6,6'-Dimeth-oxy-2,2'-{[(E,E)-hydrazine-1,2-diyl-idene]bis-(methanylyl-idene)}diphenol methanol disolvate.

The title compound, C(16)H(16)N(2)O(4)·2CH(3)OH, 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 S(1) (1)(6)] are present for the terminal vanillin-imine moieties. Two lattice methanol solvent mol-ecules 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 = 364.39

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.194

S = 1.09

1941 reflections

129 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.41 e Å−3

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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812034940/hg5235sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H16N2O4·2CH4O	F(000) = 388
Mr = 364.39	Dx = 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

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

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(Fo2) + (0.118P)2 + 0.3328P] where P = (Fo2 + 2Fc2)/3
1941 reflections	(Δ/σ)max < 0.001
129 parameters	Δρmax = 0.32 e Å−3
4 restraints	Δρmin = −0.41 e Å−3

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.

	x	y	z	Uiso*/Ueq	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*

	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)

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)

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)

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) ; (ii) .