catena-Poly[[lead(II)-μ-N′-[1-(pyridin-2-yl-κN)ethyl­idene]isonicotino­hydrazidato-κ³N′,O:N¹] perchlorate]

The Pb^II atom in the polymeric title compound, {[Pb(C₁₃H₁₁N₄O)]ClO₄}_n, is coordinated by the N′-[1-(pyridin-2-yl-κN)ethyl­idene]isonicotinohydrazidate ligand via its O,N,N′-donors and simultaneously bridged by a neighbouring ligand via the pyridin-2-yl N atom. The resultant supra­molecular chain is a zigzag along the a axis. The stereochemistry of the Pb^II atom is defined by an N₃OE donor set (E = lone pair of electrons), which results in a Ψ-trigonal–bipyramidal coordination with the O and pyridin-2-yl N atoms in axial positions. The dihedral angle between the pyridine rings of the ligand is 6.3 (3)°. The supra­molecular cationic chains are linked into a three-dimensional array via secondary Pb...O [3.133 (6) and 3.28 (7) Å] and Pb...N [3.028 (4) Å] inter­actions. Weak C—H...O inter­actions and aromatic π–π stacking [centroid–centroid separation = 3.693 (2) Å] also occur in the crystal.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.022
• wR factor = 0.056
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .         32 A   3 
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          2

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          72 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

Structural studies of coordination complexes containing the N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand are rare (Maurya et al., 2002; Abboud et al., 2007; Zhang & Liu, 2009; Hao et al., 2010). In each of these, the ligand coordinates in a tridentate mode with the terminal 4-pyridyl-N atom being non-coordinating. In the title lead(II) complex, (I), all four donor atoms participate in coordination of the Pb atom.

The asymmetric unit of (I), Fig. 1, comprises a Pb atom, a N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide anion and a perchlorate anion. The N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand coordinates a lead atom in a tridentate mode, via the N1, N2 and O1 atoms, and simultaneously bridges a symmetry related lead atom via the 4-pyridyl-N4 atom, Table 1.

The resultant N₃O donor set plus the lone pair of electrons is based on a trigonal bipyramid with the O1 and N1 atoms in axial positions [O1—Pb—N1 = 126.27 (12)°] and the remaining N atoms [N2—Pb—N4ⁱ = 90.17 (13)°] and lone pair in equatorial positions; symmetry operation i: -1/2 + x, 1.5 - y, -1/2 + z. The µ₂-bridging mode of the tetradentate N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand leads to a zigzag chain along the a axis, Fig. 2. The considerable distortions from the ideal geometry arise from the acute chelate angles (O1—Pb—N2 = 64.75 (12)° and N1—Pb—N2 = 63.45 (12)°) as well as the close approach of other donor atoms. Most notable amongst the latter are Pb···O(perchlorate) interactions with the two shortest contacts being Pb···O4ⁱⁱ of 3.133 (6) Å and Pb···O5ⁱⁱⁱ = 3.287 (7) Å for i: -1 + x, y, z and ii: 1 - x, 1 - y, 2 - z. These interactions along with Pb···N3ⁱⁱⁱ contacts of 3.028 (4) Å [iii: 1 - x, 1 - y, 2 - z] generate a three-dimensional architecture, Fig. 3.

Related literature

For the structures of metal complexes containing the N'-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand, see: Maurya et al. (2002); Abboud et al. (2007); Zhang & Liu (2009); Hao et al. (2010). For specialized crystallization techniques, see: Harrowfield et al. (1996).

S2. Experimental

A solution of methyl 2-pyridyl ketone (10 mmol) in MeOH (25 ml) was added drop wise to a solution of 4-pyridinecarboxylic acid hydrazide (10 mmol) in MeOH (15 ml). The mixture was refluxed for 6 h. The white precipitate was removed by filtration and recrystallized from MeOH solution. Then the ligand (1 mmol) was placed in one arm of a branched tube (Harrowfield et al., 1996) and a mixture of lead(II) acetate (1 mmol) and sodium perchlorate (1 mmol) in the other. Methanol was then added to fill both arms, the tube sealed and the ligand-containing arm immersed in a bath at 333 K, while the other was left at ambient temperature. After 1 week, yellow needles of (I) had deposited in the arm held at ambient temperature. They were then filtered off, washed with acetone and ether, and air dried. Yield: 75%. M.pt.: 506 K

S3. Refinement

Carbon-bound H-atoms were placed in calculated positions [C—H 0.93–0.96 Å, U_iso(H) = 1.2–1.5U_eq(parent atom)] and were included in the refinement in the riding model approximation.

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit of (I) showing displacement ellipsoids at the 35% probability level. The molecular structure has been expanded to indicate the µ2-bridging mode of the tetradentate ligand. Symmetry operation i: -1/2 + x, 1.5 - y, -1/2 + z; ii: 1/2 + x, 1.5 - y, 1/2 + z.
	Fig. 2. A view of the zigzag chain along the a axis in (I).
	Fig. 3. A view in projection down the a axis of the crystal packing in (I). The weaker Pb···O and Pb···N interactions (see text) are shown as black and blue dashed lines, respectively.

catena-Poly[[lead(II)-µ-N'-[1-(pyridin-2- yl-κN)ethylidene]isonicotinohydrazidato- κ³N',O:N¹] perchlorate]

Crystal data

[Pb(C13H11N4O)]ClO4	F(000) = 1024
Mr = 545.90	Dx = 2.268 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4195 reflections
a = 10.0620 (6) Å	θ = 2.3–25.0°
b = 14.4431 (8) Å	µ = 10.75 mm^−1
c = 11.1456 (7) Å	T = 293 K
β = 99.174 (1)°	Needle, yellow
V = 1599.03 (16) Å^3	0.29 × 0.11 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2811 independent reflections
Radiation source: fine-focus sealed tube	2392 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.691, Tmax = 1.000	k = −11→17
8396 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.056	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0241P)^2 + 1.6546P] where P = (Fo^2 + 2Fc^2)/3
2811 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Pb	0.260829 (17)	0.509355 (12)	0.899845 (16)	0.03242 (8)
O1	0.3478 (3)	0.6440 (2)	1.0129 (3)	0.0444 (9)
N1	0.3495 (4)	0.4394 (3)	0.7130 (4)	0.0376 (10)
N2	0.4858 (4)	0.5592 (3)	0.8673 (3)	0.0308 (9)
N3	0.5527 (4)	0.6241 (3)	0.9458 (4)	0.0350 (10)
N4	0.6569 (4)	0.8756 (3)	1.2492 (4)	0.0388 (10)
C1	0.4775 (5)	0.4584 (3)	0.7001 (4)	0.0341 (11)
C2	0.5405 (6)	0.4140 (4)	0.6142 (5)	0.0435 (13)
H2	0.6291	0.4280	0.6070	0.052*
C3	0.4696 (7)	0.3487 (4)	0.5400 (5)	0.0528 (15)
H3	0.5103	0.3183	0.4818	0.063*
C4	0.3396 (6)	0.3285 (4)	0.5516 (5)	0.0511 (15)
H4	0.2907	0.2843	0.5021	0.061*
C5	0.2827 (6)	0.3754 (4)	0.6388 (5)	0.0465 (13)
H5	0.1940	0.3621	0.6466	0.056*
C6	0.5476 (5)	0.5291 (3)	0.7823 (4)	0.0303 (10)
C7	0.6833 (5)	0.5647 (4)	0.7653 (5)	0.0457 (13)
H7A	0.6929	0.6278	0.7926	0.068*
H7B	0.6918	0.5617	0.6808	0.068*
H7C	0.7521	0.5275	0.8117	0.068*
C8	0.4712 (5)	0.6637 (3)	1.0126 (4)	0.0310 (11)
C9	0.5353 (5)	0.7392 (3)	1.0933 (4)	0.0328 (11)
C10	0.4698 (5)	0.7752 (3)	1.1837 (5)	0.0367 (11)
H10	0.3848	0.7541	1.1932	0.044*
C11	0.5342 (5)	0.8432 (3)	1.2592 (5)	0.0389 (12)
H11	0.4903	0.8675	1.3196	0.047*
C12	0.7181 (6)	0.8406 (4)	1.1623 (6)	0.0511 (15)
H12	0.8036	0.8621	1.1550	0.061*
C13	0.6599 (5)	0.7735 (4)	1.0819 (5)	0.0492 (14)
H13	0.7048	0.7518	1.0207	0.059*
Cl1	0.95237 (15)	0.36424 (10)	0.81424 (16)	0.0580 (4)
O2	0.8284 (6)	0.3288 (5)	0.7644 (6)	0.123 (2)
O3	1.0468 (7)	0.2953 (5)	0.8172 (8)	0.166 (4)
O4	0.9936 (6)	0.4365 (4)	0.7458 (5)	0.1034 (19)
O5	0.9435 (7)	0.3990 (5)	0.9303 (6)	0.136 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb	0.02641 (11)	0.03361 (12)	0.03622 (12)	−0.00167 (8)	0.00186 (8)	0.00472 (8)
O1	0.024 (2)	0.051 (2)	0.058 (2)	−0.0028 (16)	0.0077 (17)	−0.0170 (18)
N1	0.038 (2)	0.035 (2)	0.039 (2)	−0.0048 (18)	0.0035 (19)	−0.0047 (18)
N2	0.026 (2)	0.028 (2)	0.037 (2)	0.0003 (16)	−0.0002 (18)	−0.0026 (17)
N3	0.032 (2)	0.031 (2)	0.040 (2)	−0.0021 (17)	0.0030 (19)	−0.0055 (18)
N4	0.033 (2)	0.034 (2)	0.048 (3)	−0.0015 (18)	0.002 (2)	−0.0085 (19)
C1	0.042 (3)	0.026 (2)	0.033 (3)	0.000 (2)	0.004 (2)	0.003 (2)
C2	0.050 (3)	0.039 (3)	0.044 (3)	−0.005 (2)	0.016 (3)	−0.008 (2)
C3	0.071 (4)	0.043 (3)	0.047 (3)	−0.005 (3)	0.018 (3)	−0.011 (3)
C4	0.069 (4)	0.043 (3)	0.038 (3)	−0.017 (3)	0.001 (3)	−0.013 (3)
C5	0.038 (3)	0.044 (3)	0.055 (3)	−0.012 (2)	0.000 (3)	−0.006 (3)
C6	0.029 (3)	0.029 (2)	0.033 (3)	0.001 (2)	0.003 (2)	0.002 (2)
C7	0.041 (3)	0.052 (3)	0.046 (3)	−0.010 (3)	0.015 (3)	−0.008 (3)
C8	0.030 (3)	0.028 (2)	0.033 (3)	0.0022 (19)	−0.002 (2)	0.0010 (19)
C9	0.033 (3)	0.029 (3)	0.034 (3)	0.000 (2)	−0.001 (2)	−0.004 (2)
C10	0.030 (3)	0.037 (3)	0.043 (3)	0.000 (2)	0.005 (2)	−0.004 (2)
C11	0.037 (3)	0.040 (3)	0.040 (3)	0.001 (2)	0.008 (2)	−0.007 (2)
C12	0.036 (3)	0.051 (3)	0.070 (4)	−0.011 (3)	0.018 (3)	−0.023 (3)
C13	0.040 (3)	0.052 (3)	0.059 (4)	−0.011 (3)	0.019 (3)	−0.020 (3)
Cl1	0.0411 (8)	0.0515 (9)	0.0836 (12)	−0.0050 (7)	0.0165 (8)	0.0117 (8)
O2	0.070 (4)	0.162 (6)	0.140 (5)	−0.055 (4)	0.026 (4)	−0.042 (5)
O3	0.128 (6)	0.143 (6)	0.246 (9)	0.083 (5)	0.084 (6)	0.103 (6)
O4	0.114 (5)	0.073 (3)	0.132 (5)	−0.007 (3)	0.046 (4)	0.040 (3)
O5	0.134 (6)	0.191 (7)	0.090 (4)	−0.061 (5)	0.035 (4)	−0.037 (5)

Geometric parameters (Å, º)

Pb—O1	2.405 (3)	C4—H4	0.9300
Pb—N1	2.597 (4)	C5—H5	0.9300
Pb—N2	2.456 (4)	C6—C7	1.499 (6)
Pb—N4^i	2.472 (4)	C7—H7A	0.9600
O1—C8	1.274 (5)	C7—H7B	0.9600
N1—C1	1.347 (6)	C7—H7C	0.9600
N1—C5	1.347 (6)	C8—C9	1.494 (6)
N2—C6	1.289 (6)	C9—C13	1.372 (7)
N2—N3	1.383 (5)	C9—C10	1.389 (7)
N3—C8	1.322 (6)	C10—C11	1.385 (7)
N4—C12	1.329 (6)	C10—H10	0.9300
N4—C11	1.341 (6)	C11—H11	0.9300
N4—Pb^ii	2.472 (4)	C12—C13	1.385 (7)
C1—C2	1.387 (7)	C12—H12	0.9300
C1—C6	1.475 (7)	C13—H13	0.9300
C2—C3	1.376 (7)	Cl1—O3	1.372 (6)
C2—H2	0.9300	Cl1—O2	1.380 (5)
C3—C4	1.367 (8)	Cl1—O4	1.394 (5)
C3—H3	0.9300	Cl1—O5	1.404 (6)
C4—C5	1.381 (7)
O1—Pb—N2	64.75 (12)	N2—C6—C7	122.3 (4)
O1—Pb—N4^i	83.77 (14)	C1—C6—C7	120.9 (4)
N2—Pb—N4^i	90.17 (13)	C6—C7—H7A	109.5
O1—Pb—N1	126.27 (12)	C6—C7—H7B	109.5
N2—Pb—N1	63.45 (12)	H7A—C7—H7B	109.5
N4^i—Pb—N1	83.07 (13)	C6—C7—H7C	109.5
C8—O1—Pb	116.9 (3)	H7A—C7—H7C	109.5
C1—N1—C5	117.8 (4)	H7B—C7—H7C	109.5
C1—N1—Pb	117.6 (3)	O1—C8—N3	126.7 (4)
C5—N1—Pb	123.9 (3)	O1—C8—C9	119.3 (4)
C6—N2—N3	116.7 (4)	N3—C8—C9	114.1 (4)
C6—N2—Pb	125.0 (3)	C13—C9—C10	118.6 (4)
N3—N2—Pb	118.2 (3)	C13—C9—C8	121.4 (4)
C8—N3—N2	111.5 (4)	C10—C9—C8	120.0 (4)
C12—N4—C11	117.9 (4)	C11—C10—C9	118.4 (5)
C12—N4—Pb^ii	123.8 (3)	C11—C10—H10	120.8
C11—N4—Pb^ii	118.3 (3)	C9—C10—H10	120.8
N1—C1—C2	122.0 (5)	N4—C11—C10	123.0 (5)
N1—C1—C6	116.5 (4)	N4—C11—H11	118.5
C2—C1—C6	121.6 (5)	C10—C11—H11	118.5
C3—C2—C1	118.8 (5)	N4—C12—C13	122.8 (5)
C3—C2—H2	120.6	N4—C12—H12	118.6
C1—C2—H2	120.6	C13—C12—H12	118.6
C2—C3—C4	120.2 (5)	C9—C13—C12	119.4 (5)
C2—C3—H3	119.9	C9—C13—H13	120.3
C4—C3—H3	119.9	C12—C13—H13	120.3
C3—C4—C5	118.2 (5)	O3—Cl1—O2	108.6 (5)
C3—C4—H4	120.9	O3—Cl1—O4	106.9 (4)
C5—C4—H4	120.9	O2—Cl1—O4	112.7 (4)
N1—C5—C4	123.1 (5)	O3—Cl1—O5	112.5 (5)
N1—C5—H5	118.5	O2—Cl1—O5	108.5 (4)
C4—C5—H5	118.5	O4—Cl1—O5	107.7 (4)
N2—C6—C1	116.8 (4)
N2—Pb—O1—C8	−10.2 (3)	C3—C4—C5—N1	−0.4 (9)
N4^i—Pb—O1—C8	−103.3 (4)	N3—N2—C6—C1	178.8 (4)
N1—Pb—O1—C8	−26.7 (4)	Pb—N2—C6—C1	−0.9 (6)
O1—Pb—N1—C1	23.1 (4)	N3—N2—C6—C7	−2.2 (7)
N2—Pb—N1—C1	6.4 (3)	Pb—N2—C6—C7	178.1 (3)
N4^i—Pb—N1—C1	100.1 (3)	N1—C1—C6—N2	7.1 (7)
O1—Pb—N1—C5	−166.7 (4)	C2—C1—C6—N2	−172.7 (4)
N2—Pb—N1—C5	176.6 (4)	N1—C1—C6—C7	−171.9 (4)
N4^i—Pb—N1—C5	−89.7 (4)	C2—C1—C6—C7	8.2 (7)
O1—Pb—N2—C6	−167.9 (4)	Pb—O1—C8—N3	8.1 (6)
N4^i—Pb—N2—C6	−84.9 (4)	Pb—O1—C8—C9	−172.5 (3)
N1—Pb—N2—C6	−2.7 (3)	N2—N3—C8—O1	3.4 (7)
O1—Pb—N2—N3	12.4 (3)	N2—N3—C8—C9	−176.0 (4)
N4^i—Pb—N2—N3	95.4 (3)	O1—C8—C9—C13	−169.0 (5)
N1—Pb—N2—N3	177.6 (3)	N3—C8—C9—C13	10.5 (7)
C6—N2—N3—C8	167.1 (4)	O1—C8—C9—C10	12.2 (7)
Pb—N2—N3—C8	−13.1 (5)	N3—C8—C9—C10	−168.3 (4)
C5—N1—C1—C2	−0.4 (7)	C13—C9—C10—C11	−0.8 (8)
Pb—N1—C1—C2	170.4 (4)	C8—C9—C10—C11	178.0 (4)
C5—N1—C1—C6	179.8 (5)	C12—N4—C11—C10	0.3 (8)
Pb—N1—C1—C6	−9.5 (5)	Pb^ii—N4—C11—C10	−176.6 (4)
N1—C1—C2—C3	0.2 (8)	C9—C10—C11—N4	−0.2 (8)
C6—C1—C2—C3	−179.9 (5)	C11—N4—C12—C13	0.7 (9)
C1—C2—C3—C4	−0.2 (9)	Pb^ii—N4—C12—C13	177.4 (4)
C2—C3—C4—C5	0.2 (9)	C10—C9—C13—C12	1.7 (8)
C1—N1—C5—C4	0.5 (8)	C8—C9—C13—C12	−177.1 (5)
Pb—N1—C5—C4	−169.7 (4)	N4—C12—C13—C9	−1.7 (9)

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3^iii	0.93	2.53	3.422 (10)	160
C4—H4···O1^iv	0.93	2.45	3.277 (7)	148
C10—H10···O2^v	0.93	2.57	3.485 (8)	170

Symmetry codes: (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y−1/2, −z+3/2; (v) −x+1, −y+1, −z+2.