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The structure of the title compound, [Cu(C9H5O6)2(C3H5N3S)2]·2H2O, comprises discrete units of the four-coordinate Cu complex linked via hydrogen-bonding interactions of the wtare molecules and the amino and carboxyl­ic acid groups. The complex is trans and lies on an inversion centre. The thia­diazo­le is bound to the metal via a Cu—N [1.953 (3) Å] bond, while the acid binds via a carboxyl­ate-O atom [Cu—O 1.971 (2) Å].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017166/ci6165sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017166/ci6165Isup2.hkl
Contains datablock I

CCDC reference: 198313

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.049
  • wR factor = 0.133
  • Data-to-parameter ratio = 13.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.66 From the CIF: _reflns_number_total 3222 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3464 Completeness (_total/calc) 93.01% Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular configuration and atom-numbering scheme for the title compound, showing 50% probability displacement ellipsoids [symmetry code: (i) 1 − x, 2 − y, −z].
[Figure 2] Fig. 2. Packing diagram for the title compound. Hydrogen-bonding associations are shown as dotted lines.
trans-Bis(2-amino-5-methyl-1,3,4-thiadiazole-N)-bis(benzene-1-carboxylato-O– 3,5-dicarboxylic acid)copper(II) dihydrate top
Crystal data top
[Cu(C9H5O6)2(C3H5N3S)2]·2H2OZ = 1
Mr = 748.15F(000) = 383
Triclinic, P1Dx = 1.668 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.4671 (4) ÅCell parameters from 3147 reflections
b = 8.7971 (5) Åθ = 2.9–27.5°
c = 11.6748 (6) ŵ = 0.95 mm1
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
Data collection top
Bruker–Nonius KappaCCD area-detector
diffractometer
3222 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode2353 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
Detector resolution: 9.091 pixels mm-1θmax = 27.7°, θmin = 3.0°
ϕ and ω scansh = 1010
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 1110
Tmin = 0.936, Tmax = 0.981l = 1214
5879 measured reflections
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H 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 parametersΔρmax = 0.39 e Å3
4 restraintsΔρmin = 0.78 e Å3
Crystal data top
[Cu(C9H5O6)2(C3H5N3S)2]·2H2Oγ = 110.549 (2)°
Mr = 748.15V = 744.84 (7) Å3
Triclinic, P1Z = 1
a = 8.4671 (4) ÅMo Kα radiation
b = 8.7971 (5) ŵ = 0.95 mm1
c = 11.6748 (6) ÅT = 150 K
α = 112.096 (4)°0.07 × 0.07 × 0.02 mm
β = 90.354 (3)°
Data collection top
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 = 0.981Rint = 0.040
5879 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0494 restraints
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.39 e Å3
3222 reflectionsΔρmin = 0.78 e Å3
232 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50001.00000.00000.02718 (19)
S10.95661 (11)0.93680 (13)0.16985 (7)0.0426 (3)
C20.8217 (4)1.0443 (5)0.1072 (3)0.0317 (7)
N210.8478 (4)1.2071 (4)0.0965 (3)0.0461 (8)
H210.77681.25750.06230.058*
H220.93611.26480.12360.058*
N30.6935 (3)0.9478 (4)0.0695 (2)0.0312 (6)
N40.6936 (3)0.7828 (4)0.0904 (2)0.0351 (7)
C50.8209 (5)0.7576 (5)0.1432 (3)0.0408 (8)
C510.8503 (6)0.5897 (5)0.1788 (4)0.0580 (11)
H510.77610.51640.13960.073*
H520.97010.61720.15020.073*
H530.82430.52480.27000.073*
C60.7035 (4)1.0653 (4)0.3472 (3)0.0266 (7)
C610.6509 (4)1.0877 (4)0.2331 (3)0.0288 (7)
O600.7089 (3)1.2359 (3)0.2274 (2)0.0434 (6)
O610.5489 (3)0.9501 (3)0.14446 (17)0.0300 (5)
C70.8391 (4)1.1988 (4)0.4366 (3)0.0296 (7)
H70.89691.30590.42650.034 (9)*
C80.8928 (4)1.1793 (4)0.5419 (3)0.0271 (7)
C811.0397 (4)1.3247 (4)0.6381 (3)0.0302 (7)
O801.0775 (3)1.3241 (3)0.73832 (19)0.0380 (6)
O811.1214 (3)1.4525 (3)0.6035 (2)0.0451 (6)
H811.188 (4)1.548 (3)0.660 (3)0.056*
C90.8069 (4)1.0239 (4)0.5564 (3)0.0298 (7)
H90.84021.01040.62870.031 (8)*
C100.6725 (4)0.8876 (4)0.4664 (3)0.0310 (7)
C1010.5886 (4)0.7196 (5)0.4814 (3)0.0376 (8)
O1000.4900 (4)0.5854 (3)0.3908 (2)0.0609 (8)
O1010.6232 (4)0.7200 (3)0.5871 (2)0.0583 (8)
H1010.600 (5)0.624 (3)0.593 (4)0.073*
C110.6221 (4)0.9080 (4)0.3608 (3)0.0287 (7)
H110.53150.81350.29810.020 (7)*
O1W0.6564 (4)0.4168 (4)0.0375 (3)0.0636 (8)
H1W0.700 (6)0.495 (5)0.109 (3)0.092 (18)*
H2W0.550 (3)0.389 (10)0.043 (6)0.15 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0269 (3)0.0332 (3)0.0225 (3)0.0103 (2)0.0027 (2)0.0135 (2)
S10.0340 (5)0.0623 (7)0.0356 (5)0.0228 (5)0.0101 (4)0.0200 (4)
C20.0268 (17)0.040 (2)0.0289 (16)0.0116 (15)0.0032 (12)0.0160 (14)
N210.0417 (18)0.047 (2)0.0572 (18)0.0154 (15)0.0179 (14)0.0303 (15)
N30.0308 (15)0.0356 (16)0.0313 (14)0.0133 (13)0.0052 (11)0.0171 (12)
N40.0336 (16)0.0357 (17)0.0363 (15)0.0155 (13)0.0037 (12)0.0128 (12)
C50.043 (2)0.047 (2)0.0314 (18)0.0213 (18)0.0023 (14)0.0108 (15)
C510.058 (3)0.052 (3)0.064 (3)0.032 (2)0.003 (2)0.012 (2)
C60.0266 (17)0.0255 (17)0.0262 (16)0.0068 (14)0.0001 (12)0.0118 (13)
C610.0300 (18)0.0333 (19)0.0276 (16)0.0122 (15)0.0051 (13)0.0169 (14)
O600.0554 (16)0.0314 (14)0.0358 (13)0.0011 (12)0.0090 (10)0.0202 (10)
O610.0323 (12)0.0306 (13)0.0231 (11)0.0064 (10)0.0018 (8)0.0121 (9)
C70.0341 (18)0.0266 (18)0.0282 (16)0.0069 (14)0.0025 (12)0.0157 (13)
C80.0279 (17)0.0269 (17)0.0264 (15)0.0084 (14)0.0025 (12)0.0126 (12)
C810.0320 (18)0.0257 (17)0.0316 (17)0.0098 (14)0.0031 (13)0.0114 (13)
O800.0405 (14)0.0405 (14)0.0265 (12)0.0047 (11)0.0046 (9)0.0167 (10)
O810.0518 (16)0.0314 (14)0.0382 (14)0.0060 (12)0.0117 (11)0.0201 (11)
C90.0365 (18)0.0287 (18)0.0228 (15)0.0076 (14)0.0018 (12)0.0136 (12)
C100.0351 (19)0.0259 (17)0.0302 (16)0.0047 (14)0.0002 (13)0.0157 (13)
C1010.040 (2)0.033 (2)0.0357 (18)0.0021 (16)0.0058 (14)0.0211 (15)
O1000.0694 (19)0.0349 (15)0.0562 (16)0.0128 (14)0.0294 (13)0.0261 (13)
O1010.077 (2)0.0375 (16)0.0473 (15)0.0084 (14)0.0145 (13)0.0313 (12)
C110.0317 (18)0.0246 (17)0.0262 (16)0.0048 (14)0.0014 (12)0.0119 (13)
O1W0.057 (2)0.065 (2)0.0494 (18)0.0131 (17)0.0007 (14)0.0117 (15)
Geometric parameters (Å, º) top
Cu1—N31.953 (3)C61—O601.250 (4)
Cu1—N3i1.953 (3)C61—O611.262 (4)
Cu1—O61i1.971 (2)C7—C81.398 (4)
Cu1—O611.971 (2)C7—H70.95
S1—C21.727 (3)C8—C91.379 (4)
S1—C51.734 (4)C8—C811.493 (4)
C2—N31.317 (4)C81—O801.214 (3)
C2—N211.326 (4)C81—O811.306 (4)
N21—H210.88O81—H810.839 (19)
N21—H220.88C9—C101.384 (4)
N3—N41.379 (4)C9—H90.95
N4—C51.290 (4)C10—C111.396 (4)
C5—C511.488 (5)C10—C1011.476 (4)
C51—H510.98C101—O1001.252 (4)
C51—H520.98C101—O1011.266 (4)
C51—H530.98O101—H1010.831 (19)
C6—C71.380 (4)C11—H110.95
C6—C111.383 (4)O1W—H1W0.83 (2)
C6—C611.504 (4)O1W—H2W0.86 (2)
N3—Cu1—N3i180.0O60—C61—O61122.6 (3)
N3—Cu1—O61i89.60 (9)O60—C61—C6120.7 (3)
N3i—Cu1—O61i90.40 (9)O61—C61—C6116.8 (3)
N3—Cu1—O6190.40 (9)C61—O61—Cu1111.69 (19)
N3i—Cu1—O6189.60 (9)C6—C7—C8121.2 (3)
O61i—Cu1—O61180.0C6—C7—H7119.4
C2—S1—C587.53 (16)C8—C7—H7119.4
N3—C2—N21124.4 (3)C9—C8—C7118.9 (3)
N3—C2—S1112.3 (3)C9—C8—C81120.4 (3)
N21—C2—S1123.3 (3)C7—C8—C81120.7 (3)
C2—N21—H21120.0O80—C81—O81123.8 (3)
C2—N21—H22120.0O80—C81—C8123.2 (3)
H21—N21—H22120.0O81—C81—C8113.0 (3)
C2—N3—N4113.8 (3)C81—O81—H81117 (3)
C2—N3—Cu1129.2 (2)C8—C9—C10120.6 (3)
N4—N3—Cu1116.9 (2)C8—C9—H9119.7
C5—N4—N3112.1 (3)C10—C9—H9119.7
N4—C5—C51123.4 (4)C9—C10—C11119.8 (3)
N4—C5—S1114.3 (3)C9—C10—C101119.3 (3)
C51—C5—S1122.3 (3)C11—C10—C101120.8 (3)
C5—C51—H51109.5O100—C101—O101123.5 (3)
C5—C51—H52109.5O100—C101—C10119.6 (3)
H51—C51—H52109.5O101—C101—C10116.9 (3)
C5—C51—H53109.5C101—O101—H101119 (3)
H51—C51—H53109.5C6—C11—C10120.2 (3)
H52—C51—H53109.5C6—C11—H11119.9
C7—C6—C11119.2 (3)C10—C11—H11119.9
C7—C6—C61120.2 (3)H1W—O1W—H2W101 (6)
C11—C6—C61120.5 (3)
C5—S1—C2—N31.5 (2)N3—Cu1—O61—C6189.7 (2)
C5—S1—C2—N21179.8 (3)N3i—Cu1—O61—C6190.3 (2)
N21—C2—N3—N4179.9 (3)C11—C6—C7—C81.4 (5)
S1—C2—N3—N41.2 (3)C61—C6—C7—C8178.5 (3)
N21—C2—N3—Cu14.6 (5)C6—C7—C8—C90.6 (5)
S1—C2—N3—Cu1176.71 (14)C6—C7—C8—C81180.0 (3)
O61i—Cu1—N3—C252.2 (3)C9—C8—C81—O809.1 (5)
O61—Cu1—N3—C2127.8 (3)C7—C8—C81—O80170.2 (3)
O61i—Cu1—N3—N4123.2 (2)C9—C8—C81—O81171.6 (3)
O61—Cu1—N3—N456.8 (2)C7—C8—C81—O819.0 (4)
C2—N3—N4—C50.0 (4)C7—C8—C9—C101.7 (5)
Cu1—N3—N4—C5176.1 (2)C81—C8—C9—C10178.9 (3)
N3—N4—C5—C51178.7 (3)C8—C9—C10—C110.8 (5)
N3—N4—C5—S11.2 (3)C8—C9—C10—C101177.0 (3)
C2—S1—C5—N41.5 (2)C9—C10—C101—O100166.7 (3)
C2—S1—C5—C51178.4 (3)C11—C10—C101—O10011.0 (5)
C7—C6—C61—O6012.0 (4)C9—C10—C101—O10112.6 (5)
C11—C6—C61—O60171.0 (3)C11—C10—C101—O101169.7 (3)
C7—C6—C61—O61167.0 (3)C7—C6—C11—C102.4 (5)
C11—C6—C61—O6110.0 (4)C61—C6—C11—C10179.4 (3)
O60—C61—O61—Cu11.2 (4)C9—C10—C11—C61.4 (5)
C6—C61—O61—Cu1177.77 (19)C101—C10—C11—C6179.0 (3)
Symmetry code: (i) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21···O1Wii0.882.042.904 (5)168
N21—H22···O80iii0.882.132.949 (3)155
O81—H81···O60iv0.84 (2)1.75 (2)2.570 (3)167 (4)
O101—H101···O100v0.83 (2)1.81 (2)2.631 (3)169 (4)
O1W—H1W···O80vi0.83 (2)2.23 (3)2.993 (4)152 (5)
O1W—H2W···N4vii0.86 (2)2.30 (4)3.071 (4)150 (6)
Symmetry codes: (ii) x, y+1, z; (iii) x, y, z1; (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
Mr748.15
Crystal system, space groupTriclinic, 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)
V3)744.84 (7)
Z1
Radiation typeMo Kα
µ (mm1)0.95
Crystal size (mm)0.07 × 0.07 × 0.02
Data collection
DiffractometerBruker–Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.936, 0.981
No. of measured, independent and
observed [I > 2σ(I)] reflections
5879, 3222, 2353
Rint0.040
(sin θ/λ)max1)0.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.133, 1.06
No. of reflections3222
No. of parameters232
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
Cu1—N31.953 (3)Cu1—O611.971 (2)
N3—Cu1—O6190.40 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21···O1Wi0.882.042.904 (5)168
N21—H22···O80ii0.882.132.949 (3)155
O81—H81···O60iii0.84 (2)1.75 (2)2.570 (3)167 (4)
O101—H101···O100iv0.83 (2)1.81 (2)2.631 (3)169 (4)
O1W—H1W···O80v0.83 (2)2.23 (3)2.993 (4)152 (5)
O1W—H2W···N4vi0.86 (2)2.30 (4)3.071 (4)150 (6)
Symmetry codes: (i) x, y+1, z; (ii) x, y, z1; (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.
 

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