N,N′,N′′,N′′′-Tetra­kis(2-hydroxy­benzyl­idene)biphenyl-3,3′,4,4′-tetra­mine dimethyl­formamide solvate

The title compound, C₄₀H₃₀N₄O₄·C₃H₇NO, is an O-hydr­oxy Schiff base. The mol­ecule, which lies on a symmetry centre, exists as an enol–imine tautomer, in which two independent intra­molecular O—H...N hydrogen bonds are formed.

Key indicators

• Single-crystal X-ray study
• T = 187 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in solvent or counterion
• R factor = 0.066
• wR factor = 0.200
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT216_ALERT_3_C Disordered N3      (An/Solv) ADP max/min Ratio         6.90
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for         N3
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........         O3

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         22

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 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
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The O-Hydroxy Schiff bases derived from the reaction of o-hydroxy aldehydes with aniline have been extensively examined (Steward & Lingafelter, 1959; Calligaris et al., 1972; Maslen & Waters, 1975). There are two possible types of intramolecular hydrogen bonds in Schiff bases, namely keto-amine (N—H···O) and enol-imine (N···H—O) tautomeric forms. The present X-ray investigation shows that the title compound, C₄₀H₃₀N₄O4.C₃H₇NO, (I), prefers the enol-imine tautomeric form rather than the keto-amine tautomeric form.

The molecule is halved by a centre of symmetry; the asymmetric unit (Fig. 1), presents two strong intramolecular O—H···N hydrogen bond interactions (Table. 1). These O—H···N contacts (2.562 (3)–2.629 (3) Å) satisfy the corresponding distances of strong hydrogen bonds in the literature (Filarowski et al., 2003; K˛osar et al., 2005). Non-H atoms in (I) are not coplanar, the mean deviation of the atoms from the least-squares plane being 0.293 Å. The compound crystallizes with a DMF solvato molecule.

Related literature

For related literature, see: Calligaris et al. (1972); Filarowski et al. (2003); K˛osar et al. (2005); Maslen & Waters (1975); Steward & Lingafelter (1959).

S2. Experimental

All reagents were purchased (Adrich) and used without further purification. Compound (I) was synthesized by mixing 3,3'-diaminobenzidine (2.14 g, 10 mmol) and salicylaldehyde (4.88 g, 40 mmol) in ethanol (100 ml) at 343 K for 20 min. Then compound (I) (0.631 g, 1 mmol) was dissolved in 20 ml DMF. After heating at 373 K for 5 min, the mixture was allowed to cool and evaporate naturally. Yellow plate-shaped crystals of (I) suitable for single-crystal X-ray diffraction were obtained by evaporating the mixture at room temperature for a period of 4 d. Analysis found: C 73.5, H 5.3, N 9.8%; C₄₃H₃₇N₅O₅ requires: C 73.38, H 5.30, N 9.95%.

S3. Refinement

All H atoms were visible in difference Fourier maps but were placed in calculated positions with C—H= 0.95 Å C–H: 0.98 Å; C—H₃ and O—H: 0.84 Å, in all cases with U_iso(H) = 1.2 U_eq(C) and 1.5 U_eq(O). Non-H atoms were refined anisotropically. The maximum positive peak of 0.337 e Å^-3 in the final difference electron density map was located 1.03 Å from atom C21. The crystal data were collected at 187 K. The shape of some displacement ellipsoids in the DMF solvate suggests some kind of disorder.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.

Figures

	Fig. 1. A view of the molecule of (I), with the atom-numbering scheme and 30% probability displacement ellipsoids. The dashed line indicates the intramolecular hydrogen bonds. Some H atoms are omitted for clarity. Symmetry codes: i 1 - x, 2 - y, -z.
	Fig. 2. A packing diagram for (I).

N,N',N'',N'''-Tetrakis(2-hydroxybenzylidene)biphenyl-3,3',4,4'-tetramine dimethylformamide solvate

Crystal data

C40H30N4O4·C3H7NO	F(000) = 740
Mr = 703.78	Dx = 1.203 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.2109 (19) Å	Cell parameters from 864 reflections
b = 6.3608 (8) Å	θ = 3.7–22.8°
c = 20.119 (3) Å	µ = 0.08 mm^−1
β = 93.882 (2)°	T = 187 K
V = 1942.1 (4) Å^3	Plate, yellow
Z = 2	0.30 × 0.21 × 0.04 mm

Data collection

Bruker SMART APEX II CCD diffractometer	3426 independent reflections
Radiation source: fine-focus sealed tube	2490 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 25.0°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −18→11
Tmin = 0.976, Tmax = 0.997	k = −7→7
9558 measured reflections	l = −23→23

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.201	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1084P)^2 + 1.0323P] where P = (Fo^2 + 2Fc^2)/3
3426 reflections	(Δ/σ)max = 0.008
266 parameters	Δρmax = 0.34 e Å^−3
22 restraints	Δρmin = −0.21 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	Occ. (<1)
C1	0.48192 (15)	0.9023 (4)	0.01409 (12)	0.0269 (6)
C2	0.39813 (16)	0.8299 (4)	−0.00735 (13)	0.0307 (6)
H2	0.3646	0.9065	−0.0407	0.037*
C3	0.36209 (16)	0.6484 (4)	0.01879 (12)	0.0288 (6)
C4	0.41093 (16)	0.5308 (4)	0.06705 (12)	0.0266 (6)
C5	0.49461 (17)	0.6027 (4)	0.08812 (14)	0.0357 (7)
H5	0.5288	0.5256	0.1210	0.043*
C6	0.52886 (17)	0.7832 (4)	0.06225 (14)	0.0356 (7)
H6	0.5863	0.8275	0.0778	0.043*
C7	0.21535 (18)	0.7113 (5)	−0.01503 (13)	0.0368 (7)
H7	0.2263	0.8524	−0.0014	0.044*
C8	0.12903 (18)	0.6584 (5)	−0.04537 (14)	0.0383 (7)
C9	0.1089 (2)	0.4546 (5)	−0.06790 (15)	0.0437 (7)
C10	0.0257 (2)	0.4126 (5)	−0.09811 (17)	0.0572 (9)
H10	0.0119	0.2752	−0.1141	0.069*
C11	−0.0367 (2)	0.5690 (6)	−0.10487 (17)	0.0569 (9)
H11	−0.0934	0.5381	−0.1253	0.068*
C12	−0.0181 (2)	0.7696 (6)	−0.08249 (18)	0.0560 (9)
H12	−0.0616	0.8769	−0.0871	0.067*
C13	0.06497 (19)	0.8126 (5)	−0.05303 (16)	0.0474 (8)
H13	0.0782	0.9511	−0.0378	0.057*
C14	0.40784 (17)	0.2289 (4)	0.13573 (13)	0.0330 (6)
H14	0.4662	0.2592	0.1529	0.040*
C15	0.36358 (17)	0.0459 (4)	0.15970 (12)	0.0308 (6)
C16	0.27688 (17)	−0.0025 (4)	0.13528 (13)	0.0325 (6)
C17	0.2362 (2)	−0.1822 (4)	0.15791 (15)	0.0413 (7)
H17	0.1780	−0.2159	0.1412	0.050*
C18	0.2793 (2)	−0.3114 (4)	0.20413 (14)	0.0428 (8)
H18	0.2510	−0.4345	0.2187	0.051*
C19	0.3637 (2)	−0.2632 (5)	0.22955 (15)	0.0456 (8)
H19	0.3930	−0.3514	0.2621	0.055*
C20	0.4049 (2)	−0.0865 (5)	0.20737 (14)	0.0422 (7)
H20	0.4628	−0.0540	0.2249	0.051*
C21	0.7766 (7)	0.589 (3)	0.3218 (5)	0.228 (9)	0.50
H21	0.7556	0.5590	0.3642	0.273*	0.50
C22	0.7287 (11)	0.555 (3)	0.1895 (4)	0.237 (10)	0.50
H22A	0.7875	0.5964	0.1772	0.284*	0.50
H22B	0.6840	0.6357	0.1628	0.284*	0.50
H22C	0.7199	0.4049	0.1811	0.284*	0.50
C23	0.6224 (7)	0.556 (3)	0.2722 (6)	0.183 (7)	0.50
H23A	0.6135	0.5440	0.3199	0.219*	0.50
H23B	0.6050	0.4243	0.2498	0.219*	0.50
H23C	0.5863	0.6716	0.2531	0.219*	0.50
N1	0.27785 (14)	0.5760 (3)	−0.00565 (11)	0.0347 (6)
N2	0.37056 (13)	0.3513 (3)	0.09206 (10)	0.0287 (5)
N3	0.7204 (5)	0.601 (3)	0.2628 (3)	0.253 (10)	0.50
O1	0.16868 (15)	0.2970 (3)	−0.06137 (13)	0.0576 (7)
H1	0.2155	0.3424	−0.0420	0.086*
O2	0.23246 (12)	0.1201 (3)	0.08988 (11)	0.0465 (6)
H2A	0.2659	0.2155	0.0775	0.070*
O3	0.8612 (5)	0.622 (2)	0.3127 (4)	0.182 (6)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0278 (13)	0.0250 (13)	0.0286 (13)	−0.0023 (11)	0.0066 (10)	−0.0032 (10)
C2	0.0317 (14)	0.0255 (14)	0.0345 (14)	−0.0033 (11)	−0.0001 (11)	0.0041 (11)
C3	0.0314 (13)	0.0243 (13)	0.0307 (13)	−0.0059 (11)	0.0017 (11)	−0.0013 (11)
C4	0.0281 (13)	0.0226 (13)	0.0298 (13)	−0.0025 (10)	0.0073 (10)	−0.0010 (10)
C5	0.0327 (14)	0.0343 (15)	0.0393 (15)	−0.0036 (12)	−0.0026 (11)	0.0092 (12)
C6	0.0275 (13)	0.0340 (15)	0.0447 (16)	−0.0095 (12)	−0.0028 (12)	0.0072 (13)
C7	0.0381 (15)	0.0325 (15)	0.0392 (16)	−0.0121 (13)	−0.0018 (12)	0.0045 (12)
C8	0.0343 (15)	0.0402 (16)	0.0394 (15)	−0.0124 (13)	−0.0035 (12)	0.0104 (13)
C9	0.0447 (17)	0.0413 (17)	0.0434 (17)	−0.0120 (14)	−0.0089 (13)	0.0120 (14)
C10	0.058 (2)	0.050 (2)	0.061 (2)	−0.0285 (18)	−0.0165 (16)	0.0119 (16)
C11	0.0399 (18)	0.064 (2)	0.064 (2)	−0.0195 (17)	−0.0152 (15)	0.0195 (18)
C12	0.0387 (17)	0.060 (2)	0.068 (2)	−0.0083 (16)	−0.0056 (15)	0.0176 (18)
C13	0.0381 (16)	0.0464 (18)	0.057 (2)	−0.0076 (15)	−0.0029 (14)	0.0071 (15)
C14	0.0320 (14)	0.0311 (14)	0.0357 (14)	−0.0051 (12)	0.0010 (11)	0.0022 (12)
C15	0.0375 (14)	0.0261 (13)	0.0294 (13)	−0.0015 (11)	0.0077 (11)	0.0009 (11)
C16	0.0391 (15)	0.0269 (14)	0.0322 (14)	−0.0030 (12)	0.0069 (11)	−0.0009 (11)
C17	0.0448 (17)	0.0365 (16)	0.0437 (16)	−0.0122 (14)	0.0103 (13)	−0.0018 (13)
C18	0.064 (2)	0.0257 (14)	0.0411 (16)	−0.0081 (14)	0.0218 (15)	0.0007 (12)
C19	0.064 (2)	0.0335 (16)	0.0405 (16)	0.0023 (15)	0.0102 (15)	0.0123 (13)
C20	0.0430 (16)	0.0407 (17)	0.0426 (16)	−0.0001 (14)	0.0010 (13)	0.0077 (13)
C21	0.30 (2)	0.33 (2)	0.044 (6)	0.02 (2)	−0.022 (11)	0.011 (10)
C22	0.200 (15)	0.46 (3)	0.049 (6)	0.008 (18)	0.023 (8)	0.047 (12)
C23	0.105 (9)	0.36 (2)	0.086 (8)	0.054 (12)	0.013 (7)	0.007 (12)
N1	0.0331 (12)	0.0332 (13)	0.0369 (12)	−0.0110 (11)	−0.0053 (9)	0.0070 (10)
N2	0.0307 (11)	0.0237 (11)	0.0321 (12)	−0.0026 (9)	0.0059 (9)	0.0012 (9)
N3	0.119 (8)	0.60 (3)	0.032 (4)	0.202 (14)	−0.029 (4)	−0.015 (9)
O1	0.0574 (14)	0.0385 (12)	0.0737 (17)	−0.0128 (11)	−0.0191 (12)	0.0003 (11)
O2	0.0399 (11)	0.0408 (12)	0.0574 (13)	−0.0139 (9)	−0.0071 (10)	0.0143 (10)
O3	0.068 (4)	0.384 (16)	0.087 (5)	0.092 (8)	−0.037 (4)	−0.018 (7)

Geometric parameters (Å, º)

C1—C6	1.389 (4)	C14—C15	1.444 (3)
C1—C2	1.396 (3)	C14—H14	0.9500
C1—C1^i	1.487 (5)	C15—C20	1.394 (4)
C2—C3	1.396 (3)	C15—C16	1.410 (4)
C2—H2	0.9500	C16—O2	1.347 (3)
C3—C4	1.399 (4)	C16—C17	1.391 (4)
C3—N1	1.418 (3)	C17—C18	1.374 (4)
C4—C5	1.391 (4)	C17—H17	0.9500
C4—N2	1.406 (3)	C18—C19	1.384 (5)
C5—C6	1.378 (4)	C18—H18	0.9500
C5—H5	0.9500	C19—C20	1.375 (4)
C6—H6	0.9500	C19—H19	0.9500
C7—N1	1.287 (4)	C20—H20	0.9500
C7—C8	1.449 (4)	C21—O3	1.328 (8)
C7—H7	0.9500	C21—N3	1.418 (7)
C8—C13	1.384 (4)	C21—H21	0.9500
C8—C9	1.401 (4)	C22—N3	1.515 (7)
C9—O1	1.354 (4)	C22—H22A	0.9800
C9—C10	1.392 (4)	C22—H22B	0.9800
C10—C11	1.375 (5)	C22—H22C	0.9800
C10—H10	0.9500	C23—N3	1.542 (8)
C11—C12	1.376 (5)	C23—H23A	0.9800
C11—H11	0.9500	C23—H23B	0.9800
C12—C13	1.386 (4)	C23—H23C	0.9800
C12—H12	0.9500	O1—H1	0.8400
C13—H13	0.9500	O2—H2A	0.8400
C14—N2	1.277 (3)
C6—C1—C2	116.8 (2)	C15—C14—H14	119.2
C6—C1—C1^i	122.4 (3)	C20—C15—C16	118.4 (2)
C2—C1—C1^i	120.8 (3)	C20—C15—C14	121.2 (2)
C1—C2—C3	122.0 (2)	C16—C15—C14	120.4 (2)
C1—C2—H2	119.0	O2—C16—C17	118.9 (2)
C3—C2—H2	119.0	O2—C16—C15	121.6 (2)
C2—C3—C4	120.0 (2)	C17—C16—C15	119.5 (3)
C2—C3—N1	120.4 (2)	C18—C17—C16	120.7 (3)
C4—C3—N1	119.5 (2)	C18—C17—H17	119.7
C5—C4—C3	117.9 (2)	C16—C17—H17	119.7
C5—C4—N2	124.8 (2)	C17—C18—C19	120.4 (3)
C3—C4—N2	117.3 (2)	C17—C18—H18	119.8
C6—C5—C4	121.4 (3)	C19—C18—H18	119.8
C6—C5—H5	119.3	C20—C19—C18	119.5 (3)
C4—C5—H5	119.3	C20—C19—H19	120.2
C5—C6—C1	121.9 (2)	C18—C19—H19	120.2
C5—C6—H6	119.0	C19—C20—C15	121.5 (3)
C1—C6—H6	119.0	C19—C20—H20	119.2
N1—C7—C8	123.1 (3)	C15—C20—H20	119.2
N1—C7—H7	118.5	O3—C21—N3	114.2 (9)
C8—C7—H7	118.5	O3—C21—H21	122.9
C13—C8—C9	118.9 (3)	N3—C21—H21	122.9
C13—C8—C7	119.6 (3)	N3—C22—H22A	109.5
C9—C8—C7	121.5 (3)	N3—C22—H22B	109.5
O1—C9—C10	119.0 (3)	H22A—C22—H22B	109.5
O1—C9—C8	121.5 (3)	N3—C22—H22C	109.5
C10—C9—C8	119.4 (3)	H22A—C22—H22C	109.5
C11—C10—C9	120.3 (3)	H22B—C22—H22C	109.5
C11—C10—H10	119.8	N3—C23—H23A	109.5
C9—C10—H10	119.8	N3—C23—H23B	109.5
C10—C11—C12	120.9 (3)	H23A—C23—H23B	109.5
C10—C11—H11	119.5	N3—C23—H23C	109.5
C12—C11—H11	119.5	H23A—C23—H23C	109.5
C11—C12—C13	118.9 (3)	H23B—C23—H23C	109.5
C11—C12—H12	120.5	C7—N1—C3	118.4 (2)
C13—C12—H12	120.5	C14—N2—C4	123.8 (2)
C8—C13—C12	121.5 (3)	C21—N3—C22	136.0 (11)
C8—C13—H13	119.3	C21—N3—C23	114.8 (9)
C12—C13—H13	119.3	C22—N3—C23	103.3 (10)
N2—C14—C15	121.7 (2)	C9—O1—H1	109.5
N2—C14—H14	119.2	C16—O2—H2A	109.5
C6—C1—C2—C3	1.0 (4)	C7—C8—C13—C12	179.2 (3)
C1^i—C1—C2—C3	−179.2 (3)	C11—C12—C13—C8	−0.4 (5)
C1—C2—C3—C4	−1.3 (4)	N2—C14—C15—C20	180.0 (3)
C1—C2—C3—N1	−178.1 (2)	N2—C14—C15—C16	−0.2 (4)
C2—C3—C4—C5	0.9 (4)	C20—C15—C16—O2	179.0 (2)
N1—C3—C4—C5	177.7 (2)	C14—C15—C16—O2	−0.8 (4)
C2—C3—C4—N2	179.2 (2)	C20—C15—C16—C17	−1.7 (4)
N1—C3—C4—N2	−4.0 (3)	C14—C15—C16—C17	178.5 (2)
C3—C4—C5—C6	−0.3 (4)	O2—C16—C17—C18	179.9 (3)
N2—C4—C5—C6	−178.4 (2)	C15—C16—C17—C18	0.6 (4)
C4—C5—C6—C1	0.0 (4)	C16—C17—C18—C19	0.8 (4)
C2—C1—C6—C5	−0.3 (4)	C17—C18—C19—C20	−1.1 (4)
C1^i—C1—C6—C5	179.9 (3)	C18—C19—C20—C15	0.0 (4)
N1—C7—C8—C13	179.3 (3)	C16—C15—C20—C19	1.4 (4)
N1—C7—C8—C9	−1.4 (4)	C14—C15—C20—C19	−178.8 (3)
C13—C8—C9—O1	−179.6 (3)	C8—C7—N1—C3	174.3 (2)
C7—C8—C9—O1	1.1 (4)	C2—C3—N1—C7	−44.2 (4)
C13—C8—C9—C10	0.8 (4)	C4—C3—N1—C7	139.0 (3)
C7—C8—C9—C10	−178.5 (3)	C15—C14—N2—C4	−179.8 (2)
O1—C9—C10—C11	179.4 (3)	C5—C4—N2—C14	−2.5 (4)
C8—C9—C10—C11	−1.0 (5)	C3—C4—N2—C14	179.4 (2)
C9—C10—C11—C12	0.5 (5)	O3—C21—N3—C22	31 (3)
C10—C11—C12—C13	0.2 (5)	O3—C21—N3—C23	178.4 (16)
C9—C8—C13—C12	−0.1 (5)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N2	0.84	1.82	2.562 (3)	147
O1—H1···N1	0.84	1.88	2.629 (3)	147