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Acta Cryst. (2012). E68, m1035    [ doi:10.1107/S160053681202987X ]

Guanidinium hexaaquazinc(II) bis[tris(3-carboxypyridine-2-carboxylato)zincate]

M. Tabatabaee, Z. Derikvand and J. Attar Gharamaleki

Abstract top

In the title molecular salt, (CH6N3)1.30[Zn(H2O)6]0.35[Zn(C7H4NO4)3]2, the ZnII atom (site symmetry 3) in the anion is coordinated by three N,O-bidentate 3-carboxypyridine-2-carboxylate monoanions to generate a fac-ZnN3O3 octahedral coordination geometry. The guanidinium cation (the C atom has site symmetry 3) and the octahedral hexaaquazinc(II) dication (the Zn2+ cation has site symmetry -3) are occupationally disordered in a 1.30:0.35 ratio. In the crystal, the components are linked by O-H...O and N-H...O hydrogen bonds to generate infinite (001) sheets. Weak aromatic [pi]-[pi] stacking [centroid-centroid distance = 3.797 (8) Å] is also observed in the crystal.

Comment top

Unlike pyridine-2,6-dicarboxylic acid, which is an O,N,O-tridentate ligand (e.g. Tabatabaee, Abbasi et al., 2011), pyridine-2,3-dicarboxylic acid often acts as a bidentate chelating ligand through nitrogen and one oxygen atom of the 2-position carboxylic group, while the 3-position carboxylate oxygen atom can act as a bridging atom between metal ions to form a coordination polymer. Recently, we have reported the synthesis and characterization of two one-dimensional coordination polymers of Cd2+ and Co2+ with pyridine-2,3-dicarboxylic acid (2,3-H2pydc) (Tabatabaee, Razavimahmoudabadi et al., 2011) and in this study we wish to report the crystal structure of a mononuclear Zn(II) complex with (2,3-H2pydc) in the presence of guanidine hydrochloride.

The title compound consists of [Zn(2,3-Hpydc)3]- anions, (GH)+ and [Zn(H2O)6]2+ cations (Fig. 1). Two variant of [Zn(2,3-pydcH)3]- anions exist in 1 and to balance the charges, one protonated guanidinium cation and [Zn(H2O)6]2+ are present in 1.30: 0.35 ratio. Zn(II) ion in the title compound is six-coordinated by three (2,3-pydcH)2– anions in O,N-bidentate fashion and the geometry of the resulting ZnN3O3 coordination can be described as distorted octahedral. The bond angles around Zn(II) ion involving trans pairs of donor atoms are 165.33 (7) and for the cis pairs of donor atoms are in the range of 77.27 (7)– 98.26 (8)°. The bond distances Zn–N and Zn–O in are in accordance with those in related structures (Tabatabaee, Razavimahmoudabadi et al., 2011).

There is some hydrogen bonding interactions such as O—H···O, N—H···O between cations and anions. As was shown in figure 2, Hydrogen bonding interactions contribute to the formation of a two dimensional network cavity structure. There is also π-π stacking interactions between the aromatic rings defined by atoms N1/C2 /C6/C5/C4/C3 [symmetry code: 1-X,1-Y,1-Z; centroid-centroid distance 3.797 (8) Å; the angle between the planes 0°; the perpendicular distance between the planes 3.588 Å; the slippage 1.24 Å]. Ion pairing, hydrogen bonding, π–π stacking and van der Waals interactions are also effective for packing of the crystal structure (Fig 3).

Related literature top

For related structures, see: Tabatabaee, Abbasi et al. (2011); Tabatabaee, Razavimahmoudabadi et al. (2011).

Experimental top

An aqueous solution of pyridine-2,3-dicarboxylic acid (0.10 g, 0.67 mmol)) and Zn(NO3)2.6H2O (0.09 g, 0.3 mmol) was added to an aqueous solution of guanidine hydrochloride (0.08 g, 0.84 mmol) and NaOH (0.04 g, 1 mmol). The reaction mixture was stirred at 25°C for 3 h. Colorless prisms of the title compound were obtained after few days.

Refinement top

The hydrogen atoms of NH groups (water molecules) were found in difference Fourier synthesis. The H(C) atom positions were calculated. All hydrogen atoms were refined in isotropic approximation in riding model with the Uiso(H) parameters equal to 1.2 Ueq(Ci), for methyl groups equal to 1.5 Ueq(Cii), where U(Ci) and U(Cii) are respectively the equivalent thermal parameters of the carbon atoms to which corresponding H atoms are bonded.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of 1 (displacement ellipsoids drawn at the 50% probability level).
[Figure 2] Fig. 2. A ball and stick view of the two-dimensional network with showing cavity structure constructed by hydrogen bonds between cationic fragments and anionic complexes.
[Figure 3] Fig. 3. Illustration of polymeric chains formed by O—H···O hydrogen bonds and π-π staking interactions.
Guanidinium hexaaquazinc(II) bis[tris(3-carboxypyridine-2-carboxylato)zincate] top
Crystal data top
(CH6N3)1.30[Zn(H2O)6]0.35[Zn(C7H4NO4)3]2Dx = 1.799 Mg m−3
Mr = 1266.24Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3Cell parameters from 524 reflections
Hall symbol: -P 3θ = 3–30°
a = 14.5775 (16) ŵ = 1.31 mm−1
c = 6.3506 (16) ÅT = 120 K
V = 1168.7 (3) Å3Prism, colorless
Z = 10.25 × 0.25 × 0.20 mm
F(000) = 644
Data collection top
Bruker SMART 1000 CCD
diffractometer		2079 independent reflections
Radiation source: fine-focus sealed tube1443 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
φ and ω scansθmax = 29.0°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −11→13
Tmin = 0.731, Tmax = 0.773k = −15→19
4304 measured reflectionsl = −5→8
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)] = 0.045Hydrogen site location: mixed
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0393P)2 + 0.497P]
where P = (Fo2 + 2Fc2)/3
2079 reflections(Δ/σ)max < 0.001
129 parametersΔρmax = 0.88 e Å−3
0 restraintsΔρmin = −0.69 e Å−3
Crystal data top
(CH6N3)1.30[Zn(H2O)6]0.35[Zn(C7H4NO4)3]2Z = 1
Mr = 1266.24Mo Kα radiation
Trigonal, P3µ = 1.31 mm−1
a = 14.5775 (16) ÅT = 120 K
c = 6.3506 (16) Å0.25 × 0.25 × 0.20 mm
V = 1168.7 (3) Å3
Data collection top
Bruker SMART 1000 CCD
diffractometer		2079 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		1443 reflections with I > 2σ(I)
Tmin = 0.731, Tmax = 0.773Rint = 0.044
4304 measured reflectionsθmax = 29.0°
Refinement top
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106Δρmax = 0.88 e Å−3
S = 1.00Δρmin = −0.69 e Å−3
2079 reflectionsAbsolute structure: ?
129 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.66670.33330.70631 (8)0.02632 (17)
N10.65271 (16)0.45142 (17)0.5247 (3)0.0244 (5)
O20.80453 (15)0.64188 (14)0.9041 (3)0.0330 (4)
O30.7557 (2)0.80730 (16)0.6260 (4)0.0559 (7)
O40.63483 (15)0.69485 (15)0.8490 (3)0.0367 (5)
H4O0.63650.74650.91330.044*
O10.74921 (14)0.46921 (14)0.8890 (3)0.0308 (4)
C10.7503 (2)0.5512 (2)0.8267 (4)0.0247 (5)
C20.68666 (19)0.5418 (2)0.6313 (4)0.0235 (5)
C30.6077 (2)0.4408 (2)0.3371 (4)0.0278 (6)
H3A0.58200.37580.26310.033*
C40.5971 (2)0.5207 (2)0.2472 (4)0.0321 (6)
H4A0.56860.51280.10950.039*
C50.6284 (2)0.6119 (2)0.3589 (4)0.0329 (6)
H5A0.62060.66760.30020.039*
C60.6715 (2)0.6227 (2)0.5585 (4)0.0249 (5)
C70.6941 (2)0.7188 (2)0.6845 (4)0.0296 (6)
N1S0.9175 (4)1.0138 (4)0.7528 (8)0.0448 (11)0.65
C1S1.00001.00000.7526 (11)0.0393 (18)0.65
H1SA0.93321.07790.72470.047*
H1SB0.85560.96410.71690.047*
Zn21.00001.00001.00000.0402 (6)*0.35
O1S0.8856 (7)1.0091 (8)0.8232 (14)0.057 (3)*0.35
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0236 (2)0.0236 (2)0.0317 (3)0.01181 (11)0.0000.000
N10.0240 (11)0.0250 (12)0.0270 (10)0.0144 (10)−0.0022 (8)−0.0029 (8)
O20.0314 (10)0.0266 (10)0.0415 (10)0.0148 (9)−0.0141 (8)−0.0112 (8)
O30.0712 (17)0.0240 (12)0.0586 (14)0.0133 (12)0.0215 (12)0.0021 (10)
O40.0365 (12)0.0287 (11)0.0448 (11)0.0161 (9)0.0097 (9)−0.0063 (9)
O10.0356 (11)0.0242 (10)0.0330 (10)0.0152 (9)−0.0097 (8)−0.0006 (7)
C10.0204 (13)0.0282 (14)0.0262 (12)0.0125 (11)0.0000 (9)−0.0028 (10)
C20.0192 (13)0.0235 (13)0.0262 (11)0.0095 (11)0.0008 (10)−0.0019 (10)
C30.0267 (14)0.0295 (14)0.0289 (13)0.0153 (12)−0.0049 (10)−0.0076 (10)
C40.0330 (15)0.0404 (17)0.0274 (13)0.0216 (14)−0.0070 (11)−0.0027 (11)
C50.0371 (16)0.0323 (16)0.0376 (14)0.0236 (14)−0.0031 (12)0.0033 (12)
C60.0229 (13)0.0235 (13)0.0300 (12)0.0128 (11)0.0023 (10)0.0004 (10)
C70.0301 (15)0.0278 (15)0.0345 (14)0.0172 (13)−0.0023 (11)−0.0009 (11)
N1S0.039 (3)0.036 (3)0.055 (3)0.015 (2)−0.010 (2)−0.001 (2)
C1S0.038 (3)0.038 (3)0.042 (4)0.0189 (14)0.0000.000
Geometric parameters (Å, º) top
Zn1—O1i2.0818 (18)C4—H4A0.9500
Zn1—O12.0818 (18)C5—C61.388 (4)
Zn1—O1ii2.0818 (18)C5—H5A0.9500
Zn1—N1i2.164 (2)C6—C71.500 (4)
Zn1—N1ii2.164 (2)N1S—C1S1.314 (5)
Zn1—N12.164 (2)N1S—H1SA0.8635
N1—C31.332 (3)N1S—H1SB0.8592
N1—C21.337 (3)C1S—N1Siii1.314 (5)
O2—C11.252 (3)C1S—N1Siv1.314 (5)
O3—C71.204 (3)Zn2—O1Sv2.069 (10)
O4—C71.288 (3)Zn2—O1Siii2.069 (10)
O4—H4O0.8453Zn2—O1Svi2.069 (10)
O1—C11.252 (3)Zn2—O1S2.069 (10)
C1—C21.514 (3)Zn2—O1Svii2.069 (10)
C2—C61.383 (3)Zn2—O1Siv2.069 (10)
C3—C41.374 (4)O1S—H1SA1.0872
C3—H3A0.9500O1S—H1SB0.8897
C4—C51.369 (4)
O1i—Zn1—O191.96 (7)C4—C5—H5A120.2
O1i—Zn1—O1ii91.96 (7)C6—C5—H5A120.2
O1—Zn1—O1ii91.96 (7)C2—C6—C5117.7 (2)
O1i—Zn1—N1i77.27 (7)C2—C6—C7124.3 (2)
O1—Zn1—N1i98.26 (8)C5—C6—C7117.9 (2)
O1ii—Zn1—N1i165.33 (7)O3—C7—O4125.5 (3)
O1i—Zn1—N1ii98.26 (8)O3—C7—C6122.3 (2)
O1—Zn1—N1ii165.33 (7)O4—C7—C6112.1 (2)
O1ii—Zn1—N1ii77.27 (7)C1S—N1S—H1SA113.5
N1i—Zn1—N1ii94.25 (7)C1S—N1S—H1SB121.8
O1i—Zn1—N1165.33 (8)H1SA—N1S—H1SB117.1
O1—Zn1—N177.27 (7)N1Siii—C1S—N1Siv120.000 (7)
O1ii—Zn1—N198.26 (8)N1Siii—C1S—N1S120.000 (4)
N1i—Zn1—N194.25 (7)N1Siv—C1S—N1S120.000 (11)
N1ii—Zn1—N194.25 (7)O1Sv—Zn2—O1Siii86.7 (3)
C3—N1—C2119.1 (2)O1Sv—Zn2—O1Svi93.3 (3)
C3—N1—Zn1128.38 (18)O1Siii—Zn2—O1Svi86.7 (3)
C2—N1—Zn1112.24 (15)O1Sv—Zn2—O1S180.000 (2)
C7—O4—H4O115.7O1Siii—Zn2—O1S93.3 (3)
C1—O1—Zn1117.25 (15)O1Svi—Zn2—O1S86.7 (3)
O1—C1—O2125.7 (2)O1Sv—Zn2—O1Svii93.3 (3)
O1—C1—C2117.3 (2)O1Siii—Zn2—O1Svii180.0 (6)
O2—C1—C2116.9 (2)O1Svi—Zn2—O1Svii93.3 (3)
N1—C2—C6122.2 (2)O1S—Zn2—O1Svii86.7 (3)
N1—C2—C1114.3 (2)O1Sv—Zn2—O1Siv86.7 (3)
C6—C2—C1123.3 (2)O1Siii—Zn2—O1Siv93.3 (3)
N1—C3—C4122.0 (2)O1Svi—Zn2—O1Siv180.0 (3)
N1—C3—H3A119.0O1S—Zn2—O1Siv93.3 (3)
C4—C3—H3A119.0O1Svii—Zn2—O1Siv86.7 (3)
C5—C4—C3119.0 (2)Zn2—O1S—H1SA102.1
C5—C4—H4A120.5Zn2—O1S—H1SB118.7
C3—C4—H4A120.5H1SA—O1S—H1SB95.5
C4—C5—C6119.7 (2)
O1i—Zn1—N1—C3133.0 (3)Zn1—N1—C2—C114.2 (3)
O1—Zn1—N1—C3176.6 (2)O1—C1—C2—N1−12.2 (3)
O1ii—Zn1—N1—C3−93.3 (2)O2—C1—C2—N1163.7 (2)
N1i—Zn1—N1—C379.05 (17)O1—C1—C2—C6172.7 (2)
N1ii—Zn1—N1—C3−15.5 (2)O2—C1—C2—C6−11.4 (4)
O1i—Zn1—N1—C2−53.4 (4)C2—N1—C3—C41.5 (4)
O1—Zn1—N1—C2−9.84 (16)Zn1—N1—C3—C4174.73 (19)
O1ii—Zn1—N1—C280.30 (17)N1—C3—C4—C5−3.8 (4)
N1i—Zn1—N1—C2−107.4 (2)C3—C4—C5—C61.0 (4)
N1ii—Zn1—N1—C2158.04 (18)N1—C2—C6—C5−6.1 (4)
O1i—Zn1—O1—C1173.28 (19)C1—C2—C6—C5168.6 (2)
O1ii—Zn1—O1—C1−94.7 (2)N1—C2—C6—C7171.1 (2)
N1i—Zn1—O1—C195.86 (19)C1—C2—C6—C7−14.2 (4)
N1ii—Zn1—O1—C1−52.4 (4)C4—C5—C6—C23.7 (4)
N1—Zn1—O1—C13.33 (18)C4—C5—C6—C7−173.7 (3)
Zn1—O1—C1—O2−172.2 (2)C2—C6—C7—O3121.4 (3)
Zn1—O1—C1—C23.2 (3)C5—C6—C7—O3−61.4 (4)
C3—N1—C2—C63.6 (4)C2—C6—C7—O4−63.4 (3)
Zn1—N1—C2—C6−170.68 (19)C5—C6—C7—O4113.8 (3)
C3—N1—C2—C1−171.6 (2)
Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, x−y, z; (iii) −x+y+1, −x+2, z; (iv) −y+2, x−y+1, z; (v) −x+2, −y+2, −z+2; (vi) y, −x+y+1, −z+2; (vii) x−y+1, x, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1S—H1SA···O3iii0.862.253.032 (6)150
N1S—H1SB···O30.862.092.859 (6)149
O4—H4O···O1vi0.852.593.101 (3)120
O4—H4O···O2vi0.851.732.563 (3)167
Symmetry codes: (iii) −x+y+1, −x+2, z; (vi) y, −x+y+1, −z+2.
Selected bond lengths (Å) top
Zn1—O12.0818 (18)Zn2—O1S2.069 (10)
Zn1—N12.164 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1S—H1SA···O3i0.862.253.032 (6)150
N1S—H1SB···O30.862.092.859 (6)149
O4—H4O···O1ii0.852.593.101 (3)120
O4—H4O···O2ii0.851.732.563 (3)167
Symmetry codes: (i) −x+y+1, −x+2, z; (ii) y, −x+y+1, −z+2.
Acknowledgements top

The authors express their deepest appreciation to the late Professor Dr. H. Aghabozorg who inspired, advised and assisted during this study.

references
References top

Bruker (1998). SMART, SAINT-Plus and SADABS. Bruker AXS, Madison, Wisconsin, USA.

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

Tabatabaee, M., Abbasi, F., Kukovec, B.-M. & Nasirizadeh, N. (2011). J. Coord. Chem. 64, 1718–1728.

Tabatabaee, M., Razavimahmoudabadi, V., Kukovec, B.-M., Ghassemzadeh, M. & Neumüller, B. (2011). J. Inorg. Organomet. Polym. 21, 450–457.