research papers
The crystal structure of a new phase consisting of the inclusion of the hyperpolarizable molecule p-N,N-dimethylnitroaniline (dimethyl-para-nitroaniline or dmpNA) in the large-pore zeolite mordenite (MOR) has been determined from high-resolution synchrotron powder diffraction at 300 and 90 K. The unit-cell parameters and space group at 300 K are similar to those of as-synthesized mordenite. The crystallographic study indicates that the MOR straight channels are almost fully loaded with molecules that are disordered over eight symmetry-related sites. As expected, the molecules are located in the large 12-membered ring channel, at the intersection with the secondary eight-membered channel with which they might form hydrogen bonds. The elongation axes (and then the dipole moments) of the molecules are slightly tilted (28.57°) from [001]. The configuration found suggests an interaction of dmpNA with framework O atoms through its methyl groups.
Keywords: zeolite; guest-host system; synchrotron powder diffraction; localization in channel system.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768108025287/ck5032sup1.cif | |
Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768108025287/ck503290Ksup2.rtv | |
Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768108025287/ck5032300Ksup3.rtv | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108768108025287/ck5032sup4.pdf |
CCDC references: 718166; 718167
(90K) top
Crystal data top
|Na6(O2NC6H4N(CH3)2)1.94|[Al6Si42O96]MOR{[001](12−−ring)}(Cmcm) | c = 7.49986 (2) Å |
Mr = 202.26 | V = 2761.63 (1) Å3 |
Orthorhombic, Cmcm | Z = 16 |
Hall symbol: -C 2c 2 | Synchrotron radiation |
a = 18.04416 (6) Å | T = 90 K |
b = 20.40681 (6) Å | yellow |
Data collection top
Image plate diffractometer | Specimen mounting: Glass capillary |
Radiation source: Spring-8 BL02B2 | Data collection mode: transmission |
Ge 111 monochromator | 2θmin = 0.004°, 2θmax = 75.174°, 2θstep = 0.010° |
Refinement top
Rp = 2.151 | 116 parameters |
Rwp = 3.158 | 0 restraints |
Rexp = 0.602 | H-atom parameters not refined |
RBragg = 3.947 | (Δ/σ)max = 0.05 |
7518 data points |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Si1 | 0.3028 (1) | 0.0728 (1) | 0.0413 (3) | 1.137 (9)* | |
Si2 | 0.3034 (1) | 0.3100 (2) | 0.0462 (2) | 1.137 (9)* | |
Si3 | 0.0872 (2) | 0.3824 (2) | 0.25000 | 1.137 (9)* | |
Si4 | 0.0876 (2) | 0.2265 (2) | 0.25000 | 1.137 (9)* | |
O1 | 0.1225 (3) | 0.4150 (2) | 0.4328 (5) | 2.31 (2)* | |
O2 | 0.1245 (2) | 0.1966 (3) | 0.4298 (5) | 2.31 (2)* | |
O3 | 0.2373 (2) | 0.1245 (2) | −0.0064 (5) | 2.31 (2)* | |
O4 | 0.1006 (3) | 0.3065 (4) | 0.25000 | 2.31 (2)* | |
O5 | 0.1695 (3) | 0.1977 (4) | 0.75000 | 2.31 (2)* | |
O6 | 0.1768 (4) | 0.4212 (3) | 0.75000 | 2.31 (2)* | |
O7 | 0.2724 (4) | 0.00000 | 0.00000 | 2.31 (2)* | |
O8 | 0.25000 | 0.25000 | 0.50000 | 2.31 (2)* | |
O9 | 0.00000 | 0.4011 (5) | 0.25000 | 2.31 (2)* | |
O10 | 0.00000 | 0.2035 (5) | 0.25000 | 2.31 (2)* | |
Na1 | 0.50000 | 0.0740 (5) | 0.25000 | 8.7 (1)* | 0.8092 (8) |
Na2 | 0.50000 | 0.00000 | 0.00000 | 3.4 (1)* | 0.4988 (8) |
C1 | 0.96917 | 0.08805 | −0.15883 | 2.88 (5)* | 0.12114 (5) |
C2 | 0.99434 | 0.11504 | 0.00489 | 2.88 (5)* | 0.12114 (5) |
H1 | 1.02552 | 0.15282 | 0.00740 | 2.88 (5)* | 0.12114 (5) |
C3 | 0.97423 | 0.08795 | 0.16509 | 2.88 (5)* | 0.12114 (5) |
H2 | 0.98878 | 0.10541 | 0.27255 | 2.88 (5)* | 0.12114 (5) |
C4 | 0.92691 | 0.03429 | 0.16829 | 2.88 (5)* | 0.12114 (5) |
H3 | 0.86559 | −0.02763 | 0.01115 | 2.88 (5)* | 0.12114 (5) |
C5 | 0.90025 | 0.00719 | 0.01027 | 2.88 (5)* | 0.12114 (5) |
H4 | 0.90019 | 0.01319 | −0.25275 | 2.88 (5)* | 0.12114 (5) |
C6 | 0.92115 | 0.03353 | −0.15125 | 2.88 (5)* | 0.12114 (5) |
N1 | 0.99059 | 0.11422 | −0.31712 | 2.88 (5)* | 0.12114 (5) |
C7 | 1.03397 | 0.17357 | −0.32350 | 2.88 (5)* | 0.12114 (5) |
H7 | 1.01116 | 0.21014 | −0.25844 | 2.88 (5)* | 0.12114 (5) |
H6 | 1.04659 | 0.18559 | −0.44747 | 2.88 (5)* | 0.12114 (5) |
H5 | 1.07979 | 0.17089 | −0.25871 | 2.88 (5)* | 0.12114 (5) |
C8 | 0.96571 | 0.08522 | −0.48416 | 2.88 (5)* | 0.12114 (5) |
H10 | 0.97717 | 0.04382 | −0.49072 | 2.88 (5)* | 0.12114 (5) |
H9 | 0.98904 | 0.10803 | −0.58267 | 2.88 (5)* | 0.12114 (5) |
H8 | 0.91264 | 0.08815 | −0.50018 | 2.88 (5)* | 0.12114 (5) |
N2 | 0.90302 | 0.00831 | 0.33662 | 2.88 (5)* | 0.12114 (5) |
OA | 0.86189 | −0.04077 | 0.33595 | 2.88 (5)* | 0.12114 (5) |
OB | 0.92329 | 0.03521 | 0.47581 | 2.88 (5)* | 0.12114 (5) |
Geometric parameters (Å, º) top
Si1—O1i | 1.594 (6) | Si3—O1 | 1.652 (4) |
Si1—O3 | 1.624 (5) | Si3—O1iii | 1.652 (4) |
Si1—O6i | 1.613 (3) | Si3—O4 | 1.567 (9) |
Si1—O7 | 1.614 (3) | Si3—O9 | 1.618 (4) |
Si2—O2i | 1.573 (4) | Si4—O2 | 1.623 (5) |
Si2—O3ii | 1.554 (5) | Si4—O2iii | 1.623 (5) |
Si2—O5i | 1.613 (2) | Si4—O4 | 1.649 (9) |
Si2—O8iii | 1.596 (3) | Si4—O10 | 1.649 (4) |
O1i—Si1—O3 | 113.7 (5) | O4—Si3—O9 | 112.6 (7) |
O1i—Si1—O6i | 106.9 (4) | O2—Si4—O2iii | 112.3 (4) |
O1i—Si1—O7 | 109.5 (5) | O2—Si4—O4 | 108.3 (6) |
O3—Si1—O6i | 109.3 (4) | O2iii—Si4—O4 | 108.3 (6) |
O3—Si1—O7 | 108.0 (3) | O2—Si4—O10 | 106.6 (3) |
O6i—Si1—O7 | 109.5 (3) | O2iii—Si4—O10 | 106.6 (3) |
O2i—Si2—O3ii | 111.0 (4) | O4—Si4—O10 | 114.7 (7) |
O2i—Si2—O5i | 105.5 (3) | Si1iv—O1—Si3 | 144.4 (3) |
O2i—Si2—O8iii | 108.3 (3) | Si2iv—O2—Si4 | 146.4 (3) |
O3ii—Si2—O5i | 114.1 (4) | Si1—O3—Si2ii | 160.9 (3) |
O3ii—Si2—O8iii | 109.5 (3) | Si3—O4—Si4 | 162.9 (5) |
O5i—Si2—O8iii | 108.3 (3) | Si2iv—O5—Si2v | 142.8 (2) |
O1—Si3—O1iii | 112.1 (4) | Si1iv—O6—Si1v | 152.2 (3) |
O1—Si3—O4 | 109.8 (4) | Si1—O7—Si1vi | 140.2 (3) |
O1iii—Si3—O4 | 109.8 (6) | Si2iii—O8—Si2iv | 180.0 |
O1—Si3—O9 | 106.3 (4) | Si3—O9—Si3vii | 152.7 (4) |
O1iii—Si3—O9 | 106.3 (4) | Si4—O10—Si4vii | 146.9 (4) |
Symmetry codes: (i) −x+1/2, −y+1/2, z−1/2; (ii) −x+1/2, −y+1/2, −z; (iii) x, y, −z+1/2; (iv) −x+1/2, −y+1/2, z+1/2; (v) −x+1/2, −y+1/2, −z+1; (vi) x, −y, −z; (vii) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | H···A | D···A | D—H···A |
C2—H1···O2viii | 2.052 (4) | 2.920 (5) | 150.4 (4) |
C2—H1···O10ix | 2.143 (5) | 2.578 (7) | 106.3 (5) |
C3—H2···O10ix | 2.02 (1) | 2.49 (1) | 109.8 (8) |
C7—H5···O5x | 1.71 | 2.56 | 145 |
C7—H6···O2x | 1.70 | 2.51 | 137 |
C8—H8···O2xi | 2.37 | 2.87 | 111 |
C8—H9···O10x | 2.33 | 3.19 | 148 |
Symmetry codes: (viii) x+1, y, −z+1/2; (ix) x+1, y, z; (x) x+1, y, z−1; (xi) −x+1, y, z−1. |
(300K) top
Crystal data top
|Na6(O2NC6H4N(CH3)2)1.94|[Al6Si42O96]MOR{[001](12−−ring)}(Cmcm) | c = 7.501445 (16) Å |
Mr = 202.26 | V = 2768.58 (1) Å3 |
Orthorhombic, Cmcm | Z = 16 |
Hall symbol: -C 2c 2 | Synchrotron radiation |
a = 18.08155 (5) Å | T = 300 K |
b = 20.41153 (5) Å | yellow |
Data collection top
Image plate diffractometer | Specimen mounting: Glass capillary |
Radiation source: Spring-8 BL02B2 | Data collection mode: transmission |
Ge 111 monochromator | 2θmin = 0.065°, 2θmax = 75.165°, 2θstep = 0.010° |
Refinement top
Rp = 2.554 | 110 parameters |
Rwp = 3.677 | 0 restraints |
Rexp = 0.671 | H-atom parameters not refined |
RBragg = 4.115 | (Δ/σ)max = 0.05 |
7518 data points |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Si1 | 0.30286 (13) | 0.07241 (11) | 0.0412 (3) | 1.145 (9)* | |
Si2 | 0.30311 (11) | 0.30943 (14) | 0.0472 (2) | 1.145 (9)* | |
Si3 | 0.08617 (18) | 0.38189 (16) | 0.25000 | 1.145 (9)* | |
Si4 | 0.08822 (17) | 0.22569 (15) | 0.25000 | 1.145 (9)* | |
O1 | 0.1228 (2) | 0.4144 (2) | 0.4311 (5) | 2.27 (2)* | |
O2 | 0.1252 (2) | 0.1975 (3) | 0.4299 (5) | 2.27 (2)* | |
O3 | 0.2373 (2) | 0.1249 (2) | −0.0053 (5) | 2.27 (2)* | |
O4 | 0.0988 (3) | 0.3078 (3) | 0.25000 | 2.27 (2)* | |
O5 | 0.1699 (3) | 0.1977 (4) | 0.75000 | 2.27 (2)* | |
O6 | 0.1761 (4) | 0.4208 (3) | 0.75000 | 2.27 (2)* | |
O7 | 0.2731 (4) | 0.00000 | 0.00000 | 2.27 (2)* | |
O8 | 0.25000 | 0.25000 | 0.50000 | 2.27 (2)* | |
O9 | 0.00000 | 0.4006 (5) | 0.25000 | 2.27 (2)* | |
O10 | 0.00000 | 0.2034 (5) | 0.25000 | 2.27 (2)* | |
Na1 | 0.50000 | 0.0781 (5) | 0.25000 | 16.1 (2)* | 0.9280 (12) |
Na2 | 0.50000 | 0.00000 | 0.00000 | 2.96 (14)* | 0.4784 (8) |
C1 | 0.97222 | 0.08697 | −0.16313 | 4.74 (6)* | 0.12028 (6) |
C2 | 0.98257 | 0.11928 | 0.00269 | 4.74 (6)* | 0.12028 (6) |
H1 | 1.00633 | 0.16098 | 0.00927 | 4.74 (6)* | 0.12028 (6) |
C3 | 0.95831 | 0.09181 | 0.15894 | 4.74 (6)* | 0.12028 (6) |
H2 | 0.96323 | 0.11250 | 0.26719 | 4.74 (6)* | 0.12028 (6) |
C4 | 0.92122 | 0.03225 | 0.15531 | 4.74 (6)* | 0.12028 (6) |
H3 | 0.88124 | −0.03954 | −0.01014 | 4.74 (6)* | 0.12028 (6) |
C5 | 0.90910 | −0.00031 | −0.00532 | 4.74 (6)* | 0.12028 (6) |
H4 | 0.92331 | 0.00217 | −0.26647 | 4.74 (6)* | 0.12028 (6) |
C6 | 0.93434 | 0.02651 | −0.16251 | 4.74 (6)* | 0.12028 (6) |
N1 | 0.99781 | 0.11374 | −0.31694 | 4.74 (6)* | 0.12028 (6) |
C7 | 1.03025 | 0.17833 | −0.31859 | 4.74 (6)* | 0.12028 (6) |
H7 | 0.99786 | 0.21202 | −0.26723 | 4.74 (6)* | 0.12028 (6) |
H6 | 1.04770 | 0.19035 | −0.43906 | 4.74 (6)* | 0.12028 (6) |
H5 | 1.07167 | 0.18300 | −0.23942 | 4.74 (6)* | 0.12028 (6) |
C8 | 0.98827 | 0.07944 | −0.48563 | 4.74 (6)* | 0.12028 (6) |
H10 | 1.00700 | 0.04015 | −0.48201 | 4.74 (6)* | 0.12028 (6) |
H9 | 1.01283 | 0.10395 | −0.57916 | 4.74 (6)* | 0.12028 (6) |
H8 | 0.93690 | 0.07463 | −0.51892 | 4.74 (6)* | 0.12028 (6) |
N2 | 0.89260 | 0.00544 | 0.31822 | 4.74 (6)* | 0.12028 (6) |
OA | 0.86099 | −0.04878 | 0.31204 | 4.74 (6)* | 0.12028 (6) |
OB | 0.89963 | 0.03666 | 0.45822 | 4.74 (6)* | 0.12028 (6) |