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The title compound, [Zn(C5H7O2)2(H2O)2], crystallizes with the Zn atom on a centre of inversion and one acetyl­acetonato and one water mol­ecule in the asymmetric unit. It is isostructural with the Co, Mg, Ni, Mn and Fe complexes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803015848/lh6084sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803015848/lh6084Isup2.hkl
Contains datablock I

CCDC reference: 222798

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.020
  • wR factor = 0.056
  • Data-to-parameter ratio = 18.0

checkCIF/PLATON results

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Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ... ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Zn1 - O3 = 6.47 su
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

We report here the X-ray crystal structure analysis of diaquadiacetylacetonatozinc(II), (I). We have recently synthesized the purple coordination polymer (1) (see Scheme) from CuBr2 and 2,5-bis(pyrazol-1-yl)-1,4-dihydroxybenzene (Dinnebier et al., 2002) and have now become interested in the physical and chemical properties of the dinuclear transition metal complex (2) (see Scheme). We have therefore prepared (I), the synthesis of which has been achieved according to a literature procedure (Rudolph & Henry, 1967) as indicated in the reaction Scheme.

In (I), the Zn atom is located on a centre of inversion and the asymmetric unit contains one acetylacetonate anion and one water molecule. The acetylacetonate is almost planar (r.m.s.d. = 0.043 Å for all seven non-H atoms). The Zn atom is displaced from this plane by 0.466 (1) Å. The bond from Zn to the water molecule is significantly longer than the bonds to the acetylacetone O atoms (see Table 1). The crystal packing is stabilized by hydrogen bonds (see Table 2) from the water molecule to the two acetylacetonate O atoms.

The title compound is isostructural with the Co (Bullen, 1959; Laugier & Mathieu, 1975), Mg (Morosin, 1967), Ni (Montgomery & Lingafelter, 1964), Mn (Montgomery & Lingafelter, 1968; Onuma & Shibata, 1970), Fe (Laugier & Mathieu, 1975; Tsodikov et al., 1995) complexes.

Experimental top

The title compound was synthesized by stirring a slurry of ZnSO4, 2,4-pentadione, NaOH and water at ambient temperature. After 1 h, (I) precipitated quantitatively and was filtered off. After washing, the title compound was recrystalized from ethyl acetate (yield 64%).

Refinement top

H atoms bonded to C atoms were refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C) or 1.5 Ueq(Cmethyl)] using a riding model with C—H = 0.95 Å or methyl C—H = 0.98 Å, respectively. The methyl groups were allowed to rotate but not to tip. The H atoms bonded to O were refined isotropically.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.
(I) top
Crystal data top
[Zn(C5H7O2)2(H2O)2]F(000) = 312
Mr = 299.61Dx = 1.601 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 15112 reflections
a = 10.7987 (9) Åθ = 3.7–28.5°
b = 5.3744 (4) ŵ = 1.99 mm1
c = 11.1259 (11) ÅT = 100 K
β = 105.781 (7)°Block, colourless
V = 621.37 (9) Å30.34 × 0.25 × 0.23 mm
Z = 2
Data collection top
Stoe IPDS-II two-circle
diffractometer
1601 independent reflections
Radiation source: fine-focus sealed tube1476 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.058
ω scansθmax = 28.7°, θmin = 3.8°
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
h = 1413
Tmin = 0.495, Tmax = 0.631k = 77
10528 measured reflectionsl = 1515
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)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0336P)2 + 0.0697P]
where P = (Fo2 + 2Fc2)/3
1601 reflections(Δ/σ)max < 0.001
89 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.54 e Å3
Crystal data top
[Zn(C5H7O2)2(H2O)2]V = 621.37 (9) Å3
Mr = 299.61Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.7987 (9) ŵ = 1.99 mm1
b = 5.3744 (4) ÅT = 100 K
c = 11.1259 (11) Å0.34 × 0.25 × 0.23 mm
β = 105.781 (7)°
Data collection top
Stoe IPDS-II two-circle
diffractometer
1601 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
1476 reflections with I > 2σ(I)
Tmin = 0.495, Tmax = 0.631Rint = 0.058
10528 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0200 restraints
wR(F2) = 0.056H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.31 e Å3
1601 reflectionsΔρmin = 0.54 e Å3
89 parameters
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
Zn10.00000.50000.50000.01306 (8)
O10.14665 (8)0.72607 (15)0.59558 (7)0.01549 (16)
O20.11843 (8)0.33940 (15)0.40837 (7)0.01551 (16)
O30.05805 (9)0.21091 (16)0.64230 (8)0.01956 (17)
H3A0.074 (2)0.072 (4)0.629 (2)0.035 (5)*
H3B0.0589 (18)0.223 (4)0.7128 (18)0.034 (5)*
C10.35960 (11)0.8401 (2)0.70108 (10)0.0170 (2)
H1A0.35591.00940.66760.025*
H1B0.44660.77320.71360.025*
H1C0.33800.84330.78110.025*
C20.26444 (10)0.67686 (19)0.60989 (9)0.01366 (19)
C30.31338 (12)0.48701 (19)0.54791 (11)0.0156 (2)
H30.40390.46190.57230.019*
C40.23981 (11)0.33165 (19)0.45313 (9)0.01429 (19)
C50.30887 (12)0.1372 (2)0.39740 (10)0.0184 (2)
H5A0.27610.02830.40970.028*
H5B0.40140.14480.43860.028*
H5C0.29390.16890.30780.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01310 (11)0.01347 (11)0.01253 (11)0.00015 (6)0.00333 (7)0.00218 (5)
O10.0153 (4)0.0142 (3)0.0163 (3)0.0001 (3)0.0032 (3)0.0023 (3)
O20.0168 (4)0.0168 (4)0.0133 (3)0.0006 (3)0.0046 (3)0.0025 (3)
O30.0300 (5)0.0146 (4)0.0131 (3)0.0039 (3)0.0042 (3)0.0011 (3)
C10.0176 (5)0.0161 (5)0.0159 (4)0.0025 (4)0.0025 (4)0.0014 (4)
C20.0159 (5)0.0127 (4)0.0119 (4)0.0012 (4)0.0030 (3)0.0021 (3)
C30.0155 (5)0.0164 (5)0.0149 (5)0.0012 (4)0.0041 (4)0.0010 (3)
C40.0190 (5)0.0131 (4)0.0121 (4)0.0019 (4)0.0064 (4)0.0022 (4)
C50.0223 (5)0.0177 (5)0.0164 (4)0.0049 (4)0.0073 (4)0.0005 (4)
Geometric parameters (Å, º) top
Zn1—O22.0319 (8)C1—H1A0.9800
Zn1—O2i2.0319 (8)C1—H1B0.9800
Zn1—O12.0491 (8)C1—H1C0.9800
Zn1—O1i2.0491 (8)C2—C31.4122 (15)
Zn1—O32.1849 (8)C3—C41.4088 (15)
Zn1—O3i2.1849 (8)C3—H30.9500
O1—C21.2661 (14)C4—C51.5114 (15)
O2—C41.2700 (14)C5—H5A0.9800
O3—H3A0.79 (2)C5—H5B0.9800
O3—H3B0.78 (2)C5—H5C0.9800
C1—C21.5125 (14)
O2—Zn1—O2i180.0C2—C1—H1B109.5
O2—Zn1—O190.53 (3)H1A—C1—H1B109.5
O2i—Zn1—O189.47 (3)C2—C1—H1C109.5
O2—Zn1—O1i89.47 (3)H1A—C1—H1C109.5
O2i—Zn1—O1i90.53 (3)H1B—C1—H1C109.5
O1—Zn1—O1i180.0O1—C2—C3125.89 (10)
O2—Zn1—O388.04 (3)O1—C2—C1116.06 (9)
O2i—Zn1—O391.96 (3)C3—C2—C1118.06 (10)
O1—Zn1—O390.95 (3)C4—C3—C2125.73 (11)
O1i—Zn1—O389.05 (3)C4—C3—H3117.1
O2—Zn1—O3i91.96 (3)C2—C3—H3117.1
O2i—Zn1—O3i88.04 (3)O2—C4—C3125.86 (10)
O1—Zn1—O3i89.05 (3)O2—C4—C5115.70 (9)
O1i—Zn1—O3i90.95 (3)C3—C4—C5118.44 (10)
O3—Zn1—O3i180.0C4—C5—H5A109.5
C2—O1—Zn1123.34 (7)C4—C5—H5B109.5
C4—O2—Zn1122.72 (7)H5A—C5—H5B109.5
Zn1—O3—H3A125.0 (16)C4—C5—H5C109.5
Zn1—O3—H3B125.9 (14)H5A—C5—H5C109.5
H3A—O3—H3B109 (2)H5B—C5—H5C109.5
C2—C1—H1A109.5
O2—Zn1—O1—C221.26 (8)Zn1—O1—C2—C310.79 (14)
O2i—Zn1—O1—C2158.74 (8)Zn1—O1—C2—C1169.84 (7)
O3—Zn1—O1—C266.79 (8)O1—C2—C3—C44.82 (18)
O3i—Zn1—O1—C2113.21 (8)C1—C2—C3—C4174.54 (10)
O1—Zn1—O2—C425.62 (8)Zn1—O2—C4—C320.11 (14)
O1i—Zn1—O2—C4154.38 (8)Zn1—O2—C4—C5160.18 (7)
O3—Zn1—O2—C465.32 (8)C2—C3—C4—O20.46 (18)
O3i—Zn1—O2—C4114.68 (8)C2—C3—C4—C5179.85 (10)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1ii0.79 (2)2.09 (2)2.8715 (12)170 (2)
O3—H3B···O2iii0.78 (2)2.122 (19)2.8656 (11)158.3 (19)
Symmetry codes: (ii) x, y1, z; (iii) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Zn(C5H7O2)2(H2O)2]
Mr299.61
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)10.7987 (9), 5.3744 (4), 11.1259 (11)
β (°) 105.781 (7)
V3)621.37 (9)
Z2
Radiation typeMo Kα
µ (mm1)1.99
Crystal size (mm)0.34 × 0.25 × 0.23
Data collection
DiffractometerStoe IPDS-II two-circle
diffractometer
Absorption correctionMulti-scan
(MULABS; Spek, 1990; Blessing, 1995)
Tmin, Tmax0.495, 0.631
No. of measured, independent and
observed [I > 2σ(I)] reflections
10528, 1601, 1476
Rint0.058
(sin θ/λ)max1)0.676
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.056, 1.06
No. of reflections1601
No. of parameters89
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.31, 0.54

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).

Selected bond lengths (Å) top
Zn1—O22.0319 (8)O2—C41.2700 (14)
Zn1—O12.0491 (8)C2—C31.4122 (15)
Zn1—O32.1849 (8)C3—C41.4088 (15)
O1—C21.2661 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1i0.79 (2)2.09 (2)2.8715 (12)170 (2)
O3—H3B···O2ii0.78 (2)2.122 (19)2.8656 (11)158.3 (19)
Symmetry codes: (i) x, y1, z; (ii) x, y+1/2, z+1/2.
 

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