{μ-6,6′-Dimeth­oxy-2,2′-[ethane-1,2-diyl­bis(nitrilo­methanylyl­idene)]diphenolato-1κ4O6,O1,O1′,O6′;2κ4O1,N,N′,O1′}(methanol-1κO)(tetra­fluoridoborato-1κ2F,F′)-2-copper(II)-1-sodium

Gao, T.; Yang, Y.; Gao, P.; Zhang, J.-W.; Yang, J.-L.

doi:10.1107/S160053681102842X

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1127

doi:10.1107/S160053681102842X

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{μ-6,6′-Dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethanylylidene)]diphenolato-1κ⁴O⁶,O¹,O^1′,O^6′;2κ⁴O¹,N,N′,O^1′}(methanol-1κO)(tetrafluoridoborato-1κ²F,F′)-2-copper(II)-1-sodium

Ting Gao,^a ^* Yu Yang,^a Po Gao,^a Ju-Wen Zhang ^a and Jing-Lin Yang ^a

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

(Received 5 July 2011; accepted 15 July 2011; online 23 July 2011)

In the dinuclear salen-type title complex, [CuNa(BF₄)(C₁₈H₁₈N₂O₄)(CH₃OH)], the Cu^II atom is chelated by two O atoms and two N atoms of the deprotonated Schiff base in a square-planar geometry. The Na atom is seven-coordinate as it is linked to four O atoms of the same Schiff base ligand, one O atom of the methanol and two tetrafluoridoborate F atoms. The remaining two F atoms of the anion are disordered over two sites in a 0.598 (18):0.402 (18) ratio.

Related literature

For similar copper–sodium complexes, see: Hazra et al. (2009 ); Sasmal et al. (2010 ).

Experimental

Crystal data

[CuNa(BF₄)(C₁₈H₁₈N₂O₄)(CH₄O)]
M_r = 531.73
Monoclinic, P 2₁ /c
a = 12.885 (3) Å
b = 14.248 (5) Å
c = 13.508 (7) Å
β = 117.544 (17)°
V = 2198.7 (14) Å³
Z = 4
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 293 K
0.33 × 0.27 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.720, T_max = 0.778
20737 measured reflections
5016 independent reflections
3439 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.130
S = 1.05
5016 reflections
320 parameters
36 restraints
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.877 (2)
Cu1—O3	1.887 (2)
Cu1—N2	1.917 (3)
Cu1—N1	1.921 (3)
F1—Na1	2.533 (4)
F2—Na1	2.432 (3)
Na1—O1	2.319 (2)
Na1—O5	2.338 (3)
Na1—O3	2.349 (2)
Na1—O2	2.571 (3)
Na1—O4	2.662 (3)

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); 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: 10.1107/S160053681102842X/ng5196sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102842X/ng5196Isup2.hkl

checkCIF report

Comment top

In continuation of our study of salen-type Cu—Na heterodinuclear complexes (Hazra et al., 2009; Sasmal et al., 2010), we present here the crystal structure of the title compound. As shown in Fig. 1, the hexadentate Schiff base ligand links Cu and Na atoms into a dinuclear complex through two phenolate O atoms. The Na^I centre in (I) is seven-coordinated by four O atoms from the ligand, one O atom from the methanol and two F atoms from the tetrafluoroborate, which is similar with the bonding reported for another copper-sodium complex of the similar ligand (Sasmal et al., 2010). The Cu^II center is four-coordinate by two N atoms, two O atoms from the ligand giving rise to a square geometry.

Related literature top

For similar copper–sodium complexes, see: Hazra et al. (2009); Sasmal et al. (2010).

Experimental top

The title complex was obtained by the treatment of copper(II) acetate monohydrate (0.050 g, 0.25 mmol) with the Schiff base (0.082 g, 0.25 mmol) in water/methanol (5:15). The first two reactants were stirred for 2 h, and the mixture was stirred for another 3 h after the addition of sodium (I) tetrafluoroborate (0.052 g, 0.25 mmol). The reaction mixture was filtered; diethyl ether was allowed to diffuse slowly into the solution of the filtrate. Single crystals were obtained after several days. Analysis calculated for for C19H22BCuF4N2NaO5 C₁₉H₂₂B_1Cu1_F1_N2_NaO₅: C 42.92, H 4.17, N 5.27%; found: C 42.38, H 4.38, N 5.00%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the the title compound, showing 30% probability displacement ellipsoids.

{µ-6,6'-Dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilomethanylylidene)] diphenolato-1κ⁴O⁶,O¹,O^1',O^6'; 2κ⁴O¹,N,N',O^1'}(methanol- 1κO)(tetrafluoridoborato-1κ²F,F')- 2-copper(II)-1-sodium top

Crystal data top

[CuNa(BF₄)(C₁₈H₁₈N₂O₄)(CH₄O)]	F(000) = 1084
M_r = 531.73	D_x = 1.606 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12791 reflections
a = 12.885 (3) Å	θ = 3.0–27.5°
b = 14.248 (5) Å	µ = 1.08 mm⁻¹
c = 13.508 (7) Å	T = 293 K
β = 117.544 (17)°	Block, brown
V = 2198.7 (14) Å³	0.33 × 0.27 × 0.25 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	5016 independent reflections
Radiation source: fine-focus sealed tube	3439 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −16→16
T_min = 0.720, T_max = 0.778	k = −18→18
20737 measured reflections	l = −17→17

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0664P)² + 0.3095P] where P = (F_o² + 2F_c²)/3
5016 reflections	(Δ/σ)_max < 0.001
320 parameters	Δρ_max = 0.49 e Å⁻³
36 restraints	Δρ_min = −0.77 e Å⁻³

Crystal data top

[CuNa(BF₄)(C₁₈H₁₈N₂O₄)(CH₄O)]	V = 2198.7 (14) Å³
M_r = 531.73	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.885 (3) Å	µ = 1.08 mm⁻¹
b = 14.248 (5) Å	T = 293 K
c = 13.508 (7) Å	0.33 × 0.27 × 0.25 mm
β = 117.544 (17)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	5016 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3439 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.778	R_int = 0.057
20737 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	36 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.05	Δρ_max = 0.49 e Å⁻³
5016 reflections	Δρ_min = −0.77 e Å⁻³
320 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. ISOR 0.005 F2 F3 F4 F3' F4' ISOR 0.001 F1

SPLIT F3 F4 WITH THE OCCUPATION OF 0.60 FOR F3 AND F4, WHILE 0.40 FOR F3' AND F4'

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)
B1	0.4588 (4)	0.6368 (4)	0.7395 (4)	0.0644 (12)
C1	0.1383 (3)	0.8585 (2)	0.4357 (3)	0.0394 (7)
C2	0.2498 (3)	0.8999 (2)	0.4724 (3)	0.0428 (7)
C3	0.2622 (3)	0.9962 (2)	0.4754 (3)	0.0520 (9)
H3	0.3361	1.0228	0.5014	0.062*
C4	0.1641 (4)	1.0532 (2)	0.4394 (3)	0.0603 (10)
H4	0.1729	1.1180	0.4417	0.072*
C5	0.0555 (4)	1.0158 (2)	0.4011 (3)	0.0535 (9)
H5	−0.0093	1.0552	0.3758	0.064*
C6	0.0398 (3)	0.9171 (2)	0.3992 (3)	0.0429 (7)
C7	−0.0766 (3)	0.8817 (2)	0.3595 (3)	0.0478 (8)
H7	−0.1368	0.9255	0.3371	0.057*
C8	−0.2263 (3)	0.7663 (3)	0.3176 (4)	0.0614 (10)
H8A	−0.2794	0.8099	0.2621	0.074*
H8B	−0.2418	0.7675	0.3814	0.074*
C9	−0.2462 (3)	0.6683 (3)	0.2691 (4)	0.0608 (10)
H9A	−0.3074	0.6376	0.2800	0.073*
H9B	−0.2713	0.6717	0.1895	0.073*
C10	−0.1397 (3)	0.5225 (2)	0.3216 (3)	0.0466 (8)
H10	−0.2126	0.4936	0.2929	0.056*
C11	−0.0396 (3)	0.4631 (2)	0.3596 (3)	0.0415 (7)
C12	−0.0573 (3)	0.3646 (2)	0.3493 (3)	0.0534 (9)
H12	−0.1327	0.3409	0.3233	0.064*
C13	0.0325 (4)	0.3045 (2)	0.3764 (3)	0.0603 (10)
H13	0.0183	0.2403	0.3676	0.072*
C14	0.1472 (4)	0.3382 (2)	0.4178 (3)	0.0535 (9)
H14	0.2090	0.2966	0.4360	0.064*
C15	0.1678 (3)	0.4333 (2)	0.4312 (3)	0.0430 (7)
C16	0.0759 (3)	0.4983 (2)	0.4018 (3)	0.0395 (7)
C17	0.3769 (3)	0.4155 (3)	0.5113 (4)	0.0727 (12)
H17A	0.3755	0.3705	0.5636	0.109*
H17B	0.4464	0.4530	0.5469	0.109*
H17C	0.3763	0.3833	0.4486	0.109*
C18	0.4534 (3)	0.8701 (3)	0.5375 (4)	0.0744 (13)
H18A	0.4532	0.9091	0.4794	0.112*
H18B	0.5053	0.8180	0.5503	0.112*
H18C	0.4793	0.9061	0.6048	0.112*
C19	0.3012 (5)	0.6111 (4)	0.2577 (4)	0.111 (2)
H19A	0.2722	0.5537	0.2728	0.166*
H19B	0.3612	0.5971	0.2366	0.166*
H19C	0.2384	0.6438	0.1978	0.166*
Cu1	0.00033 (3)	0.68991 (2)	0.38549 (3)	0.03933 (15)
F1	0.3435 (3)	0.6599 (2)	0.6971 (3)	0.1045 (9)
F2	0.4815 (2)	0.6418 (2)	0.6487 (2)	0.0929 (8)
F3	0.4532 (9)	0.5441 (4)	0.7756 (5)	0.102 (3)	0.598 (18)
F4	0.5310 (7)	0.6847 (8)	0.8305 (7)	0.099 (2)	0.598 (18)
F3'	0.5214 (16)	0.5676 (9)	0.7911 (9)	0.124 (5)	0.402 (18)
F4'	0.5110 (9)	0.7239 (8)	0.8004 (10)	0.081 (3)	0.402 (18)
N1	−0.1050 (2)	0.79428 (19)	0.3521 (2)	0.0458 (7)
N2	−0.1379 (2)	0.61370 (19)	0.3237 (2)	0.0448 (6)
Na1	0.28783 (11)	0.66051 (9)	0.49108 (11)	0.0476 (3)
O1	0.13430 (18)	0.76601 (14)	0.4389 (2)	0.0481 (6)
O2	0.3381 (2)	0.83617 (16)	0.5045 (2)	0.0547 (7)
O3	0.10354 (18)	0.58764 (14)	0.4150 (2)	0.0457 (6)
O4	0.27683 (19)	0.47424 (15)	0.4739 (2)	0.0546 (6)
O5	0.3468 (3)	0.6662 (2)	0.3515 (2)	0.0732 (8)
H1	0.3777	0.7166	0.3444	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
B1	0.048 (2)	0.073 (3)	0.063 (3)	0.015 (2)	0.018 (2)	0.006 (3)
C1	0.0422 (16)	0.0348 (15)	0.0385 (17)	0.0012 (13)	0.0165 (14)	0.0022 (13)
C2	0.0480 (17)	0.0348 (15)	0.0422 (17)	−0.0006 (14)	0.0178 (14)	0.0026 (14)
C3	0.063 (2)	0.0373 (16)	0.059 (2)	−0.0128 (16)	0.0319 (18)	−0.0068 (16)
C4	0.090 (3)	0.0321 (16)	0.076 (3)	0.0003 (18)	0.053 (2)	−0.0002 (17)
C5	0.073 (2)	0.0345 (16)	0.065 (2)	0.0152 (17)	0.043 (2)	0.0065 (16)
C6	0.0543 (18)	0.0368 (15)	0.0432 (18)	0.0078 (14)	0.0272 (15)	0.0050 (14)
C7	0.0456 (17)	0.0494 (19)	0.051 (2)	0.0160 (15)	0.0244 (16)	0.0147 (16)
C8	0.0354 (17)	0.070 (2)	0.077 (3)	0.0132 (17)	0.0247 (18)	0.009 (2)
C9	0.0308 (16)	0.073 (2)	0.067 (2)	−0.0030 (16)	0.0126 (16)	0.001 (2)
C10	0.0397 (16)	0.055 (2)	0.0420 (18)	−0.0143 (15)	0.0164 (14)	−0.0059 (15)
C11	0.0465 (16)	0.0403 (16)	0.0398 (17)	−0.0078 (14)	0.0218 (14)	−0.0048 (14)
C12	0.065 (2)	0.0458 (19)	0.055 (2)	−0.0210 (17)	0.0327 (19)	−0.0045 (16)
C13	0.084 (3)	0.0321 (16)	0.070 (3)	−0.0097 (18)	0.040 (2)	−0.0048 (17)
C14	0.076 (3)	0.0350 (15)	0.059 (2)	0.0044 (16)	0.038 (2)	0.0039 (16)
C15	0.0510 (17)	0.0369 (15)	0.0497 (19)	−0.0013 (14)	0.0306 (16)	0.0006 (14)
C16	0.0462 (17)	0.0378 (15)	0.0371 (16)	−0.0022 (13)	0.0216 (14)	−0.0015 (14)
C17	0.054 (2)	0.062 (2)	0.108 (4)	0.0147 (19)	0.043 (2)	0.013 (2)
C18	0.044 (2)	0.067 (2)	0.101 (3)	−0.0151 (19)	0.024 (2)	−0.015 (2)
C19	0.142 (5)	0.108 (4)	0.074 (3)	−0.034 (4)	0.043 (3)	−0.018 (3)
Cu1	0.02938 (19)	0.0377 (2)	0.0470 (2)	0.00197 (15)	0.01437 (17)	0.00150 (17)
F1	0.0963 (12)	0.1098 (12)	0.1087 (13)	0.0003 (9)	0.0486 (9)	0.0025 (9)
F2	0.0854 (17)	0.125 (2)	0.0776 (16)	0.0071 (16)	0.0454 (14)	−0.0047 (16)
F3	0.116 (5)	0.078 (3)	0.098 (4)	0.007 (3)	0.039 (3)	0.036 (2)
F4	0.093 (4)	0.110 (5)	0.080 (3)	−0.022 (3)	0.028 (3)	−0.007 (3)
F3'	0.124 (6)	0.108 (6)	0.120 (5)	0.018 (4)	0.040 (4)	0.025 (4)
F4'	0.078 (4)	0.075 (5)	0.081 (5)	−0.004 (3)	0.028 (3)	−0.023 (4)
N1	0.0359 (13)	0.0518 (16)	0.0495 (16)	0.0087 (12)	0.0195 (12)	0.0092 (13)
N2	0.0328 (13)	0.0533 (16)	0.0444 (15)	−0.0012 (12)	0.0147 (12)	−0.0007 (13)
Na1	0.0361 (6)	0.0456 (7)	0.0581 (8)	0.0021 (5)	0.0192 (6)	0.0034 (6)
O1	0.0350 (11)	0.0301 (10)	0.0698 (15)	0.0034 (9)	0.0163 (11)	0.0073 (11)
O2	0.0383 (12)	0.0416 (12)	0.0728 (17)	−0.0061 (10)	0.0162 (12)	−0.0005 (12)
O3	0.0336 (10)	0.0344 (10)	0.0653 (15)	−0.0019 (9)	0.0195 (10)	−0.0025 (10)
O4	0.0418 (12)	0.0421 (12)	0.0812 (18)	0.0065 (10)	0.0294 (12)	0.0047 (12)
O5	0.094 (2)	0.0694 (16)	0.0692 (19)	−0.0225 (16)	0.0490 (17)	−0.0134 (15)

Geometric parameters (Å, º) top

B1—F3'	1.260 (10)	C12—H12	0.9300
B1—F4	1.336 (8)	C13—C14	1.402 (6)
B1—F1	1.363 (5)	C13—H13	0.9300
B1—F2	1.387 (6)	C14—C15	1.376 (4)
B1—F3	1.422 (8)	C14—H14	0.9300
B1—F4'	1.469 (10)	C15—O4	1.377 (4)
B1—Na1	3.064 (5)	C15—C16	1.409 (4)
C1—O1	1.320 (4)	C16—O3	1.311 (4)
C1—C6	1.404 (4)	C17—O4	1.419 (4)
C1—C2	1.414 (4)	C17—H17A	0.9600
C2—O2	1.360 (4)	C17—H17B	0.9600
C2—C3	1.380 (4)	C17—H17C	0.9600
C3—C4	1.388 (5)	C18—O2	1.424 (4)
C3—H3	0.9300	C18—H18A	0.9600
C4—C5	1.356 (5)	C18—H18B	0.9600
C4—H4	0.9300	C18—H18C	0.9600
C5—C6	1.420 (4)	C19—O5	1.371 (6)
C5—H5	0.9300	C19—H19A	0.9600
C6—C7	1.430 (5)	C19—H19B	0.9600
C7—N1	1.289 (4)	C19—H19C	0.9600
C7—H7	0.9300	Cu1—O1	1.877 (2)
C8—N1	1.465 (4)	Cu1—O3	1.887 (2)
C8—C9	1.513 (5)	Cu1—N2	1.917 (3)
C8—H8A	0.9700	Cu1—N1	1.921 (3)
C8—H8B	0.9700	Cu1—Na1	3.3236 (15)
C9—N2	1.464 (4)	F1—Na1	2.533 (4)
C9—H9A	0.9700	F2—Na1	2.432 (3)
C9—H9B	0.9700	Na1—O1	2.319 (2)
C10—N2	1.299 (4)	Na1—O5	2.338 (3)
C10—C11	1.426 (5)	Na1—O3	2.349 (2)
C10—H10	0.9300	Na1—O2	2.571 (3)
C11—C16	1.417 (4)	Na1—O4	2.662 (3)
C11—C12	1.418 (4)	O5—H1	0.8472
C12—C13	1.347 (5)

F3'—B1—F4	84.0 (6)	O2—C18—H18A	109.5
F3'—B1—F1	135.7 (11)	O2—C18—H18B	109.5
F4—B1—F1	115.0 (6)	H18A—C18—H18B	109.5
F3'—B1—F2	100.8 (8)	O2—C18—H18C	109.5
F4—B1—F2	116.5 (6)	H18A—C18—H18C	109.5
F1—B1—F2	104.5 (4)	H18B—C18—H18C	109.5
F3'—B1—F3	37.3 (7)	O5—C19—H19A	109.5
F4—B1—F3	106.4 (6)	O5—C19—H19B	109.5
F1—B1—F3	98.6 (6)	H19A—C19—H19B	109.5
F2—B1—F3	114.6 (5)	O5—C19—H19C	109.5
F3'—B1—F4'	109.9 (7)	H19A—C19—H19C	109.5
F4—B1—F4'	27.1 (4)	H19B—C19—H19C	109.5
F1—B1—F4'	99.1 (5)	O1—Cu1—O3	86.09 (9)
F2—B1—F4'	102.9 (7)	O1—Cu1—N2	177.21 (11)
F3—B1—F4'	132.5 (7)	O3—Cu1—N2	94.40 (11)
F3'—B1—Na1	130.1 (7)	O1—Cu1—N1	93.86 (11)
F4—B1—Na1	142.5 (6)	O3—Cu1—N1	178.71 (12)
F1—B1—Na1	54.7 (2)	N2—Cu1—N1	85.59 (12)
F2—B1—Na1	50.6 (2)	O1—Cu1—Na1	42.57 (7)
F3—B1—Na1	110.7 (4)	O3—Cu1—Na1	43.55 (6)
F4'—B1—Na1	115.5 (6)	N2—Cu1—Na1	137.94 (9)
O1—C1—C6	124.2 (3)	N1—Cu1—Na1	136.43 (9)
O1—C1—C2	117.0 (3)	B1—F1—Na1	99.3 (3)
C6—C1—C2	118.8 (3)	B1—F2—Na1	103.3 (2)
O2—C2—C3	125.8 (3)	C7—N1—C8	120.7 (3)
O2—C2—C1	113.5 (3)	C7—N1—Cu1	125.8 (2)
C3—C2—C1	120.7 (3)	C8—N1—Cu1	113.4 (2)
C2—C3—C4	119.8 (3)	C10—N2—C9	121.1 (3)
C2—C3—H3	120.1	C10—N2—Cu1	125.4 (2)
C4—C3—H3	120.1	C9—N2—Cu1	113.3 (2)
C5—C4—C3	121.1 (3)	O1—Na1—O5	106.39 (11)
C5—C4—H4	119.5	O1—Na1—O3	66.79 (8)
C3—C4—H4	119.5	O5—Na1—O3	107.61 (11)
C4—C5—C6	120.6 (3)	O1—Na1—F2	136.25 (11)
C4—C5—H5	119.7	O5—Na1—F2	97.21 (12)
C6—C5—H5	119.7	O3—Na1—F2	139.01 (11)
C1—C6—C5	119.0 (3)	O1—Na1—F1	96.01 (11)
C1—C6—C7	122.8 (3)	O5—Na1—F1	148.64 (12)
C5—C6—C7	118.1 (3)	O3—Na1—F1	101.22 (11)
N1—C7—C6	125.5 (3)	F2—Na1—F1	51.90 (11)
N1—C7—H7	117.3	O1—Na1—O2	62.75 (8)
C6—C7—H7	117.3	O5—Na1—O2	81.83 (10)
N1—C8—C9	109.3 (3)	O3—Na1—O2	129.21 (9)
N1—C8—H8A	109.8	F2—Na1—O2	85.51 (10)
C9—C8—H8A	109.8	F1—Na1—O2	89.52 (10)
N1—C8—H8B	109.8	O1—Na1—O4	128.03 (9)
C9—C8—H8B	109.8	O5—Na1—O4	89.32 (10)
H8A—C8—H8B	108.3	O3—Na1—O4	61.24 (7)
N2—C9—C8	110.0 (3)	F2—Na1—O4	87.64 (9)
N2—C9—H9A	109.7	F1—Na1—O4	93.96 (10)
C8—C9—H9A	109.7	O2—Na1—O4	168.04 (10)
N2—C9—H9B	109.7	O1—Na1—B1	118.99 (12)
C8—C9—H9B	109.7	O5—Na1—B1	123.34 (14)
H9A—C9—H9B	108.2	O3—Na1—B1	119.99 (13)
N2—C10—C11	125.6 (3)	F2—Na1—B1	26.14 (12)
N2—C10—H10	117.2	F1—Na1—B1	26.03 (12)
C11—C10—H10	117.2	O2—Na1—B1	90.00 (12)
C16—C11—C12	118.8 (3)	O4—Na1—B1	88.16 (12)
C16—C11—C10	122.8 (3)	O1—Na1—Cu1	33.19 (5)
C12—C11—C10	118.3 (3)	O5—Na1—Cu1	111.29 (10)
C13—C12—C11	121.5 (3)	O3—Na1—Cu1	33.61 (5)
C13—C12—H12	119.2	F2—Na1—Cu1	151.40 (9)
C11—C12—H12	119.2	F1—Na1—Cu1	99.51 (9)
C12—C13—C14	120.4 (3)	O2—Na1—Cu1	95.86 (6)
C12—C13—H13	119.8	O4—Na1—Cu1	94.84 (6)
C14—C13—H13	119.8	B1—Na1—Cu1	125.32 (11)
C15—C14—C13	119.6 (3)	C1—O1—Cu1	127.34 (19)
C15—C14—H14	120.2	C1—O1—Na1	128.05 (19)
C13—C14—H14	120.2	Cu1—O1—Na1	104.24 (10)
C14—C15—O4	124.7 (3)	C2—O2—C18	118.1 (3)
C14—C15—C16	121.6 (3)	C2—O2—Na1	118.72 (18)
O4—C15—C16	113.6 (3)	C18—O2—Na1	123.0 (2)
O3—C16—C15	117.4 (3)	C16—O3—Cu1	126.9 (2)
O3—C16—C11	124.6 (3)	C16—O3—Na1	130.14 (19)
C15—C16—C11	118.0 (3)	Cu1—O3—Na1	102.84 (9)
O4—C17—H17A	109.5	C15—O4—C17	118.8 (3)
O4—C17—H17B	109.5	C15—O4—Na1	117.52 (18)
H17A—C17—H17B	109.5	C17—O4—Na1	123.6 (2)
O4—C17—H17C	109.5	C19—O5—Na1	124.5 (3)
H17A—C17—H17C	109.5	C19—O5—H1	113.8
H17B—C17—H17C	109.5	Na1—O5—H1	117.7

Experimental details

Crystal data
Chemical formula	[CuNa(BF₄)(C₁₈H₁₈N₂O₄)(CH₄O)]
M_r	531.73
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.885 (3), 14.248 (5), 13.508 (7)
β (°)	117.544 (17)
V (Å³)	2198.7 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.33 × 0.27 × 0.25

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.720, 0.778
No. of measured, independent and observed [I > 2σ(I)] reflections	20737, 5016, 3439
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.130, 1.05
No. of reflections	5016
No. of parameters	320
No. of restraints	36
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.77

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

Selected bond lengths (Å) top

Cu1—O1	1.877 (2)	Na1—O1	2.319 (2)
Cu1—O3	1.887 (2)	Na1—O5	2.338 (3)
Cu1—N2	1.917 (3)	Na1—O3	2.349 (2)
Cu1—N1	1.921 (3)	Na1—O2	2.571 (3)
F1—Na1	2.533 (4)	Na1—O4	2.662 (3)
F2—Na1	2.432 (3)

Acknowledgements

The authors gratefully acknowledge financial support from Heilongjiang Province (11551334 and 12511386) and Heilongjiang University.

References

Hazra, S., Koner, R., Nayak, M., Sparkes, H. A., Howard, J. A. K. & Mohanta, S. (2009). Cryst. Growth Des. 9, 3603–3608. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
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Sasmal, S., Majumder, S., Hazra, S., Sparkes, H. A., Howard, J. A. K., Nayak, M. & Mohanta, S. (2010). CrystEngComm, 12, 4131–4140. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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