(E)-4-Methyl-2-{[tris(hydroxymethyl)methyl]iminiomethyl}phenolate.

In the zwitterionic title compound, C(12)H(17)NO(4), an intra-molecular N-H⋯O hydrogen bond generates a six-membered ring, producing an S(6) ring. In the crystal structure, mol-ecules are linked by inter-molecular C-H⋯O and O-H⋯O inter-actions.

Related literature

For the properties and uses of Schiff bases, see: Aydoğan et al. (2001 ▶); Barton & Ollis (1979 ▶); Layer (1963 ▶); Ingold (1969 ▶); Cohen et al. (1964 ▶); Ogawa & Harada (2003 ▶); Taggi et al. (2002 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For comparative bond lengths, see: Allen et al. (1987 ▶); Yüce et al. (2006 ▶).

Experimental

Crystal data

C12H17NO4

M = 239.27

Triclinic,

a = 6.7501 (6) Å

b = 8.5036 (8) Å

c = 11.129 (1) Å

α = 87.584 (8)°

β = 77.192 (8)°

γ = 79.215 (8)°

V = 611.9 (1) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.80 × 0.48 × 0.21 mm

Data collection

STOE IPDS II diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.942, T max = 0.979

8321 measured reflections

2409 independent reflections

2001 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.105

S = 1.09

2409 reflections

160 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.22 e Å−3

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, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536809051800/im2160sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051800/im2160Isup2.hkl

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

C12H17NO4	Z = 2
Mr = 239.27	F(000) = 256
Triclinic, P1	Dx = 1.299 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7501 (6) Å	Cell parameters from 13032 reflections
b = 8.5036 (8) Å	θ = 1.9–28.0°
c = 11.129 (1) Å	µ = 0.10 mm−1
α = 87.584 (8)°	T = 296 K
β = 77.192 (8)°	PRISM., yellow
γ = 79.215 (8)°	0.80 × 0.48 × 0.21 mm
V = 611.9 (1) Å3

STOE IPDS II diffractometer	2409 independent reflections
Radiation source: fine-focus sealed tube	2001 reflections with I > 2σ(I)
graphite	Rint = 0.022
Detector resolution: 6.67 pixels mm-1	θmax = 26.0°, θmin = 1.9°
rotation method scans	h = −8→8
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −10→10
Tmin = 0.942, Tmax = 0.979	l = −13→13
8321 measured reflections

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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105	w = 1/[σ2(Fo2) + (0.0534P)2 + 0.0953P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
2409 reflections	Δρmax = 0.25 e Å−3
160 parameters	Δρmin = −0.21 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.046 (8)

Experimental. 339 frames, detector distance = 100 mm

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
C1	0.2299 (2)	0.70721 (15)	0.73471 (12)	0.0388 (3)
C2	0.2401 (3)	0.6812 (2)	0.60930 (15)	0.0587 (4)
H2	0.1327	0.6440	0.5865	0.070*
C3	0.4045 (3)	0.7094 (3)	0.52063 (15)	0.0667 (5)
H3	0.4062	0.6888	0.4390	0.080*
C4	0.5709 (3)	0.7680 (2)	0.54645 (14)	0.0570 (4)
C5	0.5658 (2)	0.79155 (18)	0.66829 (13)	0.0476 (4)
H5	0.6752	0.8284	0.6891	0.057*
C6	0.4002 (2)	0.76175 (15)	0.76301 (12)	0.0377 (3)
C7	0.7462 (3)	0.8029 (3)	0.44497 (17)	0.0820 (6)
H7A	0.8509	0.8331	0.4804	0.123*
H7B	0.6954	0.8887	0.3946	0.123*
H7C	0.8040	0.7089	0.3952	0.123*
C8	0.4134 (2)	0.78295 (15)	0.88719 (12)	0.0364 (3)
H8	0.5246	0.8244	0.9009	0.044*
C9	0.27900 (19)	0.76614 (14)	1.11183 (11)	0.0333 (3)
C10	0.4917 (2)	0.77744 (17)	1.13130 (13)	0.0422 (3)
H10A	0.5351	0.8725	1.0910	0.051*
H10B	0.4869	0.7853	1.2186	0.051*
C11	0.1251 (2)	0.91827 (15)	1.15916 (13)	0.0409 (3)
H11A	−0.0106	0.9114	1.1465	0.049*
H11B	0.1148	0.9307	1.2467	0.049*
C12	0.2064 (2)	0.61933 (16)	1.17826 (13)	0.0395 (3)
H12A	0.3071	0.5238	1.1501	0.047*
H12B	0.1934	0.6296	1.2663	0.047*
N1	0.28000 (16)	0.74792 (12)	0.98133 (9)	0.0325 (3)
O1	0.07182 (14)	0.68314 (10)	0.82072 (9)	0.0412 (3)
O2	0.63352 (16)	0.64022 (13)	1.08193 (13)	0.0655 (4)
H14	0.7485	0.6460	1.0922	0.098*
O3	0.19503 (15)	1.05030 (11)	1.09428 (10)	0.0510 (3)
H13	0.1139	1.1327	1.1190	0.077*
O4	0.01450 (14)	0.60604 (11)	1.15400 (9)	0.0452 (3)
H4	−0.0244	0.5273	1.1897	0.068*
H1	0.179 (3)	0.7122 (19)	0.9641 (14)	0.047 (4)*

	U11	U22	U33	U12	U13	U23
C1	0.0392 (7)	0.0321 (6)	0.0448 (7)	−0.0052 (5)	−0.0094 (6)	0.0000 (5)
C2	0.0602 (10)	0.0732 (11)	0.0495 (9)	−0.0187 (8)	−0.0198 (8)	−0.0046 (8)
C3	0.0721 (12)	0.0905 (13)	0.0386 (8)	−0.0158 (10)	−0.0134 (8)	−0.0033 (8)
C4	0.0544 (10)	0.0684 (10)	0.0420 (8)	−0.0070 (8)	−0.0013 (7)	0.0030 (7)
C5	0.0414 (8)	0.0553 (8)	0.0445 (8)	−0.0127 (6)	−0.0033 (6)	0.0017 (6)
C6	0.0381 (7)	0.0357 (6)	0.0382 (7)	−0.0079 (5)	−0.0045 (5)	−0.0010 (5)
C7	0.0720 (13)	0.1168 (18)	0.0473 (10)	−0.0174 (12)	0.0065 (9)	0.0066 (10)
C8	0.0331 (6)	0.0340 (6)	0.0426 (7)	−0.0099 (5)	−0.0056 (5)	−0.0014 (5)
C9	0.0315 (6)	0.0337 (6)	0.0355 (6)	−0.0097 (5)	−0.0060 (5)	0.0001 (5)
C10	0.0380 (7)	0.0470 (7)	0.0461 (7)	−0.0147 (6)	−0.0133 (6)	0.0016 (6)
C11	0.0389 (7)	0.0360 (7)	0.0450 (7)	−0.0114 (5)	0.0017 (6)	−0.0042 (5)
C12	0.0370 (7)	0.0382 (7)	0.0457 (7)	−0.0126 (5)	−0.0109 (6)	0.0078 (5)
N1	0.0289 (5)	0.0316 (5)	0.0380 (6)	−0.0087 (4)	−0.0063 (4)	−0.0013 (4)
O1	0.0373 (5)	0.0354 (5)	0.0522 (6)	−0.0108 (4)	−0.0086 (4)	−0.0016 (4)
O2	0.0382 (6)	0.0497 (6)	0.1130 (10)	−0.0030 (5)	−0.0300 (6)	−0.0023 (6)
O3	0.0417 (6)	0.0313 (5)	0.0726 (7)	−0.0088 (4)	0.0055 (5)	−0.0010 (4)
O4	0.0361 (5)	0.0378 (5)	0.0659 (7)	−0.0156 (4)	−0.0140 (4)	0.0094 (4)

C1—O1	1.3071 (16)	C9—N1	1.4654 (16)
C1—C2	1.407 (2)	C9—C10	1.5197 (17)
C1—C6	1.4174 (19)	C9—C12	1.5282 (17)
C2—C3	1.363 (3)	C9—C11	1.5305 (18)
C2—H2	0.9300	C10—O2	1.4080 (19)
C3—C4	1.399 (3)	C10—H10A	0.9700
C3—H3	0.9300	C10—H10B	0.9700
C4—C5	1.371 (2)	C11—O3	1.4085 (16)
C4—C7	1.508 (2)	C11—H11A	0.9700
C5—C6	1.4094 (19)	C11—H11B	0.9700
C5—H5	0.9300	C12—O4	1.4060 (16)
C6—C8	1.4255 (18)	C12—H12A	0.9700
C7—H7A	0.9600	C12—H12B	0.9700
C7—H7B	0.9600	N1—H1	0.858 (18)
C7—H7C	0.9600	O2—H14	0.8200
C8—N1	1.2856 (16)	O3—H13	0.8200
C8—H8	0.9300	O4—H4	0.8200
O1—C1—C2	122.02 (13)	C10—C9—C12	110.25 (10)
O1—C1—C6	121.62 (12)	N1—C9—C11	107.87 (10)
C2—C1—C6	116.36 (13)	C10—C9—C11	109.93 (11)
C3—C2—C1	121.25 (15)	C12—C9—C11	110.19 (11)
C3—C2—H2	119.4	O2—C10—C9	109.24 (11)
C1—C2—H2	119.4	O2—C10—H10A	109.8
C2—C3—C4	123.19 (15)	C9—C10—H10A	109.8
C2—C3—H3	118.4	O2—C10—H10B	109.8
C4—C3—H3	118.4	C9—C10—H10B	109.8
C5—C4—C3	116.52 (15)	H10A—C10—H10B	108.3
C5—C4—C7	122.08 (16)	O3—C11—C9	108.51 (10)
C3—C4—C7	121.40 (16)	O3—C11—H11A	110.0
C4—C5—C6	122.10 (14)	C9—C11—H11A	110.0
C4—C5—H5	118.9	O3—C11—H11B	110.0
C6—C5—H5	118.9	C9—C11—H11B	110.0
C5—C6—C1	120.53 (12)	H11A—C11—H11B	108.4
C5—C6—C8	117.94 (12)	O4—C12—C9	109.49 (10)
C1—C6—C8	121.50 (12)	O4—C12—H12A	109.8
C4—C7—H7A	109.5	C9—C12—H12A	109.8
C4—C7—H7B	109.5	O4—C12—H12B	109.8
H7A—C7—H7B	109.5	C9—C12—H12B	109.8
C4—C7—H7C	109.5	H12A—C12—H12B	108.2
H7A—C7—H7C	109.5	C8—N1—C9	127.73 (11)
H7B—C7—H7C	109.5	C8—N1—H1	114.8 (10)
N1—C8—C6	123.60 (12)	C9—N1—H1	117.5 (10)
N1—C8—H8	118.2	C10—O2—H14	109.5
C6—C8—H8	118.2	C11—O3—H13	109.5
N1—C9—C10	111.90 (10)	C12—O4—H4	109.5
N1—C9—C12	106.62 (10)
O1—C1—C2—C3	178.89 (16)	C1—C6—C8—N1	3.4 (2)
C6—C1—C2—C3	−0.9 (2)	N1—C9—C10—O2	−57.33 (14)
C1—C2—C3—C4	−1.2 (3)	C12—C9—C10—O2	61.16 (15)
C2—C3—C4—C5	2.2 (3)	C11—C9—C10—O2	−177.17 (11)
C2—C3—C4—C7	−177.89 (19)	N1—C9—C11—O3	−62.87 (13)
C3—C4—C5—C6	−1.3 (2)	C10—C9—C11—O3	59.40 (14)
C7—C4—C5—C6	178.83 (16)	C12—C9—C11—O3	−178.89 (10)
C4—C5—C6—C1	−0.7 (2)	N1—C9—C12—O4	−55.27 (13)
C4—C5—C6—C8	177.23 (13)	C10—C9—C12—O4	−176.94 (11)
O1—C1—C6—C5	−178.02 (12)	C11—C9—C12—O4	61.54 (14)
C2—C1—C6—C5	1.7 (2)	C6—C8—N1—C9	−179.57 (11)
O1—C1—C6—C8	4.15 (19)	C10—C9—N1—C8	−20.27 (17)
C2—C1—C6—C8	−176.10 (13)	C12—C9—N1—C8	−140.89 (12)
C5—C6—C8—N1	−174.53 (13)	C11—C9—N1—C8	100.77 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1i	0.82	1.89	2.621 (1)	148
O3—H13···O1ii	0.82	1.86	2.679 (1)	178
O2—H14···O4iii	0.82	2.03	2.821 (1)	163
C8—H8···O3iv	0.93	2.35	3.272 (2)	171
C10—H10A···O3iv	0.97	2.58	3.379 (2)	140
N1—H1···O1	0.86 (2)	1.93 (2)	2.638 (1)	138 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O1i	0.82	1.89	2.621 (1)	148
O3—H13⋯O1ii	0.82	1.86	2.679 (1)	178
O2—H14⋯O4iii	0.82	2.03	2.821 (1)	163
C8—H8⋯O3iv	0.93	2.35	3.272 (2)	171
C10—H10A⋯O3iv	0.97	2.58	3.379 (2)	140
N1—H1⋯O1	0.86 (2)	1.93 (2)	2.638 (1)	138 (1)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .