Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056164/sj2412sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056164/sj2412Isup2.hkl |
CCDC reference: 672639
Benzene-1,2,4,5-tetracarboxylic acid (0.05 g, 0.22 mmol), zinc acetate (0.062 g, 0.20 mmol) and sodium hydroxide (0.08 g, 0.20 mmol) were heated in acetonitrile (25 ml) until the reagents dissolved completely. The solution was filtered; diethyl ether was layered over the solution, which was kept in a closed container. Crystals were obtained after a week.
All hydrogen atoms were located in difference Fourier maps, and were refined with distance restraints of C–H 0.95±0.01 Å and O–H 0.85±0.01 Å. Their temperature factors were freely refined.
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
[Zn2(C8H2O8)(H2O)4] | F(000) = 452 |
Mr = 452.92 | Dx = 2.170 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2515 reflections |
a = 5.259 (1) Å | θ = 2.5–26.1° |
b = 16.342 (1) Å | µ = 3.53 mm−1 |
c = 8.143 (1) Å | T = 295 K |
β = 97.939 (1)° | Block, colorless |
V = 693.1 (2) Å3 | 0.29 × 0.25 × 0.21 mm |
Z = 2 |
Bruker APEX area-detector diffractometer | 1362 independent reflections |
Radiation source: fine-focus sealed tube | 1284 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 26.1°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→5 |
Tmin = 0.428, Tmax = 0.524 | k = −19→16 |
3774 measured reflections | l = −9→10 |
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)] = 0.024 | All H-atom parameters refined |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.1318P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
1362 reflections | Δρmax = 0.41 e Å−3 |
130 parameters | Δρmin = −0.46 e Å−3 |
5 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.030 (2) |
[Zn2(C8H2O8)(H2O)4] | V = 693.1 (2) Å3 |
Mr = 452.92 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.259 (1) Å | µ = 3.53 mm−1 |
b = 16.342 (1) Å | T = 295 K |
c = 8.143 (1) Å | 0.29 × 0.25 × 0.21 mm |
β = 97.939 (1)° |
Bruker APEX area-detector diffractometer | 1362 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1284 reflections with I > 2σ(I) |
Tmin = 0.428, Tmax = 0.524 | Rint = 0.028 |
3774 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 5 restraints |
wR(F2) = 0.066 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.41 e Å−3 |
1362 reflections | Δρmin = −0.46 e Å−3 |
130 parameters |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.64624 (4) | 0.66722 (1) | 0.6294 (1) | 0.0154 (1) | |
O1 | 0.6293 (3) | 0.78505 (9) | 0.57696 (18) | 0.0215 (3) | |
O2 | 0.4252 (3) | 0.79266 (9) | 0.31917 (17) | 0.0190 (3) | |
O3 | 0.9206 (3) | 0.87008 (9) | 0.28756 (18) | 0.0199 (3) | |
O4 | 0.9313 (3) | 0.99480 (9) | 0.18210 (18) | 0.0230 (3) | |
O1w | 0.3378 (3) | 0.6354 (1) | 0.4158 (2) | 0.0230 (3) | |
O2w | 0.8804 (3) | 0.5957 (1) | 0.5220 (2) | 0.0271 (4) | |
C1 | 0.5300 (4) | 0.8244 (1) | 0.4509 (3) | 0.0145 (4) | |
C2 | 0.5241 (4) | 0.9156 (1) | 0.4733 (2) | 0.0132 (4) | |
C3 | 0.6670 (4) | 0.9715 (1) | 0.3922 (2) | 0.0142 (4) | |
C4 | 0.8534 (4) | 0.9442 (1) | 0.2782 (2) | 0.0148 (4) | |
C5 | 0.6398 (4) | 1.0548 (1) | 0.4197 (2) | 0.0155 (4) | |
H1 | 0.308 (11) | 0.672 (3) | 0.341 (5) | 0.15 (3)* | |
H2 | 0.372 (5) | 0.591 (1) | 0.370 (3) | 0.04 (1)* | |
H3 | 1.008 (4) | 0.612 (2) | 0.478 (3) | 0.04 (1)* | |
H4 | 0.795 (5) | 0.564 (2) | 0.452 (3) | 0.04 (1)* | |
H5 | 0.748 (4) | 1.091 (1) | 0.371 (3) | 0.03 (1)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0175 (2) | 0.0122 (2) | 0.0172 (2) | −0.0011 (1) | 0.0051 (1) | 0.0004 (1) |
O1 | 0.033 (1) | 0.012 (1) | 0.018 (1) | −0.001 (1) | −0.004 (1) | 0.001 (1) |
O2 | 0.024 (1) | 0.014 (1) | 0.018 (1) | 0.001 (1) | −0.003 (1) | −0.003 (1) |
O3 | 0.024 (1) | 0.016 (1) | 0.022 (1) | 0.006 (1) | 0.010 (1) | 0.000 (1) |
O4 | 0.028 (1) | 0.020 (1) | 0.024 (1) | 0.001 (1) | 0.014 (1) | 0.004 (1) |
O1w | 0.026 (1) | 0.019 (1) | 0.025 (1) | 0.002 (1) | 0.006 (1) | 0.003 (1) |
O2w | 0.019 (1) | 0.031 (1) | 0.033 (1) | −0.004 (1) | 0.009 (1) | −0.014 (1) |
C1 | 0.014 (1) | 0.014 (1) | 0.017 (1) | 0.001 (1) | 0.004 (1) | 0.000 (1) |
C2 | 0.015 (1) | 0.012 (1) | 0.013 (1) | 0.002 (1) | 0.000 (1) | 0.000 (1) |
C3 | 0.016 (1) | 0.013 (1) | 0.014 (1) | 0.002 (1) | 0.003 (1) | 0.001 (1) |
C4 | 0.014 (1) | 0.016 (1) | 0.015 (1) | 0.000 (1) | 0.001 (1) | −0.002 (1) |
C5 | 0.019 (1) | 0.014 (1) | 0.015 (1) | −0.001 (1) | 0.004 (1) | 0.001 (1) |
Zn1—O1 | 1.972 (2) | O1w—H2 | 0.85 (1) |
Zn1—O2i | 2.084 (1) | O2w—H3 | 0.85 (1) |
Zn1—O3ii | 1.965 (1) | O2w—H4 | 0.85 (1) |
Zn1—O1w | 2.269 (2) | C1—C2 | 1.502 (3) |
Zn1—O2w | 1.986 (2) | C2—C5iii | 1.394 (3) |
O1—C1 | 1.262 (3) | C2—C3 | 1.404 (3) |
O2—C1 | 1.249 (3) | C3—C5 | 1.390 (3) |
O3—C4 | 1.261 (2) | C3—C4 | 1.508 (2) |
O4—C4 | 1.246 (2) | C5—C2iii | 1.394 (3) |
O1w—H1 | 0.85 (1) | C5—H5 | 0.94 (1) |
O3ii—Zn1—O1 | 115.55 (6) | Zn1—O2w—H4 | 110 (2) |
O3ii—Zn1—O2w | 125.00 (7) | H3—O2w—H4 | 106 (3) |
O1—Zn1—O2w | 119.44 (7) | O2—C1—O1 | 124.8 (2) |
O3ii—Zn1—O2i | 92.21 (6) | O2—C1—C2 | 120.2 (2) |
O1—Zn1—O2i | 81.92 (6) | O1—C1—C2 | 114.9 (2) |
O2w—Zn1—O2i | 95.49 (6) | C5iii—C2—C3 | 119.0 (2) |
O3ii—Zn1—O1w | 89.93 (6) | C5iii—C2—C1 | 116.5 (2) |
O1—Zn1—O1w | 92.96 (6) | C3—C2—C1 | 124.5 (2) |
O2w—Zn1—O1w | 87.07 (6) | C5—C3—C2 | 119.2 (2) |
O2i—Zn1—O1w | 174.88 (6) | C5—C3—C4 | 118.6 (2) |
C1—O1—Zn1 | 132.5 (1) | C2—C3—C4 | 122.2 (2) |
C1—O2—Zn1iv | 133.5 (1) | O4—C4—O3 | 124.2 (2) |
C4—O3—Zn1v | 116.6 (1) | O4—C4—C3 | 119.3 (2) |
Zn1—O1w—H1 | 116 (4) | O3—C4—C3 | 116.5 (2) |
Zn1—O1w—H2 | 111 (2) | C3—C5—C2iii | 121.8 (2) |
H1—O1w—H2 | 109 (4) | C3—C5—H5 | 118 (2) |
Zn1—O2w—H3 | 126 (2) | C2iii—C5—H5 | 120 (2) |
O3ii—Zn1—O1—C1 | −105.7 (2) | C5iii—C2—C3—C5 | −0.6 (3) |
O2w—Zn1—O1—C1 | 73.9 (2) | C1—C2—C3—C5 | 178.2 (2) |
O2i—Zn1—O1—C1 | 165.7 (2) | C5iii—C2—C3—C4 | 178.4 (2) |
O1w—Zn1—O1—C1 | −14.4 (2) | C1—C2—C3—C4 | −2.9 (3) |
Zn1iv—O2—C1—O1 | 155.2 (2) | Zn1v—O3—C4—O4 | −3.8 (3) |
Zn1iv—O2—C1—C2 | −19.4 (3) | Zn1v—O3—C4—C3 | 176.3 (1) |
Zn1—O1—C1—O2 | −4.4 (3) | C5—C3—C4—O4 | −16.9 (3) |
Zn1—O1—C1—C2 | 170.4 (1) | C2—C3—C4—O4 | 164.1 (2) |
O2—C1—C2—C5iii | 106.5 (2) | C5—C3—C4—O3 | 163.0 (2) |
O1—C1—C2—C5iii | −68.6 (2) | C2—C3—C4—O3 | −15.9 (3) |
O2—C1—C2—C3 | −72.3 (3) | C2—C3—C5—C2iii | 0.6 (3) |
O1—C1—C2—C3 | 112.6 (2) | C4—C3—C5—C2iii | −178.4 (2) |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+1, −y+2, −z+1; (iv) x−1/2, −y+3/2, z−1/2; (v) x+1/2, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1···O1iv | 0.85 (1) | 2.33 (3) | 3.109 (2) | 152 (6) |
O1w—H1···O2 | 0.85 (1) | 2.08 (4) | 2.745 (2) | 134 (5) |
O1w—H2···O4vi | 0.85 (1) | 1.96 (1) | 2.767 (2) | 159 (3) |
O2w—H3···O1wvii | 0.85 (1) | 1.91 (1) | 2.744 (2) | 168 (3) |
O2w—H4···O4vi | 0.85 (1) | 1.89 (1) | 2.724 (2) | 172 (3) |
Symmetry codes: (iv) x−1/2, −y+3/2, z−1/2; (vi) −x+3/2, y−1/2, −z+1/2; (vii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C8H2O8)(H2O)4] |
Mr | 452.92 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 5.259 (1), 16.342 (1), 8.143 (1) |
β (°) | 97.939 (1) |
V (Å3) | 693.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.53 |
Crystal size (mm) | 0.29 × 0.25 × 0.21 |
Data collection | |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.428, 0.524 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3774, 1362, 1284 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.066, 1.06 |
No. of reflections | 1362 |
No. of parameters | 130 |
No. of restraints | 5 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.41, −0.46 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1···O2 | 0.85 (1) | 2.08 (4) | 2.745 (2) | 134 (5) |
O1w—H2···O4i | 0.85 (1) | 1.96 (1) | 2.767 (2) | 159 (3) |
O2w—H3···O1wii | 0.85 (1) | 1.91 (1) | 2.744 (2) | 168 (3) |
O2w—H4···O4i | 0.85 (1) | 1.89 (1) | 2.724 (2) | 172 (3) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1, y, z. |
The are many crystallographic studies of coordination compounds of 1,2,4,5-benzenetetracarboxylic acid (Cambridge Structural Database, Version 5.28, Nov. 2006); a water-coordinated zinc derivative with zinc in both tetrahedral and octahedral geometries has been reported (Robl, 1987; Wei et al., 1991). A slight variation of the synthesis has yielded the title diaquazinc compound, which features a trigonal-bipyramidal zinc coordination environment (Scheme I; Fig. 1).