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Acta Cryst. (2009). E65, m749    [ doi:10.1107/S1600536809020972 ]

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

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

Abstract top

The N-oxide O atom of the minoxidil unit in the 1/1 adduct with lead(II) iodide, [PbI2(C9H15N5O)]n, bridges two PbII 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 PbII atom is a distorted [psi]-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 PbII 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 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.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The amino H-atoms were similarly treated (N–H 0.88 Å).

The minoxidil molecule is disordered about a mirror plane that is perpendicular to the pyrimidinyl ring; the mirror plane also bisects piperidinyl ring. In the aromatic ring, the nitrogen atom at the 1-position shares the same site as the carbon atom at the 5-position; this site was refined as half a nitrogen atom and half a C-H group. The short H2···H4a distance of 1.74 Å is an artifact of the disorder about a mirror plane.

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
[Figure 1] 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
Mr = 670.25Dx = 2.902 Mg m−3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 5726 reflections
a = 8.1010 (1) Åθ = 2.9–28.3°
b = 13.5126 (2) ŵ = 15.02 mm−1
c = 14.0140 (2) ÅT = 140 K
V = 1534.05 (4) Å3Prism, yellow
Z = 40.20 × 0.10 × 0.05 mm
Data collection top
Bruker SMART APEX
diffractometer		1837 independent reflections
Radiation source: fine-focus sealed tube1752 reflections with I > 2σ(I)
graphiteRint = 0.028
ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.153, Tmax = 0.521k = −17→17
10101 measured reflectionsl = −18→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.018Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.043H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0233P)2 + 1.8105P]
where P = (Fo2 + 2Fc2)/3
1837 reflections(Δ/σ)max = 0.001
91 parametersΔρmax = 0.72 e Å−3
0 restraintsΔρmin = −0.90 e Å−3
Crystal data top
[PbI2(C9H15N5O)]V = 1534.05 (4) Å3
Mr = 670.25Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 8.1010 (1) ŵ = 15.02 mm−1
b = 13.5126 (2) ÅT = 140 K
c = 14.0140 (2) Å0.20 × 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)
Tmin = 0.153, Tmax = 0.521Rint = 0.028
10101 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.018H-atom parameters constrained
wR(F2) = 0.043Δρmax = 0.72 e Å−3
S = 1.05Δρmin = −0.90 e Å−3
1837 reflectionsAbsolute structure: ?
91 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pb10.55277 (2)0.75000.769395 (12)0.01565 (6)
I10.26714 (3)0.588041 (17)0.831700 (16)0.02101 (7)
O10.3482 (4)0.75000.6436 (2)0.0171 (7)
N10.3822 (5)0.75000.5481 (3)0.0137 (8)
N20.4236 (4)0.6615 (2)0.4053 (2)0.0184 (6)0.50
N30.3560 (4)0.5806 (2)0.5498 (2)0.0237 (7)
H310.35650.52260.52130.028*
H320.33400.58470.61120.028*
N40.4716 (6)0.75000.2638 (3)0.0187 (9)
C10.3887 (4)0.6625 (3)0.5000 (2)0.0183 (7)
C20.4236 (4)0.6615 (2)0.4053 (2)0.0184 (6)0.50
H20.43520.60070.37180.022*0.50
C30.4417 (6)0.75000.3590 (3)0.0173 (9)
C40.5041 (5)0.6591 (3)0.2101 (3)0.0224 (7)
H4A0.47320.60100.24930.027*
H4B0.62340.65440.19560.027*
C50.4058 (5)0.6583 (3)0.1176 (3)0.0280 (9)
H5A0.43670.59920.07980.034*
H5B0.28670.65350.13260.034*
C60.4363 (8)0.75000.0587 (4)0.0350 (14)
H6A0.55170.75000.03540.042*
H6B0.36210.75000.00260.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb10.01521 (10)0.01598 (10)0.01577 (10)0.000−0.00072 (6)0.000
I10.02066 (14)0.01606 (12)0.02631 (12)−0.00058 (9)0.00187 (9)0.00768 (8)
O10.0150 (17)0.0263 (18)0.0099 (13)0.0000.0015 (12)0.000
N10.0143 (19)0.0163 (19)0.0105 (16)0.000−0.0019 (14)0.000
N20.0168 (16)0.0230 (17)0.0155 (14)−0.0007 (13)0.0001 (12)−0.0035 (12)
N30.0270 (17)0.0148 (15)0.0294 (15)−0.0038 (13)−0.0040 (13)−0.0053 (12)
N40.026 (2)0.018 (2)0.0118 (18)0.0000.0012 (16)0.000
C10.0145 (16)0.0208 (18)0.0197 (16)−0.0011 (14)−0.0007 (13)−0.0043 (13)
C20.0168 (16)0.0230 (17)0.0155 (14)−0.0007 (13)0.0001 (12)−0.0035 (12)
C30.014 (2)0.022 (2)0.016 (2)0.000−0.0009 (18)0.000
C40.0249 (19)0.0211 (18)0.0211 (16)0.0032 (16)0.0036 (15)−0.0038 (14)
C50.025 (2)0.036 (2)0.0226 (18)−0.0012 (17)−0.0035 (15)−0.0130 (16)
C60.039 (4)0.051 (4)0.014 (2)0.000−0.006 (2)0.000
Geometric parameters (Å, °) top
Pb1—O12.419 (3)N4—C31.356 (6)
Pb1—O1i2.686 (3)N4—C41.464 (4)
Pb1—I13.3024 (3)N4—C4iii1.464 (4)
Pb1—I1ii3.1325 (3)C3—C2iii1.368 (4)
Pb1—I1i3.1325 (3)C3—N2iii1.368 (4)
Pb1—I1iii3.3024 (3)C4—C51.522 (5)
O1—N11.366 (5)C4—H4A0.9900
N1—C11.363 (4)C4—H4B0.9900
N1—C1iii1.363 (4)C5—C61.509 (5)
N2—C11.358 (4)C5—H5A0.9900
N2—C31.368 (4)C5—H5B0.9900
N3—C11.335 (4)C6—C5iii1.509 (5)
N3—H310.8800C6—H6A0.9900
N3—H320.8800C6—H6B0.9900
O1—Pb1—O1i160.22 (9)C4—N4—C4iii114.1 (4)
O1—Pb1—I1i92.88 (5)N3—C1—N2123.0 (3)
O1i—Pb1—I1i73.21 (5)N3—C1—N1116.9 (3)
O1—Pb1—I1ii92.88 (5)N2—C1—N1120.1 (3)
O1i—Pb1—I1ii73.21 (5)N4—C3—N2119.0 (2)
I1i—Pb1—I1ii88.636 (10)N4—C3—C2iii119.0 (2)
O1—Pb1—I173.30 (5)N2—C3—C2iii121.9 (4)
O1i—Pb1—I1120.29 (4)N4—C3—N2iii119.0 (2)
I1i—Pb1—I192.581 (7)N2—C3—N2iii121.9 (4)
I1ii—Pb1—I1166.169 (8)C2iii—C3—N2iii0.0 (3)
O1—Pb1—I1iii73.30 (5)N4—C4—C5110.5 (3)
O1i—Pb1—I1iii120.29 (4)N4—C4—H4A109.6
I1i—Pb1—I1iii166.169 (8)C5—C4—H4A109.6
I1ii—Pb1—I1iii92.581 (7)N4—C4—H4B109.6
I1—Pb1—I1iii83.011 (9)C5—C4—H4B109.6
Pb1iv—I1—Pb178.806 (5)H4A—C4—H4B108.1
N1—O1—Pb1125.2 (3)C6—C5—C4112.0 (4)
N1—O1—Pb1iv128.6 (3)C6—C5—H5A109.2
Pb1—O1—Pb1iv106.25 (11)C4—C5—H5A109.2
O1—N1—C1119.5 (2)C6—C5—H5B109.2
O1—N1—C1iii119.5 (2)C4—C5—H5B109.2
C1—N1—C1iii120.5 (4)H5A—C5—H5B107.9
C1—N2—C3118.5 (3)C5iii—C6—C5110.4 (4)
C1—N3—H31120.0C5iii—C6—H6A109.6
C1—N3—H32120.0C5—C6—H6A109.6
H31—N3—H32120.0C5iii—C6—H6B109.6
C3—N4—C4122.51 (19)C5—C6—H6B109.6
C3—N4—C4iii122.51 (19)H6A—C6—H6B108.1
O1—Pb1—I1—Pb1iv−35.49 (5)C3—N2—C1—N3174.6 (4)
O1i—Pb1—I1—Pb1iv160.24 (6)C3—N2—C1—N1−3.9 (5)
I1i—Pb1—I1—Pb1iv−127.726 (10)O1—N1—C1—N31.9 (5)
I1ii—Pb1—I1—Pb1iv−32.94 (2)C1iii—N1—C1—N3−169.9 (3)
I1iii—Pb1—I1—Pb1iv39.115 (7)O1—N1—C1—N2−179.5 (3)
O1i—Pb1—O1—N10.000 (2)C1iii—N1—C1—N28.7 (7)
I1i—Pb1—O1—N1−44.389 (6)C4—N4—C3—N2−7.1 (7)
I1ii—Pb1—O1—N144.389 (6)C4iii—N4—C3—N2−175.6 (4)
I1—Pb1—O1—N1−136.222 (16)C4—N4—C3—C2iii175.6 (4)
I1iii—Pb1—O1—N1136.222 (17)C4iii—N4—C3—C2iii7.1 (7)
O1i—Pb1—O1—Pb1iv180.0C4—N4—C3—N2iii175.6 (4)
I1i—Pb1—O1—Pb1iv135.611 (6)C4iii—N4—C3—N2iii7.1 (7)
I1ii—Pb1—O1—Pb1iv−135.611 (6)C1—N2—C3—N4−178.0 (4)
I1—Pb1—O1—Pb1iv43.778 (16)C1—N2—C3—C2iii−0.8 (7)
I1iii—Pb1—O1—Pb1iv−43.778 (16)C1—N2—C3—N2iii−0.8 (7)
Pb1—O1—N1—C194.1 (3)C3—N4—C4—C5134.8 (5)
Pb1iv—O1—N1—C1−85.9 (3)C4iii—N4—C4—C5−55.8 (6)
Pb1—O1—N1—C1iii−94.1 (3)N4—C4—C5—C654.1 (5)
Pb1iv—O1—N1—C1iii85.9 (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.
Acknowledgements top

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

references
References top

Akama, H., Haramura, M., Tanaka, A., Akimoto, T. & Hirayama, N. (2004). Anal. Sci. 20, 29–30.

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Martín-Islán, A. P., Martín-Ramos, D. & Sainz-Díaz, C. I. (2008). J. Pharm. Sci. 97, 815–830.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.