N,N′,N′′-Tris(2-nitro­benz­yl)-2,2′,2′′-nitrilo­triethan­aminium trichloride 1.41-hydrate

Elizondo, P.; Bernès, S.; Nájera, B.; Góngora, F.

doi:10.1107/S1600536809022399

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages o1616-o1617

doi:10.1107/S1600536809022399

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N,N′,N′′-Tris(2-nitrobenzyl)-2,2′,2′′-nitrilotriethanaminium trichloride 1.41-hydrate

Perla Elizondo,^a ^* Sylvain Bernès,^a Blanca Nájera ^a and Francisco Góngora ^a

^aDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, NL, Mexico
^*Correspondence e-mail: sylvain_bernes@Hotmail.com

(Received 17 February 2009; accepted 11 June 2009; online 20 June 2009)

The title compound, C₂₇H₃₆N₇O₆³⁺·3Cl⁻1.41H₂O, is the hydrochloride of a tripodal amine, and was structurally characterized because the free base, used as a ligand in podate complexes, is an oily material. In the cation, the secondary amine groups are protonated, and, despite the induced Coulombic repulsions, a claw-like conformation is stabilized, with a cavity approximating C₃ point symmetry. Such a topology, with the lone pair of the tertiary N atom placed inside the cavity, allows the encapsulation of guest species. Indeed, three chloride counter-ions balance the charges, one of which is located inside the cation cavity and is strongly bonded to the NH₂⁺ groups. The asymmetric unit is completed by two water molecules with occupancies 0.793 (11) and 0.621 (9). The crystal structure is formed by a complex network of efficient N—H⋯Cl and O—H⋯Cl hydrogen bonds. One nitro group also forms weak contacts with a water molecule.

Related literature

For related tripodal amine structures, see: Hossain et al. (2004 ); Coyle et al. (2006 ); McKee et al. (2006 ); Lakshminarayanan et al. (2007 ); For the role of electron-withdrawing groups in these molecules, see: Bryantsev & Hay (2005 ).

Experimental

Crystal data

C₂₇H₃₆N₇O₆³⁺·3Cl⁻·1.41H₂O
M_r = 686.47
Monoclinic, P 2₁ /n
a = 9.131 (2) Å
b = 13.009 (4) Å
c = 28.071 (7) Å
β = 94.190 (9)°
V = 3326 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 298 K
0.50 × 0.42 × 0.24 mm

Data collection

Siemens P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1996 ) T_min = 0.819, T_max = 0.924
16115 measured reflections
6712 independent reflections
4181 reflections with I > 2σ(I)
R_int = 0.042
3 standard reflections every 97 reflections intensity decay: 3.5%

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.175
S = 1.03
6712 reflections
438 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2D⋯Cl1	0.906 (10)	2.255 (11)	3.155 (2)	172 (3)
N12—H12D⋯Cl1	0.902 (10)	2.396 (19)	3.225 (3)	153 (3)
N22—H22D⋯Cl1	0.900 (10)	2.279 (11)	3.176 (3)	174 (3)
N12—H12C⋯Cl3	0.897 (10)	2.161 (11)	3.054 (3)	174 (3)
N22—H22C⋯Cl2	0.899 (10)	2.335 (14)	3.209 (3)	164 (3)
O8—H81⋯Cl1	0.850 (10)	2.35 (5)	3.115 (5)	150 (9)
O8—H82⋯Cl2	0.850 (10)	2.46 (4)	3.265 (5)	159 (10)
O7—H72⋯Cl3	0.851 (10)	2.28 (3)	3.102 (6)	163 (9)
N2—H2C⋯Cl2ⁱ	0.897 (10)	2.221 (14)	3.089 (3)	163 (3)
O7—H71⋯O6ⁱⁱ	0.851 (10)	2.45 (8)	2.965 (7)	119 (8)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z.

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022399/im2103sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022399/im2103Isup2.hkl

checkCIF report

Comment top

Tris(2-aminoethyl)amine (tren) derivatives are common starting materials for the synthesis of tripodal ligands used as podants in coordination chemistry (Coyle et al., 2006). They are also used as anions receptors aiming at the design of molecules acting as selective anion bindig sites (Hossain et al., 2004). On the other hand, for tren-based molecules bearing an aryl group, it has been shown that substitution of aryl with electron withdrawing groups enhances the stability of anions complexes (Bryantsev & Hay, 2005). Following this idea, we prepared tris[(2-nitrobenzylamino)ethyl]amine by reduction of the corresponding Schiff base, tris[(2-nitrobenzylideneamino)ethyl]amine, which had been previously characterized by X-ray diffraction (McKee et al., 2006). However, as the free base is an oil, we transformed the amine into its hydrochloride salt, (I), and now report its X-ray structure.

The asymmetric unit (Fig. 1) contains one cation and three chloride ions balancing the charges, as expected. Two sites are occupied by water molecules, for which occupancies converged to 0.79 (11) and 0.621 (9). All atoms are placed in general positions. The presence of lattice water molecules is confirmed by IR spectroscopy, as well as by the consistent network of hydrogen bonds involving all H atoms of water molecules. The three secondary amine groups of the tren derivative are protonated, generating strong Coulombic repulsions within the cation. However, a claw-like conformation is stabilized, since a Cl^- ion is placed inside the cavity and forms three strong hydrogen bonds with all NH₂⁺ groups. Such a behaviour is not systematically observed with closely related cations. For example, tris(2-benzylammonioethyl)amine cation has been crystallized with bromide or phosphate, and X-ray studies revealed that in both cases cations approximate a trigonal planar shape (Hossain et al., 2004). In the same way, the free Schiff base used as starting material for (I) is a planar molecule with crystallographic C₃ symmetry (space group R3, McKee et al., 2006). In contrast, the same cation including pentafluorobenzyl groups in place of benzyl encapsulates Cl^- or Br^- ions (Lakshminarayanan et al., 2007), as (I) does.

The supramolecular network formed by cations, anions, and water molecules in (I) is a complex arrangement of N—H···Cl and O—H···Cl hydrogen bonds. The most important, as commented above, are the NH₂⁺···Cl1 strong hydrogen bonds allowing the anion encapsulation in the cationic cavity. Chloride ions placed outside this cavity are also connected to NH₂⁺ functional groups via hydrogen bonds, one of which being intermolecular. In the asymmetric unit, water molecules also serve as donor for O—H···Cl hydrogen bonds (Fig. 2). One nitro group also forms weak intermolecular contacts with the water molecule O7.

Related literature top

For related tripodal amine structures, see: Hossain et al. (2004); Coyle et al. (2006); McKee et al. (2006); Lakshminarayanan et al. (2007); For the role of electron-withdrawing groups in these molecules, see: Bryantsev & Hay (2005).

Experimental top

Tris[(2-nitrobenzylideneamino)ethyl]amine (12.461 g, 27 mmol) was dispersed in methanol (40 ml). To achieve selective reduction, an amount of NaBH₄ (3.643 g, 96 mmol) was added in small portions at 298 K under stirring. After reduction was completed, solvent was removed and then the reduction product, tris[(2-nitrobenzylamino)ethyl]amine, was extracted with CHCl₃ (2 × 10 ml) and water (20 ml). The organic phase was dried over MgSO₄. Evaporation of the solvent under reduced pressure afforded the free base as a pale yellow oil (yield: 91%). This compound was dissolved in ethanol and HCl was added until the title white salt [m.p. 503.5–504.5 K (dec.)] had completely precipitated. Suitable single crystals were obtained by evaporation of an ethanol-water (19:1) mixture.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are shown at the 25% probability level.
	Fig. 2. A part of the crystal structure of (I). Three symmetry-related cations are represented, omitting H atoms not involved in the supramolecular network. Hydrogen bonds are represented by dashed lines, and weak contacts involving nitro groups have been omitted for clarity. Symmetry codes for cations: green x, y, z; gold 3/2 - x, 1/2 + y, 1/2 - z; blue 3/2 - x, -1/2 + y, 1/2 - z.

N,N',N''-Tris(2-nitrobenzyl)-2,2',2''- nitrilotriethanaminium trichloride 1.41-hydrate top

Crystal data top

C₂₇H₃₆N₇O₆³⁺·3Cl⁻·1.41H₂O	F(000) = 1441
M_r = 686.47	D_x = 1.371 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 503.5–504.5 (dec.) K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.131 (2) Å	Cell parameters from 69 reflections
b = 13.009 (4) Å	θ = 4.6–12.5°
c = 28.071 (7) Å	µ = 0.33 mm⁻¹
β = 94.190 (9)°	T = 298 K
V = 3326 (2) Å³	Block, colorless
Z = 4	0.50 × 0.42 × 0.24 mm

Data collection top

Siemens P4 diffractometer	4181 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 26.3°, θ_min = 2.1°
2θ/ω scans	h = −11→10
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −16→1
T_min = 0.819, T_max = 0.924	l = −34→34
16115 measured reflections	3 standard reflections every 97 reflections
6712 independent reflections	intensity decay: 3.5%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0754P)² + 1.5076P] where P = (F_o² + 2F_c²)/3
6712 reflections	(Δ/σ)_max < 0.001
438 parameters	Δρ_max = 0.34 e Å⁻³
12 restraints	Δρ_min = −0.34 e Å⁻³
0 constraints

Crystal data top

C₂₇H₃₆N₇O₆³⁺·3Cl⁻·1.41H₂O	V = 3326 (2) Å³
M_r = 686.47	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.131 (2) Å	µ = 0.33 mm⁻¹
b = 13.009 (4) Å	T = 298 K
c = 28.071 (7) Å	0.50 × 0.42 × 0.24 mm
β = 94.190 (9)°

Data collection top

Siemens P4 diffractometer	4181 reflections with I > 2σ(I)
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	R_int = 0.042
T_min = 0.819, T_max = 0.924	3 standard reflections every 97 reflections
16115 measured reflections	intensity decay: 3.5%
6712 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	12 restraints
wR(F²) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.34 e Å⁻³
6712 reflections	Δρ_min = −0.34 e Å⁻³
438 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.9829 (3)	0.79136 (19)	0.17125 (9)	0.0624 (6)
C1	0.9926 (4)	0.8169 (3)	0.22199 (11)	0.0701 (8)
H1A	0.9977	0.8911	0.2253	0.084*
H1B	1.0831	0.7887	0.2368	0.084*
C2	0.8671 (4)	0.7782 (3)	0.24840 (11)	0.0690 (8)
H2A	0.8467	0.7074	0.2393	0.083*
H2B	0.8945	0.7797	0.2824	0.083*
N2	0.7313 (3)	0.8412 (2)	0.23819 (8)	0.0586 (6)
H2C	0.758 (3)	0.9045 (12)	0.2481 (11)	0.070*
H2D	0.706 (3)	0.844 (2)	0.2064 (4)	0.070*
C3	0.6071 (4)	0.7981 (2)	0.26312 (11)	0.0668 (8)
H3A	0.6416	0.7807	0.2956	0.080*
H3B	0.5740	0.7352	0.2472	0.080*
C4	0.4792 (3)	0.8706 (2)	0.26437 (10)	0.0588 (7)
C5	0.4586 (4)	0.9520 (2)	0.23318 (11)	0.0682 (8)
H5A	0.5256	0.9624	0.2102	0.082*
C6	0.3408 (4)	1.0185 (3)	0.23509 (13)	0.0733 (9)
H6A	0.3284	1.0714	0.2129	0.088*
C7	0.2432 (4)	1.0077 (3)	0.26895 (13)	0.0736 (9)
H7A	0.1651	1.0533	0.2702	0.088*
C8	0.2608 (4)	0.9293 (3)	0.30119 (12)	0.0725 (9)
H8A	0.1957	0.9216	0.3249	0.087*
C9	0.3756 (4)	0.8620 (2)	0.29820 (10)	0.0623 (8)
N3	0.3838 (4)	0.7755 (3)	0.33158 (12)	0.0856 (9)
O1	0.3524 (4)	0.7895 (3)	0.37214 (12)	0.1437 (14)
O2	0.4250 (4)	0.6941 (2)	0.31824 (11)	0.1107 (10)
C11	1.0831 (4)	0.8554 (3)	0.14559 (14)	0.0763 (9)
H11A	1.0975	0.8234	0.1151	0.092*
H11B	1.1777	0.8573	0.1637	0.092*
C12	1.0314 (4)	0.9638 (3)	0.13682 (15)	0.0869 (11)
H12A	1.0114	0.9950	0.1670	0.104*
H12B	1.1091	1.0030	0.1235	0.104*
N12	0.8964 (3)	0.9694 (2)	0.10352 (11)	0.0709 (7)
H12C	0.907 (4)	0.923 (2)	0.0803 (9)	0.085*
H12D	0.825 (3)	0.943 (3)	0.1206 (11)	0.085*
C13	0.8715 (4)	1.0771 (3)	0.08618 (13)	0.0800 (10)
H13A	0.9484	1.0955	0.0657	0.096*
H13B	0.8785	1.1233	0.1134	0.096*
C14	0.7249 (4)	1.0919 (2)	0.05908 (11)	0.0671 (8)
C15	0.7256 (4)	1.0997 (3)	0.01013 (12)	0.0784 (10)
H15A	0.8139	1.0911	−0.0039	0.094*
C16	0.6024 (6)	1.1193 (3)	−0.01819 (15)	0.0926 (12)
H16A	0.6072	1.1236	−0.0511	0.111*
C17	0.4729 (5)	1.1328 (3)	0.00097 (16)	0.0919 (12)
H17A	0.3891	1.1470	−0.0188	0.110*
C18	0.4635 (4)	1.1258 (3)	0.04915 (17)	0.0858 (11)
H18A	0.3737	1.1342	0.0623	0.103*
C19	0.5905 (4)	1.1060 (2)	0.07840 (12)	0.0712 (9)
N13	0.5780 (6)	1.1031 (2)	0.12976 (14)	0.0969 (11)
O3	0.4647 (6)	1.1270 (4)	0.14496 (16)	0.1638 (18)
O4	0.6834 (5)	1.0783 (2)	0.15623 (10)	0.1092 (10)
C21	1.0212 (4)	0.6829 (2)	0.16548 (11)	0.0679 (8)
H21A	0.9807	0.6430	0.1906	0.081*
H21B	1.1272	0.6756	0.1689	0.081*
C22	0.9657 (4)	0.6407 (3)	0.11834 (13)	0.0758 (9)
H22A	0.9985	0.6840	0.0931	0.091*
H22B	1.0057	0.5724	0.1144	0.091*
N22	0.8036 (3)	0.63543 (19)	0.11434 (9)	0.0648 (7)
H22C	0.774 (4)	0.596 (2)	0.1381 (9)	0.078*
H22D	0.756 (3)	0.6949 (15)	0.1190 (12)	0.078*
C23	0.7439 (4)	0.5962 (3)	0.06626 (11)	0.0769 (10)
H23A	0.7383	0.6529	0.0437	0.092*
H23B	0.8114	0.5457	0.0549	0.092*
C24	0.5961 (5)	0.5488 (3)	0.06750 (11)	0.0737 (9)
C25	0.4793 (6)	0.6015 (4)	0.04688 (14)	0.0959 (12)
H25A	0.4936	0.6668	0.0345	0.115*
C26	0.3370 (7)	0.5587 (6)	0.04397 (18)	0.1311 (19)
H26A	0.2571	0.5950	0.0301	0.157*
C27	0.3195 (8)	0.4606 (7)	0.0625 (2)	0.138 (3)
H27A	0.2270	0.4303	0.0608	0.166*
C28	0.4359 (10)	0.4094 (5)	0.0827 (2)	0.140 (3)
H28A	0.4229	0.3436	0.0946	0.168*
C29	0.5702 (6)	0.4512 (3)	0.08602 (12)	0.0939 (13)
N23	0.6930 (7)	0.3884 (2)	0.10924 (12)	0.1083 (15)
O5	0.6572 (7)	0.3081 (3)	0.12602 (13)	0.205 (3)
O6	0.8142 (6)	0.4235 (3)	0.11446 (16)	0.1383 (14)
Cl1	0.61515 (8)	0.83642 (6)	0.12955 (2)	0.0618 (2)
Cl2	0.66871 (10)	0.53719 (6)	0.20643 (3)	0.0696 (2)
Cl3	0.91772 (12)	0.82403 (9)	0.01891 (4)	0.0971 (3)
O7	1.0384 (7)	0.6272 (5)	−0.0268 (2)	0.166 (3)	0.793 (11)
H71	1.046 (14)	0.658 (7)	−0.0533 (19)	0.249*	0.793 (11)
H72	1.006 (12)	0.673 (5)	−0.009 (3)	0.249*	0.793 (11)
O8	0.3919 (5)	0.6773 (5)	0.1646 (2)	0.121 (3)	0.621 (9)
H81	0.426 (9)	0.723 (5)	0.147 (3)	0.182*	0.621 (9)
H82	0.461 (7)	0.633 (6)	0.168 (4)	0.182*	0.621 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0575 (14)	0.0559 (14)	0.0721 (15)	0.0051 (12)	−0.0083 (12)	−0.0021 (12)
C1	0.0607 (19)	0.0697 (19)	0.077 (2)	0.0053 (16)	−0.0152 (16)	−0.0118 (16)
C2	0.070 (2)	0.071 (2)	0.0636 (18)	0.0112 (17)	−0.0087 (15)	−0.0050 (15)
N2	0.0642 (15)	0.0621 (14)	0.0480 (12)	0.0035 (12)	−0.0052 (11)	−0.0073 (11)
C3	0.076 (2)	0.0637 (18)	0.0605 (17)	0.0026 (16)	0.0023 (15)	0.0007 (14)
C4	0.0616 (18)	0.0628 (17)	0.0509 (15)	−0.0004 (14)	−0.0026 (13)	−0.0095 (13)
C5	0.072 (2)	0.0675 (19)	0.0659 (18)	0.0044 (17)	0.0064 (15)	0.0024 (15)
C6	0.073 (2)	0.0644 (19)	0.081 (2)	0.0048 (17)	−0.0035 (18)	0.0015 (16)
C7	0.0618 (19)	0.073 (2)	0.084 (2)	0.0042 (17)	−0.0072 (18)	−0.0149 (18)
C8	0.0571 (19)	0.088 (2)	0.073 (2)	−0.0054 (18)	0.0035 (15)	−0.0145 (18)
C9	0.0652 (19)	0.0674 (18)	0.0530 (16)	−0.0069 (16)	−0.0055 (14)	−0.0046 (14)
N3	0.087 (2)	0.096 (2)	0.075 (2)	0.0044 (19)	0.0149 (16)	0.0109 (18)
O1	0.163 (3)	0.182 (4)	0.091 (2)	0.048 (3)	0.042 (2)	0.042 (2)
O2	0.139 (3)	0.0850 (19)	0.109 (2)	0.0062 (19)	0.0188 (19)	0.0254 (17)
C11	0.060 (2)	0.075 (2)	0.092 (2)	−0.0038 (17)	−0.0063 (17)	0.0100 (18)
C12	0.078 (2)	0.072 (2)	0.105 (3)	−0.0145 (18)	−0.030 (2)	0.0173 (19)
N12	0.0734 (18)	0.0586 (16)	0.0781 (19)	−0.0116 (14)	−0.0118 (15)	0.0082 (13)
C13	0.085 (2)	0.066 (2)	0.084 (2)	−0.0186 (18)	−0.0207 (18)	0.0212 (17)
C14	0.077 (2)	0.0526 (17)	0.0688 (19)	−0.0149 (16)	−0.0133 (16)	0.0096 (14)
C15	0.087 (2)	0.076 (2)	0.071 (2)	−0.0080 (19)	−0.0006 (18)	0.0149 (17)
C16	0.115 (4)	0.082 (3)	0.077 (2)	−0.007 (2)	−0.020 (2)	0.0171 (19)
C17	0.099 (3)	0.070 (2)	0.101 (3)	−0.009 (2)	−0.035 (3)	0.016 (2)
C18	0.078 (2)	0.0571 (19)	0.123 (3)	−0.0040 (18)	0.007 (2)	0.013 (2)
C19	0.095 (3)	0.0479 (16)	0.0705 (19)	−0.0080 (16)	0.0032 (18)	0.0081 (14)
N13	0.143 (4)	0.0622 (18)	0.088 (2)	−0.004 (2)	0.030 (3)	0.0144 (17)
O3	0.183 (4)	0.170 (4)	0.150 (3)	0.037 (3)	0.090 (3)	0.048 (3)
O4	0.182 (3)	0.0783 (18)	0.0662 (16)	−0.005 (2)	−0.0007 (18)	0.0081 (13)
C21	0.0662 (19)	0.0653 (19)	0.0718 (19)	0.0132 (16)	0.0023 (15)	0.0041 (15)
C22	0.080 (2)	0.067 (2)	0.082 (2)	0.0100 (17)	0.0165 (18)	−0.0071 (17)
N22	0.088 (2)	0.0529 (14)	0.0541 (14)	0.0044 (13)	0.0074 (13)	−0.0057 (11)
C23	0.110 (3)	0.066 (2)	0.0553 (17)	−0.0139 (19)	0.0089 (17)	−0.0046 (15)
C24	0.110 (3)	0.0599 (18)	0.0524 (17)	−0.0175 (19)	0.0113 (18)	−0.0092 (14)
C25	0.123 (4)	0.096 (3)	0.068 (2)	−0.014 (3)	0.001 (2)	−0.013 (2)
C26	0.125 (5)	0.181 (6)	0.086 (3)	−0.011 (4)	−0.003 (3)	−0.042 (4)
C27	0.138 (5)	0.185 (7)	0.098 (4)	−0.088 (5)	0.044 (4)	−0.053 (4)
C28	0.207 (7)	0.133 (5)	0.087 (3)	−0.087 (5)	0.055 (4)	−0.043 (3)
C29	0.152 (4)	0.077 (2)	0.0545 (19)	−0.039 (3)	0.022 (2)	−0.0207 (18)
N23	0.213 (5)	0.0461 (18)	0.0650 (18)	−0.013 (3)	0.006 (3)	−0.0040 (14)
O5	0.416 (8)	0.075 (2)	0.113 (3)	−0.073 (3)	−0.056 (4)	0.0271 (19)
O6	0.187 (4)	0.079 (2)	0.151 (3)	0.034 (3)	0.029 (3)	0.007 (2)
Cl1	0.0686 (5)	0.0594 (4)	0.0555 (4)	0.0021 (4)	−0.0085 (3)	0.0005 (3)
Cl2	0.0815 (5)	0.0606 (4)	0.0665 (5)	0.0027 (4)	0.0050 (4)	0.0078 (3)
Cl3	0.1002 (7)	0.1081 (8)	0.0858 (6)	−0.0133 (6)	0.0264 (5)	0.0007 (5)
O7	0.139 (5)	0.212 (6)	0.145 (5)	0.047 (4)	0.003 (4)	−0.046 (4)
O8	0.077 (3)	0.125 (5)	0.163 (5)	−0.006 (3)	0.025 (3)	0.052 (4)

Geometric parameters (Å, º) top

N1—C1	1.459 (4)	C14—C19	1.389 (5)
N1—C11	1.465 (4)	C15—C16	1.354 (5)
N1—C21	1.466 (4)	C15—H15A	0.9300
C1—C2	1.497 (5)	C16—C17	1.346 (6)
C1—H1A	0.9700	C16—H16A	0.9300
C1—H1B	0.9700	C17—C18	1.364 (6)
C2—N2	1.497 (4)	C17—H17A	0.9300
C2—H2A	0.9700	C18—C19	1.396 (5)
C2—H2B	0.9700	C18—H18A	0.9300
N2—C3	1.485 (4)	C19—N13	1.455 (5)
N2—H2C	0.897 (10)	N13—O3	1.190 (5)
N2—H2D	0.906 (10)	N13—O4	1.216 (5)
C3—C4	1.504 (4)	C21—C22	1.487 (5)
C3—H3A	0.9700	C21—H21A	0.9700
C3—H3B	0.9700	C21—H21B	0.9700
C4—C5	1.378 (4)	C22—N22	1.478 (5)
C4—C9	1.393 (4)	C22—H22A	0.9700
C5—C6	1.385 (5)	C22—H22B	0.9700
C5—H5A	0.9300	N22—C23	1.507 (4)
C6—C7	1.357 (5)	N22—H22C	0.899 (10)
C6—H6A	0.9300	N22—H22D	0.900 (10)
C7—C8	1.365 (5)	C23—C24	1.487 (5)
C7—H7A	0.9300	C23—H23A	0.9700
C8—C9	1.372 (5)	C23—H23B	0.9700
C8—H8A	0.9300	C24—C25	1.361 (6)
C9—N3	1.463 (4)	C24—C29	1.398 (5)
N3—O2	1.193 (4)	C25—C26	1.411 (7)
N3—O1	1.208 (4)	C25—H25A	0.9300
C11—C12	1.501 (5)	C26—C27	1.391 (9)
C11—H11A	0.9700	C26—H26A	0.9300
C11—H11B	0.9700	C27—C28	1.345 (9)
C12—N12	1.493 (4)	C27—H27A	0.9300
C12—H12A	0.9700	C28—C29	1.338 (8)
C12—H12B	0.9700	C28—H28A	0.9300
N12—C13	1.495 (4)	C29—N23	1.498 (7)
N12—H12C	0.897 (10)	N23—O6	1.196 (6)
N12—H12D	0.902 (10)	N23—O5	1.202 (5)
C13—C14	1.503 (5)	O7—H71	0.851 (10)
C13—H13A	0.9700	O7—H72	0.851 (10)
C13—H13B	0.9700	O8—H81	0.850 (10)
C14—C15	1.378 (5)	O8—H82	0.850 (10)

C1—N1—C11	110.8 (3)	C14—C13—H13B	108.9
C1—N1—C21	109.2 (2)	H13A—C13—H13B	107.8
C11—N1—C21	109.3 (3)	C15—C14—C19	116.6 (3)
N1—C1—C2	114.4 (3)	C15—C14—C13	116.4 (3)
N1—C1—H1A	108.7	C19—C14—C13	126.8 (3)
C2—C1—H1A	108.7	C16—C15—C14	122.3 (4)
N1—C1—H1B	108.7	C16—C15—H15A	118.8
C2—C1—H1B	108.7	C14—C15—H15A	118.8
H1A—C1—H1B	107.6	C17—C16—C15	120.5 (4)
N2—C2—C1	112.0 (3)	C17—C16—H16A	119.8
N2—C2—H2A	109.2	C15—C16—H16A	119.8
C1—C2—H2A	109.2	C16—C17—C18	120.5 (4)
N2—C2—H2B	109.2	C16—C17—H17A	119.7
C1—C2—H2B	109.2	C18—C17—H17A	119.7
H2A—C2—H2B	107.9	C17—C18—C19	119.1 (4)
C3—N2—C2	110.7 (2)	C17—C18—H18A	120.5
C3—N2—H2C	114 (2)	C19—C18—H18A	120.5
C2—N2—H2C	104 (2)	C14—C19—C18	121.0 (3)
C3—N2—H2D	109 (2)	C14—C19—N13	121.3 (4)
C2—N2—H2D	111 (2)	C18—C19—N13	117.8 (4)
H2C—N2—H2D	109 (3)	O3—N13—O4	121.4 (4)
N2—C3—C4	113.3 (3)	O3—N13—C19	118.8 (5)
N2—C3—H3A	108.9	O4—N13—C19	119.8 (4)
C4—C3—H3A	108.9	N1—C21—C22	112.6 (3)
N2—C3—H3B	108.9	N1—C21—H21A	109.1
C4—C3—H3B	108.9	C22—C21—H21A	109.1
H3A—C3—H3B	107.7	N1—C21—H21B	109.1
C5—C4—C9	115.3 (3)	C22—C21—H21B	109.1
C5—C4—C3	122.5 (3)	H21A—C21—H21B	107.8
C9—C4—C3	122.2 (3)	N22—C22—C21	111.1 (3)
C4—C5—C6	121.7 (3)	N22—C22—H22A	109.4
C4—C5—H5A	119.1	C21—C22—H22A	109.4
C6—C5—H5A	119.1	N22—C22—H22B	109.4
C7—C6—C5	120.9 (3)	C21—C22—H22B	109.4
C7—C6—H6A	119.5	H22A—C22—H22B	108.0
C5—C6—H6A	119.5	C22—N22—C23	112.2 (3)
C6—C7—C8	119.4 (3)	C22—N22—H22C	109 (2)
C6—C7—H7A	120.3	C23—N22—H22C	111 (2)
C8—C7—H7A	120.3	C22—N22—H22D	116 (2)
C7—C8—C9	119.3 (3)	C23—N22—H22D	106 (2)
C7—C8—H8A	120.4	H22C—N22—H22D	102 (3)
C9—C8—H8A	120.4	C24—C23—N22	112.9 (3)
C8—C9—C4	123.4 (3)	C24—C23—H23A	109.0
C8—C9—N3	117.1 (3)	N22—C23—H23A	109.0
C4—C9—N3	119.5 (3)	C24—C23—H23B	109.0
O2—N3—O1	122.1 (4)	N22—C23—H23B	109.0
O2—N3—C9	119.0 (3)	H23A—C23—H23B	107.8
O1—N3—C9	118.9 (4)	C25—C24—C29	117.9 (4)
N1—C11—C12	114.5 (3)	C25—C24—C23	117.7 (3)
N1—C11—H11A	108.6	C29—C24—C23	124.4 (4)
C12—C11—H11A	108.6	C24—C25—C26	121.0 (5)
N1—C11—H11B	108.6	C24—C25—H25A	119.5
C12—C11—H11B	108.6	C26—C25—H25A	119.5
H11A—C11—H11B	107.6	C27—C26—C25	118.1 (6)
N12—C12—C11	112.6 (3)	C27—C26—H26A	121.0
N12—C12—H12A	109.1	C25—C26—H26A	121.0
C11—C12—H12A	109.1	C28—C27—C26	120.2 (6)
N12—C12—H12B	109.1	C28—C27—H27A	119.9
C11—C12—H12B	109.1	C26—C27—H27A	119.9
H12A—C12—H12B	107.8	C29—C28—C27	121.3 (6)
C12—N12—C13	110.5 (2)	C29—C28—H28A	119.4
C12—N12—H12C	107 (2)	C27—C28—H28A	119.4
C13—N12—H12C	114 (2)	C28—C29—C24	121.5 (6)
C12—N12—H12D	104 (2)	C28—C29—N23	117.5 (5)
C13—N12—H12D	115 (2)	C24—C29—N23	121.0 (4)
H12C—N12—H12D	104 (3)	O6—N23—O5	124.0 (6)
N12—C13—C14	113.2 (3)	O6—N23—C29	120.1 (4)
N12—C13—H13A	108.9	O5—N23—C29	115.4 (6)
C14—C13—H13A	108.9	H71—O7—H72	104 (3)
N12—C13—H13B	108.9	H81—O8—H82	104 (3)

C11—N1—C1—C2	163.5 (3)	C16—C17—C18—C19	0.9 (6)
C21—N1—C1—C2	−76.1 (3)	C15—C14—C19—C18	0.7 (5)
N1—C1—C2—N2	−75.8 (3)	C13—C14—C19—C18	175.6 (3)
C1—C2—N2—C3	177.4 (2)	C15—C14—C19—N13	−177.8 (3)
C2—N2—C3—C4	165.9 (2)	C13—C14—C19—N13	−2.9 (5)
N2—C3—C4—C5	19.9 (4)	C17—C18—C19—C14	−1.0 (5)
N2—C3—C4—C9	−158.0 (3)	C17—C18—C19—N13	177.6 (3)
C9—C4—C5—C6	−1.4 (4)	C14—C19—N13—O3	171.6 (4)
C3—C4—C5—C6	−179.5 (3)	C18—C19—N13—O3	−6.9 (5)
C4—C5—C6—C7	2.0 (5)	C14—C19—N13—O4	−7.1 (5)
C5—C6—C7—C8	−0.8 (5)	C18—C19—N13—O4	174.3 (3)
C6—C7—C8—C9	−1.0 (5)	C1—N1—C21—C22	159.9 (3)
C7—C8—C9—C4	1.7 (5)	C11—N1—C21—C22	−78.8 (3)
C7—C8—C9—N3	−176.1 (3)	N1—C21—C22—N22	−67.4 (4)
C5—C4—C9—C8	−0.5 (4)	C21—C22—N22—C23	178.1 (3)
C3—C4—C9—C8	177.6 (3)	C22—N22—C23—C24	155.5 (3)
C5—C4—C9—N3	177.2 (3)	N22—C23—C24—C25	107.9 (4)
C3—C4—C9—N3	−4.7 (4)	N22—C23—C24—C29	−75.9 (4)
C8—C9—N3—O2	143.3 (4)	C29—C24—C25—C26	−0.5 (5)
C4—C9—N3—O2	−34.6 (5)	C23—C24—C25—C26	176.0 (3)
C8—C9—N3—O1	−38.7 (5)	C24—C25—C26—C27	−0.5 (6)
C4—C9—N3—O1	143.5 (4)	C25—C26—C27—C28	0.4 (8)
C1—N1—C11—C12	−76.1 (3)	C26—C27—C28—C29	0.6 (8)
C21—N1—C11—C12	163.6 (3)	C27—C28—C29—C24	−1.7 (7)
N1—C11—C12—N12	−66.1 (4)	C27—C28—C29—N23	179.9 (5)
C11—C12—N12—C13	−165.5 (3)	C25—C24—C29—C28	1.6 (5)
C12—N12—C13—C14	−170.5 (3)	C23—C24—C29—C28	−174.6 (4)
N12—C13—C14—C15	−104.5 (4)	C25—C24—C29—N23	180.0 (3)
N12—C13—C14—C19	80.5 (4)	C23—C24—C29—N23	3.8 (5)
C19—C14—C15—C16	−0.4 (5)	C28—C29—N23—O6	−177.6 (4)
C13—C14—C15—C16	−175.9 (3)	C24—C29—N23—O6	3.9 (6)
C14—C15—C16—C17	0.4 (6)	C28—C29—N23—O5	−5.1 (5)
C15—C16—C17—C18	−0.6 (6)	C24—C29—N23—O5	176.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2D···Cl1	0.91 (1)	2.26 (1)	3.155 (2)	172 (3)
N12—H12D···Cl1	0.90 (1)	2.40 (2)	3.225 (3)	153 (3)
N22—H22D···Cl1	0.90 (1)	2.28 (1)	3.176 (3)	174 (3)
N12—H12C···Cl3	0.90 (1)	2.16 (1)	3.054 (3)	174 (3)
N22—H22C···Cl2	0.90 (1)	2.34 (1)	3.209 (3)	164 (3)
O8—H81···Cl1	0.85 (1)	2.35 (5)	3.115 (5)	150 (9)
O8—H82···Cl2	0.85 (1)	2.46 (4)	3.265 (5)	159 (10)
O7—H72···Cl3	0.85 (1)	2.28 (3)	3.102 (6)	163 (9)
N2—H2C···Cl2ⁱ	0.90 (1)	2.22 (1)	3.089 (3)	163 (3)
O7—H71···O6ⁱⁱ	0.85 (1)	2.45 (8)	2.965 (7)	119 (8)

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

Experimental details

Crystal data
Chemical formula	C₂₇H₃₆N₇O₆³⁺·3Cl⁻·1.41H₂O
M_r	686.47
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.131 (2), 13.009 (4), 28.071 (7)
β (°)	94.190 (9)
V (Å³)	3326 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.50 × 0.42 × 0.24

Data collection
Diffractometer	Siemens P4 diffractometer
Absorption correction	ψ scan (XSCANS; Siemens, 1996)
T_min, T_max	0.819, 0.924
No. of measured, independent and observed [I > 2σ(I)] reflections	16115, 6712, 4181
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.622

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.175, 1.03
No. of reflections	6712
No. of parameters	438
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.34

Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2D···Cl1	0.906 (10)	2.255 (11)	3.155 (2)	172 (3)
N12—H12D···Cl1	0.902 (10)	2.396 (19)	3.225 (3)	153 (3)
N22—H22D···Cl1	0.900 (10)	2.279 (11)	3.176 (3)	174 (3)
N12—H12C···Cl3	0.897 (10)	2.161 (11)	3.054 (3)	174 (3)
N22—H22C···Cl2	0.899 (10)	2.335 (14)	3.209 (3)	164 (3)
O8—H81···Cl1	0.850 (10)	2.35 (5)	3.115 (5)	150 (9)
O8—H82···Cl2	0.850 (10)	2.46 (4)	3.265 (5)	159 (10)
O7—H72···Cl3	0.851 (10)	2.28 (3)	3.102 (6)	163 (9)
N2—H2C···Cl2ⁱ	0.897 (10)	2.221 (14)	3.089 (3)	163 (3)
O7—H71···O6ⁱⁱ	0.851 (10)	2.45 (8)	2.965 (7)	119 (8)

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

Acknowledgements

We are grateful to Dr Amparo Salmerón Valverde (BUAP, Mexico) for measuring the IR spectrum of the title salt. The authors acknowledge the Facultad de Ciencias Químicas (UANL, Mexico) and PAYCyT for financial support (project CA1260–06).

References

Bryantsev, V. S. & Hay, B. P. (2005). Org. Lett. 7, 5031–5034. Web of Science CrossRef PubMed CAS Google Scholar
Coyle, J. L., Fuller, A., McKee, V. & Nelson, J. (2006). Acta Cryst. C62, m472–m476. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Hossain, Md. A., Liljegren, J. A., Powell, D. & Bowman-James, K. (2004). Inorg. Chem. 43, 3751–3755. CSD CrossRef PubMed CAS Google Scholar
Lakshminarayanan, P. S., Ravikumar, I., Suresh, E. & Ghosh, P. (2007). Inorg. Chem. 46, 4769–4771. Web of Science CSD CrossRef PubMed CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
McKee, V., Morgan, G. G. & Nelson, J. (2006). Acta Cryst. E62, o3747–o3749. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). XSCANS. Version 2.31. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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Volume 65| Part 7| July 2009| Pages o1616-o1617

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N,N′,N′′-Tris(2-nitro­benz­yl)-2,2′,2′′-nitrilo­triethan­aminium trichloride 1.41-hydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

N,N′,N′′-Tris(2-nitrobenzyl)-2,2′,2′′-nitrilotriethanaminium trichloride 1.41-hydrate