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The phthalate salt of diprotonated diethyl­ene­tri­amine, C4H15N3+·C8H4O4-, was obtained during ongoing studies of the hydro­lytic chemistry of phthal­imides for the synthesis of efficient sensitizers for EuIII and TbIII photo­lumin­escence.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800018432/na6014sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800018432/na6014Isup2.hkl
Contains datablock I

CCDC reference: 155862

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.040
  • wR factor = 0.119
  • Data-to-parameter ratio = 11.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
THETM_01 Alert B The value of sine(theta_max)/wavelength is less than 0.575 Calculated sin(theta_max)/wavelength = 0.5716
Author response: ... The actual value of sine(theta_max)/wavelength used, 0.572, is only slightly less than the desired value and at this point no diffraction measureably above background was detected. With copper radiation unavailable and no ready access to low temperature data collection facilities, it did not appear possible to collect meaningful intensity data beyond this point. We note that the structure is quite adequately determined despite this and trust that you will concur.

Yellow Alert Alert Level C:
PLAT_353 Alert C Long N-H Bond (0.87A) N(1) - H(1A) = 1.02 Ang. PLAT_353 Alert C Long N-H Bond (0.87A) N(3) - H(3A) = 1.03 Ang.
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

The phthalate salt [NH3(CH2)2NH(CH2)2NH3][1,2-C6H4(COO)2], (I), was obtained in the course of studies of the hydrolytic processes of phthalimides to phthalates through phthalamate intermediates which are of interest as efficient sensitizers for EuIII and TbIII photoluminescence (Barrett et al., 1995, 1998). The structure consists of sheets of cations sandwiched between two sheets of anions. There is extensive hydrogen bonding between the cations and anions.

Experimental top

The title compound was obtained by heating a mixture of 3.5 mmol of phthalic anhydride with 1.9 mmol of diethylenetriamine in an oil bath until the mixture had formed a uniform brown melt. After the melt solidified, it was ground to a powder and dissolved in aqueous ethanol from which the the product crystallized as colourless plates. Analysis calculated for C12H19N3O4: C 53.1, H 7.1, N 15.6%; found: C 53.6, H 7.1, N 15.6%.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A portion of the hydrogen-bonded network in (I).
Diethylenetriamine dihdrophthalate top
Crystal data top
C4H15N3+·C8H4O4F(000) = 576
Mr = 269.30Dx = 1.269 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.7634 (8) ÅCell parameters from 25 reflections
b = 11.025 (1) Åθ = 15.1–23.2°
c = 12.0322 (7) ŵ = 0.10 mm1
β = 115.378 (1)°T = 293 K
V = 1409.0 (2) Å3Plate, colourless
Z = 40.53 × 0.40 × 0.13 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.035
Radiation source: fine-focus sealed tubeθmax = 24.0°, θmin = 1.9°
Graphite monochromatorh = 013
θ/2θ scansk = 012
2335 measured reflectionsl = 1312
2218 independent reflections2 standard reflections every 120 min
1371 reflections with I > 2σ(I) intensity decay: 3.4%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0629P)2 + 0.1498P]
where P = (Fo2 + 2Fc2)/3
2218 reflections(Δ/σ)max = 0.001
200 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C4H15N3+·C8H4O4V = 1409.0 (2) Å3
Mr = 269.30Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.7634 (8) ŵ = 0.10 mm1
b = 11.025 (1) ÅT = 293 K
c = 12.0322 (7) Å0.53 × 0.40 × 0.13 mm
β = 115.378 (1)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.035
2335 measured reflectionsθmax = 24.0°
2218 independent reflections2 standard reflections every 120 min
1371 reflections with I > 2σ(I) intensity decay: 3.4%
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.119H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.20 e Å3
2218 reflectionsΔρmin = 0.18 e Å3
200 parameters
Special details top

Experimental. General procedures for crystal alignment, unit cell determination and refinement and collection of intensity data have been published (Mague, J. T. & Lloyd, C. L. (1988). Organometallics 7, 983–993). The crystal was mounted in a thin-walled capillary which was then flame-sealed.

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. H-atoms attached to nitrogen were refined with isotropic displacement parameters while the remainder of the H-atoms were placed in calculated positions riding on the attached carbon atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.76079 (18)0.0159 (2)0.47152 (17)0.0662 (6)
O20.92677 (15)0.11559 (16)0.60395 (15)0.0451 (5)
O31.01283 (15)0.21397 (15)0.88155 (16)0.0437 (5)
O41.01029 (15)0.01335 (15)0.86180 (16)0.0456 (5)
C10.7505 (2)0.09581 (19)0.6492 (2)0.0328 (6)
C20.8158 (2)0.1178 (2)0.7749 (2)0.0341 (6)
C30.7493 (2)0.1416 (2)0.8438 (2)0.0459 (7)
H30.79280.15690.92760.055*
C40.6202 (3)0.1429 (3)0.7900 (3)0.0608 (8)
H40.57670.15920.83710.073*
C50.5551 (2)0.1200 (3)0.6655 (3)0.0580 (8)
H50.46760.11960.62880.070*
C60.6201 (2)0.0981 (2)0.5968 (3)0.0463 (7)
H60.57580.08430.51280.056*
C70.8184 (2)0.0747 (2)0.5689 (2)0.0364 (6)
C80.9574 (2)0.1144 (2)0.8416 (2)0.0356 (6)
N11.1283 (2)0.0689 (2)0.6832 (2)0.0387 (5)
H1A1.161 (2)0.052 (2)0.619 (2)0.054 (8)*
H1B1.080 (3)0.141 (3)0.658 (3)0.082 (10)*
H1C1.070 (3)0.008 (3)0.682 (3)0.062 (9)*
N21.2352 (2)0.13870 (19)0.8313 (2)0.0417 (5)
H21.197 (2)0.133 (2)0.876 (2)0.041 (8)*
N31.1116 (2)0.3008 (2)0.6339 (2)0.0447 (6)
H3A1.084 (3)0.293 (3)0.541 (3)0.088 (11)*
H3B1.076 (2)0.375 (3)0.646 (2)0.056 (8)*
H3C1.080 (3)0.248 (3)0.660 (3)0.060 (10)*
C91.2363 (2)0.0796 (2)0.8049 (2)0.0448 (7)
H9A1.28920.14680.80420.054*
H9B1.20620.09600.86680.054*
C101.3128 (2)0.0368 (2)0.8368 (3)0.0474 (7)
H10A1.38050.03020.91900.057*
H10B1.35000.04870.77960.057*
C111.2859 (2)0.2580 (2)0.8323 (2)0.0482 (7)
H11A1.37680.25650.87750.058*
H11B1.25260.31500.87220.058*
C121.2497 (2)0.2966 (2)0.7014 (2)0.0481 (7)
H12A1.28460.37610.70030.058*
H12B1.28360.23970.66190.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0649 (13)0.0957 (16)0.0474 (12)0.0321 (12)0.0330 (11)0.0286 (11)
O20.0376 (10)0.0561 (12)0.0455 (11)0.0098 (9)0.0215 (8)0.0025 (8)
O30.0404 (10)0.0368 (10)0.0506 (11)0.0058 (8)0.0164 (8)0.0120 (8)
O40.0448 (10)0.0358 (10)0.0553 (12)0.0039 (8)0.0206 (9)0.0063 (8)
C10.0344 (13)0.0253 (12)0.0398 (14)0.0013 (10)0.0170 (11)0.0000 (10)
C20.0377 (13)0.0256 (12)0.0434 (14)0.0029 (10)0.0217 (12)0.0019 (10)
C30.0476 (16)0.0524 (16)0.0444 (15)0.0048 (13)0.0262 (13)0.0074 (13)
C40.0528 (18)0.072 (2)0.075 (2)0.0050 (15)0.0432 (17)0.0130 (17)
C50.0330 (14)0.069 (2)0.076 (2)0.0065 (14)0.0273 (15)0.0094 (17)
C60.0382 (15)0.0489 (16)0.0477 (15)0.0059 (12)0.0146 (13)0.0079 (12)
C70.0388 (14)0.0356 (13)0.0360 (14)0.0020 (11)0.0172 (12)0.0029 (11)
C80.0456 (14)0.0332 (14)0.0317 (13)0.0011 (12)0.0199 (11)0.0000 (11)
N10.0436 (12)0.0331 (12)0.0424 (13)0.0008 (11)0.0213 (11)0.0015 (10)
N20.0414 (12)0.0412 (13)0.0449 (13)0.0002 (10)0.0207 (11)0.0035 (10)
N30.0459 (14)0.0329 (13)0.0515 (16)0.0001 (11)0.0174 (12)0.0025 (11)
C90.0491 (15)0.0377 (14)0.0463 (16)0.0053 (12)0.0193 (13)0.0045 (11)
C100.0389 (14)0.0461 (16)0.0476 (16)0.0052 (12)0.0093 (13)0.0007 (12)
C110.0416 (15)0.0392 (15)0.0536 (18)0.0031 (12)0.0106 (13)0.0107 (12)
C120.0414 (15)0.0402 (15)0.0636 (19)0.0007 (12)0.0233 (14)0.0007 (13)
Geometric parameters (Å, º) top
O1—C71.253 (3)C3—C41.371 (4)
O2—C71.243 (3)C4—C51.382 (4)
O3—C81.262 (3)C5—C61.368 (4)
O4—C81.248 (3)N1—C91.476 (3)
C1—C61.386 (3)N2—C101.431 (3)
C1—C21.393 (3)N2—C111.442 (3)
C1—C71.512 (3)N3—C121.473 (3)
C2—C31.387 (3)C9—C101.519 (4)
C2—C81.509 (3)C11—C121.506 (4)
C6—C1—C2118.5 (2)O2—C7—C1118.2 (2)
C6—C1—C7119.8 (2)O1—C7—C1117.0 (2)
C2—C1—C7121.6 (2)O4—C8—O3124.7 (2)
C3—C2—C1119.5 (2)O4—C8—C2118.0 (2)
C3—C2—C8117.6 (2)O3—C8—C2117.0 (2)
C1—C2—C8122.8 (2)C10—N2—C11117.5 (2)
C4—C3—C2120.9 (3)N1—C9—C10110.4 (2)
C3—C4—C5119.8 (3)N2—C10—C9110.8 (2)
C6—C5—C4119.6 (2)N2—C11—C12108.6 (2)
C5—C6—C1121.6 (3)N3—C12—C11109.6 (2)
O2—C7—O1124.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i1.01 (3)1.75 (3)2.755 (3)171 (2)
N1—H1A···O2i1.01 (3)2.53 (3)3.271 (3)129.9 (19)
N1—H1B···O3ii0.95 (3)1.88 (4)2.826 (3)176 (3)
N1—H1C···O20.95 (3)2.06 (3)2.954 (3)156 (2)
N1—H1C···O40.95 (3)2.56 (3)3.151 (3)121 (2)
N2—H2···O30.83 (3)2.38 (3)3.042 (3)137 (2)
N2—H2···O40.83 (3)2.51 (3)3.143 (3)134 (2)
N3—H3A···O3iii1.03 (3)1.73 (4)2.752 (3)170 (3)
N3—H3B···O4iv0.96 (3)1.81 (3)2.759 (3)169 (2)
N3—H3C···O20.82 (3)2.19 (3)2.890 (3)143 (3)
Symmetry codes: (i) x+2, y, z+1; (ii) x+2, y1/2, z+3/2; (iii) x, y+1/2, z1/2; (iv) x+2, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC4H15N3+·C8H4O4
Mr269.30
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)11.7634 (8), 11.025 (1), 12.0322 (7)
β (°) 115.378 (1)
V3)1409.0 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.53 × 0.40 × 0.13
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2335, 2218, 1371
Rint0.035
θmax (°)24.0
(sin θ/λ)max1)0.572
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.119, 1.02
No. of reflections2218
No. of parameters200
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.20, 0.18

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i1.01 (3)1.75 (3)2.755 (3)171 (2)
N1—H1A···O2i1.01 (3)2.53 (3)3.271 (3)129.9 (19)
N1—H1B···O3ii0.95 (3)1.88 (4)2.826 (3)176 (3)
N1—H1C···O20.95 (3)2.06 (3)2.954 (3)156 (2)
N1—H1C···O40.95 (3)2.56 (3)3.151 (3)121 (2)
N2—H2···O30.83 (3)2.38 (3)3.042 (3)137 (2)
N2—H2···O40.83 (3)2.51 (3)3.143 (3)134 (2)
N3—H3A···O3iii1.03 (3)1.73 (4)2.752 (3)170 (3)
N3—H3B···O4iv0.96 (3)1.81 (3)2.759 (3)169 (2)
N3—H3C···O20.82 (3)2.19 (3)2.890 (3)143 (3)
Symmetry codes: (i) x+2, y, z+1; (ii) x+2, y1/2, z+3/2; (iii) x, y+1/2, z1/2; (iv) x+2, y+1/2, z+3/2.
 

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