Bis(2-{2-[2-(benzyl-carbamo-yl)phen-oxy]acetamido}-eth-yl)ammonium nitrate ethanol disolvate.

In the title compound, C(36)H(40)N(5)O(6) (+)·NO(3) (-)·2C(2)H(5)OH, the nitrate anion is disordered over the two orientations of equal occupancy while the solvent mol-ecule reveals large displacement parameters. The cation is formed by protonation of the N atom of a secondary amine in the middle of the flexible chain and the whole compound has crystallographically imposed C-2 symmetry with the crystallographic b axis. An O atom of the nitrate anion links the acidic H atoms of the cation via N-H⋯O hydrogen bonding. In addition, neighbouring cations are connected by inter-molecular N-H⋯O hydrogen bonds and π-π inter-actions between the benzamide groups of the cations [centroid-centroid distance = 4.000 (3) Å], forming a chain along [001]. The ethanol solvent mol-ecules are arranged on the side of the chain through O-H⋯O hydrogen bonds.

Related literature

Luminescent lanthanide complexes have attracted intense research inter­est due to their very narrow emission bands and large Stokes shifts, see: Wang et al. (2009 ▶); Bunzli & Piguet (2005 ▶); Stein & Wurzberg (1975 ▶). For amide-type open-chain ligands, see: Liu et al. (2009 ▶); Yi et al. (2007 ▶); Hamann et al. (2004 ▶).

Experimental

Crystal data

C36H40N5O6 +·NO3 −·2C2H6O

M = 792.88

Monoclinic,

a = 16.978 (3) Å

b = 11.405 (2) Å

c = 11.164 (2) Å

β = 108.04 (3)°

V = 2055.6 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.22 × 0.18 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.980, T max = 0.984

4901 measured reflections

1995 independent reflections

1334 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.190

S = 1.03

1995 reflections

277 parameters

45 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.32 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810052670/kp2291sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052670/kp2291Isup2.hkl

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

C36H40N5O6+·NO3−·2C2H6O	F(000) = 844
Mr = 792.88	Dx = 1.281 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C2y	Cell parameters from 1019 reflections
a = 16.978 (3) Å	θ = 2.5–20.9°
b = 11.405 (2) Å	µ = 0.09 mm−1
c = 11.164 (2) Å	T = 296 K
β = 108.04 (3)°	Block, colourless
V = 2055.6 (7) Å3	0.22 × 0.18 × 0.17 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	1995 independent reflections
Radiation source: fine-focus sealed tube	1334 reflections with I > 2σ(I)
graphite	Rint = 0.035
φ and ω scans	θmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −20→20
Tmin = 0.980, Tmax = 0.984	k = −13→13
4901 measured reflections	l = −8→13

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.190	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.1204P)2] where P = (Fo2 + 2Fc2)/3
1995 reflections	(Δ/σ)max < 0.001
277 parameters	Δρmax = 0.26 e Å−3
45 restraints	Δρmin = −0.32 e Å−3

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. The structure is non-centrosymmetric with only atoms lighter than silicon, MoKa measured Friedel data can not be used to determine absolute structure.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.1027 (3)	0.7751 (5)	0.3251 (4)	0.0729 (14)
H1	0.0513	0.8071	0.2823	0.088*
C2	0.1500 (4)	0.8244 (5)	0.4399 (4)	0.0853 (17)
H2	0.1299	0.8878	0.4742	0.102*
C3	0.2259 (4)	0.7777 (5)	0.5003 (5)	0.0903 (18)
H3	0.2585	0.8102	0.5758	0.108*
C4	0.2544 (4)	0.6830 (6)	0.4502 (5)	0.0860 (17)
H4	0.3060	0.6512	0.4923	0.103*
C5	0.2075 (3)	0.6351 (5)	0.3391 (4)	0.0723 (14)
H5	0.2275	0.5708	0.3062	0.087*
C6	0.1309 (3)	0.6806 (4)	0.2748 (4)	0.0573 (11)
C7	0.0779 (3)	0.6306 (4)	0.1506 (4)	0.0614 (12)
H7A	0.0201	0.6396	0.1453	0.074*
H7B	0.0872	0.6762	0.0828	0.074*
C8	0.0726 (2)	0.4235 (4)	0.1984 (3)	0.0492 (11)
C9	0.0862 (2)	0.2966 (4)	0.1713 (3)	0.0477 (10)
C10	0.0729 (3)	0.2155 (4)	0.2537 (4)	0.0645 (13)
H10	0.0561	0.2411	0.3210	0.077*
C11	0.0839 (4)	0.0971 (5)	0.2393 (5)	0.0802 (16)
H11	0.0741	0.0441	0.2963	0.096*
C12	0.1088 (4)	0.0581 (5)	0.1432 (5)	0.0833 (16)
H12	0.1161	−0.0218	0.1338	0.100*
C13	0.1236 (3)	0.1374 (4)	0.0576 (4)	0.0739 (14)
H13	0.1417	0.1108	−0.0081	0.089*
C14	0.1113 (2)	0.2551 (4)	0.0710 (3)	0.0506 (11)
C15	0.1448 (3)	0.3013 (4)	−0.1168 (3)	0.0582 (12)
H15A	0.1031	0.2491	−0.1691	0.070*
H15B	0.1973	0.2602	−0.0900	0.070*
C16	0.1516 (3)	0.4089 (4)	−0.1880 (4)	0.0583 (12)
C17	0.1515 (3)	0.4860 (5)	−0.3908 (4)	0.0755 (15)
H17A	0.1635	0.4531	−0.4634	0.091*
H17B	0.1978	0.5355	−0.3464	0.091*
C18	0.0744 (3)	0.5599 (4)	−0.4352 (4)	0.0633 (12)
H18A	0.0655	0.5993	−0.3635	0.076*
H18B	0.0820	0.6195	−0.4927	0.076*
C19	0.1576 (7)	0.8011 (10)	0.8043 (10)	0.190 (4)
H19A	0.1167	0.7735	0.7280	0.227*
H19B	0.2120	0.7857	0.7965	0.227*
C20	0.1476 (8)	0.9286 (12)	0.8154 (13)	0.220 (5)
H20A	0.0967	0.9441	0.8332	0.330*
H20B	0.1462	0.9660	0.7377	0.330*
H20C	0.1932	0.9589	0.8825	0.330*
N1	0.0936 (2)	0.5070 (3)	0.1313 (3)	0.0555 (9)
H1A	0.1169	0.4881	0.0756	0.067*
N2	0.1437 (2)	0.3914 (4)	−0.3083 (3)	0.0627 (10)
H2A	0.1336	0.3217	−0.3385	0.075*
N3	0.0000	0.4879 (5)	−0.5000	0.0538 (13)
HN3	−0.004 (2)	0.437 (4)	−0.435 (4)	0.061 (12)*
N4	0.0000	0.1418 (5)	0.5000	0.0692 (16)
O1	0.04311 (19)	0.4475 (3)	0.2828 (3)	0.0665 (9)
O2	0.1223 (2)	0.3375 (3)	−0.0115 (2)	0.0659 (8)
O3	0.1642 (2)	0.5043 (4)	−0.1375 (3)	0.0879 (12)
O4	0.1490 (5)	0.7383 (9)	0.9064 (8)	0.206 (3)
H4A	0.1549	0.6662	0.8924	0.247*
O5	−0.0303 (5)	0.2373 (6)	0.4705 (7)	0.086 (3)	0.50
O6	0.0685 (4)	0.1426 (7)	0.5858 (8)	0.100 (3)	0.50
O7	−0.0314 (6)	0.0489 (6)	0.4703 (11)	0.133 (4)	0.50

	U11	U22	U33	U12	U13	U23
C1	0.106 (3)	0.055 (3)	0.059 (2)	0.008 (3)	0.028 (2)	0.008 (2)
C2	0.161 (5)	0.036 (2)	0.068 (3)	−0.008 (3)	0.049 (3)	−0.002 (2)
C3	0.118 (4)	0.083 (4)	0.061 (3)	−0.036 (3)	0.016 (3)	0.004 (3)
C4	0.084 (3)	0.094 (4)	0.073 (3)	−0.021 (3)	0.013 (3)	0.002 (3)
C5	0.083 (3)	0.073 (3)	0.062 (3)	−0.006 (3)	0.025 (2)	−0.003 (2)
C6	0.084 (3)	0.049 (2)	0.0445 (18)	0.001 (2)	0.0277 (19)	0.0087 (18)
C7	0.086 (3)	0.052 (3)	0.046 (2)	0.005 (2)	0.021 (2)	0.0030 (19)
C8	0.056 (2)	0.056 (3)	0.0357 (17)	0.001 (2)	0.0152 (16)	−0.0003 (18)
C9	0.057 (2)	0.053 (2)	0.0344 (16)	−0.0033 (19)	0.0158 (15)	0.0026 (17)
C10	0.085 (3)	0.066 (3)	0.049 (2)	0.008 (2)	0.030 (2)	0.013 (2)
C11	0.122 (4)	0.068 (3)	0.056 (2)	−0.004 (3)	0.035 (3)	0.013 (2)
C12	0.128 (4)	0.052 (3)	0.079 (3)	0.000 (3)	0.046 (3)	0.011 (2)
C13	0.108 (3)	0.063 (3)	0.065 (2)	0.002 (3)	0.048 (2)	0.003 (2)
C14	0.065 (2)	0.050 (2)	0.0426 (19)	−0.005 (2)	0.0251 (17)	0.0017 (18)
C15	0.082 (2)	0.063 (3)	0.0391 (17)	0.005 (2)	0.0330 (17)	−0.0049 (19)
C16	0.069 (2)	0.066 (3)	0.0455 (19)	−0.002 (2)	0.0255 (18)	0.004 (2)
C17	0.076 (2)	0.107 (4)	0.053 (2)	0.004 (3)	0.034 (2)	0.019 (3)
C18	0.090 (3)	0.055 (3)	0.053 (2)	−0.015 (2)	0.033 (2)	0.003 (2)
C19	0.183 (6)	0.205 (8)	0.190 (7)	−0.004 (7)	0.071 (6)	0.009 (7)
C20	0.218 (7)	0.219 (8)	0.221 (8)	−0.005 (7)	0.066 (6)	−0.043 (7)
N1	0.075 (2)	0.054 (2)	0.0423 (16)	0.0008 (18)	0.0244 (15)	0.0025 (16)
N2	0.088 (2)	0.067 (2)	0.0447 (16)	0.011 (2)	0.0376 (15)	0.0073 (17)
N3	0.078 (3)	0.051 (3)	0.038 (2)	0.000	0.027 (2)	0.000
N4	0.072 (3)	0.078 (4)	0.069 (3)	0.000	0.038 (3)	0.000
O1	0.0891 (18)	0.070 (2)	0.0545 (14)	−0.0011 (17)	0.0420 (14)	−0.0032 (15)
O2	0.113 (2)	0.0502 (18)	0.0509 (13)	0.0028 (16)	0.0492 (14)	0.0024 (13)
O3	0.125 (3)	0.080 (2)	0.0584 (17)	−0.033 (2)	0.0280 (18)	−0.0035 (18)
O4	0.236 (6)	0.214 (7)	0.200 (5)	−0.015 (5)	0.117 (5)	0.006 (5)
O5	0.127 (7)	0.065 (4)	0.079 (5)	0.017 (4)	0.049 (5)	0.018 (4)
O6	0.113 (5)	0.063 (5)	0.138 (7)	0.013 (5)	0.061 (5)	−0.002 (5)
O7	0.185 (11)	0.070 (5)	0.165 (8)	−0.055 (5)	0.084 (7)	−0.062 (6)

C1—C6	1.367 (7)	C16—O3	1.214 (6)
C1—C2	1.402 (7)	C16—N2	1.322 (5)
C1—H1	0.9300	C17—N2	1.452 (6)
C2—C3	1.365 (8)	C17—C18	1.506 (7)
C2—H2	0.9300	C17—H17A	0.9700
C3—C4	1.371 (8)	C17—H17B	0.9700
C3—H3	0.9300	C18—N3	1.493 (5)
C4—C5	1.364 (7)	C18—H18A	0.9700
C4—H4	0.9300	C18—H18B	0.9700
C5—C6	1.378 (6)	C19—O4	1.392 (11)
C5—H5	0.9300	C19—C20	1.475 (14)
C6—C7	1.512 (6)	C19—H19A	0.9700
C7—N1	1.464 (6)	C19—H19B	0.9700
C7—H7A	0.9700	C20—H20A	0.9600
C7—H7B	0.9700	C20—H20B	0.9600
C8—O1	1.226 (5)	C20—H20C	0.9600
C8—N1	1.327 (5)	N1—H1A	0.8600
C8—C9	1.511 (6)	N2—H2A	0.8600
C9—C10	1.372 (6)	N3—C18i	1.493 (5)
C9—C14	1.398 (5)	N3—HN3	0.95 (4)
C10—C11	1.380 (8)	N4—O7ii	1.186 (8)
C10—H10	0.9300	N4—O7	1.186 (8)
C11—C12	1.344 (8)	N4—O5ii	1.205 (8)
C11—H11	0.9300	N4—O5	1.205 (8)
C12—C13	1.395 (7)	N4—O6	1.258 (7)
C12—H12	0.9300	N4—O6ii	1.258 (7)
C13—C14	1.374 (7)	O4—H4A	0.8491
C13—H13	0.9300	O5—O5ii	1.035 (14)
C14—O2	1.368 (5)	O5—O6ii	1.316 (10)
C15—O2	1.406 (5)	O6—O7ii	1.298 (12)
C15—C16	1.486 (6)	O6—O5ii	1.316 (10)
C15—H15A	0.9700	O7—O7ii	1.066 (18)
C15—H15B	0.9700	O7—O6ii	1.298 (12)
C6—C1—C2	121.2 (5)	O2—C15—H15B	110.3
C6—C1—H1	119.4	C16—C15—H15B	110.3
C2—C1—H1	119.4	H15A—C15—H15B	108.6
C3—C2—C1	118.7 (5)	O3—C16—N2	123.7 (4)
C3—C2—H2	120.7	O3—C16—C15	121.6 (4)
C1—C2—H2	120.7	N2—C16—C15	114.8 (4)
C2—C3—C4	120.3 (5)	N2—C17—C18	112.6 (4)
C2—C3—H3	119.8	N2—C17—H17A	109.1
C4—C3—H3	119.8	C18—C17—H17A	109.1
C5—C4—C3	120.4 (5)	N2—C17—H17B	109.1
C5—C4—H4	119.8	C18—C17—H17B	109.1
C3—C4—H4	119.8	H17A—C17—H17B	107.8
C4—C5—C6	120.9 (5)	N3—C18—C17	111.7 (4)
C4—C5—H5	119.5	N3—C18—H18A	109.3
C6—C5—H5	119.5	C17—C18—H18A	109.3
C1—C6—C5	118.5 (4)	N3—C18—H18B	109.3
C1—C6—C7	119.3 (4)	C17—C18—H18B	109.3
C5—C6—C7	122.2 (4)	H18A—C18—H18B	107.9
N1—C7—C6	114.5 (4)	O4—C19—C20	113.2 (12)
N1—C7—H7A	108.6	O4—C19—H19A	108.9
C6—C7—H7A	108.6	C20—C19—H19A	108.9
N1—C7—H7B	108.6	O4—C19—H19B	108.9
C6—C7—H7B	108.6	C20—C19—H19B	108.9
H7A—C7—H7B	107.6	H19A—C19—H19B	107.7
O1—C8—N1	121.3 (4)	C19—C20—H20A	109.5
O1—C8—C9	119.5 (4)	C19—C20—H20B	109.5
N1—C8—C9	119.2 (3)	H20A—C20—H20B	109.5
C10—C9—C14	117.6 (4)	C19—C20—H20C	109.5
C10—C9—C8	116.4 (4)	H20A—C20—H20C	109.5
C14—C9—C8	126.0 (4)	H20B—C20—H20C	109.5
C9—C10—C11	121.7 (5)	C8—N1—C7	121.0 (4)
C9—C10—H10	119.1	C8—N1—H1A	119.5
C11—C10—H10	119.1	C7—N1—H1A	119.5
C12—C11—C10	120.3 (5)	C16—N2—C17	122.1 (4)
C12—C11—H11	119.9	C16—N2—H2A	118.9
C10—C11—H11	119.9	C17—N2—H2A	118.9
C11—C12—C13	120.0 (5)	C18—N3—C18i	113.2 (5)
C11—C12—H12	120.0	C18—N3—HN3	102 (2)
C13—C12—H12	120.0	C18i—N3—HN3	117 (2)
C14—C13—C12	119.6 (5)	O7ii—N4—O5ii	127.9 (6)
C14—C13—H13	120.2	O7—N4—O5	127.9 (6)
C12—C13—H13	120.2	O7—N4—O6	116.6 (8)
O2—C14—C13	122.8 (4)	O5—N4—O6	114.7 (7)
O2—C14—C9	116.4 (4)	O7ii—N4—O6ii	116.6 (8)
C13—C14—C9	120.8 (4)	O5ii—N4—O6ii	114.7 (7)
O2—C15—C16	106.9 (4)	C14—O2—C15	119.3 (3)
O2—C15—H15A	110.3	C19—O4—H4A	107.3
C16—C15—H15A	110.3
C6—C1—C2—C3	1.2 (8)	C12—C13—C14—O2	−178.0 (4)
C1—C2—C3—C4	−1.2 (8)	C12—C13—C14—C9	1.7 (7)
C2—C3—C4—C5	0.5 (9)	C10—C9—C14—O2	178.5 (4)
C3—C4—C5—C6	0.1 (8)	C8—C9—C14—O2	−1.8 (5)
C2—C1—C6—C5	−0.5 (7)	C10—C9—C14—C13	−1.2 (6)
C2—C1—C6—C7	−179.8 (5)	C8—C9—C14—C13	178.5 (4)
C4—C5—C6—C1	−0.1 (7)	O2—C15—C16—O3	23.1 (6)
C4—C5—C6—C7	179.2 (5)	O2—C15—C16—N2	−157.5 (4)
C1—C6—C7—N1	−155.0 (4)	N2—C17—C18—N3	−56.5 (5)
C5—C6—C7—N1	25.7 (7)	O1—C8—N1—C7	−3.7 (5)
O1—C8—C9—C10	−7.0 (5)	C9—C8—N1—C7	177.2 (3)
N1—C8—C9—C10	172.1 (4)	C6—C7—N1—C8	69.5 (5)
O1—C8—C9—C14	173.3 (3)	O3—C16—N2—C17	1.6 (7)
N1—C8—C9—C14	−7.6 (5)	C15—C16—N2—C17	−177.8 (4)
C14—C9—C10—C11	0.2 (6)	C18—C17—N2—C16	−78.9 (5)
C8—C9—C10—C11	−179.6 (4)	C17—C18—N3—C18i	−169.9 (4)
C9—C10—C11—C12	0.4 (8)	C13—C14—O2—C15	1.8 (6)
C10—C11—C12—C13	0.0 (9)	C9—C14—O2—C15	−177.9 (3)
C11—C12—C13—C14	−1.1 (8)	C16—C15—O2—C14	179.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—HN3···O5iii	0.95 (4)	2.49 (5)	2.905 (9)	106 (3)
N3—HN3···O5iv	0.95 (4)	2.41 (5)	2.905 (9)	112 (3)
N3—HN3···O1iv	0.95 (4)	2.01 (4)	2.780 (3)	137 (4)
O4—H4A···O3v	0.85	1.89	2.740 (11)	178
N1—H1A···O2	0.86	1.99	2.645 (5)	132
N2—H2A···O5iv	0.86	2.14	2.813 (9)	135
N2—H2A···O6iii	0.86	2.35	3.185 (9)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—HN3⋯O5i	0.95 (4)	2.49 (5)	2.905 (9)	106 (3)
N3—HN3⋯O5ii	0.95 (4)	2.41 (5)	2.905 (9)	112 (3)
N3—HN3⋯O1ii	0.95 (4)	2.01 (4)	2.780 (3)	137 (4)
O4—H4A⋯O3iii	0.85	1.89	2.740 (11)	178
N1—H1A⋯O2	0.86	1.99	2.645 (5)	132
N2—H2A⋯O5ii	0.86	2.14	2.813 (9)	135
N2—H2A⋯O6i	0.86	2.35	3.185 (9)	163

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