catena-Poly[copper(II)-bis­(μ-2-formyl-6-meth­oxy­phenolato-κ4O2,O1:O1,O6)-[(methanol-κO)sodium]-μ-perchlorato-κ2O:O′]

Gao, T.; Gao, P.; Li, H.-F.; Zhang, J.-W.; Xu, L.-L.

doi:10.1107/S1600536812000876

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page m152

doi:10.1107/S1600536812000876

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catena-Poly[copper(II)-bis(μ-2-formyl-6-methoxyphenolato-κ⁴O²,O¹:O¹,O⁶)-[(methanol-κO)sodium]-μ-perchlorato-κ²O:O′]

Ting Gao,^a ^* Po Gao,^a Hong-Feng Li,^a Ju-Wen Zhang ^a and Li-Li Xu ^a

^aKey Laboratory of Chemical Engineering Processes & Technology for High-Efficiency Conversion, College of Heilongjiang Province, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: gaoting1218@yahoo.com.cn

(Received 22 December 2011; accepted 9 January 2012; online 14 January 2012)

In the title heterodinuclear complex, [CuNa(C₈H₇O₃)₂(ClO₄)(CH₃OH)]_n, the Cu^II ion is five-coordinated by four O atoms from two 2-formyl-6-methoxyphenolate anions and one O atom from a perchlorate anion in a distorted square-pyramidal geometry. The Na⁺ ion is six-coordinated by four O atoms from two 2-formyl-6-methoxyphenolate ligands, one O atom of a methanol molecule and one O atom of a perchlorate anion. The perchlorate anions link the Na⁺ and Cu^II ions, forming a chain along [010]. O—H⋯O hydrogen bonds connect the chains. π–π interactions are present between the benzene rings [centroid–centroid distances = 3.566 (2) and 3.702 (2) Å]. The O atoms of the perchlorate anion are disordered over two sets of sites, with an occupancy ratio of 0.481 (8):0.519 (8).

Related literature

For related structures, see: Gao et al. (2011 ); Lin & Zeng (2006 ); Yang et al. (2012 ).

Experimental

Crystal data

[CuNa(C₈H₇O₃)₂(ClO₄)(CH₄O)]
M_r = 520.29
Triclinic, $[P \overline 1]$
a = 7.9552 (16) Å
b = 8.9453 (18) Å
c = 15.563 (3) Å
α = 81.27 (3)°
β = 84.24 (3)°
γ = 68.25 (3)°
V = 1015.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 293 K
0.43 × 0.28 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.610, T_max = 0.714
9778 measured reflections
4591 independent reflections
3948 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.108
S = 1.11
4591 reflections
321 parameters
48 restraints
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H71⋯O10ⁱ	0.85	2.11	2.874 (7)	149
O7—H71⋯O11′ⁱ	0.85	2.55	3.334 (13)	154
Symmetry code: (i) x-1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812000876/hy2501sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000876/hy2501Isup2.hkl

checkCIF report

Comment top

Orthovanillin is a commercial ligand that is able to chelate 3d ions and several structure determinations are known, mainly with copper ions (Lin & Zeng, 2006). Recently, we were interested in the nature of the products obtained by reacting a 3d complex with alkali metal ions (Gao et al., 2011; Yang et al., 2012). In this paper we reacted a Cu complex with sodium perchlorate to yield a heterodinuclear complex. As shown in Fig. 1, the Cu^II ion is five-coordinated by two aldehyde O atoms and two phenolate O atoms from two orthovanillin ligands and one O atom from a perchlorate anion in a distorted square-pyramidal geometry. The Cu atom is inserted into the inner cavity surrounded by four O atoms. The Na⁺ ion is ligated by two phenolate O atoms, two methoxyl O atoms, one O atom from a methanol molecule and one O atom from a perchlorate anion. The Cu and Na atoms are bridged by the perchlorate anions, forming a one-dimensional structure along [0 1 0].

Related literature top

For related structures, see: Gao et al. (2011); Lin & Zeng (2006); Yang et al. (2012).

Experimental top

To a solution of o-vanillin (0.046 g, 0.20 mmol) in dichloromethane (5 ml) was added a solution of copper(II) acetate monohydrate (0.040 g, 0.20 mmol) and sodium perchlorate (0.028 g, 0.20 mmol) in ethanol (5 ml). The mixture was stirred, heated under reflux (30 min) and then allowed to cool to room temperature (yield: 70%). Crystals suitable for X-ray determination were obtained by slow diffusion of diethylether into the solution for one week. Analysis, calculated for C₁₇H₁₈ClCuNaO₁₁: C 39.24, H 3.49%; found: C 39.38, H 3.48%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The asymmetric unit of the title compound, showing 30% probability displacement ellipsoids. H atoms and 0.519-occupied O atoms of the perchlorate anion are not shown. [Symmetry codes: (i) x, y-1, z; (ii) x, 1+y, z.]

catena-Poly[copper(II)-bis(µ-2-formyl-6-methoxyphenolato- κ⁴O²,O¹:O¹,O⁶)-[(methanol- κO)sodium]-µ-perchlorato-κ²O:O'] top

Crystal data top

[CuNa(C₈H₇O₃)₂(ClO₄)(CH₄O)]	Z = 2
M_r = 520.29	F(000) = 530
Triclinic, P1	D_x = 1.701 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9552 (16) Å	Cell parameters from 8587 reflections
b = 8.9453 (18) Å	θ = 3.0–27.6°
c = 15.563 (3) Å	µ = 1.29 mm⁻¹
α = 81.27 (3)°	T = 293 K
β = 84.24 (3)°	Block, green
γ = 68.25 (3)°	0.43 × 0.28 × 0.28 mm
V = 1015.6 (4) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	4591 independent reflections
Radiation source: rotation anode	3948 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.610, T_max = 0.714	k = −11→11
9778 measured reflections	l = −20→20

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0586P)² + 0.4273P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
4591 reflections	Δρ_max = 0.58 e Å⁻³
321 parameters	Δρ_min = −0.59 e Å⁻³
48 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.035 (3)

Crystal data top

[CuNa(C₈H₇O₃)₂(ClO₄)(CH₄O)]	γ = 68.25 (3)°
M_r = 520.29	V = 1015.6 (4) Å³
Triclinic, P1	Z = 2
a = 7.9552 (16) Å	Mo Kα radiation
b = 8.9453 (18) Å	µ = 1.29 mm⁻¹
c = 15.563 (3) Å	T = 293 K
α = 81.27 (3)°	0.43 × 0.28 × 0.28 mm
β = 84.24 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	4591 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3948 reflections with I > 2σ(I)
T_min = 0.610, T_max = 0.714	R_int = 0.021
9778 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	48 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.11	Δρ_max = 0.58 e Å⁻³
4591 reflections	Δρ_min = −0.59 e Å⁻³
321 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	Occ. (<1)
C1	0.4762 (3)	0.6763 (3)	0.08377 (17)	0.0364 (5)
C2	0.5719 (4)	0.6802 (4)	0.00596 (19)	0.0458 (6)
H2	0.5263	0.7663	−0.0374	0.055*
C3	0.7386 (4)	0.5555 (4)	−0.0092 (2)	0.0537 (7)
H3	0.8026	0.5604	−0.0623	0.064*
C4	0.8070 (4)	0.4280 (4)	0.0531 (2)	0.0484 (7)
H4	0.9171	0.3459	0.0424	0.058*
C5	0.7105 (3)	0.4198 (3)	0.13468 (17)	0.0374 (5)
C6	0.5417 (3)	0.5456 (3)	0.15163 (16)	0.0341 (5)
C7	0.7836 (3)	0.2828 (3)	0.1967 (2)	0.0433 (6)
H7	0.8926	0.2054	0.1797	0.052*
C8	0.2420 (5)	0.9285 (4)	0.0431 (2)	0.0582 (8)
H8A	0.3249	0.9853	0.0322	0.087*
H8B	0.1275	0.9990	0.0651	0.087*
H8C	0.2256	0.8945	−0.0100	0.087*
C9	0.0881 (3)	0.6812 (3)	0.48246 (16)	0.0332 (5)
C10	0.0140 (3)	0.6796 (3)	0.56545 (18)	0.0401 (6)
H10	−0.0893	0.7658	0.5797	0.048*
C11	0.0922 (4)	0.5491 (4)	0.62961 (18)	0.0451 (6)
H11	0.0403	0.5495	0.6859	0.054*
C12	0.2432 (4)	0.4225 (3)	0.60967 (17)	0.0419 (6)
H12	0.2955	0.3374	0.6526	0.050*
C13	0.3218 (3)	0.4197 (3)	0.52328 (17)	0.0344 (5)
C14	0.2437 (3)	0.5486 (3)	0.45824 (15)	0.0302 (5)
C15	0.4787 (3)	0.2836 (3)	0.50530 (18)	0.0379 (5)
H15	0.5227	0.2051	0.5523	0.046*
C16	−0.1374 (4)	0.9355 (3)	0.4313 (2)	0.0482 (7)
H16A	−0.2361	0.8969	0.4426	0.072*
H16B	−0.1606	1.0157	0.3810	0.072*
H16C	−0.1257	0.9829	0.4807	0.072*
C17	−0.1080 (5)	0.7533 (5)	0.1549 (3)	0.0673 (9)
H17A	0.0087	0.6922	0.1305	0.101*
H17B	−0.1874	0.8128	0.1089	0.101*
H17C	−0.1579	0.6806	0.1903	0.101*
Cl1	0.36690 (9)	1.08254 (8)	0.25272 (5)	0.04494 (18)
Cu1	0.50540 (4)	0.39856 (3)	0.32609 (2)	0.03585 (13)
Na1	0.19514 (14)	0.77412 (13)	0.26850 (7)	0.0424 (3)
O1	0.3134 (3)	0.7898 (2)	0.10574 (13)	0.0450 (4)
O2	0.4454 (2)	0.5493 (2)	0.22418 (12)	0.0426 (4)
O3	0.7213 (3)	0.2523 (2)	0.27085 (13)	0.0456 (5)
O4	0.0270 (2)	0.8028 (2)	0.41576 (13)	0.0429 (4)
O5	0.3060 (2)	0.5559 (2)	0.37745 (11)	0.0372 (4)
O6	0.5644 (2)	0.2566 (2)	0.43425 (13)	0.0424 (4)
O7	−0.0898 (3)	0.8613 (3)	0.20606 (16)	0.0603 (6)
H71	−0.1953	0.9215	0.2223	0.090*
O8	0.313 (2)	0.9655 (12)	0.2973 (6)	0.134 (4)	0.481 (8)
O9	0.3691 (13)	1.1775 (13)	0.3156 (6)	0.090 (3)	0.481 (8)
O10	0.5238 (9)	1.0233 (14)	0.2027 (7)	0.104 (4)	0.481 (8)
O11	0.2316 (12)	1.1649 (14)	0.1896 (6)	0.134 (4)	0.481 (8)
O8'	0.2175 (7)	1.0358 (9)	0.2565 (7)	0.093 (3)	0.519 (8)
O9'	0.3203 (10)	1.2409 (8)	0.2718 (7)	0.086 (3)	0.519 (8)
O10'	0.4646 (19)	1.0763 (15)	0.1746 (6)	0.140 (4)	0.519 (8)
O11'	0.5004 (15)	0.9750 (12)	0.3065 (8)	0.164 (5)	0.519 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0334 (11)	0.0377 (12)	0.0389 (13)	−0.0130 (10)	−0.0007 (10)	−0.0073 (10)
C2	0.0491 (15)	0.0542 (16)	0.0385 (14)	−0.0258 (13)	0.0003 (12)	−0.0023 (12)
C3	0.0503 (16)	0.070 (2)	0.0445 (15)	−0.0287 (15)	0.0133 (13)	−0.0103 (14)
C4	0.0365 (13)	0.0568 (17)	0.0508 (16)	−0.0156 (12)	0.0138 (12)	−0.0175 (13)
C5	0.0322 (11)	0.0395 (13)	0.0410 (14)	−0.0121 (10)	0.0045 (10)	−0.0126 (10)
C6	0.0318 (11)	0.0336 (12)	0.0370 (12)	−0.0113 (10)	0.0014 (10)	−0.0087 (10)
C7	0.0299 (11)	0.0374 (13)	0.0552 (16)	−0.0022 (10)	0.0055 (11)	−0.0140 (12)
C8	0.0620 (19)	0.0440 (16)	0.0535 (18)	−0.0038 (14)	−0.0136 (15)	0.0062 (13)
C9	0.0264 (10)	0.0290 (11)	0.0407 (13)	−0.0062 (9)	0.0004 (9)	−0.0047 (9)
C10	0.0316 (11)	0.0404 (13)	0.0439 (14)	−0.0077 (10)	0.0057 (10)	−0.0111 (11)
C11	0.0447 (14)	0.0531 (16)	0.0359 (13)	−0.0170 (12)	0.0050 (11)	−0.0076 (11)
C12	0.0482 (14)	0.0424 (14)	0.0327 (12)	−0.0156 (12)	−0.0048 (11)	0.0017 (10)
C13	0.0321 (11)	0.0312 (11)	0.0384 (13)	−0.0103 (9)	−0.0040 (10)	−0.0015 (9)
C14	0.0259 (10)	0.0265 (10)	0.0351 (12)	−0.0063 (9)	−0.0003 (9)	−0.0037 (9)
C15	0.0342 (12)	0.0293 (11)	0.0428 (13)	−0.0052 (10)	−0.0073 (10)	0.0053 (10)
C16	0.0365 (13)	0.0316 (13)	0.0631 (18)	0.0043 (11)	−0.0030 (12)	−0.0086 (12)
C17	0.074 (2)	0.075 (2)	0.060 (2)	−0.033 (2)	−0.0058 (18)	−0.0119 (18)
Cl1	0.0447 (3)	0.0444 (4)	0.0470 (4)	−0.0179 (3)	0.0014 (3)	−0.0071 (3)
Cu1	0.03095 (18)	0.02748 (18)	0.0382 (2)	0.00017 (12)	0.00257 (12)	−0.00201 (12)
Na1	0.0378 (5)	0.0354 (5)	0.0444 (6)	−0.0028 (4)	−0.0055 (4)	−0.0013 (4)
O1	0.0428 (10)	0.0383 (10)	0.0424 (10)	−0.0039 (8)	−0.0028 (8)	0.0017 (8)
O2	0.0382 (9)	0.0373 (9)	0.0375 (9)	0.0003 (7)	0.0040 (8)	−0.0005 (7)
O3	0.0391 (9)	0.0340 (9)	0.0501 (11)	0.0003 (8)	0.0036 (8)	−0.0033 (8)
O4	0.0375 (9)	0.0287 (8)	0.0461 (10)	0.0041 (7)	0.0032 (8)	−0.0005 (7)
O5	0.0335 (8)	0.0295 (8)	0.0352 (9)	0.0016 (7)	0.0038 (7)	−0.0006 (7)
O6	0.0392 (9)	0.0285 (9)	0.0461 (10)	0.0017 (7)	−0.0020 (8)	−0.0006 (7)
O7	0.0401 (10)	0.0648 (14)	0.0727 (15)	−0.0083 (10)	−0.0068 (10)	−0.0239 (12)
O8	0.216 (9)	0.107 (6)	0.119 (6)	−0.117 (6)	−0.013 (6)	0.018 (5)
O9	0.090 (5)	0.121 (7)	0.091 (5)	−0.064 (5)	0.026 (4)	−0.064 (5)
O10	0.035 (3)	0.137 (7)	0.124 (7)	0.007 (3)	0.012 (3)	−0.073 (6)
O11	0.100 (5)	0.169 (8)	0.097 (5)	−0.007 (5)	−0.034 (4)	−0.001 (5)
O8'	0.046 (3)	0.078 (4)	0.174 (7)	−0.031 (3)	0.009 (3)	−0.059 (5)
O9'	0.059 (3)	0.049 (3)	0.157 (7)	−0.021 (3)	0.013 (4)	−0.038 (4)
O10'	0.193 (10)	0.154 (8)	0.071 (5)	−0.077 (7)	0.044 (6)	−0.005 (5)
O11'	0.165 (7)	0.126 (6)	0.171 (7)	−0.033 (5)	−0.086 (6)	0.073 (6)

Geometric parameters (Å, º) top

C1—O1	1.367 (3)	C16—O4	1.432 (3)
C1—C2	1.367 (4)	C16—H16A	0.9600
C1—C6	1.427 (4)	C16—H16B	0.9600
C2—C3	1.407 (4)	C16—H16C	0.9600
C2—H2	0.9300	C17—O7	1.396 (4)
C3—C4	1.360 (5)	C17—H17A	0.9600
C3—H3	0.9300	C17—H17B	0.9600
C4—C5	1.422 (4)	C17—H17C	0.9600
C4—H4	0.9300	Cl1—O8	1.347 (7)
C5—C7	1.413 (4)	Cl1—O10	1.373 (7)
C5—C6	1.428 (3)	Cl1—O10'	1.373 (9)
C6—O2	1.297 (3)	Cl1—O11'	1.390 (8)
C7—O3	1.242 (3)	Cl1—O8'	1.392 (5)
C7—H7	0.9300	Cl1—O9	1.395 (8)
C8—O1	1.426 (3)	Cl1—O9'	1.396 (7)
C8—H8A	0.9600	Cl1—O11	1.439 (8)
C8—H8B	0.9600	Cu1—O5	1.8890 (18)
C8—H8C	0.9600	Cu1—O2	1.8941 (19)
C9—C10	1.365 (4)	Cu1—O6	1.932 (2)
C9—O4	1.365 (3)	Cu1—O3	1.944 (2)
C9—C14	1.426 (3)	Cu1—O9ⁱ	2.614 (11)
C10—C11	1.407 (4)	Cu1—O9'ⁱ	2.650 (8)
C10—H10	0.9300	Cu1—Na1	3.4010 (17)
C11—C12	1.358 (4)	Na1—O5	2.342 (2)
C11—H11	0.9300	Na1—O8	2.349 (9)
C12—C13	1.424 (4)	Na1—O7	2.365 (2)
C12—H12	0.9300	Na1—O2	2.379 (2)
C13—C14	1.408 (3)	Na1—O8'	2.390 (7)
C13—C15	1.423 (3)	Na1—O4	2.533 (2)
C14—O5	1.306 (3)	Na1—O1	2.614 (2)
C15—O6	1.246 (3)	O7—H71	0.8500
C15—H15	0.9300

O1—C1—C2	125.9 (3)	O11'—Cl1—O8'	111.4 (6)
O1—C1—C6	113.0 (2)	O8—Cl1—O9	104.4 (6)
C2—C1—C6	121.1 (2)	O10—Cl1—O9	116.6 (6)
C1—C2—C3	120.7 (3)	O10'—Cl1—O9'	105.4 (7)
C1—C2—H2	119.6	O11'—Cl1—O9'	110.6 (6)
C3—C2—H2	119.6	O8'—Cl1—O9'	112.5 (4)
C4—C3—C2	120.5 (3)	O8—Cl1—O11	104.6 (7)
C4—C3—H3	119.7	O10—Cl1—O11	103.6 (6)
C2—C3—H3	119.7	O9—Cl1—O11	113.9 (6)
C3—C4—C5	120.1 (3)	O5—Cu1—O2	83.82 (8)
C3—C4—H4	119.9	O5—Cu1—O6	93.45 (8)
C5—C4—H4	119.9	O2—Cu1—O6	176.21 (8)
C7—C5—C4	118.3 (2)	O5—Cu1—O3	174.49 (8)
C7—C5—C6	121.4 (2)	O2—Cu1—O3	93.50 (9)
C4—C5—C6	120.2 (3)	O6—Cu1—O3	89.00 (8)
O2—C6—C1	118.2 (2)	O2—Cu1—O9ⁱ	107.1 (2)
O2—C6—C5	124.5 (2)	O3—Cu1—O9ⁱ	84.5 (2)
C1—C6—C5	117.2 (2)	O5—Cu1—O9ⁱ	100.9 (2)
O3—C7—C5	128.4 (2)	O6—Cu1—O9ⁱ	75.9 (2)
O3—C7—H7	115.8	O2—Cu1—O9'ⁱ	88.9 (2)
C5—C7—H7	115.8	O3—Cu1—O9'ⁱ	87.86 (19)
O1—C8—H8A	109.5	O5—Cu1—O9'ⁱ	96.87 (19)
O1—C8—H8B	109.5	O6—Cu1—O9'ⁱ	94.0 (2)
H8A—C8—H8B	109.5	O5—Na1—O8	104.4 (3)
O1—C8—H8C	109.5	O5—Na1—O7	126.05 (9)
H8A—C8—H8C	109.5	O8—Na1—O7	120.1 (3)
H8B—C8—H8C	109.5	O5—Na1—O2	64.72 (7)
C10—C9—O4	125.8 (2)	O8—Na1—O2	106.8 (4)
C10—C9—C14	120.8 (2)	O7—Na1—O2	121.84 (9)
O4—C9—C14	113.4 (2)	O5—Na1—O8'	127.7 (2)
C9—C10—C11	120.7 (2)	O8—Na1—O8'	24.3 (3)
C9—C10—H10	119.6	O7—Na1—O8'	96.63 (19)
C11—C10—H10	119.6	O2—Na1—O8'	120.27 (15)
C12—C11—C10	120.3 (2)	O5—Na1—O4	63.79 (7)
C12—C11—H11	119.9	O8—Na1—O4	87.9 (3)
C10—C11—H11	119.9	O7—Na1—O4	87.65 (8)
C11—C12—C13	120.2 (2)	O2—Na1—O4	128.46 (8)
C11—C12—H12	119.9	O8'—Na1—O4	93.2 (2)
C13—C12—H12	119.9	O5—Na1—O1	126.62 (8)
C14—C13—C15	121.7 (2)	O8—Na1—O1	92.0 (3)
C14—C13—C12	120.1 (2)	O7—Na1—O1	82.97 (9)
C15—C13—C12	118.2 (2)	O2—Na1—O1	61.92 (7)
O5—C14—C13	124.3 (2)	O8'—Na1—O1	82.4 (2)
O5—C14—C9	117.9 (2)	O4—Na1—O1	169.07 (7)
C13—C14—C9	117.9 (2)	C1—O1—C8	116.7 (2)
O6—C15—C13	128.0 (2)	C1—O1—Na1	118.00 (15)
O6—C15—H15	116.0	C8—O1—Na1	123.66 (18)
C13—C15—H15	116.0	C6—O2—Cu1	127.00 (16)
O4—C16—H16A	109.5	C6—O2—Na1	126.71 (16)
O4—C16—H16B	109.5	Cu1—O2—Na1	104.90 (9)
H16A—C16—H16B	109.5	C7—O3—Cu1	124.61 (17)
O4—C16—H16C	109.5	C9—O4—C16	117.8 (2)
H16A—C16—H16C	109.5	C9—O4—Na1	118.86 (14)
H16B—C16—H16C	109.5	C16—O4—Na1	123.15 (17)
O7—C17—H17A	109.5	C14—O5—Cu1	127.46 (15)
O7—C17—H17B	109.5	C14—O5—Na1	125.99 (14)
H17A—C17—H17B	109.5	Cu1—O5—Na1	106.52 (8)
O7—C17—H17C	109.5	C15—O6—Cu1	125.08 (16)
H17A—C17—H17C	109.5	C17—O7—Na1	114.4 (2)
H17B—C17—H17C	109.5	C17—O7—H71	108.0
O8—Cl1—O10	113.3 (8)	Na1—O7—H71	132.5
O10'—Cl1—O11'	100.0 (8)	Cl1—O8—Na1	138.4 (7)
O10'—Cl1—O8'	116.1 (7)	Cl1—O8'—Na1	131.5 (4)

Symmetry code: (i) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···O10ⁱⁱ	0.85	2.11	2.874 (7)	149
O7—H71···O11′ⁱⁱ	0.85	2.55	3.334 (13)	154

Symmetry code: (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[CuNa(C₈H₇O₃)₂(ClO₄)(CH₄O)]
M_r	520.29
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.9552 (16), 8.9453 (18), 15.563 (3)
α, β, γ (°)	81.27 (3), 84.24 (3), 68.25 (3)
V (Å³)	1015.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.43 × 0.28 × 0.28

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.610, 0.714
No. of measured, independent and observed [I > 2σ(I)] reflections	9778, 4591, 3948
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.108, 1.11
No. of reflections	4591
No. of parameters	321
No. of restraints	48
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.59

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···O10ⁱ	0.85	2.11	2.874 (7)	149
O7—H71···O11'ⁱ	0.85	2.55	3.334 (13)	154

Symmetry code: (i) x−1, y, z.

Acknowledgements

The authors gratefully acknowledge financial support from Heilongjiang Province (11551334) and Heilongjiang University.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Gao, P., Hou, H.-G., Gao, T., Yang, J.-L. & Yang, Y. (2011). Acta Cryst. E67, m1522. Web of Science CSD CrossRef IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Lin, Z.-D. & Zeng, W. (2006). Acta Cryst. E62, m1074–m1076. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, Y., Gao, P., Yang, J.-L., Hou, H.-G. & Gao, T. (2012). Acta Cryst. E68, m37. Web of Science CSD CrossRef IUCr Journals Google Scholar

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