N—H...O hydrogen bonding in the adduct of N-(2-amino­ethyl)-2-hydroxy­benz­amide with picric acid

The title adduct N-(2-ammonioethyl)-2-hydroxy­benz­amide picrate, C₉H₁₃N₂O₂⁺·C₆H₂N₃O₇⁻, contains an asymmetric N—H...O hydrogen bonds involving one N and three O atoms. The unit-cell packing is influenced by a network of intermolecular hydrogen bonds and π–π stacking of the aromatic rings.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.052
• wR factor = 0.142
• Data-to-parameter ratio = 11.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_737  Alert C D...A   Calc    3.035(4), Rep  3.0350(10) ....       4.00 su-Ratio
                     N2   -O9      1.555   2.656


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

Schiff bases are important ligands in coordination chemistry because they have applications in catalysis, medicine and magnetism, and they show biological activity (Vigato & Fenton, 1987; Yao et al., 2000). The amido group (HN—C═O) also has special biological activity and there are analogies between the amide and the Schiff bases. By combining a Schiff base and an amide in one reaction, Yao Ke-Min and co-workers suggested that the differences N properties could lead to some mixed or polymeric Schiff bases (Wu et al., 2001). Therefore, we selected N-(2-aminoethyl)-2-hydroxybenzamide for the synthesis of this type of amine. Because we could not find the KU-2 cation-exchange resin (Isagulyants et al., 1972), and the inconvenience of chromatography (Kutz et al., 1996), we made use of the amine salt formed by the amine–acid to purify the complex.

The crystal structure of the title compound, (I), showed it to be a 1:1 adduct. A plot of this adduct is shown in Fig. 1. The two aromatic rings are approximately perpendicular to one another (dihedral angle between corresponding mean planes is ca 75.9°). There are two intramolecular hydrogen bonds in the N-(2-aminioethyl)-2-hydroxybenzamide fragment, viz. O1—H1···O2 at 2.618 (3) Å and N2—H2C···O2 at 3.045 (40) Å. A difference map showed that the H atom in the hydrogen bond between phenoxy atom O3 and amino atom N2 was localized on the N atom, indicating that the N atom is positively charged and the O atom negatively charged. The connection between the acid and salicylamide moiety is completed by four additional N—H···O hydrogen bonds. Geometric parameters for the hydrogen bonds, including two C—H···O bonds, are presented in Table 1.

In the crystal, the benzene rings of N-(2-aminioethyl)-2-hydroxybenzamide are interlaced with the benzene rings of picric acid, to form columns along the a,b axis. This is illustrated in the packing diagram seen in Fig. 2. The interplanar distances between adjacent rings are about 2.96 and 3.36 Å, respectively. Each benzene ring is linked by N—H···O interactions to two adjacent nearly perpendicular aromatic ring columns related by a translation along c to give the appearance of a zigzag chain. The chains interact through N—H···O and C—H···O interactions to complete a three-dimensional network of adducts.

S2. Experimental

Salicylate (1.5 g, 10 mmol) was dissolved in neat ethylenediamine (3.0 g, 50 mmol) and refluxed for 4 h. The solution was concentrated under vacuum yielding a light-brown oil. The oil was dissolved in 20 ml e thanol and added dropwise to a same solution (20 ml) of 2,4,6-trinitrophenol (2.3 g, 10 mmol). The resulting solution was refluxed for 1 h and concentrated to 20 ml. The mixture was filtered hot. The filtrate was then kept at room temperature and yellow crystals were obtained. Analysis calculated for C₁₅H₁₅N₅O₉: C 44.01, H 3.70, N 17.11; found: C 43.70, H 3.88, N 17.00%.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of the adduct with the atom-numbering scheme and 30% displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. View of the crystal packing of N-(2-aminioethyl)-2-hydroxybenzamide picrate down the a axis.

N-(2-aminoethyl)-2-hydroxybenzamide picrate

Crystal data

C15H15N5O9	F(000) = 848
Mr = 409.32	Dx = 1.518 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.761 (3) Å	Cell parameters from 27 reflections
b = 8.005 (2) Å	θ = 3.0–13.2°
c = 17.744 (6) Å	µ = 0.13 mm^−1
β = 98.84 (3)°	T = 295 K
V = 1790.9 (8) Å^3	Monoclinic, yellow
Z = 4	0.56 × 0.44 × 0.40 mm

Data collection

Siemens P4 diffractometer	Rint = 0.020
Radiation source: normal-focus sealed tube	θmax = 25.0°, θmin = 1.8°
Graphite monochromator	h = 0→15
ω scans	k = 0→9
3305 measured reflections	l = −21→20
3154 independent reflections	3 standard reflections every 97 reflections
1801 reflections with I > 2σ(I)	intensity decay: 2.8%

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-atom parameters constrained
wR(F^2) = 0.142	w = 1/[σ^2(Fo^2) + (0.074P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max < 0.001
3154 reflections	Δρmax = 0.31 e Å^−3
265 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0056 (13)

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
O1	0.8080 (2)	−0.0748 (3)	0.51533 (13)	0.0763 (7)
H1	0.8005	−0.0641	0.5602	0.092*
O2	0.71836 (17)	0.0335 (3)	0.62923 (11)	0.0572 (6)
N1	0.5678 (2)	0.1805 (3)	0.60658 (13)	0.0510 (7)
H1N	0.5228	0.2311	0.5732	0.061*
N2	0.7215 (2)	0.2678 (3)	0.76478 (12)	0.0522 (7)
H2A	0.7193	0.1723	0.7902	0.063*
H2B	0.7517	0.3465	0.7963	0.063*
H2C	0.7591	0.2534	0.7270	0.063*
C1	0.7334 (3)	0.0136 (4)	0.47126 (17)	0.0529 (8)
C2	0.7383 (3)	0.0134 (4)	0.39318 (19)	0.0675 (10)
H2	0.7895	−0.0501	0.3743	0.081*
C3	0.6682 (3)	0.1062 (5)	0.34464 (19)	0.0707 (10)
H3	0.6725	0.1071	0.2928	0.085*
C4	0.5914 (3)	0.1980 (5)	0.37166 (18)	0.0689 (10)
H4	0.5445	0.2622	0.3382	0.083*
C5	0.5833 (3)	0.1959 (4)	0.44750 (16)	0.0560 (8)
H5	0.5300	0.2571	0.4650	0.067*
C6	0.6546 (2)	0.1026 (3)	0.49972 (14)	0.0419 (7)
C7	0.6480 (2)	0.1033 (3)	0.58249 (15)	0.0416 (7)
C8	0.5506 (2)	0.1855 (4)	0.68561 (16)	0.0563 (8)
H8A	0.5698	0.0779	0.7089	0.068*
H8B	0.4756	0.2025	0.6867	0.068*
C9	0.6122 (3)	0.3197 (4)	0.73289 (17)	0.0582 (9)
H9A	0.6155	0.4182	0.7015	0.070*
H9B	0.5746	0.3499	0.7745	0.070*
O3	0.69062 (17)	−0.0284 (2)	0.84008 (10)	0.0532 (6)
O4	0.8397 (2)	0.1505 (4)	0.92114 (14)	0.0921 (9)
O5	0.8655 (2)	0.1248 (3)	1.04270 (14)	0.0809 (8)
O6	0.6136 (3)	−0.1328 (4)	1.17567 (14)	0.1018 (10)
O7	0.4992 (3)	−0.2975 (5)	1.11658 (15)	0.1290 (14)
O8	0.4262 (2)	−0.2668 (4)	0.83869 (14)	0.0969 (10)
O9	0.5702 (2)	−0.2983 (3)	0.79256 (13)	0.0733 (7)
N3	0.8138 (2)	0.0951 (3)	0.98020 (16)	0.0571 (7)
N4	0.5694 (3)	−0.1959 (4)	1.11798 (17)	0.0727 (9)
N5	0.5229 (2)	−0.2530 (3)	0.84301 (14)	0.0557 (7)
C10	0.6675 (2)	−0.0667 (3)	0.90373 (14)	0.0397 (7)
C11	0.7197 (2)	−0.0069 (3)	0.97670 (15)	0.0415 (7)
C12	0.6879 (2)	−0.0472 (4)	1.04454 (15)	0.0482 (8)
H12	0.7242	−0.0044	1.0899	0.058*
C13	0.6025 (2)	−0.1510 (4)	1.04568 (15)	0.0484 (8)
C14	0.5481 (2)	−0.2175 (4)	0.97948 (16)	0.0497 (8)
H14	0.4905	−0.2881	0.9807	0.060*
C15	0.5807 (2)	−0.1771 (3)	0.91208 (14)	0.0423 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0764 (17)	0.0796 (18)	0.0709 (15)	0.0281 (14)	0.0048 (14)	0.0033 (14)
O2	0.0648 (15)	0.0568 (13)	0.0450 (11)	0.0143 (12)	−0.0073 (10)	0.0069 (10)
N1	0.0544 (16)	0.0581 (16)	0.0391 (13)	0.0065 (14)	0.0029 (11)	0.0021 (12)
N2	0.079 (2)	0.0457 (15)	0.0312 (12)	−0.0167 (14)	0.0073 (12)	−0.0031 (10)
C1	0.054 (2)	0.0481 (18)	0.0539 (19)	0.0038 (17)	−0.0016 (15)	−0.0049 (15)
C2	0.068 (2)	0.075 (2)	0.063 (2)	0.004 (2)	0.0197 (18)	−0.0168 (19)
C3	0.087 (3)	0.081 (3)	0.0410 (18)	−0.010 (2)	0.0013 (19)	−0.0100 (18)
C4	0.074 (2)	0.081 (2)	0.0451 (19)	0.006 (2)	−0.0094 (17)	0.0027 (18)
C5	0.061 (2)	0.060 (2)	0.0424 (17)	0.0008 (17)	−0.0066 (15)	0.0011 (15)
C6	0.0446 (17)	0.0392 (16)	0.0393 (15)	−0.0018 (14)	−0.0023 (13)	−0.0042 (13)
C7	0.0497 (18)	0.0322 (15)	0.0397 (15)	−0.0032 (14)	−0.0033 (14)	−0.0001 (13)
C8	0.0534 (19)	0.067 (2)	0.0513 (18)	−0.0085 (17)	0.0162 (15)	−0.0011 (16)
C9	0.084 (3)	0.0462 (19)	0.0497 (18)	−0.0013 (18)	0.0263 (17)	−0.0036 (15)
O3	0.0784 (15)	0.0446 (12)	0.0402 (11)	−0.0090 (11)	0.0204 (10)	0.0006 (9)
O4	0.0848 (19)	0.126 (2)	0.0659 (16)	−0.0506 (17)	0.0144 (14)	0.0073 (16)
O5	0.0853 (18)	0.0812 (18)	0.0679 (16)	−0.0286 (15)	−0.0145 (14)	0.0001 (13)
O6	0.153 (3)	0.117 (2)	0.0392 (14)	−0.017 (2)	0.0273 (16)	−0.0098 (15)
O7	0.121 (3)	0.206 (4)	0.0659 (18)	−0.069 (3)	0.0318 (17)	0.024 (2)
O8	0.0717 (19)	0.145 (3)	0.0702 (16)	−0.0466 (18)	−0.0006 (14)	0.0057 (16)
O9	0.0835 (18)	0.0843 (18)	0.0493 (13)	−0.0027 (14)	0.0018 (13)	−0.0190 (12)
N3	0.0628 (18)	0.0525 (16)	0.0533 (16)	−0.0080 (14)	0.0003 (14)	−0.0026 (14)
N4	0.081 (2)	0.093 (2)	0.0482 (18)	−0.002 (2)	0.0222 (16)	0.0105 (17)
N5	0.0615 (19)	0.0600 (18)	0.0429 (15)	−0.0146 (14)	−0.0011 (14)	0.0102 (13)
C10	0.0519 (18)	0.0316 (15)	0.0366 (15)	0.0059 (14)	0.0099 (13)	0.0037 (12)
C11	0.0484 (18)	0.0342 (15)	0.0427 (16)	−0.0015 (14)	0.0096 (13)	−0.0022 (12)
C12	0.058 (2)	0.0491 (18)	0.0365 (16)	0.0096 (16)	0.0026 (14)	−0.0046 (13)
C13	0.0539 (19)	0.060 (2)	0.0341 (15)	0.0080 (17)	0.0137 (14)	0.0057 (14)
C14	0.0488 (18)	0.0530 (19)	0.0476 (17)	−0.0024 (15)	0.0088 (14)	0.0101 (14)
C15	0.0477 (17)	0.0410 (16)	0.0365 (15)	0.0003 (14)	0.0015 (12)	0.0052 (13)

Geometric parameters (Å, º)

O1—C1	1.337 (4)	C8—H8A	0.9700
O1—H1	0.8200	C8—H8B	0.9700
O2—C7	1.256 (3)	C9—H9A	0.9700
N1—C7	1.321 (4)	C9—H9B	0.9700
N1—C8	1.453 (3)	O3—C10	1.249 (3)
N1—H1N	0.8600	O4—N3	1.229 (3)
N2—C9	1.482 (4)	O5—N3	1.223 (3)
N2—H2A	0.8900	O6—N4	1.201 (4)
N2—H2B	0.8900	O7—N4	1.207 (4)
N2—H2C	0.8900	O8—N5	1.229 (3)
C1—C6	1.390 (4)	O9—N5	1.209 (3)
C1—C2	1.397 (4)	N3—C11	1.446 (4)
C2—C3	1.363 (5)	N4—C13	1.456 (4)
C2—H2	0.9300	N5—C15	1.462 (4)
C3—C4	1.370 (5)	C10—C15	1.442 (4)
C3—H3	0.9300	C10—C11	1.444 (4)
C4—C5	1.365 (4)	C11—C12	1.366 (4)
C4—H4	0.9300	C12—C13	1.374 (4)
C5—C6	1.409 (4)	C12—H12	0.9300
C5—H5	0.9300	C13—C14	1.376 (4)
C6—C7	1.484 (4)	C14—C15	1.364 (4)
C8—C9	1.508 (4)	C14—H14	0.9300
C1—O1—H1	109.5	C9—C8—H8B	108.7
C7—N1—C8	124.4 (3)	H8A—C8—H8B	107.6
C7—N1—H1N	117.8	N2—C9—C8	113.1 (3)
C8—N1—H1N	117.8	N2—C9—H9A	109.0
C9—N2—H2A	109.5	C8—C9—H9A	109.0
C9—N2—H2B	109.5	N2—C9—H9B	109.0
H2A—N2—H2B	109.5	C8—C9—H9B	109.0
C9—N2—H2C	109.5	H9A—C9—H9B	107.8
H2A—N2—H2C	109.5	O5—N3—O4	121.7 (3)
H2B—N2—H2C	109.5	O5—N3—C11	118.5 (3)
O1—C1—C6	123.3 (3)	O4—N3—C11	119.8 (3)
O1—C1—C2	116.3 (3)	O6—N4—O7	123.4 (3)
C6—C1—C2	120.4 (3)	O6—N4—C13	119.0 (3)
C3—C2—C1	120.1 (3)	O7—N4—C13	117.6 (3)
C3—C2—H2	120.0	O9—N5—O8	122.5 (3)
C1—C2—H2	120.0	O9—N5—C15	120.0 (3)
C2—C3—C4	120.5 (3)	O8—N5—C15	117.5 (3)
C2—C3—H3	119.8	O3—C10—C15	122.4 (2)
C4—C3—H3	119.8	O3—C10—C11	126.1 (3)
C5—C4—C3	120.3 (3)	C15—C10—C11	111.5 (2)
C5—C4—H4	119.9	C12—C11—C10	123.6 (3)
C3—C4—H4	119.9	C12—C11—N3	116.9 (3)
C4—C5—C6	121.1 (3)	C10—C11—N3	119.4 (2)
C4—C5—H5	119.4	C11—C12—C13	120.0 (3)
C6—C5—H5	119.4	C11—C12—H12	120.0
C1—C6—C5	117.6 (3)	C13—C12—H12	120.0
C1—C6—C7	121.1 (3)	C12—C13—C14	121.2 (3)
C5—C6—C7	121.3 (3)	C12—C13—N4	120.0 (3)
O2—C7—N1	120.3 (3)	C14—C13—N4	118.7 (3)
O2—C7—C6	120.6 (3)	C15—C14—C13	118.4 (3)
N1—C7—C6	119.1 (3)	C15—C14—H14	120.8
N1—C8—C9	114.4 (2)	C13—C14—H14	120.8
N1—C8—H8A	108.7	C14—C15—C10	125.3 (3)
C9—C8—H8A	108.7	C14—C15—N5	117.0 (3)
N1—C8—H8B	108.7	C10—C15—N5	117.7 (2)
O1—C1—C2—C3	−177.1 (3)	O4—N3—C11—C12	−172.1 (3)
C6—C1—C2—C3	2.6 (5)	O5—N3—C11—C10	−169.8 (3)
C1—C2—C3—C4	−1.0 (6)	O4—N3—C11—C10	10.7 (4)
C2—C3—C4—C5	−0.9 (6)	C10—C11—C12—C13	0.5 (4)
C3—C4—C5—C6	1.3 (5)	N3—C11—C12—C13	−176.5 (3)
O1—C1—C6—C5	177.5 (3)	C11—C12—C13—C14	0.6 (4)
C2—C1—C6—C5	−2.2 (4)	C11—C12—C13—N4	179.2 (3)
O1—C1—C6—C7	−0.5 (5)	O6—N4—C13—C12	4.6 (5)
C2—C1—C6—C7	179.7 (3)	O7—N4—C13—C12	−174.3 (3)
C4—C5—C6—C1	0.3 (5)	O6—N4—C13—C14	−176.8 (3)
C4—C5—C6—C7	178.4 (3)	O7—N4—C13—C14	4.2 (5)
C8—N1—C7—O2	−3.0 (4)	C12—C13—C14—C15	−0.3 (4)
C8—N1—C7—C6	177.9 (3)	N4—C13—C14—C15	−178.9 (3)
C1—C6—C7—O2	5.3 (4)	C13—C14—C15—C10	−1.2 (5)
C5—C6—C7—O2	−172.7 (3)	C13—C14—C15—N5	178.6 (3)
C1—C6—C7—N1	−175.6 (3)	O3—C10—C15—C14	−176.6 (3)
C5—C6—C7—N1	6.4 (4)	C11—C10—C15—C14	2.1 (4)
C7—N1—C8—C9	83.6 (4)	O3—C10—C15—N5	3.6 (4)
N1—C8—C9—N2	−84.9 (3)	C11—C10—C15—N5	−177.6 (2)
O3—C10—C11—C12	176.9 (3)	O9—N5—C15—C14	−141.6 (3)
C15—C10—C11—C12	−1.8 (4)	O8—N5—C15—C14	38.9 (4)
O3—C10—C11—N3	−6.1 (4)	O9—N5—C15—C10	38.1 (4)
C15—C10—C11—N3	175.2 (2)	O8—N5—C15—C10	−141.3 (3)
O5—N3—C11—C12	7.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.90	2.618 (3)	146
N2—H2B···O2^i	0.89	1.99	2.865 (3)	165
N2—H2A···O3	0.89	1.90	2.779 (3)	171
N1—H1N···O5^ii	0.86	2.31	3.078 (8)	150
N2—H2A···O4	0.89	2.59	3.093 (2)	117
N2—H2C···O2	0.89	2.47	3.045 (4)	123
N2—H2C···O3^i	0.89	2.26	2.832 (4)	122
N2—H2C···O9^i	0.89	2.30	3.035 (1)	141
C2—H2···O8^iii	0.93	2.44	3.360 (6)	174
C4—H4···O9^iv	0.93	2.56	3.397 (2)	150
C5—H5···O4^ii	0.93	2.54	3.308 (6)	140
C9—H9B···O7^v	0.97	2.31	3.217 (7)	154

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y−1/2, z−1/2; (iv) −x+1, −y, −z+1; (v) −x+1, −y, −z+2.