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Acta Cryst. (2007). E63, m2552-m2553    [ doi:10.1107/S1600536807045254 ]

Dihydroxidobis(melamine-[kappa]N)zinc(II) monohydrate

G. Wang, W. Wu and L. Zhuang

Abstract top

In the title compound, dihydroxidobis(2,4,6-triamino-1,3,5-triazine-[kappa]N)zinc(II) monohydrate, [Zn(OH)2(C3N6H6)2]·H2O, ZnII is tetrahedrally coordinated by two melamine and two hydroxy groups; there is also a solvent water molecule. The dihedral angle between the two melamine rings is 86.3 (9)°. Intramolecular N-H...O and N-H...N hydrogen bonds help to stabilize the molecular conformation. Numerous intermolecular hydrogen bonds between water, hydroxy and melamine groups link the molecules into a three-dimensional supramolecular network.

Comment top

The transition metal complexes are potential photo-luminescent, paramagnetic and radioactive materials due to their attractive photochemical and photophysical properties(Ford et al., 1999). Low dimensional metal organic complexes have received great attention in recent years for their potential applications in optics, electronics, magnetics, biology, catalyst and medicine (Tandon et al., 1994). The ligand, melamine, has both acceptor and donnor atoms suitable for hydrogen bonding and is analogous to nucleobases that may lead to some interesting new chemotherapeutic possibilities (Zhu et al., 1999).

In the complex I, the zinc cation is coordinated by two melamine and two hydroxyl ligands, forming a distorted tetrahedral geometry, while intramolecular N—H···O and N—H···H hydrogen bonds help to stabilize the molecular conformation (Fig. 1). The two melamine rings make a dihedral angle of 86.3 (9) °. All of the bond lengths and angles are within normal ranges (Allen et al., 1987). The Zn—N bond lengths (2.021 Å and 2.024 Å) in the title compound are slightly shorter than that (2.039 Å) in the compound [Zn(C3N6H6)(H2O)0.5Cl2](C3N6H6)(H2O) (Yu et al., 2004). The Zn—O bond lengths (2.018 Å and 2.041 Å) are slightly longer than that (1.984 Å) in the compound [Zn(C3N6H6)(H2O)0.5Cl2](C3N6H6)(H2O) (Yu et al., 2004).

As can be seen from the packing diagram (Fig. 2), intermolecular N—H···O, N—H···N, O—H.·O and O—H···N hydrogen bonds(Table 1) link the molecules into a three-dimensional network, which may be effective in the stabilization of the crystal structure.

Related literature top

For general background, see: Ford et al. (1999); Tandon et al. (1994); Zhu et al. (1999). For a related structure, see: Yu et al. (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of zinc chloride (0.136 g, 1 mmol), melamine (0.252 g, 2 mmol), and distilled water(8 ml) was heated at 180°C for 4 days in hydrothermal tube. After being cooled to room temperature, colourless block crystals were obtained. Elemental analysis calcd for compound(I): C 19.58%, H 4.40%, N 45.60%; Found: C 19.51%, H 4.35%, N 45.53%.

Refinement top

H atoms attached to NH2 and hydroxyl groups were positioned geometrically (O—H = 0.84 and N—H = 0.86 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(N,O). H atoms from water were located in a difference map and refined with distance restraints of O—H = 0.84 \%A and Uĩso~(H) = 1.5U~eq~(O).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I) showing the atom-numbering scheme and 30% displacement ellipsoids (arbitrary spheres for the H atoms). Intramolecular hydrogen bonds are shown as double dashed lines.
[Figure 2] Fig. 2. A packing diagram of complex(I). Hydrogen bonds are shown as dashed lines.
Dihydroxidobis(melamine-κN)zinc(II) monohydrate top
Crystal data top
[Zn(OH)2(C3N6H6)2]·H2OF000 = 760
Mr = 369.70Dx = 1.865 Mg m−3
Orthorhombic, Pna21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 25 reflections
a = 17.531 (4) Åθ = 9–13º
b = 6.6251 (13) ŵ = 1.91 mm−1
c = 11.335 (2) ÅT = 293 (2) K
V = 1316.5 (5) Å3Block, colourless
Z = 40.40 × 0.40 × 0.22 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.037
Radiation source: fine-focus sealed tubeθmax = 25.1º
Monochromator: graphiteθmin = 2.3º
T = 293(2) Kh = −11→20
ω/2θ scansk = −7→7
Absorption correction: ψ scan
(North et al., 1968)		l = −13→11
Tmin = 0.508, Tmax = 0.6573 standard reflections
3467 measured reflections every 200 reflections
1843 independent reflections intensity decay: none
1682 reflections with I > 2σ(I)
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.053  w = 1/[σ2(Fo2) + (0.0759P)2 + 5.1018P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.143(Δ/σ)max < 0.001
S = 1.09Δρmax = 0.23 e Å−3
1843 reflectionsΔρmin = −0.38 e Å−3
199 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 636 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.06 (3)
Secondary atom site location: difference Fourier map
Crystal data top
[Zn(OH)2(C3N6H6)2]·H2OV = 1316.5 (5) Å3
Mr = 369.70Z = 4
Orthorhombic, Pna21Mo Kα
a = 17.531 (4) ŵ = 1.91 mm−1
b = 6.6251 (13) ÅT = 293 (2) K
c = 11.335 (2) Å0.40 × 0.40 × 0.22 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		1682 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.037
Tmin = 0.508, Tmax = 0.6573 standard reflections
3467 measured reflections every 200 reflections
1843 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.143Δρmax = 0.23 e Å−3
S = 1.09Δρmin = −0.38 e Å−3
1843 reflectionsAbsolute structure: Flack (1983), 636 Friedel pairs
199 parametersFlack parameter: 0.06 (3)
1 restraint
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*/Ueq
C11.0926 (4)0.8133 (12)0.2026 (8)0.0288 (18)
C21.2208 (4)0.9046 (10)0.1426 (11)0.0301 (16)
C31.1128 (4)1.1158 (13)0.0982 (8)0.032 (2)
C40.9359 (4)0.7899 (13)−0.0664 (9)0.0327 (19)
C50.8131 (5)0.6933 (14)−0.1435 (9)0.035 (2)
C60.8286 (4)0.9887 (13)−0.0226 (9)0.0306 (18)
N11.0653 (3)0.9865 (9)0.1520 (9)0.0303 (18)
N21.0510 (3)0.6883 (9)0.2514 (6)0.0264 (16)
H2A1.00260.70810.25470.032*
H2B1.07050.58140.28210.032*
N31.1697 (3)0.7769 (10)0.1947 (7)0.0313 (16)
N41.2893 (2)0.8706 (8)0.1433 (8)0.0246 (13)
H4A1.32050.95580.11240.030*
H4B1.30640.76140.17470.030*
N51.1901 (4)1.0702 (10)0.0957 (7)0.0319 (17)
N61.0884 (4)1.2648 (11)0.0488 (7)0.039 (2)
H6A1.04021.28850.04790.046*
H6B1.11931.34670.01450.046*
N70.9038 (4)0.9458 (10)−0.0072 (7)0.0242 (17)
N81.0043 (3)0.7584 (11)−0.0641 (8)0.041 (2)
H8A1.03380.8362−0.02400.050*
H8B1.02320.6582−0.10250.050*
N90.8892 (4)0.6602 (11)−0.1310 (7)0.0329 (17)
N100.7718 (4)0.5743 (10)−0.1966 (7)0.0318 (17)
H10A0.72390.5988−0.20350.038*
H10B0.79090.4665−0.22690.038*
N110.7853 (4)0.8644 (11)−0.0947 (7)0.0338 (16)
N120.7985 (3)1.1327 (10)0.0259 (7)0.0333 (18)
H12A0.82501.21000.07110.040*
H12B0.75091.15680.01490.040*
O10.9360 (3)1.3630 (9)0.1356 (11)0.0580 (17)
H10.93571.40610.20530.087*
O20.8931 (5)0.9344 (13)0.2726 (9)0.051 (3)
H20.91530.95810.33680.077*
O30.8689 (4)0.4538 (10)0.3936 (8)0.053 (2)
H3A0.85210.35340.43070.080*
H3B0.82860.49590.36200.080*
Zn10.95397 (4)1.06209 (11)0.13850 (11)0.0287 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.026 (4)0.027 (4)0.033 (5)0.005 (3)−0.001 (3)−0.006 (4)
C20.029 (3)0.030 (4)0.031 (4)−0.006 (3)−0.012 (5)0.002 (5)
C30.026 (4)0.037 (4)0.032 (5)−0.001 (3)0.005 (3)−0.003 (4)
C40.028 (4)0.033 (4)0.037 (5)0.003 (3)0.001 (4)−0.005 (4)
C50.036 (4)0.032 (5)0.038 (5)0.004 (4)0.001 (4)−0.0041 (4)
C60.025 (4)0.035 (4)0.033 (5)0.005 (3)−0.008 (3)0.000 (4)
N10.020 (2)0.029 (3)0.042 (5)−0.004 (2)−0.002 (4)0.009 (4)
N20.015 (3)0.021 (3)0.043 (4)0.002 (3)0.007 (3)0.018 (3)
N30.022 (3)0.027 (3)0.045 (4)−0.002 (3)0.003 (3)0.009 (3)
N40.009 (2)0.019 (3)0.047 (4)0.0011 (18)0.008 (4)0.004 (4)
N50.026 (3)0.034 (4)0.036 (4)−0.001 (3)0.002 (3)0.010 (3)
N60.018 (3)0.025 (4)0.043 (5)0.004 (3)0.011 (3)0.018 (4)
N70.020 (3)0.028 (4)0.025 (5)0.002 (3)−0.003 (3)−0.008 (3)
N80.020 (3)0.040 (4)0.064 (6)0.008 (3)−0.004 (3)−0.036 (4)
N90.028 (3)0.035 (4)0.035 (4)0.003 (3)−0.001 (3)−0.012 (4)
N100.021 (3)0.029 (3)0.045 (5)0.000 (3)−0.008 (3)−0.022 (3)
N110.028 (3)0.033 (4)0.040 (4)0.004 (3)0.002 (3)−0.010 (4)
N120.021 (3)0.034 (4)0.054 (5)0.010 (3)−0.009 (3)−0.031 (4)
O10.057 (3)0.046 (3)0.071 (5)0.007 (3)0.000 (6)0.009 (6)
O20.055 (5)0.047 (6)0.062 (7)−0.011 (4)0.005 (4)0.002 (5)
O30.032 (3)0.058 (4)0.069 (5)0.005 (3)−0.008 (3)−0.021 (4)
Zn10.0224 (4)0.0304 (5)0.0334 (5)0.0006 (3)−0.0005 (5)−0.0012 (6)
Geometric parameters (Å, °) top
C1—N21.234 (10)N2—H2A0.8600
C1—N11.369 (11)N2—H2B0.8600
C1—N31.377 (10)N4—H4A0.8600
C2—N41.222 (8)N4—H4B0.8600
C2—N51.334 (10)N6—H6A0.8600
C2—N31.366 (10)N6—H6B0.8600
C3—N61.213 (11)N7—Zn12.024 (8)
C3—N11.341 (11)N8—H8A0.8600
C3—N51.389 (10)N8—H8B0.8600
C4—N81.217 (10)N10—H10A0.8600
C4—N71.354 (11)N10—H10B0.8600
C4—N91.395 (11)N12—H12A0.8600
C5—N101.227 (11)N12—H12B0.8600
C5—N111.353 (12)O1—Zn12.018 (6)
C5—N91.359 (11)O1—H10.8396
C6—N121.221 (11)O2—Zn12.041 (10)
C6—N71.360 (11)O2—H20.8400
C6—N111.387 (11)O3—H3A0.8396
N1—Zn12.021 (6)O3—H3B0.8399
N2—C1—N1122.9 (7)C2—N5—C3124.4 (7)
N2—C1—N3119.5 (7)C3—N6—H6A120.0
N1—C1—N3117.6 (7)C3—N6—H6B120.0
N4—C2—N5123.5 (8)H6A—N6—H6B120.0
N4—C2—N3121.9 (7)C4—N7—C6119.9 (8)
N5—C2—N3114.6 (6)C4—N7—Zn1121.0 (6)
N6—C3—N1120.8 (7)C6—N7—Zn1116.5 (6)
N6—C3—N5120.7 (8)C4—N8—H8A120.0
N1—C3—N5118.4 (8)C4—N8—H8B120.0
N8—C4—N7122.0 (8)H8A—N8—H8B120.0
N8—C4—N9119.0 (8)C5—N9—C4122.2 (7)
N7—C4—N9119.0 (7)C5—N10—H10A120.0
N10—C5—N11121.8 (8)C5—N10—H10B120.0
N10—C5—N9121.8 (8)H10A—N10—H10B120.0
N11—C5—N9116.5 (9)C5—N11—C6122.8 (7)
N12—C6—N7121.7 (8)C6—N12—H12A120.0
N12—C6—N11119.5 (7)C6—N12—H12B120.0
N7—C6—N11118.9 (8)H12A—N12—H12B120.0
C3—N1—C1120.6 (6)Zn1—O1—H1108.8
C3—N1—Zn1114.0 (5)Zn1—O2—H2109.0
C1—N1—Zn1125.2 (5)H3A—O3—H3B100.5
C1—N2—H2A120.0O1—Zn1—N1113.4 (3)
C1—N2—H2B120.0O1—Zn1—N7107.2 (4)
H2A—N2—H2B120.0N1—Zn1—N7112.8 (3)
C2—N3—C1124.3 (7)O1—Zn1—O2109.8 (4)
C2—N4—H4A120.0N1—Zn1—O2110.2 (4)
C2—N4—H4B120.0N7—Zn1—O2102.9 (3)
H4A—N4—H4B120.0
N6—C3—N1—C1176.7 (9)N12—C6—N7—Zn121.0 (12)
N5—C3—N1—C1−0.4 (14)N11—C6—N7—Zn1−158.6 (7)
N6—C3—N1—Zn11.3 (12)N10—C5—N9—C4−177.1 (9)
N5—C3—N1—Zn1−175.8 (6)N11—C5—N9—C43.0 (13)
N2—C1—N1—C3−178.8 (9)N8—C4—N9—C5−175.8 (9)
N3—C1—N1—C3−0.8 (14)N7—C4—N9—C54.9 (13)
N2—C1—N1—Zn1−3.9 (13)N10—C5—N11—C6172.1 (9)
N3—C1—N1—Zn1174.1 (6)N9—C5—N11—C6−8.0 (13)
N4—C2—N3—C1176.1 (10)N12—C6—N11—C5−174.5 (9)
N5—C2—N3—C1−1.6 (15)N7—C6—N11—C55.1 (14)
N2—C1—N3—C2180.0 (9)C3—N1—Zn1—O1−33.1 (9)
N1—C1—N3—C21.8 (14)C1—N1—Zn1—O1151.7 (8)
N4—C2—N5—C3−177.3 (10)C3—N1—Zn1—N788.9 (7)
N3—C2—N5—C30.4 (15)C1—N1—Zn1—N7−86.3 (9)
N6—C3—N5—C2−176.5 (10)C3—N1—Zn1—O2−156.7 (7)
N1—C3—N5—C20.5 (14)C1—N1—Zn1—O228.1 (9)
N8—C4—N7—C6172.8 (10)C4—N7—Zn1—O1143.5 (7)
N9—C4—N7—C6−8.0 (13)C6—N7—Zn1—O1−54.9 (7)
N8—C4—N7—Zn1−26.2 (13)C4—N7—Zn1—N118.0 (8)
N9—C4—N7—Zn1153.0 (7)C6—N7—Zn1—N1179.6 (6)
N12—C6—N7—C4−177.2 (9)C4—N7—Zn1—O2−100.7 (7)
N11—C6—N7—C43.2 (13)C6—N7—Zn1—O260.9 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O20.862.443.221 (11)151
N2—H2B···N9i0.862.012.865 (9)174
N4—H4A···O1ii0.862.373.120 (8)146
N4—H4B···O2iii0.862.293.089 (11)156
N6—H6A···O10.862.142.921 (10)151
N6—H6B···O3iv0.861.912.670 (9)146
N8—H8A···N10.862.303.070 (12)150
N8—H8B···O3v0.862.032.674 (9)131
N10—H10A···O2vi0.862.343.057 (11)141
N10—H10B···N3v0.861.972.826 (9)176
N12—H12A···O10.862.313.111 (10)155
N12—H12B···N5vii0.862.292.849 (9)123
O1—H1···O3viii0.842.463.209 (14)150
O2—H2···N8ix0.842.603.288 (10)139
O3—H3A···N11x0.842.432.770 (9)105
O3—H3B···N11x0.842.232.770 (9)122
Symmetry codes: (i) −x+2, −y+1, z+1/2; (ii) x+1/2, −y+5/2, z; (iii) x+1/2, −y+3/2, z; (iv) −x+2, −y+2, z−1/2; (v) −x+2, −y+1, z−1/2; (vi) −x+3/2, y−1/2, z−1/2; (vii) x−1/2, −y+5/2, z; (viii) x, y+1, z; (ix) −x+2, −y+2, z+1/2; (x) −x+3/2, y−1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O20.862.443.221 (11)151
N2—H2B···N9i0.862.012.865 (9)174
N4—H4A···O1ii0.862.373.120 (8)146
N4—H4B···O2iii0.862.293.089 (11)156
N6—H6A···O10.862.142.921 (10)151
N6—H6B···O3iv0.861.912.670 (9)146
N8—H8A···N10.862.303.070 (12)150
N8—H8B···O3v0.862.032.674 (9)131
N10—H10A···O2vi0.862.343.057 (11)141
N10—H10B···N3v0.861.972.826 (9)176
N12—H12A···O10.862.313.111 (10)155
N12—H12B···N5vii0.862.292.849 (9)123
O1—H1···O3viii0.842.463.209 (14)150
O2—H2···N8ix0.842.603.288 (10)139
O3—H3A···N11x0.842.432.770 (9)105
O3—H3B···N11x0.842.232.770 (9)122
Symmetry codes: (i) −x+2, −y+1, z+1/2; (ii) x+1/2, −y+5/2, z; (iii) x+1/2, −y+3/2, z; (iv) −x+2, −y+2, z−1/2; (v) −x+2, −y+1, z−1/2; (vi) −x+3/2, y−1/2, z−1/2; (vii) x−1/2, −y+5/2, z; (viii) x, y+1, z; (ix) −x+2, −y+2, z+1/2; (x) −x+3/2, y−1/2, z+1/2.
Acknowledgements top

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Bruker (2000). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Ford, P. C., Cariati, E. & Bourassa, J. (1999). J. Chem. Rev. 99, 3625–3647. Should journal title be J. Chem. Res.?

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Tandon, S. S., Chen, L.-Q., Thompson, L. K. & Bridson, J. N. (1994). Inorg. Chem. 33, 490–497.

Yu, Y.-Q., Lu, C.-Z., He, X., Chen, S.-M., Zhang, Q.-Z., Chen, L.-J. & Yang, W.-B. (2004). J. Chem. Crystallogr. 34, 905–909.

Zhu, H.-G., Yu, Z., You, X.-Z., Hu, H.-M. & Huang, X.-Y. (1999). J. Chem. Crystallogr. 29, 239–242.