Non-centrosymmetric crystals of new N-benzylidene­aniline derivatives as potential materials for non-linear optics

Three new N-benzylideneaniline derivatives [p-nitrobenzylidene-p-phenyl­amineaniline (I), 2,4-dinitrobenzylidene-p-phenylamineaniline (II) and p-dinitrobenzylidene-p-diethylamineaniline (III)] containing electron–push–pull groups have been prepared. They present a planar N-benzylideneaniline core and neighbouring functional atoms, which are related through an efficient intramolecular charge transfer (CT). Two of the derivatives crystallize in non-centrosymmetric space groups, a necessary condition for non-linear optical (NLO) responses. The NLO properties were calculated for the molecular conformations determined by single-crystal X-ray diffraction as well as for the four molecules packed into each corresponding unit cell, using a quantum-chemical method at the cam-B3LYP/NLO-V level of theory. As expected from antiparallel face-to-face stacking through centrosymmetry, the main NLO descriptors – namely, the first hyperpolarizability (β_tot) and its projection on the dipole moment direction (β_vec) – are almost zero for the tetramer of derivative III. Interestingly, the calculated first hyperpolarizability decreases in the non-centrosymmetric unit-cell content of derivative II when compared to its single molecule, which may be related to its molecular pillaring, similar to that observed in derivative III. On the other hand, a desirable magnification of the NLO properties was found for packed units of derivative I, which may be a consequence of its parallel face-to-tail stacking with the CT vectors of all molecules pointing in the same direction. Moreover, the CT vector of compound I makes an angle of θ = 33.6° with its crystal polar axis, resulting in a higher-order parameter (cos³θ = 0.6) compared with the other derivatives. This is in line with the higher macroscopic second-order NLO response predicted for derivative I, β_tot = 120.4 × 10⁻³⁰ e.s.u.

Computing details

For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008).

Figures

(I) N-[4-(4-Nitrobenzylideneamino)phenyl]phenylamine

Crystal data

C19H15N3O2	F(000) = 664
Mr = 317.34	Dx = 1.369 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 10.3885 (3) Å	Cell parameters from 7992 reflections
b = 16.7902 (4) Å	θ = 3.1–29.5°
c = 8.9064 (2) Å	µ = 0.09 mm^−1
β = 97.704 (2)°	T = 150 K
V = 1539.48 (7) Å^3	Prism, red
Z = 4	0.83 × 0.41 × 0.02 mm

Data collection

Xcalibur, Atlas, Gemini ultra diffractometer	3037 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 10.4186 pixels mm^-1	θmax = 29.5°, θmin = 3.1°
ω scans	h = −13→14
15522 measured reflections	k = −22→22
3793 independent reflections	l = −11→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0511P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3793 reflections	Δρmax = 0.18 e Å^−3
220 parameters	Δρmin = −0.19 e Å^−3
2 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.2 (10)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	1.05627 (14)	0.86269 (9)	1.47754 (17)	0.0265 (3)
C6	1.08414 (14)	0.79395 (9)	1.40314 (17)	0.0292 (3)
H6	1.1406	0.7547	1.4525	0.035*
C5	1.02775 (14)	0.78394 (9)	1.25526 (16)	0.0297 (3)
H5	1.0432	0.7363	1.2031	0.036*
C4	0.94843 (13)	0.84263 (8)	1.18104 (16)	0.0257 (3)
C3	0.92257 (14)	0.91191 (8)	1.26046 (16)	0.0270 (3)
H3	0.8683	0.9521	1.2108	0.032*
C2	0.97516 (14)	0.92196 (8)	1.40943 (17)	0.0274 (3)
H2	0.9565	0.9682	1.4642	0.033*
C7	0.89574 (14)	0.83072 (9)	1.02239 (17)	0.0282 (3)
H7	0.9147	0.7825	0.9741	0.034*
C8	0.77705 (13)	0.86987 (8)	0.79143 (16)	0.0237 (3)
C13	0.81637 (14)	0.80893 (8)	0.70024 (16)	0.0275 (3)
H13	0.8815	0.7724	0.7418	0.033*
C12	0.76246 (13)	0.80116 (8)	0.55208 (16)	0.0279 (3)
H12	0.7903	0.7592	0.4926	0.033*
C11	0.66684 (13)	0.85425 (8)	0.48699 (16)	0.0255 (3)
C10	0.62932 (14)	0.91627 (9)	0.57647 (16)	0.0270 (3)
H10	0.5661	0.9538	0.5344	0.032*
C9	0.68416 (14)	0.92301 (8)	0.72616 (16)	0.0255 (3)
H9	0.6574	0.9653	0.7858	0.031*
C14	0.50850 (15)	0.87688 (8)	0.24986 (16)	0.0253 (3)
C15	0.50800 (15)	0.88379 (9)	0.09377 (17)	0.0295 (3)
H15	0.5841	0.8709	0.0504	0.035*
C16	0.39828 (16)	0.90915 (9)	0.00154 (18)	0.0348 (4)
H16	0.3985	0.912	−0.1049	0.042*
C17	0.28812 (17)	0.93035 (9)	0.06324 (18)	0.0365 (4)
H17	0.2128	0.9484	0	0.044*
C18	0.28882 (15)	0.92501 (9)	0.21836 (18)	0.0319 (3)
H18	0.2138	0.9403	0.2617	0.038*
C19	0.39729 (15)	0.89765 (9)	0.31139 (18)	0.0286 (3)
H19	0.3956	0.8931	0.4174	0.034*
N1	1.11300 (14)	0.87181 (8)	1.63661 (15)	0.0334 (3)
N2	0.82556 (11)	0.88247 (7)	0.94651 (14)	0.0266 (3)
N3	0.61950 (13)	0.84406 (9)	0.33503 (14)	0.0333 (3)
O2	1.19138 (14)	0.82128 (8)	1.69197 (14)	0.0540 (4)
O1	1.07907 (13)	0.92866 (7)	1.70810 (13)	0.0456 (3)
HN3	0.665 (2)	0.8122 (12)	0.290 (2)	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0264 (7)	0.0284 (8)	0.0250 (7)	−0.0027 (6)	0.0038 (6)	0.0016 (6)
C6	0.0277 (7)	0.0271 (8)	0.0324 (8)	0.0051 (6)	0.0021 (6)	0.0048 (6)
C5	0.0291 (8)	0.0268 (7)	0.0328 (8)	0.0060 (6)	0.0033 (6)	0.0005 (6)
C4	0.0224 (7)	0.0254 (7)	0.0299 (8)	−0.0009 (6)	0.0053 (6)	0.0030 (6)
C3	0.0239 (7)	0.0236 (7)	0.0334 (9)	0.0032 (6)	0.0031 (6)	0.0043 (6)
C2	0.0284 (8)	0.0227 (7)	0.0322 (8)	0.0002 (6)	0.0084 (6)	0.0006 (6)
C7	0.0266 (8)	0.0246 (8)	0.0325 (8)	0.0023 (6)	0.0009 (6)	−0.0015 (6)
C8	0.0207 (7)	0.0225 (7)	0.0283 (8)	−0.0007 (5)	0.0045 (6)	0.0043 (6)
C13	0.0238 (7)	0.0247 (7)	0.0346 (8)	0.0059 (6)	0.0065 (6)	0.0066 (6)
C12	0.0271 (8)	0.0241 (7)	0.0343 (8)	0.0039 (6)	0.0107 (6)	0.0003 (6)
C11	0.0245 (8)	0.0250 (7)	0.0279 (8)	−0.0012 (6)	0.0065 (6)	0.0029 (6)
C10	0.0256 (7)	0.0214 (7)	0.0329 (8)	0.0041 (5)	0.0002 (6)	0.0035 (6)
C9	0.0269 (8)	0.0190 (7)	0.0307 (8)	0.0012 (6)	0.0040 (6)	0.0000 (6)
C14	0.0259 (7)	0.0221 (7)	0.0275 (8)	−0.0025 (6)	0.0021 (6)	−0.0006 (6)
C15	0.0335 (8)	0.0251 (8)	0.0311 (8)	−0.0047 (6)	0.0093 (7)	−0.0033 (6)
C16	0.0445 (10)	0.0322 (8)	0.0272 (8)	−0.0055 (7)	0.0022 (7)	0.0012 (6)
C17	0.0352 (8)	0.0339 (9)	0.0382 (9)	−0.0009 (7)	−0.0034 (7)	0.0010 (7)
C18	0.0265 (7)	0.0309 (8)	0.0379 (9)	−0.0025 (6)	0.0032 (6)	−0.0010 (7)
C19	0.0304 (8)	0.0290 (8)	0.0268 (7)	−0.0047 (6)	0.0054 (6)	−0.0022 (6)
N1	0.0377 (7)	0.0326 (7)	0.0291 (7)	−0.0055 (6)	0.0011 (6)	0.0026 (6)
N2	0.0242 (7)	0.0268 (7)	0.0285 (7)	0.0017 (5)	0.0030 (5)	0.0029 (5)
N3	0.0317 (7)	0.0386 (8)	0.0293 (7)	0.0102 (6)	0.0030 (6)	−0.0063 (6)
O2	0.0720 (9)	0.0452 (8)	0.0389 (7)	0.0122 (7)	−0.0149 (6)	0.0034 (6)
O1	0.0534 (7)	0.0457 (7)	0.0365 (7)	−0.0015 (6)	0.0020 (5)	−0.0114 (6)

Geometric parameters (Å, º)

C1—C6	1.381 (2)	C11—N3	1.3873 (19)
C1—C2	1.390 (2)	C11—C10	1.398 (2)
C1—N1	1.468 (2)	C10—C9	1.382 (2)
C6—C5	1.378 (2)	C10—H10	0.95
C6—H6	0.95	C9—H9	0.95
C5—C4	1.393 (2)	C14—C19	1.388 (2)
C5—H5	0.95	C14—C15	1.394 (2)
C4—C3	1.406 (2)	C14—N3	1.405 (2)
C4—C7	1.459 (2)	C15—C16	1.380 (2)
C3—C2	1.376 (2)	C15—H15	0.95
C3—H3	0.95	C16—C17	1.381 (2)
C2—H2	0.95	C16—H16	0.95
C7—N2	1.2693 (18)	C17—C18	1.383 (2)
C7—H7	0.95	C17—H17	0.95
C8—C9	1.384 (2)	C18—C19	1.385 (2)
C8—C13	1.401 (2)	C18—H18	0.95
C8—N2	1.4212 (19)	C19—H19	0.95
C13—C12	1.369 (2)	N1—O1	1.2252 (18)
C13—H13	0.95	N1—O2	1.2321 (18)
C12—C11	1.401 (2)	N3—HN3	0.85 (2)
C12—H12	0.95
C6—C1—C2	122.89 (14)	C10—C11—C12	118.32 (13)
C6—C1—N1	117.87 (13)	C9—C10—C11	120.02 (13)
C2—C1—N1	119.22 (14)	C9—C10—H10	120
C5—C6—C1	118.09 (14)	C11—C10—H10	120
C5—C6—H6	121	C10—C9—C8	121.76 (13)
C1—C6—H6	121	C10—C9—H9	119.1
C6—C5—C4	121.06 (14)	C8—C9—H9	119.1
C6—C5—H5	119.5	C19—C14—C15	118.73 (14)
C4—C5—H5	119.5	C19—C14—N3	123.48 (14)
C5—C4—C3	119.16 (13)	C15—C14—N3	117.65 (13)
C5—C4—C7	118.94 (13)	C16—C15—C14	120.77 (14)
C3—C4—C7	121.90 (12)	C16—C15—H15	119.6
C2—C3—C4	120.58 (13)	C14—C15—H15	119.6
C2—C3—H3	119.7	C15—C16—C17	120.34 (15)
C4—C3—H3	119.7	C15—C16—H16	119.8
C3—C2—C1	118.18 (13)	C17—C16—H16	119.8
C3—C2—H2	120.9	C16—C17—C18	119.14 (15)
C1—C2—H2	120.9	C16—C17—H17	120.4
N2—C7—C4	122.41 (13)	C18—C17—H17	120.4
N2—C7—H7	118.8	C17—C18—C19	120.93 (15)
C4—C7—H7	118.8	C17—C18—H18	119.5
C9—C8—C13	117.94 (13)	C19—C18—H18	119.5
C9—C8—N2	116.66 (12)	C18—C19—C14	120.06 (15)
C13—C8—N2	125.40 (12)	C18—C19—H19	120
C12—C13—C8	121.00 (13)	C14—C19—H19	120
C12—C13—H13	119.5	O1—N1—O2	123.31 (14)
C8—C13—H13	119.5	O1—N1—C1	118.46 (14)
C13—C12—C11	120.93 (13)	O2—N1—C1	118.22 (13)
C13—C12—H12	119.5	C7—N2—C8	121.27 (12)
C11—C12—H12	119.5	C11—N3—C14	129.51 (13)
N3—C11—C10	123.95 (13)	C11—N3—HN3	113.4 (13)
N3—C11—C12	117.66 (13)	C14—N3—HN3	117.0 (13)
C2—C1—C6—C5	−0.5 (2)	N2—C8—C9—C10	−179.51 (12)
N1—C1—C6—C5	177.94 (13)	C19—C14—C15—C16	−1.4 (2)
C1—C6—C5—C4	2.2 (2)	N3—C14—C15—C16	174.48 (14)
C6—C5—C4—C3	−2.1 (2)	C14—C15—C16—C17	1.9 (2)
C6—C5—C4—C7	177.28 (13)	C15—C16—C17—C18	−0.7 (2)
C5—C4—C3—C2	0.2 (2)	C16—C17—C18—C19	−1.0 (2)
C7—C4—C3—C2	−179.06 (13)	C17—C18—C19—C14	1.5 (2)
C4—C3—C2—C1	1.3 (2)	C15—C14—C19—C18	−0.3 (2)
C6—C1—C2—C3	−1.2 (2)	N3—C14—C19—C18	−175.92 (14)
N1—C1—C2—C3	−179.66 (12)	C6—C1—N1—O1	−172.99 (14)
C5—C4—C7—N2	−178.16 (13)	C2—C1—N1—O1	5.5 (2)
C3—C4—C7—N2	1.1 (2)	C6—C1—N1—O2	6.2 (2)
C9—C8—C13—C12	−1.4 (2)	C2—C1—N1—O2	−175.25 (14)
N2—C8—C13—C12	179.17 (13)	C4—C7—N2—C8	179.06 (13)
C8—C13—C12—C11	0.4 (2)	C9—C8—N2—C7	169.30 (13)
C13—C12—C11—N3	178.13 (13)	C13—C8—N2—C7	−11.3 (2)
C13—C12—C11—C10	1.1 (2)	C10—C11—N3—C14	−17.3 (3)
N3—C11—C10—C9	−178.30 (13)	C12—C11—N3—C14	165.86 (14)
C12—C11—C10—C9	−1.4 (2)	C19—C14—N3—C11	−29.1 (2)
C11—C10—C9—C8	0.4 (2)	C15—C14—N3—C11	155.26 (14)
C13—C8—C9—C10	1.0 (2)

(II) N-[4-(2,4-dinitrobenzylideneamino)phenyl]phenylamine

Crystal data

C19H14N4O4	Dx = 1.426 Mg m^−3
Mr = 362.34	Cu Kα radiation, λ = 1.5418 Å
Orthorhombic, P212121	Cell parameters from 3724 reflections
a = 6.5715 (2) Å	θ = 2.6–66.5°
b = 15.0533 (4) Å	µ = 0.86 mm^−1
c = 17.0598 (5) Å	T = 150 K
V = 1687.60 (8) Å^3	Prism, red
Z = 4	0.90 × 0.11 × 0.08 mm
F(000) = 752

Data collection

Xcalibur, Atlas, Gemini ultra diffractometer	2612 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 10.4186 pixels mm^-1	θmax = 66.6°, θmin = 3.9°
ω scans	h = −4→7
6008 measured reflections	k = −16→17
2905 independent reflections	l = −17→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0533P)^2 + 0.0662P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2905 reflections	Δρmax = 0.12 e Å^−3
247 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.2 (2)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O4	0.2931 (2)	0.35218 (8)	0.71549 (7)	0.0458 (3)
N4	0.3510 (2)	0.32847 (9)	0.65055 (8)	0.0323 (3)
O3	0.4211 (2)	0.37961 (8)	0.60149 (7)	0.0419 (3)
N3	0.2920 (3)	0.43762 (10)	0.14072 (8)	0.0354 (3)
N1	0.3118 (2)	0.02368 (11)	0.74303 (10)	0.0431 (4)
N2	0.36409 (19)	0.23825 (9)	0.41748 (8)	0.0287 (3)
C8	0.3440 (2)	0.29283 (11)	0.35041 (9)	0.0266 (3)
O2	0.3226 (2)	0.05278 (10)	0.80974 (8)	0.0527 (4)
C9	0.3521 (2)	0.24951 (11)	0.27839 (9)	0.0300 (4)
H9	0.3699	0.1869	0.2772	0.036*
C5	0.3360 (2)	0.23373 (10)	0.63102 (9)	0.0271 (3)
C12	0.3088 (2)	0.43196 (10)	0.28126 (9)	0.0287 (3)
H12	0.296	0.4948	0.2824	0.034*
O1	0.2914 (3)	−0.05488 (10)	0.72680 (10)	0.0685 (5)
C7	0.3105 (2)	0.26609 (11)	0.48485 (9)	0.0273 (3)
H7	0.2599	0.3248	0.4913	0.033*
C11	0.3131 (2)	0.38779 (10)	0.20887 (9)	0.0286 (3)
C13	0.3229 (2)	0.38544 (10)	0.35097 (9)	0.0273 (3)
H13	0.3182	0.4164	0.3994	0.033*
C4	0.3279 (2)	0.20607 (10)	0.55278 (9)	0.0274 (3)
C1	0.3212 (3)	0.08660 (11)	0.67714 (9)	0.0323 (4)
C3	0.3219 (3)	0.11400 (11)	0.53990 (10)	0.0318 (4)
H3	0.3199	0.0924	0.4876	0.038*
C10	0.3349 (3)	0.29527 (11)	0.20890 (10)	0.0319 (4)
H10	0.3378	0.2639	0.1606	0.038*
C6	0.3308 (2)	0.17592 (11)	0.69367 (9)	0.0305 (4)
H6	0.3336	0.197	0.7462	0.037*
C14	0.3144 (3)	0.40395 (11)	0.06443 (9)	0.0362 (4)
C2	0.3189 (3)	0.05418 (12)	0.60095 (11)	0.0362 (4)
H2	0.3153	−0.0079	0.5912	0.043*
C19	0.4903 (3)	0.35710 (13)	0.04370 (11)	0.0459 (5)
H19	0.5948	0.3477	0.0813	0.055*
C15	0.1651 (4)	0.41896 (13)	0.00849 (10)	0.0476 (5)
H15	0.0455	0.451	0.0219	0.057*
C18	0.5118 (4)	0.32436 (14)	−0.03202 (12)	0.0605 (7)
H18	0.6297	0.2914	−0.0458	0.073*
C16	0.1915 (5)	0.38694 (14)	−0.06729 (11)	0.0616 (7)
H16	0.09	0.3979	−0.1057	0.074*
C17	0.3629 (5)	0.33957 (15)	−0.08723 (12)	0.0702 (8)
H17	0.3785	0.3174	−0.139	0.084*
H3N	0.218 (5)	0.483 (2)	0.1436 (15)	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0620 (8)	0.0414 (7)	0.0340 (7)	0.0019 (7)	0.0031 (6)	−0.0062 (6)
N4	0.0357 (7)	0.0291 (7)	0.0320 (7)	0.0028 (6)	−0.0033 (6)	0.0027 (6)
O3	0.0547 (7)	0.0299 (7)	0.0411 (7)	−0.0058 (6)	0.0011 (6)	0.0058 (5)
N3	0.0497 (9)	0.0320 (8)	0.0245 (7)	0.0076 (7)	−0.0013 (7)	0.0022 (6)
N1	0.0327 (8)	0.0425 (9)	0.0541 (10)	0.0033 (8)	0.0061 (8)	0.0206 (8)
N2	0.0269 (7)	0.0301 (7)	0.0290 (7)	−0.0045 (6)	−0.0019 (5)	0.0019 (6)
C8	0.0234 (7)	0.0306 (8)	0.0257 (8)	−0.0006 (7)	−0.0022 (7)	0.0023 (6)
O2	0.0522 (8)	0.0633 (9)	0.0426 (8)	0.0035 (8)	0.0027 (7)	0.0244 (7)
C9	0.0312 (8)	0.0268 (8)	0.0320 (8)	−0.0012 (7)	−0.0033 (7)	−0.0014 (7)
C5	0.0218 (7)	0.0281 (8)	0.0313 (8)	0.0024 (7)	0.0010 (7)	0.0037 (7)
C12	0.0274 (7)	0.0271 (8)	0.0316 (8)	0.0012 (7)	0.0002 (7)	−0.0001 (7)
O1	0.0913 (12)	0.0352 (8)	0.0791 (11)	−0.0018 (8)	0.0135 (10)	0.0234 (7)
C7	0.0226 (7)	0.0287 (9)	0.0306 (9)	0.0002 (7)	−0.0022 (6)	0.0028 (7)
C11	0.0285 (7)	0.0298 (8)	0.0277 (8)	0.0013 (7)	−0.0011 (7)	0.0020 (6)
C13	0.0248 (7)	0.0316 (9)	0.0256 (7)	−0.0010 (7)	−0.0003 (7)	−0.0031 (6)
C4	0.0209 (7)	0.0300 (8)	0.0314 (8)	0.0013 (7)	−0.0001 (7)	0.0028 (6)
C1	0.0244 (8)	0.0328 (9)	0.0396 (9)	0.0016 (7)	0.0027 (7)	0.0135 (7)
C3	0.0283 (8)	0.0316 (9)	0.0356 (9)	−0.0011 (8)	0.0007 (8)	0.0014 (7)
C10	0.0370 (8)	0.0327 (8)	0.0261 (8)	−0.0020 (8)	−0.0010 (8)	−0.0048 (7)
C6	0.0230 (7)	0.0376 (9)	0.0308 (8)	0.0010 (7)	0.0003 (7)	0.0060 (7)
C14	0.0561 (11)	0.0260 (8)	0.0266 (8)	−0.0018 (9)	−0.0004 (8)	0.0036 (6)
C2	0.0309 (8)	0.0270 (9)	0.0508 (10)	−0.0015 (8)	0.0023 (9)	0.0040 (7)
C19	0.0636 (12)	0.0389 (11)	0.0352 (10)	0.0022 (10)	0.0087 (9)	0.0035 (8)
C15	0.0736 (13)	0.0327 (10)	0.0366 (10)	−0.0053 (11)	−0.0109 (11)	0.0060 (8)
C18	0.1033 (19)	0.0414 (12)	0.0367 (11)	0.0043 (13)	0.0241 (12)	0.0033 (9)
C16	0.115 (2)	0.0374 (11)	0.0321 (10)	−0.0110 (14)	−0.0193 (13)	0.0073 (8)
C17	0.149 (3)	0.0355 (11)	0.0263 (10)	−0.0128 (15)	0.0105 (14)	−0.0008 (9)

Geometric parameters (Å, º)

O4—N4	1.2245 (18)	C11—C10	1.400 (2)
N4—O3	1.2269 (18)	C13—H13	0.95
N4—C5	1.468 (2)	C4—C3	1.404 (2)
N3—C11	1.390 (2)	C1—C6	1.375 (2)
N3—C14	1.405 (2)	C1—C2	1.388 (2)
N3—H3N	0.84 (3)	C3—C2	1.377 (2)
N1—O2	1.221 (2)	C3—H3	0.95
N1—O1	1.222 (2)	C10—H10	0.95
N1—C1	1.471 (2)	C6—H6	0.95
N2—C7	1.273 (2)	C14—C15	1.387 (3)
N2—C8	1.415 (2)	C14—C19	1.399 (3)
C8—C9	1.392 (2)	C2—H2	0.95
C8—C13	1.401 (2)	C19—C18	1.390 (3)
C9—C10	1.376 (2)	C19—H19	0.95
C9—H9	0.95	C15—C16	1.391 (3)
C5—C6	1.379 (2)	C15—H15	0.95
C5—C4	1.399 (2)	C18—C17	1.378 (4)
C12—C13	1.383 (2)	C18—H18	0.95
C12—C11	1.403 (2)	C16—C17	1.375 (4)
C12—H12	0.95	C16—H16	0.95
C7—C4	1.474 (2)	C17—H17	0.95
C7—H7	0.95
O4—N4—O3	123.43 (14)	C6—C1—C2	122.41 (15)
O4—N4—C5	117.88 (13)	C6—C1—N1	118.35 (15)
O3—N4—C5	118.69 (13)	C2—C1—N1	119.24 (16)
C11—N3—C14	124.74 (14)	C2—C3—C4	121.85 (15)
C11—N3—H3N	116.6 (19)	C2—C3—H3	119.1
C14—N3—H3N	114.1 (18)	C4—C3—H3	119.1
O2—N1—O1	124.37 (16)	C9—C10—C11	120.45 (15)
O2—N1—C1	118.58 (16)	C9—C10—H10	119.8
O1—N1—C1	117.04 (17)	C11—C10—H10	119.8
C7—N2—C8	120.87 (14)	C1—C6—C5	117.35 (15)
C9—C8—C13	118.42 (14)	C1—C6—H6	121.3
C9—C8—N2	115.99 (14)	C5—C6—H6	121.3
C13—C8—N2	125.56 (14)	C15—C14—C19	119.51 (17)
C10—C9—C8	121.52 (14)	C15—C14—N3	120.29 (18)
C10—C9—H9	119.2	C19—C14—N3	120.18 (17)
C8—C9—H9	119.2	C3—C2—C1	118.56 (16)
C6—C5—C4	123.42 (15)	C3—C2—H2	120.7
C6—C5—N4	116.04 (14)	C1—C2—H2	120.7
C4—C5—N4	120.54 (13)	C18—C19—C14	119.8 (2)
C13—C12—C11	121.04 (14)	C18—C19—H19	120.1
C13—C12—H12	119.5	C14—C19—H19	120.1
C11—C12—H12	119.5	C14—C15—C16	119.6 (2)
N2—C7—C4	119.12 (14)	C14—C15—H15	120.2
N2—C7—H7	120.4	C16—C15—H15	120.2
C4—C7—H7	120.4	C17—C18—C19	120.3 (2)
N3—C11—C10	123.16 (15)	C17—C18—H18	119.9
N3—C11—C12	118.58 (14)	C19—C18—H18	119.9
C10—C11—C12	118.24 (15)	C17—C16—C15	120.8 (2)
C12—C13—C8	120.30 (14)	C17—C16—H16	119.6
C12—C13—H13	119.9	C15—C16—H16	119.6
C8—C13—H13	119.9	C16—C17—C18	119.90 (19)
C5—C4—C3	116.37 (14)	C16—C17—H17	120
C5—C4—C7	124.80 (14)	C18—C17—H17	120
C3—C4—C7	118.67 (14)
C7—N2—C8—C9	−162.76 (14)	O2—N1—C1—C2	176.92 (16)
C7—N2—C8—C13	19.2 (2)	O1—N1—C1—C2	−3.8 (2)
C13—C8—C9—C10	−1.6 (2)	C5—C4—C3—C2	1.6 (3)
N2—C8—C9—C10	−179.85 (15)	C7—C4—C3—C2	−174.05 (15)
O4—N4—C5—C6	−23.1 (2)	C8—C9—C10—C11	1.5 (3)
O3—N4—C5—C6	156.63 (15)	N3—C11—C10—C9	−179.04 (15)
O4—N4—C5—C4	156.91 (15)	C12—C11—C10—C9	−0.2 (3)
O3—N4—C5—C4	−23.3 (2)	C2—C1—C6—C5	0.7 (3)
C8—N2—C7—C4	178.06 (13)	N1—C1—C6—C5	−178.94 (14)
C14—N3—C11—C10	−8.1 (3)	C4—C5—C6—C1	1.3 (2)
C14—N3—C11—C12	173.04 (18)	N4—C5—C6—C1	−178.62 (14)
C13—C12—C11—N3	178.04 (16)	C11—N3—C14—C15	128.94 (19)
C13—C12—C11—C10	−0.9 (2)	C11—N3—C14—C19	−52.8 (3)
C11—C12—C13—C8	0.7 (2)	C4—C3—C2—C1	0.2 (3)
C9—C8—C13—C12	0.6 (2)	C6—C1—C2—C3	−1.4 (3)
N2—C8—C13—C12	178.58 (13)	N1—C1—C2—C3	178.18 (16)
C6—C5—C4—C3	−2.4 (2)	C15—C14—C19—C18	−1.5 (3)
N4—C5—C4—C3	177.52 (14)	N3—C14—C19—C18	−179.69 (18)
C6—C5—C4—C7	172.92 (15)	C19—C14—C15—C16	0.3 (3)
N4—C5—C4—C7	−7.1 (2)	N3—C14—C15—C16	178.55 (17)
N2—C7—C4—C5	159.28 (15)	C14—C19—C18—C17	1.5 (3)
N2—C7—C4—C3	−25.5 (2)	C14—C15—C16—C17	0.8 (3)
O2—N1—C1—C6	−3.5 (2)	C15—C16—C17—C18	−0.8 (3)
O1—N1—C1—C6	175.85 (18)	C19—C18—C17—C16	−0.4 (3)

(III) N-[4-(4-Nitrobenzylideneamino)phenyl]diethylamine

Crystal data

C17H19N3O2	F(000) = 632
Mr = 297.35	Dx = 1.306 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.1019 (5) Å	Cell parameters from 4763 reflections
b = 7.6028 (3) Å	θ = 2.1–29.4°
c = 12.3616 (4) Å	µ = 0.09 mm^−1
β = 91.615 (3)°	T = 120 K
V = 1512.70 (9) Å^3	Prism, red
Z = 4	0.69 × 0.39 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur, Atlas, Gemini Ultra diffractometer	2893 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 10.4186 pixels mm^-1	θmax = 29.5°, θmin = 2.5°
ω scans	h = −20→20
13092 measured reflections	k = −7→9
3700 independent reflections	l = −16→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0607P)^2 + 0.3666P] where P = (Fo^2 + 2Fc^2)/3
3700 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.85206 (6)	0.00583 (14)	1.10158 (8)	0.0358 (3)
N2	0.47371 (6)	0.15482 (13)	0.82784 (8)	0.0222 (2)
N1	0.80569 (7)	0.12102 (15)	1.13418 (9)	0.0282 (3)
O2	0.82431 (7)	0.22062 (16)	1.20897 (9)	0.0450 (3)
C8	0.39387 (7)	0.17600 (16)	0.77967 (10)	0.0212 (3)
N3	0.15534 (6)	0.19441 (15)	0.62889 (8)	0.0237 (2)
C13	0.33222 (7)	0.28987 (16)	0.81622 (10)	0.0222 (3)
H13	0.3439	0.3632	0.877	0.027*
C6	0.66496 (8)	0.24437 (17)	1.12905 (10)	0.0258 (3)
H6	0.6767	0.3001	1.1965	0.031*
C11	0.23361 (7)	0.18855 (16)	0.67641 (10)	0.0203 (3)
C7	0.48925 (7)	0.20761 (16)	0.92443 (10)	0.0223 (3)
H7	0.4465	0.2632	0.9632	0.027*
C5	0.58793 (8)	0.26322 (17)	1.07758 (10)	0.0246 (3)
H5	0.5459	0.3302	1.111	0.029*
C9	0.37452 (7)	0.07394 (17)	0.68881 (10)	0.0232 (3)
H9	0.4161	−0.0004	0.6605	0.028*
C12	0.25475 (7)	0.29748 (16)	0.76552 (10)	0.0225 (3)
H12	0.2147	0.378	0.7912	0.027*
C3	0.63288 (8)	0.08144 (17)	0.92978 (10)	0.0228 (3)
H3	0.6219	0.0267	0.8618	0.027*
C1	0.72428 (7)	0.14265 (16)	1.07999 (10)	0.0225 (3)
C10	0.29657 (7)	0.07740 (17)	0.63837 (10)	0.0230 (3)
H10	0.2854	0.004	0.5775	0.028*
C2	0.70932 (8)	0.05892 (17)	0.98155 (10)	0.0238 (3)
H2	0.7508	−0.0124	0.9504	0.029*
C4	0.57135 (7)	0.18473 (16)	0.97704 (10)	0.0210 (3)
C16	0.06796 (9)	0.46199 (19)	0.65100 (12)	0.0347 (3)
H16A	0.1151	0.5357	0.6743	0.052*
H16B	0.0175	0.5033	0.6855	0.052*
H16C	0.0604	0.4692	0.5722	0.052*
C15	0.08482 (8)	0.27271 (18)	0.68354 (11)	0.0270 (3)
H15A	0.0957	0.2678	0.7627	0.032*
H15B	0.0345	0.2017	0.667	0.032*
C17	0.10650 (9)	−0.0838 (2)	0.54181 (13)	0.0363 (4)
H17A	0.1517	−0.1537	0.5747	0.054*
H17B	0.0905	−0.1336	0.4711	0.054*
H17C	0.0586	−0.0855	0.589	0.054*
C14	0.13551 (8)	0.10433 (18)	0.52733 (10)	0.0276 (3)
H14A	0.1854	0.1041	0.4824	0.033*
H14B	0.0915	0.171	0.4877	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0297 (5)	0.0394 (6)	0.0381 (6)	0.0075 (4)	−0.0039 (4)	0.0041 (5)
N2	0.0212 (5)	0.0201 (5)	0.0254 (6)	−0.0031 (4)	0.0004 (4)	0.0019 (4)
N1	0.0294 (6)	0.0293 (6)	0.0257 (6)	−0.0047 (5)	−0.0046 (4)	0.0047 (5)
O2	0.0450 (7)	0.0511 (7)	0.0379 (6)	−0.0039 (5)	−0.0164 (5)	−0.0112 (5)
C8	0.0205 (6)	0.0198 (6)	0.0234 (6)	−0.0029 (4)	0.0016 (5)	0.0019 (5)
N3	0.0226 (5)	0.0267 (6)	0.0216 (5)	0.0012 (4)	−0.0010 (4)	−0.0044 (4)
C13	0.0258 (6)	0.0201 (6)	0.0208 (6)	−0.0029 (5)	0.0002 (5)	−0.0019 (5)
C6	0.0356 (7)	0.0216 (7)	0.0199 (6)	−0.0021 (5)	−0.0021 (5)	−0.0017 (5)
C11	0.0213 (6)	0.0200 (6)	0.0198 (6)	−0.0025 (4)	0.0017 (4)	0.0020 (5)
C7	0.0222 (6)	0.0201 (6)	0.0249 (6)	−0.0019 (4)	0.0041 (5)	0.0020 (5)
C5	0.0286 (7)	0.0213 (6)	0.0241 (7)	0.0012 (5)	0.0040 (5)	−0.0010 (5)
C9	0.0216 (6)	0.0232 (6)	0.0251 (6)	−0.0004 (5)	0.0048 (5)	−0.0016 (5)
C12	0.0244 (6)	0.0207 (6)	0.0226 (6)	0.0014 (5)	0.0027 (5)	−0.0011 (5)
C3	0.0261 (6)	0.0221 (6)	0.0204 (6)	−0.0027 (5)	0.0009 (5)	−0.0020 (5)
C1	0.0251 (6)	0.0193 (6)	0.0228 (6)	−0.0038 (5)	−0.0026 (5)	0.0044 (5)
C10	0.0257 (6)	0.0227 (6)	0.0208 (6)	−0.0028 (5)	0.0025 (5)	−0.0036 (5)
C2	0.0252 (6)	0.0221 (6)	0.0241 (6)	−0.0002 (5)	0.0022 (5)	−0.0009 (5)
C4	0.0233 (6)	0.0178 (6)	0.0219 (6)	−0.0040 (4)	0.0018 (5)	0.0037 (5)
C16	0.0309 (7)	0.0362 (8)	0.0368 (8)	0.0086 (6)	−0.0029 (6)	−0.0062 (6)
C15	0.0215 (6)	0.0351 (8)	0.0244 (7)	−0.0009 (5)	0.0009 (5)	−0.0041 (5)
C17	0.0342 (8)	0.0331 (8)	0.0411 (9)	0.0004 (6)	−0.0076 (6)	−0.0105 (7)
C14	0.0264 (7)	0.0340 (8)	0.0220 (7)	0.0020 (5)	−0.0034 (5)	−0.0039 (5)

Geometric parameters (Å, º)

O1—N1	1.2262 (15)	C9—C10	1.3859 (17)
N2—C7	1.2776 (16)	C9—H9	0.95
N2—C8	1.4107 (15)	C12—H12	0.95
N1—O2	1.2258 (15)	C3—C2	1.3818 (17)
N1—C1	1.4644 (16)	C3—C4	1.4043 (17)
C8—C9	1.3932 (17)	C3—H3	0.95
C8—C13	1.4015 (17)	C1—C2	1.3883 (17)
N3—C11	1.3762 (15)	C10—H10	0.95
N3—C14	1.4576 (16)	C2—H2	0.95
N3—C15	1.4639 (16)	C16—C15	1.517 (2)
C13—C12	1.3814 (17)	C16—H16A	0.98
C13—H13	0.95	C16—H16B	0.98
C6—C1	1.3824 (19)	C16—H16C	0.98
C6—C5	1.3854 (18)	C15—H15A	0.99
C6—H6	0.95	C15—H15B	0.99
C11—C10	1.4106 (17)	C17—C14	1.517 (2)
C11—C12	1.4120 (17)	C17—H17A	0.98
C7—C4	1.4671 (17)	C17—H17B	0.98
C7—H7	0.95	C17—H17C	0.98
C5—C4	1.3976 (17)	C14—H14A	0.99
C5—H5	0.95	C14—H14B	0.99
C7—N2—C8	120.71 (11)	C6—C1—N1	118.87 (11)
O2—N1—O1	123.43 (11)	C2—C1—N1	118.72 (11)
O2—N1—C1	118.18 (11)	C9—C10—C11	120.77 (11)
O1—N1—C1	118.38 (11)	C9—C10—H10	119.6
C9—C8—C13	117.36 (11)	C11—C10—H10	119.6
C9—C8—N2	117.21 (11)	C3—C2—C1	118.65 (12)
C13—C8—N2	125.44 (11)	C3—C2—H2	120.7
C11—N3—C14	121.88 (10)	C1—C2—H2	120.7
C11—N3—C15	121.94 (10)	C5—C4—C3	119.31 (11)
C14—N3—C15	115.76 (10)	C5—C4—C7	119.39 (11)
C12—C13—C8	121.22 (11)	C3—C4—C7	121.28 (11)
C12—C13—H13	119.4	C15—C16—H16A	109.5
C8—C13—H13	119.4	C15—C16—H16B	109.5
C1—C6—C5	118.50 (12)	H16A—C16—H16B	109.5
C1—C6—H6	120.8	C15—C16—H16C	109.5
C5—C6—H6	120.8	H16A—C16—H16C	109.5
N3—C11—C10	122.36 (11)	H16B—C16—H16C	109.5
N3—C11—C12	120.78 (11)	N3—C15—C16	113.51 (11)
C10—C11—C12	116.86 (11)	N3—C15—H15A	108.9
N2—C7—C4	121.83 (11)	C16—C15—H15A	108.9
N2—C7—H7	119.1	N3—C15—H15B	108.9
C4—C7—H7	119.1	C16—C15—H15B	108.9
C6—C5—C4	120.68 (12)	H15A—C15—H15B	107.7
C6—C5—H5	119.7	C14—C17—H17A	109.5
C4—C5—H5	119.7	C14—C17—H17B	109.5
C10—C9—C8	122.09 (11)	H17A—C17—H17B	109.5
C10—C9—H9	119	C14—C17—H17C	109.5
C8—C9—H9	119	H17A—C17—H17C	109.5
C13—C12—C11	121.61 (11)	H17B—C17—H17C	109.5
C13—C12—H12	119.2	N3—C14—C17	113.71 (11)
C11—C12—H12	119.2	N3—C14—H14A	108.8
C2—C3—C4	120.41 (12)	C17—C14—H14A	108.8
C2—C3—H3	119.8	N3—C14—H14B	108.8
C4—C3—H3	119.8	C17—C14—H14B	108.8
C6—C1—C2	122.41 (11)	H14A—C14—H14B	107.7