Two polymorphs of a lead(II) complex with 8-hydr­oxy-2-methyl­quinoline and thio­cyanate

Two distinct polymorphs of bis­([mu]₂-methyl­quinolin-8-olato)-[kappa]³N,O:O;[kappa]³O:N,O-bis­[(isothio­cyanato-[kappa]N)lead(II)], [Pb₂(C₁₀H₈NO)₂(NCS)₂], (I), forming dinuclear complexes from a methanolic solution containing lead(II) nitrate, 2-methyl­quinolin-8-ol (M-Hq) and KSCN, crystallized concomitantly as colourless prisms [form (Ia)] and long thin colourless needles [form (Ib)]. In both cases, the complexes lie across a centre of inversion. The polymorphs differ substantially in their conformation and in their inter­actions, viz. Pb...S and [pi]-[pi] for form (Ia) and Pb...S, Pb...[pi] and C-H...[pi] for form (Ib).

S1. Comment

The synthesis of novel organic–inorganic hybrid materials in the field of supramolecular and crystal engineering has been a subject of rapid growth in recent years (Moulton & Zaworotko, 2001). Bidentate ligands containing soft and hard atoms have potential applications in catalytic and stoichiometric reactions (Kaim & Schwederski, 1995), as well as in advanced materials (Soldatov et al., 2004). Recent reports of 8-hydroxyquinoline and its derivatives with lead(II) salts include [Pb(Hq)(SCN)]_n (Shahverdizadeh et al., 2008), [Pb₂(M-Hq)₂(NO₃)₂(CH₃OH)₂] (Mohammadnezhad et al., 2009a), [Pb₂(M-Hq)₂(C₂H₃O₂)₂] (Mohammadnezhad et al., 2009b), [Pb₂(Cl-Hq)₂(C₂H₃O₂)₂] (Mohammadnezhad et al., 2009c) and [Pb₄(Hq)₆(NO₃)₂] (Zhang et al., 2008).

As part of our interest in exploring the effect of steric hindrance in lead(II) complexes with mixed ligands, we have examined isothiocyanate, due to its various coordination modes, i.e. single or bridging coordination through S, N or both, in the presence of 8-hydroxy-2-methylquinoline. In this paper we report the crystal structures of two polymorphs of [Pb(M-Hq)NCS]₂, (Ia) and (Ib), which show that the steric hindrance of a methyl group leads to the coordination of isothiocyanate only via the N atom, not via S [Please check rephrasing], in contrast with the bidentate coordination observed in [Pb(Hq)SCN]_n (Shahverdizadeh et al., 2008).

Polymorph (Ia) crystallizes in the triclinic space group P1, while polymorph (Ib) crystallizes concommitantly in the monoclinic space group P2₁/c. Perspective drawings of these compounds are shown in Figs. 1 and 2, respectively; in both cases, the Pb₂O₂ core lies across the crystallographic inversion centre. In both structures, the Pb^II ion is four-coordinated, with the M-Hq ligand acting as a bidentate chelate, along with a bridging phenoxy O atom and the N atom from the isothiocyanate. As expected, these four coordinating atoms around the Pb^II centre in both polymorphs show a hemidirected geometry with a stereochemically active lone pair. Selected bond distances and bond angles are presented in Table 1. It is notable that the major structural difference between these two polymorphs is the NCS coordination angle. In (Ia), the Pb1—N2—C1 angle is 149.7 (4)°, in contrast with a value of 136.8 (6)° in (Ib). All other angles except O1—Pb1—N2, N2—Pb1—O1ⁱ and O1ⁱ—Pb1—N1 are similar [symmetry code: (i) -x, -y + 1, -z + 1 for (Ia); -x + 1, -y + 2, -z + 1 for (Ib)] [Please check added symmetry codes]. The different conformations of the polymorphs are strongly reflected in the torsion angles containing the thiocyanate atoms N2 and C1, but also in torsion angle Pb1—O1—C8—C7 (see Table 1). The Pb···Pb distances are 3.9397 (3) and 4.0212 (17) Å for (Ia) and (Ib), respectively.

Interestingly, in contrast with the previously reported coordination polymer [Pb(Hq)SCN]_n (Shahverdizadeh et al., 2008), the steric hindrance imposed by the methyl group at the C2 position prevents the coordination of SCN as a bidentate ligand. Indeed, the larger S atom is unable to coordinate to the Pb^II ion in both cases, and hence the polymeric nature is disrupted and the coordination number decreases to four. Nevertheless, Pb···S interactions are formed for Pb1···S1ⁱⁱ and Pb^iv···S1ⁱⁱⁱ [3.6009 (14) Å] and for Pb1···S1ⁱⁱⁱ and Pb^iv···S1ⁱⁱ [3.6649 (14) Å] in compound (Ia) (Fig. 3) [symmetry codes: (ii) 1 + x, y, z; (iii) -1 - x, 1 - y, 2 - z; (iv) -x, 1 - y, 2 - z]. Different types of interaction are seen in polymorph (Ib). In addition to Pb···S interactions with distances of 3.506 (3) Å, an interaction between the Pb^II ion and the centroid Cg of the C5–C10 benzene ring is observed, with Pb···Cg = 3.171 Å (Fig. 4).

Structure (Ia) contains sheets of molecules in the ac plane held together by Pb···S interactions (Fig. 5). The sheets have the aromatic wings of the ligand protruding from each side and interdigitate to provide π–π stacking with perpendicular distances of 3.288 and 3.377 Å (Fig. 6), reflecting the different positions of the N atoms in the overlapping hetero rings.

In contrast, structure (Ib) contains chains of molecules along b which are held together by Pb···S and Pb···ring interactions. The aromatic surfaces protruding from these chains make a herring-bone formation in the bc plane (Fig. 7), with C—H···π interactions for enhancement [between C6—H6 and the centroid Cg of the C5–C10 ring at the symmetry position (-x + 1, y - 1/2, -z + 3/2), with C6···Cg = 3.458 (7) Å, H6···Cg = 2.70 Å and C6—H6···Cg = 137°].

S2. Experimental

Lead nitrate (0.33 g, 1 mmol), 2-methyl-8-hydroxyquinoline (0.16 g, 1 mmol) and KSCN (0.18 g, 2 mmol) were loaded into a convection tube. The tube was filled carefully with methanol and kept at 333 K. Crystals were collected from the side arm after several days; they were a mixture of large crystals of KNO₃, colourless prisms of (Ia) and long thin colourless needles of (Ib).

S3. Refinement

Aromatic H atoms were refined isotropically with U_iso(H) = 1.2U_eq(C), and their positions were constrained to ideal geometry using an appropriate riding model, with C—H = 0.95 Å. For methyl groups, N—C—H angles (109.5°) were kept fixed, while the torsion angle was allowed to refine, with the starting positions based on the circular Fourier synthesis averaged using the local three-fold axis; C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C).

Computing details

For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003) and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The structure of polymorph (Ia), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x, -y + 1, -z + 1.]
	Fig. 2. The structure of polymorph (Ib), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x + 1, -y + 2, -z + 1.]
	Fig. 3. The Pb···S interactions (dashed lines) in (Ia). [Symmetry codes: (ii) 1 + x, y, z; (iii) -1 - x, 1 - y, 2 - z; (iv) -x, 1 - y, 2 - z.]
	Fig. 4. The Pb···S interactions (dashed lines) in (Ib), with distances of 3.506 (3) Å. The distances to the centroid of the C5–C10 ring (also dashed lines) are 3.171 Å. [Symmetry codes: (i) -x + 1, -y + 2, -z + 1; (ii) x, y + 1, z.]
	Fig. 5. The contents of the unit-cell of (Ia), in a projection parallel to the quinoline rings.
	Fig. 6. The π–π interactions in (Ia). The overlap of the quinoline rings with a perpendicular distance of 3.288 Å is shown in the upper part, and that with a perpendicular distance of 3.377 Å is shown in the lower part.
	Fig. 7. The herring-bone formation of the aromatic surfaces in (Ib). H atoms have been omitted for clarity.

(Ia) bis(µ₂-methylquinolin-8-olato)-κ³N,O:O; κ³O:N,O-bis[(thiocyanato-κN)lead(II)]

Crystal data

[Pb2(C10H8NO)2(NCS)2]	Z = 1
Mr = 846.89	F(000) = 388
Triclinic, P1	Dx = 2.532 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8556 (5) Å	Cell parameters from 5361 reflections
b = 8.4155 (5) Å	θ = 2.5–32.2°
c = 9.1550 (6) Å	µ = 15.35 mm^−1
α = 78.524 (1)°	T = 173 K
β = 69.771 (1)°	Prism, colourless
γ = 82.813 (1)°	0.43 × 0.21 × 0.06 mm
V = 555.50 (6) Å^3

Data collection

Siemens SMART CCD area-detector diffractometer	3889 independent reflections
Radiation source: fine-focus sealed tube	3475 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ω scans	θmax = 32.9°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −11→11
Tmin = 0.095, Tmax = 0.399	k = −12→12
9987 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0343P)^2 + 0.1734P] where P = (Fo^2 + 2Fc^2)/3
3889 reflections	(Δ/σ)max = 0.001
146 parameters	Δρmax = 2.27 e Å^−3
0 restraints	Δρmin = −3.09 e Å^−3

Special details

Experimental. Data were collected at 173 K using a Siemens SMART CCD diffractometer equipped with LT-2 A cooling device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 3 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Bruker, 2003). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 5361 reflections with I>10σ(I) after integration of all the frames data using SAINT (Bruker, 2003).

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 (Ų)

	x	y	z	Uiso*/Ueq
Pb1	−0.127805 (19)	0.568883 (17)	0.705986 (17)	0.01558 (6)
S1	−0.77581 (16)	0.41746 (15)	0.87524 (16)	0.0262 (2)
O1	0.0076 (4)	0.6561 (3)	0.4438 (4)	0.0179 (6)
N1	−0.2636 (5)	0.8408 (4)	0.6202 (4)	0.0150 (6)
C1	−0.5653 (6)	0.4592 (5)	0.7797 (6)	0.0212 (9)
C2	−0.4008 (6)	0.9273 (5)	0.7092 (5)	0.0172 (8)
N2	−0.4144 (6)	0.4875 (5)	0.7106 (6)	0.0317 (10)
C3	−0.4489 (6)	1.0887 (6)	0.6483 (6)	0.0232 (9)
H3	−0.5484	1.1480	0.7119	0.028*
C4	−0.3540 (6)	1.1589 (5)	0.5000 (6)	0.0226 (9)
H4	−0.3862	1.2676	0.4609	0.027*
C5	−0.1018 (6)	1.1315 (5)	0.2474 (6)	0.0224 (9)
H5	−0.1267	1.2397	0.2016	0.027*
C6	0.0349 (7)	1.0373 (6)	0.1616 (6)	0.0224 (9)
H6	0.1044	1.0803	0.0565	0.027*
C7	0.0747 (6)	0.8758 (5)	0.2273 (5)	0.0203 (8)
H7	0.1714	0.8119	0.1662	0.024*
C8	−0.0256 (6)	0.8104 (5)	0.3792 (5)	0.0158 (7)
C9	−0.1684 (5)	0.9084 (5)	0.4694 (5)	0.0148 (7)
C10	−0.2067 (6)	1.0706 (5)	0.4030 (6)	0.0182 (8)
C11	−0.5028 (7)	0.8482 (6)	0.8725 (6)	0.0252 (10)
H11A	−0.5600	0.7534	0.8673	0.038*
H11B	−0.5967	0.9258	0.9250	0.038*
H11C	−0.4186	0.8137	0.9323	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.01534 (8)	0.01655 (8)	0.01288 (8)	0.00076 (5)	−0.00307 (5)	−0.00196 (5)
S1	0.0162 (5)	0.0268 (6)	0.0295 (6)	−0.0020 (4)	−0.0042 (4)	0.0035 (5)
O1	0.0211 (15)	0.0103 (12)	0.0166 (15)	0.0004 (10)	−0.0002 (12)	−0.0013 (11)
N1	0.0144 (15)	0.0167 (15)	0.0148 (16)	0.0001 (12)	−0.0049 (13)	−0.0053 (13)
C1	0.022 (2)	0.0177 (19)	0.023 (2)	0.0015 (15)	−0.0060 (17)	−0.0061 (17)
C2	0.0136 (17)	0.0190 (18)	0.023 (2)	0.0008 (14)	−0.0084 (16)	−0.0083 (16)
N2	0.022 (2)	0.027 (2)	0.046 (3)	−0.0052 (16)	−0.0056 (19)	−0.012 (2)
C3	0.021 (2)	0.022 (2)	0.034 (3)	0.0080 (16)	−0.0153 (19)	−0.0152 (19)
C4	0.020 (2)	0.0185 (19)	0.036 (3)	0.0046 (16)	−0.019 (2)	−0.0085 (19)
C5	0.027 (2)	0.0137 (18)	0.032 (3)	−0.0043 (16)	−0.019 (2)	0.0039 (17)
C6	0.026 (2)	0.021 (2)	0.021 (2)	−0.0089 (17)	−0.0106 (18)	0.0029 (17)
C7	0.023 (2)	0.0172 (19)	0.019 (2)	−0.0042 (15)	−0.0051 (17)	0.0002 (16)
C8	0.0171 (18)	0.0117 (16)	0.019 (2)	−0.0013 (13)	−0.0079 (16)	0.0007 (14)
C9	0.0142 (17)	0.0149 (17)	0.0188 (19)	0.0002 (13)	−0.0091 (15)	−0.0047 (15)
C10	0.0197 (19)	0.0137 (17)	0.027 (2)	−0.0013 (14)	−0.0159 (18)	−0.0018 (16)
C11	0.022 (2)	0.030 (2)	0.025 (2)	0.0057 (18)	−0.0064 (18)	−0.0143 (19)

Geometric parameters (Å, º)

Pb1—O1	2.272 (3)	C4—C10	1.420 (6)
Pb1—N2	2.418 (4)	C4—H4	0.9500
Pb1—O1^i	2.459 (3)	C5—C6	1.360 (7)
Pb1—N1	2.499 (4)	C5—C10	1.406 (7)
S1—C1	1.627 (5)	C5—H5	0.9500
O1—C8	1.349 (5)	C6—C7	1.416 (6)
O1—Pb1^i	2.459 (3)	C6—H6	0.9500
N1—C2	1.338 (5)	C7—C8	1.380 (6)
N1—C9	1.367 (6)	C7—H7	0.9500
C1—N2	1.164 (6)	C8—C9	1.422 (6)
C2—C3	1.419 (6)	C9—C10	1.420 (6)
C2—C11	1.493 (7)	C11—H11A	0.9800
C3—C4	1.356 (8)	C11—H11B	0.9800
C3—H3	0.9500	C11—H11C	0.9800
O1—Pb1—N2	101.34 (15)	C6—C5—H5	119.7
O1—Pb1—O1^i	67.30 (11)	C10—C5—H5	119.7
N2—Pb1—O1^i	82.10 (13)	C5—C6—C7	120.7 (4)
O1—Pb1—N1	69.09 (11)	C5—C6—H6	119.6
N2—Pb1—N1	80.77 (14)	C7—C6—H6	119.6
O1^i—Pb1—N1	128.43 (11)	C8—C7—C6	120.6 (4)
C8—O1—Pb1	120.1 (2)	C8—C7—H7	119.7
C8—O1—Pb1^i	124.5 (3)	C6—C7—H7	119.7
Pb1—O1—Pb1^i	112.70 (11)	O1—C8—C7	121.9 (4)
C2—N1—C9	119.7 (4)	O1—C8—C9	119.3 (4)
C2—N1—Pb1	127.2 (3)	C7—C8—C9	118.9 (4)
C9—N1—Pb1	112.7 (2)	N1—C9—C10	122.4 (4)
N2—C1—S1	179.2 (4)	N1—C9—C8	117.4 (4)
N1—C2—C3	120.6 (4)	C10—C9—C8	120.1 (4)
N1—C2—C11	118.1 (4)	C5—C10—C9	118.9 (4)
C3—C2—C11	121.4 (4)	C5—C10—C4	124.5 (4)
C1—N2—Pb1	149.7 (4)	C9—C10—C4	116.5 (4)
C4—C3—C2	120.6 (4)	C2—C11—H11A	109.5
C4—C3—H3	119.7	C2—C11—H11B	109.5
C2—C3—H3	119.7	H11A—C11—H11B	109.5
C3—C4—C10	120.2 (4)	C2—C11—H11C	109.5
C3—C4—H4	119.9	H11A—C11—H11C	109.5
C10—C4—H4	119.9	H11B—C11—H11C	109.5
C6—C5—C10	120.7 (4)
N2—Pb1—O1—C8	85.9 (3)	C5—C6—C7—C8	0.6 (7)
O1^i—Pb1—O1—C8	162.2 (4)	Pb1—O1—C8—C7	169.5 (3)
N1—Pb1—O1—C8	10.5 (3)	Pb1^i—O1—C8—C7	−30.5 (6)
N2—Pb1—O1—Pb1^i	−76.36 (16)	Pb1—O1—C8—C9	−10.9 (5)
O1^i—Pb1—O1—Pb1^i	0.0	Pb1^i—O1—C8—C9	149.1 (3)
N1—Pb1—O1—Pb1^i	−151.78 (17)	C6—C7—C8—O1	178.9 (4)
O1—Pb1—N1—C2	178.1 (4)	C6—C7—C8—C9	−0.7 (7)
N2—Pb1—N1—C2	72.1 (4)	C2—N1—C9—C10	1.5 (6)
O1^i—Pb1—N1—C2	144.2 (3)	Pb1—N1—C9—C10	−171.8 (3)
O1—Pb1—N1—C9	−9.2 (3)	C2—N1—C9—C8	−179.1 (4)
N2—Pb1—N1—C9	−115.2 (3)	Pb1—N1—C9—C8	7.6 (4)
O1^i—Pb1—N1—C9	−43.0 (3)	O1—C8—C9—N1	1.3 (6)
C9—N1—C2—C3	0.2 (6)	C7—C8—C9—N1	−179.1 (4)
Pb1—N1—C2—C3	172.4 (3)	O1—C8—C9—C10	−179.4 (4)
C9—N1—C2—C11	179.2 (4)	C7—C8—C9—C10	0.3 (6)
Pb1—N1—C2—C11	−8.5 (5)	C6—C5—C10—C9	−0.3 (6)
S1—C1—N2—Pb1	−136 (39)	C6—C5—C10—C4	−178.7 (4)
O1—Pb1—N2—C1	−159.2 (7)	N1—C9—C10—C5	179.6 (4)
O1^i—Pb1—N2—C1	135.9 (8)	C8—C9—C10—C5	0.2 (6)
N1—Pb1—N2—C1	−92.9 (8)	N1—C9—C10—C4	−1.9 (6)
N1—C2—C3—C4	−1.4 (7)	C8—C9—C10—C4	178.7 (4)
C11—C2—C3—C4	179.6 (4)	C3—C4—C10—C5	179.1 (4)
C2—C3—C4—C10	0.9 (7)	C3—C4—C10—C9	0.7 (6)
C10—C5—C6—C7	−0.1 (7)

Symmetry code: (i) −x, −y+1, −z+1.

(Ib) bis(µ₂-methylquinolin-8-olato-κ³N,O:O; κ³O:N,O)bis[(thiocyanato-κN)lead(II)]

Crystal data

[Pb2(C10H8NO)2(NCS)2]	F(000) = 776
Mr = 846.89	Dx = 2.497 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2817 reflections
a = 12.037 (5) Å	θ = 2.5–27.5°
b = 5.731 (2) Å	µ = 15.14 mm^−1
c = 16.327 (6) Å	T = 173 K
β = 90.368 (7)°	Needle, colourless
V = 1126.3 (7) Å^3	0.96 × 0.04 × 0.02 mm
Z = 2

Data collection

Siemens SMART CCD area-detector diffractometer	3502 independent reflections
Radiation source: fine-focus sealed tube	2528 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
ω scans	θmax = 31.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→17
Tmin = 0.102, Tmax = 0.752	k = −8→7
12903 measured reflections	l = −23→23

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0396P)^2 + 0.132P] where P = (Fo^2 + 2Fc^2)/3
3502 reflections	(Δ/σ)max = 0.003
146 parameters	Δρmax = 2.42 e Å^−3
0 restraints	Δρmin = −3.27 e Å^−3

Special details

Experimental. Data were collected at 173 K using a Siemens SMART CCD diffractometer equipped with LT-2 A cooling device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 15 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Bruker, 2003). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 2817 reflections with I>10σ(I) after integration of all the frames data using SAINT (Bruker, 2003).

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 (Ų)

	x	y	z	Uiso*/Ueq
Pb1	0.650738 (19)	1.14118 (4)	0.519671 (15)	0.01661 (8)
S1	0.84591 (19)	0.4726 (4)	0.41158 (17)	0.0464 (6)
N2	0.7242 (5)	0.8850 (10)	0.4178 (4)	0.0294 (15)
C1	0.7764 (6)	0.7138 (14)	0.4166 (5)	0.0241 (15)
N1	0.7459 (5)	0.8452 (9)	0.6123 (3)	0.0181 (11)
O1	0.5299 (4)	0.8511 (7)	0.5572 (3)	0.0186 (9)
C2	0.8503 (5)	0.8460 (12)	0.6398 (4)	0.0208 (14)
C3	0.8887 (6)	0.6800 (12)	0.6971 (5)	0.0249 (16)
H3	0.9635	0.6857	0.7160	0.030*
C4	0.8189 (6)	0.5113 (13)	0.7256 (5)	0.0258 (16)
H4	0.8437	0.4027	0.7657	0.031*
C5	0.6321 (6)	0.3214 (11)	0.7181 (4)	0.0227 (15)
H5	0.6540	0.2039	0.7559	0.027*
C6	0.5255 (6)	0.3230 (11)	0.6847 (4)	0.0205 (14)
H6	0.4751	0.2023	0.6991	0.025*
C7	0.4902 (6)	0.4992 (11)	0.6301 (4)	0.0195 (14)
H7	0.4168	0.4956	0.6083	0.023*
C8	0.5623 (5)	0.6792 (11)	0.6078 (4)	0.0164 (13)
C9	0.6740 (5)	0.6743 (10)	0.6391 (4)	0.0176 (13)
C10	0.7081 (6)	0.5001 (11)	0.6942 (4)	0.0186 (14)
C11	0.9297 (6)	1.0220 (14)	0.6055 (5)	0.0278 (16)
H11A	0.9016	1.0779	0.5525	0.042*
H11B	1.0026	0.9493	0.5980	0.042*
H11C	0.9366	1.1537	0.6434	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.02006 (12)	0.01503 (13)	0.01475 (13)	−0.00062 (10)	0.00219 (8)	0.00009 (11)
S1	0.0449 (13)	0.0321 (12)	0.0626 (17)	0.0096 (10)	0.0247 (12)	0.0087 (11)
N2	0.040 (4)	0.027 (4)	0.021 (3)	0.003 (3)	0.005 (3)	−0.007 (3)
C1	0.022 (3)	0.030 (4)	0.021 (4)	−0.005 (3)	0.004 (3)	0.001 (3)
N1	0.022 (3)	0.016 (3)	0.016 (3)	0.002 (2)	0.002 (2)	0.000 (2)
O1	0.020 (2)	0.017 (2)	0.018 (2)	−0.0022 (18)	−0.0027 (18)	0.0034 (19)
C2	0.022 (3)	0.028 (4)	0.012 (3)	0.002 (3)	−0.001 (3)	−0.005 (3)
C3	0.018 (3)	0.034 (4)	0.023 (4)	0.000 (3)	−0.003 (3)	0.008 (3)
C4	0.028 (4)	0.033 (4)	0.017 (4)	0.007 (3)	−0.003 (3)	0.002 (3)
C5	0.032 (4)	0.022 (4)	0.015 (3)	0.001 (3)	0.006 (3)	0.000 (3)
C6	0.027 (3)	0.020 (4)	0.015 (3)	−0.002 (3)	0.007 (3)	0.000 (3)
C7	0.025 (3)	0.016 (3)	0.018 (4)	0.002 (3)	0.002 (3)	−0.001 (3)
C8	0.021 (3)	0.016 (3)	0.012 (3)	0.003 (2)	0.001 (2)	−0.003 (2)
C9	0.020 (3)	0.015 (3)	0.018 (3)	0.004 (2)	0.003 (3)	−0.004 (2)
C10	0.029 (3)	0.020 (3)	0.007 (3)	0.004 (3)	0.003 (3)	0.000 (2)
C11	0.025 (4)	0.038 (4)	0.020 (4)	−0.003 (3)	0.003 (3)	0.003 (3)

Geometric parameters (Å, º)

Pb1—O1	2.295 (4)	C4—C10	1.427 (9)
Pb1—N2	2.393 (6)	C4—H4	0.9500
Pb1—O1^i	2.504 (4)	C5—C6	1.392 (10)
Pb1—N1	2.540 (5)	C5—C10	1.429 (9)
S1—C1	1.619 (8)	C5—H5	0.9500
N2—C1	1.165 (9)	C6—C7	1.411 (9)
N1—C2	1.333 (8)	C6—H6	0.9500
N1—C9	1.380 (8)	C7—C8	1.398 (9)
O1—C8	1.342 (7)	C7—H7	0.9500
O1—Pb1^i	2.504 (4)	C8—C9	1.436 (9)
C2—C3	1.410 (9)	C9—C10	1.404 (9)
C2—C11	1.500 (10)	C11—H11A	0.9800
C3—C4	1.365 (10)	C11—H11B	0.9800
C3—H3	0.9500	C11—H11C	0.9800
O1—Pb1—N2	88.8 (2)	C6—C5—H5	120.7
O1—Pb1—O1^i	66.24 (18)	C10—C5—H5	120.7
N2—Pb1—O1^i	89.17 (19)	C5—C6—C7	121.7 (6)
O1—Pb1—N1	68.97 (16)	C5—C6—H6	119.2
N2—Pb1—N1	80.6 (2)	C7—C6—H6	119.2
O1^i—Pb1—N1	134.17 (16)	C8—C7—C6	120.5 (6)
C1—N2—Pb1	136.8 (6)	C8—C7—H7	119.7
N2—C1—S1	177.6 (7)	C6—C7—H7	119.7
C2—N1—C9	119.2 (6)	O1—C8—C7	121.6 (6)
C2—N1—Pb1	128.3 (4)	O1—C8—C9	120.0 (6)
C9—N1—Pb1	112.5 (4)	C7—C8—C9	118.3 (6)
C8—O1—Pb1	121.0 (4)	N1—C9—C10	121.8 (6)
C8—O1—Pb1^i	124.7 (4)	N1—C9—C8	117.4 (6)
Pb1—O1—Pb1^i	113.76 (18)	C10—C9—C8	120.7 (6)
N1—C2—C3	121.7 (6)	C9—C10—C5	120.0 (6)
N1—C2—C11	118.5 (6)	C9—C10—C4	117.8 (6)
C3—C2—C11	119.7 (6)	C5—C10—C4	122.2 (6)
C4—C3—C2	120.3 (6)	C2—C11—H11A	109.5
C4—C3—H3	119.9	C2—C11—H11B	109.5
C2—C3—H3	119.9	H11A—C11—H11B	109.5
C3—C4—C10	119.1 (7)	C2—C11—H11C	109.5
C3—C4—H4	120.5	H11A—C11—H11C	109.5
C10—C4—H4	120.5	H11B—C11—H11C	109.5
C6—C5—C10	118.6 (6)
O1—Pb1—N2—C1	−68.8 (8)	C5—C6—C7—C8	0.0 (10)
O1^i—Pb1—N2—C1	−135.1 (8)	Pb1—O1—C8—C7	−178.9 (5)
N1—Pb1—N2—C1	0.1 (8)	Pb1^i—O1—C8—C7	−8.2 (8)
Pb1—N2—C1—S1	145 (16)	Pb1—O1—C8—C9	−0.2 (8)
O1—Pb1—N1—C2	−178.8 (6)	Pb1^i—O1—C8—C9	170.5 (4)
N2—Pb1—N1—C2	88.9 (6)	C6—C7—C8—O1	−178.7 (6)
O1^i—Pb1—N1—C2	168.5 (5)	C6—C7—C8—C9	2.6 (10)
O1—Pb1—N1—C9	−2.9 (4)	C2—N1—C9—C10	−0.4 (9)
N2—Pb1—N1—C9	−95.2 (5)	Pb1—N1—C9—C10	−176.7 (5)
O1^i—Pb1—N1—C9	−15.6 (5)	C2—N1—C9—C8	−179.8 (6)
N2—Pb1—O1—C8	82.1 (5)	Pb1—N1—C9—C8	3.9 (7)
O1^i—Pb1—O1—C8	171.7 (6)	O1—C8—C9—N1	−2.7 (9)
N1—Pb1—O1—C8	1.6 (4)	C7—C8—C9—N1	176.0 (6)
N2—Pb1—O1—Pb1^i	−89.6 (2)	O1—C8—C9—C10	177.9 (6)
O1^i—Pb1—O1—Pb1^i	0.0	C7—C8—C9—C10	−3.4 (9)
N1—Pb1—O1—Pb1^i	−170.1 (3)	N1—C9—C10—C5	−177.7 (6)
C9—N1—C2—C3	−1.5 (10)	C8—C9—C10—C5	1.7 (10)
Pb1—N1—C2—C3	174.1 (5)	N1—C9—C10—C4	3.2 (10)
C9—N1—C2—C11	175.6 (6)	C8—C9—C10—C4	−177.4 (6)
Pb1—N1—C2—C11	−8.8 (9)	C6—C5—C10—C9	0.9 (10)
N1—C2—C3—C4	0.6 (11)	C6—C5—C10—C4	180.0 (7)
C11—C2—C3—C4	−176.5 (7)	C3—C4—C10—C9	−4.1 (10)
C2—C3—C4—C10	2.3 (11)	C3—C4—C10—C5	176.8 (7)
C10—C5—C6—C7	−1.8 (10)

Symmetry code: (i) −x+1, −y+2, −z+1.