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Acta Cryst. (2007). E63, m3021    [ doi:10.1107/S1600536807056863 ]

(Methyl (S)-3-(imidazol-4-yl)-2-{6-[(S)-2-(imidazol-4-yl)-1-(methoxycarbonyl)ethylaminocarbonyl]pyridine-2-carbonylamino}propionato)copper(II) methanol sesquisolvate

M. T. Räisänen, M. Klinga, M. Leskelä and T. Repo

Abstract top

In the CuII title complex, [Cu(C21H21N7O6)]·1.5CH4O, two independent half-molecules of the title complex and one and a half methanol solvent molecules are in the asymmetric unit. The title complex possesses crystallographic C2 symmetry. One methanol molecule is disordered around a twofold axis. The title complex geometry agrees well with that of the dihydrate determined earlier with the exception of an N-Cu-N angle deviating by almost 10°. The CuII centre is in a distorted square-pyramidal geometry, and intermolecular hydrogen bonds stabilize the molecular packing.

Comment top

The title complex with one and a half methanol solvates crystallized in P21212 space group having two independent half molecules in the asymmetric unit sitting on a crystallographic C2 symmetry axes. Cu1, N1, C3 atoms of the one molecule and Cu2, N5 and C14 of the other molecule lie on 2-fold axes. The methanol molecule O12—C201 with site occupation factor 0.5 is disordered about a 2-fold axis. The same complex in dihydrate form instead of methanol has been previously found to crystallize in the P43212 space group (Otsuka et al., 1996, Kurosaki et al., 2001). In both complexes, geometry around a five coordinated Cu(II) cation is a distorted square pyramid (Figure 1). The measured bond lengths and angles of the title complex agree well with the values obtained for the previously determined structure (Kurosaki et al., 2001) with one exception. The N1—Cu1—N4 angle of the title complex differs as much as 9.85° less from the corresponding angle of the previously determined complex. Several intermolecular hydrogen bonds stabilize the molecular packing of the title complex.

Related literature top

For the dihydrate crystal structure determined earlier, see Otsuka et al. (1996); Kurosaki et al. (2001).

For related literature, see: An et al. (2003); Kottke & Stalke (1993); Moriuchi et al. (2001); Ryono & Weller (1987).

Experimental top

The title complex (4) was synthesized according to literature procedures. For the ligand synthesis, 2,6-pyridinedicarbonyl dichloride (1) (An et al., 2003) and L-histidine methyl ester dihydrochloride (2) (Ryono & Weller, 1987) were prepared by reacting SOCl2 with 2,6-pyridinedicarboxylic acid and L-histidine, respectively. Ligand (3) of the title complex was synthesized by coupling 1 and 2 (Moriuchi et al., 2001). Finally, 4 was synthesized at room temperature by adding a MeOH solution of (CH3COO)2Cu·H2O (0.066 g, 0.33 mmol) into a MeOH solution of 3 (0.155 g, 0.33 mmol) and stirring the blue solution formed for 70 h. After solvent removal in a vacuum, the complex was obtained as a blue powder (Kurosaki et al., 2001). Blue crystals of the title compound, suitable for X-ray analysis, were obtained from a saturated solution of MeOH–MeCN (2:1).

Refinement top

The crystal selected for the X-ray measurement at 173 K was mounted on a glass fibre using the oil drop method (Kottke & Stalke, 1993). H atoms were introduced in their calculated positions (X—H = 0.84, 0.88, 0.95, 0.98, 0.99, or 1.00 Å, Uiso=1.2 times the Ueq of the carrier atom and Uiso=1.5 times the Ueq of the carrier atom for methyl and OH H atoms) and were kept riding with fixed geometry with respect to their carrier atoms. No H atom positions were identified for the disordered methanol molecule.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: DIRAX (Duisenberg, 1992); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for the sake of clarity.
(Methyl (S)-3-(imidazol-4-yl)-\ 2-{6-[(S)-2-(imidazol-4-yl)-1-(methoxycarbonyl)ethylaminocarbonyl]pyridine-\ 2-carbonylamino}propionato)copper(II) methanol sesquisolvate top
Crystal data top
[Cu(C21H21N7O6)]·1.5CH4OF000 = 1192
Mr = 577.04Dx = 1.495 Mg m−3
Orthorhombic, P21212Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2 2abCell parameters from 23034 reflections
a = 13.701 (1) Åθ = 3.3–27.5º
b = 13.771 (1) ŵ = 0.91 mm−1
c = 13.590 (2) ÅT = 173 (2) K
V = 2564.1 (5) Å3Block, blue
Z = 40.30 × 0.20 × 0.20 mm
Data collection top
KappaCCD
diffractometer		5867 independent reflections
Radiation source: fine-focus sealed tube4185 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.064
T = 173(2) Kθmax = 27.5º
ω and φ scansθmin = 3.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −17→17
Tmin = 0.772, Tmax = 0.839k = −17→17
23034 measured reflectionsl = −17→17
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045  w = 1/[σ2(Fo2) + (0.0514P)2 + 0.3474P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.101(Δ/σ)max = 0.001
S = 0.92Δρmax = 0.36 e Å−3
5867 reflectionsΔρmin = −0.50 e Å−3
359 parametersExtinction correction: none
2 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.012 (16)
Secondary atom site location: difference Fourier map
Crystal data top
[Cu(C21H21N7O6)]·1.5CH4OV = 2564.1 (5) Å3
Mr = 577.04Z = 4
Orthorhombic, P21212Mo Kα
a = 13.701 (1) ŵ = 0.91 mm−1
b = 13.771 (1) ÅT = 173 (2) K
c = 13.590 (2) Å0.30 × 0.20 × 0.20 mm
Data collection top
KappaCCD
diffractometer		5867 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4185 reflections with I > 2σ(I)
Tmin = 0.772, Tmax = 0.839Rint = 0.064
23034 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.101Δρmax = 0.36 e Å−3
S = 0.92Δρmin = −0.50 e Å−3
5867 reflectionsAbsolute structure: Flack (1983)
359 parametersFlack parameter: −0.012 (16)
2 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu1−0.5000−0.50000.48333 (4)0.02001 (14)
O1−0.3638 (2)−0.28347 (19)0.32677 (19)0.0349 (7)
N1−0.5000−0.50000.3408 (2)0.0191 (8)
C1−0.4520 (2)−0.4300 (2)0.2937 (3)0.0214 (8)
N2−0.4164 (2)−0.38220 (19)0.4561 (2)0.0223 (7)
Cu2−0.50000.00001.00029 (3)0.01894 (14)
C2−0.4508 (3)−0.4272 (3)0.1921 (3)0.0291 (9)
H2−0.4174−0.37710.15790.035*
O2−0.2196 (2)−0.3824 (2)0.5169 (2)0.0485 (8)
N3−0.6990 (2)−0.3186 (2)0.6318 (2)0.0303 (8)
H3−0.7571−0.29480.64510.036*
O3−0.2429 (2)−0.2419 (2)0.5985 (2)0.0480 (9)
C3−0.5000−0.50000.1414 (3)0.0376 (13)
H3A−0.5000−0.50000.07150.045*
N4−0.5842 (2)−0.4186 (2)0.5793 (2)0.0236 (7)
C4−0.4052 (3)−0.3578 (2)0.3633 (3)0.0234 (8)
O4−0.26885 (19)−0.11115 (17)0.84523 (18)0.0309 (6)
N5−0.50000.00000.8564 (2)0.0216 (8)
O5−0.35581 (18)−0.26385 (17)1.03435 (18)0.0287 (6)
C5−0.3818 (3)−0.3123 (3)0.5292 (3)0.0298 (9)
H5−0.3986−0.24530.50660.036*
O6−0.21054 (19)−0.23048 (17)1.10423 (18)0.0281 (6)
C6−0.2722 (3)−0.3190 (3)0.5447 (3)0.0367 (10)
N6−0.3735 (2)−0.07025 (18)0.9725 (2)0.0190 (6)
N7−0.3301 (2)0.2171 (2)1.1365 (2)0.0247 (7)
H7−0.31010.27731.14440.030*
C7−0.1386 (3)−0.2378 (4)0.6201 (3)0.0720 (18)
H7A−0.1198−0.29510.65840.108*
H7B−0.1243−0.17890.65800.108*
H7C−0.1018−0.23650.55830.108*
N8−0.4247 (2)0.09291 (19)1.0957 (2)0.0197 (6)
C8−0.4313 (3)−0.3311 (3)0.6305 (3)0.0287 (10)
H8A−0.4052−0.39200.65880.034*
H8B−0.4146−0.27740.67590.034*
C9−0.5404 (3)−0.3388 (3)0.6225 (3)0.0245 (9)
C10−0.6110 (3)−0.2770 (3)0.6542 (3)0.0321 (9)
H10−0.6012−0.21630.68590.038*
C100−0.0049 (4)0.1275 (3)0.1186 (3)0.0557 (11)
H10A0.03770.12420.06080.084*
H10B−0.06370.08860.10690.084*
H10C0.02980.10210.17620.084*
C11−0.6796 (3)−0.4027 (3)0.5859 (3)0.0272 (9)
H11−0.7281−0.44550.56110.033*
O11−0.0318 (3)0.2254 (2)0.1361 (2)0.0625 (10)
H11A−0.06270.24680.08730.094*
C12−0.4237 (3)−0.0397 (2)0.8098 (3)0.0209 (8)
C13−0.4217 (3)−0.0407 (3)0.7086 (3)0.0345 (10)
H13−0.3681−0.06850.67440.041*
C14−0.50000.00000.6568 (4)0.0493 (17)
H14−0.50000.00000.58690.059*
C15−0.3479 (3)−0.0782 (2)0.8793 (2)0.0211 (8)
C16−0.2992 (3)−0.0964 (2)1.0444 (2)0.0222 (8)
H16−0.2344−0.07231.02090.027*
C17−0.2936 (3)−0.2061 (3)1.0588 (2)0.0222 (8)
C18−0.1962 (3)−0.3332 (2)1.1250 (3)0.0314 (9)
H18A−0.1270−0.34541.13840.047*
H18B−0.2168−0.37171.06800.047*
H18C−0.2351−0.35161.18260.047*
C19−0.3216 (3)−0.0500 (2)1.1451 (3)0.0251 (9)
H19A−0.3804−0.08111.17340.030*
H19B−0.2663−0.06241.19030.030*
C20−0.3383 (3)0.0574 (2)1.1379 (3)0.0221 (8)
C21−0.2801 (3)0.1340 (3)1.1632 (2)0.0264 (8)
H21−0.21750.13081.19330.032*
C22−0.4153 (3)0.1889 (2)1.0961 (3)0.0243 (8)
H22−0.46290.23251.07090.029*
O12−0.5670 (9)0.0368 (19)0.4155 (9)0.261 (12)0.50
C201−0.495 (3)−0.022 (4)0.3637 (9)0.127 (15)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0194 (3)0.0192 (3)0.0214 (3)−0.0025 (3)0.0000.000
O10.0409 (18)0.0325 (15)0.0313 (15)−0.0211 (14)−0.0055 (13)0.0061 (12)
N10.017 (2)0.0204 (19)0.0199 (17)−0.001 (2)0.0000.000
C10.0170 (19)0.0213 (19)0.026 (2)−0.0005 (16)−0.0040 (15)0.0020 (15)
N20.0215 (17)0.0207 (15)0.0247 (16)−0.0046 (14)−0.0053 (13)0.0008 (12)
Cu20.0188 (3)0.0179 (3)0.0201 (3)0.0005 (3)0.0000.000
C20.035 (2)0.027 (2)0.026 (2)−0.0147 (18)0.0011 (16)0.0056 (16)
O20.0286 (17)0.0528 (19)0.064 (2)−0.0093 (16)−0.0049 (16)0.0069 (16)
N30.028 (2)0.0336 (18)0.0291 (17)0.0136 (16)0.0041 (14)−0.0031 (14)
O30.044 (2)0.064 (2)0.0369 (17)−0.0329 (17)−0.0093 (14)−0.0055 (14)
C30.050 (4)0.041 (3)0.021 (2)−0.018 (4)0.0000.000
N40.0218 (17)0.0237 (16)0.0252 (16)0.0024 (15)−0.0017 (13)0.0004 (13)
C40.018 (2)0.0220 (19)0.030 (2)−0.0034 (16)−0.0042 (15)0.0019 (15)
O40.0337 (17)0.0282 (14)0.0308 (15)0.0126 (13)0.0078 (12)0.0063 (11)
N50.030 (2)0.0125 (18)0.0219 (18)−0.003 (2)0.0000.000
O50.0285 (15)0.0203 (13)0.0374 (15)−0.0036 (12)−0.0031 (12)0.0038 (11)
C50.033 (2)0.027 (2)0.030 (2)−0.0073 (17)−0.0115 (17)−0.0001 (16)
O60.0273 (15)0.0199 (13)0.0371 (15)0.0093 (12)−0.0061 (12)0.0008 (11)
C60.038 (3)0.051 (3)0.021 (2)−0.017 (2)−0.0098 (19)0.0127 (19)
N60.0195 (15)0.0163 (14)0.0210 (15)0.0040 (13)0.0000 (12)0.0002 (12)
N70.0271 (19)0.0172 (16)0.0299 (17)−0.0066 (14)−0.0002 (14)−0.0019 (13)
C70.060 (4)0.121 (5)0.035 (3)−0.061 (3)−0.012 (2)0.018 (3)
N80.0201 (16)0.0144 (15)0.0246 (16)−0.0015 (13)−0.0021 (13)−0.0025 (12)
C80.030 (2)0.030 (2)0.026 (2)−0.0027 (19)−0.0106 (18)−0.0069 (17)
C90.030 (2)0.024 (2)0.020 (2)0.0057 (17)0.0000 (16)−0.0018 (15)
C100.040 (3)0.027 (2)0.028 (2)0.004 (2)−0.0044 (18)−0.0081 (17)
C1000.066 (3)0.052 (3)0.049 (2)0.015 (3)−0.002 (3)−0.0067 (19)
C110.026 (2)0.026 (2)0.029 (2)0.0058 (17)−0.0020 (17)−0.0001 (16)
O110.081 (3)0.053 (2)0.053 (2)0.0131 (18)−0.0121 (17)−0.0071 (16)
C120.024 (2)0.0166 (16)0.0219 (18)0.0038 (15)0.0042 (16)−0.0004 (13)
C130.048 (3)0.035 (2)0.021 (2)0.016 (2)0.0094 (18)−0.0004 (15)
C140.064 (4)0.064 (4)0.020 (2)0.034 (5)0.0000.000
C150.028 (2)0.0104 (16)0.0248 (19)0.0004 (16)0.0030 (15)0.0030 (14)
C160.0180 (19)0.0203 (18)0.0283 (19)0.0000 (16)0.0024 (15)0.0039 (15)
C170.025 (2)0.0210 (19)0.0205 (18)0.0077 (18)0.0083 (15)0.0041 (14)
C180.039 (3)0.0208 (19)0.035 (2)0.0124 (18)−0.0047 (19)0.0031 (16)
C190.027 (2)0.024 (2)0.024 (2)−0.0003 (17)−0.0014 (17)−0.0001 (16)
C200.024 (2)0.0163 (19)0.026 (2)−0.0053 (17)0.0024 (16)−0.0018 (16)
C210.020 (2)0.033 (2)0.027 (2)−0.0047 (18)−0.0005 (15)−0.0049 (16)
C220.027 (2)0.0196 (19)0.026 (2)0.0002 (17)0.0006 (16)−0.0015 (15)
O120.096 (9)0.58 (4)0.103 (9)−0.084 (15)0.006 (7)−0.129 (16)
C2010.100 (13)0.23 (5)0.057 (6)−0.063 (16)−0.032 (15)0.020 (12)
Geometric parameters (Å, °) top
Cu1—N11.937 (3)N6—C161.456 (4)
Cu1—N2i2.020 (3)N7—C221.347 (4)
Cu1—N22.020 (3)N7—C211.383 (5)
Cu1—N4i2.071 (3)N7—H70.8800
Cu1—N42.071 (3)C7—H7A0.9800
O1—C41.271 (4)C7—H7B0.9800
N1—C11.331 (4)C7—H7C0.9800
N1—C1i1.331 (4)N8—C221.329 (4)
C1—C21.381 (5)N8—C201.403 (4)
C1—C41.514 (5)C8—C91.502 (5)
N2—C41.315 (4)C8—H8A0.9900
N2—C51.461 (4)C8—H8B0.9900
Cu2—N51.956 (3)C9—C101.359 (5)
Cu2—N62.020 (3)C10—H100.9500
Cu2—N6ii2.020 (3)C100—O111.416 (5)
Cu2—N82.094 (3)C100—H10A0.9800
Cu2—N8ii2.094 (3)C100—H10B0.9800
C2—C31.390 (4)C100—H10C0.9800
C2—H20.9500C11—H110.9500
O2—C61.194 (5)O11—H11A0.8400
N3—C111.342 (5)C12—C131.376 (5)
N3—C101.369 (5)C12—C151.500 (5)
N3—H30.8800C13—C141.399 (5)
O3—C61.351 (5)C13—H130.9500
O3—C71.459 (5)C14—C13ii1.399 (5)
C3—C2i1.390 (4)C14—H140.9500
C3—H3A0.9500C16—C171.525 (5)
N4—C111.328 (4)C16—C191.541 (5)
N4—C91.383 (4)C16—H161.0000
O4—C151.263 (4)C18—H18A0.9800
N5—C121.339 (4)C18—H18B0.9800
N5—C12ii1.339 (4)C18—H18C0.9800
O5—C171.213 (4)C19—C201.499 (4)
C5—C61.520 (6)C19—H19A0.9900
C5—C81.556 (5)C19—H19B0.9900
C5—H51.0000C20—C211.368 (5)
O6—C171.337 (4)C21—H210.9500
O6—C181.456 (4)C22—H220.9500
N6—C151.318 (4)O12—C2011.452 (10)
N1—Cu1—N2i79.45 (8)H7B—C7—H7C109.5
N1—Cu1—N279.45 (8)C22—N8—C20105.3 (3)
N2i—Cu1—N2158.89 (16)C22—N8—Cu2131.2 (2)
N1—Cu1—N4i129.05 (8)C20—N8—Cu2117.1 (2)
N2i—Cu1—N4i89.80 (11)C9—C8—C5112.4 (3)
N2—Cu1—N4i103.55 (11)C9—C8—H8A109.1
N1—Cu1—N4129.05 (8)C5—C8—H8A109.1
N2i—Cu1—N4103.55 (11)C9—C8—H8B109.1
N2—Cu1—N489.80 (11)C5—C8—H8B109.1
N4i—Cu1—N4101.91 (15)H8A—C8—H8B107.9
C1—N1—C1i122.5 (4)C10—C9—N4108.8 (3)
C1—N1—Cu1118.75 (19)C10—C9—C8129.9 (4)
C1i—N1—Cu1118.75 (19)N4—C9—C8121.2 (3)
N1—C1—C2120.4 (3)C9—C10—N3107.2 (3)
N1—C1—C4112.6 (3)C9—C10—H10126.4
C2—C1—C4127.0 (3)N3—C10—H10126.4
C4—N2—C5116.5 (3)O11—C100—H10A109.5
C4—N2—Cu1116.6 (2)O11—C100—H10B109.5
C5—N2—Cu1126.0 (2)H10A—C100—H10B109.5
N5—Cu2—N679.23 (8)O11—C100—H10C109.5
N5—Cu2—N6ii79.23 (8)H10A—C100—H10C109.5
N6—Cu2—N6ii158.45 (15)H10B—C100—H10C109.5
N5—Cu2—N8128.27 (8)N4—C11—N3111.6 (3)
N6—Cu2—N889.18 (11)N4—C11—H11124.2
N6ii—Cu2—N8104.23 (10)N3—C11—H11124.2
N5—Cu2—N8ii128.27 (8)C100—O11—H11A109.5
N6—Cu2—N8ii104.23 (10)N5—C12—C13119.4 (3)
N6ii—Cu2—N8ii89.18 (11)N5—C12—C15112.8 (3)
N8—Cu2—N8ii103.46 (15)C13—C12—C15127.8 (3)
C1—C2—C3118.0 (3)C12—C13—C14118.9 (4)
C1—C2—H2121.0C12—C13—H13120.5
C3—C2—H2121.0C14—C13—H13120.5
C11—N3—C10106.9 (3)C13—C14—C13ii119.7 (5)
C11—N3—H3126.6C13—C14—H14120.2
C10—N3—H3126.6C13ii—C14—H14120.2
C6—O3—C7115.5 (4)O4—C15—N6127.6 (3)
C2i—C3—C2120.6 (4)O4—C15—C12119.3 (3)
C2i—C3—H3A119.7N6—C15—C12113.0 (3)
C2—C3—H3A119.7N6—C16—C17111.5 (3)
C11—N4—C9105.5 (3)N6—C16—C19110.8 (3)
C11—N4—Cu1132.8 (2)C17—C16—C19107.9 (3)
C9—N4—Cu1117.1 (2)N6—C16—H16108.9
O1—C4—N2129.3 (3)C17—C16—H16108.9
O1—C4—C1118.3 (3)C19—C16—H16108.9
N2—C4—C1112.5 (3)O5—C17—O6124.0 (3)
C12—N5—C12ii123.6 (4)O5—C17—C16125.4 (3)
C12—N5—Cu2118.2 (2)O6—C17—C16110.6 (3)
C12ii—N5—Cu2118.2 (2)O6—C18—H18A109.5
N2—C5—C6112.1 (3)O6—C18—H18B109.5
N2—C5—C8110.5 (3)H18A—C18—H18B109.5
C6—C5—C8107.3 (3)O6—C18—H18C109.5
N2—C5—H5109.0H18A—C18—H18C109.5
C6—C5—H5109.0H18B—C18—H18C109.5
C8—C5—H5109.0C20—C19—C16112.4 (4)
C17—O6—C18116.7 (3)C20—C19—H19A109.1
O2—C6—O3124.6 (4)C16—C19—H19A109.1
O2—C6—C5126.6 (4)C20—C19—H19B109.1
O3—C6—C5108.8 (4)C16—C19—H19B109.1
C15—N6—C16116.0 (3)H19A—C19—H19B107.9
C15—N6—Cu2116.6 (2)C21—C20—N8109.0 (3)
C16—N6—Cu2126.3 (2)C21—C20—C19130.9 (4)
C22—N7—C21107.4 (3)N8—C20—C19120.0 (3)
C22—N7—H7126.3C20—C21—N7106.4 (3)
C21—N7—H7126.3C20—C21—H21126.8
O3—C7—H7A109.5N7—C21—H21126.8
O3—C7—H7B109.5N8—C22—N7111.9 (3)
H7A—C7—H7B109.5N8—C22—H22124.1
O3—C7—H7C109.5N7—C22—H22124.1
H7A—C7—H7C109.5
N2i—Cu1—N1—C1179.10 (19)N8—Cu2—N6—C1641.8 (3)
N2—Cu1—N1—C1−0.90 (19)N8ii—Cu2—N6—C16−61.9 (3)
N4i—Cu1—N1—C1−99.9 (2)N5—Cu2—N8—C2246.9 (3)
N4—Cu1—N1—C180.1 (2)N6—Cu2—N8—C22122.4 (3)
N2i—Cu1—N1—C1i−0.90 (19)N6ii—Cu2—N8—C22−40.5 (3)
N2—Cu1—N1—C1i179.10 (19)N8ii—Cu2—N8—C22−133.1 (3)
N4i—Cu1—N1—C1i80.1 (2)N5—Cu2—N8—C20−100.4 (2)
N4—Cu1—N1—C1i−99.9 (2)N6—Cu2—N8—C20−24.9 (2)
C1i—N1—C1—C20.4 (3)N6ii—Cu2—N8—C20172.2 (2)
Cu1—N1—C1—C2−179.6 (3)N8ii—Cu2—N8—C2079.6 (2)
C1i—N1—C1—C4178.7 (3)N2—C5—C8—C9−50.4 (4)
Cu1—N1—C1—C4−1.3 (3)C6—C5—C8—C9−172.9 (3)
N1—Cu1—N2—C43.3 (2)C11—N4—C9—C100.2 (4)
N2i—Cu1—N2—C43.3 (2)Cu1—N4—C9—C10159.3 (2)
N4i—Cu1—N2—C4131.2 (2)C11—N4—C9—C8179.0 (4)
N4—Cu1—N2—C4−126.6 (3)Cu1—N4—C9—C8−21.8 (5)
N1—Cu1—N2—C5171.8 (3)C5—C8—C9—C10−110.0 (5)
N2i—Cu1—N2—C5171.8 (3)C5—C8—C9—N471.4 (5)
N4i—Cu1—N2—C5−60.3 (3)N4—C9—C10—N30.6 (4)
N4—Cu1—N2—C541.9 (3)C8—C9—C10—N3−178.1 (4)
N1—C1—C2—C3−0.8 (5)C11—N3—C10—C9−1.2 (4)
C4—C1—C2—C3−178.8 (3)C9—N4—C11—N3−1.0 (4)
C1—C2—C3—C2i0.4 (2)Cu1—N4—C11—N3−155.4 (3)
N1—Cu1—N4—C1150.6 (4)C10—N3—C11—N41.4 (4)
N2i—Cu1—N4—C11−36.7 (3)C12ii—N5—C12—C130.0 (2)
N2—Cu1—N4—C11126.8 (3)Cu2—N5—C12—C13−180.0 (2)
N4i—Cu1—N4—C11−129.4 (4)C12ii—N5—C12—C15179.5 (3)
N1—Cu1—N4—C9−101.4 (2)Cu2—N5—C12—C15−0.5 (3)
N2i—Cu1—N4—C9171.3 (2)N5—C12—C13—C140.0 (5)
N2—Cu1—N4—C9−25.2 (2)C15—C12—C13—C14−179.5 (3)
N4i—Cu1—N4—C978.6 (2)C12—C13—C14—C13ii0.0 (2)
C5—N2—C4—O13.9 (5)C16—N6—C15—O44.6 (5)
Cu1—N2—C4—O1173.5 (3)Cu2—N6—C15—O4173.3 (3)
C5—N2—C4—C1−174.4 (3)C16—N6—C15—C12−173.6 (3)
Cu1—N2—C4—C1−4.8 (4)Cu2—N6—C15—C12−4.8 (4)
N1—C1—C4—O1−174.6 (3)N5—C12—C15—O4−174.9 (3)
C2—C1—C4—O13.6 (5)C13—C12—C15—O44.6 (5)
N1—C1—C4—N23.9 (4)N5—C12—C15—N63.5 (4)
C2—C1—C4—N2−177.9 (4)C13—C12—C15—N6−177.1 (3)
N6—Cu2—N5—C12−1.58 (18)C15—N6—C16—C17−80.8 (4)
N6ii—Cu2—N5—C12178.42 (18)Cu2—N6—C16—C17111.7 (3)
N8—Cu2—N5—C1278.72 (19)C15—N6—C16—C19159.0 (3)
N8ii—Cu2—N5—C12−101.28 (19)Cu2—N6—C16—C19−8.5 (4)
N6—Cu2—N5—C12ii178.42 (18)C18—O6—C17—O5−0.2 (5)
N6ii—Cu2—N5—C12ii−1.58 (18)C18—O6—C17—C16178.6 (3)
N8—Cu2—N5—C12ii−101.28 (19)N6—C16—C17—O5−17.1 (5)
N8ii—Cu2—N5—C12ii78.72 (19)C19—C16—C17—O5104.7 (4)
C4—N2—C5—C6−80.7 (4)N6—C16—C17—O6164.1 (3)
Cu1—N2—C5—C6110.7 (3)C19—C16—C17—O6−74.1 (4)
C4—N2—C5—C8159.7 (3)N6—C16—C19—C20−52.2 (4)
Cu1—N2—C5—C8−8.8 (4)C17—C16—C19—C20−174.5 (3)
C7—O3—C6—O21.6 (6)C22—N8—C20—C210.6 (4)
C7—O3—C6—C5179.9 (3)Cu2—N8—C20—C21155.7 (2)
N2—C5—C6—O2−12.9 (6)C22—N8—C20—C19−177.2 (4)
C8—C5—C6—O2108.6 (4)Cu2—N8—C20—C19−22.2 (5)
N2—C5—C6—O3168.9 (3)C16—C19—C20—C21−104.8 (5)
C8—C5—C6—O3−69.6 (4)C16—C19—C20—N872.5 (5)
N5—Cu2—N6—C153.7 (2)N8—C20—C21—N7−0.2 (4)
N6ii—Cu2—N6—C153.7 (2)C19—C20—C21—N7177.3 (4)
N8—Cu2—N6—C15−125.6 (2)C22—N7—C21—C20−0.3 (4)
N8ii—Cu2—N6—C15130.7 (2)C20—N8—C22—N7−0.8 (4)
N5—Cu2—N6—C16171.1 (3)Cu2—N8—C22—N7−150.9 (3)
N6ii—Cu2—N6—C16171.1 (3)C21—N7—C22—N80.7 (4)
Symmetry codes: (i) −x−1, −y−1, z; (ii) −x−1, −y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1iii0.881.862.719 (4)166
N7—H7···O4iv0.881.882.738 (4)163
O11—H11A···O5v0.842.002.785 (4)155
Symmetry codes: (iii) x−1/2, −y−1/2, −z+1; (iv) −x−1/2, y+1/2, −z+2; (v) −x−1/2, y+1/2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1i0.881.862.719 (4)166
N7—H7···O4ii0.881.882.738 (4)163
O11—H11A···O5iii0.842.002.785 (4)155
Symmetry codes: (i) x−1/2, −y−1/2, −z+1; (ii) −x−1/2, y+1/2, −z+2; (iii) −x−1/2, y+1/2, −z+1.
Acknowledgements top

MTR is grateful to the Magnus Ehrnrooth Foundation for financial supportis gratefully acknowledged by M·R.

references
References top

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