Poly[bis­[μ4-N-(2-hydroxy­imino­propion­yl)-N′-(2-oxidoimino­propion­yl)propane-1,3-diaminato]dimethano­lcalciumdicopper(II)]

Kalibabchuk, V.A.; Usenko, N.I.; Golenya, I.A.; Iskenderov, T.S.; Haukka, M.

doi:10.1107/S1600536809033467

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Pages m1139-m1140

doi:10.1107/S1600536809033467

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Poly[bis[μ₄-N-(2-hydroxyiminopropionyl)-N′-(2-oxidoiminopropionyl)propane-1,3-diaminato]dimethanolcalciumdicopper(II)]

Valentina A. Kalibabchuk,^a ^* Natalia I. Usenko,^b Irina A. Golenya,^b Turganbay S. Iskenderov ^c and Matti Haukka ^d

^aDepartment of General Chemistry, O. O. Bohomolets National Medical University, Shevchenko Blvd. 13, 01601 Kiev, Ukraine, ^bDepartment of Chemistry, Kiev National Taras Shevchenko University, Volodymyrska Street 64, 01033 Kiev, Ukraine, ^cDepartment of Chemistry, Karakalpakian University, Universitet Keshesi 1, 742012 Nukus, Uzbekistan, and ^dDepartment of Chemistry, University of Joensuu, PO Box 111, 80101, Joensuu, Finland
^*Correspondence e-mail: kalibabchuk@ukr.net

(Received 22 July 2009; accepted 21 August 2009; online 29 August 2009)

In the title compound, [CaCu₂(C₉H₁₃N₄O₄)₂(CH₃OH)₂]_n, the Ca^II atom lies on an inversion center and is situated in a moderately distorted octahedral environment. The Cu^II atom is in a distorted square-pyramidal geometry, defined by four N atoms belonging to the amide and oxime groups of the triply deprotonated residue of N,N′-bis(2-hydroxyiminopropanoyl)propane-1,3-diamine (H₄pap) and one oxime O atom from a neighboring Hpap ligand at the apical site, forming a dimeric [Cu₂(Hpap)₂]²⁻ unit. Each dimeric unit connects four Ca atoms and each Ca atom links four [Cu₂(Hpap)₂]²⁻ units through Ca—O(amide) bonds, leading to a three-dimensional framework. The crystal structure involves intra- and intermolecular O—H⋯O hydrogen bonds.

Related literature

For the coordination chemistry of tetradentate oxime-and-amide open-chain ligands, see: Duda et al. (1997 ); Fritsky et al. (1999 ). For oximes as efficient metal chelators, see: Gumienna-Kontecka et al. (2000 ); Onindo et al. (1995 ); Sliva et al. (1997a ,b ). For the use of oximes in stabilizing high oxidation states of metal ions, see: Fritsky et al. (1998 , 2006 ). For related structures, see: Kanderal et al. (2005 ); Fritsky (1999 ); Fritsky et al. (2000 ); Mokhir et al. (2002 ); Moroz et al. (2008 ); Wörl et al. (2005 ).

Experimental

Crystal data

[CaCu₂(C₉H₁₃N₄O₄)₂(CH₄O)₂]
M_r = 713.71
Monoclinic, P 2₁ /n
a = 10.0554 (4) Å
b = 8.7794 (3) Å
c = 15.4465 (7) Å
β = 97.882 (2)°
V = 1350.74 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.83 mm⁻¹
T = 120 K
0.28 × 0.24 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.622, T_max = 0.796
8392 measured reflections
3074 independent reflections
2573 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.079
S = 1.04
3074 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 1.11 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	1.9751 (18)
Cu1—N2	1.9469 (18)
Cu1—N3	1.9320 (19)
Cu1—N4	1.9650 (18)
Cu1—O2ⁱ	2.4646 (16)
Ca1—O3	2.3134 (16)
Ca1—O4ⁱⁱ	2.2818 (16)
Ca1—O5	2.3811 (16)
Symmetry codes: (i) -x, -y+2, -z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2	0.99	1.65	2.610 (2)	165
O5—H5O⋯O2ⁱⁱⁱ	0.94	1.79	2.681 (2)	159
Symmetry code: (iii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033467/hy2216sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033467/hy2216Isup2.hkl

checkCIF report

Comment top

N,N'-bis(2-hydroxyiminopropionylpropane)-1,2-diamine and its homologues (Duda et al., 1997; Fritsky et al., 1999), tetradentate oxime-and-amide open-chain ligands, have been intensively studied during the past 15 years as efficient polychelate ligands forming stable complexes with nickel(II) and copper(II) ions. The presence of an additional strong donor amide function in the vicinity of the oxime group results in important increase of chelating efficiency. For example, amide derivatives of 2-hydroxyiminopropanoic acid were shown to act as highly efficient chelators with respect to copper(II), nickel(II) and aluminium(III) ions (Gumienna-Kontecka et al., 2000; Onindo et al., 1995; Sliva et al., 1997a,b). Also, tetradentate oxime-and-amide open-chain ligands possess strong σ-donor capacity and thus have been successfully used for preparation of metal complexes with efficient stabilization of unusually high oxidation states of transition metal ions like Cu^III and Ni^III (Fritsky et al., 1998; Fritsky et al., 2006).

Earlier, the crystal and molecular structures of mononuclear anionic copper(II) complexes with N,N'-bis(2-hydroxyiminopropanoyl)propane-1,3-diamine (H₄pap) of composition [Li(H₂O)₄][Cu(Hpap)].2H₂O (Duda et al., 1997) and PPh₄[Cu(Hpap)].4.5H₂O (Kanderal et al., 2005) have been reported, as well as a series of modular cationic and anionic complex compounds containing [Cu(Hpap)]^- anions (Fritsky et al., 2000). The present report describes the crystal structure of the title compound, a three-dimensional coordination polymer of composition [CaCu₂(Hpap)₂(CH₃OH)₂], featuring copper(II) complex anions connected by calcium ions.

The structure of the title compound is presented in Fig. 1. The ligand in the complex anion is coordinated in a tetradentate fashion forming three condensed chelate rings and being triply deprotonated. In the complex anion the Cu^II atom is situated in a distorted square-pyramidal geometry. The basal plane is defined by four N atoms belonging to the deprotonated amide and oxime groups of the Hpap ligand, which adopt a pseudo-macrocyclic conformation due to the presence of an intramolecular hydrogen bond uniting the cis-oximate O atoms. The apical position is occupied by the oxime O2 atom, and as a result, two neighboring Cu complex anions are united into a centrosymmetric [Cu₂(Hpap)₂]^2- dimer, with a Cu···Cuⁱ [symmetry code: (i) -x, 2-y, -z] separation of 4.164 (1) Å. Each dimeric unit connects four Ca atoms and each Ca links four dimeric [Cu₂(Hpap)₂]^2- units.

The basal plane of the Cu1 atom exhibits tetrahedral distortion with deviations of the N atoms from the mean plane defined by them by 0.025 (1) Å. Cu1 is displaced by 0.255 (1) Å from this plane in the direction of the apical O atom. The observed Cu—N distances (Table 1) are normal for the complexes with N-coordinated amide and oxime groups (Fritsky et al., 1998; Fritsky et al., 2006). A noticeable difference between Cu—N(amide) and Cu—N(oxime) distances is observed. The O1···O2 separation of the intramolecular hydrogen bond is equal to 2.610 (2) Å, which is close to the values reported for the analogous complexes with lithium and tetraphenylphosponium cations. The C═N, C═O, N—O and C—N bond lengths are typical for 2-hydroxyiminopropanoic acid and its amide derivatives (Fritsky, 1999; Mokhir et al., 2002; Moroz et al., 2008).

The Ca^II atom occupies a special position and is situated in moderately distorted octahedral environment (Fig. 1). The Ca—O bond distances are similar to the reported ones for six-coordinate calcium complexes (Wörl et al., 2005). The axial bond length Ca1—O5 [2.381 (1) Å] are somewhat longer than the equatorial ones. The O—Ca—O anlges values are in the range 84.31 (6) to 95.69 (6)°. The coordination geometry of the Ca atom is formed by six O atoms belonging to two methanol molecules and four amide groups. Thus, each Ca atom unites four dimeric Cu complex anionic unit. These Ca—O bonds, together with the intermolecular O—H···O hydrogen bonds between the methanol OH group and oxime O2 atom (Table 2), lead to a three-dimensional framework (Fig. 2).

Related literature top

For the coordination chemistry of tetradentate oxime-and-amide open-chain ligands, see: Duda et al. (1997); Fritsky et al. (1999). For oximes as efficient metal chelators, see: Gumienna-Kontecka et al. (2000); Onindo et al. (1995); Sliva et al. (1997a,b). For the use of oximes in stabilizing high oxidation states of metal ions, see: Fritsky et al. (1998, 2006). For related structures, see: Kanderal et al. (2005); Fritsky (1999); Fritsky et al. (2000); Mokhir et al. (2002); Moroz et al. (2008); Wörl et al. (2005).

Experimental top

A solution of N,N'-bis(2-hydroxyiminopropanoyl)propane-1,3-diamine (0.244 g, 1 mmol) in 10 ml of methanol was heated to 323 K and added with stirring to a solution of copper(II) chloride dihydrate (0.170 g, 1 mmol) in water (5 ml). Then an aqueous solution of calcium hydrocarbonate (4 ml, 1 M) was added. The obtained mixture was stirred at 323 K for 10 min and then filtered. The filtrate was cooled, filtered and set aside for crystallization at room temperature. The resulting dark-red crystals formed within 12 h were separated by filtration, washed with water and air-dried (yield 78%). N,N'-bis(2-hydroxyiminopropanoyl)propane-1,3-diamine was prepared according to the reported procedure (Duda et al., 1997).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound. Displacement ellipsoids are shown at the 50% probability level. Hydrogen bonds are indicated by dashed lines. [Symmetry codes: (i) -x, 2-y, -z; (ii) 1/2-x, 1/2+y, 1/2-z; (iv) -x, 2-y, 1-z; (v) -1/2+x, 3/2-y, 1/2+z.]
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are indicated by dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Poly[bis[µ₄-N-(2-hydroxyiminopropionyl)-N'-(2-oxidoiminopropionyl)propane-1,3-diaminato]dimethanolcalciumdicopper(II)] top

Crystal data top

[CaCu₂(C₉H₁₃N₄O₄)₂(CH₄O)₂]	F(000) = 736
M_r = 713.71	D_x = 1.755 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3254 reflections
a = 10.0554 (4) Å	θ = 1.0–27.5°
b = 8.7794 (3) Å	µ = 1.83 mm⁻¹
c = 15.4465 (7) Å	T = 120 K
β = 97.882 (2)°	Block, dark red
V = 1350.74 (9) Å³	0.28 × 0.24 × 0.13 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	3074 independent reflections
Radiation source: fine-focus sealed tube	2573 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.035
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 2.6°
ϕ and ω scans with κ offset	h = −11→13
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→10
T_min = 0.622, T_max = 0.796	l = −20→19
8392 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0351P)² + 1.0009P] where P = (F_o² + 2F_c²)/3
3074 reflections	(Δ/σ)_max = 0.002
192 parameters	Δρ_max = 1.11 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[CaCu₂(C₉H₁₃N₄O₄)₂(CH₄O)₂]	V = 1350.74 (9) Å³
M_r = 713.71	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.0554 (4) Å	µ = 1.83 mm⁻¹
b = 8.7794 (3) Å	T = 120 K
c = 15.4465 (7) Å	0.28 × 0.24 × 0.13 mm
β = 97.882 (2)°

Data collection top

Nonius KappaCCD diffractometer	3074 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2573 reflections with I > 2σ(I)
T_min = 0.622, T_max = 0.796	R_int = 0.035
8392 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.04	Δρ_max = 1.11 e Å⁻³
3074 reflections	Δρ_min = −0.56 e Å⁻³
192 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.07005 (3)	0.90813 (3)	0.122024 (17)	0.01389 (10)
Ca1	0.0000	1.0000	0.5000	0.01418 (14)
O1	−0.02176 (17)	1.23359 (18)	0.11376 (10)	0.0201 (4)
H1O	0.0287	1.2169	0.0643	0.030*
O2	0.11916 (16)	1.14306 (18)	−0.00651 (10)	0.0171 (3)
O3	−0.05881 (17)	0.92919 (19)	0.35557 (10)	0.0213 (4)
O4	0.38614 (16)	0.70750 (19)	0.04006 (11)	0.0210 (4)
O5	−0.21320 (16)	1.12267 (19)	0.48180 (11)	0.0219 (4)
H5O	−0.2529	1.2181	0.4868	0.033*
N1	−0.01214 (18)	1.0977 (2)	0.15866 (12)	0.0146 (4)
N2	0.01537 (19)	0.8358 (2)	0.23095 (12)	0.0173 (4)
N3	0.1956 (2)	0.7474 (2)	0.10597 (12)	0.0180 (4)
N4	0.15835 (18)	1.0068 (2)	0.03093 (12)	0.0144 (4)
C1	−0.1226 (3)	1.2240 (3)	0.27158 (17)	0.0288 (6)
H1A	−0.0570	1.3063	0.2843	0.043*
H1B	−0.1542	1.1913	0.3259	0.043*
H1C	−0.1989	1.2607	0.2305	0.043*
C2	−0.0587 (2)	1.0934 (3)	0.23219 (15)	0.0169 (5)
C3	−0.0343 (2)	0.9408 (3)	0.27836 (15)	0.0168 (5)
C4	0.0562 (3)	0.6895 (3)	0.27209 (15)	0.0225 (5)
H4A	−0.0109	0.6109	0.2505	0.027*
H4B	0.0575	0.6985	0.3361	0.027*
C5	0.1924 (3)	0.6394 (3)	0.25333 (17)	0.0294 (6)
H5A	0.2165	0.5452	0.2872	0.035*
H5B	0.2581	0.7185	0.2762	0.035*
C6	0.2103 (3)	0.6087 (3)	0.15904 (17)	0.0251 (5)
H6A	0.3006	0.5648	0.1570	0.030*
H6B	0.1429	0.5329	0.1340	0.030*
C7	0.2839 (2)	0.7824 (3)	0.05361 (14)	0.0163 (5)
C8	0.2556 (2)	0.9315 (3)	0.00510 (14)	0.0158 (4)
C9	0.3318 (2)	0.9800 (3)	−0.06579 (15)	0.0219 (5)
H9A	0.2709	1.0303	−0.1120	0.033*
H9B	0.3720	0.8905	−0.0899	0.033*
H9C	0.4028	1.0511	−0.0423	0.033*
C10	−0.3241 (2)	1.0385 (3)	0.43680 (17)	0.0251 (5)
H10A	−0.2903	0.9503	0.4076	0.038*
H10B	−0.3758	1.1041	0.3931	0.038*
H10C	−0.3821	1.0035	0.4789	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01633 (15)	0.01304 (15)	0.01304 (14)	0.00299 (10)	0.00462 (10)	0.00150 (10)
Ca1	0.0144 (3)	0.0150 (3)	0.0135 (3)	−0.0026 (2)	0.0032 (2)	−0.0004 (2)
O1	0.0261 (9)	0.0151 (8)	0.0197 (8)	0.0043 (7)	0.0050 (7)	0.0032 (7)
O2	0.0183 (8)	0.0135 (7)	0.0195 (8)	0.0018 (6)	0.0021 (6)	0.0054 (6)
O3	0.0271 (9)	0.0250 (9)	0.0130 (8)	−0.0030 (7)	0.0071 (7)	−0.0015 (7)
O4	0.0192 (8)	0.0214 (8)	0.0231 (8)	0.0078 (7)	0.0053 (7)	−0.0014 (7)
O5	0.0176 (9)	0.0183 (8)	0.0293 (9)	0.0011 (6)	0.0012 (7)	−0.0042 (7)
N1	0.0148 (9)	0.0136 (9)	0.0153 (9)	0.0007 (7)	0.0015 (7)	0.0017 (7)
N2	0.0221 (10)	0.0158 (9)	0.0146 (9)	0.0019 (8)	0.0053 (8)	0.0026 (8)
N3	0.0225 (10)	0.0155 (9)	0.0167 (9)	0.0049 (8)	0.0057 (8)	0.0039 (8)
N4	0.0139 (9)	0.0140 (9)	0.0148 (9)	0.0009 (7)	0.0003 (7)	0.0009 (7)
C1	0.0398 (16)	0.0247 (13)	0.0239 (13)	0.0110 (11)	0.0120 (11)	−0.0002 (11)
C2	0.0155 (11)	0.0186 (11)	0.0165 (11)	0.0013 (9)	0.0020 (9)	−0.0017 (9)
C3	0.0148 (11)	0.0200 (11)	0.0151 (10)	−0.0021 (9)	0.0007 (8)	0.0000 (9)
C4	0.0309 (14)	0.0201 (12)	0.0175 (11)	0.0041 (10)	0.0071 (10)	0.0046 (10)
C5	0.0306 (14)	0.0299 (14)	0.0277 (14)	0.0073 (11)	0.0043 (11)	0.0093 (12)
C6	0.0306 (14)	0.0202 (12)	0.0257 (13)	0.0113 (10)	0.0082 (11)	0.0045 (10)
C7	0.0169 (11)	0.0165 (11)	0.0146 (10)	0.0030 (9)	−0.0008 (8)	−0.0016 (9)
C8	0.0148 (11)	0.0186 (11)	0.0138 (10)	0.0004 (9)	0.0010 (8)	−0.0012 (9)
C9	0.0195 (12)	0.0265 (13)	0.0209 (12)	0.0005 (10)	0.0065 (9)	0.0019 (10)
C10	0.0199 (12)	0.0237 (12)	0.0304 (13)	−0.0006 (10)	−0.0007 (10)	−0.0041 (11)

Geometric parameters (Å, º) top

Cu1—N1	1.9751 (18)	C1—C2	1.486 (3)
Cu1—N2	1.9469 (18)	C1—H1A	0.9800
Cu1—N3	1.9320 (19)	C1—H1B	0.9800
Cu1—N4	1.9650 (18)	C1—H1C	0.9800
Cu1—O2ⁱ	2.4646 (16)	C2—C3	1.522 (3)
Ca1—O3	2.3134 (16)	C4—C5	1.504 (4)
Ca1—O4ⁱⁱ	2.2818 (16)	C4—H4A	0.9900
Ca1—O5	2.3811 (16)	C4—H4B	0.9900
O1—N1	1.377 (2)	C5—C6	1.516 (4)
O1—H1O	0.9852	C5—H5A	0.9900
O2—N4	1.363 (2)	C5—H5B	0.9900
O3—C3	1.255 (3)	C6—H6A	0.9900
O4—C7	1.262 (3)	C6—H6B	0.9900
O5—C10	1.436 (3)	C7—C8	1.516 (3)
O5—H5O	0.9358	C8—C9	1.482 (3)
N1—C2	1.287 (3)	C9—H9A	0.9800
N2—C3	1.317 (3)	C9—H9B	0.9800
N2—C4	1.466 (3)	C9—H9C	0.9800
N3—C7	1.316 (3)	C10—H10A	0.9800
N3—C6	1.464 (3)	C10—H10B	0.9800
N4—C8	1.288 (3)	C10—H10C	0.9800

N3—Cu1—N2	98.02 (8)	H1B—C1—H1C	109.5
N3—Cu1—N4	82.10 (8)	N1—C2—C1	124.7 (2)
N2—Cu1—N4	166.31 (8)	N1—C2—C3	112.64 (19)
N3—Cu1—N1	163.47 (8)	C1—C2—C3	122.6 (2)
N2—Cu1—N1	81.29 (8)	O3—C3—N2	127.6 (2)
N4—Cu1—N1	94.69 (8)	O3—C3—C2	118.5 (2)
N3—Cu1—O2ⁱ	103.12 (7)	N2—C3—C2	113.87 (19)
N2—Cu1—O2ⁱ	106.54 (7)	N2—C4—C5	112.4 (2)
N4—Cu1—O2ⁱ	86.66 (6)	N2—C4—H4A	109.1
N1—Cu1—O2ⁱ	92.83 (7)	C5—C4—H4A	109.1
O4ⁱⁱⁱ—Ca1—O4ⁱⁱ	180.00 (8)	N2—C4—H4B	109.1
O4ⁱⁱⁱ—Ca1—O3^iv	91.40 (6)	C5—C4—H4B	109.1
O4ⁱⁱ—Ca1—O3^iv	88.60 (6)	H4A—C4—H4B	107.9
O4ⁱⁱⁱ—Ca1—O3	88.60 (6)	C4—C5—C6	117.9 (2)
O4ⁱⁱ—Ca1—O3	91.40 (6)	C4—C5—H5A	107.8
O3^iv—Ca1—O3	180.0	C6—C5—H5A	107.8
O4ⁱⁱⁱ—Ca1—O5	85.18 (6)	C4—C5—H5B	107.8
O4ⁱⁱ—Ca1—O5	94.82 (6)	C6—C5—H5B	107.8
O3^iv—Ca1—O5	95.69 (6)	H5A—C5—H5B	107.2
O3—Ca1—O5	84.31 (6)	N3—C6—C5	112.0 (2)
O4ⁱⁱⁱ—Ca1—O5^iv	94.82 (6)	N3—C6—H6A	109.2
O4ⁱⁱ—Ca1—O5^iv	85.18 (6)	C5—C6—H6A	109.2
O3^iv—Ca1—O5^iv	84.31 (6)	N3—C6—H6B	109.2
O3—Ca1—O5^iv	95.69 (6)	C5—C6—H6B	109.2
O5—Ca1—O5^iv	180.0	H6A—C6—H6B	107.9
N1—O1—H1O	104.7	O4—C7—N3	127.8 (2)
C10—O5—H5O	100.9	O4—C7—C8	118.0 (2)
C2—N1—O1	117.47 (18)	N3—C7—C8	114.15 (19)
C2—N1—Cu1	116.42 (15)	N4—C8—C9	124.9 (2)
O1—N1—Cu1	126.09 (14)	N4—C8—C7	112.86 (19)
C3—N2—C4	118.48 (19)	C9—C8—C7	122.2 (2)
C3—N2—Cu1	115.18 (15)	C8—C9—H9A	109.5
C4—N2—Cu1	124.40 (15)	C8—C9—H9B	109.5
C7—N3—C6	120.9 (2)	H9A—C9—H9B	109.5
C7—N3—Cu1	114.57 (15)	C8—C9—H9C	109.5
C6—N3—Cu1	123.60 (15)	H9A—C9—H9C	109.5
C8—N4—O2	120.42 (18)	H9B—C9—H9C	109.5
C8—N4—Cu1	115.63 (15)	O5—C10—H10A	109.5
O2—N4—Cu1	123.91 (13)	O5—C10—H10B	109.5
C2—C1—H1A	109.5	H10A—C10—H10B	109.5
C2—C1—H1B	109.5	O5—C10—H10C	109.5
H1A—C1—H1B	109.5	H10A—C10—H10C	109.5
C2—C1—H1C	109.5	H10B—C10—H10C	109.5
H1A—C1—H1C	109.5

N3—Cu1—N1—C2	−87.3 (3)	N2—Cu1—N4—O2	−93.4 (3)
N2—Cu1—N1—C2	1.52 (17)	N1—Cu1—N4—O2	−21.15 (16)
N4—Cu1—N1—C2	−165.30 (17)	O2ⁱ—Cu1—N4—O2	71.42 (16)
O2ⁱ—Cu1—N1—C2	107.82 (17)	Cu1ⁱ—Cu1—N4—O2	50.60 (13)
Cu1ⁱ—Cu1—N1—C2	150.40 (17)	O1—N1—C2—C1	0.4 (3)
N3—Cu1—N1—O1	91.4 (3)	Cu1—N1—C2—C1	179.3 (2)
N2—Cu1—N1—O1	−179.78 (18)	O1—N1—C2—C3	−176.28 (17)
N4—Cu1—N1—O1	13.41 (17)	Cu1—N1—C2—C3	2.5 (2)
O2ⁱ—Cu1—N1—O1	−73.47 (17)	C4—N2—C3—O3	−4.2 (4)
Cu1ⁱ—Cu1—N1—O1	−30.90 (16)	Cu1—N2—C3—O3	−169.08 (19)
N3—Cu1—N2—C3	157.38 (17)	C4—N2—C3—C2	173.6 (2)
N4—Cu1—N2—C3	67.8 (4)	Cu1—N2—C3—C2	8.8 (2)
N1—Cu1—N2—C3	−5.93 (16)	N1—C2—C3—O3	170.6 (2)
O2ⁱ—Cu1—N2—C3	−96.30 (17)	C1—C2—C3—O3	−6.2 (3)
Cu1ⁱ—Cu1—N2—C3	−65.8 (2)	N1—C2—C3—N2	−7.4 (3)
N3—Cu1—N2—C4	−6.4 (2)	C1—C2—C3—N2	175.8 (2)
N4—Cu1—N2—C4	−96.0 (4)	C3—N2—C4—C5	−133.0 (2)
N1—Cu1—N2—C4	−169.8 (2)	Cu1—N2—C4—C5	30.3 (3)
O2ⁱ—Cu1—N2—C4	99.87 (19)	N2—C4—C5—C6	−62.6 (3)
Cu1ⁱ—Cu1—N2—C4	130.39 (16)	C7—N3—C6—C5	132.3 (2)
N2—Cu1—N3—C7	−159.43 (17)	Cu1—N3—C6—C5	−35.9 (3)
N4—Cu1—N3—C7	6.74 (16)	C4—C5—C6—N3	65.8 (3)
N1—Cu1—N3—C7	−73.0 (3)	Ca1^v—O4—C7—N3	57.7 (5)
O2ⁱ—Cu1—N3—C7	91.42 (17)	Ca1^v—O4—C7—C8	−122.4 (3)
Cu1ⁱ—Cu1—N3—C7	45.67 (17)	C6—N3—C7—O4	1.4 (4)
N2—Cu1—N3—C6	9.4 (2)	Cu1—N3—C7—O4	170.55 (19)
N4—Cu1—N3—C6	175.6 (2)	C6—N3—C7—C8	−178.6 (2)
N1—Cu1—N3—C6	95.8 (3)	Cu1—N3—C7—C8	−9.4 (2)
O2ⁱ—Cu1—N3—C6	−99.71 (19)	O2—N4—C8—C9	−0.9 (3)
Cu1ⁱ—Cu1—N3—C6	−145.46 (18)	Cu1—N4—C8—C9	176.75 (18)
N3—Cu1—N4—C8	−2.44 (16)	O2—N4—C8—C7	−179.45 (17)
N2—Cu1—N4—C8	89.0 (4)	Cu1—N4—C8—C7	−1.8 (2)
N1—Cu1—N4—C8	161.24 (16)	O4—C7—C8—N4	−172.59 (19)
O2ⁱ—Cu1—N4—C8	−106.19 (16)	N3—C7—C8—N4	7.3 (3)
Cu1ⁱ—Cu1—N4—C8	−127.01 (18)	O4—C7—C8—C9	8.9 (3)
N3—Cu1—N4—O2	175.17 (17)	N3—C7—C8—C9	−171.2 (2)

Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x−1/2, −y+3/2, z+1/2; (iv) −x, −y+2, −z+1; (v) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2	0.99	1.65	2.610 (2)	165
O5—H5O···O2^vi	0.94	1.79	2.681 (2)	159

Symmetry code: (vi) x−1/2, −y+5/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[CaCu₂(C₉H₁₃N₄O₄)₂(CH₄O)₂]
M_r	713.71
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	10.0554 (4), 8.7794 (3), 15.4465 (7)
β (°)	97.882 (2)
V (Å³)	1350.74 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.83
Crystal size (mm)	0.28 × 0.24 × 0.13

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.622, 0.796
No. of measured, independent and observed [I > 2σ(I)] reflections	8392, 3074, 2573
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.04
No. of reflections	3074
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.11, −0.56

Computer programs: COLLECT (Nonius, 1998), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top

Cu1—N1	1.9751 (18)	Cu1—O2ⁱ	2.4646 (16)
Cu1—N2	1.9469 (18)	Ca1—O3	2.3134 (16)
Cu1—N3	1.9320 (19)	Ca1—O4ⁱⁱ	2.2818 (16)
Cu1—N4	1.9650 (18)	Ca1—O5	2.3811 (16)

Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2	0.99	1.65	2.610 (2)	165
O5—H5O···O2ⁱⁱⁱ	0.94	1.79	2.681 (2)	159

Symmetry code: (iii) x−1/2, −y+5/2, z+1/2.

Acknowledgements

The authors thank the Ministry of Education and Science of Ukraine for financial support (grant No. M/263–2008).

References

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