trans-Bis[(E)-4-(4-methoxy­styr­yl)­pyridine]­dinitratocopper(II)

The title compound, [Cu(NO₃)₂(C₁₄H₁₃NO)₂], has been synthesized by the reaction of (E)-4-(4-methoxy­styr­yl)­pyridine with Cu(NO₃)₂ at room temperature in CH₃OH. The mononuclear complex sits across a crystallographic centre of inversion. The Cu^II ion is six-coordinated in a distorted octa­hedral fashion by the trans-disposed pyridine N atoms of two pyridine ligands and asymmetrically by two O atoms from each of the two nitrate ligands, where one of the Cu-O distances is quite long at 2.452 (3) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.044
• wR factor = 0.118
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O2      ..       8.48 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O3      ..       8.53 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The heteroarylethene derivatives have attracted attention due to their optical properties and wide applications in nonlinear optical material (Saltiel et al., 1995, 1996, 2005, Lubczyk et al., 2002, Vansant et al., 1980, Taylor & Martin 1974). A series of heteroarylethene molecules coordinated through donor nitrogen atoms has been reported (Shi et al., 2004a,b, 2005, 2006). The investigation of the optical properties of heteroarylethene complexes in terms of structural correlation is still a challenging field. Herein we report the synthesis and crystal structure of a copper(II) complex with (E)-4-(4-methoxystyryl)pyridine (Mepy).

The neutral complex [Cu(Mepy)₂(NO₃)₂], (I), crystallizes with the unique molecule lying across a crystallographic centre of inversion. Each Cu^II ion is 6-coordinated in a distorted octahedral fashion by the trans-disposed pyridine N-atoms of two pyridine ligands and by two O-atoms from each of the two nitrato ligands, as shown in Fig. 1. Selected geometric parameters are given in Table 1. One of the N—O distances from each nitrato ligand is quite long at 2.452 (3) Å. In the Mepy ligands, the dihedral angle between the planes of the pyridinyl and phenyl rings is 14.5 (2)°.

Related literature

For nonlinear optical materials, see: Saltiel et al. (1995, 1996, 2005); Lubczyk et al. (2002); Taylor & Martin (1974); Vansant et al. (1980). For heteroarylethene molecules, see: Shi et al. (2004a,b, 2005, 2006). For the synthesis of the title compound, see: Zhang et al., 2000.

S2. Experimental

The (E)-4-(4-methoxystyryl)pyridine ligand (Mepy) was synthesized according to the literature methods (Zhang et al., 2000, Shi et al., 2004b). A solution of 4-Methoxybenzaldehyde (1.91 g, 14 mmol) in 2 ml DMF was added dropwise to a mixture of 4-methylpyridine (0.94 g, 10 mmol) and KOH (1.12 g, 20 mmol) in 15 ml DMF at 338 K over 2 h under nitrogen atmosphere. The mixture was then refluxed for another 2 h, cooled down and poured into 100 ml cold water. The resulting precipitate was filtered off and recrystallized from methanol/water (Vm:Vw=1:1) to give yellow crystals (yield 67%, m.p. 407 K).

The title compound was synthesized by the following method. Mepy ligand (0.42 g, 2.0 mmol) in CH₃OH (30 ml) was added dropwise to a solution of Cu(NO₃)₂.4H₂O (0.53 g, 1 mmol) in CH₃OH (30 ml) with stirring for 1 h at room temperature. Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation after 2 days. Yield 55%. Decomp. point: 525 K.

S3. Refinement

All H atoms were initially located in a difference Fourier map. The C—H atoms were then constrained to an ideal geometry, with C(methyl)—H distances of 0.96 Å and U_iso(H) = 1.5U_eq(C), and C(phenyl)—H distances of 0.93 Å and U_iso(H) = 1.2U_eq(C).

Computing details

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

Figures

Fig. 1. The molecular structure of complex (I) with displacement ellipsoids at the 30% probability level. H atoms are shown as small spheres of arbitrary radii. Symmetry code: (A) 1 - x, 2 - y, 1 - z.

trans-Bis[(E)-4-(4-methoxystyryl)pyridine]dinitratocopper(II)

Crystal data

[Cu(NO3)2(C14H13NO)2]	F(000) = 630
Mr = 610.07	Dx = 1.446 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.0605 (19) Å	Cell parameters from 1408 reflections
b = 12.714 (3) Å	θ = 2.3–21.3°
c = 12.450 (3) Å	µ = 0.84 mm^−1
β = 102.312 (4)°	T = 293 K
V = 1401.3 (5) Å^3	Black, green
Z = 2	0.22 × 0.14 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2469 independent reflections
Radiation source: fine-focus sealed tube	1401 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
phi and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
Tmin = 0.838, Tmax = 0.921	k = −15→10
6918 measured reflections	l = −14→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0469P)^2 + 0.266P] where P = (Fo^2 + 2Fc^2)/3
2469 reflections	(Δ/σ)max < 0.001
188 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.5000	1.0000	0.5000	0.0403 (2)
O1	1.3800 (4)	0.7888 (2)	−0.1442 (3)	0.0647 (9)
O2	0.3170 (3)	1.0079 (2)	0.3732 (2)	0.0483 (7)
O3	0.3939 (3)	1.1665 (2)	0.4188 (3)	0.0592 (9)
O4	0.1994 (4)	1.1421 (2)	0.2859 (3)	0.0694 (10)
N1	0.6334 (4)	0.9889 (3)	0.3935 (3)	0.0413 (8)
N2	0.3010 (4)	1.1078 (3)	0.3579 (3)	0.0462 (9)
C1	0.7574 (5)	1.0471 (4)	0.4018 (4)	0.0586 (14)
H1	0.7763	1.0992	0.4554	0.070*
C2	0.8589 (5)	1.0340 (3)	0.3350 (4)	0.0585 (14)
H2	0.9436	1.0771	0.3440	0.070*
C3	0.8358 (5)	0.9567 (3)	0.2539 (3)	0.0402 (10)
C4	0.7036 (5)	0.8984 (3)	0.2442 (3)	0.0453 (11)
H4A	0.6805	0.8468	0.1903	0.054*
C5	0.6073 (5)	0.9163 (3)	0.3131 (4)	0.0455 (11)
H5	0.5195	0.8764	0.3039	0.055*
C6	0.9475 (5)	0.9402 (3)	0.1863 (4)	0.0471 (11)
H6	1.0307	0.9848	0.1998	0.057*
C7	0.9436 (5)	0.8689 (3)	0.1078 (4)	0.0449 (11)
H7	0.8576	0.8271	0.0908	0.054*
C8	1.0605 (5)	0.8493 (3)	0.0455 (3)	0.0427 (11)
C9	1.2057 (5)	0.8901 (4)	0.0755 (4)	0.0566 (13)
H9	1.2305	0.9308	0.1389	0.068*
C10	1.3148 (5)	0.8729 (4)	0.0149 (4)	0.0575 (13)
H10	1.4105	0.9021	0.0372	0.069*
C11	1.2804 (5)	0.8117 (3)	−0.0788 (4)	0.0457 (11)
C12	1.1379 (5)	0.7688 (3)	−0.1100 (4)	0.0576 (13)
H12	1.1141	0.7274	−0.1728	0.069*
C13	1.0300 (5)	0.7871 (3)	−0.0481 (4)	0.0509 (12)
H13	0.9348	0.7570	−0.0700	0.061*
C14	1.5184 (6)	0.8457 (4)	−0.1266 (5)	0.0746 (16)
H14A	1.4975	0.9198	−0.1313	0.112*
H14B	1.5733	0.8264	−0.1816	0.112*
H14C	1.5777	0.8294	−0.0550	0.112*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0381 (4)	0.0492 (4)	0.0373 (4)	0.0021 (4)	0.0162 (3)	0.0008 (4)
O1	0.065 (2)	0.076 (2)	0.064 (2)	0.0086 (18)	0.0382 (19)	−0.0114 (17)
O2	0.0531 (18)	0.0437 (17)	0.0520 (18)	0.0019 (17)	0.0197 (14)	−0.0018 (16)
O3	0.059 (2)	0.058 (2)	0.057 (2)	−0.0076 (17)	0.0034 (18)	−0.0056 (16)
O4	0.052 (2)	0.073 (2)	0.073 (3)	0.0021 (17)	−0.0084 (19)	0.0208 (19)
N1	0.0384 (19)	0.048 (2)	0.041 (2)	0.0017 (18)	0.0155 (15)	−0.0013 (19)
N2	0.038 (2)	0.059 (3)	0.044 (2)	0.002 (2)	0.0137 (19)	0.002 (2)
C1	0.060 (3)	0.065 (3)	0.059 (3)	−0.019 (2)	0.030 (3)	−0.024 (2)
C2	0.051 (3)	0.063 (3)	0.068 (4)	−0.023 (2)	0.027 (3)	−0.018 (2)
C3	0.041 (3)	0.044 (2)	0.039 (3)	0.0035 (19)	0.016 (2)	0.0062 (19)
C4	0.050 (3)	0.042 (3)	0.048 (3)	−0.002 (2)	0.020 (2)	−0.006 (2)
C5	0.039 (3)	0.049 (3)	0.052 (3)	−0.006 (2)	0.020 (2)	0.000 (2)
C6	0.046 (3)	0.053 (3)	0.049 (3)	−0.003 (2)	0.025 (2)	−0.001 (2)
C7	0.041 (3)	0.054 (3)	0.042 (3)	−0.001 (2)	0.015 (2)	0.003 (2)
C8	0.041 (3)	0.050 (3)	0.038 (3)	0.009 (2)	0.012 (2)	0.001 (2)
C9	0.050 (3)	0.081 (3)	0.041 (3)	0.001 (3)	0.013 (2)	−0.029 (2)
C10	0.040 (3)	0.078 (3)	0.057 (3)	−0.004 (2)	0.015 (2)	−0.016 (3)
C11	0.049 (3)	0.050 (3)	0.043 (3)	0.014 (2)	0.021 (2)	0.000 (2)
C12	0.064 (3)	0.066 (3)	0.045 (3)	0.003 (3)	0.016 (3)	−0.018 (2)
C13	0.048 (3)	0.062 (3)	0.045 (3)	−0.004 (2)	0.012 (2)	−0.006 (2)
C14	0.085 (4)	0.068 (3)	0.087 (4)	0.011 (3)	0.056 (3)	0.012 (3)

Geometric parameters (Å, º)

Cu1—N1	1.980 (3)	C5—H5	0.9300
Cu1—O2	2.034 (3)	C6—C7	1.328 (5)
Cu1—O3	2.452 (3)	C6—H6	0.9300
O1—C11	1.369 (5)	C7—C8	1.462 (5)
O1—C14	1.424 (5)	C7—H7	0.9300
O2—N2	1.288 (4)	C8—C13	1.386 (6)
O3—N2	1.252 (4)	C8—C9	1.389 (6)
O4—N2	1.221 (4)	C9—C10	1.382 (6)
N1—C1	1.330 (5)	C9—H9	0.9300
N1—C5	1.345 (5)	C10—C11	1.381 (6)
C1—C2	1.376 (6)	C10—H10	0.9300
C1—H1	0.9300	C11—C12	1.379 (6)
C2—C3	1.392 (6)	C12—C13	1.387 (6)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.392 (5)	C13—H13	0.9300
C3—C6	1.463 (5)	C14—H14A	0.9600
C4—C5	1.367 (5)	C14—H14B	0.9600
C4—H4A	0.9300	C14—H14C	0.9600
N1^i—Cu1—N1	180	C7—C6—H6	116.3
N1—Cu1—O2	89.81 (12)	C3—C6—H6	116.3
N1—Cu1—O3	91.55 (11)	C6—C7—C8	126.8 (4)
O2^i—Cu1—O2	180	C6—C7—H7	116.6
O2—Cu1—O3	56.93 (11)	C8—C7—H7	116.6
C11—O1—C14	118.1 (4)	C13—C8—C9	116.5 (4)
N2—O2—Cu1	102.1 (2)	C13—C8—C7	120.4 (4)
C1—N1—C5	116.7 (3)	C9—C8—C7	123.0 (4)
C1—N1—Cu1	122.3 (3)	C10—C9—C8	122.7 (4)
C5—N1—Cu1	120.8 (3)	C10—C9—H9	118.7
O4—N2—O3	122.4 (4)	C8—C9—H9	118.7
O4—N2—O2	120.3 (4)	C11—C10—C9	119.5 (4)
O3—N2—O2	117.3 (4)	C11—C10—H10	120.3
N1—C1—C2	123.3 (4)	C9—C10—H10	120.3
N1—C1—H1	118.3	O1—C11—C12	116.4 (4)
C2—C1—H1	118.3	O1—C11—C10	124.3 (4)
C1—C2—C3	120.4 (4)	C12—C11—C10	119.3 (4)
C1—C2—H2	119.8	C11—C12—C13	120.4 (4)
C3—C2—H2	119.8	C11—C12—H12	119.8
C4—C3—C2	115.7 (4)	C13—C12—H12	119.8
C4—C3—C6	124.2 (4)	C8—C13—C12	121.6 (4)
C2—C3—C6	120.2 (4)	C8—C13—H13	119.2
C5—C4—C3	120.6 (4)	C12—C13—H13	119.2
C5—C4—H4A	119.7	O1—C14—H14A	109.5
C3—C4—H4A	119.7	O1—C14—H14B	109.5
N1—C5—C4	123.2 (4)	H14A—C14—H14B	109.5
N1—C5—H5	118.4	O1—C14—H14C	109.5
C4—C5—H5	118.4	H14A—C14—H14C	109.5
C7—C6—C3	127.5 (4)	H14B—C14—H14C	109.5
N1—Cu1—O2—N2	−92.2 (2)	C4—C3—C6—C7	−0.8 (7)
O2^i—Cu1—N1—C1	−47.6 (4)	C2—C3—C6—C7	178.5 (4)
O2—Cu1—N1—C1	132.4 (4)	C3—C6—C7—C8	−176.1 (4)
O2^i—Cu1—N1—C5	127.9 (3)	C6—C7—C8—C13	−167.3 (4)
O2—Cu1—N1—C5	−52.1 (3)	C6—C7—C8—C9	13.0 (7)
Cu1—O2—N2—O4	179.9 (3)	C13—C8—C9—C10	1.5 (7)
Cu1—O2—N2—O3	0.4 (4)	C7—C8—C9—C10	−178.8 (4)
C5—N1—C1—C2	−1.8 (7)	C8—C9—C10—C11	−0.7 (7)
Cu1—N1—C1—C2	173.8 (4)	C14—O1—C11—C12	169.2 (4)
N1—C1—C2—C3	−0.3 (8)	C14—O1—C11—C10	−11.6 (6)
C1—C2—C3—C4	2.0 (7)	C9—C10—C11—O1	−179.4 (4)
C1—C2—C3—C6	−177.4 (4)	C9—C10—C11—C12	−0.2 (7)
C2—C3—C4—C5	−1.6 (6)	O1—C11—C12—C13	179.5 (4)
C6—C3—C4—C5	177.7 (4)	C10—C11—C12—C13	0.3 (7)
C1—N1—C5—C4	2.3 (6)	C9—C8—C13—C12	−1.5 (7)
Cu1—N1—C5—C4	−173.5 (3)	C7—C8—C13—C12	178.8 (4)
C3—C4—C5—N1	−0.5 (7)	C11—C12—C13—C8	0.6 (7)

Symmetry code: (i) −x+1, −y+2, −z+1.