Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106041692/sk3044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106041692/sk3044Isup2.hkl |
CCDC reference: 628513
The title complex was prepared under continuous stirring with successive addition of dimethylmalonic acid (0.53 g, 4 mmol), Na2CO3 (0.22 g, 2 mmol), Zn(NO3)2·6H2O (0.49 g, 2 mmol) and barium nitrate (0.52 g 2 mmol) to distilled water (30 ml) at room temperature. After filtration, slow evaporation over a period of three week at room temperature provided colorless plate-like crystals of (I).
The H atoms of the water molecule were found in difference Fourier maps. However, during refinement, they were fixed at O–H distances of 0.85 Å and their Uiso(H) values were set at 1.2Ueq(O). The H atoms of methyl groups were treated as riding, with C–H = 0.96 Å and Uiso(H) = 1.5Ueq(C).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Zn(C5H6O4)(H2O)] | F(000) = 432 |
Mr = 213.48 | Dx = 2.048 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2430 reflections |
a = 8.7030 (15) Å | θ = 2.4–26.4° |
b = 8.5986 (15) Å | µ = 3.52 mm−1 |
c = 9.4773 (16) Å | T = 294 K |
β = 102.532 (3)° | Plate, colorless |
V = 692.3 (2) Å3 | 0.16 × 0.14 × 0.08 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1226 independent reflections |
Radiation source: fine-focus sealed tube | 1095 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→10 |
Tmin = 0.585, Tmax = 0.762 | k = −10→10 |
3431 measured reflections | l = −11→9 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0351P)2 + 0.2489P] where P = (Fo2 + 2Fc2)/3 |
1226 reflections | (Δ/σ)max < 0.001 |
102 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
[Zn(C5H6O4)(H2O)] | V = 692.3 (2) Å3 |
Mr = 213.48 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.7030 (15) Å | µ = 3.52 mm−1 |
b = 8.5986 (15) Å | T = 294 K |
c = 9.4773 (16) Å | 0.16 × 0.14 × 0.08 mm |
β = 102.532 (3)° |
Bruker SMART CCD area-detector diffractometer | 1226 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1095 reflections with I > 2σ(I) |
Tmin = 0.585, Tmax = 0.762 | Rint = 0.025 |
3431 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.35 e Å−3 |
1226 reflections | Δρmin = −0.34 e Å−3 |
102 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.36802 (3) | 1.15706 (3) | 0.14054 (3) | 0.01770 (12) | |
O1 | 0.4384 (2) | 0.94483 (19) | 0.23933 (18) | 0.0242 (4) | |
O2 | 0.41908 (19) | 0.73675 (17) | 0.36938 (17) | 0.0215 (4) | |
O3 | 0.2773 (2) | 1.20331 (19) | 0.31001 (17) | 0.0240 (4) | |
O4 | 0.2543 (2) | 1.15105 (17) | 0.53252 (18) | 0.0225 (4) | |
C1 | 0.3724 (3) | 0.8702 (3) | 0.3221 (2) | 0.0161 (5) | |
C2 | 0.2260 (3) | 0.9367 (2) | 0.3679 (2) | 0.0174 (5) | |
C3 | 0.2563 (3) | 1.1090 (3) | 0.4073 (2) | 0.0163 (5) | |
C4 | 0.0842 (3) | 0.9267 (3) | 0.2373 (3) | 0.0295 (6) | |
H4A | 0.0620 | 0.8197 | 0.2123 | 0.044* | |
H4B | 0.1092 | 0.9805 | 0.1563 | 0.044* | |
H4C | −0.0063 | 0.9739 | 0.2622 | 0.044* | |
C5 | 0.1885 (4) | 0.8473 (3) | 0.4951 (3) | 0.0307 (7) | |
H5A | 0.2777 | 0.8508 | 0.5750 | 0.046* | |
H5B | 0.1649 | 0.7411 | 0.4674 | 0.046* | |
H5C | 0.0993 | 0.8937 | 0.5230 | 0.046* | |
O5 | 0.2936 (2) | 1.03312 (19) | −0.04362 (17) | 0.0245 (4) | |
H5D | 0.3321 | 0.9459 | −0.0605 | 0.029* | |
H5E | 0.2885 | 1.1026 | −0.1080 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02421 (19) | 0.01388 (18) | 0.01636 (18) | −0.00081 (10) | 0.00736 (12) | 0.00131 (10) |
O1 | 0.0276 (10) | 0.0201 (9) | 0.0282 (9) | 0.0061 (7) | 0.0133 (8) | 0.0078 (7) |
O2 | 0.0248 (9) | 0.0132 (8) | 0.0283 (9) | 0.0052 (7) | 0.0098 (8) | 0.0047 (7) |
O3 | 0.0442 (11) | 0.0134 (8) | 0.0183 (8) | 0.0001 (8) | 0.0157 (8) | 0.0009 (7) |
O4 | 0.0347 (11) | 0.0175 (9) | 0.0168 (9) | −0.0053 (7) | 0.0086 (8) | −0.0031 (6) |
C1 | 0.0170 (12) | 0.0150 (11) | 0.0150 (11) | −0.0008 (9) | 0.0007 (10) | −0.0028 (9) |
C2 | 0.0196 (12) | 0.0129 (11) | 0.0209 (12) | 0.0003 (9) | 0.0070 (10) | 0.0003 (9) |
C3 | 0.0186 (12) | 0.0141 (11) | 0.0172 (12) | 0.0012 (9) | 0.0059 (10) | 0.0000 (9) |
C4 | 0.0210 (14) | 0.0328 (15) | 0.0337 (15) | −0.0019 (11) | 0.0038 (12) | −0.0123 (12) |
C5 | 0.0462 (18) | 0.0152 (13) | 0.0390 (17) | 0.0024 (11) | 0.0276 (15) | 0.0036 (11) |
O5 | 0.0388 (11) | 0.0128 (8) | 0.0218 (9) | 0.0021 (7) | 0.0059 (8) | 0.0003 (7) |
Zn1—O3 | 1.9776 (16) | C2—C3 | 1.537 (3) |
Zn1—O2i | 1.9967 (17) | C2—C4 | 1.549 (3) |
Zn1—O5 | 2.0276 (16) | C4—H4A | 0.9600 |
Zn1—O4ii | 2.0761 (16) | C4—H4B | 0.9600 |
Zn1—O1 | 2.0815 (16) | C4—H4C | 0.9600 |
O1—C1 | 1.246 (3) | C5—H5A | 0.9600 |
O2—C1 | 1.266 (3) | C5—H5B | 0.9600 |
O3—C3 | 1.271 (3) | C5—H5C | 0.9600 |
O4—C3 | 1.244 (3) | O5—H5D | 0.8503 |
C1—C2 | 1.543 (3) | O5—H5E | 0.8481 |
C2—C5 | 1.523 (3) | ||
O3—Zn1—O2i | 120.48 (7) | C3—C2—C4 | 108.22 (19) |
O3—Zn1—O5 | 134.07 (8) | C1—C2—C4 | 108.50 (19) |
O2i—Zn1—O5 | 105.44 (7) | O4—C3—O3 | 122.8 (2) |
O3—Zn1—O1 | 86.63 (7) | O4—C3—C2 | 118.3 (2) |
O2i—Zn1—O1 | 97.86 (7) | O3—C3—C2 | 118.88 (19) |
O2i—Zn1—O4ii | 92.98 (7) | C2—C4—H4A | 109.5 |
O3—Zn1—O4ii | 90.52 (7) | C2—C4—H4B | 109.5 |
O5—Zn1—O4ii | 87.95 (7) | H4A—C4—H4B | 109.5 |
O5—Zn1—O1 | 86.23 (7) | C2—C4—H4C | 109.5 |
O4ii—Zn1—O1 | 168.74 (7) | H4A—C4—H4C | 109.5 |
C1—O1—Zn1 | 127.18 (15) | H4B—C4—H4C | 109.5 |
C1—O2—Zn1iii | 121.59 (15) | C2—C5—H5A | 109.5 |
C3—O3—Zn1 | 127.36 (15) | C2—C5—H5B | 109.5 |
C3—O4—Zn1iv | 126.67 (15) | H5A—C5—H5B | 109.5 |
O1—C1—O2 | 122.3 (2) | C2—C5—H5C | 109.5 |
O1—C1—C2 | 120.5 (2) | H5A—C5—H5C | 109.5 |
O2—C1—C2 | 117.2 (2) | H5B—C5—H5C | 109.5 |
C5—C2—C3 | 110.45 (19) | Zn1—O5—H5D | 124.0 |
C5—C2—C1 | 111.6 (2) | Zn1—O5—H5E | 101.9 |
C3—C2—C1 | 108.48 (18) | H5D—O5—H5E | 116.6 |
C5—C2—C4 | 109.6 (2) | ||
O3—Zn1—O1—C1 | 29.59 (19) | O1—C1—C2—C3 | −44.4 (3) |
O2i—Zn1—O1—C1 | 149.91 (19) | O2—C1—C2—C3 | 137.1 (2) |
O5—Zn1—O1—C1 | −105.0 (2) | O1—C1—C2—C4 | 72.9 (3) |
O4ii—Zn1—O1—C1 | −46.0 (4) | O2—C1—C2—C4 | −105.6 (2) |
O2i—Zn1—O3—C3 | −109.3 (2) | Zn1iv—O4—C3—O3 | −27.1 (3) |
O5—Zn1—O3—C3 | 69.3 (2) | Zn1iv—O4—C3—C2 | 155.24 (16) |
O4ii—Zn1—O3—C3 | 156.9 (2) | Zn1—O3—C3—O4 | 152.96 (19) |
O1—Zn1—O3—C3 | −12.2 (2) | Zn1—O3—C3—C2 | −29.4 (3) |
Zn1—O1—C1—O2 | 175.34 (15) | C5—C2—C3—O4 | 3.2 (3) |
Zn1—O1—C1—C2 | −3.1 (3) | C1—C2—C3—O4 | −119.4 (2) |
Zn1iii—O2—C1—O1 | 16.3 (3) | C4—C2—C3—O4 | 123.1 (2) |
Zn1iii—O2—C1—C2 | −165.24 (15) | C5—C2—C3—O3 | −174.6 (2) |
O1—C1—C2—C5 | −166.3 (2) | C1—C2—C3—O3 | 62.9 (3) |
O2—C1—C2—C5 | 15.2 (3) | C4—C2—C3—O3 | −54.6 (3) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+5/2, z−1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+5/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5E···O3ii | 0.85 | 1.83 | 2.645 (2) | 159 |
O5—H5D···O2v | 0.85 | 1.92 | 2.765 (2) | 170 |
Symmetry codes: (ii) x, −y+5/2, z−1/2; (v) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C5H6O4)(H2O)] |
Mr | 213.48 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 8.7030 (15), 8.5986 (15), 9.4773 (16) |
β (°) | 102.532 (3) |
V (Å3) | 692.3 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.52 |
Crystal size (mm) | 0.16 × 0.14 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.585, 0.762 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3431, 1226, 1095 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.059, 1.06 |
No. of reflections | 1226 |
No. of parameters | 102 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.34 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL.
Zn1—O3 | 1.9776 (16) | O1—C1 | 1.246 (3) |
Zn1—O2i | 1.9967 (17) | O2—C1 | 1.266 (3) |
Zn1—O5 | 2.0276 (16) | O3—C3 | 1.271 (3) |
Zn1—O4ii | 2.0761 (16) | O4—C3 | 1.244 (3) |
Zn1—O1 | 2.0815 (16) | ||
O3—Zn1—O2i | 120.48 (7) | O3—Zn1—O4ii | 90.52 (7) |
O3—Zn1—O5 | 134.07 (8) | O5—Zn1—O4ii | 87.95 (7) |
O2i—Zn1—O5 | 105.44 (7) | O5—Zn1—O1 | 86.23 (7) |
O3—Zn1—O1 | 86.63 (7) | O4ii—Zn1—O1 | 168.74 (7) |
O2i—Zn1—O1 | 97.86 (7) | O1—C1—O2 | 122.3 (2) |
O2i—Zn1—O4ii | 92.98 (7) | O4—C3—O3 | 122.8 (2) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+5/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5E···O3ii | 0.85 | 1.83 | 2.645 (2) | 159 |
O5—H5D···O2iii | 0.85 | 1.92 | 2.765 (2) | 170 |
Symmetry codes: (ii) x, −y+5/2, z−1/2; (iii) x, −y+3/2, z−1/2. |
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From a coordination standpoint, malonate is a versatile ligand, displaying a variety of bonding modes. For example, mono-deprotonation of malonic acid can lead to complexes containing the coordinated HOOCCH2CO2 (malH) anion. This anion is known to bond to metals simultaneously via chelating bidentate and monodentate carboxylate groups, e.g. in [Cu(malH)2] (Delgado, Sanchiz et al., 2004). Deprotonation of the parent acid generates the [CH2(CO2)2]2- (mal2−) dianion, which can be found coordinating to metals both through two distal carboxylate O atoms to form a six-membered ring and through non-chelating O atoms to build up bridged compounds, as in {[Co(H2O)2][Co(mal)2(H2O)2]}n (Delgado, Hernandez-Molina et al., 2004). In heterobimetallic malonate complexes involving transition and alkaline-earth metals, malonate dianions have also been used to construct coordination polymers by acting as chelating bidentate ligands or as simple bridges between metal centers. Consequently, many heteronuclear malonate complexes have been synthesized and structurally characterized (Djeghri et al., 2005, 2006; Gil de Muro et al., 1998, 2000, 2004; Guo & Cao, 2006; Guo & Guo, 2006; Fu et al., 2006).
Although many complexes that use malonate as a ligand have been synthesized, up to now only a few complexes that use dimethylmalonate as a ligand are known to us (Zhang et al., 2002). Five-coordinated complexes of the metal ions are not common, and these are mainly complexes involving copper, malonate and other ligands (Sieroń, 2004; Xiong et al., 2001). For the complexes of Zn and the malonate ligand, five-coordinated complexes are rarely reported. In the course of our study of heterobimetallic malonate complexes involving zinc and alkaline-earth metals, using dimethylmalonic acid, we expected a structure similar or isotypic to that of [BaZn(C3H2O4)2(H2O)4]n (Guo & Guo, 2006), but interestingly, a completely different crystal structure was obtained, the title novel five-coordinated dimethylmalonate–zinc complex, (I), and we report its crystal structure here.
The asymmetric unit in the structure of (I) comprises one Zn atom, one complete dimethylmalonate dianion and one water molecule. The structure is shown in Fig. 1 in a symmetry-expanded view, which displays the full coordination of the Zn atom. Selected geometric parameters are given in Table 1.
The Zn atoms are five-coordinated by two chelating O atoms (atoms O1 and O3) of the dimethylmalonate dianion, one O atom from the water molecule (O5) and two O atoms (O2i and O4ii; see Table 1 for symmetry code) in a monodentate fashion from two symmetry-related dimethylmalonate anions. The Zn atom deviates 0.0120 (3) Å from the least-squares plane defined by atoms O5, O2i and O3 atoms; all of the cis O—Zn—O bond angles (see Table 1) are close to 90° [in the range 86.23 (7)–97.86 (7)°; Table 1], the trans angle O4ii—Zn1—O1 is 168.74 (7)°, and the structure index τ, indicating the relative amount of trigonality (τ = 0 for a square pyramid and τ = 1 for a trigonal bipyramid; Addison et al., 1984), is 0.58, and thus the coordination geometry of Zn is closer to distorted trigonal–bipyramidal than to square–pyramidal.
In the present structure, the variability of the malonate ligand can be clearly seen (Fig. 1). The whole dimethylmalonate molecule chelates the Zn atom to form a six-membered ring. The resulting six-membered chelate ring (Zn1/O1/C1–C3/O3) has a boat conformation, with atoms Zn1 and C2 lying 0.4166 (4) and 0.6295 (8) Å, respectively, out of the O1/C1/C3/O3 mean plane. Atom O2 of the O1/C1/O2 carboxylate group adopts a monodentate mode to connect to Zni (see Fig. 1 for symmetry codes); thus, the two Zn atoms are linked together via atoms O1, C1 and O2. This results in a Zn1···Zn1i distance of 5.098 (8) Å. Similarly, atom O4 of the O3/C3/O4 carboxylate group coordinates to Znii with a Zn1···Zn1ii distance of 5.001 (1) Å. Two Zn atoms are linked together via these carboxylate groups acting in monodentate mode, forming a 12-membered ring. Four Zn atoms are associated into a 16-membered ring via carboxylate groups acting in chelating and monodentate fashions. Each Zn atom is connected to four other Zn atoms through biscarboxylate bridges in the bc plane, resulting in planes perpendicular to the [100] direction. A complete two-dimensional polymeric layer is formed in the direction of the bc plane (Fig. 2).
The Zn—Owater bond and the Zn—Odimethylmalonate bonds (see Table 1) are somewhat shorter than those in the six-coordinated complex [CaZn(mal)2(H2O)4]n (Fu et al., 2006), and are comparable with the values reported for five-coordinated zinc complex involving carboxylate and containing other ligands (Erxleben, 2001). The O—C—O angles for two carboxylate groups are almost the same (O1—C1—O2 122.3 (2) and O4—C3—O3 122.8 (2)°, respectively). The two C—O bond distances (O1—C1 and O2—C1) of the carboxylate group of O1/C1/O2 are 1.246 (3) and 1.266 (3) Å, respectively, while the two C—O bond distances (O4—C3 and O3—C3) of the carboxylate group of O3/C3/O4 are 1.271 (3) and 1.244 (3) Å, respectively. This indicates that the mesomeric effect for the carboxylate group of O1/C1/O2 is larger than that of the carboxylate group of O3/C3/O4.
The crystal structure owes its formation to a strong intermolecular hydrogen bond (Brown, 1976) between atom O3ii and atom H5E of the water molecule. Hydrogen bonding also plays an important role in the stabilization of the extended two-dimensional network structure (Table 2). The structure consists of alternating layers in the [100] direction. The neighbouring layers are linked together to build up a three-dimensional network mainly by van der Waals forces.