Synchrotron powder diffraction characterization of the zeolite-based (p-N,N-dimethylnitroaniline-mordenite) guest-host phase

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.

Computing details

For both compounds, program(s) used to refine structure: FULLPROF.

(90K)

Crystal data

|Na6(O2NC6H4N(CH3)2)1.94|[Al6Si42O96]MOR{[001](12−−ring)}(Cmcm)	c = 7.49986 (2) Å
Mr = 202.26	V = 2761.63 (1) Å^3
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

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

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 (Ų)

	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)

Si1—O1^i	1.594 (6)	Si3—O1	1.652 (4)
Si1—O3	1.624 (5)	Si3—O1^iii	1.652 (4)
Si1—O6^i	1.613 (3)	Si3—O4	1.567 (9)
Si1—O7	1.614 (3)	Si3—O9	1.618 (4)
Si2—O2^i	1.573 (4)	Si4—O2	1.623 (5)
Si2—O3^ii	1.554 (5)	Si4—O2^iii	1.623 (5)
Si2—O5^i	1.613 (2)	Si4—O4	1.649 (9)
Si2—O8^iii	1.596 (3)	Si4—O10	1.649 (4)
O1^i—Si1—O3	113.7 (5)	O4—Si3—O9	112.6 (7)
O1^i—Si1—O6^i	106.9 (4)	O2—Si4—O2^iii	112.3 (4)
O1^i—Si1—O7	109.5 (5)	O2—Si4—O4	108.3 (6)
O3—Si1—O6^i	109.3 (4)	O2^iii—Si4—O4	108.3 (6)
O3—Si1—O7	108.0 (3)	O2—Si4—O10	106.6 (3)
O6^i—Si1—O7	109.5 (3)	O2^iii—Si4—O10	106.6 (3)
O2^i—Si2—O3^ii	111.0 (4)	O4—Si4—O10	114.7 (7)
O2^i—Si2—O5^i	105.5 (3)	Si1^iv—O1—Si3	144.4 (3)
O2^i—Si2—O8^iii	108.3 (3)	Si2^iv—O2—Si4	146.4 (3)
O3^ii—Si2—O5^i	114.1 (4)	Si1—O3—Si2^ii	160.9 (3)
O3^ii—Si2—O8^iii	109.5 (3)	Si3—O4—Si4	162.9 (5)
O5^i—Si2—O8^iii	108.3 (3)	Si2^iv—O5—Si2^v	142.8 (2)
O1—Si3—O1^iii	112.1 (4)	Si1^iv—O6—Si1^v	152.2 (3)
O1—Si3—O4	109.8 (4)	Si1—O7—Si1^vi	140.2 (3)
O1^iii—Si3—O4	109.8 (6)	Si2^iii—O8—Si2^iv	180.0
O1—Si3—O9	106.3 (4)	Si3—O9—Si3^vii	152.7 (4)
O1^iii—Si3—O9	106.3 (4)	Si4—O10—Si4^vii	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)

D—H···A	H···A	D···A	D—H···A
C2—H1···O2^viii	2.052 (4)	2.920 (5)	150.4 (4)
C2—H1···O10^ix	2.143 (5)	2.578 (7)	106.3 (5)
C3—H2···O10^ix	2.02 (1)	2.49 (1)	109.8 (8)
C7—H5···O5^x	1.71	2.56	145
C7—H6···O2^x	1.70	2.51	137
C8—H8···O2^xi	2.37	2.87	111
C8—H9···O10^x	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)

Crystal data

|Na6(O2NC6H4N(CH3)2)1.94|[Al6Si42O96]MOR{[001](12−−ring)}(Cmcm)	c = 7.501445 (16) Å
Mr = 202.26	V = 2768.58 (1) Å^3
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

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

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 (Ų)

	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)