Single crystals of the 4,4’-diamoniumdiphenylmethan sulfate hydrate, denoted DDPS, were grown by slow evaporation solution technique at room temperature. The compound was characterized by single crystal X-ray diffraction, IR and thermal analysis (TG-DTA). It crystallizes in the monoclinic system (space group C2/c) with the following unit cell dimensions: a = 17.7635(10) Å, b = 9.3796(10) Å, c = 27.5676(10) Å, β = 97.367(2), V = 4555.2(6) Å. The structure was solved by the direct method and refined to final R value of 0.0472 for 2108 independent reflections. The anions are hydrogen bonded to each other, forming clusters [HS 2O 8] 3﹣ parallel to the plan (a, b). The water molecules connect these clusters via O-H···O hydrogen bonds. The organic cations are attached to the clusters through N-H···O hydrogen bonds, forming an infinite three-dimensional network.
The chemistry of hybrid materials has received an important growth in last two decades; it was an impressive area of research for many investigations in different field of sciences [
The title compound (DDPS) is an additional example for illustrating the templating effect of aromatic ammonium molecules on sulfate. In addition, structural considerations resulting from crystallographic studies, some organic sulfates exhibit non-linear optical properties [
By slow evaporation single crystals of the studied compound were obtained from a solution of 4,4’-diaminodiphenylmethan [Sigma-Aldrich] and sulfuric acid (98 wt% from Fluka) as obtained from commercial sources without further purification. A solution of 4,4’-diaminodiphenylmethan (1.98 g, 0.01 mol) in 200 mL of water was added to a solution of sulfuric acid. The resulting solution was filtered through paper and left at room temperature. After several days, transparent and good single crystals were produced, which were filtered and air dried.
The intensity data collection was performed using an Enraf-Noniusdiffracto- meter and monochromated Mo radiation (λ = 0.71073 Å). Pertinent details of the crystal structure of (C13H16N2)1.5HSO4SO4·H1.5O are listed. The strategy used for the structure determination and its final results are gathered in
Compound | (C13H16N2)1.5HSO4 SO4·H1.5O |
---|---|
Color/shape | Colorless/prismatic |
Formula weight | 511.06 g/mol |
Crystal system | monoclinic |
Space group | C2/c(15) |
Temperature, K | 293(2) |
Unit cell dimensions | |
a = 17.7635(10) Å | |
b = 9.3796(10) Å | β = 97.37(2) |
c = 27.5676(10) Å | |
Cell volume, Å3 | 4555.2(6) |
Z | 8 |
Density (calculated), g/cm3 | 1.490 |
Absorption coefficient, mm−1 | 0.291 |
diffraction measurement device | Enraf-Nonius CAD4 |
Radiation, graphite monochr | MoKα (λ = 0.71073 Å) |
Max. crystal dimensions, mm | 0.15 × 0.2 × 0.3 |
θ range | 2 - 25.00 |
Range of h, k | −16 ≤ h ≤ 16, −2 ≤ k ≤ 9, 0 ≤ l ≤ 26 |
Number of independent ref. | 2108 |
Unique reflexions included: (I > 2σI) | 1807 |
Computer programs | SHELX-97 [ |
Data reductions programs | Denzo [ |
Refined parameters | 409 |
Goodness of fit on F2 | 1.00 |
R | 0.0472 |
Rw | 0.1265 |
Extinction coefficient | 0.0002(3) |
Δρmin./Δρmax. (e/Å3) | −0.480/0.311 |
Langest shift error max/min | 0.0002/0.000 |
Fourier maps using the SHELXL-97 programs [
IR spectrum of DDPS was recorded at room temperature with a Biored FTS 6000 FTIR spectrometer over the wave number range of 4000 - 400 cm−1 with a resolution of about 4 cm−1. Thin, transparent pellet was made by compacting an intimate mixture obtained by shaking 2 mg of the samples in 100 mg of KBr.
Setaram TG-DTA92 thermoanalyzer was used to perform thermal analysis on samples of DDPS. The TG-DTA thermograms were obtained with 21.5 mg. Samples were placed in an open platinum crucible and heated in air with 5˚C/ min heating rate; an empty crucible was used as reference.
The crystal of the title compound is built up from 4,4’-diamoniumdiphenyl- methan cations, two types of sulfate anions with different ionization state, i.e. [HSO4]− monoanions and [SO4]2− dianions, and from water molecules.
A view of the structure projected along the b axis is reported in
S(1) | O(1) | O(2) | O(3) | O(4) |
---|---|---|---|---|
O(1) | 1.4449(4) | 113.25(2) | 112.45(2) | 102.9(2) |
O(2) | 2.3827(4) | 1.4082(4) | 111.43(2) | 109.92(2) |
O(3) | 2.3920(4) | 2.3474(4) | 1.4327(4) | 106.29(2) |
O(4) | 2.3448(4) | 2.4251(4) | 2.3894(4) | 1.5520(4) |
O(4)―H(O4) = 0.70(17) S(1)―O(4)―H(O4) = 126(10) | ||||
S(2) | O(5) | O(6) | O(7) | O(8) |
O(5) | 1.4382(4) | 108.69(2) | 111.63(2) | 110.19(2) |
O(6) | 2.3581(4) | 1.4638(4) | 109.86(2) | 108.71(2) |
O(7) | 2.4108(4) | 2.4062(4) | 1.4761(4) | 107.72(2) |
O(8) | 2.3746(4) | 2.3738(4) | 2.9233(4) | 1.4573(4) |
Cation A | |||
---|---|---|---|
C(1)―C(2) | 1.496(5) | C(2)―C(1)―C(2) | 119.3(6) |
C(2)―C(3) | 1.388(7) | C(3)―C(2)―C(1) | 118.0(4) |
C(2)―C(7) | 1.384(7) | C(4)―C(3)―C(2) | 122.4(5) |
C(3)―C(4)―C(5) | 119.8(5) | ||
C(4)―C(5) | 1.374(6) | C(7)―C(2)―C(3) | 115.8(5) |
C(7)―C(2)―C(1) | 126.0(5) | ||
C(5)―C(6) | 1.362(6) | C(6)―C(7)―C(2) | 122.3(5) |
C(6)―C(7) | 1.358(7) | C(7)―C(6)―C(5) | 120.2(5) |
C(6)―C(5)―C(4) | 119.4(5) | ||
N(1)―C(5) | 1.435(6) | C(6)―C(5)―N(1) | 120.9(4) |
C(4)―C(5)―N(1) | 119.7(4) | ||
Cation B | |||
N(3)―C(18) | 1.451(6) | C(9)―C(8)―C(13) | 120.5(4) |
N(2)―C(8) | 1.450(6) | C(9)―C(8)―N(2) | 119.6(4) |
C(8)―C(9) | 1.369(6) | C(13)―C(8)―N(2) | 119.9(4) |
C(8)―C(13) | 1.374(6) | ||
C(9)―C(10) | 1.360(7) | C(10)―C(9)―C(8) | 119.4(5) |
C(10)―C(11) | 1.387(6) | C(9)―C(10)―C(11) | 122.6(5) |
C(11)―C(12) | 1.395(6) | C(10)―C(11)―C(12) | 115.7(4) |
C(11)―C(14) | 1.480(7) | C(10)―C(11)―(C14) | 121.6(4) |
C(12)―C(11)―(C14) | 122.7(4) | ||
C(12)―C(13) | 1.357(7) | C(13)―C(12)―C(11) | 122.8(5) |
C(14)―C(15) | 1.510(6) | C(12)―C(13)―C(8) | 119.0(5) |
C(14)―1C(14) | 1.12(5) | C(11)―C(14)―(C15) | 117.7(4) |
C(14)―2(C14) | 0.80(5) | C(11)―C(14)―1(C14) | 111(2) |
C(15)―C(14)―1(C14) | 111(2) | ||
C(15)―C(16) | 1.395(6) | C(11)―C(14)―2(C14) | 115(4) |
1.372(6) | C(15)―C(14) ―2C(14) | 105(3) | |
1C(14)―C(14)―2C(14) | 96(4) | ||
C(15)―C(20) | 1.379(6) | C(16)―C(15)―C(20) | 118.2(4) |
C(16)―C(17) | 1.402(6) | C(16)―C(15)―C(14) | 119.3(4) |
C(17)―C(18) | 1.349(6) | C(20)―C(15)―C(14) | 122.5(4) |
C(18)―C(19) | |||
C(15) ―C(16)―C(17) | 121.8(4) | ||
C(18)―C(17) | 1.402(6) | C(16)―C(17)―C(18) | 118.9(4) |
C(18)―C(19) | 1.349(6) | C(19)―C(18)―C(17) | 119.7(4) |
C(19)―C(20) | 1.382(6) | C(19)―C(18)―N(3) | 120.9(4) |
C(17)―C(18)―N(3) | 119.5(4) | ||
C(18)―C(19)―C(20) | 121.2(4) | ||
C(19)―C(20)―C(15) | 120.2(4) |
dimensional network of structural units formed by clusters [HS2O8]3− sulfate, water molecules and organic cations. The mineral skeleton of this compound is formed by basic [SO4]2− and acidic [HSO4]− groups which are interconnected via O(4)−H・・・O(8) hydrogen bond leading to the formation of isolated clusters in the (a, b) plane. The same type of hydrogen bonds O−H・・・O links these mineral entities together, in pairs, via two water molecules which share a hydrogen atom located on a C2 axis, to form a finite chains parallel to c axis (
The short distance O(4)・・・O(8) = 2.5151(6) Å, shows that this hydrogen bond was considered strong. Distances and bond angles describing the anions [SO4]2− and [HSO4]− are illustrated in
Å), which is typical value, however, one of the remaining S−O bonds (S1−O4; 1,5520(4) Å), is slightly shorter than the others S1−O2 and S1−O3; this fact can be explained by the location of a proton on oxygen O(4) of the anion , this characteristic is in line with those observed in the protonated oxoanions [
Main geometrical characteristics of these cations are summarized in
N(O)―H | H・・・O | N(O)・・・O | N(O)―H・・・O | |
---|---|---|---|---|
N(1)―H(1)N(1)・・・O(7)(i) | 1.064 | 1.757(6) | 2.814(5) | 172(4) |
N(1)―H(2)N(1)・・・O(5)(ii) | 1.044 | 2.458(7) | 3.195(6) | 139(4) |
N(1)―H(3)N(1)・・・O(1)(iii) | 0.694 | 2.148(4) | 2.841(6) | 175(4) |
N(2)―H(1)N(2)・・・O(6)(iv) | 0.922 | 1.884(5) | 2.795(5) | 169(4) |
N(2)―H(2)N(2)・・・O(3)(ii) | 0.844 | 2.043(4) | 2.882(6) | 172(4) |
N(2)―H(3)N(2)・・・O(5) | 0.891 | 2.004(5) | 2.857(6) | 160(4) |
N(3)―H(1)N(3)・・・O(1)(v) | 1.044 | 1.986(6) | 3.021(5) | 170(4) |
N(3)―H(1)N(3)・・・O(4)(v) | 1.045 | 2.4580(6) | 3.1945(6) | 127(4) |
N(3)―H(2)N(3)・・・O(7)(ii) | 0.929 | 1.880(4) | 2.796(6) | 169(1) |
N(3)―H(3)N(3)・・・O(6)(vi) | 0.774 | 2.032(4) | 2.787(6) | 165(4) |
OW―H2OW・・・O(3)(vii) | 1.045 | 2.008(4) | 2.923(6) | 144(6) |
O(4)―HO(4)・・・O(8)(vi) | 0.705 | 2.4410(2) | 2.5151(6) | 87(12) |
1Symmetrycode: i: x − 1/2, −y + 3/2, z − 1/2; ii: −x + 3/2, y + 1/2, −z + 3/2; iii: x − 1/2, y + 3/2; ziv: −x + 3/2, −y + 3/2, −z + 2; v: x − 1/2, y + 1/2, z vi: x, −y + 1, z − 1/2; vii: x − 1, y, z.
Recently, several researches on the vibrational properties of organic sulfates containing HSO4 and SO4 groups had been widely investigated [
These studies have been focused, essentially, on the relationship between symmetry considerations and normalmodes vibrations of these groups. The common result is that these groups loose theirs free state symmetry (Td for SO4 and C3v for HSO4) to be C1 under the effect of its incorporation in the complex and its interaction with its crystalline environment. As a result, the vibrational properties are affected by moving the degeneracy of some normal modes, splitting of some IR active modes and appearance of some IR inactive modes. Here, we recall that the free ion SO4, in its ideal Td symmetry are ν1 = 981 cm−1, ν2 = 451 cm−1, ν3 = 1104 cm−1 and ν4 = 614 cm−1 [
While that connected to the symmetry of valence SO4 group is presented by the band 992 cm−1. Bands observed in the 992 - 1186 cm−1, on asymmetrical valence vibration νs(SO4) δas(SO4) region.
The simultaneous TG?DTA analysis curves of (C13H16N2)1.5HSO4SO4·H1.5O were carried out in air at a heating rate of 5˚C/min on a sample of 21.5 mg placed in a platinum crucible and heated from ambient to 325˚C. The result obtained during the decomposition of the title compound is illustrated in
The crystals of the 4,4’-diamoniumdiphenylmethan sulfate hydrate, (C13H16N2)1.5 HSO4SO4·H1.5O, have been synthesized by slow evaporation method at room temperature. The X-ray diffraction helped us to determine the cell parameters and the space group. The structural study showed that the anionic groups SO4 and HSO4 are gathered by inter-anionic strong hydrogen bonds giving birth to clusters
[HS2O8]3−. It is also shown the scheme of hydrogen bonds connecting various organic cations with the sulfates clusters to yield a three-dimensional network.
The detailed vibrational spectral analysis, supported by an analysis using group theory, of the organic and the inorganic moieties was carried out leading to the counting and the allocation of frequencies characteristic of the compound.
The TG-DTA data allowed us to verify that the title salt is thermally stable up to 185˚C. The stability of the compound below this temperature can be explained by the different strong bonds observed by the X-ray diffraction. The thermal decomposition above 185˚C takes place in two steps. The endothermic peaks at 197˚C and 238˚C are due to the thermal decomposition with release of the uncoordinated water and degradation of organic entities.
Moreover, a study of the electrical conductivity of the reported compound could open to it opportunities on applied plan.
Issa, T.B. and Benhamada, L. (2017) Crystal Structure, Ther- mal Behavior and Vibrational Spectra of 4,4’Diamoniumdiphenylmethan Sulfate Hy- drate. Open Journal of Inorganic Chemistry, 7, 61-73. https://doi.org/10.4236/ojic.2017.72004
The final atomic coordinate and thermal parameters are given in
Atom | X(σ) | Y(σ) | Z(σ) | Ueq (Å2) |
---|---|---|---|---|
S(1) | 0.96253(6) | 0.06080(11) | 0.56840(4) | 0.0344(4) |
S(2) | 0.84920(5) | 0.52069(10) | 1.00769(4) | 0.0283(4) |
O(1) | 1.03122(15) | -0.0216(3) | 0.57994(12) | 0.0434(9) |
O(2) | 0.90586(18) | -0.0113(4) | 0.53733(14) | 0.0689(11) |
O(3) | 0.93390(17) | 0.1135(3) | 0.61125(12) | 0.0524(9) |
O(4) | 0.9901(2) | 0.1931(3) | 0.54180(16) | 0.0618(11) |
O(5) | 0.85254(17) | 0.5729(3) | 0.95896(11) | 0.0488(9) |
O(6) | 0.77454(16) | 0.5547(3) | 1.02175(12) | 0.0454(9) |
O(7) | 0.86231(16) | 0.3654(3) | 1.01099(11) | 0.0442(9) |
O(8) | 0.90720(17) | 0.5895(3) | 1.04201(12) | 0.0556(10) |
N(1) | 0.5054(3) | 1.1817(6) | 0.56520(16) | 0.0349(12) |
N(2) | 0.7194(3) | 0.7146(5) | 0.91374(16) | 0.0340(10) |
N(3) | 0.6685(3) | 0.6334(5) | 0.55215(16) | 0.0328(10) |
C(1) | 0.5000 | 0.9100(7) | 0.75000 | 0.0437(18) |
C(2) | 0.5022(2) | 0.9906(4) | 0.70337(16) | 0.0317(11) |
C(3) | 0.5366(3) | 0.9261(6) | 0.66661(19) | 0.0383(13) |
C(4) | 0.5383(2) | 0.9876(5) | 0.6223(2) | 0.0336(12) |
C(5) | 0.5051(2) | 1.1185(4) | 0.61256(15) | 0.0280(11) |
C(6) | 0.4700(3) | 1.1843(6) | 0.64757(18) | 0.0406(13) |
C(7) | 0.4686(3) | 1.1215(5) | 0.6918(2) | 0.0439(14) |
C(8) | 0.7374(2) | 0.7624(4) | 0.86656(15) | 0.0310(11) |
C(9) | 0.8020(3) | 0.7143(5) | 0.84970(18) | 0.0424(12) |
C(10) | 0.8195(3) | 0.7618(5) | 0.80590(18) | 0.0435(13) |
C(11) | 0.7741(2) | 0.8577(4) | 0.77711(16) | 0.0347(11) |
C(12) | 0.7085(3) | 0.9018(5) | 0.7957(2) | 0.0470(14) |
C(13) | 0.6903(3) | 0.8574(5) | 0.83955(19) | 0.0424(13) |
C(14) | 0.7949(3) | 0.9094(7) | 0.72988(18) | 0.0466(14) |
C(15) | 0.7634(2) | 0.8299(4) | 0.68415(15) | 0.0309(11) |
C(16) | 0.7894(3) | 0.8622(5) | 0.64072(17) | 0.0365(11) |
C(17) | 0.7606(2) | 0.7969(4) | 0.59745(19) | 0.0367(12) |
C(18) | 0.7017(2) | 0.6976(4) | 0.59778(15) | 0.0288(11) |
C(19) | 0.6766(3) | 0.6634(5) | 0.64043(17) | 0.0347(12) |
C(20) | 0.7059(2) | 0.7285(4) | 0.68375(17) | 0.0351(11) |