Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104032512/fg1801sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104032512/fg1801Isup2.hkl |
CCDC reference: 264782
Compound (I) was prepared by mixing a solution of R-lactamide (0.272 g, 3 mmol) in hot acetic acid (5 ml, 353 K) and a solution of ZnBr2 (0.496 g, 2 mmol) in boiling acetic acid (10 ml). Upon slow cooling, crystals of (I) were recovered.
C– and N-bound H atoms were placed in calculated positions, with C—H distances of 0.96 or 0.98 Å, N—H distances of 0.86 Å and Uiso(H) values of 1.2Ueq(C,N), and were refined in the riding-model approximation. Coordinates for hydroxy atom H2 were located in a difference map and then allowed for as riding, with a Uiso(H) value of 1.2Ueq(O). The absolute configuration of (I) was known from the synthesis route and the Flack value [0.06 (6)] is entirely in agreement with the known configuration.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Zn(C3H7NO2)3][ZnBr4] | Dx = 2.161 Mg m−3 Dm = 2.14 (2) Mg m−3 Dm measured by flotation (CCl4 / C2H4Br2) |
Mr = 717.67 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P63 | Cell parameters from 25 reflections |
Hall symbol: P 6c | θ = 7.5–13.6° |
a = 11.337 (5) Å | µ = 9.45 mm−1 |
c = 9.910 (5) Å | T = 293 K |
V = 1103.1 (9) Å3 | Parallelepiped, colourless |
Z = 2 | 0.30 × 0.20 × 0.15 mm |
F(000) = 688 |
Enraf–Nonius CAD-4 diffractometer | 818 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.130 |
Graphite monochromator | θmax = 30.0°, θmin = 3.6° |
ω – 2θ scans | h = −15→15 |
Absorption correction: empirical (using intensity measurements) multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | k = −15→15 |
Tmin = 0.131, Tmax = 0.284 | l = 0→13 |
6629 measured reflections | 3 standard reflections every 60 min |
1109 independent reflections | intensity decay: 1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0315P)2 + 0.1638P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
1109 reflections | Δρmax = 0.66 e Å−3 |
75 parameters | Δρmin = −0.70 e Å−3 |
1 restraint | Absolute structure: Flack (1983), No. of Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.06 (6) |
[Zn(C3H7NO2)3][ZnBr4] | Z = 2 |
Mr = 717.67 | Mo Kα radiation |
Hexagonal, P63 | µ = 9.45 mm−1 |
a = 11.337 (5) Å | T = 293 K |
c = 9.910 (5) Å | 0.30 × 0.20 × 0.15 mm |
V = 1103.1 (9) Å3 |
Enraf–Nonius CAD-4 diffractometer | 818 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | Rint = 0.130 |
Tmin = 0.131, Tmax = 0.284 | 3 standard reflections every 60 min |
6629 measured reflections | intensity decay: 1% |
1109 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.088 | Δρmax = 0.66 e Å−3 |
S = 1.02 | Δρmin = −0.70 e Å−3 |
1109 reflections | Absolute structure: Flack (1983), No. of Friedel pairs? |
75 parameters | Absolute structure parameter: 0.06 (6) |
1 restraint |
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 | 1.0000 | 1.0000 | 0.00000 (15) | 0.0286 (3) | |
O1 | 0.8802 (5) | 1.0503 (5) | −0.1175 (6) | 0.0312 (12) | |
O2 | 0.8371 (5) | 0.9595 (7) | 0.1247 (7) | 0.0415 (15) | |
H2 | 0.8269 | 0.9405 | 0.2135 | 0.050* | |
N1 | 0.6730 (7) | 1.0320 (8) | −0.1394 (9) | 0.049 (2) | |
H1A | 0.6850 | 1.0493 | −0.2243 | 0.059* | |
H1B | 0.5983 | 1.0168 | −0.1016 | 0.059* | |
C1 | 0.7684 (8) | 1.0288 (8) | −0.0673 (9) | 0.0305 (18) | |
C2 | 0.7424 (8) | 1.0003 (9) | 0.0816 (8) | 0.0298 (18) | |
H20 | 0.6491 | 0.9257 | 0.0959 | 0.036* | |
C3 | 0.7623 (11) | 1.1273 (10) | 0.1519 (11) | 0.055 (3) | |
H3A | 0.7497 | 1.1109 | 0.2473 | 0.083* | |
H3B | 0.6971 | 1.1506 | 0.1184 | 0.083* | |
H3C | 0.8527 | 1.2010 | 0.1348 | 0.083* | |
Br1 | 0.36350 (9) | 0.88266 (8) | 0.03123 (12) | 0.0423 (2) | |
Br2 | 0.3333 | 0.6667 | 0.35162 (19) | 0.0587 (5) | |
Zn2 | 0.3333 | 0.6667 | 0.11173 (19) | 0.0380 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0318 (4) | 0.0318 (4) | 0.0222 (7) | 0.0159 (2) | 0.000 | 0.000 |
O1 | 0.036 (3) | 0.037 (3) | 0.022 (2) | 0.020 (3) | 0.006 (2) | 0.006 (2) |
O2 | 0.035 (3) | 0.069 (4) | 0.026 (3) | 0.030 (3) | 0.004 (2) | 0.016 (3) |
N1 | 0.052 (5) | 0.082 (6) | 0.036 (4) | 0.050 (5) | 0.006 (3) | 0.010 (4) |
C1 | 0.029 (4) | 0.027 (4) | 0.038 (5) | 0.017 (4) | 0.002 (4) | 0.004 (3) |
C2 | 0.026 (4) | 0.040 (5) | 0.018 (3) | 0.012 (4) | 0.006 (3) | 0.002 (3) |
C3 | 0.071 (7) | 0.066 (7) | 0.042 (6) | 0.044 (6) | 0.000 (5) | −0.009 (5) |
Br1 | 0.0423 (5) | 0.0392 (5) | 0.0466 (5) | 0.0214 (4) | 0.0062 (4) | 0.0055 (4) |
Br2 | 0.0689 (8) | 0.0689 (8) | 0.0383 (9) | 0.0345 (4) | 0.000 | 0.000 |
Zn2 | 0.0354 (6) | 0.0354 (6) | 0.0430 (10) | 0.0177 (3) | 0.000 | 0.000 |
Zn1—O2i | 2.073 (6) | N1—H1B | 0.86 |
Zn1—O2 | 2.073 (6) | C1—C2 | 1.507 (11) |
Zn1—O2ii | 2.073 (6) | C2—C3 | 1.511 (12) |
Zn1—O1ii | 2.074 (5) | C2—H20 | 0.98 |
Zn1—O1 | 2.074 (5) | C3—H3A | 0.96 |
Zn1—O1i | 2.074 (5) | C3—H3B | 0.96 |
O1—C1 | 1.266 (9) | C3—H3C | 0.96 |
O2—C2 | 1.431 (9) | Br1—Zn2 | 2.4315 (15) |
O2—H2 | 0.90 | Br2—Zn2 | 2.377 (3) |
N1—C1 | 1.312 (10) | Zn2—Br1iii | 2.4315 (15) |
N1—H1A | 0.86 | Zn2—Br1iv | 2.4315 (15) |
O2i—Zn1—O2 | 88.1 (2) | O1—C1—N1 | 122.7 (7) |
O2i—Zn1—O2ii | 88.1 (2) | O1—C1—C2 | 119.7 (7) |
O2—Zn1—O2ii | 88.1 (2) | N1—C1—C2 | 117.6 (7) |
O2i—Zn1—O1ii | 156.0 (2) | O2—C2—C1 | 105.3 (6) |
O2—Zn1—O1ii | 109.2 (2) | O2—C2—C3 | 113.1 (7) |
O2ii—Zn1—O1ii | 76.2 (2) | C1—C2—C3 | 109.1 (7) |
O2i—Zn1—O1 | 109.2 (2) | O2—C2—H20 | 109.7 |
O2—Zn1—O1 | 76.2 (2) | C1—C2—H20 | 109.7 |
O2ii—Zn1—O1 | 156.0 (2) | C3—C2—H20 | 109.7 |
O1ii—Zn1—O1 | 91.6 (2) | C2—C3—H3A | 109.5 |
O2i—Zn1—O1i | 76.2 (2) | C2—C3—H3B | 109.5 |
O2—Zn1—O1i | 156.0 (2) | H3A—C3—H3B | 109.5 |
O2ii—Zn1—O1i | 109.2 (2) | C2—C3—H3C | 109.5 |
O1ii—Zn1—O1i | 91.6 (2) | H3A—C3—H3C | 109.5 |
O1—Zn1—O1i | 91.6 (2) | H3B—C3—H3C | 109.5 |
C1—O1—Zn1 | 117.1 (5) | Br2—Zn2—Br1 | 109.15 (6) |
C2—O2—Zn1 | 118.7 (4) | Br2—Zn2—Br1iii | 109.15 (6) |
C2—O2—H2 | 110.0 | Br1—Zn2—Br1iii | 109.79 (6) |
Zn1—O2—H2 | 129.1 | Br2—Zn2—Br1iv | 109.15 (6) |
C1—N1—H1A | 120.0 | Br1—Zn2—Br1iv | 109.79 (6) |
C1—N1—H1B | 120.0 | Br1iii—Zn2—Br1iv | 109.79 (6) |
H1A—N1—H1B | 120.0 | ||
O2i—Zn1—O1—C1 | −86.4 (6) | O1i—Zn1—O2—C2 | 53.0 (9) |
O2—Zn1—O1—C1 | −3.3 (6) | Zn1—O1—C1—N1 | −166.9 (7) |
O2ii—Zn1—O1—C1 | 47.5 (9) | Zn1—O1—C1—C2 | 14.2 (9) |
O1ii—Zn1—O1—C1 | 106.0 (7) | Zn1—O2—C2—C1 | 15.9 (8) |
O1i—Zn1—O1—C1 | −162.4 (6) | Zn1—O2—C2—C3 | −103.2 (7) |
O2i—Zn1—O2—C2 | 101.9 (7) | O1—C1—C2—O2 | −19.2 (10) |
O2ii—Zn1—O2—C2 | −169.9 (6) | N1—C1—C2—O2 | 161.8 (7) |
O1ii—Zn1—O2—C2 | −95.1 (6) | O1—C1—C2—C3 | 102.4 (9) |
O1—Zn1—O2—C2 | −8.3 (6) | N1—C1—C2—C3 | −76.5 (10) |
Symmetry codes: (i) −x+y+1, −x+2, z; (ii) −y+2, x−y+1, z; (iii) −y+1, x−y+1, z; (iv) −x+y, −x+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1v | 0.90 | 1.82 | 2.696 (8) | 166 |
N1—H1A···Br1vi | 0.86 | 2.68 | 3.487 (8) | 157 |
N1—H1B···Br1 | 0.86 | 2.66 | 3.478 (8) | 158 |
Symmetry codes: (v) x−y+1, x, z+1/2; (vi) −x+1, −y+2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C3H7NO2)3][ZnBr4] |
Mr | 717.67 |
Crystal system, space group | Hexagonal, P63 |
Temperature (K) | 293 |
a, c (Å) | 11.337 (5), 9.910 (5) |
V (Å3) | 1103.1 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 9.45 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) |
Tmin, Tmax | 0.131, 0.284 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6629, 1109, 818 |
Rint | 0.130 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.088, 1.02 |
No. of reflections | 1109 |
No. of parameters | 75 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −0.70 |
Absolute structure | Flack (1983), No. of Friedel pairs? |
Absolute structure parameter | 0.06 (6) |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1996), WinGX (Farrugia, 1999).
Zn1—O2 | 2.073 (6) | Br1—Zn2 | 2.4315 (15) |
Zn1—O1 | 2.074 (5) | Br2—Zn2 | 2.377 (3) |
N1—C1 | 1.312 (10) | ||
O2—Zn1—O2i | 88.1 (2) | C2—O2—Zn1 | 118.7 (4) |
O2i—Zn1—O1 | 156.0 (2) | Br2—Zn2—Br1 | 109.15 (6) |
O1—Zn1—O1ii | 91.6 (2) | Br1—Zn2—Br1iii | 109.79 (6) |
C1—O1—Zn1 | 117.1 (5) |
Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, z; (iii) −y+1, x−y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1iv | 0.90 | 1.82 | 2.696 (8) | 166 |
N1—H1A···Br1v | 0.86 | 2.68 | 3.487 (8) | 157 |
N1—H1B···Br1 | 0.86 | 2.66 | 3.478 (8) | 158 |
Symmetry codes: (iv) x−y+1, x, z+1/2; (v) −x+1, −y+2, z−1/2. |
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Metal-containing proteins have been studied in relation to severe diseases. Alzheimer's and mad cow diseases imply metal–protein interactions. Metalloproteases are implied in cancer dispersion and angiotensin converting enzyme (ACE) in blood pressure control. For theses reasons, amide–metal complexes have attracted much interest. Following our work on metal–amide crystalline complexes (Bekaert et al., 2002a; Bekaert et al., 2002b; Bekaert et al., 2003), we now report a new zinc complex< (I), with 2-hydroxypropanamide (lactamide).
Compound (I) (Fig. 1) contains one monomeric six-coordinate zinc complex cation, [Zn(C3H7NO2)3]2+, and one tetrahedral [ZnBr4]2− anion. In both the cation and the anion, the Zn atoms lie on threefold axes in space group P63. In the cation, the Zn atom is surrounded by three symmetry-related R-lactamide ligands, coordinated in a bidentate fashion via amide atom O1 and hydroxy atom O2, and their symmetry equivalents. The Zn coordination may be described as distorted octahedral. The O1—Zn1—O1* angles [* is either at (1 − x + y, 2 − x,z) or (2 − y,1 + x-y,z)] are 91.6 (2)°, while the O2—Zn1—O2* angles are 88.1 (2)°. The Zn1(O1)3 and Zn1(O2)3 moieties are rotated about the threefold axis, some 31° from a fully eclipsed conformation, and the three symmetry-related trans O—Zn—O angles are 156.0 (2)°. The two Zn—O distances (Table 1) are not significantly different and are in agreement with those reported in the literature. Among the rare crystal structures of the metal complexes with lactamide or its derivatives, described in the literature, two coordination modes are possible, viz. N,O-coordination in [copper(II)-(N-pyridin-2-ylmethyl)chlorolactamide] monohydrate? (Tounsi et al., 2004) and O,O-coordination for the lactamide moiety in molybdenum(VI)oxodiperoxo N,N-dimethyllactamide (Winter et al., 1980); this latter structure is similar to that of (I), with the same geometry for the lactamide entity.
In the crystal structure the individual cation complexes are linked into chains running parallel to the c axis by inter-ion N—H···O hydrogen bonds (Table 2 and Fig. 2). Such chains are cross-linked by the use of the O2 hydroxy group forming inter-cation O—H···O hydrogen bonds with amide atom O1. The fact that both Zn1 and Zn2 lie on threefold axes in space group P63 then leads to a three-dimensional hydrogen-bonded network.