6,6′-Dimeth­oxy-2,2′-{[(E,E)-hydrazine-1,2-diyl­idene]bis­(methanylyl­idene)}diphenol methanol disolvate

Randell, N.M.; Thompson, L.K.; Dawe, L.N.

doi:10.1107/S1600536812034940

organic compounds

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6,6′-Dimethoxy-2,2′-{[(E,E)-hydrazine-1,2-diylidene]bis(methanylylidene)}diphenol methanol disolvate

Nicholas M. Randell,^a Laurence K. Thompson ^a and Louise N. Dawe ^b ^*

^aDepartment of Chemistry, Memorial University of Newfoundland, St Johns, NL, Canada A1B 3X7, and ^bDepartment of Chemistry and C-CART X-Ray Diffraction Laboratory, Memorial University of Newfoundland, St Johns, NL, Canada A1B 3X7
^*Correspondence e-mail: louise.dawe@mun.ca

(Received 25 July 2012; accepted 7 August 2012; online 15 August 2012)

The title compound, C₁₆H₁₆N₂O₄·2CH₃OH, is a hydrazone in an E geometric arrangement, with an inversion centre at the mid-point of the N—N bond. A symmetry-related pair of six-membered hydrogen-bonded rings [graph-set motif S¹₁(6)] are present for the terminal vanillin–imine moieties. Two lattice methanol solvent molecules are present per formula unit (Z′ = 1/2), which form hydrogen-bonded chains along [010] with two orientations due to disorder of the methanol H-atom.

Related literature

The synthesis of the title compound was originally reported by Lin et al. (2009 ); however, in this study, it was obtained from (2Z,6Z,N′2E,N′6E)-N′2,N′6-bis(2-hydroxy-3-methoxybenzylidene)pyridine-2,6-bis(carbohydrazonic) acid (Vadavi et al. 2011 ). The title compound has been used in the synthesis of first-row transition metal complexes (Zou et al. 2011 ) and in the synthesis of lanthanide complexes (Davidson et al. 2006 ). A solvent-free structure of the title compound has been previously reported (Lu et al. 2011 ) and contains a similar intramolecular hydrogen-bonding motif (Bernstein et al. 1995 , Etter et al. 1990 ) to that reported herein.

Experimental

Crystal data

C₁₆H₁₆N₂O₄·2CH₄O
M_r = 364.39
Monoclinic, P 2₁ /c
a = 20.517 (2) Å
b = 4.8374 (5) Å
c = 21.366 (3) Å
β = 153.566 (7)°
V = 944.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 163 K
0.59 × 0.14 × 0.13 mm

Data collection

Rigaku Saturn70 CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.725, T_max = 1.000
12068 measured reflections
1941 independent reflections
1651 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.194
S = 1.09
1941 reflections
129 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.88 (3)	1.77 (7)	2.613 (5)	160 (3)
O3—H3A⋯O3ⁱ	0.89 (8)	1.91 (7)	2.754 (4)	157 (9)
O3—H3B⋯O3ⁱⁱ	0.88 (7)	1.98 (7)	2.715 (4)	140 (5)
Symmetry codes: (i) -x, -y+1, -z; (ii) -x, -y, -z.

Data collection: CrystalClear-SM Expert (Rigaku, 2009 ); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812034940/hg5235sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812034940/hg5235Isup2.hkl

checkCIF report

Comment top

The synthesis of this compound was performed because of its intriguing interactions with both transition and lanthanide metals. The ability for the vanillin moieties to bridge multiple metal centers to form polymetallic clusters has potential applications in the fields of molecular magnetics and supramolecular chemistry.

While the previously reported solventless structure (Lu et al. 2011) and the title compound are comprised of two vanillin-imine moieties, in the title compound, these are related by an inversion centre about the N1ⁱ—N1 bond (i = 1 - x,2 - y,1 - z). There are two available geometries for the hydrazone functional group, the E and Z isomers. Both this report, and the previously reported structure, feature the E isomer (Figure 1).

There are multiple hydrogen bonding interactions, one intramolecular for the main molecule and one intermolecular hydrogen bonding chain, however, there are no discernable hydrogen bonding interaction between the main molecule and the solvent methanol molecules. The intramolecular hydrogen bond between N1 and H1 forms a stable six-membered hydrogen bound ring with graph set notation S¹₁(6) (one hydrogen bond donor, and one acceptor enclosed in a six-membered ring; Figure 1) (Bernstein et al. 1995, Etter et al. 1990). This interaction was also present in the previous report (Lu et al. 2011). This structural motif would likely provide an energetic barrier to rotation about the C2—C3 bond, which would be required to maximize the number of metals that could be incorporated into a cluster for further study.

A second hydrogen bond interaction is present as a one-dimensional chain of solvent methanol molecules, with graph set notation of C¹₁(2) (Figure 2.) The methanolic protons, H3A and H3B, are disordered, with occupancy of 1/2, and when extended packing diagrams are examined, it can be seen that the hydrogen bonded chains propagate along [0 1 0] (i.e. run parallel to the b axis), with the disorder representing a reversal in the D—H···A orientation.

Related literature top

The synthesis of the title compound was originally reported by Lin et al. (2009); however, in this report, the title compound was obtained from (2Z,6Z,N'2E,N'6E)-N'2,N'6-bis(2-hydroxy-3-methoxybenzylidene)pyridine-2,6-bis(carbohydrazonic) acid (Vadavi et al. 2011). The title compound has been used in the synthesis of first-row transition metal complexes (Zou et al. 2011) and in the synthesis of lanthanide complexes (Davidson et al. 2006). A solvent-free structure of the title compound has been previously reported (Lu et al. 2011) and contains a similar intramolecular hydrogen-bonding motif (Bernstein et al. 1995, Etter et al. 1990) to that reported herein.

Experimental top

DyCl₃.H₂O (0.06 g; 0.2 mmol) was dissolved in methanol (20 mL). (2Z,6Z,N'2E,N'6E)-N'2,N'6-bis(2-hydroxy-3-methoxybenzylidene)pyridine-2,6-bis(carbohydrazonic) acid (Vadavi et al. 2011) (0.05 g; 0.1 mmol) was added and the solution was refluxed for 3 h. Upon cooling, the resulting solution was gravity filtered and left for slow evaporation at room temperature to yield yellow-orange crystals of the title compound.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: CrystalClear-SM Expert (Rigaku, 2009); data reduction: CrystalClear-SM Expert (Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Molecular structure of the title compound at 50% probability ellipsoid level. Symmetry operator i = 1 - x, 2 - y, 1 - z; iv = 1 - x, 1 - y, 1 - z.

Packed unit cell of the title compound, highlighting the hydrogen bonding chains which propagate along [0 1 0]. One of the disordered H-atoms is omitted from each methanol molecule.

6,6'-Dimethoxy-2,2'-{[(E,E)-hydrazine-1,2- diylidene]bis(methanylylidene)}diphenol methanol disolvate top

Crystal data top

C₁₆H₁₆N₂O₄·2CH₄O	F(000) = 388
M_r = 364.39	D_x = 1.282 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 9154 reflections
a = 20.517 (2) Å	θ = 3.4–27.6°
b = 4.8374 (5) Å	µ = 0.10 mm⁻¹
c = 21.366 (3) Å	T = 163 K
β = 153.566 (7)°	Irregular, yellow
V = 944.0 (3) Å³	0.59 × 0.14 × 0.13 mm
Z = 2

Data collection top

Rigaku Saturn70 CCD diffractometer	1941 independent reflections
Radiation source: fine-focus sealed tube	1651 reflections with I > 2σ(I)
Graphite - Rigaku SHINE monochromator	R_int = 0.036
Detector resolution: 14.63 pixels mm^-1	θ_max = 26.5°, θ_min = 3.4°
ω scans	h = −25→25
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −5→6
T_min = 0.725, T_max = 1.000	l = −26→26
12068 measured reflections

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.118P)² + 0.3328P] where P = (F_o² + 2F_c²)/3
1941 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.32 e Å⁻³
4 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₆H₁₆N₂O₄·2CH₄O	V = 944.0 (3) Å³
M_r = 364.39	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 20.517 (2) Å	µ = 0.10 mm⁻¹
b = 4.8374 (5) Å	T = 163 K
c = 21.366 (3) Å	0.59 × 0.14 × 0.13 mm
β = 153.566 (7)°

Data collection top

Rigaku Saturn70 CCD diffractometer	1941 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	1651 reflections with I > 2σ(I)
T_min = 0.725, T_max = 1.000	R_int = 0.036
12068 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	4 restraints
wR(F²) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.32 e Å⁻³
1941 reflections	Δρ_min = −0.41 e Å⁻³
129 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)
O2	0.26395 (15)	0.6929 (3)	0.38898 (14)	0.0446 (4)
H2	0.318 (3)	0.797 (6)	0.411 (3)	0.067*
C3	0.51958 (19)	0.5637 (4)	0.61567 (19)	0.0321 (4)
C4	0.6264 (2)	0.3959 (4)	0.73588 (19)	0.0360 (5)
H4	0.7240	0.4131	0.8082	0.043*
C2	0.37270 (19)	0.5380 (4)	0.50753 (18)	0.0341 (5)
C1	0.3337 (2)	0.3422 (4)	0.52005 (19)	0.0357 (5)
C6	0.4408 (2)	0.1796 (4)	0.6393 (2)	0.0367 (5)
H6	0.4151	0.0514	0.6478	0.044*
C5	0.5869 (2)	0.2059 (4)	0.74696 (19)	0.0381 (5)
H5	0.6580	0.0949	0.8265	0.046*
O1	0.18781 (15)	0.3354 (3)	0.40867 (15)	0.0490 (5)
N1	0.46904 (17)	0.9117 (3)	0.49594 (16)	0.0353 (4)
C8	0.5634 (2)	0.7607 (4)	0.60529 (19)	0.0347 (4)
H8	0.6619	0.7772	0.6796	0.042*
C7	0.1407 (2)	0.1307 (5)	0.4117 (2)	0.0498 (6)
H7A	0.0360	0.1364	0.3253	0.075*
H7B	0.1839	0.1667	0.4890	0.075*
H7C	0.1704	−0.0487	0.4229	0.075*
O3	0.0380 (3)	0.2477 (5)	0.0577 (3)	0.0813 (7)
H3A	0.032 (10)	0.428 (5)	0.044 (9)	0.122*	0.50
H3B	−0.024 (7)	0.138 (13)	−0.015 (5)	0.122*	0.50
C9	0.0339 (3)	0.2220 (7)	0.1198 (3)	0.0704 (8)
H9A	−0.0661	0.2228	0.0478	0.106*
H9B	0.0853	0.3742	0.1827	0.106*
H9C	0.0796	0.0516	0.1713	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0338 (7)	0.0509 (9)	0.0391 (8)	0.0011 (6)	0.0315 (7)	0.0087 (6)
C3	0.0351 (9)	0.0337 (10)	0.0352 (9)	−0.0036 (7)	0.0323 (8)	−0.0044 (7)
C4	0.0330 (9)	0.0410 (10)	0.0353 (9)	−0.0003 (7)	0.0308 (9)	−0.0011 (8)
C2	0.0345 (9)	0.0356 (10)	0.0340 (9)	0.0001 (7)	0.0309 (9)	0.0006 (7)
C1	0.0339 (9)	0.0396 (10)	0.0364 (9)	−0.0047 (8)	0.0318 (9)	−0.0036 (8)
C6	0.0442 (10)	0.0364 (10)	0.0427 (10)	−0.0035 (8)	0.0404 (10)	−0.0019 (8)
C5	0.0406 (10)	0.0400 (10)	0.0367 (9)	0.0033 (8)	0.0349 (9)	0.0035 (8)
O1	0.0352 (7)	0.0593 (10)	0.0456 (8)	−0.0025 (6)	0.0354 (7)	0.0066 (7)
N1	0.0399 (8)	0.0368 (9)	0.0410 (9)	−0.0055 (7)	0.0376 (8)	−0.0037 (7)
C8	0.0370 (9)	0.0376 (10)	0.0389 (9)	−0.0043 (7)	0.0351 (9)	−0.0050 (8)
C7	0.0427 (11)	0.0598 (14)	0.0506 (12)	−0.0086 (10)	0.0422 (11)	−0.0013 (10)
O3	0.0841 (14)	0.0932 (16)	0.0861 (14)	−0.0099 (12)	0.0783 (14)	−0.0147 (13)
C9	0.0518 (13)	0.098 (2)	0.0550 (14)	0.0091 (14)	0.0472 (13)	0.0002 (14)

Geometric parameters (Å, º) top

O2—C2	1.354 (2)	O1—C7	1.425 (3)
O2—H2	0.88 (3)	N1—C8	1.281 (3)
C3—C2	1.402 (3)	N1—N1ⁱ	1.407 (3)
C3—C4	1.407 (3)	C8—H8	0.9300
C3—C8	1.456 (3)	C7—H7A	0.9600
C4—C5	1.378 (3)	C7—H7B	0.9600
C4—H4	0.9300	C7—H7C	0.9600
C2—C1	1.412 (3)	O3—C9	1.409 (4)
C1—O1	1.367 (2)	O3—H3A	0.89 (2)
C1—C6	1.383 (3)	O3—H3B	0.88 (2)
C6—C5	1.395 (3)	C9—H9A	0.9600
C6—H6	0.9300	C9—H9B	0.9600
C5—H5	0.9300	C9—H9C	0.9600

C2—O2—H2	98.1 (19)	C8—N1—N1ⁱ	113.50 (19)
C2—C3—C4	119.54 (17)	N1—C8—C3	121.36 (17)
C2—C3—C8	121.05 (17)	N1—C8—H8	119.3
C4—C3—C8	119.41 (16)	C3—C8—H8	119.3
C5—C4—C3	120.29 (17)	O1—C7—H7A	109.5
C5—C4—H4	119.9	O1—C7—H7B	109.5
C3—C4—H4	119.9	H7A—C7—H7B	109.5
O2—C2—C3	122.92 (17)	O1—C7—H7C	109.5
O2—C2—C1	117.48 (16)	H7A—C7—H7C	109.5
C3—C2—C1	119.59 (17)	H7B—C7—H7C	109.5
O1—C1—C6	125.69 (17)	C9—O3—H3A	106 (3)
O1—C1—C2	114.56 (16)	C9—O3—H3B	113 (4)
C6—C1—C2	119.74 (17)	H3A—O3—H3B	118 (7)
C1—C6—C5	120.61 (17)	O3—C9—H9A	109.5
C1—C6—H6	119.7	O3—C9—H9B	109.5
C5—C6—H6	119.7	H9A—C9—H9B	109.5
C4—C5—C6	120.23 (17)	O3—C9—H9C	109.5
C4—C5—H5	119.9	H9A—C9—H9C	109.5
C6—C5—H5	119.9	H9B—C9—H9C	109.5
C1—O1—C7	117.07 (16)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.88 (3)	1.77 (7)	2.613 (5)	160 (3)
O3—H3A···O3ⁱⁱ	0.89 (8)	1.91 (7)	2.754 (4)	157 (9)
O3—H3B···O3ⁱⁱⁱ	0.88 (7)	1.98 (7)	2.715 (4)	140 (5)

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₄·2CH₄O
M_r	364.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	163
a, b, c (Å)	20.517 (2), 4.8374 (5), 21.366 (3)
β (°)	153.566 (7)
V (Å³)	944.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.59 × 0.14 × 0.13

Data collection
Diffractometer	Rigaku Saturn70 CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.725, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12068, 1941, 1651
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.194, 1.09
No. of reflections	1941
No. of parameters	129
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.41

Computer programs: CrystalClear-SM Expert (Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.88 (3)	1.77 (7)	2.613 (5)	160 (3)
O3—H3A···O3ⁱ	0.89 (8)	1.91 (7)	2.754 (4)	157 (9)
O3—H3B···O3ⁱⁱ	0.88 (7)	1.98 (7)	2.715 (4)	140 (5)

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

Acknowledgements

We thank NSERC (Canada) for financial support for these studies.

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6,6′-Dimeth­­oxy-2,2′-{[(E,E)-hydrazine-1,2-diyl­­idene]bis­­(methanylyl­­idene)}diphenol methanol disolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

6,6′-Dimethoxy-2,2′-{[(E,E)-hydrazine-1,2-diylidene]bis(methanylylidene)}diphenol methanol disolvate