Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017166/ci6165sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017166/ci6165Isup2.hkl |
CCDC reference: 198313
The title compound was prepared according to the literature procedure of Smith et al. (1996) by the partial digestion of excess copper(II) carbonate in a 50% aqueous ethanol solution containing equimolar amounts of trimesic acid and 2-amino-5-methyl-1,3-thiadiazole. Crystals were obtained by the total evaporation of the filtered solvent.
All methyl and amino H atoms were included in the refinement, at calculated positions, as riding models with C—H set to 0.98 Å (CH3) and N—H set to 0.88 Å, while the three aromatic H atoms were included at calculated positions with C—H set to 0.95 Å but their isotropic displacement parameters were freely refined. The two water H atoms were initially located from a difference map but were then restrained to an O—H distance of 0.83 Å while their isotropic displacement parameters were freely refined. The two carboxylic acid H atoms were generated at the most probable positions based on the position of the adjacent hydrogen-bond acceptor atom and were restrained to an O—H distance of 0.83 Å, while the isotropic displacement parameters were set equal to 1.25 times Ueq of the preceding normal atom. In the difference map, the deepest hole of −0.78 e Å−3 was 0.88 Å from Cu1.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.
[Cu(C9H5O6)2(C3H5N3S)2]·2H2O | Z = 1 |
Mr = 748.15 | F(000) = 383 |
Triclinic, P1 | Dx = 1.668 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4671 (4) Å | Cell parameters from 3147 reflections |
b = 8.7971 (5) Å | θ = 2.9–27.5° |
c = 11.6748 (6) Å | µ = 0.95 mm−1 |
α = 112.096 (4)° | T = 150 K |
β = 90.354 (3)° | Prism, purple |
γ = 110.549 (2)° | 0.07 × 0.07 × 0.02 mm |
V = 744.84 (7) Å3 |
Bruker–Nonius KappaCCD area-detector diffractometer | 3222 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2353 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.7°, θmin = 3.0° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −11→10 |
Tmin = 0.936, Tmax = 0.981 | l = −12→14 |
5879 measured reflections |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0527P)2] where P = (Fo2 + 2Fc2)/3 |
3222 reflections | (Δ/σ)max < 0.001 |
232 parameters | Δρmax = 0.39 e Å−3 |
4 restraints | Δρmin = −0.78 e Å−3 |
[Cu(C9H5O6)2(C3H5N3S)2]·2H2O | γ = 110.549 (2)° |
Mr = 748.15 | V = 744.84 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.4671 (4) Å | Mo Kα radiation |
b = 8.7971 (5) Å | µ = 0.95 mm−1 |
c = 11.6748 (6) Å | T = 150 K |
α = 112.096 (4)° | 0.07 × 0.07 × 0.02 mm |
β = 90.354 (3)° |
Bruker–Nonius KappaCCD area-detector diffractometer | 3222 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 2353 reflections with I > 2σ(I) |
Tmin = 0.936, Tmax = 0.981 | Rint = 0.040 |
5879 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 4 restraints |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.39 e Å−3 |
3222 reflections | Δρmin = −0.78 e Å−3 |
232 parameters |
Geometry. Mean plane data ex SHELXL97 Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.6136 (0.0077) x − 1.2098 (0.0125) y + 9.5641 (0.0068) z = 0.6898 (0.0106) * 0.0092 (0.0013) S1 * −0.0094 (0.0016) C2 * 0.0050 (0.0018) N3 * 0.0046 (0.0018) N4 * −0.0094 (0.0017) C5 Rms deviation of fitted atoms = 0.0078 − 7.1789 (0.0056) x + 4.2535 (0.0100) y + 4.3751 (0.0133) z = 0.9873 (0.0111) Angle to previous plane (with approximate e.s.d.) = 85.10 (0.08) * 0.0123 (0.0021) C6 * −0.0015 (0.0021) C7 * −0.0096 (0.0022) C8 * 0.0099 (0.0023) C9 * 0.0010 (0.0023) C10 * −0.0121 (0.0022) C11 Rms deviation of fitted atoms = 0.0091 |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 1.0000 | 0.0000 | 0.02718 (19) | |
S1 | 0.95661 (11) | 0.93680 (13) | −0.16985 (7) | 0.0426 (3) | |
C2 | 0.8217 (4) | 1.0443 (5) | −0.1072 (3) | 0.0317 (7) | |
N21 | 0.8478 (4) | 1.2071 (4) | −0.0965 (3) | 0.0461 (8) | |
H21 | 0.7768 | 1.2575 | −0.0623 | 0.058* | |
H22 | 0.9361 | 1.2648 | −0.1236 | 0.058* | |
N3 | 0.6935 (3) | 0.9478 (4) | −0.0695 (2) | 0.0312 (6) | |
N4 | 0.6936 (3) | 0.7828 (4) | −0.0904 (2) | 0.0351 (7) | |
C5 | 0.8209 (5) | 0.7576 (5) | −0.1432 (3) | 0.0408 (8) | |
C51 | 0.8503 (6) | 0.5897 (5) | −0.1788 (4) | 0.0580 (11) | |
H51 | 0.7761 | 0.5164 | −0.1396 | 0.073* | |
H52 | 0.9701 | 0.6172 | −0.1502 | 0.073* | |
H53 | 0.8243 | 0.5248 | −0.2700 | 0.073* | |
C6 | 0.7035 (4) | 1.0653 (4) | 0.3472 (3) | 0.0266 (7) | |
C61 | 0.6509 (4) | 1.0877 (4) | 0.2331 (3) | 0.0288 (7) | |
O60 | 0.7089 (3) | 1.2359 (3) | 0.2274 (2) | 0.0434 (6) | |
O61 | 0.5489 (3) | 0.9501 (3) | 0.14446 (17) | 0.0300 (5) | |
C7 | 0.8391 (4) | 1.1988 (4) | 0.4366 (3) | 0.0296 (7) | |
H7 | 0.8969 | 1.3059 | 0.4265 | 0.034 (9)* | |
C8 | 0.8928 (4) | 1.1793 (4) | 0.5419 (3) | 0.0271 (7) | |
C81 | 1.0397 (4) | 1.3247 (4) | 0.6381 (3) | 0.0302 (7) | |
O80 | 1.0775 (3) | 1.3241 (3) | 0.73832 (19) | 0.0380 (6) | |
O81 | 1.1214 (3) | 1.4525 (3) | 0.6035 (2) | 0.0451 (6) | |
H81 | 1.188 (4) | 1.548 (3) | 0.660 (3) | 0.056* | |
C9 | 0.8069 (4) | 1.0239 (4) | 0.5564 (3) | 0.0298 (7) | |
H9 | 0.8402 | 1.0104 | 0.6287 | 0.031 (8)* | |
C10 | 0.6725 (4) | 0.8876 (4) | 0.4664 (3) | 0.0310 (7) | |
C101 | 0.5886 (4) | 0.7196 (5) | 0.4814 (3) | 0.0376 (8) | |
O100 | 0.4900 (4) | 0.5854 (3) | 0.3908 (2) | 0.0609 (8) | |
O101 | 0.6232 (4) | 0.7200 (3) | 0.5871 (2) | 0.0583 (8) | |
H101 | 0.600 (5) | 0.624 (3) | 0.593 (4) | 0.073* | |
C11 | 0.6221 (4) | 0.9080 (4) | 0.3608 (3) | 0.0287 (7) | |
H11 | 0.5315 | 0.8135 | 0.2981 | 0.020 (7)* | |
O1W | 0.6564 (4) | 0.4168 (4) | 0.0375 (3) | 0.0636 (8) | |
H1W | 0.700 (6) | 0.495 (5) | 0.109 (3) | 0.092 (18)* | |
H2W | 0.550 (3) | 0.389 (10) | 0.043 (6) | 0.15 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0269 (3) | 0.0332 (3) | 0.0225 (3) | 0.0103 (2) | 0.0027 (2) | 0.0135 (2) |
S1 | 0.0340 (5) | 0.0623 (7) | 0.0356 (5) | 0.0228 (5) | 0.0101 (4) | 0.0200 (4) |
C2 | 0.0268 (17) | 0.040 (2) | 0.0289 (16) | 0.0116 (15) | 0.0032 (12) | 0.0160 (14) |
N21 | 0.0417 (18) | 0.047 (2) | 0.0572 (18) | 0.0154 (15) | 0.0179 (14) | 0.0303 (15) |
N3 | 0.0308 (15) | 0.0356 (16) | 0.0313 (14) | 0.0133 (13) | 0.0052 (11) | 0.0171 (12) |
N4 | 0.0336 (16) | 0.0357 (17) | 0.0363 (15) | 0.0155 (13) | 0.0037 (12) | 0.0128 (12) |
C5 | 0.043 (2) | 0.047 (2) | 0.0314 (18) | 0.0213 (18) | −0.0023 (14) | 0.0108 (15) |
C51 | 0.058 (3) | 0.052 (3) | 0.064 (3) | 0.032 (2) | 0.003 (2) | 0.012 (2) |
C6 | 0.0266 (17) | 0.0255 (17) | 0.0262 (16) | 0.0068 (14) | 0.0001 (12) | 0.0118 (13) |
C61 | 0.0300 (18) | 0.0333 (19) | 0.0276 (16) | 0.0122 (15) | 0.0051 (13) | 0.0169 (14) |
O60 | 0.0554 (16) | 0.0314 (14) | 0.0358 (13) | 0.0011 (12) | −0.0090 (10) | 0.0202 (10) |
O61 | 0.0323 (12) | 0.0306 (13) | 0.0231 (11) | 0.0064 (10) | −0.0018 (8) | 0.0121 (9) |
C7 | 0.0341 (18) | 0.0266 (18) | 0.0282 (16) | 0.0069 (14) | 0.0025 (12) | 0.0157 (13) |
C8 | 0.0279 (17) | 0.0269 (17) | 0.0264 (15) | 0.0084 (14) | 0.0025 (12) | 0.0126 (12) |
C81 | 0.0320 (18) | 0.0257 (17) | 0.0316 (17) | 0.0098 (14) | 0.0031 (13) | 0.0114 (13) |
O80 | 0.0405 (14) | 0.0405 (14) | 0.0265 (12) | 0.0047 (11) | −0.0046 (9) | 0.0167 (10) |
O81 | 0.0518 (16) | 0.0314 (14) | 0.0382 (14) | −0.0060 (12) | −0.0117 (11) | 0.0201 (11) |
C9 | 0.0365 (18) | 0.0287 (18) | 0.0228 (15) | 0.0076 (14) | −0.0018 (12) | 0.0136 (12) |
C10 | 0.0351 (19) | 0.0259 (17) | 0.0302 (16) | 0.0047 (14) | 0.0002 (13) | 0.0157 (13) |
C101 | 0.040 (2) | 0.033 (2) | 0.0357 (18) | 0.0021 (16) | −0.0058 (14) | 0.0211 (15) |
O100 | 0.0694 (19) | 0.0349 (15) | 0.0562 (16) | −0.0128 (14) | −0.0294 (13) | 0.0261 (13) |
O101 | 0.077 (2) | 0.0375 (16) | 0.0473 (15) | −0.0084 (14) | −0.0145 (13) | 0.0313 (12) |
C11 | 0.0317 (18) | 0.0246 (17) | 0.0262 (16) | 0.0048 (14) | −0.0014 (12) | 0.0119 (13) |
O1W | 0.057 (2) | 0.065 (2) | 0.0494 (18) | 0.0131 (17) | −0.0007 (14) | 0.0117 (15) |
Cu1—N3 | 1.953 (3) | C61—O60 | 1.250 (4) |
Cu1—N3i | 1.953 (3) | C61—O61 | 1.262 (4) |
Cu1—O61i | 1.971 (2) | C7—C8 | 1.398 (4) |
Cu1—O61 | 1.971 (2) | C7—H7 | 0.95 |
S1—C2 | 1.727 (3) | C8—C9 | 1.379 (4) |
S1—C5 | 1.734 (4) | C8—C81 | 1.493 (4) |
C2—N3 | 1.317 (4) | C81—O80 | 1.214 (3) |
C2—N21 | 1.326 (4) | C81—O81 | 1.306 (4) |
N21—H21 | 0.88 | O81—H81 | 0.839 (19) |
N21—H22 | 0.88 | C9—C10 | 1.384 (4) |
N3—N4 | 1.379 (4) | C9—H9 | 0.95 |
N4—C5 | 1.290 (4) | C10—C11 | 1.396 (4) |
C5—C51 | 1.488 (5) | C10—C101 | 1.476 (4) |
C51—H51 | 0.98 | C101—O100 | 1.252 (4) |
C51—H52 | 0.98 | C101—O101 | 1.266 (4) |
C51—H53 | 0.98 | O101—H101 | 0.831 (19) |
C6—C7 | 1.380 (4) | C11—H11 | 0.95 |
C6—C11 | 1.383 (4) | O1W—H1W | 0.83 (2) |
C6—C61 | 1.504 (4) | O1W—H2W | 0.86 (2) |
N3—Cu1—N3i | 180.0 | O60—C61—O61 | 122.6 (3) |
N3—Cu1—O61i | 89.60 (9) | O60—C61—C6 | 120.7 (3) |
N3i—Cu1—O61i | 90.40 (9) | O61—C61—C6 | 116.8 (3) |
N3—Cu1—O61 | 90.40 (9) | C61—O61—Cu1 | 111.69 (19) |
N3i—Cu1—O61 | 89.60 (9) | C6—C7—C8 | 121.2 (3) |
O61i—Cu1—O61 | 180.0 | C6—C7—H7 | 119.4 |
C2—S1—C5 | 87.53 (16) | C8—C7—H7 | 119.4 |
N3—C2—N21 | 124.4 (3) | C9—C8—C7 | 118.9 (3) |
N3—C2—S1 | 112.3 (3) | C9—C8—C81 | 120.4 (3) |
N21—C2—S1 | 123.3 (3) | C7—C8—C81 | 120.7 (3) |
C2—N21—H21 | 120.0 | O80—C81—O81 | 123.8 (3) |
C2—N21—H22 | 120.0 | O80—C81—C8 | 123.2 (3) |
H21—N21—H22 | 120.0 | O81—C81—C8 | 113.0 (3) |
C2—N3—N4 | 113.8 (3) | C81—O81—H81 | 117 (3) |
C2—N3—Cu1 | 129.2 (2) | C8—C9—C10 | 120.6 (3) |
N4—N3—Cu1 | 116.9 (2) | C8—C9—H9 | 119.7 |
C5—N4—N3 | 112.1 (3) | C10—C9—H9 | 119.7 |
N4—C5—C51 | 123.4 (4) | C9—C10—C11 | 119.8 (3) |
N4—C5—S1 | 114.3 (3) | C9—C10—C101 | 119.3 (3) |
C51—C5—S1 | 122.3 (3) | C11—C10—C101 | 120.8 (3) |
C5—C51—H51 | 109.5 | O100—C101—O101 | 123.5 (3) |
C5—C51—H52 | 109.5 | O100—C101—C10 | 119.6 (3) |
H51—C51—H52 | 109.5 | O101—C101—C10 | 116.9 (3) |
C5—C51—H53 | 109.5 | C101—O101—H101 | 119 (3) |
H51—C51—H53 | 109.5 | C6—C11—C10 | 120.2 (3) |
H52—C51—H53 | 109.5 | C6—C11—H11 | 119.9 |
C7—C6—C11 | 119.2 (3) | C10—C11—H11 | 119.9 |
C7—C6—C61 | 120.2 (3) | H1W—O1W—H2W | 101 (6) |
C11—C6—C61 | 120.5 (3) | ||
C5—S1—C2—N3 | 1.5 (2) | N3—Cu1—O61—C61 | 89.7 (2) |
C5—S1—C2—N21 | −179.8 (3) | N3i—Cu1—O61—C61 | −90.3 (2) |
N21—C2—N3—N4 | −179.9 (3) | C11—C6—C7—C8 | −1.4 (5) |
S1—C2—N3—N4 | −1.2 (3) | C61—C6—C7—C8 | −178.5 (3) |
N21—C2—N3—Cu1 | 4.6 (5) | C6—C7—C8—C9 | −0.6 (5) |
S1—C2—N3—Cu1 | −176.71 (14) | C6—C7—C8—C81 | 180.0 (3) |
O61i—Cu1—N3—C2 | 52.2 (3) | C9—C8—C81—O80 | −9.1 (5) |
O61—Cu1—N3—C2 | −127.8 (3) | C7—C8—C81—O80 | 170.2 (3) |
O61i—Cu1—N3—N4 | −123.2 (2) | C9—C8—C81—O81 | 171.6 (3) |
O61—Cu1—N3—N4 | 56.8 (2) | C7—C8—C81—O81 | −9.0 (4) |
C2—N3—N4—C5 | 0.0 (4) | C7—C8—C9—C10 | 1.7 (5) |
Cu1—N3—N4—C5 | 176.1 (2) | C81—C8—C9—C10 | −178.9 (3) |
N3—N4—C5—C51 | −178.7 (3) | C8—C9—C10—C11 | −0.8 (5) |
N3—N4—C5—S1 | 1.2 (3) | C8—C9—C10—C101 | 177.0 (3) |
C2—S1—C5—N4 | −1.5 (2) | C9—C10—C101—O100 | −166.7 (3) |
C2—S1—C5—C51 | 178.4 (3) | C11—C10—C101—O100 | 11.0 (5) |
C7—C6—C61—O60 | −12.0 (4) | C9—C10—C101—O101 | 12.6 (5) |
C11—C6—C61—O60 | 171.0 (3) | C11—C10—C101—O101 | −169.7 (3) |
C7—C6—C61—O61 | 167.0 (3) | C7—C6—C11—C10 | 2.4 (5) |
C11—C6—C61—O61 | −10.0 (4) | C61—C6—C11—C10 | 179.4 (3) |
O60—C61—O61—Cu1 | 1.2 (4) | C9—C10—C11—C6 | −1.4 (5) |
C6—C61—O61—Cu1 | −177.77 (19) | C101—C10—C11—C6 | −179.0 (3) |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···O1Wii | 0.88 | 2.04 | 2.904 (5) | 168 |
N21—H22···O80iii | 0.88 | 2.13 | 2.949 (3) | 155 |
O81—H81···O60iv | 0.84 (2) | 1.75 (2) | 2.570 (3) | 167 (4) |
O101—H101···O100v | 0.83 (2) | 1.81 (2) | 2.631 (3) | 169 (4) |
O1W—H1W···O80vi | 0.83 (2) | 2.23 (3) | 2.993 (4) | 152 (5) |
O1W—H2W···N4vii | 0.86 (2) | 2.30 (4) | 3.071 (4) | 150 (6) |
Symmetry codes: (ii) x, y+1, z; (iii) x, y, z−1; (iv) −x+2, −y+3, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x+2, −y+2, −z+1; (vii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C9H5O6)2(C3H5N3S)2]·2H2O |
Mr | 748.15 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 8.4671 (4), 8.7971 (5), 11.6748 (6) |
α, β, γ (°) | 112.096 (4), 90.354 (3), 110.549 (2) |
V (Å3) | 744.84 (7) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.95 |
Crystal size (mm) | 0.07 × 0.07 × 0.02 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.936, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5879, 3222, 2353 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.133, 1.06 |
No. of reflections | 3222 |
No. of parameters | 232 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.78 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···O1Wi | 0.88 | 2.04 | 2.904 (5) | 168 |
N21—H22···O80ii | 0.88 | 2.13 | 2.949 (3) | 155 |
O81—H81···O60iii | 0.84 (2) | 1.75 (2) | 2.570 (3) | 167 (4) |
O101—H101···O100iv | 0.83 (2) | 1.81 (2) | 2.631 (3) | 169 (4) |
O1W—H1W···O80v | 0.83 (2) | 2.23 (3) | 2.993 (4) | 152 (5) |
O1W—H2W···N4vi | 0.86 (2) | 2.30 (4) | 3.071 (4) | 150 (6) |
Symmetry codes: (i) x, y+1, z; (ii) x, y, z−1; (iii) −x+2, −y+3, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+2, −y+2, −z+1; (vi) −x+1, −y+1, −z. |
Copper is commonly known to form tetracarboxylato-O,O'-bridged dimers of the copper(II) acetate hydrate type (van Nickerk & Schoening, 1953) when complexed with a carboxylic acid. In the absence of other ligands, including water, these formations polymerize, with the axial substituent groups being a carboxylate-O atom from a neighbouring Cu dimer. When a suitable ligand is present then discrete units are produced (Smith et al., 1996). However, none of the currently known structures of Cu with trimesic acid exhibit such bridged dimers. Instead a variety of five- and six-coordination geometries are observed, with only one displaying a carboxylato-O,O'-bridged dimer (Chui, Lo et al., 1999). This structure comprises a combination of Cu, benzene-1,3,5-tricarboxylate and water, although another structural variant of these is also known in which one carboxylate remains as an acid (Pech & Pickardt, 1988). Other characterized structures based on these three components include the addition of Na+ (Chui, Siu & Williams, 1999), pyridine (Chui, Lo et al., 1999), imidazole and N-methylimidazole (Cheng et al., 2001), whereas more complex structures include the Cu atoms coordinated by multidentate ligands, such as tris(2-pyridylmethyl)amine (Oshio & Ichida, 1995) and 3,10-dimethyl-1,3,5,8,10,12-hexaazacyclotetradecane (Ko et al., 2002). All except for the Oshio & Ichida (1995) complex are coordination polymers. In a series of syntheses intending to produce more Cu coordination complexes containing acid analogues of benzene-1,3,5-tricarboxylate, the title compound, (I), was prepared.
The addition of trimesic acid to a digestion of copper(II) carbonate in 50% aqueous ethanol yielded an instant emerald green precipitate. Total evaporation of the solvent following removal of the insoluble material yielded very little coloured product that was not suitably crystalline for single-crystal analysis. The same result was obtained each time when suitable N-heterocyclics are added in an attempt to prevent instant insolubility of the emerald green material. However, total evaporation of the filtered solvent following the use of 2-amino-5-methyl-1,3,4-thiadiazole yielded a sprinkling of purple-coloured prisms which were suitable for structure determination.
The structure of (I) comprises discrete units of the four-coordinate Cu complex linked via hydrogen-bonding interactions from lattice waters and the amino and carboxylic acid groups. Selected Cu bonds are listed in Table 1, while hydrogen-bonding geometries are given in Table 2. Being a symmetrical square-planar trans complex, the Cu atom is located on an inversion centre with one of each ligand and a water molecule in the asymmetric unit (Fig. 1). The thiadiazole binds to atom Cu1 via N3 and, following the loss of one acid H atom, the trimesic acid binds via atom O61, leaving the remaining two acid groups intact. The dihedral angle between the thiadiazole ring and the benzene ring is 85.1 (1)°. The 3-carboxy group (O81) associates to the non-bound carboxylate-O atom (O60) in group-1, whereas the 5-carboxy group associates across another inversion centre to itself (O101—H···O100) (Fig. 2). The water molecule hydrogen bonds to both N4 and the carbonyl-O atom of the 3-carboxy group (O80). One amino association also binds O80, while both O61 and O1W are subject to the other. The overall result is a complex three-dimensional hydrogen-bonded network that is totally different to the other Cu–trimesate complexes.