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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): m1546.
Published online 2010 November 13. doi:  10.1107/S1600536810045836
PMCID: PMC3011735

Poly[di-μ2-aqua-μ4-chlorido-μ4-(2-mercaptopyrimidine-4,6-diolato-κ4 O:O:O′:O′)-disodium(I)]

Abstract

In the title coordination polymer, [Na2(C4H3N2O2S)Cl(H2O)2]n, the NaI ion lies on a twofold rotation axis and the chloride anion on an inversion center. The NaI ion is six-coordinated by two O atoms from two zwitterionic 2-mercaptopyrimidine-4,6-diolate ligands (mm2 symmetry), two water O atoms (m symmetry) and two Cl atoms in a distorted octa­hedral geometry. Adjacent NaI ions are bridged by an olate group, a water mol­ecule and a chloride anion into a three-dimensional network. The crystal structure is further stabil­ized by N—H(...)Cl, O—H(...)O and O—H(...)S hydrogen bonds.

Related literature

For organic–inorganic hybrid compounds with 2-mercaptopyrimidine-4,6-diol derivatives, see: Carballo et al. (1996 [triangle]).

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Object name is e-66-m1546-scheme1.jpg

Experimental

Crystal data

  • [Na2(C4H3N2O2S)Cl(H2O)2]
  • M r = 260.61
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1546-efi1.jpg
  • a = 16.815 (3) Å
  • b = 6.5938 (13) Å
  • c = 8.8587 (18) Å
  • V = 982.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.68 mm−1
  • T = 290 K
  • 0.12 × 0.11 × 0.09 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.923, T max = 0.942
  • 4752 measured reflections
  • 633 independent reflections
  • 581 reflections with I > 2σ(I)
  • R int = 0.017

Refinement

  • R[F 2 > 2σ(F 2)] = 0.024
  • wR(F 2) = 0.062
  • S = 1.09
  • 633 reflections
  • 46 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045836/hy2376sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045836/hy2376Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported financially by the National Basic Research Program of China (grant No. 2007CB808003) and the National Natural Science Foundation of China (grant Nos. 20973082, 20921003, 20703019).

supplementary crystallographic information

Comment

2-Mercaptopyrimidine-4,6-diol and its derivatives have been used widely to build organic-inorganic hybrids due to their diverse properties (Carballo et al. 1996). During the course of on-going crystal engineering studies on nickel salts, we obtained two types of crystals different in color, green and colorless. We herein report the crystal structure of the colorless one, the title compound.

The coordination environment around NaI ion is shown in Fig. 1, with atom numbering scheme. The NaI ion is six-coordinated in a distorted octahedral geometry by two O atoms from two 2-mercaptopyrimidine-4,6-diolate ligands, two water O atoms and two Cl atoms. The 2-mercaptopyrimidine-4,6-diolate anion serving as a bridging ligand coordinates to four NaI ions. The crystal structure is stabilized by N—H···Cl, O—H···O and O—H···S hydrogen bonds (Table 1).

Experimental

2-Mercaptopyrimidine-4,6-diol (1.44 g, 10 mmol) and NiCl2.6H2O (3.28 g, 10 mmol) were dissolved in hot water (20 ml) and the pH value was adjusted to about 5 by using dilute NaOH solution with stirring. The mixture was heated for one hour and then cooled to room temperature. The precipitate was washed by dilute HCl and the filtrate was allowed to evaporate at room temperature for two weeks, generating two types of block crystals, one was colorless and the other was green.

Refinement

C- and N-bound H atoms were positioned geometrically (C—H = 0.93, N—H = 0.86 Å) and refined as riding atom, with Uiso(H) = 1.2Ueq(C,N). Water H atoms were located in a difference Fourier map and refined as riding, with Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
The asymmetric unit of the title compound, with symmetry-related atoms to complete the ligand and Na coordination. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (A): 1-x, 1/2-y, z; (B): x, 1-y, 2-z; (C): x, -1/2+y, 2-z; ...

Crystal data

[Na2(C4H3N2O2S)Cl(H2O)2]F(000) = 528
Mr = 260.61Dx = 1.762 Mg m3
Orthorhombic, ImmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2b 2Cell parameters from 4272 reflections
a = 16.815 (3) Åθ = 3.3–27.4°
b = 6.5938 (13) ŵ = 0.68 mm1
c = 8.8587 (18) ÅT = 290 K
V = 982.2 (3) Å3Block, colorless
Z = 40.12 × 0.11 × 0.09 mm

Data collection

Rigaku R-AXIS RAPID diffractometer633 independent reflections
Radiation source: rotation anode581 reflections with I > 2σ(I)
graphiteRint = 0.017
ω scansθmax = 27.4°, θmin = 3.9°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −21→19
Tmin = 0.923, Tmax = 0.942k = −8→8
4752 measured reflectionsl = −11→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0282P)2 + 1.0461P] where P = (Fo2 + 2Fc2)/3
633 reflections(Δ/σ)max = 0.002
46 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.30 e Å3

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

xyzUiso*/Ueq
C10.50000.25000.7898 (3)0.0222 (5)
C20.42785 (10)0.25001.02887 (18)0.0174 (3)
C30.50000.25001.1064 (3)0.0199 (5)
H30.50000.25001.21130.024*
Cl10.25000.25000.75000.02138 (17)
N10.43218 (8)0.25000.87105 (16)0.0204 (3)
H10.38810.25000.82200.025*
Na10.25570 (4)0.50001.00000.0256 (2)
O10.35874 (7)0.25001.08459 (14)0.0242 (3)
O20.16839 (8)0.25001.10168 (15)0.0294 (3)
H2A0.15330.25001.19780.044*
H2B0.12320.25001.05380.044*
S10.50000.25000.60136 (8)0.0531 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0155 (11)0.0313 (13)0.0197 (11)0.0000.0000.000
C20.0158 (7)0.0182 (7)0.0182 (8)0.0000.0019 (6)0.000
C30.0178 (11)0.0262 (12)0.0158 (10)0.0000.0000.000
Cl10.0201 (3)0.0286 (3)0.0154 (3)0.000−0.0028 (2)0.000
N10.0127 (7)0.0314 (8)0.0172 (7)0.000−0.0013 (5)0.000
Na10.0288 (4)0.0236 (4)0.0245 (4)0.0000.000−0.0031 (3)
O10.0141 (6)0.0382 (7)0.0204 (6)0.0000.0030 (5)0.000
O20.0206 (6)0.0449 (8)0.0225 (6)0.0000.0013 (5)0.000
S10.0199 (3)0.1243 (10)0.0150 (3)0.0000.0000.000

Geometric parameters (Å, °)

C1—N11.3484 (19)N1—H10.8600
C1—S11.670 (3)Na1—O22.3842 (11)
C2—O11.263 (2)Na1—O12.5062 (11)
C2—C31.394 (2)Na1—Cl1i2.7625 (4)
C2—N11.400 (2)Na1—Na1ii3.2969 (6)
C3—H30.9300O2—H2A0.8885
Cl1—Na12.7625 (4)O2—H2B0.8701
N1iii—C1—N1115.5 (2)O2—Na1—Cl1i95.07 (3)
N1iii—C1—S1122.25 (11)O2ii—Na1—Cl1i82.47 (3)
N1—C1—S1122.25 (11)O1ii—Na1—Cl1i82.60 (3)
O1—C2—C3127.48 (16)O1—Na1—Cl1i100.18 (3)
O1—C2—N1115.99 (15)Cl1—Na1—Cl1i176.03 (3)
C3—C2—N1116.53 (15)O2—Na1—Na1ii133.74 (3)
C2iii—C3—C2121.0 (2)O2ii—Na1—Na1ii46.26 (3)
C2iii—C3—H3119.5O1ii—Na1—Na1ii48.87 (2)
C2—C3—H3119.5O1—Na1—Na1ii131.13 (2)
Na1—Cl1—Na1iv180.0Cl1—Na1—Na1ii126.636 (8)
Na1—Cl1—Na1v73.272 (15)Cl1i—Na1—Na1ii53.364 (8)
Na1iv—Cl1—Na1v106.728 (15)O2—Na1—Na1v46.26 (3)
Na1—Cl1—Na1vi106.728 (15)O2ii—Na1—Na1v133.74 (3)
Na1iv—Cl1—Na1vi73.272 (16)O1ii—Na1—Na1v131.13 (2)
Na1v—Cl1—Na1vi180.0O1—Na1—Na1v48.87 (2)
C1—N1—C2125.23 (16)Cl1—Na1—Na1v53.364 (8)
C1—N1—H1117.4Cl1i—Na1—Na1v126.636 (8)
C2—N1—H1117.4Na1ii—Na1—Na1v180.00 (5)
O2—Na1—O2ii103.98 (6)C2—O1—Na1v121.29 (7)
O2—Na1—O1ii173.45 (5)C2—O1—Na1121.29 (7)
O2ii—Na1—O1ii81.84 (4)Na1v—O1—Na182.26 (4)
O2—Na1—O181.84 (4)Na1—O2—Na1v87.48 (5)
O2ii—Na1—O1173.45 (5)Na1—O2—H2A122.5
O1ii—Na1—O192.53 (5)Na1v—O2—H2A122.5
O2—Na1—Cl182.47 (3)Na1—O2—H2B110.7
O2ii—Na1—Cl195.07 (3)Na1v—O2—H2B110.7
O1ii—Na1—Cl1100.18 (3)H2A—O2—H2B102.6
O1—Na1—Cl182.60 (3)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.862.413.2457 (15)165
O2—H2A···O1vii0.891.942.8164 (19)169
O2—H2B···S1viii0.872.493.3545 (15)176

Symmetry codes: (vii) −x+1/2, −y+1/2, −z+5/2; (viii) x−1/2, −y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2376).

References

  • Carballo, R., Casas, J. S., Garcia-Tasende, M. S., Sanchez, A., Sordo, J. & Vazquez-Lopez, E. M. (1996). J. Organomet. Chem.525, 49–55.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography