Crystal structure of 2-hydroxy-N-(2-hydroxyethyl)-N-{2-hydroxy-3-[(E)-N-hydroxyethanimidoyl]-5-methylbenzyl}ethanaminium acetate monohydrate.

The structure of the title hydrated mol-ecular salt, C14H23N2O4 (+)·C2H3O2 (-)·H2O, was determined as part of a wider study on the use of the mol-ecule as a polydentate ligand in the synthesis of Mn(III) clusters with magnetic properties. The cation features intra-molecular O-H⋯N and N-H⋯O hydrogen-bond inter-actions. The crystal structure features a range of inter-molecular hydrogen-bonding inter-actions, principally O-H⋯O inter-actions between all three species in the asymmetric unit. An R (2) 4(8) graph-set hydrogen-bonding motif between the anion and water mol-ecules serves as a unit which links to the cation via the di-ethano-lamine group. Each O atom of the acetate anion accepts two hydrogen bonds.

Related literature

For background literature on Mn-containing single mol­ecule magnets, see: Inglis et al. (2012 ▸); Milios et al. (2007 ▸); Tasiopoulos & Perlepes (2008 ▸). For examples of the use of 3-{[bis­(2-hy­droxy­eth­yl)amino]­meth­yl}-2-hy­droxy-5-methyl­benzaldehyde in the synthesis of magnetic Mn cluster compounds, see: Sanz et al. (2014a ▸,b ▸) – mol­ecular wheels; Frost et al. (2014 ▸) – tetra­hedron cage. For examples of other magnentic oxime-containing clusters, see: Vlahopoulou et al. (2009 ▸); Stamatatos et al. (2007 ▸). For a review of pyrid­yl–oxime coordination chemistry, see: Milios et al. (2006 ▸). For the synthesis of 3-{[bis­(2-hy­droxy­eth­yl)amino]­meth­yl}-2-hy­droxy-5-methylbenzaldehyde, see: Wang et al. (2006 ▸).

Experimental

Crystal data

C14H23N2O4 +·C2H3O2 −·H2O

M = 360.40

Monoclinic,

a = 14.4338 (5) Å

b = 10.4786 (3) Å

c = 12.4045 (4) Å

β = 101.593 (3)°

V = 1837.86 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 120 K

0.48 × 0.38 × 0.18 mm

Data collection

Agilent SuperNova diffractometer

Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014 ▸) T min = 0.942, T max = 0.975

38067 measured reflections

5542 independent reflections

4362 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.129

S = 1.09

5542 reflections

338 parameters

All H-atom parameters refined

Δρmax = 0.33 e Å−3

Δρmin = −0.24 e Å−3

Data collection: CrysAlis PRO (Agilent, 2014 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015002418/hb7350sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002418/hb7350Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015002418/hb7350Isup3.cdx

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015002418/hb7350Isup4.cml

Click here for additional data file.

4 L . DOI: 10.1107/S2056989015002418/hb7350fig1.tif

The asymmetric unit of H4 L. Displacement ellipsoids are at the 50% probability level and C-bound H atoms have been omitted.

Click here for additional data file.

4 L x y z x y z x y z . DOI: 10.1107/S2056989015002418/hb7350fig2.tif

Hydrogen-bonding inter­actions, indicated by dashed lines, in the crystal structure of H4 L. Symmetry operations for equivalent atoms: $1, 1 − x, −y, 2 − z; $2, x,  − y,  + z; $3, 1 − x, − + y,  − z.

CCDC reference: 1047385

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H23N2O4+·C2H3O2−·H2O	F(000) = 776
Mr = 360.40	Dx = 1.303 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.4338 (5) Å	Cell parameters from 10187 reflections
b = 10.4786 (3) Å	θ = 3.5–30.2°
c = 12.4045 (4) Å	µ = 0.10 mm−1
β = 101.593 (3)°	T = 120 K
V = 1837.86 (10) Å3	Block, colourless
Z = 4	0.48 × 0.38 × 0.18 mm

Agilent SuperNova diffractometer	5542 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4362 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.054
Detector resolution: 5.1574 pixels mm-1	θmax = 31.1°, θmin = 3.1°
ω scans	h = −20→20
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	k = −15→13
Tmin = 0.942, Tmax = 0.975	l = −18→17
38067 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054	All H-atom parameters refined
wR(F2) = 0.129	w = 1/[σ2(Fo2) + (0.0431P)2 + 0.9291P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
5542 reflections	Δρmax = 0.33 e Å−3
338 parameters	Δρmin = −0.24 e Å−3
0 restraints

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. All H atoms were located in a difference Fourier map and refined freely.

	x	y	z	Uiso*/Ueq
O1	0.25286 (7)	−0.10957 (10)	0.65849 (9)	0.0229 (2)
H1	0.2395 (15)	−0.050 (2)	0.6990 (18)	0.046 (6)*
O2	0.14106 (9)	0.14279 (11)	0.81376 (9)	0.0320 (3)
H2	0.2011 (17)	0.160 (2)	0.8484 (19)	0.054 (7)*
O3	0.24215 (8)	0.03539 (12)	0.40801 (10)	0.0304 (3)
H3	0.2659 (18)	0.107 (3)	0.418 (2)	0.060 (7)*
O4	0.45674 (8)	−0.04092 (11)	0.61916 (10)	0.0300 (3)
H4	0.4552 (16)	−0.026 (2)	0.686 (2)	0.055 (7)*
N1	0.15152 (9)	0.03976 (12)	0.74689 (10)	0.0232 (3)
N2	0.32127 (9)	−0.19342 (12)	0.47375 (10)	0.0220 (3)
H2A	0.3117 (13)	−0.1223 (18)	0.5112 (15)	0.028 (5)*
C1	0.16920 (10)	−0.16143 (13)	0.60648 (11)	0.0202 (3)
C2	0.17518 (10)	−0.26194 (13)	0.53438 (12)	0.0223 (3)
C3	0.09294 (11)	−0.32024 (14)	0.47871 (12)	0.0246 (3)
H3A	0.0993 (13)	−0.3890 (18)	0.4276 (15)	0.029 (5)*
C4	0.00394 (11)	−0.27997 (14)	0.49290 (12)	0.0243 (3)
C5	−0.00027 (10)	−0.17826 (14)	0.56389 (11)	0.0213 (3)
H5	−0.0609 (13)	−0.1492 (17)	0.5733 (14)	0.024 (4)*
C6	0.08079 (10)	−0.11679 (13)	0.62184 (11)	0.0192 (3)
C7	0.07274 (10)	−0.00789 (14)	0.69504 (11)	0.0203 (3)
C8	−0.02208 (11)	0.04239 (17)	0.70539 (14)	0.0264 (3)
H8A	−0.0567 (16)	0.073 (2)	0.638 (2)	0.053 (6)*
H8B	−0.0153 (17)	0.104 (2)	0.757 (2)	0.058 (7)*
H8C	−0.0601 (16)	−0.026 (2)	0.7244 (18)	0.052 (6)*
C9	−0.08552 (13)	−0.34031 (18)	0.43012 (14)	0.0323 (4)
H9A	−0.1036 (15)	−0.305 (2)	0.3569 (18)	0.042 (6)*
H9B	−0.1359 (18)	−0.334 (2)	0.474 (2)	0.063 (7)*
H9C	−0.0770 (15)	−0.429 (2)	0.4181 (18)	0.048 (6)*
C10	0.27174 (11)	−0.30209 (14)	0.51927 (14)	0.0261 (3)
H10A	0.2691 (13)	−0.3701 (19)	0.4675 (16)	0.032 (5)*
H10B	0.3144 (13)	−0.3244 (17)	0.5908 (15)	0.027 (5)*
C11	0.27852 (12)	−0.16896 (15)	0.35473 (12)	0.0259 (3)
H11A	0.2117 (13)	−0.1940 (17)	0.3425 (14)	0.024 (4)*
H11B	0.3108 (13)	−0.2206 (19)	0.3119 (15)	0.032 (5)*
C12	0.28636 (12)	−0.02870 (16)	0.33149 (13)	0.0294 (3)
H12A	0.3503 (14)	−0.0019 (18)	0.3386 (15)	0.032 (5)*
H12B	0.2514 (13)	−0.0128 (18)	0.2536 (15)	0.030 (5)*
C13	0.42648 (11)	−0.21255 (17)	0.49313 (14)	0.0288 (3)
H13A	0.4494 (12)	−0.1530 (17)	0.4413 (14)	0.025 (4)*
H13B	0.4385 (12)	−0.3021 (18)	0.4792 (14)	0.027 (4)*
C14	0.47242 (12)	−0.17376 (17)	0.60884 (14)	0.0298 (3)
H14A	0.5399 (14)	−0.1927 (18)	0.6200 (15)	0.034 (5)*
H14B	0.4445 (13)	−0.2225 (18)	0.6635 (15)	0.030 (5)*
O5	0.30047 (8)	0.22604 (11)	0.92796 (9)	0.0297 (3)
O6	0.38120 (9)	0.06607 (11)	1.01687 (10)	0.0349 (3)
C15	0.34399 (10)	0.17389 (14)	1.01535 (13)	0.0242 (3)
C16	0.35169 (15)	0.24691 (19)	1.12192 (15)	0.0347 (4)
H16A	0.409 (2)	0.234 (3)	1.167 (3)	0.098 (11)*
H16B	0.348 (2)	0.337 (3)	1.110 (3)	0.101 (11)*
H16C	0.307 (2)	0.221 (3)	1.162 (3)	0.108 (12)*
O7	0.46060 (14)	0.00383 (17)	0.83335 (12)	0.0569 (5)
H7A	0.4274 (18)	0.028 (3)	0.873 (2)	0.059 (8)*
H7B	0.5160 (19)	−0.016 (3)	0.875 (2)	0.064 (8)*

	U11	U22	U33	U12	U13	U23
O1	0.0198 (5)	0.0238 (5)	0.0247 (5)	0.0018 (4)	0.0037 (4)	−0.0027 (4)
O2	0.0276 (6)	0.0354 (6)	0.0320 (6)	0.0025 (5)	0.0035 (5)	−0.0167 (5)
O3	0.0300 (6)	0.0243 (6)	0.0361 (6)	−0.0018 (5)	0.0048 (5)	−0.0022 (5)
O4	0.0306 (6)	0.0328 (6)	0.0282 (6)	0.0025 (5)	0.0099 (5)	−0.0019 (5)
N1	0.0251 (6)	0.0229 (6)	0.0216 (6)	0.0016 (5)	0.0051 (5)	−0.0044 (5)
N2	0.0225 (6)	0.0208 (6)	0.0233 (6)	0.0035 (5)	0.0062 (5)	−0.0030 (5)
C1	0.0223 (7)	0.0177 (6)	0.0208 (6)	0.0002 (5)	0.0046 (5)	0.0031 (5)
C2	0.0268 (7)	0.0167 (6)	0.0251 (7)	0.0020 (5)	0.0096 (6)	0.0036 (5)
C3	0.0343 (8)	0.0166 (6)	0.0247 (7)	−0.0023 (6)	0.0098 (6)	0.0001 (5)
C4	0.0291 (8)	0.0232 (7)	0.0218 (6)	−0.0063 (6)	0.0077 (6)	0.0005 (5)
C5	0.0214 (7)	0.0226 (7)	0.0208 (6)	−0.0016 (5)	0.0070 (5)	0.0025 (5)
C6	0.0223 (7)	0.0180 (6)	0.0178 (6)	−0.0002 (5)	0.0053 (5)	0.0029 (5)
C7	0.0223 (7)	0.0218 (7)	0.0177 (6)	0.0008 (5)	0.0061 (5)	0.0017 (5)
C8	0.0227 (8)	0.0304 (8)	0.0271 (7)	0.0018 (6)	0.0075 (6)	−0.0024 (6)
C9	0.0333 (9)	0.0343 (9)	0.0303 (8)	−0.0124 (7)	0.0085 (7)	−0.0093 (7)
C10	0.0301 (8)	0.0185 (7)	0.0312 (8)	0.0048 (6)	0.0097 (6)	0.0005 (6)
C11	0.0294 (8)	0.0282 (8)	0.0204 (6)	−0.0018 (6)	0.0057 (6)	−0.0049 (6)
C12	0.0313 (9)	0.0310 (8)	0.0251 (7)	−0.0038 (6)	0.0039 (6)	0.0016 (6)
C13	0.0217 (8)	0.0337 (9)	0.0326 (8)	0.0081 (6)	0.0091 (6)	−0.0046 (7)
C14	0.0224 (8)	0.0337 (9)	0.0331 (8)	0.0074 (6)	0.0050 (6)	−0.0006 (7)
O5	0.0302 (6)	0.0252 (6)	0.0310 (6)	−0.0027 (4)	−0.0003 (5)	0.0003 (4)
O6	0.0394 (7)	0.0216 (6)	0.0417 (7)	0.0006 (5)	0.0032 (5)	−0.0002 (5)
C15	0.0192 (7)	0.0219 (7)	0.0311 (7)	−0.0064 (5)	0.0043 (6)	−0.0005 (6)
C16	0.0391 (10)	0.0332 (9)	0.0309 (8)	−0.0034 (7)	0.0044 (7)	−0.0042 (7)
O7	0.0679 (11)	0.0706 (11)	0.0285 (7)	0.0369 (9)	0.0011 (7)	−0.0062 (7)

O1—H1	0.85 (2)	C8—H8B	0.91 (3)
O1—C1	1.3625 (17)	C8—H8C	0.96 (2)
O2—H2	0.91 (2)	C9—H9A	0.97 (2)
O2—N1	1.3880 (16)	C9—H9B	0.99 (3)
O3—H3	0.82 (3)	C9—H9C	0.96 (2)
O3—C12	1.415 (2)	C10—H10A	0.95 (2)
O4—H4	0.85 (2)	C10—H10B	1.001 (18)
O4—C14	1.420 (2)	C11—H11A	0.982 (18)
N1—C7	1.2891 (19)	C11—H11B	0.94 (2)
N2—H2A	0.903 (19)	C11—C12	1.506 (2)
N2—C10	1.513 (2)	C12—H12A	0.952 (19)
N2—C11	1.5034 (19)	C12—H12B	1.009 (18)
N2—C13	1.503 (2)	C13—H13A	0.999 (18)
C1—C2	1.396 (2)	C13—H13B	0.976 (19)
C1—C6	1.408 (2)	C13—C14	1.511 (2)
C2—C3	1.389 (2)	C14—H14A	0.98 (2)
C2—C10	1.503 (2)	C14—H14B	0.996 (19)
C3—H3A	0.976 (19)	O5—C15	1.2628 (18)
C3—C4	1.396 (2)	O6—C15	1.2495 (19)
C4—C5	1.392 (2)	C15—C16	1.512 (2)
C4—C9	1.506 (2)	C16—H16A	0.91 (3)
C5—H5	0.955 (18)	C16—H16B	0.96 (4)
C5—C6	1.401 (2)	C16—H16C	0.92 (4)
C6—C7	1.4773 (19)	O7—H7A	0.79 (3)
C7—C8	1.496 (2)	O7—H7B	0.89 (3)
C8—H8A	0.95 (2)
C1—O1—H1	106.8 (15)	H9A—C9—H9C	104.1 (18)
N1—O2—H2	103.4 (15)	H9B—C9—H9C	106 (2)
C12—O3—H3	107.3 (18)	N2—C10—H10A	105.6 (11)
C14—O4—H4	107.4 (17)	N2—C10—H10B	104.7 (10)
C7—N1—O2	114.11 (12)	C2—C10—N2	110.81 (12)
C10—N2—H2A	107.2 (12)	C2—C10—H10A	112.3 (11)
C11—N2—H2A	106.8 (11)	C2—C10—H10B	112.1 (10)
C11—N2—C10	111.31 (12)	H10A—C10—H10B	110.8 (15)
C13—N2—H2A	106.4 (11)	N2—C11—H11A	107.6 (10)
C13—N2—C10	112.21 (12)	N2—C11—H11B	107.6 (11)
C13—N2—C11	112.46 (12)	N2—C11—C12	108.81 (12)
O1—C1—C2	116.19 (13)	H11A—C11—H11B	109.9 (15)
O1—C1—C6	123.00 (13)	C12—C11—H11A	109.9 (10)
C2—C1—C6	120.80 (13)	C12—C11—H11B	112.7 (12)
C1—C2—C10	118.00 (13)	O3—C12—C11	105.86 (13)
C3—C2—C1	119.59 (14)	O3—C12—H12A	111.0 (11)
C3—C2—C10	122.41 (13)	O3—C12—H12B	111.0 (10)
C2—C3—H3A	117.7 (11)	C11—C12—H12A	112.2 (12)
C2—C3—C4	121.35 (14)	C11—C12—H12B	107.6 (11)
C4—C3—H3A	120.9 (11)	H12A—C12—H12B	109.2 (15)
C3—C4—C9	121.51 (14)	N2—C13—H13A	105.6 (10)
C5—C4—C3	118.00 (14)	N2—C13—H13B	108.1 (10)
C5—C4—C9	120.44 (15)	N2—C13—C14	110.65 (12)
C4—C5—H5	118.6 (11)	H13A—C13—H13B	113.1 (15)
C4—C5—C6	122.59 (14)	C14—C13—H13A	107.7 (10)
C6—C5—H5	118.8 (11)	C14—C13—H13B	111.5 (10)
C1—C6—C7	121.69 (13)	O4—C14—C13	107.57 (13)
C5—C6—C1	117.66 (13)	O4—C14—H14A	111.1 (12)
C5—C6—C7	120.65 (13)	O4—C14—H14B	110.4 (11)
N1—C7—C6	115.82 (13)	C13—C14—H14A	108.3 (11)
N1—C7—C8	123.45 (13)	C13—C14—H14B	110.4 (11)
C6—C7—C8	120.73 (13)	H14A—C14—H14B	109.1 (15)
C7—C8—H8A	112.0 (14)	O5—C15—C16	117.90 (14)
C7—C8—H8B	110.1 (15)	O6—C15—O5	122.85 (15)
C7—C8—H8C	109.7 (14)	O6—C15—C16	119.25 (15)
H8A—C8—H8B	110 (2)	C15—C16—H16A	111 (2)
H8A—C8—H8C	104.4 (19)	C15—C16—H16B	112 (2)
H8B—C8—H8C	110 (2)	C15—C16—H16C	113 (2)
C4—C9—H9A	111.6 (13)	H16A—C16—H16B	105 (3)
C4—C9—H9B	109.7 (14)	H16A—C16—H16C	106 (3)
C4—C9—H9C	111.5 (13)	H16B—C16—H16C	111 (3)
H9A—C9—H9B	113.5 (19)	H7A—O7—H7B	107 (2)
O1—C1—C2—C3	179.65 (12)	C3—C2—C10—N2	118.43 (15)
O1—C1—C2—C10	−0.96 (19)	C3—C4—C5—C6	−0.8 (2)
O1—C1—C6—C5	−179.83 (12)	C4—C5—C6—C1	−0.1 (2)
O1—C1—C6—C7	1.0 (2)	C4—C5—C6—C7	179.07 (13)
O2—N1—C7—C6	179.25 (11)	C5—C6—C7—N1	178.18 (13)
O2—N1—C7—C8	−0.1 (2)	C5—C6—C7—C8	−2.5 (2)
N2—C11—C12—O3	−55.59 (16)	C6—C1—C2—C3	−1.3 (2)
N2—C13—C14—O4	−63.57 (17)	C6—C1—C2—C10	178.13 (13)
C1—C2—C3—C4	0.3 (2)	C9—C4—C5—C6	−178.27 (14)
C1—C2—C10—N2	−60.94 (17)	C10—N2—C11—C12	148.01 (13)
C1—C6—C7—N1	−2.68 (19)	C10—N2—C13—C14	−81.01 (16)
C1—C6—C7—C8	176.67 (13)	C10—C2—C3—C4	−179.04 (14)
C2—C1—C6—C5	1.1 (2)	C11—N2—C10—C2	−72.47 (15)
C2—C1—C6—C7	−178.03 (12)	C11—N2—C13—C14	152.57 (14)
C2—C3—C4—C5	0.7 (2)	C13—N2—C10—C2	160.50 (12)
C2—C3—C4—C9	178.13 (14)	C13—N2—C11—C12	−85.09 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.85 (2)	1.78 (2)	2.5368 (16)	148 (2)
O2—H2···O5	0.91 (2)	1.71 (2)	2.5985 (16)	165 (2)
O3—H3···O5i	0.82 (3)	1.82 (3)	2.6335 (17)	171 (3)
O4—H4···O7	0.85 (2)	1.84 (2)	2.6875 (19)	176 (2)
N2—H2A···O1	0.903 (19)	2.168 (18)	2.8121 (16)	127.6 (15)
O7—H7A···O6	0.79 (3)	2.07 (3)	2.823 (2)	159 (3)
O7—H7B···O6ii	0.89 (3)	1.86 (3)	2.738 (2)	169 (2)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1H1N1	0.85(2)	1.78(2)	2.5368(16)	148(2)
O2H2O5	0.91(2)	1.71(2)	2.5985(16)	165(2)
O3H3O5i	0.82(3)	1.82(3)	2.6335(17)	171(3)
O4H4O7	0.85(2)	1.84(2)	2.6875(19)	176(2)
N2H2AO1	0.903(19)	2.168(18)	2.8121(16)	127.6(15)
O7H7AO6	0.79(3)	2.07(3)	2.823(2)	159(3)
O7H7BO6ii	0.89(3)	1.86(3)	2.738(2)	169(2)

Symmetry codes: (i) ; (ii) .