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Acta Cryst. (2009). E65, m755    [ doi:10.1107/S1600536809021370 ]

Tripotassium bis(acetato-[kappa]2O,O')(thiocyanato-[kappa]N)plumbate(II) dithiocyanate

S. W. Ng

Abstract top

In the crystal structure of the title salt, K3[Pb(CH3COO)2(NCS)](NCS)2, the [Pb(CH3COO)2(NCS)]- anion exists as a covalently bonded entity in which the acetate anions chelate in an anisobidentate manner. The Pb atom shows a distorted [psi]-octahedral coordination to four acetate O atoms and one isocyanate N atom, with the stereochemically active lone pair occupying one of the six sites. When the three longer Pb...S interactions are considered, the eight-coordinate geometry is based on a dodecahedron. The Pb(CH3COO)2(NCS)]- anion has mirror symmetry. The potassium cations connect the other constituents into a three-dimensional network through electrostatic K...N and K...S interactions.

Related literature top

In [K6Pb6(CH3CO2)12(NCS)2](NCS)4, the acetate groups link the lead(II) atoms into a chain; see: Morsali & Mahjoub (2004).

Experimental top

2,4-Diamino-6-(1-piperidinyl)-2,4-pyrimidine N-oxide (commercial name: minoxidil) (0.5 mmol, 0.10 g), lead(II) acetate (0.5 mmol, 0.17 g) and potassium thiocyanate (1 mmol, 0.10 g) were dissolved in methanol (100 ml). The solution was concentrated to a smaller volume and this was mixed with a similar volume of chloroform. Colorless prisms separated after several days.

Refinement top

Hydrogen atoms were placed at calculated positions (C–H 0.98 Å) and were treated as riding on the carbon atom with U(H) set to 1.5Ueq(C). The final difference Fourier map had a deep hole at 1 Å from N1.

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 ellipsoid plot (Barbour, 2001) of a portion of the polymeric structure of K3Pb(NCS)3(CH3CO2)2 at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry operation i: x, 1.5-y, z.
[Figure 2] Fig. 2. Detail showing the dodecahedral geometry of the Pb(II) atom.
Tripotassium bis(acetato-κ2O,O')(thiocyanato-κN)plumbate(II) dithiocyanate top
Crystal data top
K3[Pb(C2H3O2)2(NCS)](NCS)2F(000) = 576
Mr = 616.82Dx = 2.352 Mg m−3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 4971 reflections
a = 6.1968 (1) Åθ = 2.9–28.3°
b = 19.2499 (3) ŵ = 10.77 mm−1
c = 7.6354 (1) ÅT = 140 K
β = 106.982 (1)°Block, colorless
V = 871.10 (2) Å30.25 × 0.20 × 0.08 mm
Z = 2
Data collection top
Bruker SMART APEX
diffractometer		2045 independent reflections
Radiation source: fine-focus sealed tube2015 reflections with I > 2σ(I)
graphiteRint = 0.023
ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→8
Tmin = 0.174, Tmax = 0.480k = −25→25
6058 measured reflectionsl = −9→9
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)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.03P)2 + 1.3438P]
where P = (Fo2 + 2Fc2)/3
2045 reflections(Δ/σ)max = 0.001
104 parametersΔρmax = 0.81 e Å−3
0 restraintsΔρmin = −2.00 e Å−3
Crystal data top
K3[Pb(C2H3O2)2(NCS)](NCS)2V = 871.10 (2) Å3
Mr = 616.82Z = 2
Monoclinic, P21/mMo Kα radiation
a = 6.1968 (1) ŵ = 10.77 mm−1
b = 19.2499 (3) ÅT = 140 K
c = 7.6354 (1) Å0.25 × 0.20 × 0.08 mm
β = 106.982 (1)°
Data collection top
Bruker SMART APEX
diffractometer		2045 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2015 reflections with I > 2σ(I)
Tmin = 0.174, Tmax = 0.480Rint = 0.023
6058 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.056Δρmax = 0.81 e Å−3
S = 1.16Δρmin = −2.00 e Å−3
2045 reflectionsAbsolute structure: ?
104 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pb10.41686 (3)0.75000.47400 (2)0.01158 (7)
K10.85392 (14)0.59423 (4)0.42518 (12)0.01948 (17)
K20.74409 (19)0.75000.09371 (15)0.0160 (2)
S11.1475 (2)0.75000.8492 (2)0.0247 (3)
S20.65682 (16)0.62677 (5)0.76528 (14)0.01949 (19)
N10.8449 (7)0.75000.4972 (6)0.0151 (9)
N20.2738 (6)0.54336 (19)0.6214 (6)0.0289 (8)
O10.4696 (4)0.66654 (13)0.2532 (4)0.0162 (5)
O20.1161 (4)0.66405 (13)0.2588 (4)0.0171 (5)
C10.2743 (6)0.63941 (18)0.2063 (5)0.0146 (7)
C20.2360 (7)0.5741 (2)0.0917 (6)0.0236 (8)
H2A0.22830.53410.16890.035*
H2B0.36090.56780.03880.035*
H2C0.09400.5782−0.00690.035*
C30.9724 (8)0.75000.6432 (7)0.0142 (10)
C40.4309 (6)0.57822 (19)0.6821 (5)0.0180 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb10.01294 (11)0.01291 (10)0.01004 (11)0.0000.00516 (7)0.000
K10.0164 (4)0.0153 (4)0.0286 (4)0.0018 (3)0.0095 (3)0.0037 (3)
K20.0168 (5)0.0192 (5)0.0129 (5)0.0000.0058 (4)0.000
S10.0184 (6)0.0388 (8)0.0144 (6)0.0000.0011 (5)0.000
S20.0194 (4)0.0185 (4)0.0210 (5)−0.0041 (3)0.0065 (4)−0.0016 (4)
N10.0119 (19)0.020 (2)0.013 (2)0.0000.0035 (17)0.000
N20.0217 (18)0.0232 (17)0.036 (2)−0.0019 (14)0.0000 (16)0.0014 (15)
O10.0136 (12)0.0192 (12)0.0162 (13)−0.0004 (9)0.0050 (10)−0.0031 (10)
O20.0142 (12)0.0194 (12)0.0191 (13)0.0017 (9)0.0071 (10)−0.0002 (10)
C10.0171 (16)0.0143 (15)0.0107 (16)0.0017 (12)0.0015 (13)0.0049 (13)
C20.0234 (19)0.0199 (18)0.025 (2)−0.0010 (15)0.0034 (17)−0.0079 (16)
C30.012 (2)0.012 (2)0.020 (3)0.0000.008 (2)0.000
C40.0175 (18)0.0142 (16)0.0205 (19)0.0032 (13)0.0031 (15)0.0034 (14)
Geometric parameters (Å, °) top
Pb1—O12.419 (3)K2—S2vi3.3788 (13)
Pb1—O1i2.419 (3)K2—S2vii3.3788 (13)
Pb1—O22.669 (3)S1—C31.630 (5)
Pb1—O2i2.669 (3)S2—C41.649 (4)
Pb1—N12.606 (4)S2—K2viii3.3788 (13)
Pb1—S1ii3.713 (1)N1—C31.163 (7)
Pb1—S23.294 (1)N1—K1i3.0520 (12)
Pb1—S2i3.294 (1)N2—C41.162 (5)
K1—O2iii2.696 (3)N2—K1iv2.757 (4)
K1—O12.740 (3)N2—K1ii2.774 (4)
K1—N2iv2.757 (4)O1—C11.270 (4)
K1—N2iii2.774 (4)O2—C11.255 (5)
K1—N13.0520 (12)O2—K1ii2.696 (3)
K1—S23.2373 (13)O2—K2ii2.818 (3)
K2—O2v2.818 (3)C1—C21.509 (5)
K2—O2iii2.818 (3)C2—H2A0.9800
K2—O12.858 (3)C2—H2B0.9800
K2—O1i2.858 (3)C2—H2C0.9800
K2—N12.959 (5)C3—K1i3.404 (3)
O1—Pb1—O1i83.23 (13)O2v—K2—S1ix143.98 (5)
O1—Pb1—N172.87 (9)O2iii—K2—S1ix143.98 (5)
O1i—Pb1—N172.87 (9)O1—K2—S1ix64.83 (6)
O1—Pb1—O251.04 (8)O1i—K2—S1ix64.83 (6)
O1i—Pb1—O2101.23 (8)N1—K2—S1ix114.20 (9)
N1—Pb1—O2123.76 (9)S2vi—K2—S1ix72.51 (3)
O1—Pb1—O2i101.23 (8)S2vii—K2—S1ix72.51 (3)
O1i—Pb1—O2i51.04 (8)S1vi—K2—S1ix120.08 (5)
N1—Pb1—O2i123.76 (9)C3—S1—K2viii97.79 (19)
O2—Pb1—O2i76.62 (11)C3—S1—K2x142.1 (2)
O2iii—K1—O194.59 (8)K2viii—S1—K2x120.08 (5)
O2iii—K1—N2iv127.44 (11)C4—S2—K193.34 (15)
O1—K1—N2iv104.45 (9)C4—S2—K2viii128.15 (15)
O2iii—K1—N2iii80.28 (10)K1—S2—K2viii135.65 (4)
O1—K1—N2iii170.07 (10)C3—N1—Pb1117.3 (4)
N2iv—K1—N2iii85.36 (11)C3—N1—K2151.1 (4)
O2iii—K1—N168.92 (10)Pb1—N1—K291.61 (13)
O1—K1—N161.85 (10)C3—N1—K197.45 (9)
N2iv—K1—N1161.31 (12)Pb1—N1—K193.42 (8)
N2iii—K1—N1108.25 (11)K2—N1—K179.74 (8)
O2iii—K1—S2134.60 (6)C3—N1—K1i97.45 (9)
O1—K1—S278.90 (6)Pb1—N1—K1i93.42 (8)
N2iv—K1—S297.35 (9)K2—N1—K1i79.74 (8)
N2iii—K1—S298.58 (9)K1—N1—K1i158.52 (17)
N1—K1—S268.55 (9)C4—N2—K1iv141.4 (3)
O2v—K2—O2iii71.90 (11)C4—N2—K1ii123.8 (3)
O2v—K2—O1130.58 (9)K1iv—N2—K1ii94.64 (11)
O2iii—K2—O189.45 (8)C1—O1—Pb199.1 (2)
O2v—K2—O1i89.45 (8)C1—O1—K1123.3 (2)
O2iii—K2—O1i130.58 (9)Pb1—O1—K1106.18 (9)
O1—K2—O1i68.41 (10)C1—O1—K2138.4 (2)
O2v—K2—N168.78 (9)Pb1—O1—K298.16 (8)
O2iii—K2—N168.78 (9)K1—O1—K286.99 (8)
O1—K2—N161.80 (9)C1—O2—Pb187.8 (2)
O1i—K2—N161.80 (9)C1—O2—K1ii126.6 (2)
O2v—K2—S2vi132.59 (7)Pb1—O2—K1ii115.30 (10)
O2iii—K2—S2vi81.51 (6)C1—O2—K2ii133.8 (2)
O1—K2—S2vi86.29 (6)Pb1—O2—K2ii104.14 (8)
O1i—K2—S2vi136.45 (7)K1ii—O2—K2ii88.66 (8)
N1—K2—S2vi135.40 (2)O2—C1—O1121.6 (3)
O2v—K2—S2vii81.51 (6)O2—C1—C2119.6 (3)
O2iii—K2—S2vii132.59 (7)O1—C1—C2118.8 (3)
O1—K2—S2vii136.45 (6)C1—C2—H2A109.5
O1i—K2—S2vii86.29 (6)C1—C2—H2B109.5
N1—K2—S2vii135.40 (2)H2A—C2—H2B109.5
S2vi—K2—S2vii89.19 (4)C1—C2—H2C109.5
O2v—K2—S1vi67.87 (6)H2A—C2—H2C109.5
O2iii—K2—S1vi67.87 (6)H2B—C2—H2C109.5
O1—K2—S1vi145.78 (5)N1—C3—S1179.1 (5)
O1i—K2—S1vi145.78 (5)N1—C3—K1i62.76 (9)
N1—K2—S1vi125.72 (9)S1—C3—K1i117.37 (8)
S2vi—K2—S1vi65.92 (3)N2—C4—S2178.7 (4)
S2vii—K2—S1vi65.92 (3)
O2iii—K1—S2—C4150.92 (15)O1i—Pb1—O1—C1−114.5 (2)
O1—K1—S2—C465.45 (14)N1—Pb1—O1—C1171.4 (2)
N2iv—K1—S2—C4−37.91 (15)O2—Pb1—O1—C1−4.14 (19)
N2iii—K1—S2—C4−124.30 (15)O2i—Pb1—O1—C1−66.5 (2)
N1—K1—S2—C4129.38 (15)O1i—Pb1—O1—K1116.73 (7)
O2iii—K1—S2—K2viii−9.98 (11)N1—Pb1—O1—K142.61 (10)
O1—K1—S2—K2viii−95.45 (7)O2—Pb1—O1—K1−132.90 (14)
N2iv—K1—S2—K2viii161.19 (9)O2i—Pb1—O1—K1164.73 (9)
N2iii—K1—S2—K2viii74.80 (9)O1i—Pb1—O1—K227.51 (11)
N1—K1—S2—K2viii−31.52 (10)N1—Pb1—O1—K2−46.61 (9)
O1—Pb1—N1—C3−135.98 (7)O2—Pb1—O1—K2137.88 (13)
O1i—Pb1—N1—C3135.98 (7)O2i—Pb1—O1—K275.51 (9)
O2—Pb1—N1—C3−131.78 (8)O2iii—K1—O1—C1145.2 (3)
O2i—Pb1—N1—C3131.78 (8)N2iv—K1—O1—C114.7 (3)
O1—Pb1—N1—K244.02 (7)N1—K1—O1—C1−151.6 (3)
O1i—Pb1—N1—K2−44.02 (7)S2—K1—O1—C1−80.2 (3)
O2—Pb1—N1—K248.22 (8)O2iii—K1—O1—Pb1−101.92 (10)
O2i—Pb1—N1—K2−48.22 (8)N2iv—K1—O1—Pb1127.50 (12)
O1—Pb1—N1—K1−35.79 (10)N1—K1—O1—Pb1−38.80 (11)
O1i—Pb1—N1—K1−123.83 (13)S2—K1—O1—Pb132.68 (7)
O2—Pb1—N1—K1−31.60 (15)O2iii—K1—O1—K2−4.30 (8)
O2i—Pb1—N1—K1−128.03 (8)N2iv—K1—O1—K2−134.88 (10)
O1—Pb1—N1—K1i123.83 (13)N1—K1—O1—K258.82 (11)
O1i—Pb1—N1—K1i35.79 (10)S2—K1—O1—K2130.30 (6)
O2—Pb1—N1—K1i128.03 (8)O2v—K2—O1—C1158.4 (3)
O2i—Pb1—N1—K1i31.60 (15)O2iii—K2—O1—C1−136.3 (3)
O2v—K2—N1—C3−39.03 (6)O1i—K2—O1—C189.0 (3)
O2iii—K2—N1—C339.03 (6)N1—K2—O1—C1157.7 (4)
O1—K2—N1—C3140.36 (6)S2vi—K2—O1—C1−54.7 (3)
O1i—K2—N1—C3−140.36 (7)S2vii—K2—O1—C130.2 (4)
S2vi—K2—N1—C390.78 (10)S1vi—K2—O1—C1−89.4 (4)
S2vii—K2—N1—C3−90.78 (10)S1ix—K2—O1—C117.7 (3)
S1vi—K2—N1—C30.000 (2)O2v—K2—O1—Pb144.69 (13)
S1ix—K2—N1—C3180.000 (3)O2iii—K2—O1—Pb1110.02 (9)
O2v—K2—N1—Pb1140.97 (6)O1i—K2—O1—Pb1−24.68 (10)
O2iii—K2—N1—Pb1−140.97 (6)N1—K2—O1—Pb143.94 (8)
O1—K2—N1—Pb1−39.64 (6)S2vi—K2—O1—Pb1−168.45 (8)
O1i—K2—N1—Pb139.64 (6)S2vii—K2—O1—Pb1−83.54 (10)
S2vi—K2—N1—Pb1−89.22 (10)S1vi—K2—O1—Pb1156.87 (8)
S2vii—K2—N1—Pb189.22 (10)S1ix—K2—O1—Pb1−96.05 (8)
S1vi—K2—N1—Pb1180.0O2v—K2—O1—K1−61.24 (11)
S1ix—K2—N1—Pb10.0O2iii—K2—O1—K14.10 (8)
O2v—K2—N1—K1−125.85 (11)O1i—K2—O1—K1−130.60 (4)
O2iii—K2—N1—K1−47.79 (8)N1—K2—O1—K1−61.98 (8)
O1—K2—N1—K153.55 (7)S2vi—K2—O1—K185.63 (6)
O1i—K2—N1—K1132.82 (11)S2vii—K2—O1—K1170.54 (5)
S2vi—K2—N1—K13.96 (16)S1vi—K2—O1—K150.94 (14)
S2vii—K2—N1—K1−177.60 (6)S1ix—K2—O1—K1158.03 (8)
S1vi—K2—N1—K1−86.82 (7)O1—Pb1—O2—C14.13 (19)
S1ix—K2—N1—K193.18 (7)O1i—Pb1—O2—C175.8 (2)
O2v—K2—N1—K1i47.79 (8)N1—Pb1—O2—C1−1.0 (2)
O2iii—K2—N1—K1i125.85 (11)O2i—Pb1—O2—C1120.85 (18)
O1—K2—N1—K1i−132.82 (11)O1—Pb1—O2—K1ii134.06 (15)
O1i—K2—N1—K1i−53.55 (7)O1i—Pb1—O2—K1ii−154.31 (10)
S2vi—K2—N1—K1i177.60 (6)N1—Pb1—O2—K1ii128.90 (11)
S2vii—K2—N1—K1i−3.96 (16)O2i—Pb1—O2—K1ii−109.23 (8)
S1vi—K2—N1—K1i86.82 (7)O1—Pb1—O2—K2ii−130.64 (13)
S1ix—K2—N1—K1i−93.18 (7)O1i—Pb1—O2—K2ii−59.01 (10)
O2iii—K1—N1—C3−100.2 (4)N1—Pb1—O2—K2ii−135.80 (10)
O1—K1—N1—C3152.1 (4)O2i—Pb1—O2—K2ii−13.92 (12)
N2iv—K1—N1—C3106.4 (5)Pb1—O2—C1—O1−7.2 (3)
N2iii—K1—N1—C3−28.7 (4)K1ii—O2—C1—O1−127.5 (3)
S2—K1—N1—C363.5 (3)K2ii—O2—C1—O1100.3 (4)
O2iii—K1—N1—Pb1141.70 (14)Pb1—O2—C1—C2170.0 (3)
O1—K1—N1—Pb134.03 (9)K1ii—O2—C1—C249.7 (4)
N2iv—K1—N1—Pb1−11.7 (4)K2ii—O2—C1—C2−82.5 (4)
N2iii—K1—N1—Pb1−146.82 (12)Pb1—O1—C1—O28.0 (4)
S2—K1—N1—Pb1−54.57 (9)K1—O1—C1—O2124.4 (3)
O2iii—K1—N1—K250.68 (9)K2—O1—C1—O2−105.3 (4)
O1—K1—N1—K2−56.99 (9)Pb1—O1—C1—C2−169.2 (3)
N2iv—K1—N1—K2−102.7 (4)K1—O1—C1—C2−52.9 (4)
N2iii—K1—N1—K2122.16 (11)K2—O1—C1—C277.4 (4)
S2—K1—N1—K2−145.59 (10)Pb1—N1—C3—K1i−97.76 (12)
O2iii—K1—N1—K1i33.4 (4)K2—N1—C3—K1i82.24 (12)
O1—K1—N1—K1i−74.3 (4)K1—N1—C3—K1i164.5 (2)
N2iv—K1—N1—K1i−120.0 (5)K2viii—S1—C3—K1i97.27 (19)
N2iii—K1—N1—K1i104.8 (4)K2x—S1—C3—K1i−82.73 (19)
S2—K1—N1—K1i−162.9 (5)
Symmetry codes: (i) x, −y+3/2, z; (ii) x−1, y, z; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) x+1, −y+3/2, z; (vi) x, y, z−1; (vii) x, −y+3/2, z−1; (viii) x, y, z+1; (ix) x−1, y, z−1; (x) x+1, y, z+1.
Acknowledgements top

I thank Dr Maryam Ranjbar of the Iranian Research Organization for Science and Technology for providing the crystal, and the University of Malaya for supporting this study.

references
References top

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