supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

hy2411 scheme

Acta Cryst. (2011). E67, m435-m436    [ doi:10.1107/S1600536811008452 ]

Bis(1-methyl-4-oxoimidazolidin-2-iminium) diaquabis(pyridine-2,4-dicarboxylato-[kappa]2N,O2)zincate(II) dihydrate

H. Aghabozorg, F. Jafarbak, M. Mirzaei and B. Notash

Abstract top

In the title compound, (C4H8N3O)2[Zn(C7H3NO4)2(H2O)2]·2H2O, the ZnII ion is six-coordinated in a distorted octahedral geometry by two pyridine-2,4-dicarboxylate (pydc) ligands in the equatorial plane and two water molecules in the axial positions. The pydc ligands act as bidentate chelating ligands through one carboxylate O atom and the pyridine N atom. Intermolecular N-H...O, O-H...O and weak C-H...O hydrogen bonds stabilize the crystal structure.

Comment top

Many organic aromatic ligands and metal ions may aggregate into supramolecular networks using coordination and hydrogen bonds and π–π stacking interactions (Aghabozorg et al., 2008b). Metal complexes of pyridine-(di)carboxylates possess versatile structural motifs, which finally aggregate to various supramolecular architectures with interesting properties. We have previously reported several compounds containing creatinine (creat), pyridine-2,6-dicarboxylic acid (pydcH2) and various metals, such as (creatH)(pydcH).H2O (Moghimi et al., 2004), (creatH)2[Bi(pydc)2]2.4H2O (Moghimi et al., 2005), (creatH)[Zn(pydc)(pydcH)].4H2O (Aghabozorg et al., 2008c), (creatH)[Cr(pydc)2](pydcH2).6H2O (Aghabozorg et al., 2008a) and (H3O)(creatH)[Ni(pydc)2].3H2O (Attar Gharamaleki et al., 2009). For more details and related literature see our recent review article on proton-transfer compounds (Aghabozorg et al., 2008b).

We describe here the crystal structure of the title compound. The compound contains a [Zn(pydc)2(H2O)2]2- anion, two (creatH)+ cations and two uncoordinated water molecules (Fig. 1). In the anion, the ZnII atom is six-coordinated by two N atoms and two O atoms from two pydc ligands and two water molecules, with the bond length range of 2.0819 (14)–2.1957 (15) Å. The coordination environment around ZnII is distorted octahedral. Intermolecular N—H···O, O—H···O, and weak C—H···O hydrogen bonds play an important role in the stabilization of the crystal structure (Fig. 2 and Table 1).

Related literature top

For a review article on proton-transfer compounds, see: Aghabozorg et al. (2008b). For related structures, see: Aghabozorg et al. (2008a,c); Attar Gharamaleki et al. (2009); Moghimi et al. (2004, 2005).

Experimental top

The reaction of pyridine-2,4-dicarboxylic acid (83 mg, 0.5 mmol) in 10 ml distilled water, creatinine (56 mg, 0.5 mmol) in 5 ml distilled water and Zn(NO3)2.4H2O (65 mg, 0.25 mmol) in 10 ml distilled water in a 2:2:1 molar ratio gave colorless block crystals of the title compound after slow evaporation of the solvent at the room temperature. The crystals obtained were stable in air.

Refinement top

H atoms of water molecules and NH group were found in a difference Fourier map and refined isotropically. H5A was refined with a distance restraint of O—H = 0.79 (2) Å. H atoms on C atoms and NH2 group were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH), 0.97 (CH2) and 0.96 (CH3) Å and N—H = 0.86 Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C, N).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) -x+1, -y, -z+1.]
[Figure 2] Fig. 2. The packing diagram of the title compound. Intermolecular hydrogen bonds are shown as blue dashed lines.
Bis(1-methyl-4-oxoimidazolidin-2-iminium) diaquabis(pyridine-2,4-dicarboxylato-κ2N,O2)zincate(II) dihydrate top
Crystal data top
(C4H8N3O)2[Zn(C7H3NO4)2(H2O)2]·2H2OZ = 1
Mr = 695.93F(000) = 360.0
Triclinic, P1Dx = 1.639 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.3209 (11) ÅCell parameters from 3787 reflections
b = 8.3893 (17) Åθ = 2.5–29.2°
c = 16.621 (3) ŵ = 0.96 mm−1
α = 81.58 (3)°T = 298 K
β = 85.26 (3)°Block, colorless
γ = 74.09 (3)°0.30 × 0.20 × 0.15 mm
V = 705.1 (3) Å3
Data collection top
Stoe IPDS-2
diffractometer		3787 independent reflections
Radiation source: fine-focus sealed tube3206 reflections with I > 2σ(I)
graphiteRint = 0.043
ω scansθmax = 29.2°, θmin = 2.5°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)		h = −7→7
Tmin = 0.793, Tmax = 0.862k = −11→11
7743 measured reflectionsl = −18→22
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.059P)2]
where P = (Fo2 + 2Fc2)/3
3787 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.46 e Å−3
1 restraintΔρmin = −0.48 e Å−3
Crystal data top
(C4H8N3O)2[Zn(C7H3NO4)2(H2O)2]·2H2Oγ = 74.09 (3)°
Mr = 695.93V = 705.1 (3) Å3
Triclinic, P1Z = 1
a = 5.3209 (11) ÅMo Kα radiation
b = 8.3893 (17) ŵ = 0.96 mm−1
c = 16.621 (3) ÅT = 298 K
α = 81.58 (3)°0.30 × 0.20 × 0.15 mm
β = 85.26 (3)°
Data collection top
Stoe IPDS-2
diffractometer		3787 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)		3206 reflections with I > 2σ(I)
Tmin = 0.793, Tmax = 0.862Rint = 0.043
7743 measured reflectionsθmax = 29.2°
Refinement top
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090Δρmax = 0.46 e Å−3
S = 1.05Δρmin = −0.48 e Å−3
3787 reflectionsAbsolute structure: ?
226 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.50000.00000.50000.02707 (9)
O10.2451 (2)0.02688 (14)0.40534 (7)0.0301 (2)
O20.1143 (3)0.18980 (16)0.28950 (8)0.0395 (3)
O30.4093 (3)0.72611 (16)0.22032 (9)0.0432 (3)
O40.7237 (3)0.74523 (17)0.29581 (9)0.0462 (4)
O50.8365 (2)−0.13001 (16)0.42711 (8)0.0325 (3)
O60.1878 (3)0.07267 (19)0.03511 (9)0.0476 (3)
O70.0855 (4)0.6692 (3)0.09580 (15)0.0641 (5)
N10.5314 (2)0.22674 (15)0.43582 (8)0.0239 (2)
N20.6139 (3)0.25207 (17)0.11654 (9)0.0313 (3)
N30.4814 (3)0.02055 (17)0.13579 (9)0.0305 (3)
N40.7948 (3)0.03970 (18)0.22119 (10)0.0379 (4)
H4B0.89470.09430.23590.045*
H4A0.7965−0.05790.24620.045*
C10.3894 (3)0.27280 (17)0.36902 (9)0.0228 (3)
C20.3856 (3)0.41957 (18)0.31741 (9)0.0266 (3)
H20.28190.45050.27240.032*
C30.5398 (3)0.51957 (17)0.33430 (9)0.0252 (3)
C40.6886 (3)0.46909 (18)0.40272 (10)0.0282 (3)
H40.79510.53260.41510.034*
C50.6774 (3)0.32360 (19)0.45239 (10)0.0277 (3)
H50.77460.29210.49880.033*
C60.2358 (3)0.15364 (18)0.35239 (9)0.0251 (3)
C70.5555 (3)0.67753 (19)0.27867 (10)0.0302 (3)
C80.6413 (3)0.10458 (19)0.16135 (10)0.0275 (3)
C90.3457 (3)0.1124 (2)0.07056 (11)0.0322 (3)
C100.4348 (3)0.2712 (2)0.05257 (11)0.0348 (4)
H10A0.52270.2790−0.00080.042*
H10B0.28870.36940.05550.042*
C110.7495 (4)0.3769 (2)0.12415 (12)0.0360 (4)
H11A0.86930.33640.16730.054*
H11B0.62470.47810.13620.054*
H11C0.84450.39880.07390.054*
H30.453 (6)−0.081 (4)0.155 (2)0.076 (9)*
H7A0.113 (8)0.685 (5)0.136 (2)0.085 (13)*
H5B0.952 (5)−0.078 (3)0.4112 (15)0.048 (7)*
H7B0.025 (7)0.763 (5)0.072 (2)0.083 (11)*
H5A0.818 (6)−0.174 (3)0.3900 (14)0.060 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.03224 (15)0.02409 (13)0.02854 (15)−0.01705 (9)−0.01220 (10)0.00935 (9)
O10.0344 (6)0.0286 (5)0.0326 (6)−0.0204 (4)−0.0115 (5)0.0074 (4)
O20.0513 (7)0.0399 (6)0.0359 (7)−0.0273 (6)−0.0237 (6)0.0088 (5)
O30.0569 (8)0.0353 (6)0.0435 (7)−0.0273 (6)−0.0233 (6)0.0156 (5)
O40.0700 (9)0.0397 (7)0.0419 (7)−0.0400 (7)−0.0218 (7)0.0124 (5)
O50.0335 (6)0.0362 (6)0.0326 (6)−0.0182 (5)−0.0065 (5)−0.0004 (5)
O60.0467 (8)0.0542 (8)0.0483 (8)−0.0211 (6)−0.0229 (6)−0.0009 (7)
O70.0781 (13)0.0550 (10)0.0624 (12)−0.0174 (9)−0.0188 (10)−0.0093 (9)
N10.0256 (6)0.0233 (5)0.0251 (6)−0.0117 (4)−0.0077 (5)0.0029 (4)
N20.0348 (7)0.0267 (6)0.0343 (7)−0.0152 (5)−0.0096 (6)0.0081 (5)
N30.0394 (7)0.0280 (6)0.0295 (7)−0.0187 (5)−0.0106 (6)0.0031 (5)
N40.0529 (9)0.0315 (7)0.0369 (8)−0.0264 (6)−0.0225 (7)0.0119 (6)
C10.0247 (6)0.0227 (6)0.0242 (7)−0.0125 (5)−0.0057 (5)0.0013 (5)
C20.0323 (7)0.0246 (6)0.0254 (7)−0.0140 (6)−0.0099 (6)0.0053 (5)
C30.0301 (7)0.0208 (6)0.0268 (7)−0.0121 (5)−0.0059 (6)0.0028 (5)
C40.0328 (8)0.0247 (7)0.0321 (8)−0.0164 (6)−0.0092 (6)0.0013 (6)
C50.0313 (7)0.0266 (7)0.0286 (7)−0.0141 (6)−0.0130 (6)0.0041 (6)
C60.0269 (7)0.0254 (6)0.0273 (7)−0.0149 (5)−0.0071 (6)0.0010 (5)
C70.0424 (9)0.0228 (6)0.0296 (8)−0.0173 (6)−0.0054 (6)0.0024 (6)
C80.0335 (8)0.0254 (7)0.0269 (7)−0.0152 (6)−0.0047 (6)0.0024 (6)
C90.0321 (8)0.0349 (8)0.0308 (8)−0.0108 (6)−0.0080 (6)−0.0005 (6)
C100.0338 (8)0.0338 (8)0.0354 (9)−0.0111 (6)−0.0113 (7)0.0094 (7)
C110.0402 (9)0.0273 (7)0.0435 (10)−0.0180 (6)−0.0069 (7)0.0055 (7)
Geometric parameters (Å, °) top
Zn1—N12.0819 (14)N3—H30.91 (4)
Zn1—O12.1087 (13)N4—C81.298 (2)
Zn1—O52.1957 (15)N4—H4B0.8600
O1—C61.2696 (18)N4—H4A0.8600
O2—C61.2303 (19)C1—C21.390 (2)
O3—C71.244 (2)C1—C61.520 (2)
O4—C71.254 (2)C2—C31.393 (2)
O5—H5B0.85 (3)C2—H20.9300
O5—H5A0.79 (2)C3—C41.387 (2)
O6—C91.207 (2)C3—C71.519 (2)
O7—H7A0.74 (4)C4—C51.383 (2)
O7—H7B0.82 (4)C4—H40.9300
N1—C51.3367 (19)C5—H50.9300
N1—C11.3437 (19)C9—C101.514 (3)
N2—C81.325 (2)C10—H10A0.9700
N2—C101.449 (2)C10—H10B0.9700
N2—C111.449 (2)C11—H11A0.9600
N3—C91.368 (2)C11—H11B0.9600
N3—C81.370 (2)C11—H11C0.9600
N1—Zn1—N1i180.000 (1)C1—C2—H2120.6
N1—Zn1—O179.39 (5)C3—C2—H2120.6
N1i—Zn1—O1100.61 (5)C4—C3—C2118.38 (13)
N1—Zn1—O1i100.61 (5)C4—C3—C7119.66 (14)
N1i—Zn1—O1i79.39 (5)C2—C3—C7121.92 (14)
O1—Zn1—O1i180.00 (4)C5—C4—C3119.50 (14)
N1—Zn1—O589.26 (6)C5—C4—H4120.2
N1i—Zn1—O590.74 (6)C3—C4—H4120.2
O1—Zn1—O591.70 (5)N1—C5—C4122.15 (14)
O1i—Zn1—O588.30 (5)N1—C5—H5118.9
N1—Zn1—O5i90.74 (6)C4—C5—H5118.9
N1i—Zn1—O5i89.26 (6)O2—C6—O1126.60 (14)
O1—Zn1—O5i88.30 (5)O2—C6—C1117.01 (13)
O1i—Zn1—O5i91.70 (5)O1—C6—C1116.38 (13)
O5—Zn1—O5i180.000 (1)O3—C7—O4125.95 (15)
C6—O1—Zn1114.83 (9)O3—C7—C3118.71 (14)
Zn1—O5—H5B116.8 (17)O4—C7—C3115.32 (14)
Zn1—O5—H5A121 (2)N4—C8—N2127.93 (15)
H5B—O5—H5A106 (3)N4—C8—N3121.60 (14)
H7A—O7—H7B103 (4)N2—C8—N3110.47 (13)
C5—N1—C1118.96 (13)O6—C9—N3126.13 (17)
C5—N1—Zn1127.89 (10)O6—C9—C10127.74 (16)
C1—N1—Zn1113.12 (10)N3—C9—C10106.12 (14)
C8—N2—C10110.12 (14)N2—C10—C9102.65 (13)
C8—N2—C11127.22 (14)N2—C10—H10A111.2
C10—N2—C11122.56 (14)C9—C10—H10A111.2
C9—N3—C8110.51 (14)N2—C10—H10B111.2
C9—N3—H3118 (2)C9—C10—H10B111.2
C8—N3—H3131 (2)H10A—C10—H10B109.2
C8—N4—H4B120.0N2—C11—H11A109.5
C8—N4—H4A120.0N2—C11—H11B109.5
H4B—N4—H4A120.0H11A—C11—H11B109.5
N1—C1—C2122.12 (13)N2—C11—H11C109.5
N1—C1—C6116.08 (12)H11A—C11—H11C109.5
C2—C1—C6121.80 (13)H11B—C11—H11C109.5
C1—C2—C3118.85 (13)
N1—Zn1—O1—C63.82 (11)C3—C4—C5—N11.5 (3)
N1i—Zn1—O1—C6−176.18 (11)Zn1—O1—C6—O2175.35 (14)
O5—Zn1—O1—C6−85.11 (12)Zn1—O1—C6—C1−5.02 (18)
O5i—Zn1—O1—C694.89 (12)N1—C1—C6—O2−176.70 (15)
O1—Zn1—N1—C5−179.66 (15)C2—C1—C6—O22.4 (2)
O1i—Zn1—N1—C50.34 (15)N1—C1—C6—O13.6 (2)
O5—Zn1—N1—C5−87.80 (14)C2—C1—C6—O1−177.22 (14)
O5i—Zn1—N1—C592.20 (14)C4—C3—C7—O3−175.83 (16)
O1—Zn1—N1—C1−1.69 (11)C2—C3—C7—O36.3 (3)
O1i—Zn1—N1—C1178.31 (11)C4—C3—C7—O45.8 (2)
O5—Zn1—N1—C190.17 (11)C2—C3—C7—O4−172.14 (17)
O5i—Zn1—N1—C1−89.83 (11)C10—N2—C8—N4176.19 (18)
C5—N1—C1—C2−1.2 (2)C11—N2—C8—N4−0.2 (3)
Zn1—N1—C1—C2−179.41 (12)C10—N2—C8—N3−3.2 (2)
C5—N1—C1—C6177.91 (14)C11—N2—C8—N3−179.64 (17)
Zn1—N1—C1—C6−0.26 (17)C9—N3—C8—N4−178.09 (16)
N1—C1—C2—C31.9 (2)C9—N3—C8—N21.4 (2)
C6—C1—C2—C3−177.24 (14)C8—N3—C9—O6−179.20 (18)
C1—C2—C3—C4−0.8 (2)C8—N3—C9—C101.0 (2)
C1—C2—C3—C7177.16 (15)C8—N2—C10—C93.57 (19)
C2—C3—C4—C5−0.8 (2)C11—N2—C10—C9−179.80 (16)
C7—C3—C4—C5−178.81 (15)O6—C9—C10—N2177.51 (19)
C1—N1—C5—C4−0.5 (2)N3—C9—C10—N2−2.67 (19)
Zn1—N1—C5—C4177.40 (12)
Symmetry codes: (i) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O3ii0.91 (3)1.87 (3)2.764 (2)165 (3)
N4—H4A···O4ii0.861.862.706 (2)168
N4—H4B···O2iii0.861.922.771 (2)169
O5—H5A···O4ii0.79 (2)1.95 (3)2.729 (2)171 (3)
O5—H5B···O1iii0.85 (3)1.98 (3)2.8088 (17)165 (2)
O7—H7A···O30.73 (4)2.32 (4)2.968 (3)148 (4)
O7—H7B···O6iv0.82 (4)2.26 (4)2.993 (3)149 (4)
C5—H5···O5v0.932.463.308 (2)152
C11—H11A···O2iii0.962.483.425 (3)167
Symmetry codes: (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x, −y+1, −z; (v) −x+2, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O3i0.91 (3)1.87 (3)2.764 (2)165 (3)
N4—H4A···O4i0.861.862.706 (2)168
N4—H4B···O2ii0.861.922.771 (2)169
O5—H5A···O4i0.79 (2)1.95 (3)2.729 (2)171 (3)
O5—H5B···O1ii0.85 (3)1.98 (3)2.8088 (17)165 (2)
O7—H7A···O30.73 (4)2.32 (4)2.968 (3)148 (4)
O7—H7B···O6iii0.82 (4)2.26 (4)2.993 (3)149 (4)
C5—H5···O5iv0.932.463.308 (2)152
C11—H11A···O2ii0.962.483.425 (3)167
Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) −x, −y+1, −z; (iv) −x+2, −y, −z+1.
Acknowledgements top

We are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

references
References top

Aghabozorg, H., Derikvand, Z., Olmstead, M. M. & Attar Gharamaleki, J. (2008a). Acta Cryst. E64, m1234–m1235.

Aghabozorg, H., Manteghi, F. & Sheshmani, S. (2008b). J. Iran. Chem. Soc. 5, 184–227.

Aghabozorg, H., Ramezanipour, F., Sleimannejad, J., Sharif, M. A., Shokrollahi, A., Shamsipur, M., Moghimi, A., Attar Gharamaleki, J., Lippolis, V. & Blake, A. (2008c). Pol. J. Chem. 82, 487–507.

Attar Gharamaleki, J., Aghabozorg, H., Derikvand, Z. & Yousefi, M. (2009). Acta Cryst. E65, m824–m825.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Moghimi, A., Sharif, M. A. & Aghabozorg, H. (2004). Acta Cryst. E60, o1790–o1792.

Moghimi, A., Sharif, M. A., Shokrollahi, A., Shamsipur, M. & Aghabozorg, H. (2005). Z. Anorg. Allg. Chem. 631, 902–908.

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

Stoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany.