Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015994/cv6141sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015994/cv6141Isup2.hkl |
CCDC reference: 198300
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- H-atom completeness 39%
- Disorder in solvent or counterion
- R factor = 0.032
- wR factor = 0.097
- Data-to-parameter ratio = 13.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 21.00 Perc. PLAT_353 Alert C Long N-H Bond (0.87A) N - H14 = 1.05 Ang. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C10 H26 N2 O16 Zn1 Atom count from _chemical_formula_moiety:H8 N2 O2 FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C10 H26 N2 O16 Zn1 Atom count from the _atom_site data: C10 H10 N2 O16 Zn1 CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C10 H26 N2 O16 Zn TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 40.00 40.00 0.00 H 104.00 40.00 64.00 N 8.00 8.00 0.00 O 64.00 64.00 0.00 Zn 4.00 4.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional? CHEMW_03 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_weight 495.70 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 10.00 120.11 H 1.01 10.00 10.08 N 14.01 2.00 28.01 O 16.00 16.00 255.98 Zn 65.39 1.00 65.39 Calculated formula weight 479.58 The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
A mixture of Zn(CH3COO)2·3H2O (0.043 g, 0.2 mmol), 1,2,4,5-benzenetetracarboxylic dianhydride (0.043 g, 0.2 mmol), NH3·H2O (1 ml) and H2O (6 ml) with a molar ratio of 1:1:278:1667 (solution PH=8 ~9) was heated in a stainless steel reactor with a Teflon liner at 433 K for three d. It produced a colorless solution. After evaporation for several days at room temperature, colorless diamond-like crystals were obtained.
The phenyl ring and ammonium hydrogen atoms were located in a difference Fourier map and their positions and isotropic displacement parameters were refined. Atom O3w is equally disordered over two positions (O3w—O3w' distance: 1.523 Å). The occupancy of atom O5w is 0.496 and assigned to 0.5. The refinement is unstable if the occupancy of O5w is assigned to 1. The hydrogen atoms of the water O atoms were not located in the difference Fourier map, and were not assigned to water O atoms owing to the complexities of the structure.
Data collection: Bruker SMART; cell refinement: SMART (Bruker, 1999); data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Zn(C10H2O8)](NH4)2·8H2O | F(000) = 1032 |
Mr = 495.70 | Dx = 1.683 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 50 reflections |
a = 11.555 (2) Å | θ = 2.2–27.5° |
b = 15.300 (3) Å | µ = 1.34 mm−1 |
c = 11.072 (2) Å | T = 293 K |
β = 91.97 (3)° | Diamond, colorless |
V = 1956.4 (7) Å3 | 0.20 × 0.19 × 0.10 mm |
Z = 4 |
Siemems SMART CCD diffractometer | 2242 independent reflections |
Radiation source: fine-focus sealed tube | 2015 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.010 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→14 |
Tmin = 0.762, Tmax = 0.877 | k = −19→18 |
4233 measured reflections | l = −14→14 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0773P)2 + 1.4324P] where P = (Fo2 + 2Fc2)/3 |
2242 reflections | (Δ/σ)max < 0.001 |
166 parameters | Δρmax = 0.66 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
[Zn(C10H2O8)](NH4)2·8H2O | V = 1956.4 (7) Å3 |
Mr = 495.70 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.555 (2) Å | µ = 1.34 mm−1 |
b = 15.300 (3) Å | T = 293 K |
c = 11.072 (2) Å | 0.20 × 0.19 × 0.10 mm |
β = 91.97 (3)° |
Siemems SMART CCD diffractometer | 2242 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2015 reflections with I > 2σ(I) |
Tmin = 0.762, Tmax = 0.877 | Rint = 0.010 |
4233 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.66 e Å−3 |
2242 reflections | Δρmin = −0.59 e Å−3 |
166 parameters |
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 | Occ. (<1) | |
Zn1 | 0.5000 | 0.494950 (16) | 0.2500 | 0.01785 (13) | |
O1 | 0.38370 (12) | 0.56214 (9) | 0.15306 (13) | 0.0270 (3) | |
O2 | 0.52526 (13) | 0.65120 (11) | 0.09969 (16) | 0.0366 (4) | |
O3 | 0.1452 (2) | 0.84669 (13) | 0.27795 (15) | 0.0538 (5) | |
O4 | 0.08978 (13) | 0.93339 (9) | 0.12755 (14) | 0.0292 (3) | |
C1 | 0.42225 (17) | 0.62977 (12) | 0.10034 (17) | 0.0235 (4) | |
C2 | 0.33176 (16) | 0.68962 (11) | 0.04435 (17) | 0.0221 (4) | |
C3 | 0.27625 (18) | 0.74539 (13) | 0.12211 (18) | 0.0257 (4) | |
C4 | 0.19476 (16) | 0.80621 (12) | 0.07962 (17) | 0.0226 (4) | |
C5 | 0.13959 (17) | 0.86542 (13) | 0.16921 (18) | 0.0267 (4) | |
N | 0.7271 (3) | 0.5761 (2) | 0.0020 (3) | 0.0574 (6) | |
O1W | 0.1645 (4) | 0.5424 (5) | 0.2555 (6) | 0.177 (2) | |
O2W | 0.0000 | 0.5920 (11) | 0.7500 | 0.361 (10) | |
O3W | 0.3966 (5) | 0.2159 (4) | 0.0572 (6) | 0.0801 (16) | 0.50 |
O3W' | 0.4277 (6) | 0.1764 (5) | −0.0637 (11) | 0.137 (4) | 0.50 |
O4W | 0.4212 (7) | 0.9401 (5) | 0.012 (2) | 0.517 (16) | |
O5W | 0.4706 (12) | 0.1707 (6) | 0.1937 (10) | 0.162 (5) | 0.50 |
H1 | 0.302 (3) | 0.748 (2) | 0.212 (3) | 0.050 (8)* | |
H11 | 0.774 (6) | 0.630 (5) | 0.020 (6) | 0.15 (2)* | |
H12 | 0.741 (9) | 0.520 (6) | 0.044 (11) | 0.22 (4)* | |
H13 | 0.668 (7) | 0.587 (4) | 0.046 (7) | 0.16 (3)* | |
H14 | 0.695 (8) | 0.573 (5) | −0.088 (9) | 0.23 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02137 (18) | 0.01547 (17) | 0.01684 (18) | 0.000 | 0.00242 (11) | 0.000 |
O1 | 0.0313 (7) | 0.0220 (6) | 0.0275 (7) | 0.0057 (5) | −0.0006 (6) | 0.0048 (5) |
O2 | 0.0272 (8) | 0.0402 (9) | 0.0424 (9) | 0.0038 (6) | −0.0003 (6) | 0.0083 (7) |
O3 | 0.0826 (14) | 0.0575 (11) | 0.0215 (8) | 0.0381 (10) | 0.0065 (8) | −0.0012 (8) |
O4 | 0.0384 (8) | 0.0225 (7) | 0.0272 (7) | 0.0115 (5) | 0.0081 (6) | −0.0019 (5) |
C1 | 0.0285 (9) | 0.0225 (9) | 0.0195 (8) | 0.0086 (7) | 0.0002 (7) | −0.0017 (7) |
C2 | 0.0261 (9) | 0.0178 (8) | 0.0224 (9) | 0.0059 (6) | 0.0005 (7) | 0.0012 (7) |
C3 | 0.0340 (10) | 0.0248 (9) | 0.0180 (8) | 0.0087 (7) | −0.0001 (7) | −0.0007 (7) |
C4 | 0.0281 (9) | 0.0201 (8) | 0.0198 (9) | 0.0066 (7) | 0.0038 (7) | −0.0011 (6) |
C5 | 0.0325 (10) | 0.0256 (9) | 0.0222 (9) | 0.0077 (7) | 0.0030 (7) | −0.0042 (7) |
N | 0.0534 (15) | 0.0608 (17) | 0.0581 (17) | −0.0100 (12) | 0.0052 (13) | −0.0016 (13) |
O1W | 0.096 (3) | 0.241 (6) | 0.197 (6) | −0.005 (4) | 0.052 (4) | −0.027 (6) |
O2W | 0.300 (18) | 0.292 (18) | 0.48 (3) | 0.000 | −0.125 (18) | 0.000 |
O3W | 0.100 (4) | 0.061 (3) | 0.079 (4) | −0.036 (3) | −0.007 (3) | 0.007 (3) |
O3W' | 0.085 (5) | 0.067 (4) | 0.258 (13) | −0.027 (3) | 0.005 (6) | 0.038 (6) |
O4W | 0.191 (9) | 0.168 (7) | 1.18 (5) | −0.034 (6) | −0.075 (16) | 0.164 (16) |
O5W | 0.191 (12) | 0.128 (6) | 0.174 (12) | −0.019 (7) | 0.086 (11) | −0.025 (6) |
Zn1—O4i | 1.9744 (14) | C2—C4v | 1.398 (3) |
Zn1—O4ii | 1.9744 (14) | C3—C4 | 1.394 (3) |
Zn1—O1iii | 1.9789 (14) | C3—H1 | 1.04 (3) |
Zn1—O1 | 1.9789 (14) | C4—C2v | 1.398 (3) |
O1—C1 | 1.276 (2) | C4—C5 | 1.501 (2) |
O2—C1 | 1.235 (3) | N—H11 | 1.01 (7) |
O3—C5 | 1.237 (3) | N—H12 | 0.99 (10) |
O4—C5 | 1.268 (2) | N—H13 | 0.86 (8) |
O4—Zn1iv | 1.9744 (14) | N—H14 | 1.05 (10) |
C1—C2 | 1.507 (2) | O3W—O3W' | 1.523 (12) |
C2—C3 | 1.385 (3) | O5W—O5Wiii | 1.40 (2) |
O4i—Zn1—O4ii | 123.02 (9) | C2—C3—H1 | 120.2 (17) |
O4i—Zn1—O1iii | 104.91 (6) | C4—C3—H1 | 117.8 (17) |
O4ii—Zn1—O1iii | 103.79 (6) | C3—C4—C2v | 118.99 (17) |
O4i—Zn1—O1 | 103.79 (6) | C3—C4—C5 | 118.49 (17) |
O4ii—Zn1—O1 | 104.91 (6) | C2v—C4—C5 | 122.52 (16) |
O1iii—Zn1—O1 | 117.40 (8) | O3—C5—O4 | 123.50 (18) |
C1—O1—Zn1 | 115.35 (12) | O3—C5—C4 | 119.60 (17) |
C5—O4—Zn1iv | 112.59 (13) | O4—C5—C4 | 116.89 (17) |
O2—C1—O1 | 124.74 (17) | H11—N—H12 | 124 (6) |
O2—C1—C2 | 119.43 (17) | H11—N—H13 | 99 (5) |
O1—C1—C2 | 115.64 (17) | H12—N—H13 | 91 (6) |
C3—C2—C4v | 119.46 (16) | H11—N—H14 | 113 (6) |
C3—C2—C1 | 116.62 (17) | H12—N—H14 | 116 (7) |
C4v—C2—C1 | 123.87 (16) | H13—N—H14 | 107 (6) |
C2—C3—C4 | 121.55 (18) |
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, y, −z+1/2; (iv) x−1/2, y+1/2, z; (v) −x+1/2, −y+3/2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C10H2O8)](NH4)2·8H2O |
Mr | 495.70 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.555 (2), 15.300 (3), 11.072 (2) |
β (°) | 91.97 (3) |
V (Å3) | 1956.4 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.34 |
Crystal size (mm) | 0.20 × 0.19 × 0.10 |
Data collection | |
Diffractometer | Siemems SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.762, 0.877 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4233, 2242, 2015 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.097, 0.98 |
No. of reflections | 2242 |
No. of parameters | 166 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.66, −0.59 |
Computer programs: Bruker SMART, SMART (Bruker, 1999), SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
Zn1—O4i | 1.9744 (14) | O2—C1 | 1.235 (3) |
Zn1—O1 | 1.9789 (14) | O3—C5 | 1.237 (3) |
O1—C1 | 1.276 (2) | O4—C5 | 1.268 (2) |
O4ii—Zn1—O4i | 123.02 (9) | O1iii—Zn1—O1 | 117.40 (8) |
O4ii—Zn1—O1 | 103.79 (6) | O2—C1—O1 | 124.74 (17) |
O4i—Zn1—O1 | 104.91 (6) | O3—C5—O4 | 123.50 (18) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, y−1/2, z; (iii) −x+1, y, −z+1/2. |
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Aromatic poly-carboxylic ligands have a versatile coordination modes as they can form bridges between metallic centers, generating various molecular topologies and architectures, as well as having potential application as functional materials. They find widespread application in heterogeneous catalysis, chemical absorption and magnetism. Owing to their widespread utility (Yaghi et al., 1996), a considerable number of reports based on metal–aromatic poly-carboxylic coordination polymers have appeared over the past few years (Yaghi et al., 1997). 1,2,4,5-Benzenetetracarboxylic acid (H4btec) has four carboxyl groups, eight O-donor atoms that may be completely or partly deprotonated, inducing rich coordination modes and allowing novel structure with higher dimensions. It has been reported that an increase in pH results in a higher connectivity level of the ligands, which in turn leads to a higher dimensionality of the crystal structure (Pan et al., 2001). We adjusted the PH value to 9 ~10 by NH3·H2O and fortunately obtained the title compound, (I).
{(NH4)2Zn[C6H2(COO)4]·8H2O}n is a three-dimensional polymer containing one-dimensional nanoporous channels along the c axis with guest water molecules and the ammonium cation. All the carboxyl groups of H4btec are deprotonated, in agreement with the IR data in which no absorption peaks are observed around 1700 cm−1 for COOH. There is a strong absorption peak at 1603 cm−1 for υas(CO).
Only one type of coordination mode of btec4− is present in the structure. Each carboxylate group adopts a monodentate chelating mode, coordinating one Zn atom. Therefore, each btec4− acts as a µ4-bridge linking four Zn centers and each central Zn atom attaches to four btec4− ligands, forming a slightly distorted tetrahedron around Zn2+, with Zn···O bond lengths ranging from 1.974 (2) to 1.978 (2) Å, similar to other related Zn···O distances (Robl.,1992). Zn2+ is situated on the twofold axis and the four O atoms in a pair are related to each other by the twofold axis; the btec4− phenyl ring is centrosymmetric. The closest Zn···Zn distance is 5.538 (1) Å, indicating the lack of any direct metal–metal interaction. The macrocyclic unit [Zn4(btec)4]12−, which forms a rhombus sheet, with a Zn···Zn distance of 9.587 (1) Å, constitutes the basic building block of the structure. Every building block is linked together through Zn···O bonds to generate a three-dimensional structure with a nanoporous rhomboid channel along the c axis. The dimensions of this large channel are 11.555 (2) Å × 15.100 (3) Å. It accommodates ammonium cations and water molecules associated into a centrosymmetric network by intermolecular hydrogen bonds. Different kinds of hydrogen bonding are observed in the structure: (a) hydrogen bonding among water molecules [O···O distance: 1.845 (2)–3.039 (2) Å]; (b) hydrogen bonding of water molecules and carboxylate oxygen atoms [O···O distance: 2.725 (8)–3.028 (1) Å]; (c) hydrogen bonding between the ammonium cation and carboxylate oxygen atoms [N···O distance: 2.847 (2)–3.016 (2) Å]; (d) hydrogen bonding between the ammonium cation and water molecules [N···O distance:2.894 (2)–3.058 (2) Å]. The guest water molecules and ammonium cations are obviously essential to stablize the crystal structure.