C2 | 0.6725 (10) | 0.1185 (9) | 0.0840 (11) | 0.032 (2) | |
C3 | 0.5461 (11) | 0.1696 (9) | 0.0632 (12) | 0.042 (3) | |
H3 | 0.5300 | 0.2326 | −0.0143 | 0.050* | |
C4 | 0.4468 (11) | 0.1286 (12) | 0.1544 (14) | 0.047 (3) | |
H4 | 0.3613 | 0.1612 | 0.1388 | 0.057* | |
C5 | 0.4719 (12) | 0.0400 (11) | 0.2684 (15) | 0.051 (3) | |
H5 | 0.4043 | 0.0122 | 0.3341 | 0.062* | |
C6 | 0.6000 (12) | −0.0100 (12) | 0.2874 (12) | 0.045 (3) | |
H6 | 0.6171 | −0.0721 | 0.3656 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pb1 | 0.0311 (3) | 0.0292 (3) | 0.0300 (3) | 0.00098 (16) | −0.00076 (16) | 0.00509 (14) |
O1 | 0.041 (5) | 0.039 (4) | 0.041 (4) | 0.010 (3) | 0.010 (3) | 0.015 (3) |
O2 | 0.073 (6) | 0.052 (5) | 0.083 (6) | −0.006 (4) | −0.040 (5) | 0.005 (4) |
O3 | 0.072 (7) | 0.057 (5) | 0.104 (8) | −0.010 (5) | −0.045 (6) | −0.022 (5) |
O4 | 0.052 (6) | 0.050 (5) | 0.086 (7) | 0.015 (4) | −0.008 (5) | 0.013 (5) |
N1 | 0.040 (5) | 0.040 (5) | 0.027 (4) | 0.001 (4) | −0.006 (4) | 0.002 (4) |
N2 | 0.037 (6) | 0.058 (6) | 0.039 (5) | 0.006 (5) | 0.003 (4) | 0.000 (5) |
C1 | 0.042 (7) | 0.046 (6) | 0.056 (7) | 0.018 (6) | 0.008 (5) | 0.018 (5) |
C2 | 0.035 (6) | 0.029 (5) | 0.032 (5) | 0.004 (5) | −0.002 (4) | −0.001 (4) |
C3 | 0.048 (7) | 0.036 (6) | 0.042 (6) | 0.013 (5) | 0.003 (5) | 0.004 (5) |
C4 | 0.039 (7) | 0.055 (7) | 0.048 (6) | 0.014 (6) | −0.005 (5) | −0.012 (6) |
C5 | 0.037 (7) | 0.068 (8) | 0.049 (7) | 0.004 (6) | 0.014 (5) | −0.010 (6) |
C6 | 0.042 (7) | 0.053 (7) | 0.041 (6) | 0.005 (7) | −0.004 (5) | 0.002 (6) |
Geometric parameters (Å, º) top
Pb1—O1 | 2.255 (6) | N1—C2 | 1.328 (12) |
Pb1—O1i | 2.330 (7) | N1—C6 | 1.334 (14) |
Pb1—N1 | 2.589 (9) | C1—C2 | 1.516 (15) |
Pb1—O2 | 2.621 (7) | C1—H1A | 0.9700 |
Pb1—O3ii | 2.748 (8) | C1—H1B | 0.9700 |
Pb1—O2ii | 2.885 (8) | C2—C3 | 1.384 (13) |
Pb1—O4 | 3.036 (8) | C3—C4 | 1.340 (15) |
O1—C1 | 1.422 (12) | C3—H3 | 0.9300 |
O1—Pb1i | 2.330 (7) | C4—C5 | 1.341 (17) |
O2—N2 | 1.267 (10) | C4—H4 | 0.9300 |
O3—N2 | 1.223 (11) | C5—C6 | 1.393 (16) |
O3—Pb1iii | 2.748 (8) | C5—H5 | 0.9300 |
O4—N2 | 1.239 (11) | C6—H6 | 0.9300 |
| | | |
O1—Pb1—O1i | 67.7 (3) | C2—N1—C6 | 118.8 (9) |
O1—Pb1—N1 | 67.1 (3) | C2—N1—Pb1 | 115.2 (7) |
O1i—Pb1—N1 | 133.4 (2) | C6—N1—Pb1 | 125.9 (7) |
O1—Pb1—O2 | 79.2 (2) | O3—N2—O4 | 125.0 (9) |
O1i—Pb1—O2 | 91.8 (3) | O3—N2—O2 | 115.6 (9) |
N1—Pb1—O2 | 90.4 (3) | O4—N2—O2 | 119.3 (9) |
O1—Pb1—O3ii | 90.8 (2) | O1—C1—C2 | 112.8 (8) |
O1i—Pb1—O3ii | 89.5 (3) | O1—C1—H1A | 109.0 |
N1—Pb1—O3ii | 80.5 (3) | C2—C1—H1A | 109.0 |
O2—Pb1—O3ii | 168.6 (2) | O1—C1—H1B | 109.0 |
O1—Pb1—O2ii | 125.7 (2) | C2—C1—H1B | 109.0 |
O1i—Pb1—O2ii | 81.5 (3) | H1A—C1—H1B | 107.8 |
N1—Pb1—O2ii | 117.2 (3) | N1—C2—C3 | 121.1 (10) |
O2—Pb1—O2ii | 147.50 (7) | N1—C2—C1 | 116.5 (9) |
O3ii—Pb1—O2ii | 43.8 (2) | C3—C2—C1 | 122.4 (9) |
O1—Pb1—O4 | 116.4 (2) | C4—C3—C2 | 120.1 (10) |
O1i—Pb1—O4 | 84.8 (3) | C4—C3—H3 | 119.9 |
N1—Pb1—O4 | 125.6 (2) | C2—C3—H3 | 119.9 |
O2—Pb1—O4 | 44.2 (2) | C3—C4—C5 | 119.4 (11) |
O3ii—Pb1—O4 | 147.2 (2) | C3—C4—H4 | 120.3 |
O2ii—Pb1—O4 | 103.3 (2) | C5—C4—H4 | 120.3 |
C1—O1—Pb1 | 123.3 (6) | C4—C5—C6 | 119.4 (12) |
C1—O1—Pb1i | 123.9 (6) | C4—C5—H5 | 120.3 |
Pb1—O1—Pb1i | 112.3 (3) | C6—C5—H5 | 120.3 |
N2—O2—Pb1 | 108.0 (6) | N1—C6—C5 | 121.1 (11) |
N2—O3—Pb1iii | 104.2 (6) | N1—C6—H6 | 119.4 |
N2—O4—Pb1 | 88.3 (5) | C5—C6—H6 | 119.4 |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+2, y−1/2, −z+1/2; (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 |
C5—H5···O4iv | 0.93 | 2.58 | 3.416 (16) | 150 |
C4—H4···O3v | 0.93 | 2.56 | 3.380 (13) | 148 |
Symmetry codes: (iv) x−1, y, z; (v) x−1, −y+1/2, z−1/2. |
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