Zwitterionic (E)-2-hydr­oxy-6-[(o-tolyl­iminio)meth­yl]phenolate 0.07-hydrate

The title compound, C₁₄H₁₃NO₂·0.07H₂O, crystallizes in a zwitterionic form. The dihedral angle between the aromatic rings is 29.23 (4)°. An N—H...O hydrogen bond generates an S(6) ring motif and inter­molecular O—H...O hydrogen bonds generate a centrosymmetric R₂²(10) dimer.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• H-atom completeness 99%
• Disorder in solvent or counterion
• R factor = 0.052
• wR factor = 0.147
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O1     ..  O3      ..       2.77 Ang.

Alert level C
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       3.17 Sigma
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.74 mm
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      14.00 Perc.
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........         O1
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....        <O3

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C14 H13.14 N1 O2.07
            Atom count from the _atom_site data:  C14 H13 N1 O2.07
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    8
           From the CIF: _chemical_formula_sum  C14 H13.14 N O2.07
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        112.00    112.00    0.00
           H        105.12    104.00    1.12
           N          8.00      8.00    0.00
           O         16.56     16.56    0.00

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

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(E)-2-hydroxy-6-[(o-tolyliminio)methyl]phenolate 0.07-hydrate

Crystal data

C14H13NO2·0.07H2O	F(000) = 966
Mr = 228.52	Dx = 1.314 Mg m^−3
Monoclinic, C2/c	Melting point = 384–385 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 23.9334 (14) Å	Cell parameters from 16009 reflections
b = 7.2265 (5) Å	θ = 2.7–27.3°
c = 13.9798 (10) Å	µ = 0.09 mm^−1
β = 107.135 (5)°	T = 296 K
V = 2310.6 (3) Å^3	Prism, colourless
Z = 8	0.74 × 0.55 × 0.31 mm

Data collection

Stoe IPDS-2 diffractometer	2571 independent reflections
Radiation source: fine-focus sealed tube	1917 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.091
Detector resolution: 6.67 pixels mm^-1	θmax = 27.3°, θmin = 3.0°
ω scans	h = −30→30
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −9→9
Tmin = 0.945, Tmax = 0.975	l = −17→17
17777 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.147	w = 1/[σ^2(Fo^2) + (0.12P)^2 + 0.2796P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
2571 reflections	Δρmax = 0.17 e Å^−3
168 parameters	Δρmin = −0.17 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (6)

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	0.49961 (6)	0.4542 (2)	0.12132 (9)	0.0564 (4)
C2	0.51704 (6)	0.2776 (2)	0.09788 (10)	0.0584 (4)
C3	0.57502 (7)	0.2563 (3)	0.09266 (11)	0.0700 (5)
C4	0.61333 (7)	0.4015 (3)	0.11587 (12)	0.0775 (5)
H4	0.6518	0.3841	0.1156	0.093*
C5	0.59593 (8)	0.5740 (3)	0.13977 (12)	0.0772 (5)
H5	0.6226	0.6710	0.1548	0.093*
C6	0.53988 (7)	0.6022 (3)	0.14133 (11)	0.0673 (4)
H6	0.5282	0.7191	0.1556	0.081*
C7	0.44178 (6)	0.4820 (2)	0.12575 (9)	0.0549 (4)
H7	0.4306	0.6001	0.1392	0.066*
C8	0.34574 (6)	0.3702 (2)	0.11492 (9)	0.0512 (3)
C9	0.31695 (7)	0.5377 (2)	0.09384 (11)	0.0618 (4)
H9	0.3356	0.6389	0.0756	0.074*
C10	0.26080 (8)	0.5555 (3)	0.09968 (13)	0.0737 (5)
H10	0.2417	0.6689	0.0864	0.088*
C11	0.23302 (8)	0.4056 (3)	0.12511 (14)	0.0767 (5)
H11	0.1951	0.4172	0.1294	0.092*
C12	0.26123 (8)	0.2389 (3)	0.14413 (13)	0.0723 (5)
H12	0.2417	0.1379	0.1605	0.087*
C13	0.31800 (7)	0.2156 (2)	0.13976 (10)	0.0584 (4)
C14	0.34870 (9)	0.0330 (2)	0.16143 (15)	0.0791 (5)
H14A	0.3234	−0.0560	0.1785	0.119*
H14B	0.3837	0.0465	0.2164	0.119*
H14C	0.3587	−0.0084	0.1033	0.119*
N1	0.40398 (5)	0.34905 (17)	0.11179 (8)	0.0538 (3)
H1	0.4212 (11)	0.243 (2)	0.0977 (19)	0.142 (10)*
O1	0.48180 (5)	0.13363 (16)	0.07991 (9)	0.0681 (3)
O2	0.59204 (6)	0.0894 (3)	0.06620 (12)	0.0950 (5)
H2	0.5634 (14)	0.016 (5)	0.032 (2)	0.148 (12)*
O3	0.5000	0.9181 (18)	0.2500	0.083 (4)	0.14

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0536 (8)	0.0719 (9)	0.0444 (6)	−0.0061 (7)	0.0154 (5)	0.0025 (6)
C2	0.0503 (8)	0.0769 (10)	0.0491 (7)	−0.0004 (7)	0.0163 (6)	0.0051 (6)
C3	0.0528 (9)	0.0978 (13)	0.0599 (8)	0.0073 (8)	0.0175 (7)	0.0043 (8)
C4	0.0464 (9)	0.1247 (17)	0.0609 (9)	−0.0053 (9)	0.0151 (7)	0.0064 (9)
C5	0.0621 (10)	0.1081 (15)	0.0602 (8)	−0.0267 (10)	0.0161 (7)	0.0011 (9)
C6	0.0653 (10)	0.0817 (11)	0.0549 (8)	−0.0150 (8)	0.0176 (7)	0.0002 (7)
C7	0.0593 (9)	0.0581 (8)	0.0491 (7)	−0.0014 (7)	0.0189 (6)	−0.0019 (6)
C8	0.0511 (8)	0.0570 (8)	0.0472 (6)	−0.0031 (6)	0.0170 (5)	−0.0060 (5)
C9	0.0615 (9)	0.0583 (9)	0.0692 (9)	0.0003 (7)	0.0250 (7)	−0.0011 (7)
C10	0.0635 (10)	0.0788 (11)	0.0808 (10)	0.0127 (8)	0.0243 (8)	−0.0039 (8)
C11	0.0564 (9)	0.0979 (14)	0.0812 (11)	−0.0009 (9)	0.0284 (8)	−0.0056 (9)
C12	0.0638 (10)	0.0823 (12)	0.0765 (10)	−0.0182 (9)	0.0293 (8)	−0.0033 (8)
C13	0.0616 (9)	0.0619 (9)	0.0536 (7)	−0.0083 (7)	0.0201 (6)	−0.0056 (6)
C14	0.0898 (13)	0.0602 (10)	0.0929 (12)	−0.0083 (9)	0.0358 (10)	0.0041 (8)
N1	0.0544 (7)	0.0573 (7)	0.0532 (6)	−0.0003 (6)	0.0213 (5)	−0.0020 (5)
O1	0.0618 (7)	0.0667 (7)	0.0808 (7)	0.0019 (5)	0.0289 (5)	−0.0032 (5)
O2	0.0580 (8)	0.1184 (12)	0.1093 (10)	0.0143 (8)	0.0260 (7)	−0.0173 (9)
O3	0.125 (13)	0.052 (7)	0.081 (8)	0.000	0.043 (8)	0.000

Geometric parameters (Å, º)

C1—C2	1.411 (2)	C8—N1	1.4157 (19)
C1—C6	1.412 (2)	C9—C10	1.376 (2)
C1—C7	1.418 (2)	C9—H9	0.93
C2—O1	1.3160 (19)	C10—C11	1.372 (3)
C2—C3	1.419 (2)	C10—H10	0.93
C3—O2	1.359 (2)	C11—C12	1.368 (3)
C3—C4	1.368 (3)	C11—H11	0.93
C4—C5	1.386 (3)	C12—C13	1.388 (2)
C4—H4	0.93	C12—H12	0.93
C5—C6	1.363 (3)	C13—C14	1.497 (2)
C5—H5	0.93	C14—H14A	0.96
C6—H6	0.93	C14—H14B	0.96
C7—N1	1.2946 (19)	C14—H14C	0.96
C7—H7	0.93	N1—H1	0.918 (10)
C8—C9	1.381 (2)	O2—H2	0.89 (3)
C8—C13	1.395 (2)
C2—C1—C6	120.01 (14)	C10—C9—H9	119.9
C2—C1—C7	119.87 (13)	C8—C9—H9	119.9
C6—C1—C7	120.12 (15)	C11—C10—C9	119.87 (17)
O1—C2—C1	122.86 (13)	C11—C10—H10	120.1
O1—C2—C3	119.08 (15)	C9—C10—H10	120.1
C1—C2—C3	118.06 (14)	C12—C11—C10	119.78 (16)
O2—C3—C4	120.75 (16)	C12—C11—H11	120.1
O2—C3—C2	119.08 (16)	C10—C11—H11	120.1
C4—C3—C2	120.15 (17)	C11—C12—C13	122.11 (16)
C3—C4—C5	121.24 (16)	C11—C12—H12	118.9
C3—C4—H4	119.4	C13—C12—H12	118.9
C5—C4—H4	119.4	C12—C13—C8	117.23 (15)
C6—C5—C4	120.36 (17)	C12—C13—C14	121.77 (15)
C6—C5—H5	119.8	C8—C13—C14	121.00 (14)
C4—C5—H5	119.8	C13—C14—H14A	109.5
C5—C6—C1	120.05 (18)	C13—C14—H14B	109.5
C5—C6—H6	120.0	H14A—C14—H14B	109.5
C1—C6—H6	120.0	C13—C14—H14C	109.5
N1—C7—C1	122.39 (14)	H14A—C14—H14C	109.5
N1—C7—H7	118.8	H14B—C14—H14C	109.5
C1—C7—H7	118.8	C7—N1—C8	124.48 (13)
C9—C8—C13	120.74 (14)	C7—N1—H1	108.2 (18)
C9—C8—N1	121.45 (13)	C8—N1—H1	127.3 (18)
C13—C8—N1	117.81 (13)	C3—O2—H2	115 (2)
C10—C9—C8	120.24 (16)
C6—C1—C2—O1	179.02 (13)	C6—C1—C7—N1	−177.29 (13)
C7—C1—C2—O1	−0.3 (2)	C13—C8—C9—C10	1.7 (2)
C6—C1—C2—C3	−1.6 (2)	N1—C8—C9—C10	−178.50 (14)
C7—C1—C2—C3	179.02 (12)	C8—C9—C10—C11	−1.0 (3)
O1—C2—C3—O2	2.0 (2)	C9—C10—C11—C12	−0.3 (3)
C1—C2—C3—O2	−177.33 (14)	C10—C11—C12—C13	0.8 (3)
O1—C2—C3—C4	−176.75 (14)	C11—C12—C13—C8	0.0 (2)
C1—C2—C3—C4	3.9 (2)	C11—C12—C13—C14	179.54 (16)
O2—C3—C4—C5	177.86 (16)	C9—C8—C13—C12	−1.2 (2)
C2—C3—C4—C5	−3.4 (2)	N1—C8—C13—C12	179.00 (12)
C3—C4—C5—C6	0.5 (3)	C9—C8—C13—C14	179.23 (14)
C4—C5—C6—C1	1.8 (2)	N1—C8—C13—C14	−0.6 (2)
C2—C1—C6—C5	−1.2 (2)	C1—C7—N1—C8	−179.65 (12)
C7—C1—C6—C5	178.18 (13)	C9—C8—N1—C7	26.2 (2)
C2—C1—C7—N1	2.0 (2)	C13—C8—N1—C7	−154.06 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1^i	0.89 (3)	1.95 (3)	2.787 (2)	157 (3)
N1—H1···O1	0.92 (1)	1.73 (2)	2.5651 (16)	149 (3)

Symmetry code: (i) −x+1, −y, −z.