The tetrel bonding role in supramolecular aggregation of lead(II) acetate and a thio­semi­carbazide derivative

A new Pb^II coordination complex [PbL(OAc)], which was readily synthesized from a mixture of Pb(OAc)₂·3H₂O and 1-(pyridin-2-yl)benzyl­idene-4-phenyl­thio­semicarbazide (HL) is reported. The crystal structure analysis of [PbL(OAc)] showed that the Pb^II cation is N,N′,S-chelated by the tridentate pincer-type ligand L and by the oxygen atoms of the acetate anion. In addition, the metal centre forms Pb...O and Pb...S tetrel bonds with an adjacent complex molecule, yielding a 1D zigzag polymeric chain, which is reinforced by N—H...O hydrogen bonds and π...π interactions. These chains are interlinked by C—H...py non-covalent interactions, realized between one of the acetate hydrogen atoms and the pyridine rings. According to the Hirshfeld surface analysis, the crystal packing is mainly characterized by intermolecular H...H, H...C and H...O contacts, followed by H...N, H...S, C...C, C...N, Pb...H, Pb...O and Pb...S contacts. The FTIR and ¹H NMR spectra of [PbL(OAc)] testify to the deprotonation of the parent ligand HL, while the acetate ligand exhibits an anisobidentate coordination mode as established by means of single-crystal X-ray diffraction and FTIR spectroscopy. Lastly, theoretical calculations at the PBE0-D3/def2-TZVP level of theory have been used to analyze and characterize the Pb...O and Pb...S tetrel bonds observed in the crystal of [PbL(OAc)], using a combination of QTAIM (Quantum Theory of Atoms in Molecules) and NCIPlot (Non-Covalent Interaction Plot) computational tools.

Computing details

Data collection: APEX3 Software (Bruker, 2019); cell refinement: APEX3 Software (Bruker, 2019); data reduction: APEX3 Software (Bruker, 2019); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2013); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: PLATON (Spek, 2019); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2013).

(I)

Crystal data

C21H18N4O2PbS	F(000) = 572
Mr = 597.64	Dx = 2.035 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.9341 (3) Å	Cell parameters from 9172 reflections
b = 8.0140 (3) Å	θ = 2.6–36.4°
c = 15.3431 (6) Å	µ = 8.78 mm^−1
β = 91.259 (1)°	T = 100 K
V = 975.34 (6) Å^3	Plate, yellow
Z = 2	0.36 × 0.14 × 0.03 mm

Data collection

Bruker D8 VENTURE PHOTON III-14 diffractometer	5796 reflections with I > 2σ(I)
Radiation source: microfocus sealed tube	Rint = 0.043
ω and phi scans	θmax = 30.5°, θmin = 2.7°
Absorption correction: multi-scan SADABS	h = −11→11
Tmin = 0.500, Tmax = 1.000	k = −11→11
49015 measured reflections	l = −21→21
5956 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.015	H-atom parameters constrained
wR(F^2) = 0.034	w = 1/[σ^2(Fo^2) + (0.011P)^2 + 0.6765P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
5956 reflections	Δρmax = 0.59 e Å^−3
262 parameters	Δρmin = −0.83 e Å^−3
1 restraint	Absolute structure: Flack x determined using 2643 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.017 (3)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pb1	0.05513 (2)	0.62125 (2)	0.06365 (2)	0.01198 (3)
S1	−0.16612 (11)	0.87318 (11)	0.11064 (6)	0.01481 (15)
O1	0.2972 (3)	0.7953 (4)	0.06055 (17)	0.0187 (5)
O2	0.1760 (4)	0.8336 (3)	−0.06990 (19)	0.0191 (5)
N1	0.2224 (4)	0.4242 (4)	0.1634 (2)	0.0136 (5)
N2	0.1222 (4)	0.7309 (3)	0.21602 (19)	0.0116 (5)
N3	0.0799 (4)	0.8896 (4)	0.24122 (18)	0.0121 (5)
N4	−0.0931 (3)	1.1177 (7)	0.21776 (15)	0.0136 (4)
H4A	−0.1637	1.1648	0.1802	0.016*
C1	0.2576 (4)	0.2671 (4)	0.1423 (2)	0.0157 (6)
H1	0.2000	0.2192	0.0934	0.019*
C2	0.3730 (4)	0.1690 (4)	0.1883 (2)	0.0168 (7)
H2	0.3946	0.0570	0.1715	0.020*
C3	0.4565 (5)	0.2404 (4)	0.2593 (3)	0.0187 (7)
H3	0.5375	0.1780	0.2921	0.022*
C4	0.4205 (5)	0.4047 (4)	0.2823 (2)	0.0153 (6)
H4	0.4766	0.4552	0.3308	0.018*
C5	0.3012 (4)	0.4945 (4)	0.2335 (2)	0.0114 (6)
C6	0.2531 (4)	0.6665 (4)	0.2564 (2)	0.0111 (6)
C7	−0.0456 (4)	0.9582 (4)	0.1962 (2)	0.0120 (6)
C8	−0.0481 (4)	1.2176 (4)	0.2894 (2)	0.0123 (6)
C9	0.0552 (4)	1.1664 (4)	0.3591 (2)	0.0155 (7)
H9	0.1022	1.0574	0.3596	0.019*
C10	0.0898 (5)	1.2755 (4)	0.4281 (2)	0.0161 (6)
H10	0.1608	1.2403	0.4753	0.019*
C11	0.0217 (5)	1.4354 (4)	0.4288 (2)	0.0163 (6)
H11	0.0447	1.5086	0.4763	0.020*
C12	−0.0808 (5)	1.4862 (4)	0.3594 (2)	0.0169 (7)
H12	−0.1277	1.5953	0.3594	0.020*
C13	−0.1153 (4)	1.3805 (4)	0.2901 (2)	0.0155 (6)
H13	−0.1844	1.4178	0.2427	0.019*
C14	0.3566 (4)	0.7570 (4)	0.3235 (2)	0.0125 (6)
C15	0.5242 (4)	0.7952 (4)	0.3052 (2)	0.0148 (6)
H15	0.5703	0.7630	0.2511	0.018*
C16	0.6238 (5)	0.8801 (4)	0.3664 (3)	0.0179 (7)
H16	0.7375	0.9063	0.3538	0.022*
C17	0.5575 (5)	0.9270 (5)	0.4459 (3)	0.0196 (7)
H17	0.6253	0.9866	0.4872	0.024*
C18	0.3920 (5)	0.8864 (5)	0.4651 (2)	0.0185 (7)
H18	0.3473	0.9163	0.5199	0.022*
C19	0.2913 (4)	0.8018 (4)	0.4037 (2)	0.0148 (6)
H19	0.1781	0.7747	0.4168	0.018*
C20	0.2925 (4)	0.8615 (4)	−0.0148 (2)	0.0139 (6)
C21	0.4285 (4)	0.9847 (5)	−0.0360 (3)	0.0181 (7)
H21A	0.5261	0.9669	0.0031	0.027*
H21B	0.3859	1.0985	−0.0285	0.027*
H21C	0.4623	0.9690	−0.0965	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.01329 (5)	0.01144 (4)	0.01115 (5)	−0.00052 (8)	−0.00120 (3)	−0.00075 (8)
S1	0.0138 (4)	0.0156 (4)	0.0149 (4)	0.0007 (3)	−0.0039 (3)	−0.0024 (3)
O1	0.0166 (12)	0.0250 (13)	0.0143 (12)	−0.0042 (10)	−0.0009 (9)	0.0046 (10)
O2	0.0214 (13)	0.0196 (13)	0.0163 (13)	−0.0013 (10)	−0.0042 (11)	0.0012 (11)
N1	0.0122 (12)	0.0133 (13)	0.0155 (14)	−0.0002 (10)	0.0018 (10)	−0.0019 (10)
N2	0.0130 (12)	0.0089 (11)	0.0131 (13)	0.0005 (10)	0.0017 (10)	0.0005 (10)
N3	0.0145 (12)	0.0111 (12)	0.0105 (12)	0.0011 (10)	−0.0016 (10)	−0.0021 (10)
N4	0.0155 (10)	0.0120 (10)	0.0131 (10)	0.001 (2)	−0.0029 (8)	0.0011 (19)
C1	0.0175 (16)	0.0141 (15)	0.0155 (16)	−0.0027 (12)	0.0023 (12)	−0.0031 (12)
C2	0.0205 (16)	0.0110 (14)	0.0191 (16)	0.0008 (11)	0.0057 (13)	−0.0003 (11)
C3	0.0212 (17)	0.0139 (15)	0.0210 (18)	0.0045 (13)	−0.0001 (14)	0.0024 (13)
C4	0.0179 (16)	0.0131 (15)	0.0149 (15)	0.0005 (12)	−0.0013 (13)	0.0006 (12)
C5	0.0112 (14)	0.0117 (14)	0.0114 (14)	−0.0011 (11)	0.0027 (11)	0.0005 (11)
C6	0.0110 (13)	0.0106 (15)	0.0118 (14)	−0.0009 (10)	0.0015 (11)	−0.0002 (10)
C7	0.0125 (14)	0.0132 (14)	0.0103 (14)	−0.0012 (11)	0.0012 (11)	0.0005 (11)
C8	0.0123 (14)	0.0125 (14)	0.0121 (15)	−0.0004 (11)	0.0024 (11)	0.0005 (11)
C9	0.0177 (15)	0.0138 (15)	0.0148 (15)	0.0005 (11)	−0.0018 (12)	−0.0006 (11)
C10	0.0189 (16)	0.0175 (16)	0.0118 (15)	−0.0013 (13)	−0.0025 (12)	−0.0013 (12)
C11	0.0200 (16)	0.0143 (15)	0.0148 (16)	−0.0025 (13)	0.0038 (13)	−0.0037 (12)
C12	0.0178 (16)	0.0132 (15)	0.0200 (17)	0.0013 (12)	0.0039 (13)	−0.0018 (13)
C13	0.0152 (15)	0.0141 (15)	0.0173 (16)	0.0023 (12)	0.0024 (12)	0.0003 (12)
C14	0.0142 (14)	0.0098 (13)	0.0133 (15)	0.0002 (11)	−0.0016 (12)	0.0007 (11)
C15	0.0160 (16)	0.0132 (15)	0.0152 (16)	0.0011 (12)	−0.0006 (12)	0.0021 (12)
C16	0.0148 (15)	0.0141 (15)	0.0248 (18)	−0.0003 (13)	−0.0030 (13)	0.0018 (14)
C17	0.0197 (17)	0.0159 (16)	0.0228 (18)	0.0001 (13)	−0.0093 (14)	−0.0018 (14)
C18	0.0237 (17)	0.0197 (16)	0.0118 (15)	0.0050 (14)	−0.0040 (13)	−0.0033 (13)
C19	0.0144 (15)	0.0168 (15)	0.0133 (15)	0.0008 (12)	0.0005 (12)	−0.0020 (12)
C20	0.0138 (14)	0.0124 (14)	0.0156 (16)	0.0029 (12)	0.0011 (12)	−0.0015 (12)
C21	0.0145 (15)	0.0203 (17)	0.0196 (17)	−0.0024 (13)	0.0032 (13)	0.0022 (14)

Geometric parameters (Å, º)

Pb1—O1	2.375 (3)	C6—C14	1.491 (5)
Pb1—N2	2.543 (3)	C8—C9	1.395 (5)
Pb1—N1	2.551 (3)	C8—C13	1.410 (5)
Pb1—S1	2.7809 (9)	C9—C10	1.396 (5)
Pb1—O2	2.846 (3)	C9—H9	0.9500
Pb1—O2^i	2.949 (3)	C10—C11	1.391 (5)
S1—C7	1.745 (4)	C10—H10	0.9500
O1—C20	1.272 (4)	C11—C12	1.388 (5)
O2—C20	1.259 (4)	C11—H11	0.9500
O2—Pb1^ii	2.949 (3)	C12—C13	1.382 (5)
N1—C1	1.332 (4)	C12—H12	0.9500
N1—C5	1.354 (4)	C13—H13	0.9500
N2—C6	1.304 (4)	C14—C19	1.392 (5)
N2—N3	1.373 (4)	C14—C15	1.399 (5)
N3—C7	1.319 (4)	C15—C16	1.392 (5)
N4—C7	1.375 (6)	C15—H15	0.9500
N4—C8	1.400 (5)	C16—C17	1.392 (5)
N4—H4A	0.8800	C16—H16	0.9500
C1—C2	1.388 (5)	C17—C18	1.390 (5)
C1—H1	0.9500	C17—H17	0.9500
C2—C3	1.386 (5)	C18—C19	1.398 (5)
C2—H2	0.9500	C18—H18	0.9500
C3—C4	1.394 (5)	C19—H19	0.9500
C3—H3	0.9500	C20—C21	1.504 (5)
C4—C5	1.394 (5)	C21—H21A	0.9800
C4—H4	0.9500	C21—H21B	0.9800
C5—C6	1.475 (5)	C21—H21C	0.9800
O1—Pb1—N2	70.27 (9)	N3—C7—N4	118.0 (3)
O1—Pb1—N1	88.01 (9)	N3—C7—S1	128.7 (3)
N2—Pb1—N1	64.32 (9)	N4—C7—S1	113.3 (2)
O1—Pb1—S1	95.39 (7)	C9—C8—N4	124.7 (3)
N2—Pb1—S1	68.35 (7)	C9—C8—C13	118.8 (3)
N1—Pb1—S1	128.08 (7)	N4—C8—C13	116.5 (3)
O1—Pb1—O2	49.38 (8)	C8—C9—C10	120.0 (3)
N2—Pb1—O2	112.84 (8)	C8—C9—H9	120.1
N1—Pb1—O2	128.53 (9)	C10—C9—H9	120.0
S1—Pb1—O2	88.69 (6)	C11—C10—C9	120.9 (3)
O1—Pb1—O2^i	164.51 (9)	C11—C10—H10	119.4
N2—Pb1—O2^i	110.98 (9)	C9—C10—H10	119.7
N1—Pb1—O2^i	79.19 (8)	C12—C11—C10	119.0 (3)
S1—Pb1—O2^i	99.36 (6)	C12—C11—H11	120.5
O2—Pb1—O2^i	135.28 (4)	C10—C11—H11	120.5
C7—S1—Pb1	98.04 (11)	C13—C12—C11	120.9 (3)
C20—O1—Pb1	104.8 (2)	C13—C12—H12	119.6
C20—O2—Pb1	82.9 (2)	C11—C12—H12	119.5
C20—O2—Pb1^ii	106.7 (2)	C12—C13—C8	120.4 (3)
Pb1—O2—Pb1^ii	102.97 (9)	C12—C13—H13	119.8
C1—N1—C5	119.4 (3)	C8—C13—H13	119.8
C1—N1—Pb1	123.2 (2)	C19—C14—C15	119.7 (3)
C5—N1—Pb1	116.3 (2)	C19—C14—C6	121.7 (3)
C6—N2—N3	115.5 (3)	C15—C14—C6	118.6 (3)
C6—N2—Pb1	116.6 (2)	C16—C15—C14	120.0 (3)
N3—N2—Pb1	122.1 (2)	C16—C15—H15	119.9
C7—N3—N2	115.1 (3)	C14—C15—H15	120.1
C7—N4—C8	130.8 (3)	C17—C16—C15	120.3 (3)
C7—N4—H4A	114.5	C17—C16—H16	119.9
C8—N4—H4A	114.6	C15—C16—H16	119.9
N1—C1—C2	123.4 (3)	C18—C17—C16	120.0 (3)
N1—C1—H1	118.3	C18—C17—H17	120.0
C2—C1—H1	118.2	C16—C17—H17	120.0
C3—C2—C1	117.7 (3)	C17—C18—C19	119.9 (3)
C3—C2—H2	121.1	C17—C18—H18	120.1
C1—C2—H2	121.2	C19—C18—H18	120.0
C2—C3—C4	119.4 (3)	C14—C19—C18	120.2 (3)
C2—C3—H3	120.3	C14—C19—H19	120.0
C4—C3—H3	120.2	C18—C19—H19	119.8
C5—C4—C3	119.5 (3)	O2—C20—O1	122.9 (3)
C5—C4—H4	120.2	O2—C20—C21	119.4 (3)
C3—C4—H4	120.3	O1—C20—C21	117.6 (3)
N1—C5—C4	120.5 (3)	C20—C21—H21A	109.4
N1—C5—C6	117.4 (3)	C20—C21—H21B	109.5
C4—C5—C6	122.0 (3)	H21A—C21—H21B	109.5
N2—C6—C5	117.7 (3)	C20—C21—H21C	109.4
N2—C6—C14	123.8 (3)	H21A—C21—H21C	109.5
C5—C6—C14	118.5 (3)	H21B—C21—H21C	109.5
C6—N2—N3—C7	175.7 (3)	C7—N4—C8—C13	177.5 (3)
Pb1—N2—N3—C7	23.5 (4)	N4—C8—C9—C10	−178.9 (3)
C5—N1—C1—C2	−0.3 (5)	C13—C8—C9—C10	0.3 (5)
Pb1—N1—C1—C2	167.9 (3)	C8—C9—C10—C11	0.3 (5)
N1—C1—C2—C3	−0.7 (5)	C9—C10—C11—C12	−0.4 (5)
C1—C2—C3—C4	0.9 (5)	C10—C11—C12—C13	−0.1 (5)
C2—C3—C4—C5	−0.1 (5)	C11—C12—C13—C8	0.8 (5)
C1—N1—C5—C4	1.2 (5)	C9—C8—C13—C12	−0.9 (5)
Pb1—N1—C5—C4	−167.8 (2)	N4—C8—C13—C12	178.4 (3)
C1—N1—C5—C6	−177.6 (3)	N2—C6—C14—C19	66.4 (5)
Pb1—N1—C5—C6	13.4 (4)	C5—C6—C14—C19	−114.0 (4)
C3—C4—C5—N1	−1.0 (5)	N2—C6—C14—C15	−114.4 (4)
C3—C4—C5—C6	177.7 (3)	C5—C6—C14—C15	65.1 (4)
N3—N2—C6—C5	178.4 (3)	C19—C14—C15—C16	−1.1 (5)
Pb1—N2—C6—C5	−27.8 (4)	C6—C14—C15—C16	179.7 (3)
N3—N2—C6—C14	−2.0 (5)	C14—C15—C16—C17	0.1 (5)
Pb1—N2—C6—C14	151.8 (3)	C15—C16—C17—C18	1.1 (5)
N1—C5—C6—N2	9.6 (4)	C16—C17—C18—C19	−1.4 (6)
C4—C5—C6—N2	−169.2 (3)	C15—C14—C19—C18	0.8 (5)
N1—C5—C6—C14	−170.0 (3)	C6—C14—C19—C18	180.0 (3)
C4—C5—C6—C14	11.2 (5)	C17—C18—C19—C14	0.4 (5)
N2—N3—C7—N4	−179.4 (3)	Pb1—O2—C20—O1	−1.0 (3)
N2—N3—C7—S1	1.1 (4)	Pb1^ii—O2—C20—O1	100.5 (3)
C8—N4—C7—N3	−10.8 (5)	Pb1—O2—C20—C21	−177.8 (3)
C8—N4—C7—S1	168.7 (3)	Pb1^ii—O2—C20—C21	−76.3 (3)
Pb1—S1—C7—N3	−19.5 (3)	Pb1—O1—C20—O2	1.2 (4)
Pb1—S1—C7—N4	161.0 (2)	Pb1—O1—C20—C21	178.1 (2)
C7—N4—C8—C9	−3.2 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2^ii	0.88	2.17	2.917 (5)	143
C9—H9···N3	0.95	2.26	2.872 (4)	121
C21—H21A···S1^iii	0.98	3.01	3.986 (4)	173

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