supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, m472    [ doi:10.1107/S1600536809011064 ]

Aqua(dicyanamido){[mu]-6,6'-dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}copper(II)sodium(I)

Y.-M. Shen and W. Wang

Abstract top

The molecule of the title compound, [CuNa(C18H18N2O4)(C2N3)(H2O)], is almost planar, the maximum deviation from the molecular plane being 0.48 (4) Å. The coordination environment of the Cu2+ ion is distorted square-planar and it is N2O2-chelated by the Schiff base ligand. The Na+ cation has a distorted octahedral environment defined by the four O atoms of the 6,6'-dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolate ligand, a water ligand and a dicyanamide anion.

Comment top

The dicyanamide ligand N(CN)2, has attracted attention in the past four years for the buildup of interesting extended architectures. Its versatile coordination behavior and its ability to organize solids into polymeric structures with a rich diversity of magnetic properties have attracted interest toward this research area (Ohba et al., 2000). N,N-disalicylideneethylenediamine type Schiff bases ligands present versatile steric, electronic and lipophilic properties (Correia et al. 2005). We report here the synthesis and crystal structure of the title compound.

The molecular structure is shown in Fig.1. The values of the geometric parameters in (I) are normal (Costes et al. 2004) (Table 1). The copper and sodium cations are connected via two bridging oxygen atoms of the ligand. The Na atom is coordinated by the four O atoms of the 6,6'-Dimethoxy-2,2'-(ethane-1,2-diyldiiminodimethylene)diphenol ligand, a water ligand and a dicyanamide anion while the four-coordinate Cu gives a planar coordination.

Related literature top

For chemical background, see: Ohba et al. (2000). For related structures, see: Correia et al. (2005); Costes et al.(2004).

Experimental top

A mixture of 6,6'-Dimethoxy-2,2'-(ethane-1,2-diyldiiminodimethylene)diphenol (1 mmol) and copper chloride (1 mmol) in methanol (15 ml) was stirred for 30 min and sodium dicyanamide (1 mmol) was added, stirred for another 15 min and then filtered. The resulting clear blue solution was vapor at room temperature for 7 days, after which large blue block-shaped crystals of the title complex suitable for X-ray diffraction analysis were obtained.

Refinement top

The H atoms were fixed geometrically and were treated as riding on their parent C atoms, with C–H distances in the range of 0.93–0.97Å and with Uiso(H) = 1.2Ueq(parent atom), or Uiso(H) = 1.5Ueq(Cmethyl).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The independent molecules of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Aqua(dicyanamido){µ-6,6'-dimethoxy-2,2'-[ethane-1,2- diylbis(nitrilomethylidyne)]diphenolato}copper(II)sodium(I) top
Crystal data top
[CuNa(C18H18N2O4)(C2N3)(H2O)]F(000) = 1020
Mr = 496.94Dx = 1.500 Mg m−3
Dm = 1.500 Mg m−3
Dm measured by not measured
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3562 reflections
a = 7.5974 (14) Åθ = 2.8–25.0°
b = 22.999 (4) ŵ = 1.05 mm−1
c = 12.876 (3) ÅT = 293 K
β = 101.986 (4)°Block, blue
V = 2200.7 (7) Å30.23 × 0.21 × 0.19 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4314 independent reflections
Radiation source: fine-focus sealed tube2996 reflections with I > 2σ(I)
graphiteRint = 0.034
φ and ω scansθmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −9→8
Tmin = 0.794, Tmax = 0.825k = −27→28
11729 measured reflectionsl = −15→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0747P)2 + 0.4736P]
where P = (Fo2 + 2Fc2)/3
4314 reflections(Δ/σ)max = 0.001
291 parametersΔρmax = 0.41 e Å−3
54 restraintsΔρmin = −0.49 e Å−3
Crystal data top
[CuNa(C18H18N2O4)(C2N3)(H2O)]V = 2200.7 (7) Å3
Mr = 496.94Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.5974 (14) ŵ = 1.05 mm−1
b = 22.999 (4) ÅT = 293 K
c = 12.876 (3) Å0.23 × 0.21 × 0.19 mm
β = 101.986 (4)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4314 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2996 reflections with I > 2σ(I)
Tmin = 0.794, Tmax = 0.825Rint = 0.034
11729 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.142Δρmax = 0.41 e Å−3
S = 1.03Δρmin = −0.49 e Å−3
4314 reflectionsAbsolute structure: ?
291 parametersFlack parameter: ?
54 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cu10.24890 (6)0.506744 (19)0.06032 (4)0.04808 (19)
Na10.36641 (19)0.38275 (6)0.20334 (11)0.0492 (4)
O10.2721 (4)0.48218 (10)0.1952 (2)0.0513 (6)
O20.3153 (4)0.42658 (12)0.3689 (2)0.0705 (8)
O30.3315 (3)0.43211 (10)0.03987 (18)0.0472 (6)
O40.4284 (4)0.32308 (11)0.0497 (2)0.0619 (7)
O50.1622 (4)0.30926 (12)0.2164 (2)0.0690 (8)
H5B0.12860.28760.16680.083*
H5A0.10300.30440.26140.083*
N10.1661 (4)0.58079 (13)0.0845 (3)0.0549 (8)
N20.2233 (4)0.52876 (15)−0.0761 (3)0.0556 (8)
N30.9191 (5)0.2881 (2)0.3649 (3)0.0874 (10)
N40.6425 (6)0.3426 (2)0.2955 (3)0.0896 (11)
N51.0355 (6)0.26675 (19)0.5447 (3)0.0868 (12)
C10.1804 (5)0.57156 (17)0.2676 (4)0.0603 (11)
C20.2396 (5)0.51238 (16)0.2741 (3)0.0492 (9)
C30.2601 (6)0.48344 (18)0.3710 (3)0.0592 (10)
C40.2247 (7)0.5129 (2)0.4559 (4)0.0818 (15)
H40.23710.49380.52070.098*
C50.1700 (8)0.5713 (3)0.4488 (5)0.0953 (17)
H50.14930.59030.50890.114*
C60.1479 (7)0.5995 (2)0.3589 (4)0.0807 (14)
H60.11050.63810.35530.097*
C70.1477 (6)0.60141 (17)0.1718 (4)0.0656 (12)
H70.10900.63980.17240.079*
C80.3386 (8)0.3935 (2)0.4617 (3)0.0885 (16)
H8A0.42100.41290.51750.133*
H8B0.38610.35600.44940.133*
H8C0.22480.38870.48200.133*
C90.3045 (5)0.4367 (2)−0.1448 (3)0.0630 (11)
C100.3413 (5)0.40704 (17)−0.0485 (3)0.0482 (9)
C110.3903 (5)0.34713 (18)−0.0474 (3)0.0575 (10)
C120.4003 (7)0.3185 (2)−0.1381 (4)0.0846 (15)
H120.43100.2794−0.13640.101*
C130.3647 (9)0.3482 (4)−0.2317 (5)0.112 (2)
H130.37150.3289−0.29430.134*
C140.3192 (8)0.4058 (3)−0.2353 (4)0.0973 (18)
H140.29740.4249−0.30040.117*
C150.2507 (5)0.4971 (2)−0.1515 (3)0.0637 (12)
H150.23470.5145−0.21810.076*
C160.4985 (7)0.26442 (18)0.0605 (4)0.0851 (15)
H16A0.40740.23790.02600.128*
H16B0.53310.25470.13450.128*
H16C0.60140.26180.02830.128*
C170.1101 (7)0.6168 (2)−0.0103 (4)0.0847 (15)
H17A−0.02010.6196−0.02810.102*
H17B0.15900.65570.00290.102*
C180.1742 (8)0.5909 (2)−0.0959 (4)0.0906 (16)
H18A0.27890.6122−0.10720.109*
H18B0.08190.5939−0.16020.109*
C190.7693 (7)0.3174 (2)0.3323 (3)0.0738 (10)
C200.9740 (6)0.2781 (2)0.4624 (4)0.0659 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0467 (3)0.0467 (3)0.0492 (3)−0.0028 (2)0.0064 (2)0.0091 (2)
Na10.0568 (9)0.0453 (8)0.0444 (8)0.0046 (7)0.0079 (6)0.0042 (6)
O10.0734 (18)0.0380 (13)0.0434 (14)0.0046 (12)0.0140 (12)0.0000 (11)
O20.115 (3)0.0577 (17)0.0409 (15)0.0092 (17)0.0201 (15)0.0046 (13)
O30.0575 (15)0.0475 (14)0.0362 (13)0.0008 (12)0.0090 (11)0.0018 (11)
O40.0793 (19)0.0461 (15)0.0653 (19)0.0003 (13)0.0264 (15)−0.0075 (13)
O50.088 (2)0.0678 (18)0.0566 (17)−0.0200 (16)0.0264 (15)−0.0101 (14)
N10.0471 (18)0.0396 (17)0.074 (2)−0.0016 (14)0.0039 (16)0.0128 (16)
N20.0464 (18)0.063 (2)0.053 (2)−0.0063 (15)0.0016 (15)0.0218 (17)
N30.076 (2)0.125 (2)0.0618 (19)0.0281 (19)0.0156 (17)0.0111 (19)
N40.077 (2)0.121 (3)0.065 (2)0.025 (2)0.0029 (17)0.0089 (19)
N50.097 (3)0.087 (3)0.071 (2)0.019 (2)0.003 (2)0.015 (2)
C10.056 (2)0.050 (2)0.072 (3)0.0021 (19)0.008 (2)−0.019 (2)
C20.051 (2)0.047 (2)0.050 (2)−0.0018 (17)0.0113 (17)−0.0081 (17)
C30.065 (3)0.065 (3)0.049 (2)−0.002 (2)0.0145 (19)−0.011 (2)
C40.095 (4)0.104 (4)0.047 (3)0.000 (3)0.015 (2)−0.017 (2)
C50.113 (4)0.098 (4)0.076 (4)0.009 (4)0.024 (3)−0.043 (3)
C60.083 (3)0.068 (3)0.089 (4)0.016 (3)0.015 (3)−0.031 (3)
C70.061 (3)0.037 (2)0.093 (4)0.0035 (19)0.003 (2)−0.006 (2)
C80.126 (4)0.097 (4)0.046 (3)0.000 (3)0.026 (3)0.019 (2)
C90.044 (2)0.102 (4)0.043 (2)−0.003 (2)0.0081 (17)−0.002 (2)
C100.040 (2)0.068 (2)0.037 (2)−0.0084 (18)0.0090 (15)−0.0053 (18)
C110.055 (2)0.066 (3)0.056 (3)−0.010 (2)0.0186 (19)−0.019 (2)
C120.089 (4)0.091 (4)0.075 (3)−0.002 (3)0.022 (3)−0.031 (3)
C130.119 (5)0.160 (6)0.059 (4)0.019 (5)0.024 (3)−0.037 (4)
C140.099 (4)0.158 (6)0.036 (3)0.007 (4)0.017 (2)−0.008 (3)
C150.048 (2)0.101 (4)0.040 (2)−0.006 (2)0.0053 (18)0.019 (2)
C160.110 (4)0.044 (2)0.109 (4)−0.001 (2)0.041 (3)−0.011 (2)
C170.079 (3)0.074 (3)0.099 (4)0.016 (3)0.014 (3)0.046 (3)
C180.109 (4)0.079 (3)0.079 (4)0.001 (3)0.009 (3)0.036 (3)
C190.069 (2)0.103 (3)0.0486 (19)0.016 (2)0.0115 (18)0.0103 (19)
C200.062 (2)0.082 (2)0.0536 (19)0.0124 (18)0.0107 (17)0.0120 (19)
Geometric parameters (Å, °) top
Cu1—O11.799 (2)C3—C41.360 (6)
Cu1—N21.800 (3)C4—C51.404 (7)
Cu1—N11.864 (3)C4—H40.9300
Cu1—O31.865 (2)C5—C61.306 (7)
Na1—O52.324 (3)C5—H50.9300
Na1—O32.357 (3)C6—H60.9300
Na1—N42.373 (4)C7—H70.9300
Na1—O12.392 (3)C8—H8A0.9600
Na1—O22.461 (3)C8—H8B0.9600
Na1—O42.531 (3)C8—H8C0.9600
O1—C21.297 (4)C9—C141.389 (7)
O2—C31.375 (5)C9—C101.392 (5)
O2—C81.397 (5)C9—C151.446 (6)
O3—C101.292 (4)C10—C111.427 (6)
O4—C111.343 (5)C11—C121.356 (6)
O4—C161.446 (5)C12—C131.363 (8)
O5—H5B0.8078C12—H120.9300
O5—H5A0.8118C13—C141.368 (9)
N1—C71.254 (6)C13—H130.9300
N1—C171.463 (5)C14—H140.9300
N2—C151.264 (5)C15—H150.9300
N2—C181.485 (6)C16—H16A0.9600
N3—C201.260 (5)C16—H16B0.9600
N3—C191.314 (6)C16—H16C0.9600
N4—C191.139 (5)C17—C181.426 (7)
N5—C201.097 (5)C17—H17A0.9700
C1—C71.389 (6)C17—H17B0.9700
C1—C61.406 (6)C18—H18A0.9700
C1—C21.430 (5)C18—H18B0.9700
C2—C31.393 (6)
O1—Cu1—N2177.98 (13)C6—C5—C4121.0 (5)
O1—Cu1—N195.42 (13)C6—C5—H5119.5
N2—Cu1—N186.24 (16)C4—C5—H5119.5
O1—Cu1—O383.04 (10)C5—C6—C1120.1 (5)
N2—Cu1—O395.30 (14)C5—C6—H6120.0
N1—Cu1—O3178.45 (13)C1—C6—H6120.0
O5—Na1—O3117.51 (11)N1—C7—C1125.2 (4)
O5—Na1—N4102.41 (15)N1—C7—H7117.4
O3—Na1—N4123.91 (13)C1—C7—H7117.4
O5—Na1—O1120.00 (11)O2—C8—H8A109.5
O3—Na1—O161.53 (9)O2—C8—H8B109.5
N4—Na1—O1128.31 (15)H8A—C8—H8B109.5
O5—Na1—O290.42 (11)O2—C8—H8C109.5
O3—Na1—O2124.57 (10)H8A—C8—H8C109.5
N4—Na1—O290.49 (13)H8B—C8—H8C109.5
O1—Na1—O263.05 (9)C14—C9—C10117.4 (5)
O5—Na1—O484.12 (10)C14—C9—C15120.8 (5)
O3—Na1—O464.40 (9)C10—C9—C15121.8 (4)
N4—Na1—O483.75 (13)O3—C10—C9121.9 (4)
O1—Na1—O4125.91 (10)O3—C10—C11119.0 (3)
O2—Na1—O4171.02 (11)C9—C10—C11119.1 (4)
C2—O1—Cu1126.3 (2)O4—C11—C12124.2 (4)
C2—O1—Na1125.6 (2)O4—C11—C10114.4 (3)
Cu1—O1—Na1108.12 (11)C12—C11—C10121.4 (4)
C3—O2—C8119.1 (3)C11—C12—C13118.9 (5)
C3—O2—Na1120.7 (2)C11—C12—H12120.6
C8—O2—Na1120.2 (3)C13—C12—H12120.6
C10—O3—Cu1128.2 (2)C12—C13—C14121.2 (5)
C10—O3—Na1123.7 (2)C12—C13—H13119.4
Cu1—O3—Na1107.21 (11)C14—C13—H13119.4
C11—O4—C16118.6 (3)C13—C14—C9122.1 (5)
C11—O4—Na1117.7 (2)C13—C14—H14119.0
C16—O4—Na1123.7 (3)C9—C14—H14119.0
Na1—O5—H5B119.8N2—C15—C9126.6 (4)
Na1—O5—H5A128.9N2—C15—H15116.7
H5B—O5—H5A110.5C9—C15—H15116.7
C7—N1—C17117.8 (4)O4—C16—H16A109.5
C7—N1—Cu1126.8 (3)O4—C16—H16B109.5
C17—N1—Cu1115.3 (3)H16A—C16—H16B109.5
C15—N2—C18119.8 (4)O4—C16—H16C109.5
C15—N2—Cu1125.9 (3)H16A—C16—H16C109.5
C18—N2—Cu1114.2 (3)H16B—C16—H16C109.5
C20—N3—C19119.8 (4)C18—C17—N1108.8 (4)
C19—N4—Na1171.6 (5)C18—C17—H17A109.9
C7—C1—C6119.1 (4)N1—C17—H17A109.9
C7—C1—C2121.2 (4)C18—C17—H17B109.9
C6—C1—C2119.6 (4)N1—C17—H17B109.9
O1—C2—C3116.2 (3)H17A—C17—H17B108.3
O1—C2—C1124.9 (4)C17—C18—N2112.5 (4)
C3—C2—C1118.8 (4)C17—C18—H18A109.1
C4—C3—O2126.9 (4)N2—C18—H18A109.1
C4—C3—C2118.5 (4)C17—C18—H18B109.1
O2—C3—C2114.5 (3)N2—C18—H18B109.1
C3—C4—C5121.9 (5)H18A—C18—H18B107.8
C3—C4—H4119.0N4—C19—N3174.1 (5)
C5—C4—H4119.0N5—C20—N3173.2 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5B···N5i0.812.022.826 (5)178
O5—H5A···N3ii0.812.152.961 (5)173
Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5B···N5i0.812.022.826 (5)178
O5—H5A···N3ii0.812.152.961 (5)173
Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x−1, y, z.
Acknowledgements top

This work was supported by the Zhejiang Provincial Natural Science Foundation (Y4080395).

references
References top

Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Correia, I., Duarte, M. T., Piedade, M. F. M., Jackush, T., Kiss, T., Castro, M. M., Geraldes, C. A., Carlos, F. G. C. & Avecilla, F. (2005). Eur. J. Inorg. Chem. pp. 732–744.

Costes, J.-P., Novitchi, G., Shova, S., Dahan, F., Donnadieu, B. & Tuchagues, J.-P. (2004). Inorg. Chem. 43, 7792–7799.

Ohba, M. & Okawa, H. (2000). Coord. Chem. Rev. 198, 313–328.

Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.