{μ-6,6′-Dimeth­oxy-2,2′-[cyclo­hexane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}methanol-μ-nitrato-dinitratocopper(II)europium(III)

Bao, Y.; Li, G.-M.; Yang, F.; Yan, P.-F.; Chen, P.

doi:10.1107/S1600536810039103

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page m1379

https://doi.org/10.1107/S1600536810039103

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{μ-6,6′-Dimethoxy-2,2′-[cyclohexane-1,2-diylbis(nitrilomethylidyne)]diphenolato}methanol-μ-nitrato-dinitratocopper(II)europium(III)

Yan Bao,^a Guang-Ming Li,^a ^* Fan Yang,^a Peng-Fei Yan ^a and Peng Chen ^a

^aSchool of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: gmli_2000@163.com

(Received 15 July 2010; accepted 30 September 2010; online 9 October 2010)

In the title dinuclear salen-type complex, [CuEu(C₂₂H₂₄N₂O₄)(NO₃)₃(CH₃OH)], the Cu^II ion is five-coordinated to two imine N atoms and two phenolate O atoms and one O from the bridging nitrate group. The Eu^III ion is ligated to three nitrate groups, four O atoms from the salen-type ligand and one methanol molecule, leading to a distorted tenfold coordination for the rare earth cation. One of the three nitrate anions is disordered over two positions in a 0.66 (5):0.34 (5) ratio.

Related literature

For the synthesis of the ligand, see: Aslantaş et al. (2007 ); Mohamed et al. (2003 ). For similar copper lanthanide complexes with a similar salen-like ligand, see: Costes et al. (2000 , 2008 ); Koner et al. (2005 ); Sun et al. (2009 ).

Experimental

Crystal data

[CuEu(C₂₂H₂₄N₂O₄)(NO₃)₃(CH₄O)]
M_r = 814.02
Monoclinic, C 2/c
a = 29.305 (6) Å
b = 14.233 (3) Å
c = 14.141 (3) Å
β = 103.36 (3)°
V = 5739 (2) Å³
Z = 8
Mo Kα radiation
μ = 2.99 mm⁻¹
T = 295 K
0.14 × 0.12 × 0.11 mm

Data collection

Bruker SMART1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.677, T_max = 0.727
27154 measured reflections
6537 independent reflections
4621 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.091
S = 1.07
6537 reflections
420 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −1.11 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2003 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810039103/rk2221sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039103/rk2221Isup2.hkl

checkCIF report

Comment top

In continuation of our studies of salen-type lanthanide complexes (Aslantaş et al., 2007, Mohamed et al., 2003, Sun et al., 2009), we present here the crystal structure of the title compound. The Eu^III center is ligated to two bidentate nitrate groups and four oxygen atoms from the ligand, one oxygen, from the bridging nitrate group and one methanol molecule (Fig. 1). It is similar to the previously reported structures (Costes et al., 2000, 2008; Koner et al., 2005). The decacoordinated Eu^III ion presents a narrow spread in Eu–O bond distances 2.338 (18)-2.786 (4)Å. The Cu(II) ion is five-coordinated by two imine nitrogen atoms, two phenol oxygen atoms from the imine-phenolate ligand and one oxygen atom from the bridgin nitrate group.

Related literature top

For the synthesis of the ligand, see: Aslantaş et al. (2007); Mohamed et al. (2003). For similar copper lanthanide complexes with the similar salen-like ligand, see: Costes et al. (2000, 2008); Koner et al. (2005); Sun et al. (2009).

Experimental top

To a 2:3 MeOH/MeCN solution (35 ml) of [(H₂L)Eu(NO₃)₃] (0.2253 g, 0.3 mmol) was added an aqueous solution (10 ml) of Cu(OAc)₂˙H₂O (0.0597 g, 0.3 mmol) at ambient temperature. After stirring for 5 hrs, the solution was filtered to remove the suspended particles. Red single crystals suitable for X-ray determination were obtained by slow diffusion of diethylether into the filtrate in one week. For CuEu(C₂₂H₂₄N₂O₄)(NO₃)₃CH₃OH elemental anal. - Calc.: for C₂₃H₂₈N₅O₁₄EuCu: C, 33.93; H, 3.47; N, 8.60 wt%, Found: C, 33.85; H, 3.55; N, 8.58 wt%.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius. Only minor fragment is presented.

{µ-6,6'-Dimethoxy-2,2'-[cyclohexane-1,2-diylbis(nitrilomethylidyne)]diphenolato}methanol-µ-nitrato-dinitratocopper(II)europium(III) top

Crystal data top

[CuEu(C₂₂H₂₄N₂O₄)(NO₃)₃(CH₄O)]	F(000) = 3240
M_r = 814.02	D_x = 1.884 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5035 reflections
a = 29.305 (6) Å	θ = 3.2–27.5°
b = 14.233 (3) Å	µ = 2.99 mm⁻¹
c = 14.141 (3) Å	T = 295 K
β = 103.36 (3)°	Block, red
V = 5739 (2) Å³	0.14 × 0.12 × 0.11 mm
Z = 8

Data collection top

Bruker SMART1000 CCD diffractometer	6537 independent reflections
Radiation source: fine-focus sealed tube	4621 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
φ and ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −37→37
T_min = 0.677, T_max = 0.727	k = −18→18
27154 measured reflections	l = −15→18

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0119P)² + 37.7609P] where P = (F_o² + 2F_c²)/3
6537 reflections	(Δ/σ)_max = 0.001
420 parameters	Δρ_max = 0.80 e Å⁻³
13 restraints	Δρ_min = −1.11 e Å⁻³

Crystal data top

[CuEu(C₂₂H₂₄N₂O₄)(NO₃)₃(CH₄O)]	V = 5739 (2) Å³
M_r = 814.02	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 29.305 (6) Å	µ = 2.99 mm⁻¹
b = 14.233 (3) Å	T = 295 K
c = 14.141 (3) Å	0.14 × 0.12 × 0.11 mm
β = 103.36 (3)°

Data collection top

Bruker SMART1000 CCD diffractometer	6537 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	4621 reflections with I > 2σ(I)
T_min = 0.677, T_max = 0.727	R_int = 0.061
27154 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	13 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0119P)² + 37.7609P] where P = (F_o² + 2F_c²)/3
6537 reflections	Δρ_max = 0.80 e Å⁻³
420 parameters	Δρ_min = −1.11 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.3809 (2)	0.1512 (4)	1.0213 (4)	0.0473 (14)
C2	0.3876 (2)	0.1293 (4)	1.1185 (4)	0.0547 (16)
H2	0.4176	0.1285	1.1584	0.066*
C3	0.3492 (2)	0.1086 (4)	1.1562 (4)	0.0584 (16)
H3	0.3537	0.0939	1.2218	0.070*
C4	0.3048 (2)	0.1093 (4)	1.0985 (4)	0.0532 (15)
H4	0.2795	0.0954	1.1253	0.064*
C5	0.2970 (2)	0.1309 (4)	0.9987 (4)	0.0441 (13)
C6	0.33567 (19)	0.1511 (4)	0.9591 (4)	0.0436 (13)
C7	0.2496 (2)	0.1251 (4)	0.9423 (4)	0.0537 (15)
H7	0.2265	0.1118	0.9759	0.064*
C8	0.1873 (2)	0.1153 (7)	0.7934 (5)	0.083 (2)
H8	0.1880	0.0502	0.7713	0.099*
C9	0.1494 (2)	0.1200 (6)	0.8445 (5)	0.082 (2)
H9B	0.1488	0.1819	0.8728	0.099*
H9A	0.1549	0.0742	0.8967	0.099*
C10	0.1024 (3)	0.1002 (7)	0.7742 (6)	0.107 (3)
H10B	0.1015	0.0348	0.7545	0.128*
H10A	0.0774	0.1098	0.8079	0.128*
C11	0.0934 (3)	0.1604 (7)	0.6856 (6)	0.101 (3)
H11B	0.0643	0.1411	0.6419	0.121*
H11A	0.0898	0.2252	0.7040	0.121*
C12	0.1320 (2)	0.1540 (6)	0.6347 (5)	0.080 (2)
H12B	0.1263	0.1980	0.5808	0.096*
H12A	0.1327	0.0912	0.6084	0.096*
C13	0.1794 (2)	0.1757 (6)	0.7026 (5)	0.0666 (19)
H13	0.1787	0.2414	0.7230	0.080*
C14	0.21981 (19)	0.1500 (4)	0.5736 (4)	0.0474 (14)
H14	0.1905	0.1488	0.5308	0.057*
C15	0.26093 (18)	0.1363 (3)	0.5334 (4)	0.0385 (12)
C16	0.25278 (19)	0.1125 (4)	0.4346 (4)	0.0460 (13)
H16	0.2222	0.1086	0.3976	0.055*
C17	0.2893 (2)	0.0952 (4)	0.3927 (4)	0.0509 (15)
H17	0.2832	0.0795	0.3271	0.061*
C18	0.3357 (2)	0.1004 (4)	0.4462 (4)	0.0490 (14)
H18	0.3604	0.0866	0.4175	0.059*
C19	0.34390 (18)	0.1265 (4)	0.5425 (4)	0.0403 (12)
C20	0.30715 (18)	0.1460 (4)	0.5875 (4)	0.0386 (12)
C21	0.4269 (2)	0.1079 (5)	0.5650 (4)	0.0580 (16)
H21C	0.4224	0.0446	0.5411	0.087*
H21B	0.4552	0.1113	0.6151	0.087*
H21A	0.4292	0.1493	0.5128	0.087*
C22	0.4637 (2)	0.1721 (6)	1.0336 (5)	0.078 (2)
H22C	0.4670	0.2154	1.0868	0.117*
H22B	0.4849	0.1891	0.9940	0.117*
H22A	0.4707	0.1097	1.0584	0.117*
Cu1	0.27684 (2)	0.16473 (5)	0.76583 (5)	0.04484 (17)
Eu1	0.391175 (10)	0.21945 (2)	0.78342 (2)	0.04713 (10)
N1	0.23598 (16)	0.1366 (4)	0.8502 (3)	0.0517 (12)
N2	0.22134 (15)	0.1633 (3)	0.6631 (3)	0.0479 (11)
N3	0.4412 (2)	0.0431 (4)	0.8185 (4)	0.0630 (14)
N4	0.4195 (2)	0.3467 (4)	0.6366 (4)	0.0655 (15)
N5	0.3249 (2)	0.3768 (4)	0.8509 (4)	0.0585 (14)
O1	0.41630 (13)	0.1752 (3)	0.9760 (3)	0.0545 (10)
O2	0.33298 (13)	0.1674 (3)	0.8659 (3)	0.0512 (10)
O3	0.31885 (12)	0.1711 (3)	0.6814 (2)	0.0460 (9)
O4	0.38772 (12)	0.1352 (3)	0.6041 (3)	0.0486 (9)
O5	0.39729 (16)	0.0448 (3)	0.8079 (3)	0.0659 (12)
O6	0.4629 (2)	−0.0297 (4)	0.8364 (4)	0.1043 (19)
O7	0.46107 (14)	0.1212 (3)	0.8105 (3)	0.0603 (11)
O8	0.44971 (15)	0.2885 (3)	0.6778 (3)	0.0654 (11)
O9	0.4283 (2)	0.4068 (4)	0.5823 (4)	0.109 (2)
O10	0.37998 (17)	0.3414 (3)	0.6562 (3)	0.0713 (13)
O11'	0.3692 (5)	0.3500 (9)	0.882 (2)	0.087 (5)	0.66 (5)
O11	0.3575 (9)	0.3580 (12)	0.823 (3)	0.052 (8)	0.34 (5)
O12	0.31496 (19)	0.4366 (4)	0.9023 (4)	0.0886 (17)
O13'	0.3033 (13)	0.3411 (8)	0.7776 (11)	0.102 (9)	0.66 (5)
O13	0.2839 (6)	0.3421 (16)	0.806 (2)	0.056 (6)	0.34 (5)
O14	0.45773 (15)	0.3208 (3)	0.8693 (3)	0.0666 (12)
H14O	0.4821	0.3055	0.8486	0.08 (2)*
C23	0.4620 (4)	0.4001 (7)	0.9424 (8)	0.145 (4)
H23C	0.4639	0.4590	0.9104	0.218*
H23B	0.4898	0.3913	0.9930	0.218*
H23A	0.4350	0.4003	0.9700	0.218*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.048 (3)	0.053 (3)	0.038 (3)	0.008 (3)	0.004 (3)	−0.005 (3)
C2	0.060 (4)	0.060 (4)	0.036 (3)	0.017 (3)	−0.006 (3)	−0.004 (3)
C3	0.075 (5)	0.065 (4)	0.034 (3)	0.017 (3)	0.011 (3)	0.004 (3)
C4	0.063 (4)	0.058 (4)	0.040 (3)	0.005 (3)	0.015 (3)	0.002 (3)
C5	0.048 (3)	0.049 (3)	0.034 (3)	0.005 (3)	0.008 (2)	0.001 (2)
C6	0.047 (3)	0.048 (3)	0.033 (3)	0.007 (3)	0.003 (2)	−0.001 (2)
C7	0.051 (4)	0.068 (4)	0.047 (4)	0.008 (3)	0.020 (3)	0.013 (3)
C8	0.035 (4)	0.154 (8)	0.055 (4)	0.007 (4)	0.005 (3)	0.027 (5)
C9	0.064 (5)	0.111 (6)	0.071 (5)	−0.007 (4)	0.013 (4)	0.019 (4)
C10	0.055 (5)	0.157 (9)	0.104 (7)	−0.025 (5)	0.011 (5)	0.050 (6)
C11	0.056 (5)	0.154 (9)	0.090 (6)	−0.005 (5)	0.011 (4)	0.014 (6)
C12	0.033 (3)	0.139 (7)	0.066 (5)	0.015 (4)	0.004 (3)	0.013 (4)
C13	0.035 (3)	0.109 (6)	0.056 (4)	0.005 (3)	0.010 (3)	0.017 (4)
C14	0.035 (3)	0.058 (4)	0.044 (3)	−0.002 (3)	−0.004 (2)	0.003 (3)
C15	0.037 (3)	0.040 (3)	0.035 (3)	0.001 (2)	0.003 (2)	0.005 (2)
C16	0.041 (3)	0.053 (3)	0.037 (3)	−0.004 (3)	−0.006 (2)	0.002 (2)
C17	0.060 (4)	0.060 (4)	0.031 (3)	−0.002 (3)	0.007 (3)	0.000 (3)
C18	0.050 (3)	0.059 (4)	0.040 (3)	0.001 (3)	0.014 (3)	−0.002 (3)
C19	0.039 (3)	0.049 (3)	0.033 (3)	−0.003 (2)	0.010 (2)	0.002 (2)
C20	0.040 (3)	0.043 (3)	0.031 (3)	−0.001 (2)	0.005 (2)	0.006 (2)
C21	0.042 (3)	0.079 (5)	0.055 (4)	0.008 (3)	0.016 (3)	−0.002 (3)
C22	0.045 (4)	0.108 (6)	0.067 (5)	0.008 (4)	−0.014 (3)	0.003 (4)
Cu1	0.0323 (3)	0.0680 (5)	0.0333 (4)	0.0023 (3)	0.0059 (3)	0.0017 (3)
Eu1	0.03248 (14)	0.06129 (19)	0.04366 (16)	−0.00211 (15)	0.00070 (11)	−0.00113 (15)
N1	0.037 (3)	0.077 (4)	0.041 (3)	0.005 (2)	0.009 (2)	0.014 (2)
N2	0.030 (2)	0.069 (3)	0.042 (3)	0.001 (2)	0.003 (2)	0.003 (2)
N3	0.066 (4)	0.070 (4)	0.047 (3)	0.017 (3)	0.000 (3)	0.001 (3)
N4	0.074 (4)	0.074 (4)	0.045 (3)	−0.010 (3)	0.005 (3)	0.004 (3)
N5	0.077 (4)	0.053 (3)	0.053 (4)	−0.003 (3)	0.028 (3)	0.004 (3)
O1	0.037 (2)	0.081 (3)	0.040 (2)	0.007 (2)	−0.0019 (18)	0.0002 (19)
O2	0.039 (2)	0.078 (3)	0.034 (2)	0.003 (2)	0.0021 (17)	0.0062 (19)
O3	0.034 (2)	0.070 (3)	0.033 (2)	−0.0068 (18)	0.0078 (16)	−0.0075 (18)
O4	0.032 (2)	0.073 (3)	0.040 (2)	0.0018 (18)	0.0079 (17)	−0.0034 (19)
O5	0.052 (3)	0.072 (3)	0.068 (3)	−0.008 (2)	0.004 (2)	−0.003 (2)
O6	0.098 (4)	0.082 (4)	0.121 (5)	0.035 (3)	0.000 (4)	0.017 (3)
O7	0.040 (2)	0.077 (3)	0.060 (3)	0.002 (2)	0.005 (2)	0.004 (2)
O8	0.052 (3)	0.078 (3)	0.062 (3)	0.000 (2)	0.003 (2)	0.004 (2)
O9	0.117 (5)	0.120 (5)	0.090 (4)	−0.014 (4)	0.025 (4)	0.041 (4)
O10	0.057 (3)	0.077 (3)	0.078 (3)	0.001 (2)	0.011 (3)	0.011 (3)
O11'	0.059 (6)	0.086 (7)	0.114 (16)	0.011 (5)	0.019 (8)	−0.003 (7)
O11	0.038 (11)	0.047 (8)	0.082 (18)	−0.001 (6)	0.034 (11)	−0.008 (9)
O12	0.111 (4)	0.077 (3)	0.098 (4)	−0.006 (3)	0.065 (4)	−0.024 (3)
O13'	0.19 (2)	0.064 (6)	0.036 (6)	0.013 (8)	−0.014 (9)	0.001 (4)
O13	0.045 (10)	0.091 (11)	0.034 (11)	0.017 (7)	0.011 (6)	0.005 (8)
O14	0.049 (3)	0.083 (3)	0.067 (3)	−0.015 (2)	0.013 (2)	−0.022 (2)
C23	0.121 (9)	0.118 (8)	0.174 (11)	−0.018 (7)	−0.012 (8)	−0.056 (8)

Geometric parameters (Å, º) top

C1—C2	1.378 (8)	C20—O3	1.340 (6)
C1—O1	1.383 (7)	C21—O4	1.437 (6)
C1—C6	1.411 (7)	C21—H21C	0.9600
C2—C3	1.383 (8)	C21—H21B	0.9600
C2—H2	0.9300	C21—H21A	0.9600
C3—C4	1.366 (8)	C22—O1	1.439 (7)
C3—H3	0.9300	C22—H22C	0.9600
C4—C5	1.411 (7)	C22—H22B	0.9600
C4—H4	0.9300	C22—H22A	0.9600
C5—C6	1.404 (7)	Cu1—O3	1.905 (3)
C5—C7	1.436 (8)	Cu1—O2	1.906 (4)
C6—O2	1.323 (6)	Cu1—N2	1.914 (4)
C7—N1	1.282 (7)	Cu1—N1	1.917 (5)
C7—H7	0.9300	Cu1—Eu1	3.3927 (10)
C8—C9	1.458 (9)	Eu1—O11	2.330 (17)
C8—N1	1.497 (8)	Eu1—O3	2.374 (3)
C8—C13	1.518 (9)	Eu1—O2	2.395 (4)
C8—H8	0.9800	Eu1—O7	2.436 (4)
C9—C10	1.528 (10)	Eu1—O10	2.467 (5)
C9—H9B	0.9700	Eu1—O11'	2.494 (18)
C9—H9A	0.9700	Eu1—O14	2.503 (4)
C10—C11	1.490 (10)	Eu1—O5	2.511 (5)
C10—H10B	0.9700	Eu1—O8	2.706 (4)
C10—H10A	0.9700	Eu1—O1	2.725 (4)
C11—C12	1.478 (10)	Eu1—O4	2.785 (4)
C11—H11B	0.9700	Eu1—N3	2.891 (6)
C11—H11A	0.9700	N3—O6	1.212 (7)
C12—C13	1.525 (8)	N3—O5	1.261 (6)
C12—H12B	0.9700	N3—O7	1.271 (7)
C12—H12A	0.9700	N4—O9	1.215 (7)
C13—N2	1.475 (7)	N4—O8	1.254 (7)
C13—H13	0.9800	N4—O10	1.254 (7)
C14—N2	1.270 (7)	N5—O11	1.146 (16)
C14—C15	1.459 (7)	N5—O13'	1.196 (12)
C14—H14	0.9300	N5—O12	1.199 (7)
C15—C20	1.400 (7)	N5—O13	1.32 (2)
C15—C16	1.403 (7)	N5—O11'	1.324 (16)
C16—C17	1.360 (8)	O11'—O11	0.829 (18)
C16—H16	0.9300	O11—O13'	1.59 (2)
C17—C18	1.396 (8)	O13'—O13	0.77 (2)
C17—H17	0.9300	O14—C23	1.516 (10)
C18—C19	1.379 (7)	O14—H14O	0.8608
C18—H18	0.9300	C23—H23C	0.9600
C19—O4	1.381 (6)	C23—H23B	0.9600
C19—C20	1.399 (7)	C23—H23A	0.9600

C2—C1—O1	124.7 (5)	O7—Eu1—O14	73.87 (16)
C2—C1—C6	121.2 (6)	O10—Eu1—O14	84.60 (16)
O1—C1—C6	114.1 (5)	O11'—Eu1—O14	64.7 (3)
C1—C2—C3	119.4 (6)	O11—Eu1—O5	145.6 (6)
C1—C2—H2	120.3	O3—Eu1—O5	79.76 (14)
C3—C2—H2	120.3	O2—Eu1—O5	70.27 (14)
C4—C3—C2	121.0 (6)	O7—Eu1—O5	51.62 (14)
C4—C3—H3	119.5	O10—Eu1—O5	142.23 (15)
C2—C3—H3	119.5	O11'—Eu1—O5	132.8 (6)
C3—C4—C5	120.8 (6)	O14—Eu1—O5	118.75 (15)
C3—C4—H4	119.6	O11—Eu1—O8	100.6 (5)
C5—C4—H4	119.6	O3—Eu1—O8	111.12 (12)
C6—C5—C4	118.9 (5)	O2—Eu1—O8	174.02 (13)
C6—C5—C7	123.9 (5)	O7—Eu1—O8	71.23 (15)
C4—C5—C7	117.1 (5)	O10—Eu1—O8	48.42 (14)
O2—C6—C5	124.4 (5)	O11'—Eu1—O8	108.4 (4)
O2—C6—C1	116.9 (5)	O14—Eu1—O8	62.38 (14)
C5—C6—C1	118.7 (5)	O5—Eu1—O8	113.67 (15)
N1—C7—C5	126.2 (5)	O11—Eu1—O1	89.2 (10)
N1—C7—H7	116.9	O3—Eu1—O1	122.53 (12)
C5—C7—H7	116.9	O2—Eu1—O1	60.03 (12)
C9—C8—N1	117.7 (6)	O7—Eu1—O1	71.76 (13)
C9—C8—C13	114.0 (6)	O10—Eu1—O1	148.33 (15)
N1—C8—C13	106.2 (5)	O11'—Eu1—O1	70.1 (7)
C9—C8—H8	106.0	O14—Eu1—O1	69.39 (14)
N1—C8—H8	106.0	O5—Eu1—O1	68.86 (13)
C13—C8—H8	106.0	O8—Eu1—O1	125.17 (12)
C8—C9—C10	110.2 (7)	O11—Eu1—O4	130.9 (11)
C8—C9—H9B	109.6	O3—Eu1—O4	58.82 (11)
C10—C9—H9B	109.6	O2—Eu1—O4	115.45 (12)
C8—C9—H9A	109.6	O7—Eu1—O4	75.43 (13)
C10—C9—H9A	109.6	O10—Eu1—O4	70.60 (14)
H9B—C9—H9A	108.1	O11'—Eu1—O4	150.3 (7)
C11—C10—C9	113.5 (7)	O14—Eu1—O4	123.37 (13)
C11—C10—H10B	108.9	O5—Eu1—O4	71.69 (13)
C9—C10—H10B	108.9	O8—Eu1—O4	63.13 (12)
C11—C10—H10A	108.9	O1—Eu1—O4	139.01 (12)
C9—C10—H10A	108.9	O11—Eu1—N3	156.8 (10)
H10B—C10—H10A	107.7	O3—Eu1—N3	101.48 (15)
C12—C11—C10	111.5 (7)	O2—Eu1—N3	92.16 (16)
C12—C11—H11B	109.3	O7—Eu1—N3	25.85 (14)
C10—C11—H11B	109.3	O10—Eu1—N3	135.45 (16)
C12—C11—H11A	109.3	O11'—Eu1—N3	137.5 (7)
C10—C11—H11A	109.3	O14—Eu1—N3	96.30 (17)
H11B—C11—H11A	108.0	O5—Eu1—N3	25.78 (14)
C11—C12—C13	111.6 (6)	O8—Eu1—N3	92.80 (16)
C11—C12—H12B	109.3	O1—Eu1—N3	67.59 (13)
C13—C12—H12B	109.3	O4—Eu1—N3	72.12 (13)
C11—C12—H12A	109.3	C7—N1—C8	123.6 (5)
C13—C12—H12A	109.3	C7—N1—Cu1	124.5 (4)
H12B—C12—H12A	108.0	C8—N1—Cu1	111.3 (4)
N2—C13—C8	105.9 (5)	C14—N2—C13	123.7 (5)
N2—C13—C12	117.0 (6)	C14—N2—Cu1	125.9 (4)
C8—C13—C12	110.9 (6)	C13—N2—Cu1	110.4 (4)
N2—C13—H13	107.5	O6—N3—O5	120.8 (7)
C8—C13—H13	107.5	O6—N3—O7	122.5 (6)
C12—C13—H13	107.5	O5—N3—O7	116.7 (5)
N2—C14—C15	124.5 (5)	O6—N3—Eu1	177.7 (5)
N2—C14—H14	117.8	O5—N3—Eu1	60.0 (3)
C15—C14—H14	117.8	O7—N3—Eu1	56.7 (3)
C20—C15—C16	119.2 (5)	O9—N4—O8	122.0 (7)
C20—C15—C14	123.8 (5)	O9—N4—O10	121.5 (7)
C16—C15—C14	117.0 (5)	O8—N4—O10	116.5 (6)
C17—C16—C15	120.5 (5)	O9—N4—Eu1	172.0 (6)
C17—C16—H16	119.7	O8—N4—Eu1	63.9 (3)
C15—C16—H16	119.7	O10—N4—Eu1	52.8 (3)
C16—C17—C18	121.3 (5)	O11—N5—O13'	85.5 (11)
C16—C17—H17	119.4	O11—N5—O12	135.6 (13)
C18—C17—H17	119.4	O13'—N5—O12	132.2 (17)
C19—C18—C17	118.4 (5)	O11—N5—O13	119.4 (13)
C19—C18—H18	120.8	O13'—N5—O13	35.4 (10)
C17—C18—H18	120.8	O12—N5—O13	103.4 (12)
C18—C19—O4	124.9 (5)	O11—N5—O11'	38.4 (11)
C18—C19—C20	121.7 (5)	O13'—N5—O11'	116.5 (11)
O4—C19—C20	113.4 (4)	O12—N5—O11'	111.2 (12)
O3—C20—C19	117.1 (5)	O13—N5—O11'	139.9 (11)
O3—C20—C15	124.1 (5)	C1—O1—C22	117.3 (5)
C19—C20—C15	118.8 (5)	C1—O1—Eu1	117.5 (3)
O4—C21—H21C	109.5	C22—O1—Eu1	125.1 (4)
O4—C21—H21B	109.5	C6—O2—Cu1	125.4 (3)
H21C—C21—H21B	109.5	C6—O2—Eu1	130.9 (3)
O4—C21—H21A	109.5	Cu1—O2—Eu1	103.56 (16)
H21C—C21—H21A	109.5	C20—O3—Cu1	123.6 (3)
H21B—C21—H21A	109.5	C20—O3—Eu1	131.9 (3)
O1—C22—H22C	109.5	Cu1—O3—Eu1	104.37 (15)
O1—C22—H22B	109.5	C19—O4—C21	116.2 (4)
H22C—C22—H22B	109.5	C19—O4—Eu1	116.5 (3)
O1—C22—H22A	109.5	C21—O4—Eu1	127.0 (3)
H22C—C22—H22A	109.5	N3—O5—Eu1	94.2 (4)
H22B—C22—H22A	109.5	N3—O7—Eu1	97.5 (3)
O3—Cu1—O2	83.82 (15)	N4—O8—Eu1	91.6 (4)
O3—Cu1—N2	94.78 (18)	N4—O10—Eu1	103.3 (4)
O2—Cu1—N2	178.52 (19)	O11—O11'—N5	59.1 (16)
O3—Cu1—N1	170.7 (2)	O11—O11'—Eu1	69 (2)
O2—Cu1—N1	95.66 (18)	N5—O11'—Eu1	113.0 (14)
N2—Cu1—N1	85.8 (2)	O11'—O11—N5	83 (2)
O3—Cu1—Eu1	42.67 (10)	O11'—O11—O13'	122 (2)
O2—Cu1—Eu1	43.33 (11)	N5—O11—O13'	48.6 (8)
N2—Cu1—Eu1	135.19 (14)	O11'—O11—Eu1	92 (2)
N1—Cu1—Eu1	138.63 (15)	N5—O11—Eu1	135.5 (12)
O11—Eu1—O3	91.4 (8)	O13'—O11—Eu1	102.4 (15)
O11—Eu1—O2	75.9 (5)	O13—O13'—N5	81 (2)
O3—Eu1—O2	64.54 (12)	O13—O13'—O11	125 (2)
O11—Eu1—O7	146.6 (9)	N5—O13'—O11	45.9 (8)
O3—Eu1—O7	121.96 (14)	O13—O13'—Eu1	135 (2)
O2—Eu1—O7	114.39 (14)	N5—O13'—Eu1	86.7 (16)
O11—Eu1—O10	65.7 (9)	O11—O13'—Eu1	47.4 (11)
O3—Eu1—O10	79.09 (14)	O13'—O13—N5	64 (2)
O2—Eu1—O10	125.68 (14)	C23—O14—Eu1	133.8 (5)
O7—Eu1—O10	118.94 (16)	C23—O14—H14O	118.5
O11—Eu1—O11'	19.4 (5)	Eu1—O14—H14O	107.7
O3—Eu1—O11'	104.2 (4)	O14—C23—H23C	109.5
O2—Eu1—O11'	69.7 (4)	O14—C23—H23B	109.5
O7—Eu1—O11'	131.0 (6)	H23C—C23—H23B	109.5
O10—Eu1—O11'	82.8 (7)	O14—C23—H23A	109.5
O11—Eu1—O14	73.8 (7)	H23C—C23—H23A	109.5
O3—Eu1—O14	161.47 (15)	H23B—C23—H23A	109.5
O2—Eu1—O14	120.33 (14)

Experimental details

Crystal data
Chemical formula	[CuEu(C₂₂H₂₄N₂O₄)(NO₃)₃(CH₄O)]
M_r	814.02
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	29.305 (6), 14.233 (3), 14.141 (3)
β (°)	103.36 (3)
V (Å³)	5739 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.99
Crystal size (mm)	0.14 × 0.12 × 0.11

Data collection
Diffractometer	Bruker SMART1000 CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.677, 0.727
No. of measured, independent and observed [I > 2σ(I)] reflections	27154, 6537, 4621
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.091, 1.07
No. of reflections	6537
No. of parameters	420
No. of restraints	13
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0119P)² + 37.7609P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.80, −1.11

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (grant Nos. 20872030 and 20972043), Heilongjiang Province (grant Nos. 2009RFXXG201, GC09A402 and 2010td03) and Heilongjiang University.

References

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