Aqua­(3-formyl-2-oxidobenzoato-κ2O1,O2)(1,10-phenanthroline-κ2N,N′)copper(II) methanol solvate

Zhang, W.; Cui, Q.; Chang, L.; Yu, Z.

doi:10.1107/S1600536807067967

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page m294

doi:10.1107/S1600536807067967

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Aqua(3-formyl-2-oxidobenzoato-κ²O¹,O²)(1,10-phenanthroline-κ²N,N′)copper(II) methanol solvate

Wu Zhang,^a Qingxia Cui,^a Ling Chang ^a and Zhaowen Yu ^a ^*

^aInstitute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, Henan, People's Republic of China
^*Correspondence e-mail: zhw@henu.edu.cn

(Received 10 November 2007; accepted 20 December 2007; online 4 January 2008)

In the structure of the title complex, [Cu(C₈H₄O₄)(C₁₂H₈N₂)(H₂O)]·CH₄O, the Cu^II ion is pentacoordinated in a tetragonal–pyramidal geometry, with two O atoms of the 3-formyl-2-oxidobenzoate (3-formylsalicylate) anion and two N atoms of 1,10-phenanthroline occupying the basal plane, and a water O atom located at the apical site. The structure displays O—H⋯O hydrogen bonding.

Related literature

For related literature, see: Erxleben & Schumacher (2001 ); Ma et al. (2007 ); Akitsu & Einaga (2006 ); Yu, Cui et al. (2007 ); Yu, Hao et al. (2006 ); Costes et al. (2004 ); Karmakar et al. (2005 ).

Experimental

Crystal data

[Cu(C₈H₄O₄)(C₁₂H₈N₂)(H₂O)]·CH₄O
M_r = 457.91
Triclinic, $[P \overline 1]$
a = 8.6714 (11) Å
b = 10.3895 (13) Å
c = 11.7617 (14) Å
α = 115.125 (2)°
β = 95.859 (2)°
γ = 93.589 (2)°
V = 947.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 296 (2) K
0.21 × 0.16 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: none
4953 measured reflections
3336 independent reflections
2336 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.100
S = 0.94
3336 reflections
273 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1W	2.348 (3)
Cu1—O2	1.898 (2)
Cu1—O3	1.898 (2)
Cu1—N1	2.016 (3)
Cu1—N2	2.011 (3)

O1W—Cu1—O2	93.40 (11)
O1W—Cu1—O3	90.04 (10)
O1W—Cu1—N1	96.50 (11)
O1W—Cu1—N2	97.69 (10)
O2—Cu1—O3	94.32 (10)
O2—Cu1—N1	88.77 (11)
O2—Cu1—N2	166.01 (11)
O3—Cu1—N1	172.59 (11)
O3—Cu1—N2	94.17 (11)
N1—Cu1—N2	81.55 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O1ⁱ	0.82	1.89	2.703 (4)	171
O1W—H1WB⋯O5ⁱⁱ	0.85	1.93	2.747 (4)	162
O1W—H1WA⋯O4ⁱⁱⁱ	0.85	2.00	2.844 (4)	170
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067967/kj2080sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067967/kj2080Isup2.hkl

checkCIF report

Comment top

The Schiff bases of 3-formylsalicylic acid with diamines have been studied for many years and their binuclear complexes have been intensively investigated in view of the interesting magnetic interaction between the bridged metals (Akitsu & Einaga, 2006; Karmakar et al., 2005; Costes et al., 2004). Recently some complexes with the schiff base of 3-formysalicylic acid and monoamines (Yu, Hao et al., 2006; Yu, Cui et al., 2007; Erxleben & Schumacher, 2001; Ma et al., 2007) have also been reported. But to our knowledge, complexes using 3-formylsalicylic acid directly as ligand have received much less attention. Here we synthesized a multicomponent complex, containing 3-formylsalicylic acid and 1,10-phenanthroline.

The Cu^II ion is coordinated in distorted square pyramid, where the basal plane is formed by NNOO atoms coming from 1,10-phenanthroline and 3-formylsalcylate anion; the apical site is occupied by the O atom of water. The 3-formylsalicylate anion acts as a bidentate ligand. The O atom of the formyl group is not coordinated.

There are three kinds of intermolecular hydrogen bonds in the crystal. One is between the H atom of water and the O atom of methanol, the second is between the H atom of water and the formyl O atom, the third is between the H atom of methanol and the uncoordinated O atom of the carboxylate group. The intermolecular hydrogen bonds link the molecules into a onedimensional chain, running in the [1 - 1 0] direction (Figure 2).

Related literature top

For related literature, see: Erxleben & Schumacher (2001); Ma et al. (2007); Akitsu & Einaga (2006); Yu, Cui et al. (2007). Yu, Hao et al. (2006); Costes et al. (2004); Karmakar et al. (2005).

Experimental top

3-formylsalicylic acid (0.166 g, 1.0 mmol) was dissolved in 10 ml NaOH (0.080 g, 2.0 mmol) aqueous solution. To this solution, 15 ml me thanol solution containing 1,10-phenanthroline (0.1982 g, 1 mmol) and CuCl₂.2H₂O (0.1705 g, 1 mmol) was added. The mixture was stirred at ambient temperature for 2 h, then filtered to give a green solution. The filtrate was airproofed and kept at room temperature. Two weeks later, green block-shaped crystal of X-ray quality were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL (Bruker, 2005).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular packing of the title compound. Hydrogen bonds are indicated by dashed lines.

Aqua(3-formyl-2-oxidobenzoato-κ²O¹,O²)(1,10-phenanthroline- κ²N,N')copper(II) methanol solvate top

Crystal data top

[Cu(C₈H₄O₄)(C₁₂H₈N₂)(H₂O)]·CH₄O	Z = 2
M_r = 457.91	F(000) = 470
Triclinic, P1	D_x = 1.605 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6714 (11) Å	Cell parameters from 1476 reflections
b = 10.3895 (13) Å	θ = 2.4–23.1°
c = 11.7617 (14) Å	µ = 1.20 mm⁻¹
α = 115.125 (2)°	T = 296 K
β = 95.859 (2)°	Block, green
γ = 93.589 (2)°	0.21 × 0.16 × 0.15 mm
V = 947.7 (2) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	2336 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.061
Graphite monochromator	θ_max = 25.0°, θ_min = 1.9°
ϕ and ω scans	h = −10→8
4953 measured reflections	k = −11→12
3336 independent reflections	l = −13→11

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0357P)²] where P = (F_o² + 2F_c²)/3
3336 reflections	(Δ/σ)_max < 0.001
273 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Cu(C₈H₄O₄)(C₁₂H₈N₂)(H₂O)]·CH₄O	γ = 93.589 (2)°
M_r = 457.91	V = 947.7 (2) Å³
Triclinic, P1	Z = 2
a = 8.6714 (11) Å	Mo Kα radiation
b = 10.3895 (13) Å	µ = 1.20 mm⁻¹
c = 11.7617 (14) Å	T = 296 K
α = 115.125 (2)°	0.21 × 0.16 × 0.15 mm
β = 95.859 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2336 reflections with I > 2σ(I)
4953 measured reflections	R_int = 0.061
3336 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 0.94	Δρ_max = 0.56 e Å⁻³
3336 reflections	Δρ_min = −0.40 e Å⁻³
273 parameters

Special details top

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.

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 > σ(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
Cu1	0.04891 (5)	0.15042 (5)	0.43931 (4)	0.04238 (18)
O1W	0.2655 (3)	0.2918 (3)	0.4306 (3)	0.0690 (8)
H1WA	0.3370	0.2382	0.4054	0.083*
H1WB	0.2452	0.3275	0.3785	0.083*
N1	−0.1078 (3)	0.2009 (3)	0.3305 (3)	0.0395 (7)
N2	0.0517 (3)	−0.0202 (3)	0.2729 (3)	0.0366 (7)
O1	0.0334 (3)	0.4719 (2)	0.7766 (2)	0.0541 (7)
O2	−0.0072 (3)	0.3010 (3)	0.5848 (2)	0.0518 (7)
O3	0.1798 (3)	0.0801 (2)	0.5341 (2)	0.0433 (6)
O4	0.5232 (3)	−0.0845 (3)	0.6619 (3)	0.0694 (9)
C1	0.2080 (4)	0.2978 (3)	0.7301 (3)	0.0344 (8)
C2	0.2507 (4)	0.1602 (3)	0.6484 (3)	0.0347 (8)
C3	0.3754 (4)	0.1093 (4)	0.6985 (3)	0.0364 (8)
C4	0.4531 (4)	0.1902 (4)	0.8211 (4)	0.0455 (9)
H4A	0.5349	0.1545	0.8517	0.055*
C5	0.4121 (5)	0.3205 (4)	0.8972 (4)	0.0517 (10)
H5A	0.4649	0.3738	0.9788	0.062*
C6	0.2905 (4)	0.3714 (4)	0.8503 (3)	0.0433 (9)
H6A	0.2624	0.4601	0.9025	0.052*
C7	0.0722 (4)	0.3618 (4)	0.6951 (3)	0.0377 (8)
C8	0.4236 (4)	−0.0293 (4)	0.6237 (4)	0.0480 (10)
H8A	0.3748	−0.0798	0.5404	0.058*
C9	−0.1828 (4)	0.3141 (4)	0.3596 (4)	0.0511 (10)
H9A	−0.1596	0.3876	0.4413	0.061*
C10	−0.2942 (5)	0.3298 (4)	0.2752 (4)	0.0560 (11)
H10A	−0.3451	0.4116	0.3005	0.067*
C11	−0.3287 (5)	0.2251 (4)	0.1550 (4)	0.0554 (11)
H11A	−0.4043	0.2347	0.0979	0.066*
C12	−0.2512 (4)	0.1027 (4)	0.1166 (3)	0.0429 (9)
C13	−0.2754 (5)	−0.0140 (4)	−0.0074 (4)	0.0534 (11)
H13A	−0.3494	−0.0119	−0.0695	0.064*
C14	−0.1935 (5)	−0.1267 (4)	−0.0360 (4)	0.0546 (11)
H14A	−0.2120	−0.2007	−0.1177	0.066*
C15	−0.0787 (4)	−0.1356 (4)	0.0558 (3)	0.0421 (9)
C16	0.0130 (5)	−0.2480 (4)	0.0336 (3)	0.0505 (10)
H16A	0.0007	−0.3254	−0.0461	0.061*
C17	0.1192 (5)	−0.2437 (4)	0.1277 (4)	0.0493 (10)
H17A	0.1810	−0.3178	0.1126	0.059*
C18	0.1366 (4)	−0.1285 (4)	0.2479 (3)	0.0429 (9)
H18A	0.2095	−0.1276	0.3120	0.051*
C19	−0.0538 (4)	−0.0235 (4)	0.1789 (3)	0.0362 (8)
C20	−0.1402 (4)	0.0960 (4)	0.2081 (3)	0.0373 (8)
C21	0.6449 (6)	0.4308 (6)	0.6735 (6)	0.108 (2)
H21A	0.6025	0.4468	0.7501	0.162*
H21B	0.6887	0.3416	0.6434	0.162*
H21C	0.5635	0.4275	0.6103	0.162*
O5	0.7606 (4)	0.5414 (3)	0.6979 (3)	0.0751 (9)
H5	0.8459	0.5183	0.7138	0.113*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0434 (3)	0.0424 (3)	0.0300 (3)	0.0188 (2)	0.00278 (19)	0.0037 (2)
O1W	0.0605 (19)	0.0671 (19)	0.092 (2)	0.0250 (16)	0.0175 (17)	0.0422 (18)
N1	0.0402 (18)	0.0358 (17)	0.0363 (17)	0.0096 (15)	0.0087 (14)	0.0085 (14)
N2	0.0324 (17)	0.0363 (17)	0.0342 (17)	0.0068 (14)	0.0089 (14)	0.0074 (14)
O1	0.0666 (19)	0.0384 (15)	0.0413 (15)	0.0236 (14)	0.0049 (14)	0.0001 (13)
O2	0.0540 (17)	0.0520 (16)	0.0321 (14)	0.0283 (14)	0.0016 (12)	0.0000 (12)
O3	0.0487 (16)	0.0346 (13)	0.0327 (14)	0.0154 (12)	−0.0007 (12)	0.0014 (11)
O4	0.0579 (19)	0.0649 (19)	0.092 (2)	0.0275 (16)	0.0107 (17)	0.0382 (18)
C1	0.036 (2)	0.0324 (19)	0.0313 (19)	0.0047 (16)	0.0042 (16)	0.0100 (16)
C2	0.034 (2)	0.036 (2)	0.034 (2)	0.0034 (17)	0.0070 (16)	0.0144 (17)
C3	0.032 (2)	0.037 (2)	0.042 (2)	0.0041 (17)	0.0067 (17)	0.0188 (18)
C4	0.036 (2)	0.051 (2)	0.055 (3)	0.0044 (19)	0.0007 (19)	0.030 (2)
C5	0.054 (3)	0.049 (2)	0.042 (2)	−0.003 (2)	−0.012 (2)	0.015 (2)
C6	0.050 (2)	0.033 (2)	0.037 (2)	0.0011 (18)	0.0020 (18)	0.0064 (17)
C7	0.041 (2)	0.034 (2)	0.032 (2)	0.0050 (17)	0.0070 (17)	0.0079 (17)
C8	0.041 (2)	0.049 (2)	0.057 (3)	0.011 (2)	0.012 (2)	0.024 (2)
C9	0.049 (2)	0.046 (2)	0.055 (3)	0.014 (2)	0.009 (2)	0.018 (2)
C10	0.050 (3)	0.054 (3)	0.068 (3)	0.019 (2)	0.008 (2)	0.029 (2)
C11	0.051 (3)	0.064 (3)	0.060 (3)	0.006 (2)	−0.003 (2)	0.038 (3)
C12	0.039 (2)	0.050 (2)	0.042 (2)	−0.0015 (19)	0.0021 (18)	0.025 (2)
C13	0.057 (3)	0.062 (3)	0.041 (2)	−0.011 (2)	−0.009 (2)	0.029 (2)
C14	0.066 (3)	0.053 (3)	0.033 (2)	−0.012 (2)	−0.001 (2)	0.010 (2)
C15	0.044 (2)	0.042 (2)	0.033 (2)	−0.0061 (19)	0.0078 (18)	0.0098 (17)
C16	0.058 (3)	0.042 (2)	0.034 (2)	−0.003 (2)	0.016 (2)	−0.0004 (19)
C17	0.054 (3)	0.036 (2)	0.048 (2)	0.0128 (19)	0.022 (2)	0.0048 (19)
C18	0.037 (2)	0.043 (2)	0.044 (2)	0.0078 (18)	0.0091 (18)	0.0141 (18)
C19	0.037 (2)	0.038 (2)	0.0274 (19)	−0.0022 (17)	0.0053 (16)	0.0089 (16)
C20	0.035 (2)	0.043 (2)	0.032 (2)	−0.0003 (18)	0.0048 (17)	0.0157 (18)
C21	0.068 (4)	0.116 (5)	0.173 (6)	0.040 (4)	0.040 (4)	0.085 (5)
O5	0.078 (2)	0.0586 (19)	0.085 (2)	0.0297 (18)	0.001 (2)	0.0276 (18)

Geometric parameters (Å, º) top

Cu1—O1W	2.348 (3)	C8—H8A	0.9300
Cu1—O2	1.898 (2)	C9—C10	1.381 (5)
Cu1—O3	1.898 (2)	C9—H9A	0.9300
Cu1—N1	2.016 (3)	C10—C11	1.356 (5)
Cu1—N2	2.011 (3)	C10—H10A	0.9300
O1W—H1WA	0.8500	C11—C12	1.399 (5)
O1W—H1WB	0.8499	C11—H11A	0.9300
N1—C9	1.312 (4)	C12—C20	1.396 (5)
N1—C20	1.373 (4)	C12—C13	1.430 (5)
N2—C18	1.327 (4)	C13—C14	1.344 (5)
N2—C19	1.348 (4)	C13—H13A	0.9300
O1—C7	1.234 (4)	C14—C15	1.430 (5)
O2—C7	1.273 (4)	C14—H14A	0.9300
O3—C2	1.301 (4)	C15—C16	1.401 (5)
O4—C8	1.216 (4)	C15—C19	1.403 (4)
C1—C6	1.380 (5)	C16—C17	1.350 (5)
C1—C2	1.441 (4)	C16—H16A	0.9300
C1—C7	1.494 (5)	C17—C18	1.397 (5)
C2—C3	1.415 (5)	C17—H17A	0.9300
C3—C4	1.394 (5)	C18—H18A	0.9300
C3—C8	1.448 (5)	C19—C20	1.424 (5)
C4—C5	1.363 (5)	C21—O5	1.388 (5)
C4—H4A	0.9300	C21—H21A	0.9600
C5—C6	1.375 (5)	C21—H21B	0.9600
C5—H5A	0.9300	C21—H21C	0.9600
C6—H6A	0.9300	O5—H5	0.8200

O1W—Cu1—O2	93.40 (11)	C3—C8—H8A	117.6
O1W—Cu1—O3	90.04 (10)	N1—C9—C10	123.4 (4)
O1W—Cu1—N1	96.50 (11)	N1—C9—H9A	118.3
O1W—Cu1—N2	97.69 (10)	C10—C9—H9A	118.3
O2—Cu1—O3	94.32 (10)	C11—C10—C9	119.5 (4)
O2—Cu1—N1	88.77 (11)	C11—C10—H10A	120.2
O2—Cu1—N2	166.01 (11)	C9—C10—H10A	120.2
O3—Cu1—N1	172.59 (11)	C10—C11—C12	120.2 (4)
O3—Cu1—N2	94.17 (11)	C10—C11—H11A	119.9
N1—Cu1—N2	81.55 (11)	C12—C11—H11A	119.9
Cu1—O1W—H1WA	107.8	C20—C12—C11	116.4 (4)
Cu1—O1W—H1WB	112.5	C20—C12—C13	118.0 (4)
H1WA—O1W—H1WB	107.7	C11—C12—C13	125.6 (4)
C9—N1—C20	117.2 (3)	C14—C13—C12	121.4 (4)
C9—N1—Cu1	130.2 (3)	C14—C13—H13A	119.3
C20—N1—Cu1	112.5 (2)	C12—C13—H13A	119.3
C18—N2—C19	118.4 (3)	C13—C14—C15	121.6 (4)
C18—N2—Cu1	128.5 (3)	C13—C14—H14A	119.2
C19—N2—Cu1	113.0 (2)	C15—C14—H14A	119.2
C7—O2—Cu1	126.8 (2)	C16—C15—C19	116.4 (4)
C2—O3—Cu1	123.3 (2)	C16—C15—C14	125.3 (4)
C6—C1—C2	118.7 (3)	C19—C15—C14	118.3 (4)
C6—C1—C7	117.6 (3)	C17—C16—C15	120.0 (3)
C2—C1—C7	123.6 (3)	C17—C16—H16A	120.0
O3—C2—C3	118.8 (3)	C15—C16—H16A	120.0
O3—C2—C1	124.2 (3)	C16—C17—C18	120.2 (4)
C3—C2—C1	117.0 (3)	C16—C17—H17A	119.9
C4—C3—C2	120.9 (3)	C18—C17—H17A	119.9
C4—C3—C8	118.5 (3)	N2—C18—C17	121.7 (4)
C2—C3—C8	120.6 (3)	N2—C18—H18A	119.2
C5—C4—C3	121.6 (3)	C17—C18—H18A	119.2
C5—C4—H4A	119.2	N2—C19—C15	123.5 (3)
C3—C4—H4A	119.2	N2—C19—C20	116.9 (3)
C4—C5—C6	118.3 (4)	C15—C19—C20	119.6 (3)
C4—C5—H5A	120.8	N1—C20—C12	123.3 (3)
C6—C5—H5A	120.8	N1—C20—C19	115.7 (3)
C5—C6—C1	123.6 (3)	C12—C20—C19	121.0 (3)
C5—C6—H6A	118.2	O5—C21—H21A	109.5
C1—C6—H6A	118.2	O5—C21—H21B	109.5
O1—C7—O2	120.1 (3)	H21A—C21—H21B	109.5
O1—C7—C1	118.9 (3)	O5—C21—H21C	109.5
O2—C7—C1	120.9 (3)	H21A—C21—H21C	109.5
O4—C8—C3	124.8 (4)	H21B—C21—H21C	109.5
O4—C8—H8A	117.6	C21—O5—H5	109.5

O2—Cu1—N1—C9	12.7 (3)	C6—C1—C7—O2	178.7 (3)
N2—Cu1—N1—C9	−177.4 (3)	C2—C1—C7—O2	−5.4 (5)
O1W—Cu1—N1—C9	−80.5 (3)	C4—C3—C8—O4	3.6 (5)
O2—Cu1—N1—C20	−165.8 (2)	C2—C3—C8—O4	−175.6 (3)
N2—Cu1—N1—C20	4.1 (2)	C20—N1—C9—C10	2.1 (5)
O1W—Cu1—N1—C20	100.9 (2)	Cu1—N1—C9—C10	−176.3 (3)
O2—Cu1—N2—C18	−134.6 (4)	N1—C9—C10—C11	−0.8 (6)
O3—Cu1—N2—C18	−7.3 (3)	C9—C10—C11—C12	−0.5 (6)
N1—Cu1—N2—C18	178.7 (3)	C10—C11—C12—C20	0.4 (5)
O1W—Cu1—N2—C18	83.3 (3)	C10—C11—C12—C13	−179.2 (4)
O2—Cu1—N2—C19	42.0 (6)	C20—C12—C13—C14	−0.5 (5)
O3—Cu1—N2—C19	169.2 (2)	C11—C12—C13—C14	179.1 (4)
N1—Cu1—N2—C19	−4.7 (2)	C12—C13—C14—C15	0.2 (6)
O1W—Cu1—N2—C19	−100.2 (2)	C13—C14—C15—C16	−179.2 (3)
O3—Cu1—O2—C7	25.9 (3)	C13—C14—C15—C19	0.7 (5)
N2—Cu1—O2—C7	153.2 (4)	C19—C15—C16—C17	−0.6 (5)
N1—Cu1—O2—C7	−160.8 (3)	C14—C15—C16—C17	179.3 (3)
O1W—Cu1—O2—C7	−64.4 (3)	C15—C16—C17—C18	0.8 (6)
O2—Cu1—O3—C2	−27.2 (3)	C19—N2—C18—C17	0.2 (5)
N2—Cu1—O3—C2	163.9 (3)	Cu1—N2—C18—C17	176.6 (2)
O1W—Cu1—O3—C2	66.2 (3)	C16—C17—C18—N2	−0.7 (5)
Cu1—O3—C2—C3	−163.8 (2)	C18—N2—C19—C15	0.0 (5)
Cu1—O3—C2—C1	17.9 (4)	Cu1—N2—C19—C15	−176.9 (2)
C6—C1—C2—O3	178.8 (3)	C18—N2—C19—C20	−178.5 (3)
C7—C1—C2—O3	2.8 (5)	Cu1—N2—C19—C20	4.6 (4)
C6—C1—C2—C3	0.4 (5)	C16—C15—C19—N2	0.2 (5)
C7—C1—C2—C3	−175.5 (3)	C14—C15—C19—N2	−179.7 (3)
O3—C2—C3—C4	−178.9 (3)	C16—C15—C19—C20	178.6 (3)
C1—C2—C3—C4	−0.5 (5)	C14—C15—C19—C20	−1.2 (5)
O3—C2—C3—C8	0.3 (5)	C9—N1—C20—C12	−2.3 (5)
C1—C2—C3—C8	178.7 (3)	Cu1—N1—C20—C12	176.5 (3)
C2—C3—C4—C5	0.2 (5)	C9—N1—C20—C19	178.4 (3)
C8—C3—C4—C5	−179.0 (3)	Cu1—N1—C20—C19	−2.9 (4)
C3—C4—C5—C6	0.2 (5)	C11—C12—C20—N1	1.1 (5)
C4—C5—C6—C1	−0.3 (6)	C13—C12—C20—N1	−179.4 (3)
C2—C1—C6—C5	−0.1 (5)	C11—C12—C20—C19	−179.7 (3)
C7—C1—C6—C5	176.1 (3)	C13—C12—C20—C19	−0.1 (5)
Cu1—O2—C7—O1	169.4 (2)	N2—C19—C20—N1	−1.1 (4)
Cu1—O2—C7—C1	−13.8 (5)	C15—C19—C20—N1	−179.7 (3)
C6—C1—C7—O1	−4.5 (5)	N2—C19—C20—C12	179.5 (3)
C2—C1—C7—O1	171.4 (3)	C15—C19—C20—C12	0.9 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1ⁱ	0.82	1.89	2.703 (4)	171
O1W—H1WB···O5ⁱⁱ	0.85	1.93	2.747 (4)	162
O1W—H1WA···O4ⁱⁱⁱ	0.85	2.00	2.844 (4)	170

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

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₄O₄)(C₁₂H₈N₂)(H₂O)]·CH₄O
M_r	457.91
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.6714 (11), 10.3895 (13), 11.7617 (14)
α, β, γ (°)	115.125 (2), 95.859 (2), 93.589 (2)
V (Å³)	947.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.20
Crystal size (mm)	0.21 × 0.16 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4953, 3336, 2336
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.100, 0.94
No. of reflections	3336
No. of parameters	273
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.40

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2005).

Selected geometric parameters (Å, º) top

Cu1—O1W	2.348 (3)	Cu1—N1	2.016 (3)
Cu1—O2	1.898 (2)	Cu1—N2	2.011 (3)
Cu1—O3	1.898 (2)

O1W—Cu1—O2	93.40 (11)	O2—Cu1—N1	88.77 (11)
O1W—Cu1—O3	90.04 (10)	O2—Cu1—N2	166.01 (11)
O1W—Cu1—N1	96.50 (11)	O3—Cu1—N1	172.59 (11)
O1W—Cu1—N2	97.69 (10)	O3—Cu1—N2	94.17 (11)
O2—Cu1—O3	94.32 (10)	N1—Cu1—N2	81.55 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1ⁱ	0.82	1.89	2.703 (4)	170.7
O1W—H1WB···O5ⁱⁱ	0.85	1.93	2.747 (4)	162.2
O1W—H1WA···O4ⁱⁱⁱ	0.85	2.00	2.844 (4)	170.3

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

Acknowledgements

The authors are grateful for financial support from the Henan Administration of Science and Technology (grant No. 0111030700).

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