catena-Poly[lead(II)-[μ-2,4-diamino-6-(piperidin-1-yl)pyrimidine N-oxide-κ2O:O]di-μ-iodido]

Ranjbar, M.; Najafi, S.H.M.; Ng, S.W.

doi:10.1107/S1600536809020972

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page m749

doi:10.1107/S1600536809020972

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catena-Poly[lead(II)-[μ-2,4-diamino-6-(piperidin-1-yl)pyrimidine N-oxide-κ²O:O]di-μ-iodido]

Maryam Ranjbar,^a S. Heidar Mahmoudi Najafi ^a and Seik Weng Ng ^b ^*

^aInstitute of Chemical Industries, Iranian Research Organization for Science and Technology, PO Box 15815-358, Tehran, Iran, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 1 June 2009; accepted 3 June 2009; online 6 June 2009)

The N-oxide O atom of the minoxidil unit in the 1/1 adduct with lead(II) iodide, [PbI₂(C₉H₁₅N₅O)]_n, bridges two Pb^II atoms, as do each of the I atoms. The bridging interactions give rise to a linear chain motif that propagates along the a axis of the orthorhombic unit cell. The coordination sphere around the six-coordinate Pb^II atom is a distorted ψ-monocapped octahedron in which the stereochemically active lone pair caps one of the faces defined by the O and I atoms forming the longer Pb—O or Pb—I bonds. The Pb^II atom lies on a mirror plane; the mirror plane is perpendicular to the pyrimidine ring and it bisects the piperidine ring. The aromatic ring is disordered about the mirror plane with respect to the 1-nitrogen and 5-carbon atoms.

Related literature

For the crystal structure of minoxidil, see: Akama et al. (2004 ); Martín-Islán et al. (2008 ).

Experimental

Crystal data

[PbI₂(C₉H₁₅N₅O)]
M_r = 670.25
Orthorhombic, P n m a
a = 8.1010 (1) Å
b = 13.5126 (2) Å
c = 14.0140 (2) Å
V = 1534.05 (4) Å³
Z = 4
Mo Kα radiation
μ = 15.02 mm⁻¹
T = 140 K
0.20 × 0.10 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.153, T_max = 0.521 (expected range = 0.139–0.472)
10101 measured reflections
1837 independent reflections
1752 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.043
S = 1.05
1837 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809020972/tk2471sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020972/tk2471Isup2.hkl

checkCIF report

Related literature top

For the crystal structure of minoxidil, see: Akama et al. (2004); Martín-Islán et al. (2008).

Experimental top

Minoxidil [6-(1-piperidinyl)-2,4-pyrimidinediamide 3-oxide) (0.10 g, 0.5 mmol), lead(II) acetate (0.17 g, 0.5 mmol) and potassium iodide (0.16 g, 1 mmol) were placed one arm of a two-arm glass tube. Methanol was added to fill both arms. The tube was sealed and the arm containing the reactants immersed in an oil bath at 333 K while the other arm was kept at ambient temperature. After 10 days, light-brown crystals deposited in the cooler arm. These were collected, washed with acetone and ether, and finally air dried.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellisoid plot (Barbour, 2001) of the lead diiodide–minoxidil adduct extended to show the coordination geometries of two lead atoms of the linear chain formed in the crystal structure. Atoms comprising the asymmetric unit are labelled, probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius. Only one component of the disorder is shown.

catena-Poly[lead(II)-[µ-2,4-diamino-6-(piperidin-1-yl)pyrimidine N-oxide-κ²O:O]di-µ-iodido] top

Crystal data top

[PbI₂(C₉H₁₅N₅O)]	F(000) = 1200
M_r = 670.25	D_x = 2.902 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 5726 reflections
a = 8.1010 (1) Å	θ = 2.9–28.3°
b = 13.5126 (2) Å	µ = 15.02 mm⁻¹
c = 14.0140 (2) Å	T = 140 K
V = 1534.05 (4) Å³	Prism, yellow
Z = 4	0.20 × 0.10 × 0.05 mm

Data collection top

Bruker SMART APEX diffractometer	1837 independent reflections
Radiation source: fine-focus sealed tube	1752 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.153, T_max = 0.521	k = −17→17
10101 measured reflections	l = −18→18

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)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.043	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0233P)² + 1.8105P] where P = (F_o² + 2F_c²)/3
1837 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −0.90 e Å⁻³

Crystal data top

[PbI₂(C₉H₁₅N₅O)]	V = 1534.05 (4) Å³
M_r = 670.25	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 8.1010 (1) Å	µ = 15.02 mm⁻¹
b = 13.5126 (2) Å	T = 140 K
c = 14.0140 (2) Å	0.20 × 0.10 × 0.05 mm

Data collection top

Bruker SMART APEX diffractometer	1837 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1752 reflections with I > 2σ(I)
T_min = 0.153, T_max = 0.521	R_int = 0.028
10101 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.043	H-atom parameters constrained
S = 1.05	Δρ_max = 0.72 e Å⁻³
1837 reflections	Δρ_min = −0.90 e Å⁻³
91 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pb1	0.55277 (2)	0.7500	0.769395 (12)	0.01565 (6)
I1	0.26714 (3)	0.588041 (17)	0.831700 (16)	0.02101 (7)
O1	0.3482 (4)	0.7500	0.6436 (2)	0.0171 (7)
N1	0.3822 (5)	0.7500	0.5481 (3)	0.0137 (8)
N2	0.4236 (4)	0.6615 (2)	0.4053 (2)	0.0184 (6)	0.50
N3	0.3560 (4)	0.5806 (2)	0.5498 (2)	0.0237 (7)
H31	0.3565	0.5226	0.5213	0.028*
H32	0.3340	0.5847	0.6112	0.028*
N4	0.4716 (6)	0.7500	0.2638 (3)	0.0187 (9)
C1	0.3887 (4)	0.6625 (3)	0.5000 (2)	0.0183 (7)
C2	0.4236 (4)	0.6615 (2)	0.4053 (2)	0.0184 (6)	0.50
H2	0.4352	0.6007	0.3718	0.022*	0.50
C3	0.4417 (6)	0.7500	0.3590 (3)	0.0173 (9)
C4	0.5041 (5)	0.6591 (3)	0.2101 (3)	0.0224 (7)
H4A	0.4732	0.6010	0.2493	0.027*
H4B	0.6234	0.6544	0.1956	0.027*
C5	0.4058 (5)	0.6583 (3)	0.1176 (3)	0.0280 (9)
H5A	0.4367	0.5992	0.0798	0.034*
H5B	0.2867	0.6535	0.1326	0.034*
C6	0.4363 (8)	0.7500	0.0587 (4)	0.0350 (14)
H6A	0.5517	0.7500	0.0354	0.042*
H6B	0.3621	0.7500	0.0026	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.01521 (10)	0.01598 (10)	0.01577 (10)	0.000	−0.00072 (6)	0.000
I1	0.02066 (14)	0.01606 (12)	0.02631 (12)	−0.00058 (9)	0.00187 (9)	0.00768 (8)
O1	0.0150 (17)	0.0263 (18)	0.0099 (13)	0.000	0.0015 (12)	0.000
N1	0.0143 (19)	0.0163 (19)	0.0105 (16)	0.000	−0.0019 (14)	0.000
N2	0.0168 (16)	0.0230 (17)	0.0155 (14)	−0.0007 (13)	0.0001 (12)	−0.0035 (12)
N3	0.0270 (17)	0.0148 (15)	0.0294 (15)	−0.0038 (13)	−0.0040 (13)	−0.0053 (12)
N4	0.026 (2)	0.018 (2)	0.0118 (18)	0.000	0.0012 (16)	0.000
C1	0.0145 (16)	0.0208 (18)	0.0197 (16)	−0.0011 (14)	−0.0007 (13)	−0.0043 (13)
C2	0.0168 (16)	0.0230 (17)	0.0155 (14)	−0.0007 (13)	0.0001 (12)	−0.0035 (12)
C3	0.014 (2)	0.022 (2)	0.016 (2)	0.000	−0.0009 (18)	0.000
C4	0.0249 (19)	0.0211 (18)	0.0211 (16)	0.0032 (16)	0.0036 (15)	−0.0038 (14)
C5	0.025 (2)	0.036 (2)	0.0226 (18)	−0.0012 (17)	−0.0035 (15)	−0.0130 (16)
C6	0.039 (4)	0.051 (4)	0.014 (2)	0.000	−0.006 (2)	0.000

Geometric parameters (Å, º) top

Pb1—O1	2.419 (3)	N4—C3	1.356 (6)
Pb1—O1ⁱ	2.686 (3)	N4—C4	1.464 (4)
Pb1—I1	3.3024 (3)	N4—C4ⁱⁱⁱ	1.464 (4)
Pb1—I1ⁱⁱ	3.1325 (3)	C3—C2ⁱⁱⁱ	1.368 (4)
Pb1—I1ⁱ	3.1325 (3)	C3—N2ⁱⁱⁱ	1.368 (4)
Pb1—I1ⁱⁱⁱ	3.3024 (3)	C4—C5	1.522 (5)
O1—N1	1.366 (5)	C4—H4A	0.9900
N1—C1	1.363 (4)	C4—H4B	0.9900
N1—C1ⁱⁱⁱ	1.363 (4)	C5—C6	1.509 (5)
N2—C1	1.358 (4)	C5—H5A	0.9900
N2—C3	1.368 (4)	C5—H5B	0.9900
N3—C1	1.335 (4)	C6—C5ⁱⁱⁱ	1.509 (5)
N3—H31	0.8800	C6—H6A	0.9900
N3—H32	0.8800	C6—H6B	0.9900

O1—Pb1—O1ⁱ	160.22 (9)	C4—N4—C4ⁱⁱⁱ	114.1 (4)
O1—Pb1—I1ⁱ	92.88 (5)	N3—C1—N2	123.0 (3)
O1ⁱ—Pb1—I1ⁱ	73.21 (5)	N3—C1—N1	116.9 (3)
O1—Pb1—I1ⁱⁱ	92.88 (5)	N2—C1—N1	120.1 (3)
O1ⁱ—Pb1—I1ⁱⁱ	73.21 (5)	N4—C3—N2	119.0 (2)
I1ⁱ—Pb1—I1ⁱⁱ	88.636 (10)	N4—C3—C2ⁱⁱⁱ	119.0 (2)
O1—Pb1—I1	73.30 (5)	N2—C3—C2ⁱⁱⁱ	121.9 (4)
O1ⁱ—Pb1—I1	120.29 (4)	N4—C3—N2ⁱⁱⁱ	119.0 (2)
I1ⁱ—Pb1—I1	92.581 (7)	N2—C3—N2ⁱⁱⁱ	121.9 (4)
I1ⁱⁱ—Pb1—I1	166.169 (8)	C2ⁱⁱⁱ—C3—N2ⁱⁱⁱ	0.0 (3)
O1—Pb1—I1ⁱⁱⁱ	73.30 (5)	N4—C4—C5	110.5 (3)
O1ⁱ—Pb1—I1ⁱⁱⁱ	120.29 (4)	N4—C4—H4A	109.6
I1ⁱ—Pb1—I1ⁱⁱⁱ	166.169 (8)	C5—C4—H4A	109.6
I1ⁱⁱ—Pb1—I1ⁱⁱⁱ	92.581 (7)	N4—C4—H4B	109.6
I1—Pb1—I1ⁱⁱⁱ	83.011 (9)	C5—C4—H4B	109.6
Pb1^iv—I1—Pb1	78.806 (5)	H4A—C4—H4B	108.1
N1—O1—Pb1	125.2 (3)	C6—C5—C4	112.0 (4)
N1—O1—Pb1^iv	128.6 (3)	C6—C5—H5A	109.2
Pb1—O1—Pb1^iv	106.25 (11)	C4—C5—H5A	109.2
O1—N1—C1	119.5 (2)	C6—C5—H5B	109.2
O1—N1—C1ⁱⁱⁱ	119.5 (2)	C4—C5—H5B	109.2
C1—N1—C1ⁱⁱⁱ	120.5 (4)	H5A—C5—H5B	107.9
C1—N2—C3	118.5 (3)	C5ⁱⁱⁱ—C6—C5	110.4 (4)
C1—N3—H31	120.0	C5ⁱⁱⁱ—C6—H6A	109.6
C1—N3—H32	120.0	C5—C6—H6A	109.6
H31—N3—H32	120.0	C5ⁱⁱⁱ—C6—H6B	109.6
C3—N4—C4	122.51 (19)	C5—C6—H6B	109.6
C3—N4—C4ⁱⁱⁱ	122.51 (19)	H6A—C6—H6B	108.1

O1—Pb1—I1—Pb1^iv	−35.49 (5)	C3—N2—C1—N3	174.6 (4)
O1ⁱ—Pb1—I1—Pb1^iv	160.24 (6)	C3—N2—C1—N1	−3.9 (5)
I1ⁱ—Pb1—I1—Pb1^iv	−127.726 (10)	O1—N1—C1—N3	1.9 (5)
I1ⁱⁱ—Pb1—I1—Pb1^iv	−32.94 (2)	C1ⁱⁱⁱ—N1—C1—N3	−169.9 (3)
I1ⁱⁱⁱ—Pb1—I1—Pb1^iv	39.115 (7)	O1—N1—C1—N2	−179.5 (3)
O1ⁱ—Pb1—O1—N1	0.000 (2)	C1ⁱⁱⁱ—N1—C1—N2	8.7 (7)
I1ⁱ—Pb1—O1—N1	−44.389 (6)	C4—N4—C3—N2	−7.1 (7)
I1ⁱⁱ—Pb1—O1—N1	44.389 (6)	C4ⁱⁱⁱ—N4—C3—N2	−175.6 (4)
I1—Pb1—O1—N1	−136.222 (16)	C4—N4—C3—C2ⁱⁱⁱ	175.6 (4)
I1ⁱⁱⁱ—Pb1—O1—N1	136.222 (17)	C4ⁱⁱⁱ—N4—C3—C2ⁱⁱⁱ	7.1 (7)
O1ⁱ—Pb1—O1—Pb1^iv	180.0	C4—N4—C3—N2ⁱⁱⁱ	175.6 (4)
I1ⁱ—Pb1—O1—Pb1^iv	135.611 (6)	C4ⁱⁱⁱ—N4—C3—N2ⁱⁱⁱ	7.1 (7)
I1ⁱⁱ—Pb1—O1—Pb1^iv	−135.611 (6)	C1—N2—C3—N4	−178.0 (4)
I1—Pb1—O1—Pb1^iv	43.778 (16)	C1—N2—C3—C2ⁱⁱⁱ	−0.8 (7)
I1ⁱⁱⁱ—Pb1—O1—Pb1^iv	−43.778 (16)	C1—N2—C3—N2ⁱⁱⁱ	−0.8 (7)
Pb1—O1—N1—C1	94.1 (3)	C3—N4—C4—C5	134.8 (5)
Pb1^iv—O1—N1—C1	−85.9 (3)	C4ⁱⁱⁱ—N4—C4—C5	−55.8 (6)
Pb1—O1—N1—C1ⁱⁱⁱ	−94.1 (3)	N4—C4—C5—C6	54.1 (5)
Pb1^iv—O1—N1—C1ⁱⁱⁱ	85.9 (3)	C4—C5—C6—C5ⁱⁱⁱ	−53.5 (6)

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

Experimental details

Crystal data
Chemical formula	[PbI₂(C₉H₁₅N₅O)]
M_r	670.25
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	140
a, b, c (Å)	8.1010 (1), 13.5126 (2), 14.0140 (2)
V (Å³)	1534.05 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	15.02
Crystal size (mm)	0.20 × 0.10 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.153, 0.521
No. of measured, independent and observed [I > 2σ(I)] reflections	10101, 1837, 1752
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.043, 1.05
No. of reflections	1837
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.90

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

We thank IROST and the University of Malaya for supporting this study.

References

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