Copper(II) complexes of pentadentate 17-membered macrocyclic di­amido­diamines with N, O or S as additional donors

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.

S1. Comment

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 d_xy, d_xz, d_yz group of orbitals to d_x2-y2; the band at lower energy to an electron transition from d_z2 to d_x2-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 ν_d-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 (d_z2 → d_x2-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.

S2. Experimental

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): g_parallel and g_{perpendicular}, respectively, 2.2170 and 2.0442 for (I), 2.2098 and 2.0469 for (II), and 2.2034 and 2.0415 for (III).

S3. Refinement

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.

Computing details

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).

Figures

	Fig. 1. A view of the molecule of (I) with 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the molecule of (II) with 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. A view of the molecule of (III) with 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.

(I) (2,6-dioxo-1,4,7,11,14-pentaazacycloheptadecanato)copper(II) tetrahydrate

Crystal data

[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) Å^3	Tablet, dark blue
Z = 4	0.48 × 0.4 × 0.11 mm

Data collection

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

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0764P)^2 + 0.2709P] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max < 0.001
R[F^2 > 2σ(F^2)] = 0.040	Δρmax = 0.67 e Å^−3
wR(F^2) = 0.104	Δρmin = −0.54 e Å^−3
S = 1.11	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/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)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N—H···O1^i	0.90	2.16	2.997 (6)	155
O1—H1A···O3^ii	0.85	2.01	2.825 (5)	157
O1—H1B···O21^iii	0.85	2.07	2.910 (5)	173
O2—H2A···O21^ii	0.85	2.12	2.955 (5)	172
O2—H2B···O4	0.85	2.03	2.835 (5)	158
O3—H3A···O2^iv	0.85	1.99	2.825 (6)	166
O3—H3B···O22^iii	0.85	1.89	2.732 (6)	174
O4—H4A···O21^iii	0.85	1.93	2.770 (4)	170
O4—H4B···O22^v	0.85	1.82	2.665 (4)	176
N71—H71···O4^i	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

Crystal data

[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) Å^3	0.43 × 0.29 × 0.29 mm
Z = 4

Data collection

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

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0565P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.043	(Δ/σ)max < 0.001
wR(F^2) = 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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O21^i	0.85	1.9	2.744 (6)	174
O1—H1B···O4^ii	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···O2^ii	0.85	1.99	2.803 (7)	161
O5—H5A···O3	0.85	2.02	2.852 (8)	165
O5—H5B···O2^iii	0.85	1.96	2.723 (8)	149
N71—H71···O21^ii	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

Crystal data

[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) Å^3	0.32 × 0.26 × 0.14 mm
Z = 2

Data collection

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

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0756P)^2 + 0.7615P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.047	(Δ/σ)max < 0.001
wR(F^2) = 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+0.001xFc^2λ^3/sin(2θ)]^-1/4
119 parameters	Extinction coefficient: 0.0022 (8)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cu—N3	1.967 (3)	C5—H5B	0.97
Cu—N3^i	1.967 (3)	C6—N7	1.470 (7)
Cu—N7^i	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—C1^i	1.783 (4)	N7—H7	0.91
O2—C2	1.264 (4)	N7—H71	0.91
N3—C2	1.309 (4)	C8A—C8A^i	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—C8B^i	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—N3^i	98.29 (15)	C4—C5—H5B	108.3
N3—Cu—N7^i	167.40 (13)	H5A—C5—H5B	107.4
N3^i—Cu—N7^i	87.76 (12)	N7—C6—C5	114.4 (4)
N3—Cu—N7	87.76 (12)	N7—C6—H6A	108.7
N3^i—Cu—N7	167.40 (13)	C5—C6—H6A	108.7
N7^i—Cu—N7	84.28 (19)	N7—C6—H6B	108.7
N3—Cu—S	81.37 (9)	C5—C6—H6B	108.7
N3^i—Cu—S	81.37 (9)	H6A—C6—H6B	107.6
N7^i—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—C1^i	101.3 (3)	C6—N7—Cu	116.0 (3)
C1—S—Cu	91.87 (14)	C8A—N7—Cu	109.4 (4)
C1^i—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	C8A^i—C8A—N7	117.1 (4)
O2—C2—N3	126.1 (4)	C8A^i—C8A—H8A1	108
O2—C2—C1	114.5 (3)	N7—C8A—H8A1	108
N3—C2—C1	119.4 (3)	C8A^i—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	C8B^i—C8B—N7	121.9 (3)
N3—C4—H4B	109.7	C8B^i—C8B—H8B1	106.9
C5—C4—H4B	109.7	N7—C8B—H8B1	106.9
H4A—C4—H4B	108.2	C8B^i—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)
N3^i—Cu—S—C1	−100.6 (2)	N3—C4—C5—C6	65.3 (6)
N7^i—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—C1^i	100.6 (2)	C5—C6—N7—C8B	−173.9 (5)
N3^i—Cu—S—C1^i	0.78 (19)	C5—C6—N7—Cu	55.7 (5)
N7^i—Cu—S—C1^i	−83.5 (2)	N3—Cu—N7—C6	−50.1 (3)
N7—Cu—S—C1^i	−175.1 (2)	N3^i—Cu—N7—C6	69.0 (7)
N3^i—Cu—N3—C2	80.6 (3)	N7^i—Cu—N7—C6	120.1 (3)
N7^i—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)	N3^i—Cu—N7—C8A	−36.9 (8)
N3^i—Cu—N3—C4	−110.6 (2)	N7^i—Cu—N7—C8A	14.2 (5)
N7^i—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)	N3^i—Cu—N7—C8B	−71.3 (8)
C1^i—S—C1—C2	−91.3 (4)	N7^i—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—C8A^i	−131.6 (3)
Cu—N3—C2—O2	178.0 (3)	C8B—N7—C8A—C8A^i	72.4 (9)
C4—N3—C2—C1	−168.5 (3)	Cu—N7—C8A—C8A^i	−11.8 (4)
Cu—N3—C2—C1	−0.2 (5)	C6—N7—C8B—C8B^i	−117.8 (4)
S—C1—C2—O2	−179.2 (3)	C8A—N7—C8B—C8B^i	−88.1 (10)
S—C1—C2—N3	−0.8 (6)	Cu—N7—C8B—C8B^i	17.5 (4)
C2—N3—C4—C5	97.9 (4)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···O2^ii	0.85	1.93	2.749 (5)	163
O1—H1D···O2^iii	0.85	2.05	2.813 (5)	148
O3—H3···O1	0.85	2.15	2.932 (4)	152
N7—H7···O1^iv	0.91	2.14	3.040 (5)	173
N7—H71···O1^iv	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.