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The crystal structures of (2,6-dioxo-1,4,7,11,14-pentaazacycloheptadecanato)copper(II) tetrahydrate, [Cu(C12H23N5O2)]·4H2O, (I), (3,16-dioxo-1-oxa-4,8,11,15-tetraazacycloheptadecanato)copper(II) pentahydrate, [Cu(C12H22N4O3)]·5H2O, (II), and (3,16-dioxo-1-thia-4,8,11,15-tetraazacycloheptadecanato)copper(II) trihydrate, [Cu(C12H22N4O2S)]·3H2O, (III), are reported. The coordination geometry in each case is approximately square pyramidal with two amine groups and two deprotonated amide groups in the basal plane. The apical position is occupied by an amine group, an ether O atom or a thio S atom. Trigonal distortion increases in the sequence S < O < N as apical donor. The relation between the distortion in the basal plane of the complexes and the maxima in their electronic spectra is discussed.
Supporting information
CCDC references: 217134; 217135; 217136
The title complexes were obtained by mixing in water at room temperature equimolar amounts of Cu(ClO4)2·6H2O (444.6 mg, 1.20 mmol) and the ligands L1 (478.4 mg, 1.20 mmol), L2 (345.9 mg, 1.20 mmol) or L3 (455.8 mg, 1.20 mmol) in their hydrated hydrochloride form, and by adding a calculated amount of a concentrated aqueous 1.0 M KOH solution to bring the pH to 7. The solvent was then evaporated on a rotary evaporator and the solid residue taken up in ethanol. Diethyl ether was then added to the ethanol solution to precipitate most of the inorganic salts. The ethanol solution was then evaporated and the remaining solid dissolved in water. The aqueous solution was allowed to concentrate slowly. After about two weeks, crystals of the three complexes were obtained [yields: 203.6 mg (42%) for (I); 345.9 mg (68%) for (II); 300.6 mg (62%) for (III)]. Suitable crystals were selected for X-ray structure determination. Analysis found (calculated for C12H23CuN5O2·4H2O, %): C 35.3 (35.6), Cu 15.5 (15.7), N 16.9 (17.3); found (calculated for C12H22CuN4O3·5H2O, %): C 33.8 (34.0), Cu 14.8 (15.0), N 13.1 (13.2); found (calculated for C12H22CuN4O2S·3H2O, %): C 35.5 (35.6), Cu 15.7 (15.7), N 13.8 (13.9). The number of solvate water molecules in each complex was also determined from titrations of known amounts of complex in water with standardized hydrochloric acid, and is the nearest whole number value determined from the equivalence point in the titrations. IR spectra (KBr pellets): ν (cm−1) 3400–3200 (br), 1599 (s), 1585 (s), 1305 (s), 1100 (s) for (I); 3415 (br), 3168 (s), 3087 (s), 1599 (s), 1321 (s), 1112 (s) for (II); 3392 (br), 3226 (br), 1592 (s), 1565 (s), 1385 (s), 1041 (s) for (III). EPR (powders at room temperature) 34.00 GHz (Q-band): gparallel and gperpendicular, respectively, 2.2170 and 2.0442 for (I), 2.2098 and 2.0469 for (II), and 2.2034 and 2.0415 for (III).
The coordinates of the water H atoms in the three compounds were calculated by the program HYDROGEN (Nardelli, 1999) and introduced in the refinements keeping the O—H distances and the H—O—H angles constrained. All other H atoms were treated as riding, with C—H distances of 0.97Åand N—H distances in the range 0.85–0/90 Å. The structure of (III) has pseudosymmetry, with a mirror plane through atoms Cu, S and O3 for all atoms except C8A and C8B. The pseudo-symmetry resulted in high correlation factors and poor convergence on refinement in space group P21. Therefore, the structure was refined in the centrosymmetric space group P21/m with a disorder model for C8A/C8B. The structure of (III) was refined with three solvate water molecules in accord with the chemical analysis, although the occupancy of water atom O3 refined from the initial value of 0.5 to 0.385. The occupancy of the other O atom (O1) did not change from the initial value of 1 when it was refined, so it was fixed at 1.
Data collection: XSCANS (Siemens, 1996) for (I), (III); DIF4 (Stoe & Cie, 1992) for (II). Cell refinement: XSCANS for (I), (III); DIF4 for (II). Data reduction: REDUCE in XSCANS for (I), (III); REDU4 (Stoe & Cie, 1992) for (II). For all compounds, program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).
(I) (2,6-dioxo-1,4,7,11,14-pentaazacycloheptadecanato)copper(II) tetrahydrate
top
Crystal data top
[Cu(C12H23N5O2)]·4H2O | F(000) = 860 |
Mr = 404.96 | Dx = 1.44 Mg m−3 |
Orthorhombic, Pna21 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2c -2n | Cell parameters from 41 reflections |
a = 13.3375 (5) Å | θ = 10.9–27.7° |
b = 8.9992 (3) Å | µ = 1.98 mm−1 |
c = 15.5637 (4) Å | T = 293 K |
V = 1868.06 (11) Å3 | Tablet, dark blue |
Z = 4 | 0.48 × 0.4 × 0.11 mm |
Data collection top
Siemens P4 four-circle diffractometer | Rint = 0.033 |
ω/2θ scans | θmax = 69.1° |
Absorption correction: ψ scan (XEMP; Siemens, 1989) | h = −1→16 |
Tmin = 0.400, Tmax = 0.804 | k = −1→10 |
2267 measured reflections | l = −16→1 |
1856 independent reflections | 3 standard reflections every 100 reflections |
1824 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0764P)2 + 0.2709P] where P = (Fo2 + 2Fc2)/3 |
Least-squares matrix: full | (Δ/σ)max < 0.001 |
R[F2 > 2σ(F2)] = 0.040 | Δρmax = 0.67 e Å−3 |
wR(F2) = 0.104 | Δρmin = −0.54 e Å−3 |
S = 1.11 | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1856 reflections | Extinction coefficient: 0.0062 (5) |
218 parameters | Absolute structure: Flack (1983), 138 Friedel pairs |
H-atom parameters constrained | Absolute structure parameter: 0.03 (4) |
Crystal data top
[Cu(C12H23N5O2)]·4H2O | V = 1868.06 (11) Å3 |
Mr = 404.96 | Z = 4 |
Orthorhombic, Pna21 | Cu Kα radiation |
a = 13.3375 (5) Å | µ = 1.98 mm−1 |
b = 8.9992 (3) Å | T = 293 K |
c = 15.5637 (4) Å | 0.48 × 0.4 × 0.11 mm |
Data collection top
Siemens P4 four-circle diffractometer | 1824 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XEMP; Siemens, 1989) | Rint = 0.033 |
Tmin = 0.400, Tmax = 0.804 | 3 standard reflections every 100 reflections |
2267 measured reflections | intensity decay: 3% |
1856 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.104 | Δρmax = 0.67 e Å−3 |
S = 1.11 | Δρmin = −0.54 e Å−3 |
1856 reflections | Absolute structure: Flack (1983), 138 Friedel pairs |
218 parameters | Absolute structure parameter: 0.03 (4) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu | 0.22964 (3) | −0.09467 (5) | 0.14705 (5) | 0.0348 (2) | |
N | 0.2048 (2) | 0.0652 (4) | 0.2588 (2) | 0.0408 (7) | |
H | 0.2604 | 0.1035 | 0.2829 | 0.053* | |
C11 | 0.1463 (3) | 0.1861 (4) | 0.2221 (3) | 0.0468 (9) | |
H11A | 0.1914 | 0.2645 | 0.2037 | 0.061* | |
H11B | 0.1026 | 0.2267 | 0.266 | 0.061* | |
C21 | 0.0829 (2) | 0.1358 (4) | 0.1455 (3) | 0.0410 (7) | |
O21 | 0.0119 (2) | 0.2256 (3) | 0.1236 (2) | 0.0559 (9) | |
N31 | 0.1088 (2) | 0.0142 (3) | 0.1083 (2) | 0.0392 (6) | |
C41 | 0.0631 (3) | −0.0270 (5) | 0.0262 (3) | 0.0455 (9) | |
H41A | 0.002 | 0.0298 | 0.0183 | 0.059* | |
H41B | 0.0451 | −0.1315 | 0.0278 | 0.059* | |
C51 | 0.1319 (4) | 0.0001 (6) | −0.0493 (4) | 0.0585 (12) | |
H51A | 0.1468 | 0.1055 | −0.0525 | 0.076* | |
H51B | 0.0972 | −0.0274 | −0.1017 | 0.076* | |
C61 | 0.2300 (3) | −0.0857 (6) | −0.0444 (4) | 0.0547 (14) | |
H61A | 0.2149 | −0.191 | −0.0419 | 0.071* | |
H61B | 0.2677 | −0.0678 | −0.0967 | 0.071* | |
N71 | 0.2934 (2) | −0.0462 (4) | 0.0302 (2) | 0.0433 (7) | |
H71 | 0.2958 | 0.0493 | 0.0306 | 0.056* | |
C81 | 0.3943 (3) | −0.1133 (5) | 0.0261 (3) | 0.0502 (10) | |
H81A | 0.437 | −0.0559 | −0.0119 | 0.065* | |
H81B | 0.39 | −0.2139 | 0.004 | 0.065* | |
C12 | 0.1506 (4) | −0.0215 (6) | 0.3244 (3) | 0.0604 (13) | |
H12A | 0.083 | 0.0175 | 0.329 | 0.079* | |
H12B | 0.1832 | −0.006 | 0.3794 | 0.079* | |
C22 | 0.1441 (3) | −0.1845 (5) | 0.3084 (3) | 0.0459 (9) | |
O22 | 0.1164 (3) | −0.2661 (4) | 0.3714 (2) | 0.0609 (8) | |
N32 | 0.1691 (2) | −0.2332 (3) | 0.2326 (2) | 0.0402 (7) | |
C42 | 0.1870 (4) | −0.3922 (4) | 0.2214 (4) | 0.0483 (10) | |
H42A | 0.1656 | −0.4227 | 0.1645 | 0.063* | |
H42B | 0.1485 | −0.4478 | 0.2634 | 0.063* | |
C52 | 0.2974 (4) | −0.4245 (5) | 0.2327 (4) | 0.0568 (12) | |
H52A | 0.3172 | −0.3932 | 0.2899 | 0.074* | |
H52B | 0.3073 | −0.5311 | 0.2293 | 0.074* | |
C62 | 0.3659 (3) | −0.3509 (5) | 0.1684 (3) | 0.0528 (11) | |
H62A | 0.4338 | −0.3863 | 0.1775 | 0.069* | |
H62B | 0.3457 | −0.3801 | 0.111 | 0.069* | |
N72 | 0.3653 (2) | −0.1860 (4) | 0.1741 (2) | 0.0410 (7) | |
H72 | 0.3829 | −0.1572 | 0.2252 | 0.053* | |
C82 | 0.4380 (3) | −0.1147 (5) | 0.1158 (3) | 0.0482 (10) | |
H82A | 0.5006 | −0.1694 | 0.1162 | 0.063* | |
H82B | 0.4513 | −0.0139 | 0.1346 | 0.063* | |
O1 | 0.4064 (3) | −0.7935 (4) | 0.2825 (3) | 0.0717 (10) | |
H1A | 0.4323 | −0.8698 | 0.3068 | 0.093* | |
H1B | 0.4364 | −0.7812 | 0.2351 | 0.093* | |
O2 | 0.1407 (3) | −0.5830 (4) | 0.0157 (3) | 0.0700 (10) | |
H2A | 0.0998 | −0.6307 | 0.0469 | 0.091* | |
H2B | 0.1998 | −0.6047 | 0.0321 | 0.091* | |
O3 | 0.4414 (3) | −0.0813 (4) | 0.3484 (3) | 0.0644 (9) | |
H3A | 0.4097 | −0.0926 | 0.3952 | 0.084* | |
H3B | 0.4978 | −0.124 | 0.3534 | 0.084* | |
O4 | 0.3324 (2) | −0.7155 (4) | 0.0343 (2) | 0.0571 (8) | |
H4A | 0.3847 | −0.729 | 0.064 | 0.074* | |
H4B | 0.3478 | −0.7268 | −0.0183 | 0.074* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.0331 (3) | 0.0395 (3) | 0.0317 (4) | 0.00230 (15) | 0.0027 (2) | 0.0025 (2) |
N | 0.0366 (13) | 0.0457 (15) | 0.040 (2) | 0.0019 (13) | −0.0033 (15) | −0.0007 (15) |
C11 | 0.0479 (18) | 0.0421 (17) | 0.050 (3) | 0.0057 (15) | −0.0090 (19) | −0.0082 (18) |
C21 | 0.0381 (13) | 0.0446 (15) | 0.040 (2) | 0.0031 (13) | −0.0053 (18) | 0.005 (2) |
O21 | 0.0518 (14) | 0.0561 (14) | 0.060 (2) | 0.0189 (12) | −0.0104 (14) | −0.0032 (14) |
N31 | 0.0380 (14) | 0.0438 (15) | 0.0357 (16) | 0.0013 (11) | 0.0003 (13) | 0.0012 (13) |
C41 | 0.0402 (16) | 0.058 (2) | 0.038 (2) | 0.0000 (15) | −0.0048 (16) | −0.0022 (17) |
C51 | 0.061 (2) | 0.064 (3) | 0.050 (3) | −0.002 (2) | −0.003 (2) | 0.008 (2) |
C61 | 0.054 (3) | 0.079 (4) | 0.032 (3) | 0.0070 (19) | 0.0056 (18) | 0.000 (2) |
N71 | 0.0410 (14) | 0.0497 (16) | 0.039 (2) | 0.0001 (14) | 0.0040 (14) | 0.0050 (15) |
C81 | 0.0429 (19) | 0.063 (2) | 0.045 (3) | 0.0017 (16) | 0.0108 (19) | 0.0039 (18) |
C12 | 0.081 (3) | 0.062 (3) | 0.038 (3) | 0.006 (2) | 0.017 (2) | −0.001 (2) |
C22 | 0.0409 (17) | 0.062 (2) | 0.035 (2) | −0.0047 (16) | 0.0018 (16) | 0.0072 (18) |
O22 | 0.073 (2) | 0.0697 (19) | 0.0403 (19) | −0.0183 (15) | 0.0076 (15) | 0.0083 (15) |
N32 | 0.0441 (14) | 0.0411 (15) | 0.0354 (19) | −0.0023 (12) | 0.0028 (13) | 0.0023 (13) |
C42 | 0.055 (2) | 0.043 (2) | 0.047 (3) | −0.0042 (14) | 0.004 (2) | 0.0047 (17) |
C52 | 0.064 (3) | 0.045 (2) | 0.062 (3) | 0.0079 (19) | −0.004 (3) | 0.009 (2) |
C62 | 0.0507 (18) | 0.0475 (19) | 0.060 (3) | 0.0114 (16) | 0.0058 (19) | 0.0029 (18) |
N72 | 0.0371 (12) | 0.0475 (15) | 0.038 (2) | 0.0047 (11) | −0.0004 (12) | −0.0005 (12) |
C82 | 0.0351 (16) | 0.0542 (19) | 0.055 (3) | −0.0018 (14) | 0.0073 (17) | −0.0010 (17) |
O1 | 0.0587 (18) | 0.076 (2) | 0.081 (3) | −0.0044 (16) | 0.0066 (19) | 0.005 (2) |
O2 | 0.069 (2) | 0.083 (2) | 0.058 (3) | 0.0073 (16) | −0.0065 (19) | 0.0093 (18) |
O3 | 0.0587 (18) | 0.086 (2) | 0.048 (2) | 0.0074 (16) | −0.0013 (17) | 0.0025 (17) |
O4 | 0.0480 (15) | 0.079 (2) | 0.0445 (19) | −0.0051 (14) | −0.0038 (14) | 0.0018 (15) |
Geometric parameters (Å, º) top
Cu—N31 | 1.980 (3) | C12—C22 | 1.491 (8) |
Cu—N32 | 1.995 (3) | C12—H12A | 0.97 |
Cu—N72 | 2.032 (3) | C12—H12B | 0.97 |
Cu—N71 | 2.055 (4) | C22—O22 | 1.279 (5) |
Cu—N | 2.281 (4) | C22—N32 | 1.301 (6) |
N—C11 | 1.456 (5) | N32—C42 | 1.461 (5) |
N—C12 | 1.475 (6) | C42—C52 | 1.511 (7) |
N—H | 0.9 | C42—H42A | 0.97 |
C11—C21 | 1.530 (6) | C42—H42B | 0.97 |
C11—H11A | 0.97 | C52—C62 | 1.509 (7) |
C11—H11B | 0.97 | C52—H52A | 0.97 |
C21—N31 | 1.285 (5) | C52—H52B | 0.97 |
C21—O21 | 1.291 (4) | C62—N72 | 1.487 (5) |
N31—C41 | 1.463 (5) | C62—H62A | 0.97 |
C41—C51 | 1.511 (7) | C62—H62B | 0.97 |
C41—H41A | 0.97 | N72—C82 | 1.474 (5) |
C41—H41B | 0.97 | N72—H72 | 0.8684 |
C51—C61 | 1.521 (7) | C82—H82A | 0.97 |
C51—H51A | 0.97 | C82—H82B | 0.97 |
C51—H51B | 0.97 | O1—H1A | 0.8559 |
C61—N71 | 1.480 (7) | O1—H1B | 0.8469 |
C61—H61A | 0.97 | O2—H2A | 0.8468 |
C61—H61B | 0.97 | O2—H2B | 0.8509 |
N71—C81 | 1.477 (5) | O3—H3A | 0.8485 |
N71—H71 | 0.8602 | O3—H3B | 0.8491 |
C81—C82 | 1.513 (7) | O4—H4A | 0.8463 |
C81—H81A | 0.97 | O4—H4B | 0.8498 |
C81—H81B | 0.97 | | |
| | | |
N31—Cu—N32 | 100.6 (1) | N71—C81—C82 | 108.3 (4) |
N31—Cu—N72 | 171.2 (1) | N71—C81—H81A | 110 |
N32—Cu—N72 | 88.2 (1) | C82—C81—H81A | 110 |
N31—Cu—N71 | 87.8 (1) | N71—C81—H81B | 110 |
N32—Cu—N71 | 153.0 (1) | C82—C81—H81B | 110 |
N72—Cu—N71 | 84.3 (1) | H81A—C81—H81B | 108.4 |
N31—Cu—N | 78.6 (1) | N—C12—C22 | 115.7 (4) |
N32—Cu—N | 80.0 (1) | N—C12—H12A | 108.4 |
N72—Cu—N | 103.1 (1) | C22—C12—H12A | 108.4 |
N71—Cu—N | 126.9 (1) | N—C12—H12B | 108.4 |
C11—N—C12 | 113.8 (4) | C22—C12—H12B | 108.4 |
C11—N—Cu | 104.5 (3) | H12A—C12—H12B | 107.4 |
C12—N—Cu | 105.4 (3) | O22—C22—N32 | 125.2 (4) |
C11—N—H | 108.6 | O22—C22—C12 | 116.9 (4) |
C12—N—H | 108.5 | N32—C22—C12 | 117.9 (4) |
Cu—N—H | 116.1 | C22—N32—C42 | 118.6 (4) |
N—C11—C21 | 112.4 (3) | C22—N32—Cu | 119.9 (3) |
N—C11—H11A | 109.1 | C42—N32—Cu | 117.8 (3) |
C21—C11—H11A | 109.1 | N32—C42—C52 | 109.5 (4) |
N—C11—H11B | 109.1 | N32—C42—H42A | 109.8 |
C21—C11—H11B | 109.1 | C52—C42—H42A | 109.8 |
H11A—C11—H11B | 107.9 | N32—C42—H42B | 109.8 |
N31—C21—O21 | 127.7 (4) | C52—C42—H42B | 109.8 |
N31—C21—C11 | 117.1 (3) | H42A—C42—H42B | 108.2 |
O21—C21—C11 | 115.2 (3) | C62—C52—C42 | 115.4 (4) |
C21—N31—C41 | 119.8 (3) | C62—C52—H52A | 108.4 |
C21—N31—Cu | 120.1 (3) | C42—C52—H52A | 108.4 |
C41—N31—Cu | 118.6 (3) | C62—C52—H52B | 108.4 |
N31—C41—C51 | 112.7 (3) | C42—C52—H52B | 108.4 |
N31—C41—H41A | 109.1 | H52A—C52—H52B | 107.5 |
C51—C41—H41A | 109.1 | N72—C62—C52 | 113.3 (4) |
N31—C41—H41B | 109.1 | N72—C62—H62A | 108.9 |
C51—C41—H41B | 109.1 | C52—C62—H62A | 108.9 |
H41A—C41—H41B | 107.8 | N72—C62—H62B | 108.9 |
C41—C51—C61 | 113.7 (4) | C52—C62—H62B | 108.9 |
C41—C51—H51A | 108.8 | H62A—C62—H62B | 107.7 |
C61—C51—H51A | 108.8 | C82—N72—C62 | 113.2 (3) |
C41—C51—H51B | 108.8 | C82—N72—Cu | 106.4 (2) |
C61—C51—H51B | 108.8 | C62—N72—Cu | 113.3 (2) |
H51A—C51—H51B | 107.7 | C82—N72—H72 | 104.9 |
N71—C61—C51 | 114.1 (4) | C62—N72—H72 | 110.5 |
N71—C61—H61A | 108.7 | Cu—N72—H72 | 108 |
C51—C61—H61A | 108.7 | N72—C82—C81 | 108.6 (3) |
N71—C61—H61B | 108.7 | N72—C82—H82A | 110 |
C51—C61—H61B | 108.7 | C81—C82—H82A | 110 |
H61A—C61—H61B | 107.6 | N72—C82—H82B | 110 |
C81—N71—C61 | 112.9 (4) | C81—C82—H82B | 110 |
C81—N71—Cu | 109.2 (3) | H82A—C82—H82B | 108.3 |
C61—N71—Cu | 114.0 (3) | H1A—O1—H1B | 107.4 |
C81—N71—H71 | 112 | H2A—O2—H2B | 107.9 |
C61—N71—H71 | 105.5 | H3A—O3—H3B | 107.9 |
Cu—N71—H71 | 102.7 | H4A—O4—H4B | 108.1 |
| | | |
N31—Cu—N—C11 | −22.6 (3) | N—Cu—N71—C61 | −125.3 (3) |
N32—Cu—N—C11 | −125.7 (3) | C61—N71—C81—C82 | −159.6 (4) |
N72—Cu—N—C11 | 148.5 (3) | Cu—N71—C81—C82 | −31.7 (4) |
N71—Cu—N—C11 | 55.8 (3) | C11—N—C12—C22 | 124.3 (4) |
N31—Cu—N—C12 | 97.7 (3) | Cu—N—C12—C22 | 10.3 (5) |
N32—Cu—N—C12 | −5.4 (3) | N—C12—C22—O22 | 166.1 (4) |
N72—Cu—N—C12 | −91.2 (3) | N—C12—C22—N32 | −12.4 (6) |
N71—Cu—N—C12 | 176.1 (3) | O22—C22—N32—C42 | −13.1 (6) |
C12—N—C11—C21 | −87.2 (5) | C12—C22—N32—C42 | 165.3 (4) |
Cu—N—C11—C21 | 27.3 (4) | O22—C22—N32—Cu | −171.1 (3) |
N—C11—C21—N31 | −19.4 (5) | C12—C22—N32—Cu | 7.3 (5) |
N—C11—C21—O21 | 163.6 (4) | N31—Cu—N32—C22 | −77.1 (3) |
O21—C21—N31—C41 | 7.2 (6) | N72—Cu—N32—C22 | 102.8 (3) |
C11—C21—N31—C41 | −169.3 (3) | N71—Cu—N32—C22 | 176.6 (3) |
O21—C21—N31—Cu | 173.7 (3) | N—Cu—N32—C22 | −0.8 (3) |
C11—C21—N31—Cu | −2.8 (5) | N31—Cu—N32—C42 | 124.7 (3) |
N32—Cu—N31—C21 | 92.1 (3) | N72—Cu—N32—C42 | −55.4 (3) |
N71—Cu—N31—C21 | −113.7 (3) | N71—Cu—N32—C42 | 18.4 (5) |
N—Cu—N31—C21 | 14.7 (3) | N—Cu—N32—C42 | −159.0 (3) |
N32—Cu—N31—C41 | −101.3 (3) | C22—N32—C42—C52 | −93.4 (5) |
N71—Cu—N31—C41 | 52.9 (3) | Cu—N32—C42—C52 | 65.1 (5) |
N—Cu—N31—C41 | −178.7 (3) | N32—C42—C52—C62 | −62.4 (6) |
C21—N31—C41—C51 | 103.3 (4) | C42—C52—C62—N72 | 64.3 (6) |
Cu—N31—C41—C51 | −63.4 (4) | C52—C62—N72—C82 | 175.6 (4) |
N31—C41—C51—C61 | 59.6 (5) | C52—C62—N72—Cu | −63.1 (5) |
C41—C51—C61—N71 | −62.3 (6) | N32—Cu—N72—C82 | 176.7 (3) |
C51—C61—N71—C81 | −171.0 (4) | N71—Cu—N72—C82 | 22.6 (3) |
C51—C61—N71—Cu | 63.6 (5) | N—Cu—N72—C82 | −104.0 (3) |
N31—Cu—N71—C81 | −178.7 (3) | N32—Cu—N72—C62 | 51.7 (3) |
N32—Cu—N71—C81 | −69.4 (4) | N71—Cu—N72—C62 | −102.4 (3) |
N72—Cu—N71—C81 | 5.3 (3) | N—Cu—N72—C62 | 131.0 (3) |
N—Cu—N71—C81 | 107.4 (3) | C62—N72—C82—C81 | 78.7 (4) |
N31—Cu—N71—C61 | −51.3 (3) | Cu—N72—C82—C81 | −46.4 (4) |
N32—Cu—N71—C61 | 57.9 (4) | N71—C81—C82—N72 | 52.5 (4) |
N72—Cu—N71—C61 | 132.6 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H···O1i | 0.90 | 2.16 | 2.997 (6) | 155 |
O1—H1A···O3ii | 0.85 | 2.01 | 2.825 (5) | 157 |
O1—H1B···O21iii | 0.85 | 2.07 | 2.910 (5) | 173 |
O2—H2A···O21ii | 0.85 | 2.12 | 2.955 (5) | 172 |
O2—H2B···O4 | 0.85 | 2.03 | 2.835 (5) | 158 |
O3—H3A···O2iv | 0.85 | 1.99 | 2.825 (6) | 166 |
O3—H3B···O22iii | 0.85 | 1.89 | 2.732 (6) | 174 |
O4—H4A···O21iii | 0.85 | 1.93 | 2.770 (4) | 170 |
O4—H4B···O22v | 0.85 | 1.82 | 2.665 (4) | 176 |
N71—H71···O4i | 0.86 | 2.17 | 3.023 (5) | 169 |
N72—H72···O3 | 0.87 | 2.18 | 3.045 (5) | 174 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) x+1/2, −y−1/2, z; (iv) −x+1/2, y+1/2, z+1/2; (v) −x+1/2, y−1/2, z−1/2. |
(II) (3,16-dioxo-1-oxa-4,8,11,15-tetraazacycloheptadecanato)copper(II) pentahydrate
top
Crystal data top
[Cu(C12H22N4O3)]·5H2O | F(000) = 900 |
Mr = 423.96 | Dx = 1.448 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 25 reflections |
a = 12.098 (9) Å | θ = 20–25° |
b = 20.337 (14) Å | µ = 1.17 mm−1 |
c = 8.134 (5) Å | T = 293 K |
β = 103.68 (5)° | Prism, blue |
V = 1944 (2) Å3 | 0.43 × 0.29 × 0.29 mm |
Z = 4 | |
Data collection top
Stoe Stadi-4 four-circle diffractometer | Rint = 0.033 |
ω scans | θmax = 27.5° |
Absorption correction: ψ scan (EMPIR; Stoe & Cie, 1989) | h = −15→15 |
Tmin = 0.670, Tmax = 0.710 | k = −26→2 |
3348 measured reflections | l = −2→10 |
3020 independent reflections | 3 standard reflections every 60 min |
2510 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0565P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.043 | (Δ/σ)max < 0.001 |
wR(F2) = 0.101 | Δρmax = 0.47 e Å−3 |
S = 1.04 | Δρmin = −0.60 e Å−3 |
3020 reflections | Absolute structure: Flack (1983), 773 Friedel pairs |
226 parameters | Absolute structure parameter: −0.005 (18) |
Crystal data top
[Cu(C12H22N4O3)]·5H2O | V = 1944 (2) Å3 |
Mr = 423.96 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 12.098 (9) Å | µ = 1.17 mm−1 |
b = 20.337 (14) Å | T = 293 K |
c = 8.134 (5) Å | 0.43 × 0.29 × 0.29 mm |
β = 103.68 (5)° | |
Data collection top
Stoe Stadi-4 four-circle diffractometer | 2510 reflections with I > 2σ(I) |
Absorption correction: ψ scan (EMPIR; Stoe & Cie, 1989) | Rint = 0.033 |
Tmin = 0.670, Tmax = 0.710 | 3 standard reflections every 60 min |
3348 measured reflections | intensity decay: 3% |
3020 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.101 | Δρmax = 0.47 e Å−3 |
S = 1.04 | Δρmin = −0.60 e Å−3 |
3020 reflections | Absolute structure: Flack (1983), 773 Friedel pairs |
226 parameters | Absolute structure parameter: −0.005 (18) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu | 0.24173 (4) | 0.12333 (2) | 0.08756 (6) | 0.02720 (14) | |
O | 0.3412 (3) | 0.02130 (18) | 0.1808 (5) | 0.0320 (9) | |
O21 | 0.0866 (3) | −0.05303 (17) | −0.0726 (5) | 0.0430 (9) | |
O22 | 0.5514 (3) | 0.08538 (19) | −0.0261 (5) | 0.0435 (9) | |
N31 | 0.1432 (3) | 0.0556 (2) | −0.0433 (6) | 0.0326 (10) | |
N32 | 0.3700 (3) | 0.1218 (2) | −0.0263 (6) | 0.0308 (10) | |
N71 | 0.1095 (3) | 0.1525 (2) | 0.1895 (6) | 0.0322 (11) | |
H71 | 0.1061 | 0.1187 | 0.2603 | 0.042* | |
N72 | 0.3259 (3) | 0.1978 (2) | 0.2267 (6) | 0.0335 (10) | |
H72 | 0.3999 | 0.1895 | 0.2792 | 0.043* | |
C11 | 0.2673 (3) | −0.0297 (2) | 0.0998 (9) | 0.0357 (13) | |
H11A | 0.2499 | −0.058 | 0.1863 | 0.046* | |
H11B | 0.3075 | −0.056 | 0.0332 | 0.046* | |
C12 | 0.4473 (4) | 0.0255 (3) | 0.1337 (8) | 0.0404 (13) | |
H12A | 0.4599 | −0.0153 | 0.0791 | 0.053* | |
H12B | 0.5077 | 0.0299 | 0.2355 | 0.053* | |
C21 | 0.1570 (4) | −0.0066 (3) | −0.0138 (7) | 0.0333 (12) | |
C22 | 0.4557 (4) | 0.0819 (2) | 0.0165 (7) | 0.0320 (11) | |
C41 | 0.0316 (4) | 0.0780 (3) | −0.1452 (8) | 0.0425 (13) | |
H41A | −0.0047 | 0.0426 | −0.218 | 0.055* | |
H41B | 0.0428 | 0.1145 | −0.2165 | 0.055* | |
C42 | 0.3817 (5) | 0.1828 (3) | −0.1186 (8) | 0.0447 (14) | |
H42A | 0.3107 | 0.1918 | −0.1999 | 0.058* | |
H42B | 0.4403 | 0.1769 | −0.1806 | 0.058* | |
C51 | −0.0440 (4) | 0.0995 (3) | −0.0321 (9) | 0.0447 (14) | |
H51A | −0.1198 | 0.1075 | −0.1012 | 0.058* | |
H51B | −0.0493 | 0.0639 | 0.0451 | 0.058* | |
C52 | 0.4123 (4) | 0.2410 (3) | 0.0001 (8) | 0.0443 (14) | |
H52A | 0.488 | 0.2341 | 0.0707 | 0.058* | |
H52B | 0.4149 | 0.2801 | −0.0671 | 0.058* | |
C61 | −0.0029 (4) | 0.1605 (3) | 0.0696 (8) | 0.0426 (15) | |
H61A | 0.0018 | 0.1961 | −0.0076 | 0.055* | |
H61B | −0.0585 | 0.1728 | 0.1327 | 0.055* | |
C62 | 0.3320 (4) | 0.2536 (3) | 0.1134 (8) | 0.0411 (13) | |
H62A | 0.3569 | 0.2925 | 0.1811 | 0.053* | |
H62B | 0.2566 | 0.2623 | 0.0437 | 0.053* | |
C81 | 0.1419 (4) | 0.2129 (3) | 0.2908 (8) | 0.0398 (13) | |
H81A | 0.102 | 0.2146 | 0.381 | 0.052* | |
H81B | 0.1204 | 0.2513 | 0.2195 | 0.052* | |
C82 | 0.2671 (4) | 0.2136 (3) | 0.3644 (8) | 0.0430 (13) | |
H82A | 0.2907 | 0.2565 | 0.4117 | 0.056* | |
H82B | 0.2869 | 0.1812 | 0.4542 | 0.056* | |
O1 | 0.8552 (3) | 0.0677 (2) | 0.3716 (6) | 0.0563 (11) | |
H1A | 0.9262 | 0.0626 | 0.3814 | 0.073* | |
H1B | 0.8372 | 0.0466 | 0.4515 | 0.073* | |
O2 | 0.6466 (4) | 0.1167 (2) | −0.2930 (7) | 0.0608 (12) | |
H2A | 0.6173 | 0.1071 | −0.2109 | 0.079* | |
H2B | 0.6999 | 0.142 | −0.2563 | 0.079* | |
O3 | 0.7114 (4) | 0.1691 (2) | 0.1932 (7) | 0.0639 (13) | |
H3A | 0.6799 | 0.1404 | 0.1216 | 0.083* | |
H3B | 0.7746 | 0.1535 | 0.248 | 0.083* | |
O4 | 0.7347 (4) | −0.00322 (18) | 0.0895 (8) | 0.0519 (9) | |
H4A | 0.6782 | 0.0218 | 0.051 | 0.067* | |
H4B | 0.7126 | −0.0332 | 0.1472 | 0.067* | |
O5 | 0.5540 (4) | 0.1749 (3) | 0.4042 (7) | 0.0805 (17) | |
H5A | 0.606 | 0.1797 | 0.3509 | 0.105* | |
H5B | 0.5745 | 0.1441 | 0.4757 | 0.105* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.01878 (19) | 0.0313 (2) | 0.0324 (3) | −0.0002 (3) | 0.00789 (18) | 0.0005 (4) |
O | 0.0256 (16) | 0.038 (2) | 0.033 (2) | −0.0002 (16) | 0.0079 (16) | −0.0032 (19) |
O21 | 0.0336 (18) | 0.0419 (18) | 0.054 (3) | −0.0096 (15) | 0.0123 (19) | −0.017 (2) |
O22 | 0.0217 (15) | 0.062 (2) | 0.050 (2) | 0.0011 (16) | 0.0153 (17) | 0.001 (2) |
N31 | 0.0218 (18) | 0.040 (2) | 0.035 (3) | −0.0014 (17) | 0.0042 (19) | 0.001 (2) |
N32 | 0.0242 (19) | 0.040 (2) | 0.029 (2) | 0.0014 (18) | 0.0082 (18) | 0.004 (2) |
N71 | 0.025 (2) | 0.034 (2) | 0.041 (3) | 0.0031 (18) | 0.015 (2) | 0.006 (2) |
N72 | 0.0217 (17) | 0.037 (2) | 0.041 (3) | −0.0008 (16) | 0.0077 (19) | −0.006 (2) |
C11 | 0.025 (3) | 0.033 (2) | 0.050 (3) | 0.0013 (17) | 0.011 (3) | 0.002 (3) |
C12 | 0.022 (2) | 0.047 (3) | 0.053 (4) | 0.003 (2) | 0.011 (2) | 0.007 (3) |
C21 | 0.028 (2) | 0.041 (3) | 0.033 (3) | −0.005 (2) | 0.011 (2) | −0.007 (3) |
C22 | 0.027 (2) | 0.040 (3) | 0.030 (3) | −0.004 (2) | 0.007 (2) | −0.008 (2) |
C41 | 0.028 (2) | 0.047 (3) | 0.048 (4) | 0.000 (2) | 0.000 (3) | 0.004 (3) |
C42 | 0.037 (3) | 0.061 (4) | 0.040 (3) | 0.007 (3) | 0.017 (3) | 0.015 (3) |
C51 | 0.021 (2) | 0.052 (3) | 0.059 (4) | 0.001 (2) | 0.005 (3) | 0.005 (3) |
C52 | 0.034 (3) | 0.045 (3) | 0.057 (4) | 0.003 (2) | 0.016 (3) | 0.018 (3) |
C61 | 0.021 (2) | 0.044 (3) | 0.063 (4) | 0.0071 (19) | 0.011 (3) | 0.010 (3) |
C62 | 0.031 (3) | 0.035 (3) | 0.057 (4) | 0.001 (2) | 0.010 (3) | 0.002 (3) |
C81 | 0.035 (3) | 0.041 (3) | 0.051 (4) | 0.001 (2) | 0.024 (3) | −0.007 (3) |
C82 | 0.037 (3) | 0.054 (3) | 0.041 (3) | 0.000 (2) | 0.014 (3) | −0.008 (3) |
O1 | 0.0366 (19) | 0.075 (3) | 0.057 (3) | 0.008 (2) | 0.010 (2) | 0.015 (3) |
O2 | 0.068 (3) | 0.057 (2) | 0.065 (3) | −0.001 (2) | 0.032 (3) | 0.011 (2) |
O3 | 0.052 (2) | 0.065 (3) | 0.071 (3) | 0.004 (2) | 0.008 (2) | −0.008 (3) |
O4 | 0.0431 (18) | 0.0522 (18) | 0.066 (2) | 0.001 (3) | 0.0237 (18) | 0.009 (3) |
O5 | 0.041 (2) | 0.140 (5) | 0.056 (3) | 0.028 (3) | 0.003 (2) | 0.002 (3) |
Geometric parameters (Å, º) top
Cu—N31 | 1.963 (4) | C42—C52 | 1.517 (9) |
Cu—N32 | 1.987 (4) | C42—H42A | 0.97 |
Cu—N72 | 2.017 (4) | C42—H42B | 0.97 |
Cu—N71 | 2.056 (4) | C51—C61 | 1.509 (8) |
Cu—O | 2.428 (4) | C51—H51A | 0.97 |
O—C11 | 1.425 (6) | C51—H51B | 0.97 |
O—C12 | 1.427 (6) | C52—C62 | 1.510 (8) |
O21—C21 | 1.286 (6) | C52—H52A | 0.97 |
O22—C22 | 1.286 (6) | C52—H52B | 0.97 |
N31—C21 | 1.291 (7) | C61—H61A | 0.97 |
N31—C41 | 1.479 (6) | C61—H61B | 0.97 |
N32—C22 | 1.298 (6) | C62—H62A | 0.97 |
N32—C42 | 1.474 (7) | C62—H62B | 0.97 |
N71—C81 | 1.480 (7) | C81—C82 | 1.491 (7) |
N71—C61 | 1.483 (7) | C81—H81A | 0.97 |
N71—H71 | 0.90 | C81—H81B | 0.97 |
N72—C62 | 1.474 (7) | C82—H82A | 0.97 |
N72—C82 | 1.496 (7) | C82—H82B | 0.97 |
N72—H72 | 0.9123 | O1—H1A | 0.85 |
C11—C21 | 1.507 (7) | O1—H1B | 0.85 |
C11—H11A | 0.97 | O2—H2A | 0.85 |
C11—H11B | 0.97 | O2—H2B | 0.82 |
C12—C22 | 1.510 (8) | O3—H3A | 0.85 |
C12—H12A | 0.97 | O3—H3B | 0.85 |
C12—H12B | 0.97 | O4—H4A | 0.85 |
C41—C51 | 1.507 (8) | O4—H4B | 0.85 |
C41—H41A | 0.97 | O5—H5A | 0.85 |
C41—H41B | 0.97 | O5—H5B | 0.85 |
| | | |
N31—Cu—N32 | 100.2 (2) | C51—C41—H41A | 109.5 |
N31—Cu—N72 | 173.2 (2) | N31—C41—H41B | 109.5 |
N32—Cu—N72 | 85.8 (2) | C51—C41—H41B | 109.5 |
N31—Cu—N71 | 89.4 (2) | H41A—C41—H41B | 108.1 |
N32—Cu—N71 | 163.9 (2) | N32—C42—C52 | 111.8 (5) |
N72—Cu—N71 | 84.0 (2) | N32—C42—H42A | 109.3 |
N31—Cu—O | 76.2 (2) | C52—C42—H42A | 109.3 |
N32—Cu—O | 75.4 (2) | N32—C42—H42B | 109.3 |
N72—Cu—O | 108.6 (2) | C52—C42—H42B | 109.3 |
N71—Cu—O | 119.7 (2) | H42A—C42—H42B | 107.9 |
C11—O—C12 | 115.2 (4) | C61—C51—C41 | 113.8 (4) |
C11—O—Cu | 105.5 (3) | C61—C51—H51A | 108.8 |
C12—O—Cu | 106.0 (3) | C41—C51—H51A | 108.8 |
C21—N31—C41 | 117.9 (4) | C61—C51—H51B | 108.8 |
C21—N31—Cu | 123.5 (4) | C41—C51—H51B | 108.8 |
C41—N31—Cu | 116.3 (3) | H51A—C51—H51B | 107.7 |
C22—N32—C42 | 119.8 (4) | C62—C52—C42 | 115.2 (4) |
C22—N32—Cu | 123.2 (4) | C62—C52—H52A | 108.5 |
C42—N32—Cu | 113.8 (3) | C42—C52—H52A | 108.5 |
C81—N71—C61 | 110.9 (4) | C62—C52—H52B | 108.5 |
C81—N71—Cu | 109.5 (3) | C42—C52—H52B | 108.5 |
C61—N71—Cu | 116.5 (4) | H52A—C52—H52B | 107.5 |
C81—N71—H71 | 108.8 | N71—C61—C51 | 113.7 (4) |
C61—N71—H71 | 109.3 | N71—C61—H61A | 108.8 |
Cu—N71—H71 | 101.3 | C51—C61—H61A | 108.8 |
C62—N72—C82 | 114.0 (4) | N71—C61—H61B | 108.8 |
C62—N72—Cu | 108.7 (4) | C51—C61—H61B | 108.8 |
C82—N72—Cu | 108.3 (3) | H61A—C61—H61B | 107.7 |
C62—N72—H72 | 104.3 | N72—C62—C52 | 112.7 (4) |
C82—N72—H72 | 106.1 | N72—C62—H62A | 109 |
Cu—N72—H72 | 115.6 | C52—C62—H62A | 109 |
O—C11—C21 | 115.1 (4) | N72—C62—H62B | 109 |
O—C11—H11A | 108.5 | C52—C62—H62B | 109 |
C21—C11—H11A | 108.5 | H62A—C62—H62B | 107.8 |
O—C11—H11B | 108.5 | N71—C81—C82 | 110.0 (4) |
C21—C11—H11B | 108.5 | N71—C81—H81A | 109.7 |
H11A—C11—H11B | 107.5 | C82—C81—H81A | 109.7 |
O—C12—C22 | 114.5 (4) | N71—C81—H81B | 109.7 |
O—C12—H12A | 108.6 | C82—C81—H81B | 109.7 |
C22—C12—H12A | 108.6 | H81A—C81—H81B | 108.2 |
O—C12—H12B | 108.6 | N72—C82—C81 | 108.4 (5) |
C22—C12—H12B | 108.6 | N72—C82—H82A | 110 |
H12A—C12—H12B | 107.6 | C81—C82—H82A | 110 |
O21—C21—N31 | 127.2 (5) | N72—C82—H82B | 110 |
O21—C21—C11 | 114.4 (4) | C81—C82—H82B | 110 |
N31—C21—C11 | 118.4 (5) | H82A—C82—H82B | 108.4 |
O22—C22—N32 | 127.3 (5) | H1A—O1—H1B | 107.7 |
O22—C22—C12 | 114.3 (4) | H2A—O2—H2B | 107.2 |
N32—C22—C12 | 118.4 (4) | H3A—O3—H3B | 107.7 |
N31—C41—C51 | 110.6 (5) | H4A—O4—H4B | 107.6 |
N31—C41—H41A | 109.5 | H5A—O5—H5B | 107.7 |
| | | |
N31—Cu—O—C11 | −5.1 (3) | O—Cu—N72—C82 | −98.7 (3) |
N32—Cu—O—C11 | −109.7 (4) | C12—O—C11—C21 | −115.9 (5) |
N72—Cu—O—C11 | 169.9 (3) | Cu—O—C11—C21 | 0.6 (6) |
N71—Cu—O—C11 | 76.2 (4) | C11—O—C12—C22 | 105.0 (5) |
N31—Cu—O—C12 | 117.6 (4) | Cu—O—C12—C22 | −11.3 (5) |
N32—Cu—O—C12 | 12.9 (3) | C41—N31—C21—O21 | 5.0 (9) |
N72—Cu—O—C12 | −67.5 (4) | Cu—N31—C21—O21 | 167.1 (4) |
N71—Cu—O—C12 | −161.2 (3) | C41—N31—C21—C11 | −175.8 (5) |
N32—Cu—N31—C21 | 82.5 (4) | Cu—N31—C21—C11 | −13.7 (7) |
N71—Cu—N31—C21 | −110.5 (4) | O—C11—C21—O21 | −173.4 (5) |
O—Cu—N31—C21 | 10.4 (4) | O—C11—C21—N31 | 7.3 (8) |
N32—Cu—N31—C41 | −115.1 (4) | C42—N32—C22—O22 | −7.2 (8) |
N71—Cu—N31—C41 | 51.9 (4) | Cu—N32—C22—O22 | −165.6 (4) |
O—Cu—N31—C41 | 172.8 (4) | C42—N32—C22—C12 | 170.7 (5) |
N31—Cu—N32—C22 | −86.7 (4) | Cu—N32—C22—C12 | 12.2 (7) |
N72—Cu—N32—C22 | 96.5 (4) | O—C12—C22—O22 | −179.8 (4) |
N71—Cu—N32—C22 | 147.2 (7) | O—C12—C22—N32 | 2.1 (7) |
O—Cu—N32—C22 | −14.0 (4) | C21—N31—C41—C51 | 95.2 (6) |
N31—Cu—N32—C42 | 113.7 (4) | Cu—N31—C41—C51 | −68.2 (5) |
N72—Cu—N32—C42 | −63.1 (4) | C22—N32—C42—C52 | −95.3 (6) |
N71—Cu—N32—C42 | −12.4 (10) | Cu—N32—C42—C52 | 65.0 (5) |
O—Cu—N32—C42 | −173.6 (4) | N31—C41—C51—C61 | 67.1 (6) |
N31—Cu—N71—C81 | −173.0 (4) | N32—C42—C52—C62 | −55.2 (6) |
N32—Cu—N71—C81 | −45.6 (10) | C81—N71—C61—C51 | −177.2 (5) |
N72—Cu—N71—C81 | 5.2 (4) | Cu—N71—C61—C51 | 56.6 (6) |
O—Cu—N71—C81 | 113.3 (3) | C41—C51—C61—N71 | −62.5 (7) |
N31—Cu—N71—C61 | −46.1 (4) | C82—N72—C62—C52 | 167.8 (4) |
N32—Cu—N71—C61 | 81.2 (9) | Cu—N72—C62—C52 | −71.2 (5) |
N72—Cu—N71—C61 | 132.1 (4) | C42—C52—C62—N72 | 60.8 (6) |
O—Cu—N71—C61 | −119.9 (4) | C61—N71—C81—C82 | −160.5 (5) |
N32—Cu—N72—C62 | 63.8 (3) | Cu—N71—C81—C82 | −30.5 (6) |
N71—Cu—N72—C62 | −103.7 (3) | C62—N72—C82—C81 | 78.3 (6) |
O—Cu—N72—C62 | 136.9 (3) | Cu—N72—C82—C81 | −42.8 (5) |
N32—Cu—N72—C82 | −171.8 (4) | N71—C81—C82—N72 | 48.5 (6) |
N71—Cu—N72—C82 | 20.6 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O21i | 0.85 | 1.9 | 2.744 (6) | 174 |
O1—H1B···O4ii | 0.85 | 2.06 | 2.865 (7) | 159 |
O2—H2A···O22 | 0.85 | 1.91 | 2.762 (7) | 180 |
O3—H3A···O22 | 0.85 | 2.06 | 2.863 (7) | 158 |
O3—H3B···O1 | 0.85 | 2.13 | 2.862 (7) | 144 |
O4—H4A···O22 | 0.85 | 1.99 | 2.839 (6) | 176 |
O4—H4B···O2ii | 0.85 | 1.99 | 2.803 (7) | 161 |
O5—H5A···O3 | 0.85 | 2.02 | 2.852 (8) | 165 |
O5—H5B···O2iii | 0.85 | 1.96 | 2.723 (8) | 149 |
N71—H71···O21ii | 0.90 | 1.96 | 2.858 (6) | 173 |
N72—H72···O5 | 0.91 | 1.92 | 2.834 (7) | 176 |
Symmetry codes: (i) x+1, −y, z+1/2; (ii) x, −y, z+1/2; (iii) x, y, z+1. |
(III) (3,16-dioxo-1-thia-4,8,11,15-tetraazacycloheptadecanato)copper(II) trihydrate
top
Crystal data top
[Cu(C12H22N4O2S)]·3H2O | F(000) = 426 |
Mr = 403.98 | Dx = 1.526 Mg m−3 |
Monoclinic, P21/m | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yb | Cell parameters from 38 reflections |
a = 7.4905 (6) Å | θ = 22.0–56.0° |
b = 16.1160 (9) Å | µ = 3.13 mm−1 |
c = 7.6404 (4) Å | T = 293 K |
β = 107.553 (5)° | Prism, dark blue |
V = 879.38 (10) Å3 | 0.32 × 0.26 × 0.14 mm |
Z = 2 | |
Data collection top
Siemens P4 four-circle diffractometer | Rint = 0.050 |
ω/2θ scans | θmax = 68.9° |
Absorption correction: ψ scan (XEMP; Siemens, 1989) | h = −1→9 |
Tmin = 0.43, Tmax = 0.645 | k = −19→1 |
2013 measured reflections | l = −7→7 |
1536 independent reflections | 3 standard reflections every 100 reflections |
1415 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0756P)2 + 0.7615P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.047 | (Δ/σ)max < 0.001 |
wR(F2) = 0.133 | Δρmax = 0.41 e Å−3 |
S = 1.07 | Δρmin = −0.61 e Å−3 |
1536 reflections | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
119 parameters | Extinction coefficient: 0.0022 (8) |
Crystal data top
[Cu(C12H22N4O2S)]·3H2O | V = 879.38 (10) Å3 |
Mr = 403.98 | Z = 2 |
Monoclinic, P21/m | Cu Kα radiation |
a = 7.4905 (6) Å | µ = 3.13 mm−1 |
b = 16.1160 (9) Å | T = 293 K |
c = 7.6404 (4) Å | 0.32 × 0.26 × 0.14 mm |
β = 107.553 (5)° | |
Data collection top
Siemens P4 four-circle diffractometer | 1415 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XEMP; Siemens, 1989) | Rint = 0.050 |
Tmin = 0.43, Tmax = 0.645 | 3 standard reflections every 100 reflections |
2013 measured reflections | intensity decay: 3% |
1536 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 119 parameters |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.41 e Å−3 |
1536 reflections | Δρmin = −0.61 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu | 0.14839 (7) | 0.25 | 0.16805 (8) | 0.0363 (3) | |
S | −0.03643 (16) | 0.25 | −0.18876 (17) | 0.0490 (4) | |
O2 | −0.2583 (4) | 0.06648 (19) | 0.0234 (5) | 0.0818 (10) | |
N3 | −0.0243 (4) | 0.15770 (16) | 0.1648 (4) | 0.0438 (6) | |
C1 | −0.1777 (6) | 0.1644 (3) | −0.1638 (6) | 0.0727 (13) | |
H1A | −0.3075 | 0.1817 | −0.2117 | 0.094* | |
H1B | −0.1591 | 0.1204 | −0.243 | 0.094* | |
C2 | −0.1523 (5) | 0.1273 (2) | 0.0224 (6) | 0.0530 (9) | |
C4 | 0.0219 (6) | 0.1112 (2) | 0.3363 (6) | 0.0603 (10) | |
H4A | −0.0817 | 0.0752 | 0.3366 | 0.078* | |
H4B | 0.0428 | 0.1493 | 0.4388 | 0.078* | |
C5 | 0.1944 (8) | 0.0603 (3) | 0.3571 (8) | 0.0863 (15) | |
H5A | 0.2132 | 0.0248 | 0.4636 | 0.112* | |
H5B | 0.1726 | 0.0246 | 0.2505 | 0.112* | |
C6 | 0.3690 (7) | 0.1077 (4) | 0.3778 (8) | 0.0891 (16) | |
H6A | 0.3983 | 0.1392 | 0.491 | 0.116* | |
H6B | 0.4706 | 0.0688 | 0.3886 | 0.116* | |
N7 | 0.3603 (4) | 0.1650 (2) | 0.2257 (5) | 0.0658 (9) | |
H7 | 0.3636 | 0.1374 | 0.1228 | 0.086* | 0.5 |
H71 | 0.3296 | 0.1317 | 0.1248 | 0.086* | 0.5 |
C8A | 0.5410 (10) | 0.2070 (6) | 0.3201 (14) | 0.067 (3) | 0.5 |
H8A1 | 0.5819 | 0.1884 | 0.4467 | 0.087* | 0.5 |
H8A2 | 0.6335 | 0.1884 | 0.2632 | 0.087* | 0.5 |
C8B | 0.5273 (10) | 0.2156 (5) | 0.2030 (14) | 0.066 (2) | 0.5 |
H8B1 | 0.6374 | 0.1982 | 0.3002 | 0.086* | 0.5 |
H8B2 | 0.546 | 0.1982 | 0.0883 | 0.086* | 0.5 |
O1 | 0.3529 (4) | 0.0847 (2) | 0.8635 (5) | 0.0850 (10) | |
H1C | 0.3047 | 0.0387 | 0.8794 | 0.11* | |
H1D | 0.4621 | 0.0658 | 0.8764 | 0.11* | |
O3 | 0.3671 (8) | 0.25 | 0.7079 (9) | 0.1079 (18) | |
H3 | 0.3267 | 0.202 | 0.7221 | 0.14* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.0272 (4) | 0.0348 (4) | 0.0432 (5) | 0 | 0.0053 (3) | 0 |
S | 0.0473 (6) | 0.0522 (7) | 0.0458 (8) | 0 | 0.0116 (5) | 0 |
O2 | 0.0739 (19) | 0.0593 (16) | 0.102 (2) | −0.0358 (14) | 0.0103 (17) | 0.0017 (17) |
N3 | 0.0420 (13) | 0.0386 (13) | 0.0483 (17) | −0.0018 (11) | 0.0100 (11) | 0.0018 (12) |
C1 | 0.084 (3) | 0.054 (2) | 0.059 (3) | −0.026 (2) | −0.011 (2) | −0.0017 (18) |
C2 | 0.0445 (17) | 0.0396 (16) | 0.069 (2) | −0.0090 (13) | 0.0084 (16) | −0.0004 (16) |
C4 | 0.073 (2) | 0.0509 (19) | 0.057 (2) | −0.0066 (18) | 0.0208 (18) | 0.0064 (17) |
C5 | 0.118 (4) | 0.062 (2) | 0.075 (3) | 0.028 (3) | 0.023 (3) | 0.026 (2) |
C6 | 0.072 (3) | 0.097 (4) | 0.084 (3) | 0.042 (3) | 0.003 (2) | 0.011 (3) |
N7 | 0.0384 (14) | 0.0604 (18) | 0.093 (3) | 0.0106 (13) | 0.0119 (15) | −0.0107 (18) |
C8A | 0.028 (3) | 0.099 (6) | 0.069 (6) | 0.012 (3) | 0.005 (4) | 0.015 (5) |
C8B | 0.033 (3) | 0.086 (6) | 0.078 (6) | 0.014 (3) | 0.015 (4) | −0.006 (5) |
O1 | 0.081 (2) | 0.0687 (19) | 0.098 (3) | −0.0170 (15) | 0.0158 (18) | 0.0154 (18) |
O3 | 0.095 (4) | 0.110 (4) | 0.131 (5) | 0 | 0.053 (4) | 0 |
Geometric parameters (Å, º) top
Cu—N3 | 1.967 (3) | C5—H5B | 0.97 |
Cu—N3i | 1.967 (3) | C6—N7 | 1.470 (7) |
Cu—N7i | 2.042 (3) | C6—H6A | 0.97 |
Cu—N7 | 2.042 (3) | C6—H6B | 0.97 |
Cu—S | 2.6594 (13) | N7—C8A | 1.490 (8) |
S—C1 | 1.783 (4) | N7—C8B | 1.547 (9) |
S—C1i | 1.783 (4) | N7—H7 | 0.91 |
O2—C2 | 1.264 (4) | N7—H71 | 0.91 |
N3—C2 | 1.309 (4) | C8A—C8Ai | 1.385 (19) |
N3—C4 | 1.458 (5) | C8A—H8A1 | 0.97 |
C1—C2 | 1.501 (6) | C8A—H8A2 | 0.97 |
C1—H1A | 0.97 | C8B—C8Bi | 1.108 (17) |
C1—H1B | 0.97 | C8B—H8B1 | 0.97 |
C4—C5 | 1.498 (6) | C8B—H8B2 | 0.97 |
C4—H4A | 0.97 | O1—H1C | 0.85 |
C4—H4B | 0.97 | O1—H1D | 0.85 |
C5—C6 | 1.482 (7) | O3—H3 | 0.85 |
C5—H5A | 0.97 | | |
| | | |
N3—Cu—N3i | 98.29 (15) | C4—C5—H5B | 108.3 |
N3—Cu—N7i | 167.40 (13) | H5A—C5—H5B | 107.4 |
N3i—Cu—N7i | 87.76 (12) | N7—C6—C5 | 114.4 (4) |
N3—Cu—N7 | 87.76 (12) | N7—C6—H6A | 108.7 |
N3i—Cu—N7 | 167.40 (13) | C5—C6—H6A | 108.7 |
N7i—Cu—N7 | 84.28 (19) | N7—C6—H6B | 108.7 |
N3—Cu—S | 81.37 (9) | C5—C6—H6B | 108.7 |
N3i—Cu—S | 81.37 (9) | H6A—C6—H6B | 107.6 |
N7i—Cu—S | 110.58 (11) | C6—N7—C8A | 94.9 (5) |
N7—Cu—S | 110.58 (11) | C6—N7—C8B | 125.1 (5) |
C1—S—C1i | 101.3 (3) | C6—N7—Cu | 116.0 (3) |
C1—S—Cu | 91.87 (14) | C8A—N7—Cu | 109.4 (4) |
C1i—S—Cu | 91.87 (13) | C8B—N7—Cu | 103.0 (4) |
C2—N3—C4 | 118.1 (3) | C6—N7—H7 | 111.7 |
C2—N3—Cu | 127.4 (2) | C8A—N7—H7 | 112.5 |
C4—N3—Cu | 113.6 (2) | C8B—N7—H7 | 85.8 |
C2—C1—S | 120.0 (3) | Cu—N7—H7 | 111.3 |
C2—C1—H1A | 107.3 | C6—N7—H71 | 103.8 |
S—C1—H1A | 107.3 | C8A—N7—H71 | 129.7 |
C2—C1—H1B | 107.3 | C8B—N7—H71 | 102.8 |
S—C1—H1B | 107.3 | Cu—N7—H71 | 103.4 |
H1A—C1—H1B | 106.9 | C8Ai—C8A—N7 | 117.1 (4) |
O2—C2—N3 | 126.1 (4) | C8Ai—C8A—H8A1 | 108 |
O2—C2—C1 | 114.5 (3) | N7—C8A—H8A1 | 108 |
N3—C2—C1 | 119.4 (3) | C8Ai—C8A—H8A2 | 108 |
N3—C4—C5 | 109.9 (3) | N7—C8A—H8A2 | 108 |
N3—C4—H4A | 109.7 | H8A1—C8A—H8A2 | 107.3 |
C5—C4—H4A | 109.7 | C8Bi—C8B—N7 | 121.9 (3) |
N3—C4—H4B | 109.7 | C8Bi—C8B—H8B1 | 106.9 |
C5—C4—H4B | 109.7 | N7—C8B—H8B1 | 106.9 |
H4A—C4—H4B | 108.2 | C8Bi—C8B—H8B2 | 106.9 |
C6—C5—C4 | 115.7 (4) | N7—C8B—H8B2 | 106.9 |
C6—C5—H5A | 108.3 | H8B1—C8B—H8B2 | 106.7 |
C4—C5—H5A | 108.3 | H1C—O1—H1D | 96.1 |
C6—C5—H5B | 108.3 | | |
| | | |
N3—Cu—S—C1 | −0.78 (19) | Cu—N3—C4—C5 | −72.0 (4) |
N3i—Cu—S—C1 | −100.6 (2) | N3—C4—C5—C6 | 65.3 (6) |
N7i—Cu—S—C1 | 175.1 (2) | C4—C5—C6—N7 | −57.7 (6) |
N7—Cu—S—C1 | 83.5 (2) | C5—C6—N7—C8A | 170.1 (6) |
N3—Cu—S—C1i | 100.6 (2) | C5—C6—N7—C8B | −173.9 (5) |
N3i—Cu—S—C1i | 0.78 (19) | C5—C6—N7—Cu | 55.7 (5) |
N7i—Cu—S—C1i | −83.5 (2) | N3—Cu—N7—C6 | −50.1 (3) |
N7—Cu—S—C1i | −175.1 (2) | N3i—Cu—N7—C6 | 69.0 (7) |
N3i—Cu—N3—C2 | 80.6 (3) | N7i—Cu—N7—C6 | 120.1 (3) |
N7i—Cu—N3—C2 | −161.4 (6) | S—Cu—N7—C6 | −130.1 (3) |
N7—Cu—N3—C2 | −110.5 (3) | N3—Cu—N7—C8A | −156.0 (5) |
S—Cu—N3—C2 | 0.7 (3) | N3i—Cu—N7—C8A | −36.9 (8) |
N3i—Cu—N3—C4 | −110.6 (2) | N7i—Cu—N7—C8A | 14.2 (5) |
N7i—Cu—N3—C4 | 7.4 (7) | S—Cu—N7—C8A | 124.1 (5) |
N7—Cu—N3—C4 | 58.3 (3) | N3—Cu—N7—C8B | 169.6 (4) |
S—Cu—N3—C4 | 169.5 (2) | N3i—Cu—N7—C8B | −71.3 (8) |
C1i—S—C1—C2 | −91.3 (4) | N7i—Cu—N7—C8B | −20.2 (5) |
Cu—S—C1—C2 | 1.0 (4) | S—Cu—N7—C8B | 89.7 (4) |
C4—N3—C2—O2 | 9.7 (6) | C6—N7—C8A—C8Ai | −131.6 (3) |
Cu—N3—C2—O2 | 178.0 (3) | C8B—N7—C8A—C8Ai | 72.4 (9) |
C4—N3—C2—C1 | −168.5 (3) | Cu—N7—C8A—C8Ai | −11.8 (4) |
Cu—N3—C2—C1 | −0.2 (5) | C6—N7—C8B—C8Bi | −117.8 (4) |
S—C1—C2—O2 | −179.2 (3) | C8A—N7—C8B—C8Bi | −88.1 (10) |
S—C1—C2—N3 | −0.8 (6) | Cu—N7—C8B—C8Bi | 17.5 (4) |
C2—N3—C4—C5 | 97.9 (4) | | |
Symmetry code: (i) x, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1C···O2ii | 0.85 | 1.93 | 2.749 (5) | 163 |
O1—H1D···O2iii | 0.85 | 2.05 | 2.813 (5) | 148 |
O3—H3···O1 | 0.85 | 2.15 | 2.932 (4) | 152 |
N7—H7···O1iv | 0.91 | 2.14 | 3.040 (5) | 173 |
N7—H71···O1iv | 0.91 | 2.2 | 3.040 (5) | 155 |
Symmetry codes: (ii) −x, −y, −z+1; (iii) x+1, y, z+1; (iv) x, y, z−1. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | [Cu(C12H23N5O2)]·4H2O | [Cu(C12H22N4O3)]·5H2O | [Cu(C12H22N4O2S)]·3H2O |
Mr | 404.96 | 423.96 | 403.98 |
Crystal system, space group | Orthorhombic, Pna21 | Monoclinic, Cc | Monoclinic, P21/m |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 13.3375 (5), 8.9992 (3), 15.5637 (4) | 12.098 (9), 20.337 (14), 8.134 (5) | 7.4905 (6), 16.1160 (9), 7.6404 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 103.68 (5), 90 | 90, 107.553 (5), 90 |
V (Å3) | 1868.06 (11) | 1944 (2) | 879.38 (10) |
Z | 4 | 4 | 2 |
Radiation type | Cu Kα | Mo Kα | Cu Kα |
µ (mm−1) | 1.98 | 1.17 | 3.13 |
Crystal size (mm) | 0.48 × 0.4 × 0.11 | 0.43 × 0.29 × 0.29 | 0.32 × 0.26 × 0.14 |
|
Data collection |
Diffractometer | Siemens P4 four-circle diffractometer | Stoe Stadi-4 four-circle diffractometer | Siemens P4 four-circle diffractometer |
Absorption correction | ψ scan (XEMP; Siemens, 1989) | ψ scan (EMPIR; Stoe & Cie, 1989) | ψ scan (XEMP; Siemens, 1989) |
Tmin, Tmax | 0.400, 0.804 | 0.670, 0.710 | 0.43, 0.645 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2267, 1856, 1824 | 3348, 3020, 2510 | 2013, 1536, 1415 |
Rint | 0.033 | 0.033 | 0.050 |
(sin θ/λ)max (Å−1) | 0.606 | 0.650 | 0.605 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.104, 1.11 | 0.043, 0.101, 1.04 | 0.047, 0.133, 1.07 |
No. of reflections | 1856 | 3020 | 1536 |
No. of parameters | 218 | 226 | 119 |
No. of restraints | ? | ? | ? |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.54 | 0.47, −0.60 | 0.41, −0.61 |
Absolute structure | Flack (1983), 138 Friedel pairs | Flack (1983), 773 Friedel pairs | ? |
Absolute structure parameter | 0.03 (4) | −0.005 (18) | ? |
Selected geometric parameters (Å, º) for (I) topCu—N31 | 1.980 (3) | Cu—N71 | 2.055 (4) |
Cu—N32 | 1.995 (3) | Cu—N | 2.281 (4) |
Cu—N72 | 2.032 (3) | | |
| | | |
N31—Cu—N32 | 100.6 (1) | N72—Cu—N71 | 84.3 (1) |
N31—Cu—N72 | 171.2 (1) | N31—Cu—N | 78.6 (1) |
N32—Cu—N72 | 88.2 (1) | N32—Cu—N | 80.0 (1) |
N31—Cu—N71 | 87.8 (1) | N72—Cu—N | 103.1 (1) |
N32—Cu—N71 | 153.0 (1) | N71—Cu—N | 126.9 (1) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H···O1i | 0.90 | 2.16 | 2.997 (6) | 155 |
O1—H1A···O3ii | 0.85 | 2.01 | 2.825 (5) | 157 |
O1—H1B···O21iii | 0.85 | 2.07 | 2.910 (5) | 173 |
O2—H2A···O21ii | 0.85 | 2.12 | 2.955 (5) | 172 |
O2—H2B···O4 | 0.85 | 2.03 | 2.835 (5) | 158 |
O3—H3A···O2iv | 0.85 | 1.99 | 2.825 (6) | 166 |
O3—H3B···O22iii | 0.85 | 1.89 | 2.732 (6) | 174 |
O4—H4A···O21iii | 0.85 | 1.93 | 2.770 (4) | 170 |
O4—H4B···O22v | 0.85 | 1.82 | 2.665 (4) | 176 |
N71—H71···O4i | 0.86 | 2.17 | 3.023 (5) | 169 |
N72—H72···O3 | 0.87 | 2.18 | 3.045 (5) | 174 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) x+1/2, −y−1/2, z; (iv) −x+1/2, y+1/2, z+1/2; (v) −x+1/2, y−1/2, z−1/2. |
Selected geometric parameters (Å, º) for (II) topCu—N31 | 1.963 (4) | Cu—N71 | 2.056 (4) |
Cu—N32 | 1.987 (4) | Cu—O | 2.428 (4) |
Cu—N72 | 2.017 (4) | | |
| | | |
N31—Cu—N32 | 100.2 (2) | N72—Cu—N71 | 84.0 (2) |
N31—Cu—N72 | 173.2 (2) | N31—Cu—O | 76.2 (2) |
N32—Cu—N72 | 85.8 (2) | N32—Cu—O | 75.4 (2) |
N31—Cu—N71 | 89.4 (2) | N72—Cu—O | 108.6 (2) |
N32—Cu—N71 | 163.9 (2) | N71—Cu—O | 119.7 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O21i | 0.85 | 1.9 | 2.744 (6) | 174 |
O1—H1B···O4ii | 0.85 | 2.06 | 2.865 (7) | 159 |
O2—H2A···O22 | 0.85 | 1.91 | 2.762 (7) | 180 |
O3—H3A···O22 | 0.85 | 2.06 | 2.863 (7) | 158 |
O3—H3B···O1 | 0.85 | 2.13 | 2.862 (7) | 144 |
O4—H4A···O22 | 0.85 | 1.99 | 2.839 (6) | 176 |
O4—H4B···O2ii | 0.85 | 1.99 | 2.803 (7) | 161 |
O5—H5A···O3 | 0.85 | 2.02 | 2.852 (8) | 165 |
O5—H5B···O2iii | 0.85 | 1.96 | 2.723 (8) | 149 |
N71—H71···O21ii | 0.90 | 1.96 | 2.858 (6) | 173 |
N72—H72···O5 | 0.91 | 1.92 | 2.834 (7) | 176 |
Symmetry codes: (i) x+1, −y, z+1/2; (ii) x, −y, z+1/2; (iii) x, y, z+1. |
Selected geometric parameters (Å, º) for (III) topCu—N3 | 1.967 (3) | Cu—N7 | 2.042 (3) |
Cu—N3i | 1.967 (3) | Cu—S | 2.6594 (13) |
Cu—N7i | 2.042 (3) | | |
| | | |
N3—Cu—N3i | 98.29 (15) | N7i—Cu—N7 | 84.28 (19) |
N3—Cu—N7i | 167.40 (13) | N3—Cu—S | 81.37 (9) |
N3i—Cu—N7i | 87.76 (12) | N3i—Cu—S | 81.37 (9) |
N3—Cu—N7 | 87.76 (12) | N7i—Cu—S | 110.58 (11) |
N3i—Cu—N7 | 167.40 (13) | N7—Cu—S | 110.58 (11) |
Symmetry code: (i) x, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1C···O2ii | 0.85 | 1.93 | 2.749 (5) | 163 |
O1—H1D···O2iii | 0.85 | 2.05 | 2.813 (5) | 148 |
O3—H3···O1 | 0.85 | 2.15 | 2.932 (4) | 152 |
N7—H7···O1iv | 0.91 | 2.14 | 3.040 (5) | 173 |
N7—H71···O1iv | 0.91 | 2.2 | 3.040 (5) | 155 |
Symmetry codes: (ii) −x, −y, −z+1; (iii) x+1, y, z+1; (iv) x, y, z−1. |
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The coordination chemistries in aqueous solutions of 2,6-dioxo-1,4,7,11,14-pentaazacycloheptadecane (L1), of 1-oxa-3,16-dioxo-4,8,11,15-tetraazacycloheptadecane (L2) and of 1-thia-3,16-dioxo-4,8,11,15-tetraazacycloheptadecane (L3) with Cu2+ ions have been published recently (Steenland et al., 1997, 1999). The main complexes formed with the three ligands were found to be a CuLH-2 complex, (I) with L1, (II) with L2 and (III) with L3. LH-2 in the three complexes indicates the twice deprotonated ligand. The electronic spectra of these CuLH-2 complexes exhibited two well defined maxima of about the same intensity, resulting in twin peaks. They were found at 14 490 cm−1 (ε = 133 M−1 cm−1) and 18 520 cm−1 (ε = 125 M−1 cm−1) for (I), at 16 050 cm−1 (ε = 157 M−1 cm−1) and 19 420 cm−1 (ε = 115 M−1 cm−1) with for (II), and at 15 400 cm−1 (ε = 154 M−1 cm−1) and 19 610 cm−1 (ε = 150 M−1 cm−1) for (III).
The band at the highest energy may be attributed for each complex to an electron transition from the dxy, dxz, dyz group of orbitals to dx2-y2; the band at lower energy to an electron transition from dz2 to dx2-y2 (Hathaway & Billing, 1970; Lever, 1984). The observation that the peak at the highest energy, thus reflecting the in-plane ligand field strength, had the lowest value (18 520 cm−1) for the strongest CuLH-2 complex, viz. (I) and the largest value (19 610 cm−1) for the weakest CuLH-2 complex, viz. (III), was puzzling and not readily understood from the thermodynamic stabilities of the complexes. Moreover, the νd-d bands of the copper(II) complex of the fully saturated 1,4,7,11,14-pentaazacycloheptadecane, (IV) were found at even lower wavenumbers, viz. 17 180 cm−1 (ε = 180 M−1 cm−1) and a shoulder at 11 900 cm−1 (ε = 65 M−1 cm−1) (Hay et al., 1984). A five-coordinate square-pyramidal structure was proposed for this latter CuL complex, which was later confirmed by X-ray crystallography (Boeyens et al., 1990) to be a conformer in which the nitrogen (indicated in Scheme by an asterisk) in the apical position is linked to its two neighbour N atoms in the basal plane by an ethylene and a propylene chain, respectively. The four N atoms in the basal plane form consecutive 5–6-5-membered linked chelate rings with the copper ion.
To get a better understanding of these observations, the CuLH-2 complexes of the three title ligands were prepared and obtained in the solid state. The structures of the three complexes consist of discrete neutral CuLH-2 entities solvated by a number of water molecules [see Figs. 1, 2 and 3 for (I), (II) and (III), respectively]. The coordination geometry in each of the three complexes is square-pyramidal overall, with two amine groups and the two deprotonated amide groups making up the basal plane. A fifth amine group in (I), the ether O atom in (II) and the thio S atom in (III) occupy the axial position. Each of the CuLH-2 entities forms hydrogen bonds with the water molecules through the amide O atoms and through the secondary amine groups (see Tables 2, 4 and 6 for details). In (I), the amine N—H group is also involved. Water O atoms act as both donors and acceptors with other water molecules. All hydrogen bonds combine to form an extensive three-dimensional framework. It is remarkable that only in compound (II) is there a direct hydrogen bond contact between complex units, via an N71—H71···O21 hydrogen bond.
The three CuLH-2 complex entities occur in the same conformation with consecutive 6–5-6-linked chelate rings in the basal plane. The angular structural parameter τ as an index for trigonality in these five-coordinate structures (Addison et al., 1984) is 0.30 in (I), 0.16 in (II), and 0.03 in (III). The distortion from a regular square-pyramidal geometry is thus the largest with the nitrogen donor and the lowest with the sulfur in tthe axial position. The two six-membered chelate rings in the three complexes are chairs, distorted towards a boat, and with a high puckering amplitude. Q values (Cremer & Pople, 1975) are on average 0.654 (5) in (I), 0.701 (5) in (II) and 0.676 (11) in (III). The conformations of the five-membered chelate rings (Duax et al., 1976) are envelope with a local pseudo-mirror along C82 and the mid-point of Cu···N71 for (I) and (II), and a half-chair with a local pseudo-twofold axis along Cu and the mid-point of C8A—C8B for (III). The weighted average Cu—N bond distance in the basal plane is 2.01 (2) Å in (I), 2.01 (2) Å in (II) and 2.00 (3) Å in (III). These bond lengths are appreciably shorter than in CuL complex (IV) [2.07 (6) Å; Hay et al., 1984]. This is certainly due to the presence of the two negatively charged amide N atoms in the basal plane and offers an obvious explanation for the much stronger in-plane ligand field in these CuLH-2 complexes compared with the in-plane ligand field in the CuL complex (IV). Also, the difference in the sequence of the linked chelate rings is a consequence of the presence in the basal plane of the two deprotonated N atoms, being stronger σ-donors than the amine N atoms (Miyoshi et al., 1983). The observed sequence of the in-plane ligand-field strength for the three CuLH-2 complexes, being (III) > (II) > (I), can now be understood from the distortion of the basal plane formed by the four independent N atoms (N31, N32, N71 and N72) in compounds (I) and (II). In (III),there is no distortion at all due to mirror symmetry in the basal plane formed by atoms N3 and N7. In fact, the largest displacement from the mean plane through atoms N31, N32, N71 and N72 is observed for N72, viz. 0.099 (4) Å in (II) and the largest value 0.298 (3) Å in (I). The displacement of the Cu from the mean plane does not follow the same trend for the three complexes, but again the largest displacement is observed in (I) [0.203 (1) Å] compared with 0.134 (1) Å in (II) or 0.182 (1) Å in (III).
In the axial position, the nitrogen donor, which is the strongest of the three donors, produces the strongest deviation in the basal plane, resulting in the weakest in-plane ligand field. The sulfur donor with the longest Cu—S axial bond distance causes less distortion in the basal plane, resulting in the strongest in-plane ligand field. The position of the peak with the lowest energy (dz2 → dx2-y2 transition) is then determined by two aspects: first, the stronger the intrinsic axial donor strength (N > S > O) the lower the energy for this transition to occur; second, the stronger the in-plane ligand field (N < O < S) the higher the energy for this transition. These two aspects combine and result in the lowest position of the second peak for (I) with the N atom in the axial position. Deviation of the axial donor from a position more or less perpendicular above the mid-point in the basal plane may explain the much higher molar absorptivity of this transition and the appearance of the twin peak feature in the electronic spectra of these CuLH-2 complexes.