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
CCDC reference: 155862
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
|
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
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%.
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.
Diethylenetriamine dihdrophthalate
top
Crystal data top
C4H15N3+·C8H4O4− | F(000) = 576 |
Mr = 269.30 | Dx = 1.269 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.7634 (8) Å | Cell parameters from 25 reflections |
b = 11.025 (1) Å | θ = 15.1–23.2° |
c = 12.0322 (7) Å | µ = 0.10 mm−1 |
β = 115.378 (1)° | T = 293 K |
V = 1409.0 (2) Å3 | Plate, colourless |
Z = 4 | 0.53 × 0.40 × 0.13 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.035 |
Radiation source: fine-focus sealed tube | θmax = 24.0°, θmin = 1.9° |
Graphite monochromator | h = 0→13 |
θ/2θ scans | k = 0→12 |
2335 measured reflections | l = −13→12 |
2218 independent reflections | 2 standard reflections every 120 min |
1371 reflections with I > 2σ(I) | intensity decay: 3.4% |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H 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 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C4H15N3+·C8H4O4− | V = 1409.0 (2) Å3 |
Mr = 269.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.7634 (8) Å | µ = 0.10 mm−1 |
b = 11.025 (1) Å | T = 293 K |
c = 12.0322 (7) Å | 0.53 × 0.40 × 0.13 mm |
β = 115.378 (1)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.035 |
2335 measured reflections | θmax = 24.0° |
2218 independent reflections | 2 standard reflections every 120 min |
1371 reflections with I > 2σ(I) | intensity decay: 3.4% |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.119 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.20 e Å−3 |
2218 reflections | Δρmin = −0.18 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
O1 | 0.76079 (18) | 0.0159 (2) | 0.47152 (17) | 0.0662 (6) | |
O2 | 0.92677 (15) | 0.11559 (16) | 0.60395 (15) | 0.0451 (5) | |
O3 | 1.01283 (15) | 0.21397 (15) | 0.88155 (16) | 0.0437 (5) | |
O4 | 1.01029 (15) | 0.01335 (15) | 0.86180 (16) | 0.0456 (5) | |
C1 | 0.7505 (2) | 0.09581 (19) | 0.6492 (2) | 0.0328 (6) | |
C2 | 0.8158 (2) | 0.1178 (2) | 0.7749 (2) | 0.0341 (6) | |
C3 | 0.7493 (2) | 0.1416 (2) | 0.8438 (2) | 0.0459 (7) | |
H3 | 0.7928 | 0.1569 | 0.9276 | 0.055* | |
C4 | 0.6202 (3) | 0.1429 (3) | 0.7900 (3) | 0.0608 (8) | |
H4 | 0.5767 | 0.1592 | 0.8371 | 0.073* | |
C5 | 0.5551 (2) | 0.1200 (3) | 0.6655 (3) | 0.0580 (8) | |
H5 | 0.4676 | 0.1196 | 0.6288 | 0.070* | |
C6 | 0.6201 (2) | 0.0981 (2) | 0.5968 (3) | 0.0463 (7) | |
H6 | 0.5758 | 0.0843 | 0.5128 | 0.056* | |
C7 | 0.8184 (2) | 0.0747 (2) | 0.5689 (2) | 0.0364 (6) | |
C8 | 0.9574 (2) | 0.1144 (2) | 0.8416 (2) | 0.0356 (6) | |
N1 | 1.1283 (2) | −0.0689 (2) | 0.6832 (2) | 0.0387 (5) | |
H1A | 1.161 (2) | −0.052 (2) | 0.619 (2) | 0.054 (8)* | |
H1B | 1.080 (3) | −0.141 (3) | 0.658 (3) | 0.082 (10)* | |
H1C | 1.070 (3) | −0.008 (3) | 0.682 (3) | 0.062 (9)* | |
N2 | 1.2352 (2) | 0.13870 (19) | 0.8313 (2) | 0.0417 (5) | |
H2 | 1.197 (2) | 0.133 (2) | 0.876 (2) | 0.041 (8)* | |
N3 | 1.1116 (2) | 0.3008 (2) | 0.6339 (2) | 0.0447 (6) | |
H3A | 1.084 (3) | 0.293 (3) | 0.541 (3) | 0.088 (11)* | |
H3B | 1.076 (2) | 0.375 (3) | 0.646 (2) | 0.056 (8)* | |
H3C | 1.080 (3) | 0.248 (3) | 0.660 (3) | 0.060 (10)* | |
C9 | 1.2363 (2) | −0.0796 (2) | 0.8049 (2) | 0.0448 (7) | |
H9A | 1.2892 | −0.1468 | 0.8042 | 0.054* | |
H9B | 1.2062 | −0.0960 | 0.8668 | 0.054* | |
C10 | 1.3128 (2) | 0.0368 (2) | 0.8368 (3) | 0.0474 (7) | |
H10A | 1.3805 | 0.0302 | 0.9190 | 0.057* | |
H10B | 1.3500 | 0.0487 | 0.7796 | 0.057* | |
C11 | 1.2859 (2) | 0.2580 (2) | 0.8323 (2) | 0.0482 (7) | |
H11A | 1.3768 | 0.2565 | 0.8775 | 0.058* | |
H11B | 1.2526 | 0.3150 | 0.8722 | 0.058* | |
C12 | 1.2497 (2) | 0.2966 (2) | 0.7014 (2) | 0.0481 (7) | |
H12A | 1.2846 | 0.3761 | 0.7003 | 0.058* | |
H12B | 1.2836 | 0.2397 | 0.6619 | 0.058* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0649 (13) | 0.0957 (16) | 0.0474 (12) | −0.0321 (12) | 0.0330 (11) | −0.0286 (11) |
O2 | 0.0376 (10) | 0.0561 (12) | 0.0455 (11) | −0.0098 (9) | 0.0215 (8) | −0.0025 (8) |
O3 | 0.0404 (10) | 0.0368 (10) | 0.0506 (11) | −0.0058 (8) | 0.0164 (8) | −0.0120 (8) |
O4 | 0.0448 (10) | 0.0358 (10) | 0.0553 (12) | 0.0039 (8) | 0.0206 (9) | 0.0063 (8) |
C1 | 0.0344 (13) | 0.0253 (12) | 0.0398 (14) | −0.0013 (10) | 0.0170 (11) | 0.0000 (10) |
C2 | 0.0377 (13) | 0.0256 (12) | 0.0434 (14) | −0.0029 (10) | 0.0217 (12) | −0.0019 (10) |
C3 | 0.0476 (16) | 0.0524 (16) | 0.0444 (15) | −0.0048 (13) | 0.0262 (13) | −0.0074 (13) |
C4 | 0.0528 (18) | 0.072 (2) | 0.075 (2) | −0.0050 (15) | 0.0432 (17) | −0.0130 (17) |
C5 | 0.0330 (14) | 0.069 (2) | 0.076 (2) | −0.0065 (14) | 0.0273 (15) | −0.0094 (17) |
C6 | 0.0382 (15) | 0.0489 (16) | 0.0477 (15) | −0.0059 (12) | 0.0146 (13) | −0.0079 (12) |
C7 | 0.0388 (14) | 0.0356 (13) | 0.0360 (14) | −0.0020 (11) | 0.0172 (12) | 0.0029 (11) |
C8 | 0.0456 (14) | 0.0332 (14) | 0.0317 (13) | −0.0011 (12) | 0.0199 (11) | 0.0000 (11) |
N1 | 0.0436 (12) | 0.0331 (12) | 0.0424 (13) | −0.0008 (11) | 0.0213 (11) | −0.0015 (10) |
N2 | 0.0414 (12) | 0.0412 (13) | 0.0449 (13) | 0.0002 (10) | 0.0207 (11) | −0.0035 (10) |
N3 | 0.0459 (14) | 0.0329 (13) | 0.0515 (16) | 0.0001 (11) | 0.0174 (12) | 0.0025 (11) |
C9 | 0.0491 (15) | 0.0377 (14) | 0.0463 (16) | 0.0053 (12) | 0.0193 (13) | 0.0045 (11) |
C10 | 0.0389 (14) | 0.0461 (16) | 0.0476 (16) | 0.0052 (12) | 0.0093 (13) | 0.0007 (12) |
C11 | 0.0416 (15) | 0.0392 (15) | 0.0536 (18) | −0.0031 (12) | 0.0106 (13) | −0.0107 (12) |
C12 | 0.0414 (15) | 0.0402 (15) | 0.0636 (19) | 0.0007 (12) | 0.0233 (14) | 0.0007 (13) |
Geometric parameters (Å, º) top
O1—C7 | 1.253 (3) | C3—C4 | 1.371 (4) |
O2—C7 | 1.243 (3) | C4—C5 | 1.382 (4) |
O3—C8 | 1.262 (3) | C5—C6 | 1.368 (4) |
O4—C8 | 1.248 (3) | N1—C9 | 1.476 (3) |
C1—C6 | 1.386 (3) | N2—C10 | 1.431 (3) |
C1—C2 | 1.393 (3) | N2—C11 | 1.442 (3) |
C1—C7 | 1.512 (3) | N3—C12 | 1.473 (3) |
C2—C3 | 1.387 (3) | C9—C10 | 1.519 (4) |
C2—C8 | 1.509 (3) | C11—C12 | 1.506 (4) |
| | | |
C6—C1—C2 | 118.5 (2) | O2—C7—C1 | 118.2 (2) |
C6—C1—C7 | 119.8 (2) | O1—C7—C1 | 117.0 (2) |
C2—C1—C7 | 121.6 (2) | O4—C8—O3 | 124.7 (2) |
C3—C2—C1 | 119.5 (2) | O4—C8—C2 | 118.0 (2) |
C3—C2—C8 | 117.6 (2) | O3—C8—C2 | 117.0 (2) |
C1—C2—C8 | 122.8 (2) | C10—N2—C11 | 117.5 (2) |
C4—C3—C2 | 120.9 (3) | N1—C9—C10 | 110.4 (2) |
C3—C4—C5 | 119.8 (3) | N2—C10—C9 | 110.8 (2) |
C6—C5—C4 | 119.6 (2) | N2—C11—C12 | 108.6 (2) |
C5—C6—C1 | 121.6 (3) | N3—C12—C11 | 109.6 (2) |
O2—C7—O1 | 124.8 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 1.01 (3) | 1.75 (3) | 2.755 (3) | 171 (2) |
N1—H1A···O2i | 1.01 (3) | 2.53 (3) | 3.271 (3) | 129.9 (19) |
N1—H1B···O3ii | 0.95 (3) | 1.88 (4) | 2.826 (3) | 176 (3) |
N1—H1C···O2 | 0.95 (3) | 2.06 (3) | 2.954 (3) | 156 (2) |
N1—H1C···O4 | 0.95 (3) | 2.56 (3) | 3.151 (3) | 121 (2) |
N2—H2···O3 | 0.83 (3) | 2.38 (3) | 3.042 (3) | 137 (2) |
N2—H2···O4 | 0.83 (3) | 2.51 (3) | 3.143 (3) | 134 (2) |
N3—H3A···O3iii | 1.03 (3) | 1.73 (4) | 2.752 (3) | 170 (3) |
N3—H3B···O4iv | 0.96 (3) | 1.81 (3) | 2.759 (3) | 169 (2) |
N3—H3C···O2 | 0.82 (3) | 2.19 (3) | 2.890 (3) | 143 (3) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y+1/2, z−1/2; (iv) −x+2, y+1/2, −z+3/2. |
Experimental details
Crystal data |
Chemical formula | C4H15N3+·C8H4O4− |
Mr | 269.30 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.7634 (8), 11.025 (1), 12.0322 (7) |
β (°) | 115.378 (1) |
V (Å3) | 1409.0 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.53 × 0.40 × 0.13 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2335, 2218, 1371 |
Rint | 0.035 |
θmax (°) | 24.0 |
(sin θ/λ)max (Å−1) | 0.572 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.119, 1.02 |
No. of reflections | 2218 |
No. of parameters | 200 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.18 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 1.01 (3) | 1.75 (3) | 2.755 (3) | 171 (2) |
N1—H1A···O2i | 1.01 (3) | 2.53 (3) | 3.271 (3) | 129.9 (19) |
N1—H1B···O3ii | 0.95 (3) | 1.88 (4) | 2.826 (3) | 176 (3) |
N1—H1C···O2 | 0.95 (3) | 2.06 (3) | 2.954 (3) | 156 (2) |
N1—H1C···O4 | 0.95 (3) | 2.56 (3) | 3.151 (3) | 121 (2) |
N2—H2···O3 | 0.83 (3) | 2.38 (3) | 3.042 (3) | 137 (2) |
N2—H2···O4 | 0.83 (3) | 2.51 (3) | 3.143 (3) | 134 (2) |
N3—H3A···O3iii | 1.03 (3) | 1.73 (4) | 2.752 (3) | 170 (3) |
N3—H3B···O4iv | 0.96 (3) | 1.81 (3) | 2.759 (3) | 169 (2) |
N3—H3C···O2 | 0.82 (3) | 2.19 (3) | 2.890 (3) | 143 (3) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y+1/2, z−1/2; (iv) −x+2, y+1/2, −z+3/2. |
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.