Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680100188X/ya6007sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680100188X/ya6007Isup2.hkl |
CCDC reference: 159714
Benzene-1,3,5-tricarboxylic acid (99.4 mg), cadmium acetate (128 mg) and water (10 ml) were placed inside a 23 ml Parr bomb. Once sealed, the bomb was heated to 483 K at 100 K h-1. After maintaining this temperature for 2 h, the bomb was cooled to 463 K at 5 K h-1, and after 6 h at 463 K was cooled to room temperature at 4 K h-1. The bomb was opened and the colourless solid collected by filtration, washed with water and dried in air. IR spectra were obtained using a pressed KBr disk, using the ATI FT–IR system (Mattson Genesis series).
The carboxylic acid and water H atoms (H4, H7A, H7B, H8A and H8B) were located in the difference map and were refined isotropically. Other H atoms were placed in geometrically calculated positions and included in the refinement in the riding model approximation. The highest residual density value was 1.50 e Å3 at 0.53 Å from O6.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX in OSCAIL (McArdle, 1994, 2000), ATOMS (Dowty, 1999) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Cd(C9H4O6)(H2O)2] | F(000) = 1384 |
Mr = 356.55 | Dx = 2.225 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.7328 (9) Å | Cell parameters from 5038 reflections |
b = 9.1088 (4) Å | θ = 2.5–31.5° |
c = 13.3636 (6) Å | µ = 2.09 mm−1 |
β = 117.884 (1)° | T = 293 K |
V = 2123.12 (16) Å3 | Block, colourless |
Z = 8 | 0.3 × 0.1 × 0.1 mm |
Bruker SMART 1000 CCD area-detector diffractometer | 3512 independent reflections |
Radiation source: fine-focus sealed tube | 2892 reflections with I > 2σ(I)' |
Graphite monochromator | Rint = 0.027 |
ϕ–ω scans | θmax = 31.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −27→28 |
Tmin = 0.679, Tmax = 0.928 | k = −13→11 |
9718 measured reflections | l = −19→18 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0443P)2] where P = (Fo2 + 2Fc2)/3 |
3512 reflections | (Δ/σ)max = 0.004 |
178 parameters | Δρmax = 1.50 e Å−3 |
0 restraints | Δρmin = −1.24 e Å−3 |
[Cd(C9H4O6)(H2O)2] | V = 2123.12 (16) Å3 |
Mr = 356.55 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.7328 (9) Å | µ = 2.09 mm−1 |
b = 9.1088 (4) Å | T = 293 K |
c = 13.3636 (6) Å | 0.3 × 0.1 × 0.1 mm |
β = 117.884 (1)° |
Bruker SMART 1000 CCD area-detector diffractometer | 3512 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2892 reflections with I > 2σ(I)' |
Tmin = 0.679, Tmax = 0.928 | Rint = 0.027 |
9718 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 1.50 e Å−3 |
3512 reflections | Δρmin = −1.24 e Å−3 |
178 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. In general, H atoms were placed geometrically and refined using a riding model. Those H-atoms in the water molecules and coordinated to O(4) were located from the difference Fourier map and freely refined, resulting in two slightly short O—H bond lengths. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.687943 (8) | 0.596639 (15) | 0.306263 (13) | 0.02501 (6) | |
O1 | 0.57508 (9) | 0.71297 (17) | 0.19291 (15) | 0.0338 (4) | |
O2 | 0.66510 (10) | 0.87374 (18) | 0.28706 (15) | 0.0305 (4) | |
C1 | 0.59721 (11) | 0.8448 (2) | 0.21845 (17) | 0.0203 (4) | |
C2 | 0.54019 (11) | 0.9647 (2) | 0.16342 (16) | 0.0173 (3) | |
C3 | 0.56389 (11) | 1.1099 (2) | 0.18466 (17) | 0.0191 (4) | |
H3 | 0.6149 | 1.1316 | 0.2336 | 0.023* | |
C4 | 0.51184 (11) | 1.2232 (2) | 0.13320 (17) | 0.0193 (4) | |
O3 | 0.61022 (11) | 1.39649 (16) | 0.22526 (19) | 0.0408 (5) | |
O4 | 0.49129 (10) | 1.47841 (19) | 0.11398 (18) | 0.0431 (5) | |
H4 | 0.513 (2) | 1.570 (3) | 0.133 (3) | 0.042 (9)* | |
C5 | 0.54226 (12) | 1.3750 (2) | 0.16124 (19) | 0.0234 (4) | |
C6 | 0.43503 (11) | 1.1925 (2) | 0.06043 (16) | 0.0203 (4) | |
H6 | 0.4002 | 1.2686 | 0.0272 | 0.024* | |
C7 | 0.41071 (11) | 1.0468 (2) | 0.03777 (16) | 0.0185 (3) | |
C8 | 0.32913 (11) | 1.0101 (2) | −0.04461 (16) | 0.0209 (4) | |
O5 | 0.27966 (10) | 1.10853 (18) | −0.08861 (17) | 0.0346 (4) | |
O6 | 0.31282 (10) | 0.87555 (18) | −0.07048 (14) | 0.0280 (3)* | |
C9 | 0.46349 (11) | 0.9333 (2) | 0.08902 (16) | 0.0188 (4) | |
H9 | 0.4474 | 0.8362 | 0.0735 | 0.023* | |
O7 | 0.72039 (12) | 0.5924 (2) | 0.15562 (19) | 0.0340 (4) | |
H7A | 0.751 (3) | 0.539 (5) | 0.170 (3) | 0.078 (15)* | |
H7B | 0.725 (3) | 0.659 (5) | 0.146 (3) | 0.062 (14)* | |
O8 | 0.65948 (14) | 0.6168 (2) | 0.4548 (2) | 0.0390 (5) | |
H8A | 0.668 (2) | 0.693 (5) | 0.485 (3) | 0.073 (14)* | |
H8B | 0.672 (3) | 0.562 (5) | 0.492 (4) | 0.080 (17)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.01422 (8) | 0.01641 (8) | 0.03118 (10) | 0.00101 (5) | −0.00043 (6) | −0.00069 (5) |
O1 | 0.0226 (8) | 0.0121 (7) | 0.0469 (10) | 0.0001 (6) | −0.0005 (7) | −0.0002 (6) |
O2 | 0.0162 (7) | 0.0202 (7) | 0.0415 (9) | 0.0020 (6) | 0.0021 (6) | 0.0032 (6) |
C1 | 0.0176 (9) | 0.0151 (8) | 0.0248 (9) | 0.0012 (7) | 0.0071 (8) | 0.0019 (7) |
C2 | 0.0152 (8) | 0.0118 (8) | 0.0225 (9) | 0.0016 (6) | 0.0068 (7) | 0.0003 (6) |
C3 | 0.0140 (8) | 0.0139 (8) | 0.0245 (9) | −0.0007 (6) | 0.0048 (7) | −0.0012 (6) |
C4 | 0.0168 (8) | 0.0139 (8) | 0.0231 (9) | −0.0013 (7) | 0.0058 (7) | −0.0002 (7) |
O3 | 0.0186 (8) | 0.0150 (8) | 0.0616 (12) | −0.0029 (6) | −0.0038 (8) | −0.0045 (7) |
O4 | 0.0193 (8) | 0.0146 (8) | 0.0678 (13) | 0.0007 (6) | −0.0027 (8) | −0.0008 (8) |
C5 | 0.0179 (9) | 0.0137 (8) | 0.0299 (10) | −0.0005 (7) | 0.0039 (8) | −0.0017 (7) |
C6 | 0.0161 (8) | 0.0150 (8) | 0.0233 (9) | −0.0002 (6) | 0.0038 (7) | −0.0005 (7) |
C7 | 0.0133 (8) | 0.0166 (8) | 0.0200 (8) | −0.0019 (7) | 0.0032 (7) | 0.0000 (7) |
C8 | 0.0149 (8) | 0.0208 (9) | 0.0211 (9) | −0.0020 (7) | 0.0035 (7) | 0.0021 (7) |
O5 | 0.0155 (7) | 0.0248 (8) | 0.0448 (10) | 0.0017 (6) | −0.0014 (7) | 0.0045 (7) |
C9 | 0.0162 (8) | 0.0162 (8) | 0.0205 (9) | −0.0025 (6) | 0.0056 (7) | −0.0010 (7) |
O7 | 0.0289 (10) | 0.0263 (10) | 0.0402 (10) | 0.0034 (8) | 0.0106 (8) | 0.0031 (8) |
O8 | 0.0448 (12) | 0.0270 (10) | 0.0433 (11) | −0.0046 (8) | 0.0190 (10) | −0.0043 (9) |
Cd1—O1 | 2.2851 (15) | C4—C6 | 1.394 (3) |
Cd1—O2 | 2.5557 (16) | C4—C5 | 1.484 (3) |
Cd1—O3i | 2.3011 (16) | O3—Cd1iii | 2.3010 (16) |
Cd1—O5ii | 2.5225 (17) | O4—H4 | 0.92 (3) |
Cd1—O6ii | 2.2479 (18) | C6—C7 | 1.396 (3) |
Cd1—O7 | 2.381 (2) | C6—H6 | 0.9300 |
Cd1—O8 | 2.309 (2) | C7—C9 | 1.398 (3) |
C1—O1 | 1.269 (2) | C7—C8 | 1.503 (3) |
C1—O2 | 1.247 (3) | O5—Cd1iv | 2.5225 (17) |
C5—O3 | 1.223 (3) | O6—Cd1iv | 2.2479 (17) |
C5—O4 | 1.305 (3) | C9—H9 | 0.9300 |
C8—O5 | 1.251 (2) | O7—H7A | 0.73 (5) |
C8—O6 | 1.273 (2) | O7—H7B | 0.63 (4) |
C1—C2 | 1.492 (3) | O8—H8A | 0.78 (4) |
C3—C4 | 1.390 (3) | O8—H8B | 0.66 (4) |
C3—H3 | 0.9300 | ||
O6ii—Cd1—O1 | 145.90 (6) | C2—C3—C4 | 120.41 (18) |
O6ii—Cd1—O3i | 134.03 (6) | C2—C3—H3 | 119.8 |
O1—Cd1—O3i | 80.04 (6) | C4—C3—H3 | 119.8 |
O6ii—Cd1—O8 | 89.15 (7) | C3—C4—C6 | 120.47 (18) |
O1—Cd1—O8 | 88.82 (8) | C3—C4—C5 | 116.67 (17) |
O3i—Cd1—O8 | 95.22 (8) | C6—C4—C5 | 122.85 (18) |
O6ii—Cd1—O7 | 89.16 (7) | C5—O3—Cd1iii | 136.67 (14) |
O1—Cd1—O7 | 90.64 (7) | C5—O4—H4 | 112 (2) |
O3i—Cd1—O7 | 88.46 (8) | O3—C5—O4 | 124.60 (19) |
O8—Cd1—O7 | 176.13 (8) | O3—C5—C4 | 120.49 (18) |
O6ii—Cd1—O5ii | 54.57 (6) | O4—C5—C4 | 114.91 (18) |
O1—Cd1—O5ii | 159.34 (6) | C4—C6—C7 | 119.57 (18) |
O3i—Cd1—O5ii | 79.73 (6) | C4—C6—H6 | 120.2 |
O8—Cd1—O5ii | 88.84 (8) | C7—C6—H6 | 120.2 |
O7—Cd1—O5ii | 93.00 (7) | C6—C7—C9 | 119.67 (17) |
O6ii—Cd1—O2 | 92.51 (6) | C6—C7—C8 | 120.81 (17) |
O1—Cd1—O2 | 53.42 (5) | C9—C7—C8 | 119.48 (17) |
O3i—Cd1—O2 | 133.45 (6) | O5—C8—O6 | 121.3 (2) |
O8—Cd1—O2 | 84.56 (7) | O5—C8—C7 | 121.21 (18) |
O7—Cd1—O2 | 92.04 (7) | O6—C8—C7 | 117.46 (17) |
O5ii—Cd1—O2 | 146.56 (5) | C2—C9—C7 | 120.54 (17) |
C1—O1—Cd1 | 98.89 (12) | C2—C9—H9 | 119.7 |
C1—O2—Cd1 | 86.77 (12) | C7—C9—H9 | 119.7 |
O2—C1—O1 | 120.91 (18) | Cd1—O7—H7A | 108 (3) |
O2—C1—C2 | 120.73 (18) | Cd1—O7—H7B | 106 (4) |
O1—C1—C2 | 118.35 (18) | H7A—O7—H7B | 121 (5) |
C3—C2—C9 | 119.33 (17) | Cd1—O8—H8A | 116 (3) |
C3—C2—C1 | 119.51 (17) | Cd1—O8—H8B | 115 (4) |
C9—C2—C1 | 121.15 (17) | H8A—O8—H8B | 112 (5) |
O6ii—Cd1—O1—C1 | −3.2 (2) | C1—C2—C3—C4 | 179.25 (19) |
O3i—Cd1—O1—C1 | 179.00 (16) | C2—C3—C4—C6 | 0.6 (3) |
O8—Cd1—O1—C1 | 83.49 (15) | C2—C3—C4—C5 | 179.77 (19) |
O7—Cd1—O1—C1 | −92.68 (15) | Cd1iii—O3—C5—O4 | 3.2 (5) |
O5ii—Cd1—O1—C1 | 167.08 (18) | Cd1iii—O3—C5—C4 | −175.93 (18) |
O2—Cd1—O1—C1 | −0.61 (13) | C3—C4—C5—O3 | 1.1 (4) |
O6ii—Cd1—O2—C1 | 179.14 (14) | C6—C4—C5—O3 | −179.7 (2) |
O1—Cd1—O2—C1 | 0.61 (13) | C3—C4—C5—O4 | −178.1 (2) |
O3i—Cd1—O2—C1 | 0.08 (18) | C6—C4—C5—O4 | 1.1 (3) |
O8—Cd1—O2—C1 | −91.96 (14) | C3—C4—C6—C7 | −1.1 (3) |
O7—Cd1—O2—C1 | 89.89 (14) | C5—C4—C6—C7 | 179.77 (19) |
O5ii—Cd1—O2—C1 | −171.54 (13) | C4—C6—C7—C9 | 0.5 (3) |
Cd1—O2—C1—O1 | −1.0 (2) | C4—C6—C7—C8 | −177.02 (19) |
Cd1—O2—C1—C2 | 179.63 (18) | C6—C7—C8—O5 | −5.3 (3) |
Cd1—O1—C1—O2 | 1.2 (2) | C9—C7—C8—O5 | 177.1 (2) |
Cd1—O1—C1—C2 | −179.48 (15) | C6—C7—C8—O6 | 172.62 (19) |
O2—C1—C2—C3 | 3.2 (3) | C9—C7—C8—O6 | −5.0 (3) |
O1—C1—C2—C3 | −176.2 (2) | C3—C2—C9—C7 | −1.1 (3) |
O2—C1—C2—C9 | −178.1 (2) | C1—C2—C9—C7 | −179.80 (19) |
O1—C1—C2—C9 | 2.6 (3) | C6—C7—C9—C2 | 0.5 (3) |
C9—C2—C3—C4 | 0.5 (3) | C8—C7—C9—C2 | 178.14 (18) |
Symmetry codes: (i) x, y−1, z; (ii) x+1/2, −y+3/2, z+1/2; (iii) x, y+1, z; (iv) x−1/2, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O2v | 0.73 (5) | 2.11 (5) | 2.836 (3) | 176 (5) |
O7—H7B···O5vi | 0.63 (4) | 2.24 (4) | 2.867 (3) | 170 (5) |
O8—H8A···O6vii | 0.78 (4) | 1.95 (4) | 2.730 (3) | 175 (4) |
O8—H8B···O7viii | 0.66 (4) | 2.39 (4) | 3.044 (3) | 167 (5) |
O4—H4···O1iii | 0.92 (3) | 1.71 (3) | 2.604 (2) | 164 (3) |
Symmetry codes: (iii) x, y+1, z; (v) −x+3/2, y−1/2, −z+1/2; (vi) −x+1, −y+2, −z; (vii) −x+1, y, −z+1/2; (viii) x, −y+1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C9H4O6)(H2O)2] |
Mr | 356.55 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 19.7328 (9), 9.1088 (4), 13.3636 (6) |
β (°) | 117.884 (1) |
V (Å3) | 2123.12 (16) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.09 |
Crystal size (mm) | 0.3 × 0.1 × 0.1 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.679, 0.928 |
No. of measured, independent and observed [I > 2σ(I)'] reflections | 9718, 3512, 2892 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.735 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.071, 0.97 |
No. of reflections | 3512 |
No. of parameters | 178 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.50, −1.24 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX in OSCAIL (McArdle, 1994, 2000), ATOMS (Dowty, 1999) and ORTEP-3 (Farrugia, 1997), SHELXL97.
Cd1—O1 | 2.2851 (15) | C1—O1 | 1.269 (2) |
Cd1—O2 | 2.5557 (16) | C1—O2 | 1.247 (3) |
Cd1—O3i | 2.3011 (16) | C5—O3 | 1.223 (3) |
Cd1—O5ii | 2.5225 (17) | C5—O4 | 1.305 (3) |
Cd1—O6ii | 2.2479 (18) | C8—O5 | 1.251 (2) |
Cd1—O7 | 2.381 (2) | C8—O6 | 1.273 (2) |
Cd1—O8 | 2.309 (2) | ||
O6ii—Cd1—O1 | 145.90 (6) | O1—Cd1—O5ii | 159.34 (6) |
O6ii—Cd1—O3i | 134.03 (6) | O3i—Cd1—O5ii | 79.73 (6) |
O1—Cd1—O3i | 80.04 (6) | O8—Cd1—O5ii | 88.84 (8) |
O6ii—Cd1—O8 | 89.15 (7) | O7—Cd1—O5ii | 93.00 (7) |
O1—Cd1—O8 | 88.82 (8) | O6ii—Cd1—O2 | 92.51 (6) |
O3i—Cd1—O8 | 95.22 (8) | O1—Cd1—O2 | 53.42 (5) |
O6ii—Cd1—O7 | 89.16 (7) | O3i—Cd1—O2 | 133.45 (6) |
O1—Cd1—O7 | 90.64 (7) | O8—Cd1—O2 | 84.56 (7) |
O3i—Cd1—O7 | 88.46 (8) | O7—Cd1—O2 | 92.04 (7) |
O8—Cd1—O7 | 176.13 (8) | O5ii—Cd1—O2 | 146.56 (5) |
O6ii—Cd1—O5ii | 54.57 (6) |
Symmetry codes: (i) x, y−1, z; (ii) x+1/2, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O2iii | 0.73 (5) | 2.11 (5) | 2.836 (3) | 176 (5) |
O7—H7B···O5iv | 0.63 (4) | 2.24 (4) | 2.867 (3) | 170 (5) |
O8—H8A···O6v | 0.78 (4) | 1.95 (4) | 2.730 (3) | 175 (4) |
O8—H8B···O7vi | 0.66 (4) | 2.39 (4) | 3.044 (3) | 167 (5) |
O4—H4···O1vii | 0.92 (3) | 1.71 (3) | 2.604 (2) | 164 (3) |
Symmetry codes: (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+1, −y+2, −z; (v) −x+1, y, −z+1/2; (vi) x, −y+1, z+1/2; (vii) x, y+1, z. |
[Cd(C9H4O6)(H2O)2]n, (I), was synthesized as part of a study into polymeric compounds containing metals and benzene-1,3,5-tricarboxylic acid (BTC) (Plater et al., 1997, 1998, 1999; Yaghi et al., 1996).
The title compound was shown to be polymeric, with the Cd atom coordinated to seven O atoms, the Cd—O bond lengths varying in the range 2.2479 (18)–2.5557 (16) Å (Fig. 1 and Table 1), thus showing good agreement with previously reported Cd—O values.
The O atoms coordinating each metal atom belong to three BTC molecules; two of these are bonded via bidentate chelating carboxylate groups (C1/O1/O2 and C8/O5/O6), whilst the third one is coordinated in a monodentate manner through its carboxylic carbonyl O3 atom. Each Cd atom is also bonded to two water molecules.
The Cd atoms and BTC ligands form a two-dimensional infinite network tiled with `macrocycles', each comprising three Cd atoms and three BTC groups (Fig. 2). The layers are parallel to the 101 plane, the distance between the planes of neighbouring layers being equal to 3.2508 (2) Å. Water molecules are located between the layers with the Cd—O7 and Cd—O8 vectors approximately perpendicular to the network layer planes (inclination angles are 90 and 85° for Cd—O7 and Cd—O8 respectively; Fig. 3).
The C5/O3/O4 carboxylic group hydrogen (H4) was objectively located from the difference Fourier map; it participates in the intra-layer hydrogen bond with one of the carboxylate O atoms (O1). The position of this carboxylic H atom is consistent with the C—O bond lengths values (see Table 1) and IR data. In contrast, the H atoms of water molecules are responsible for inter-layer hydrogen bonding (Table 2).