2',2'-(Ethane-1,2-diyl­idene)bis­(2-hydroxy­benzhydrazide) dimethyl sulfoxide disolvate

The title mol­ecule, C₁₆H₁₄N₄O₄, lies on a crystallographic inversion center and all bond lengths and angles show normal values. The crystal structure is stabilized by inter­molecular hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.044
• wR factor = 0.124
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000)         100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         S1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.13

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

Bishydrazone ligands and complexs with glyoxal have been intensively studied, due to their interesting biological and material properties (Alessandro et al., 1996; Gabriela & Uwe, 1997; Sulekh et al., 2004). We report herein the synthesis and crystal structure of the title compound (I). The molecular structure of (I) (Fig. 1) has crystallographic inversion symmetry. In the crystal structure, intermolecular N–H–O hydrogen bonds link hydrazone molecules with two dimethyl sulfoxide solvent molecules, forming three component clusters. These clusters are further connected by weak intermolecular C–H–S and C–H–O hydrogen bonds (Fig. 2; Table 1).

Related literature

For related literature, see: Alessandro et al. (1996); Gabriela & Uwe (1997); Sulekh et al. (2004).

S2. Experimental

To a solution of salicylhydrazide (3.04 g, 20 mmol)in absolute ethanol (40 ml) a solution of glyoxal (40%)(1.55 g, 10 mmol) was added at 323 K. The mixture was left to react at reflux for 6 h, then the yellow product in the form of needle was filtered, washed with hot ethanol (20 ml portion) three times and dried in vacuo. Crystals suitable for X-ray diffraction were obtained from a dimethyl sulfoxide solution of (I) over a period of approximately three weeks.

S3. Refinement

After their location in the difference map, H-atoms bonded to C and O were fixed geometrically at ideal positions and allowed to ride on the parent atoms with C—H = 0.93 - 0.96Å and O—H = 0.82 Å. The positional parameters of the H atom bonded to N1 were allowed to refine. All H atoms were included in the refinement with U_iso(H) = 1.2U_eq(C, N)or U_iso(H)= 1.5U_eq(C_methyl and O).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Molecular structure of (I) showing 30% probability displacement ellipsoids. Unlabeled atoms are related by the symmetry operator (-x, -y, 2 - z)
	Fig. 2. Partial packing plot of (I) with dashed lines indicating hydrogen bonds.

2',2'-(Ethane-1,2-diylidene)bis(2-hydroxybenzohydrazide) dimethyl sulfoxide disolvate

Crystal data

C16H14N4O4·2C2H6OS	Z = 1
Mr = 482.57	F(000) = 254
Triclinic, P1	Dx = 1.345 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9739 (7) Å	Cell parameters from 1568 reflections
b = 8.5125 (8) Å	θ = 2.3–28.2°
c = 9.0215 (8) Å	µ = 0.27 mm^−1
α = 78.031 (1)°	T = 294 K
β = 85.704 (1)°	Block, colorless
γ = 85.295 (1)°	0.30 × 0.20 × 0.20 mm
V = 595.97 (9) Å^3

Data collection

Bruker SMART CCD diffractometer	1684 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.057
Graphite monochromator	θmax = 25.0°, θmin = 2.3°
φ and ω scans	h = −9→9
3262 measured reflections	k = −8→10
2071 independent reflections	l = −10→10

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) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0532P)^2 + 0.1619P] where P = (Fo^2 + 2Fc^2)/3
2071 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.30 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
C1	0.2762 (3)	0.5595 (2)	0.9492 (2)	0.0389 (5)
C2	0.3586 (3)	0.6821 (3)	0.8469 (3)	0.0461 (6)
C3	0.4365 (3)	0.7962 (3)	0.9019 (3)	0.0567 (7)
H3	0.4924	0.8759	0.8348	0.068*
C4	0.4316 (3)	0.7921 (3)	1.0542 (3)	0.0560 (7)
H4	0.4839	0.8696	1.0897	0.067*
C5	0.3505 (3)	0.6748 (3)	1.1563 (3)	0.0537 (6)
H5	0.3480	0.6729	1.2599	0.064*
C6	0.2734 (3)	0.5608 (3)	1.1030 (3)	0.0470 (6)
H6	0.2178	0.4822	1.1719	0.056*
C7	0.2029 (3)	0.4338 (3)	0.8875 (2)	0.0397 (5)
C8	0.0311 (3)	0.0654 (2)	1.0270 (2)	0.0394 (5)
H8	0.0317	0.0630	1.1305	0.047*
C9	−0.0242 (4)	0.2384 (4)	0.5576 (3)	0.0732 (8)
H9A	−0.1146	0.3043	0.5067	0.110*
H9B	−0.0134	0.2670	0.6538	0.110*
H9C	−0.0480	0.1272	0.5735	0.110*
C10	0.2997 (4)	0.1336 (4)	0.5665 (3)	0.0784 (9)
H10A	0.2641	0.0265	0.5783	0.118*
H10B	0.2947	0.1632	0.6639	0.118*
H10C	0.4133	0.1376	0.5230	0.118*
N2	0.0853 (2)	0.1844 (2)	0.9302 (2)	0.0407 (4)
N1	0.1446 (2)	0.3054 (2)	0.9877 (2)	0.0391 (4)
O1	0.3692 (3)	0.6902 (2)	0.6955 (2)	0.0726 (6)
H1	0.3241	0.6141	0.6766	0.109*
O4	0.1500 (3)	0.1961 (2)	0.30909 (19)	0.0745 (6)
O9	0.1975 (2)	0.4444 (2)	0.74889 (18)	0.0603 (5)
S1	0.16523 (9)	0.26925 (8)	0.44551 (7)	0.0586 (3)
H1A	0.152 (3)	0.292 (3)	1.081 (3)	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0413 (12)	0.0325 (11)	0.0437 (12)	−0.0057 (9)	−0.0076 (9)	−0.0063 (9)
C2	0.0519 (14)	0.0374 (12)	0.0483 (14)	−0.0100 (10)	−0.0092 (10)	−0.0022 (10)
C3	0.0696 (17)	0.0377 (13)	0.0635 (17)	−0.0212 (12)	−0.0082 (13)	−0.0033 (11)
C4	0.0644 (16)	0.0352 (13)	0.0751 (19)	−0.0142 (11)	−0.0097 (13)	−0.0203 (12)
C5	0.0649 (16)	0.0505 (14)	0.0528 (15)	−0.0121 (12)	−0.0037 (12)	−0.0231 (12)
C6	0.0550 (14)	0.0420 (12)	0.0460 (13)	−0.0164 (11)	0.0030 (10)	−0.0107 (10)
C7	0.0426 (12)	0.0387 (12)	0.0389 (12)	−0.0095 (9)	−0.0074 (9)	−0.0061 (9)
C8	0.0492 (13)	0.0396 (12)	0.0315 (11)	−0.0138 (10)	−0.0060 (9)	−0.0067 (9)
C9	0.0708 (19)	0.105 (2)	0.0483 (16)	−0.0080 (16)	−0.0116 (13)	−0.0231 (15)
C10	0.088 (2)	0.087 (2)	0.0624 (18)	0.0104 (17)	−0.0126 (16)	−0.0243 (16)
N2	0.0519 (11)	0.0355 (10)	0.0375 (10)	−0.0138 (8)	−0.0063 (8)	−0.0080 (8)
N1	0.0492 (11)	0.0355 (9)	0.0351 (9)	−0.0162 (8)	−0.0052 (8)	−0.0065 (8)
O1	0.1101 (16)	0.0623 (12)	0.0456 (10)	−0.0445 (11)	−0.0098 (10)	0.0054 (9)
O4	0.1213 (17)	0.0750 (12)	0.0327 (9)	−0.0324 (12)	−0.0007 (10)	−0.0151 (9)
O9	0.0939 (13)	0.0549 (10)	0.0350 (9)	−0.0351 (9)	−0.0142 (8)	−0.0005 (7)
S1	0.0887 (5)	0.0536 (4)	0.0363 (4)	−0.0194 (3)	−0.0035 (3)	−0.0100 (3)

Geometric parameters (Å, º)

C1—C6	1.388 (3)	C8—C8^i	1.439 (4)
C1—C2	1.412 (3)	C8—H8	0.9300
C1—C7	1.482 (3)	C9—S1	1.761 (3)
C2—O1	1.350 (3)	C9—H9A	0.9600
C2—C3	1.386 (3)	C9—H9B	0.9600
C3—C4	1.365 (4)	C9—H9C	0.9600
C3—H3	0.9300	C10—S1	1.767 (3)
C4—C5	1.377 (3)	C10—H10A	0.9600
C4—H4	0.9300	C10—H10B	0.9600
C5—C6	1.374 (3)	C10—H10C	0.9600
C5—H5	0.9300	N2—N1	1.375 (2)
C6—H6	0.9300	N1—H1A	0.83 (3)
C7—O9	1.238 (2)	O1—H1	0.8200
C7—N1	1.356 (3)	O4—S1	1.5065 (17)
C8—N2	1.274 (3)
C6—C1—C2	117.9 (2)	N2—C8—H8	120.6
C6—C1—C7	123.6 (2)	C8^i—C8—H8	120.6
C2—C1—C7	118.5 (2)	S1—C9—H9A	109.5
O1—C2—C3	117.9 (2)	S1—C9—H9B	109.5
O1—C2—C1	122.2 (2)	H9A—C9—H9B	109.5
C3—C2—C1	119.8 (2)	S1—C9—H9C	109.5
C4—C3—C2	120.3 (2)	H9A—C9—H9C	109.5
C4—C3—H3	119.8	H9B—C9—H9C	109.5
C2—C3—H3	119.8	S1—C10—H10A	109.5
C3—C4—C5	121.0 (2)	S1—C10—H10B	109.5
C3—C4—H4	119.5	H10A—C10—H10B	109.5
C5—C4—H4	119.5	S1—C10—H10C	109.5
C6—C5—C4	119.1 (2)	H10A—C10—H10C	109.5
C6—C5—H5	120.4	H10B—C10—H10C	109.5
C4—C5—H5	120.4	C8—N2—N1	116.44 (18)
C5—C6—C1	121.8 (2)	C7—N1—N2	117.79 (18)
C5—C6—H6	119.1	C7—N1—H1A	124 (2)
C1—C6—H6	119.1	N2—N1—H1A	118 (2)
O9—C7—N1	121.09 (19)	C2—O1—H1	109.5
O9—C7—C1	121.12 (19)	O4—S1—C9	106.46 (13)
N1—C7—C1	117.78 (19)	O4—S1—C10	106.43 (13)
N2—C8—C8^i	118.7 (2)	C9—S1—C10	98.08 (15)
C6—C1—C2—O1	179.4 (2)	C7—C1—C6—C5	176.5 (2)
C7—C1—C2—O1	1.5 (3)	C6—C1—C7—O9	174.6 (2)
C6—C1—C2—C3	1.5 (3)	C2—C1—C7—O9	−7.6 (3)
C7—C1—C2—C3	−176.4 (2)	C6—C1—C7—N1	−6.5 (3)
O1—C2—C3—C4	−179.1 (2)	C2—C1—C7—N1	171.3 (2)
C1—C2—C3—C4	−1.1 (4)	C8^i—C8—N2—N1	−179.4 (2)
C2—C3—C4—C5	0.3 (4)	O9—C7—N1—N2	2.5 (3)
C3—C4—C5—C6	−0.1 (4)	C1—C7—N1—N2	−176.43 (17)
C4—C5—C6—C1	0.6 (4)	C8—N2—N1—C7	−179.9 (2)
C2—C1—C6—C5	−1.3 (3)

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4^ii	0.83 (3)	2.05 (3)	2.858 (2)	164 (3)
C6—H6···S1^ii	0.93	2.77	3.636 (2)	156
C6—H6···O4^ii	0.93	2.57	3.449 (3)	157
C8—H8···O4^ii	0.93	2.44	3.213 (3)	141
O1—H1···O9	0.82	1.81	2.538 (2)	147
C9—H9B···N2	0.96	2.61	3.465 (3)	149

Symmetry code: (ii) x, y, z+1.