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

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

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

In the Cu^II 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 Cu^II centre is in a distorted square-pyramidal geometry, and intermolecular hydrogen bonds stabilize the molecular packing.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056863/cs2055sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056863/cs2055Isup2.hkl Contains datablock I

CCDC reference: 672663

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.005 Å
Disorder in solvent or counterion
R factor = 0.045
wR factor = 0.101
Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.36 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.27 Ratio
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      25.00 Perc.
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........        O12
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C21 H21 Cu N7 O6
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C21 H21 Cu N7 O6
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              C O

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C22.5 H25 Cu1 N7 O7.5
            Atom count from _chemical_formula_moiety:C22.5 H27 Cu1 N7 O7.5
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.48
           From the CIF: _reflns_number_total               5867
           Count of symmetry unique reflns         3306
           Completeness (_total/calc)            177.47%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2561
           Fraction of Friedel pairs measured     0.775
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C16    = .          S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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).

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

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)]·1.5CH₄O	F(000) = 1192
M_r = 577.04	D_x = 1.495 Mg m⁻³
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 23034 reflections
a = 13.701 (1) Å	θ = 3.3–27.5°
b = 13.771 (1) Å	µ = 0.91 mm⁻¹
c = 13.590 (2) Å	T = 173 K
V = 2564.1 (5) Å³	Block, blue
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

KappaCCD diffractometer	5867 independent reflections
Radiation source: fine-focus sealed tube	4185 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ω and ϕ scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
T_min = 0.772, T_max = 0.839	k = −17→17
23034 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0514P)² + 0.3474P] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max = 0.001
5867 reflections	Δρ_max = 0.36 e Å⁻³
359 parameters	Δρ_min = −0.50 e Å⁻³
2 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.012 (16)

Crystal data top

[Cu(C₂₁H₂₁N₇O₆)]·1.5CH₄O	V = 2564.1 (5) Å³
M_r = 577.04	Z = 4
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 13.701 (1) Å	µ = 0.91 mm⁻¹
b = 13.771 (1) Å	T = 173 K
c = 13.590 (2) Å	0.30 × 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)
T_min = 0.772, T_max = 0.839	R_int = 0.064
23034 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.101	Δρ_max = 0.36 e Å⁻³
S = 0.92	Δρ_min = −0.50 e Å⁻³
5867 reflections	Absolute structure: Flack (1983)
359 parameters	Absolute structure parameter: −0.012 (16)
2 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	−0.5000	−0.5000	0.48333 (4)	0.02001 (14)
O1	−0.3638 (2)	−0.28347 (19)	0.32677 (19)	0.0349 (7)
N1	−0.5000	−0.5000	0.3408 (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	−0.5000	0.0000	1.00029 (3)	0.01894 (14)
C2	−0.4508 (3)	−0.4272 (3)	0.1921 (3)	0.0291 (9)
H2	−0.4174	−0.3771	0.1579	0.035*
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	−0.2948	0.6451	0.036*
O3	−0.2429 (2)	−0.2419 (2)	0.5985 (2)	0.0480 (9)
C3	−0.5000	−0.5000	0.1414 (3)	0.0376 (13)
H3A	−0.5000	−0.5000	0.0715	0.045*
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	−0.5000	0.0000	0.8564 (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	−0.2453	0.5066	0.036*
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	−0.3101	0.2773	1.1444	0.030*
C7	−0.1386 (3)	−0.2378 (4)	0.6201 (3)	0.0720 (18)
H7A	−0.1198	−0.2951	0.6584	0.108*
H7B	−0.1243	−0.1789	0.6580	0.108*
H7C	−0.1018	−0.2365	0.5583	0.108*
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	−0.3920	0.6588	0.034*
H8B	−0.4146	−0.2774	0.6759	0.034*
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	−0.2163	0.6859	0.038*
C100	−0.0049 (4)	0.1275 (3)	0.1186 (3)	0.0557 (11)
H10A	0.0377	0.1242	0.0608	0.084*
H10B	−0.0637	0.0886	0.1069	0.084*
H10C	0.0298	0.1021	0.1762	0.084*
C11	−0.6796 (3)	−0.4027 (3)	0.5859 (3)	0.0272 (9)
H11	−0.7281	−0.4455	0.5611	0.033*
O11	−0.0318 (3)	0.2254 (2)	0.1361 (2)	0.0625 (10)
H11A	−0.0627	0.2468	0.0873	0.094*
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	−0.0685	0.6744	0.041*
C14	−0.5000	0.0000	0.6568 (4)	0.0493 (17)
H14	−0.5000	0.0000	0.5869	0.059*
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	−0.0723	1.0209	0.027*
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	−0.3454	1.1384	0.047*
H18B	−0.2168	−0.3717	1.0680	0.047*
H18C	−0.2351	−0.3516	1.1826	0.047*
C19	−0.3216 (3)	−0.0500 (2)	1.1451 (3)	0.0251 (9)
H19A	−0.3804	−0.0811	1.1734	0.030*
H19B	−0.2663	−0.0624	1.1903	0.030*
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	−0.2175	0.1308	1.1933	0.032*
C22	−0.4153 (3)	0.1889 (2)	1.0961 (3)	0.0243 (8)
H22	−0.4629	0.2325	1.0709	0.029*
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

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0194 (3)	0.0192 (3)	0.0214 (3)	−0.0025 (3)	0.000	0.000
O1	0.0409 (18)	0.0325 (15)	0.0313 (15)	−0.0211 (14)	−0.0055 (13)	0.0061 (12)
N1	0.017 (2)	0.0204 (19)	0.0199 (17)	−0.001 (2)	0.000	0.000
C1	0.0170 (19)	0.0213 (19)	0.026 (2)	−0.0005 (16)	−0.0040 (15)	0.0020 (15)
N2	0.0215 (17)	0.0207 (15)	0.0247 (16)	−0.0046 (14)	−0.0053 (13)	0.0008 (12)
Cu2	0.0188 (3)	0.0179 (3)	0.0201 (3)	0.0005 (3)	0.000	0.000
C2	0.035 (2)	0.027 (2)	0.026 (2)	−0.0147 (18)	0.0011 (16)	0.0056 (16)
O2	0.0286 (17)	0.0528 (19)	0.064 (2)	−0.0093 (16)	−0.0049 (16)	0.0069 (16)
N3	0.028 (2)	0.0336 (18)	0.0291 (17)	0.0136 (16)	0.0041 (14)	−0.0031 (14)
O3	0.044 (2)	0.064 (2)	0.0369 (17)	−0.0329 (17)	−0.0093 (14)	−0.0055 (14)
C3	0.050 (4)	0.041 (3)	0.021 (2)	−0.018 (4)	0.000	0.000
N4	0.0218 (17)	0.0237 (16)	0.0252 (16)	0.0024 (15)	−0.0017 (13)	0.0004 (13)
C4	0.018 (2)	0.0220 (19)	0.030 (2)	−0.0034 (16)	−0.0042 (15)	0.0019 (15)
O4	0.0337 (17)	0.0282 (14)	0.0308 (15)	0.0126 (13)	0.0078 (12)	0.0063 (11)
N5	0.030 (2)	0.0125 (18)	0.0219 (18)	−0.003 (2)	0.000	0.000
O5	0.0285 (15)	0.0203 (13)	0.0374 (15)	−0.0036 (12)	−0.0031 (12)	0.0038 (11)
C5	0.033 (2)	0.027 (2)	0.030 (2)	−0.0073 (17)	−0.0115 (17)	−0.0001 (16)
O6	0.0273 (15)	0.0199 (13)	0.0371 (15)	0.0093 (12)	−0.0061 (12)	0.0008 (11)
C6	0.038 (3)	0.051 (3)	0.021 (2)	−0.017 (2)	−0.0098 (19)	0.0127 (19)
N6	0.0195 (15)	0.0163 (14)	0.0210 (15)	0.0040 (13)	0.0000 (12)	0.0002 (12)
N7	0.0271 (19)	0.0172 (16)	0.0299 (17)	−0.0066 (14)	−0.0002 (14)	−0.0019 (13)
C7	0.060 (4)	0.121 (5)	0.035 (3)	−0.061 (3)	−0.012 (2)	0.018 (3)
N8	0.0201 (16)	0.0144 (15)	0.0246 (16)	−0.0015 (13)	−0.0021 (13)	−0.0025 (12)
C8	0.030 (2)	0.030 (2)	0.026 (2)	−0.0027 (19)	−0.0106 (18)	−0.0069 (17)
C9	0.030 (2)	0.024 (2)	0.020 (2)	0.0057 (17)	0.0000 (16)	−0.0018 (15)
C10	0.040 (3)	0.027 (2)	0.028 (2)	0.004 (2)	−0.0044 (18)	−0.0081 (17)
C100	0.066 (3)	0.052 (3)	0.049 (2)	0.015 (3)	−0.002 (3)	−0.0067 (19)
C11	0.026 (2)	0.026 (2)	0.029 (2)	0.0058 (17)	−0.0020 (17)	−0.0001 (16)
O11	0.081 (3)	0.053 (2)	0.053 (2)	0.0131 (18)	−0.0121 (17)	−0.0071 (16)
C12	0.024 (2)	0.0166 (16)	0.0219 (18)	0.0038 (15)	0.0042 (16)	−0.0004 (13)
C13	0.048 (3)	0.035 (2)	0.021 (2)	0.016 (2)	0.0094 (18)	−0.0004 (15)
C14	0.064 (4)	0.064 (4)	0.020 (2)	0.034 (5)	0.000	0.000
C15	0.028 (2)	0.0104 (16)	0.0248 (19)	0.0004 (16)	0.0030 (15)	0.0030 (14)
C16	0.0180 (19)	0.0203 (18)	0.0283 (19)	0.0000 (16)	0.0024 (15)	0.0039 (15)
C17	0.025 (2)	0.0210 (19)	0.0205 (18)	0.0077 (18)	0.0083 (15)	0.0041 (14)
C18	0.039 (3)	0.0208 (19)	0.035 (2)	0.0124 (18)	−0.0047 (19)	0.0031 (16)
C19	0.027 (2)	0.024 (2)	0.024 (2)	−0.0003 (17)	−0.0014 (17)	−0.0001 (16)
C20	0.024 (2)	0.0163 (19)	0.026 (2)	−0.0053 (17)	0.0024 (16)	−0.0018 (16)
C21	0.020 (2)	0.033 (2)	0.027 (2)	−0.0047 (18)	−0.0005 (15)	−0.0049 (16)
C22	0.027 (2)	0.0196 (19)	0.026 (2)	0.0002 (17)	0.0006 (16)	−0.0015 (15)
O12	0.096 (9)	0.58 (4)	0.103 (9)	−0.084 (15)	0.006 (7)	−0.129 (16)
C201	0.100 (13)	0.23 (5)	0.057 (6)	−0.063 (16)	−0.032 (15)	0.020 (12)

Geometric parameters (Å, º) top

Cu1—N1	1.937 (3)	N6—C16	1.456 (4)
Cu1—N2ⁱ	2.020 (3)	N7—C22	1.347 (4)
Cu1—N2	2.020 (3)	N7—C21	1.383 (5)
Cu1—N4ⁱ	2.071 (3)	N7—H7	0.8800
Cu1—N4	2.071 (3)	C7—H7A	0.9800
O1—C4	1.271 (4)	C7—H7B	0.9800
N1—C1	1.331 (4)	C7—H7C	0.9800
N1—C1ⁱ	1.331 (4)	N8—C22	1.329 (4)
C1—C2	1.381 (5)	N8—C20	1.403 (4)
C1—C4	1.514 (5)	C8—C9	1.502 (5)
N2—C4	1.315 (4)	C8—H8A	0.9900
N2—C5	1.461 (4)	C8—H8B	0.9900
Cu2—N5	1.956 (3)	C9—C10	1.359 (5)
Cu2—N6	2.020 (3)	C10—H10	0.9500
Cu2—N6ⁱⁱ	2.020 (3)	C100—O11	1.416 (5)
Cu2—N8	2.094 (3)	C100—H10A	0.9800
Cu2—N8ⁱⁱ	2.094 (3)	C100—H10B	0.9800
C2—C3	1.390 (4)	C100—H10C	0.9800
C2—H2	0.9500	C11—H11	0.9500
O2—C6	1.194 (5)	O11—H11A	0.8400
N3—C11	1.342 (5)	C12—C13	1.376 (5)
N3—C10	1.369 (5)	C12—C15	1.500 (5)
N3—H3	0.8800	C13—C14	1.399 (5)
O3—C6	1.351 (5)	C13—H13	0.9500
O3—C7	1.459 (5)	C14—C13ⁱⁱ	1.399 (5)
C3—C2ⁱ	1.390 (4)	C14—H14	0.9500
C3—H3A	0.9500	C16—C17	1.525 (5)
N4—C11	1.328 (4)	C16—C19	1.541 (5)
N4—C9	1.383 (4)	C16—H16	1.0000
O4—C15	1.263 (4)	C18—H18A	0.9800
N5—C12	1.339 (4)	C18—H18B	0.9800
N5—C12ⁱⁱ	1.339 (4)	C18—H18C	0.9800
O5—C17	1.213 (4)	C19—C20	1.499 (4)
C5—C6	1.520 (6)	C19—H19A	0.9900
C5—C8	1.556 (5)	C19—H19B	0.9900
C5—H5	1.0000	C20—C21	1.368 (5)
O6—C17	1.337 (4)	C21—H21	0.9500
O6—C18	1.456 (4)	C22—H22	0.9500
N6—C15	1.318 (4)	O12—C201	1.452 (10)

N1—Cu1—N2ⁱ	79.45 (8)	H7B—C7—H7C	109.5
N1—Cu1—N2	79.45 (8)	C22—N8—C20	105.3 (3)
N2ⁱ—Cu1—N2	158.89 (16)	C22—N8—Cu2	131.2 (2)
N1—Cu1—N4ⁱ	129.05 (8)	C20—N8—Cu2	117.1 (2)
N2ⁱ—Cu1—N4ⁱ	89.80 (11)	C9—C8—C5	112.4 (3)
N2—Cu1—N4ⁱ	103.55 (11)	C9—C8—H8A	109.1
N1—Cu1—N4	129.05 (8)	C5—C8—H8A	109.1
N2ⁱ—Cu1—N4	103.55 (11)	C9—C8—H8B	109.1
N2—Cu1—N4	89.80 (11)	C5—C8—H8B	109.1
N4ⁱ—Cu1—N4	101.91 (15)	H8A—C8—H8B	107.9
C1—N1—C1ⁱ	122.5 (4)	C10—C9—N4	108.8 (3)
C1—N1—Cu1	118.75 (19)	C10—C9—C8	129.9 (4)
C1ⁱ—N1—Cu1	118.75 (19)	N4—C9—C8	121.2 (3)
N1—C1—C2	120.4 (3)	C9—C10—N3	107.2 (3)
N1—C1—C4	112.6 (3)	C9—C10—H10	126.4
C2—C1—C4	127.0 (3)	N3—C10—H10	126.4
C4—N2—C5	116.5 (3)	O11—C100—H10A	109.5
C4—N2—Cu1	116.6 (2)	O11—C100—H10B	109.5
C5—N2—Cu1	126.0 (2)	H10A—C100—H10B	109.5
N5—Cu2—N6	79.23 (8)	O11—C100—H10C	109.5
N5—Cu2—N6ⁱⁱ	79.23 (8)	H10A—C100—H10C	109.5
N6—Cu2—N6ⁱⁱ	158.45 (15)	H10B—C100—H10C	109.5
N5—Cu2—N8	128.27 (8)	N4—C11—N3	111.6 (3)
N6—Cu2—N8	89.18 (11)	N4—C11—H11	124.2
N6ⁱⁱ—Cu2—N8	104.23 (10)	N3—C11—H11	124.2
N5—Cu2—N8ⁱⁱ	128.27 (8)	C100—O11—H11A	109.5
N6—Cu2—N8ⁱⁱ	104.23 (10)	N5—C12—C13	119.4 (3)
N6ⁱⁱ—Cu2—N8ⁱⁱ	89.18 (11)	N5—C12—C15	112.8 (3)
N8—Cu2—N8ⁱⁱ	103.46 (15)	C13—C12—C15	127.8 (3)
C1—C2—C3	118.0 (3)	C12—C13—C14	118.9 (4)
C1—C2—H2	121.0	C12—C13—H13	120.5
C3—C2—H2	121.0	C14—C13—H13	120.5
C11—N3—C10	106.9 (3)	C13—C14—C13ⁱⁱ	119.7 (5)
C11—N3—H3	126.6	C13—C14—H14	120.2
C10—N3—H3	126.6	C13ⁱⁱ—C14—H14	120.2
C6—O3—C7	115.5 (4)	O4—C15—N6	127.6 (3)
C2ⁱ—C3—C2	120.6 (4)	O4—C15—C12	119.3 (3)
C2ⁱ—C3—H3A	119.7	N6—C15—C12	113.0 (3)
C2—C3—H3A	119.7	N6—C16—C17	111.5 (3)
C11—N4—C9	105.5 (3)	N6—C16—C19	110.8 (3)
C11—N4—Cu1	132.8 (2)	C17—C16—C19	107.9 (3)
C9—N4—Cu1	117.1 (2)	N6—C16—H16	108.9
O1—C4—N2	129.3 (3)	C17—C16—H16	108.9
O1—C4—C1	118.3 (3)	C19—C16—H16	108.9
N2—C4—C1	112.5 (3)	O5—C17—O6	124.0 (3)
C12—N5—C12ⁱⁱ	123.6 (4)	O5—C17—C16	125.4 (3)
C12—N5—Cu2	118.2 (2)	O6—C17—C16	110.6 (3)
C12ⁱⁱ—N5—Cu2	118.2 (2)	O6—C18—H18A	109.5
N2—C5—C6	112.1 (3)	O6—C18—H18B	109.5
N2—C5—C8	110.5 (3)	H18A—C18—H18B	109.5
C6—C5—C8	107.3 (3)	O6—C18—H18C	109.5
N2—C5—H5	109.0	H18A—C18—H18C	109.5
C6—C5—H5	109.0	H18B—C18—H18C	109.5
C8—C5—H5	109.0	C20—C19—C16	112.4 (4)
C17—O6—C18	116.7 (3)	C20—C19—H19A	109.1
O2—C6—O3	124.6 (4)	C16—C19—H19A	109.1
O2—C6—C5	126.6 (4)	C20—C19—H19B	109.1
O3—C6—C5	108.8 (4)	C16—C19—H19B	109.1
C15—N6—C16	116.0 (3)	H19A—C19—H19B	107.9
C15—N6—Cu2	116.6 (2)	C21—C20—N8	109.0 (3)
C16—N6—Cu2	126.3 (2)	C21—C20—C19	130.9 (4)
C22—N7—C21	107.4 (3)	N8—C20—C19	120.0 (3)
C22—N7—H7	126.3	C20—C21—N7	106.4 (3)
C21—N7—H7	126.3	C20—C21—H21	126.8
O3—C7—H7A	109.5	N7—C21—H21	126.8
O3—C7—H7B	109.5	N8—C22—N7	111.9 (3)
H7A—C7—H7B	109.5	N8—C22—H22	124.1
O3—C7—H7C	109.5	N7—C22—H22	124.1
H7A—C7—H7C	109.5

N2ⁱ—Cu1—N1—C1	179.10 (19)	N8—Cu2—N6—C16	41.8 (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—C22	46.9 (3)
N4—Cu1—N1—C1	80.1 (2)	N6—Cu2—N8—C22	122.4 (3)
N2ⁱ—Cu1—N1—C1ⁱ	−0.90 (19)	N6ⁱⁱ—Cu2—N8—C22	−40.5 (3)
N2—Cu1—N1—C1ⁱ	179.10 (19)	N8ⁱⁱ—Cu2—N8—C22	−133.1 (3)
N4ⁱ—Cu1—N1—C1ⁱ	80.1 (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—C2	0.4 (3)	N6ⁱⁱ—Cu2—N8—C20	172.2 (2)
Cu1—N1—C1—C2	−179.6 (3)	N8ⁱⁱ—Cu2—N8—C20	79.6 (2)
C1ⁱ—N1—C1—C4	178.7 (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—C4	3.3 (2)	C11—N4—C9—C10	0.2 (4)
N2ⁱ—Cu1—N2—C4	3.3 (2)	Cu1—N4—C9—C10	159.3 (2)
N4ⁱ—Cu1—N2—C4	131.2 (2)	C11—N4—C9—C8	179.0 (4)
N4—Cu1—N2—C4	−126.6 (3)	Cu1—N4—C9—C8	−21.8 (5)
N1—Cu1—N2—C5	171.8 (3)	C5—C8—C9—C10	−110.0 (5)
N2ⁱ—Cu1—N2—C5	171.8 (3)	C5—C8—C9—N4	71.4 (5)
N4ⁱ—Cu1—N2—C5	−60.3 (3)	N4—C9—C10—N3	0.6 (4)
N4—Cu1—N2—C5	41.9 (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—C2ⁱ	0.4 (2)	Cu1—N4—C11—N3	−155.4 (3)
N1—Cu1—N4—C11	50.6 (4)	C10—N3—C11—N4	1.4 (4)
N2ⁱ—Cu1—N4—C11	−36.7 (3)	C12ⁱⁱ—N5—C12—C13	0.0 (2)
N2—Cu1—N4—C11	126.8 (3)	Cu2—N5—C12—C13	−180.0 (2)
N4ⁱ—Cu1—N4—C11	−129.4 (4)	C12ⁱⁱ—N5—C12—C15	179.5 (3)
N1—Cu1—N4—C9	−101.4 (2)	Cu2—N5—C12—C15	−0.5 (3)
N2ⁱ—Cu1—N4—C9	171.3 (2)	N5—C12—C13—C14	0.0 (5)
N2—Cu1—N4—C9	−25.2 (2)	C15—C12—C13—C14	−179.5 (3)
N4ⁱ—Cu1—N4—C9	78.6 (2)	C12—C13—C14—C13ⁱⁱ	0.0 (2)
C5—N2—C4—O1	3.9 (5)	C16—N6—C15—O4	4.6 (5)
Cu1—N2—C4—O1	173.5 (3)	Cu2—N6—C15—O4	173.3 (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—O1	3.6 (5)	C13—C12—C15—O4	4.6 (5)
N1—C1—C4—N2	3.9 (4)	N5—C12—C15—N6	3.5 (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—C12	178.42 (18)	Cu2—N6—C16—C17	111.7 (3)
N8—Cu2—N5—C12	78.72 (19)	C15—N6—C16—C19	159.0 (3)
N8ⁱⁱ—Cu2—N5—C12	−101.28 (19)	Cu2—N6—C16—C19	−8.5 (4)
N6—Cu2—N5—C12ⁱⁱ	178.42 (18)	C18—O6—C17—O5	−0.2 (5)
N6ⁱⁱ—Cu2—N5—C12ⁱⁱ	−1.58 (18)	C18—O6—C17—C16	178.6 (3)
N8—Cu2—N5—C12ⁱⁱ	−101.28 (19)	N6—C16—C17—O5	−17.1 (5)
N8ⁱⁱ—Cu2—N5—C12ⁱⁱ	78.72 (19)	C19—C16—C17—O5	104.7 (4)
C4—N2—C5—C6	−80.7 (4)	N6—C16—C17—O6	164.1 (3)
Cu1—N2—C5—C6	110.7 (3)	C19—C16—C17—O6	−74.1 (4)
C4—N2—C5—C8	159.7 (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—O2	1.6 (6)	C22—N8—C20—C21	0.6 (4)
C7—O3—C6—C5	179.9 (3)	Cu2—N8—C20—C21	155.7 (2)
N2—C5—C6—O2	−12.9 (6)	C22—N8—C20—C19	−177.2 (4)
C8—C5—C6—O2	108.6 (4)	Cu2—N8—C20—C19	−22.2 (5)
N2—C5—C6—O3	168.9 (3)	C16—C19—C20—C21	−104.8 (5)
C8—C5—C6—O3	−69.6 (4)	C16—C19—C20—N8	72.5 (5)
N5—Cu2—N6—C15	3.7 (2)	N8—C20—C21—N7	−0.2 (4)
N6ⁱⁱ—Cu2—N6—C15	3.7 (2)	C19—C20—C21—N7	177.3 (4)
N8—Cu2—N6—C15	−125.6 (2)	C22—N7—C21—C20	−0.3 (4)
N8ⁱⁱ—Cu2—N6—C15	130.7 (2)	C20—N8—C22—N7	−0.8 (4)
N5—Cu2—N6—C16	171.1 (3)	Cu2—N8—C22—N7	−150.9 (3)
N6ⁱⁱ—Cu2—N6—C16	171.1 (3)	C21—N7—C22—N8	0.7 (4)

Symmetry codes: (i) −x−1, −y−1, z; (ii) −x−1, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱⁱⁱ	0.88	1.86	2.719 (4)	166
N7—H7···O4^iv	0.88	1.88	2.738 (4)	163
O11—H11A···O5^v	0.84	2.00	2.785 (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.

Experimental details

Crystal data
Chemical formula	[Cu(C₂₁H₂₁N₇O₆)]·1.5CH₄O
M_r	577.04
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	173
a, b, c (Å)	13.701 (1), 13.771 (1), 13.590 (2)
V (Å³)	2564.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.772, 0.839
No. of measured, independent and observed [I > 2σ(I)] reflections	23034, 5867, 4185
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.101, 0.92
No. of reflections	5867
No. of parameters	359
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.50
Absolute structure	Flack (1983)
Absolute structure parameter	−0.012 (16)

Computer programs: COLLECT (Nonius, 2002), DIRAX (Duisenberg, 1992), EVALCCD (Duisenberg et al., 2003), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).