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Poly[di-μ2-aqua-μ4-chlorido-μ4-(2-mercapto­pyrimidine-4,6-diolato-κ4O:O:O′:O′)-disodium(I)]

aState Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China
*Correspondence e-mail: wulx@jlu.edu.cn

(Received 5 November 2010; accepted 8 November 2010; online 13 November 2010)

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[Carballo, R., Casas, J. S., Garcia-Tasende, M. S., Sanchez, A., Sordo, J. & Vazquez-Lopez, E. M. (1996). J. Organomet. Chem. 525, 49-55.]).

[Scheme 1]

Experimental

Crystal data
  • [Na2(C4H3N2O2S)Cl(H2O)2]

  • Mr = 260.61

  • Orthorhombic, I m m a

  • 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.923, Tmax = 0.942

  • 4752 measured reflections

  • 633 independent reflections

  • 581 reflections with I > 2σ(I)

  • Rint = 0.017

Refinement
  • R[F2 > 2σ(F2)] = 0.024

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯Cl1 0.86 2.41 3.2457 (15) 165
O2—H2A⋯O1i 0.89 1.94 2.8164 (19) 169
O2—H2B⋯S1ii 0.87 2.49 3.3545 (15) 176
Symmetry codes: (i) [-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{5\over 2}}]; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: RAPID-AUTO (Rigaku, 1998[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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).

Structure description top

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).

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

Computing details top

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

Figures top
[Figure 1] 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; (D): 1/2-x, 1-y, 1/2+z; (E): 1/2-x, -y, 1/2+z; (F) x, -y, 2-z.]
Poly[di-µ2-aqua-µ4-chlorido-µ4-(2-mercaptopyrimidine-4,6-diolato- κ4O:O:O':O')-disodium(I)] top
Crystal data top
[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 top
Rigaku R-AXIS RAPID
diffractometer
633 independent reflections
Radiation source: rotation anode581 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
ω scansθmax = 27.4°, θmin = 3.9°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 2119
Tmin = 0.923, Tmax = 0.942k = 88
4752 measured reflectionsl = 1111
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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062H-atom parameters constrained
S = 1.09 w = 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
Crystal data top
[Na2(C4H3N2O2S)Cl(H2O)2]V = 982.2 (3) Å3
Mr = 260.61Z = 4
Orthorhombic, ImmaMo Kα radiation
a = 16.815 (3) ŵ = 0.68 mm1
b = 6.5938 (13) ÅT = 290 K
c = 8.8587 (18) Å0.12 × 0.11 × 0.09 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer
633 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
581 reflections with I > 2σ(I)
Tmin = 0.923, Tmax = 0.942Rint = 0.017
4752 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.062H-atom parameters constrained
S = 1.09Δρmax = 0.26 e Å3
633 reflectionsΔρmin = 0.30 e Å3
46 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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)0.0000.0028 (2)0.000
N10.0127 (7)0.0314 (8)0.0172 (7)0.0000.0013 (5)0.000
Na10.0288 (4)0.0236 (4)0.0245 (4)0.0000.0000.0031 (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, º) top
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, y1/2, z+2; (vi) x+1/2, y+1, z1/2.
Hydrogen-bond geometry (Å, º) top
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) x1/2, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[Na2(C4H3N2O2S)Cl(H2O)2]
Mr260.61
Crystal system, space groupOrthorhombic, Imma
Temperature (K)290
a, b, c (Å)16.815 (3), 6.5938 (13), 8.8587 (18)
V3)982.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.68
Crystal size (mm)0.12 × 0.11 × 0.09
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.923, 0.942
No. of measured, independent and
observed [I > 2σ(I)] reflections
4752, 633, 581
Rint0.017
(sin θ/λ)max1)0.647
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.062, 1.09
No. of reflections633
No. of parameters46
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.30

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.862.413.2457 (15)165
O2—H2A···O1i0.891.942.8164 (19)169
O2—H2B···S1ii0.872.493.3545 (15)176
Symmetry codes: (i) x+1/2, y+1/2, z+5/2; (ii) x1/2, y+1/2, z+3/2.
 

Acknowledgements

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).

References

First citationCarballo, R., Casas, J. S., Garcia-Tasende, M. S., Sanchez, A., Sordo, J. & Vazquez-Lopez, E. M. (1996). J. Organomet. Chem. 525, 49–55.  CSD CrossRef CAS Web of Science Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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