Space group revsion of the triclinic polymorph of salicyl­aldehyde azine

Saeed, A.; Bolte, M.; Arshad, M.

doi:10.1107/S160053681105478X

organic compounds

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Volume 68| Part 2| February 2012| Page o255

doi:10.1107/S160053681105478X

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Space group revsion of the triclinic polymorph of salicylaldehyde azine

Aamer Saeed,^a ^* Michael Bolte ^b and Muhammad Arshad ^c

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany, and ^cChemistry Division, Directorate of Science, PINSTECH, Nilore, Islamabad, Pakistan
^*Correspondence e-mail: aamersaeed@yahoo.com

(Received 25 November 2011; accepted 20 December 2011; online 7 January 2012)

The structure of the title compound, C₁₄H₁₂N₂O₂ {systematic name: 2,2′-[hydrazinediylidenebis(methanylylidene)]diphenol}, has already been determined in the triclinic space group P $[\overline{1}]$ with Z = 4 [El-Medani, Aboaly, Abdalla & Ramadan (2004 ). Spectrosc. Lett. 37, 619–632]. However, the correct space group should be P2₁/c with Z = 4. This structure is a new polymorph of the already known monoclinic polymorph of salicyladehyde azine, which crystallizes in space group P2₁/n with Z = 2. The benzene rings form a dihedral angle of 46.12 (9)°. Two intramolucular O—H⋯N hydrogen bonds occur.

Related literature

For the structure of salicylaldehyde azine in P $[\overline{1}]$ with Z=4, see El-Medani et al. (2004). For the other monoclinic polymorph of salicyladehyde azine, see for example Xue et al. (1994 ).

Experimental

Crystal data

C₁₄H₁₂N₂O₂
M_r = 240.26
Monoclinic, P 2₁ /c
a = 16.3621 (11) Å
b = 5.9180 (4) Å
c = 13.1706 (9) Å
β = 113.639 (5)°
V = 1168.31 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.28 × 0.19 × 0.12 mm

Data collection

Stoe IPDS II two-circle diffractometer
14742 measured reflections
2189 independent reflections
1977 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.116
S = 1.17
2189 reflections
172 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.95 (3)	1.81 (3)	2.6454 (19)	145 (2)
O1A—H1A⋯N1A	0.95 (3)	1.82 (3)	2.6532 (19)	145 (2)

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681105478X/zj2044sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681105478X/zj2044Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681105478X/zj2044Isup3.cml

checkCIF report

Comment top

The structure of the title compound, C₁₄H₁₂N₂O₂, has already been determined in the triclinic space group P1 with Z=4 [El-Medani, Aboaly, Abdalla & Ramadan (2004). Spectrosc. Lett. 37, 619–632]. However, the correct space group should be P2₁/c with Z=4. The authors have determined the unit-cell parameters correctly, however, they thought that the structure is triclinic with four molecules in the asymmetric unit, whereas the correct description should be in the monoclinic crystal systems with two half molecules in the asymmetric unit. This structure is a new polymorph of the already known monoclinic polymorph of salicyladehyde azine, which crystallizes in the space group P2₁/n with Z=2.

The title compound crystallizes with two half molecules in the asymmetric unit, both of which are located on a crystallographic centre of inversion. The molecules are essentially planar (r.m.s. deviation for all non H-atoms 0.021 and 0.018 Å, for the two molecules in the asymmetric unit). Bond lengths and angles are in the normal ranges.

In the already known monoclinic polymorph there is just one half molecule in the asymmetric unit which is located on a centre of inversion. The dihedral angle between symmetry equivalent molecules is 64.6°. The title compound, on the other hand, crystallizes with two half molecules in the asymmetric unit, which enclose a dihedral angle of 47.4°. The dihedral angle between symmetry equivalent molecules is 67.5°. Thus the difference between the two monoclinic polymorphs is the different mutual orientation of the molecules in the unit cell.

Related literature top

For the structure of salicylaldehyde azine in P1 with Z=4, see El-Medani et al. (2004). For the other monoclinic polymorph of salicyladehyde azine, see for example Xue et al. (1994).

Experimental top

Hydrazine hydrate, (1 mmol) dissolved in 5 ml ethanol was added dropwise to a solution of salicylaldehyde, (2.2 mmol) in 10 ml ethanol at room temperature with continuous stirring. The reaction mixture was reflux for 4 h and completion monitored by TLC. The reaction mixture was concentrated and resulted product was separated. Single crystal of the compound, suitable for X-ray crystallography, was grown by slow evaporation from an ethyl acetate-ethanol solution (2:1). as colourless crystals: Anal. calcd. for C₁₄H₁₂N₂O₂: C, 44.95; H, C, 69.99; H, 5.03; N, 11.66 98%; found: C, 69.99; H, 5.03; N, 11.66; %.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of title compound showing the two molecules in the asymmetric unit. Displacement ellipsoids are drawn at the 50% probability level. The atoms of the second molecule in the asymmetric unit are labelled with suffix A. Symmetry operators: (B): 2 - x,1 - y,-z, (C): 1 - x,1 - y,-z.
	Fig. 2. Packing diagram of the title compound with view along the b axis.

2-((1E)-{(E)-2-[(2-hydroxyphenyl)methylidene]hydrazin-1- ylidene}methyl)phenol top

Crystal data top

C₁₄H₁₂N₂O₂	F(000) = 504
M_r = 240.26	D_x = 1.366 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 14708 reflections
a = 16.3621 (11) Å	θ = 3.4–26.2°
b = 5.9180 (4) Å	µ = 0.09 mm⁻¹
c = 13.1706 (9) Å	T = 173 K
β = 113.639 (5)°	Plate, light brown
V = 1168.31 (14) Å³	0.28 × 0.19 × 0.12 mm
Z = 4

Data collection top

Stoe IPDS II two-circle diffractometer	1977 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.079
Graphite monochromator	θ_max = 25.7°, θ_min = 3.4°
ω scans	h = −19→19
14742 measured reflections	k = −7→7
2189 independent reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.116	w = 1/[σ²(F_o²) + (0.0386P)² + 0.5421P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max < 0.001
2189 reflections	Δρ_max = 0.18 e Å⁻³
172 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.029 (3)

Crystal data top

C₁₄H₁₂N₂O₂	V = 1168.31 (14) Å³
M_r = 240.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.3621 (11) Å	µ = 0.09 mm⁻¹
b = 5.9180 (4) Å	T = 173 K
c = 13.1706 (9) Å	0.28 × 0.19 × 0.12 mm
β = 113.639 (5)°

Data collection top

Stoe IPDS II two-circle diffractometer	1977 reflections with I > 2σ(I)
14742 measured reflections	R_int = 0.079
2189 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.18 e Å⁻³
2189 reflections	Δρ_min = −0.16 e Å⁻³
172 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
O1	0.87613 (9)	0.1392 (2)	0.06801 (11)	0.0380 (4)
H1	0.9110 (17)	0.204 (4)	0.0324 (19)	0.059 (7)*
N1	0.97379 (9)	0.4503 (2)	0.02477 (11)	0.0281 (3)
C1	0.90680 (10)	0.5083 (3)	0.15398 (13)	0.0253 (4)
C2	0.86776 (11)	0.2920 (3)	0.14005 (13)	0.0274 (4)
C3	0.81945 (12)	0.2302 (3)	0.20203 (14)	0.0317 (4)
H3	0.7920	0.0857	0.1917	0.038*
C4	0.81141 (12)	0.3789 (3)	0.27845 (14)	0.0341 (4)
H4	0.7785	0.3352	0.3205	0.041*
C5	0.85078 (12)	0.5913 (3)	0.29465 (15)	0.0358 (4)
H5	0.8457	0.6917	0.3481	0.043*
C6	0.89718 (11)	0.6543 (3)	0.23210 (14)	0.0312 (4)
H6	0.9233	0.8005	0.2422	0.037*
C7	0.95815 (11)	0.5834 (3)	0.09241 (13)	0.0264 (4)
H7	0.9807	0.7334	0.1021	0.032*
O1A	0.62345 (9)	0.8865 (2)	0.17775 (10)	0.0357 (3)
H1A	0.5876 (18)	0.814 (5)	0.111 (2)	0.066 (8)*
N1A	0.52522 (10)	0.5585 (2)	0.04906 (11)	0.0283 (3)
C1A	0.59119 (10)	0.5328 (3)	0.24640 (13)	0.0248 (4)
C2A	0.63079 (11)	0.7490 (3)	0.26375 (13)	0.0267 (4)
C3A	0.67951 (11)	0.8257 (3)	0.37086 (14)	0.0306 (4)
H3A	0.7069	0.9703	0.3822	0.037*
C4A	0.68836 (12)	0.6931 (3)	0.46105 (14)	0.0331 (4)
H4A	0.7218	0.7473	0.5339	0.040*
C5A	0.64861 (12)	0.4804 (3)	0.44581 (14)	0.0331 (4)
H5A	0.6539	0.3904	0.5079	0.040*
C6A	0.60154 (11)	0.4023 (3)	0.33969 (13)	0.0284 (4)
H6A	0.5754	0.2561	0.3294	0.034*
C7A	0.54094 (11)	0.4405 (3)	0.13719 (13)	0.0263 (4)
H7A	0.5191	0.2900	0.1303	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0503 (8)	0.0324 (7)	0.0411 (7)	−0.0115 (6)	0.0286 (6)	−0.0101 (6)
N1	0.0308 (7)	0.0300 (8)	0.0273 (7)	−0.0024 (6)	0.0155 (6)	0.0022 (6)
C1	0.0227 (8)	0.0290 (9)	0.0242 (8)	−0.0001 (6)	0.0094 (6)	0.0002 (6)
C2	0.0271 (8)	0.0298 (9)	0.0251 (8)	−0.0010 (7)	0.0103 (7)	−0.0018 (7)
C3	0.0291 (9)	0.0329 (9)	0.0348 (9)	−0.0043 (7)	0.0145 (7)	0.0030 (7)
C4	0.0287 (9)	0.0463 (11)	0.0327 (9)	0.0014 (8)	0.0180 (7)	0.0046 (8)
C5	0.0325 (9)	0.0450 (11)	0.0350 (9)	0.0001 (8)	0.0189 (8)	−0.0079 (8)
C6	0.0282 (9)	0.0319 (9)	0.0350 (9)	−0.0018 (7)	0.0141 (7)	−0.0053 (7)
C7	0.0258 (8)	0.0268 (8)	0.0263 (8)	−0.0003 (6)	0.0101 (6)	0.0019 (6)
O1A	0.0482 (8)	0.0300 (7)	0.0301 (7)	−0.0072 (6)	0.0170 (6)	0.0017 (5)
N1A	0.0332 (7)	0.0296 (8)	0.0234 (7)	−0.0005 (6)	0.0125 (6)	−0.0030 (6)
C1A	0.0224 (8)	0.0283 (8)	0.0260 (8)	0.0033 (6)	0.0121 (6)	0.0008 (6)
C2A	0.0277 (8)	0.0276 (8)	0.0282 (8)	0.0017 (7)	0.0146 (7)	0.0015 (7)
C3A	0.0286 (9)	0.0302 (9)	0.0339 (9)	−0.0025 (7)	0.0136 (7)	−0.0039 (7)
C4A	0.0289 (9)	0.0421 (10)	0.0268 (9)	−0.0001 (8)	0.0094 (7)	−0.0030 (7)
C5A	0.0325 (9)	0.0399 (10)	0.0264 (9)	0.0023 (8)	0.0114 (7)	0.0057 (7)
C6A	0.0270 (8)	0.0299 (9)	0.0293 (9)	0.0012 (7)	0.0124 (7)	0.0035 (7)
C7A	0.0273 (8)	0.0273 (8)	0.0274 (8)	0.0012 (7)	0.0142 (7)	−0.0007 (7)

Geometric parameters (Å, º) top

O1—C2	1.357 (2)	O1A—C2A	1.360 (2)
O1—H1	0.95 (3)	O1A—H1A	0.95 (3)
N1—C7	1.289 (2)	N1A—C7A	1.289 (2)
N1—N1ⁱ	1.398 (3)	N1A—N1Aⁱⁱ	1.405 (3)
C1—C6	1.400 (2)	C1A—C6A	1.403 (2)
C1—C2	1.409 (2)	C1A—C2A	1.411 (2)
C1—C7	1.452 (2)	C1A—C7A	1.447 (2)
C2—C3	1.394 (2)	C2A—C3A	1.389 (2)
C3—C4	1.382 (3)	C3A—C4A	1.382 (2)
C3—H3	0.9500	C3A—H3A	0.9500
C4—C5	1.390 (3)	C4A—C5A	1.394 (3)
C4—H4	0.9500	C4A—H4A	0.9500
C5—C6	1.377 (2)	C5A—C6A	1.377 (2)
C5—H5	0.9500	C5A—H5A	0.9500
C6—H6	0.9500	C6A—H6A	0.9500
C7—H7	0.9500	C7A—H7A	0.9500

C2—O1—H1	108.9 (15)	C2A—O1A—H1A	108.8 (16)
C7—N1—N1ⁱ	113.21 (17)	C7A—N1A—N1Aⁱⁱ	113.13 (17)
C6—C1—C2	118.53 (15)	C6A—C1A—C2A	118.12 (15)
C6—C1—C7	118.83 (15)	C6A—C1A—C7A	118.90 (15)
C2—C1—C7	122.62 (15)	C2A—C1A—C7A	122.99 (15)
O1—C2—C3	118.33 (16)	O1A—C2A—C3A	118.27 (15)
O1—C2—C1	121.93 (15)	O1A—C2A—C1A	121.73 (15)
C3—C2—C1	119.74 (15)	C3A—C2A—C1A	119.99 (15)
C4—C3—C2	120.09 (17)	C4A—C3A—C2A	120.49 (16)
C4—C3—H3	120.0	C4A—C3A—H3A	119.8
C2—C3—H3	120.0	C2A—C3A—H3A	119.8
C3—C4—C5	120.94 (16)	C3A—C4A—C5A	120.45 (16)
C3—C4—H4	119.5	C3A—C4A—H4A	119.8
C5—C4—H4	119.5	C5A—C4A—H4A	119.8
C6—C5—C4	119.08 (17)	C6A—C5A—C4A	119.22 (16)
C6—C5—H5	120.5	C6A—C5A—H5A	120.4
C4—C5—H5	120.5	C4A—C5A—H5A	120.4
C5—C6—C1	121.60 (17)	C5A—C6A—C1A	121.71 (16)
C5—C6—H6	119.2	C5A—C6A—H6A	119.1
C1—C6—H6	119.2	C1A—C6A—H6A	119.1
N1—C7—C1	121.24 (15)	N1A—C7A—C1A	121.26 (15)
N1—C7—H7	119.4	N1A—C7A—H7A	119.4
C1—C7—H7	119.4	C1A—C7A—H7A	119.4

C6—C1—C2—O1	−178.31 (15)	C6A—C1A—C2A—O1A	−179.65 (15)
C7—C1—C2—O1	0.3 (2)	C7A—C1A—C2A—O1A	0.5 (2)
C6—C1—C2—C3	1.2 (2)	C6A—C1A—C2A—C3A	1.0 (2)
C7—C1—C2—C3	179.82 (15)	C7A—C1A—C2A—C3A	−178.84 (15)
O1—C2—C3—C4	178.26 (15)	O1A—C2A—C3A—C4A	179.50 (16)
C1—C2—C3—C4	−1.3 (3)	C1A—C2A—C3A—C4A	−1.1 (3)
C2—C3—C4—C5	0.2 (3)	C2A—C3A—C4A—C5A	0.1 (3)
C3—C4—C5—C6	1.0 (3)	C3A—C4A—C5A—C6A	1.0 (3)
C4—C5—C6—C1	−1.0 (3)	C4A—C5A—C6A—C1A	−1.2 (3)
C2—C1—C6—C5	−0.1 (3)	C2A—C1A—C6A—C5A	0.2 (2)
C7—C1—C6—C5	−178.71 (16)	C7A—C1A—C6A—C5A	179.97 (15)
N1ⁱ—N1—C7—C1	−178.38 (16)	N1Aⁱⁱ—N1A—C7A—C1A	−179.39 (16)
C6—C1—C7—N1	175.52 (15)	C6A—C1A—C7A—N1A	176.00 (15)
C2—C1—C7—N1	−3.1 (2)	C2A—C1A—C7A—N1A	−4.2 (2)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.95 (3)	1.81 (3)	2.6454 (19)	145 (2)
O1A—H1A···N1A	0.95 (3)	1.82 (3)	2.6532 (19)	145 (2)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₂
M_r	240.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	16.3621 (11), 5.9180 (4), 13.1706 (9)
β (°)	113.639 (5)
V (Å³)	1168.31 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.28 × 0.19 × 0.12

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14742, 2189, 1977
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.116, 1.17
No. of reflections	2189
No. of parameters	172
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.16

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.95 (3)	1.81 (3)	2.6454 (19)	145 (2)
O1A—H1A···N1A	0.95 (3)	1.82 (3)	2.6532 (19)	145 (2)

References

El-Medani, S. M., Aboaly, M. M., Abdalla, H. H. & Ramadan, R. M. (2004). Spectrosc. Lett. 37, 619–632. CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
Xu, X.-X., You, X.-Z., Sun, Z.-F., Wang, X. & Liu, H.-X. (1994). Acta Cryst. C50, 1169–1171. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar

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