Nonlinear optical organic–inorganic crystals: synthesis, structural analysis and verification of harmonic generation in tri-(o-chloro­anilinium nitrate)

The structural and nonlinear optical properties of a new anilinium hybrid crystal of chemical formula (C₆H₇NCl⁺·NO₃⁻)₃ have been investigated. The crystal structure was determined from single-crystal X-ray diffraction measurements performed at a temperature of 100 K which show that the compound crystallizes in a noncentrosymmetric space group (Pna2₁). The structural analysis was coupled with Hirshfeld surface analysis to evaluate the contribution of the different intermolecular interactions to the formation of supramolecular assemblies in the solid state that exhibit nonlinear optical features. This analysis reveals that the studied compound is characterized by a three-dimensional network of hydrogen bonds and the main contributions are provided by the O...H, C...H, H...H and Cl...H interactions, which alone represent ∼85% of the total contributions to the Hirshfeld surfaces. It is noteworthy that the halogen...H contributions are quite comparable with those of the H...H contacts. The nonlinear optical properties were investigated by nonlinear diffuse femtosecond-pulse reflectometry and the obtained results were compared with those of the reference material LiNbO₃. The hybrid crystals exhibit notable second (SHG) and third (THG) harmonic generation which confirms its polarity is generated by the different intermolecular interactions. These measurements also highlight that the THG signal of the new anilinium compound normalized to its SHG counterpart is more pronounced than for LiNbO₃.

Computing details

Data collection: CrysAlis PRO 1.171.38.46 (Rigaku Oxford Diffraction, 2017); cell refinement: CrysAlis PRO 1.171.38.46 (Rigaku Oxford Diffraction, 2017); data reduction: CrysAlis PRO 1.171.38.46 (Rigaku Oxford Diffraction, 2017); program(s) used to solve structure: SHELXS97 (Sheldrick, 2014); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: 'enCIFer (Allen et al., 2004)'.

tri-(o-Chloroanilinium Nitrate

Crystal data

3((C6H7ClN)^+·(NO3)^−)	Dx = 1.529 Mg m^−3
Mr = 571.76	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 117559 reflections
a = 16.8015 (5) Å	θ = 3.0–37.9°
b = 6.5945 (2) Å	µ = 0.43 mm^−1
c = 22.4243 (6) Å	T = 100 K
V = 2484.56 (12) Å^3	Prism, brown
Z = 4	0.22 × 0.18 × 0.14 mm
F(000) = 1176

Data collection

SuperNova, Dual, Cu at zero, Atlas diffractometer	13028 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	9377 reflections with I > 2σ(I)
Detector resolution: 10.4508 pixels mm^-1	Rint = 0.072
ω scans	θmax = 37.9°, θmin = 3.0°
Absorption correction: multi-scan CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2017) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −28→28
Tmin = 0.826, Tmax = 0.992	k = −11→11
117559 measured reflections	l = −38→38

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.047	w = 1/[σ^2(Fo^2) + (0.0342P)^2 + 0.1157P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.099	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.45 e Å^−3
13028 reflections	Δρmin = −0.38 e Å^−3
409 parameters	Absolute structure: Flack x determined using 3499 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
1 restraint	Absolute structure parameter: −0.050 (16)

Special details

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

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

	x	y	z	Uiso*/Ueq
Cl1	0.38372 (3)	0.16209 (7)	0.24812 (3)	0.02480 (10)
Cl2	0.11473 (3)	0.78871 (9)	0.41627 (3)	0.02871 (13)
Cl3	0.38460 (4)	0.32023 (10)	0.58072 (2)	0.02871 (14)
O7	0.24503 (8)	0.62791 (19)	0.65042 (7)	0.0190 (3)
O6	0.24147 (9)	0.8922 (2)	0.32153 (7)	0.0209 (3)
O1	0.24883 (9)	0.3831 (2)	0.47678 (7)	0.0225 (3)
O2	0.25547 (9)	0.0581 (2)	0.48710 (7)	0.0236 (3)
O4	0.25759 (10)	0.5715 (2)	0.30643 (7)	0.0270 (3)
O8	0.25819 (10)	0.9537 (2)	0.64560 (8)	0.0275 (3)
O3	0.17049 (9)	0.2300 (3)	0.53939 (8)	0.0284 (4)
O5	0.32754 (10)	0.7245 (2)	0.37433 (8)	0.0286 (3)
O9	0.32904 (9)	0.7808 (2)	0.70863 (8)	0.0278 (3)
N6	0.27838 (10)	0.7897 (2)	0.66911 (7)	0.0166 (3)
N4	0.22386 (9)	0.2216 (2)	0.50211 (7)	0.0163 (3)
N5	0.27653 (10)	0.7290 (3)	0.33496 (7)	0.0173 (3)
N1	0.31848 (10)	0.2376 (3)	0.36864 (7)	0.0168 (3)
N2	0.18133 (10)	0.7134 (3)	0.53670 (8)	0.0156 (3)
N3	0.32057 (10)	0.2974 (3)	0.70392 (8)	0.0168 (3)
C8	0.09461 (11)	0.7114 (3)	0.53327 (8)	0.0152 (3)
C15	0.45232 (12)	0.3177 (3)	0.75138 (12)	0.0218 (4)
C14	0.40697 (11)	0.3123 (3)	0.69968 (9)	0.0149 (3)
C18	0.52529 (14)	0.3378 (3)	0.63992 (12)	0.0282 (5)
C1	0.44176 (12)	0.1889 (3)	0.31153 (9)	0.0184 (4)
C2	0.40471 (12)	0.2229 (3)	0.36588 (9)	0.0169 (3)
C13	0.44297 (12)	0.3228 (3)	0.64420 (9)	0.0192 (4)
C6	0.52416 (14)	0.1773 (3)	0.30787 (12)	0.0280 (5)
C3	0.44992 (12)	0.2439 (3)	0.41743 (12)	0.0242 (4)
C7	0.05730 (12)	0.7435 (3)	0.47897 (10)	0.0204 (4)
C4	0.53223 (14)	0.2306 (4)	0.41372 (15)	0.0322 (5)
C9	0.05007 (13)	0.6738 (3)	0.58416 (11)	0.0227 (4)
C17	0.57056 (13)	0.3435 (3)	0.69158 (15)	0.0338 (6)
C10	−0.03246 (14)	0.6678 (4)	0.58037 (14)	0.0307 (5)
C5	0.56884 (15)	0.1985 (4)	0.35975 (15)	0.0348 (6)
C16	0.53468 (13)	0.3330 (3)	0.74694 (16)	0.0304 (5)
C12	−0.02524 (14)	0.7382 (4)	0.47510 (13)	0.0300 (5)
C11	−0.06960 (14)	0.6990 (4)	0.52598 (15)	0.0348 (6)
H3A	0.3037 (15)	0.183 (4)	0.6891 (13)	0.019 (6)*
H3C	0.3067 (16)	0.294 (4)	0.7413 (16)	0.038 (8)*
H6	0.5497 (15)	0.151 (4)	0.2714 (12)	0.026 (7)*
H9	0.0758 (15)	0.654 (4)	0.6191 (13)	0.022 (7)*
H2B	0.2008 (15)	0.614 (4)	0.5155 (12)	0.022 (6)*
H2C	0.1949 (16)	0.696 (4)	0.5770 (14)	0.024 (7)*
H18	0.5470 (15)	0.349 (4)	0.6007 (12)	0.027 (7)*
H1C	0.3026 (16)	0.332 (4)	0.3477 (14)	0.028 (7)*
H2A	0.2001 (16)	0.832 (4)	0.5258 (13)	0.025 (7)*
H1A	0.2971 (16)	0.126 (4)	0.3589 (13)	0.025 (7)*
H12	−0.0468 (16)	0.763 (4)	0.4384 (14)	0.039 (8)*
H3B	0.2973 (14)	0.393 (4)	0.6858 (12)	0.017 (6)*
H15	0.4295 (16)	0.306 (4)	0.7873 (14)	0.025 (7)*
H16	0.5629 (17)	0.337 (4)	0.7823 (14)	0.035 (8)*
H17	0.6259 (19)	0.367 (5)	0.6864 (17)	0.053 (10)*
H1B	0.3026 (16)	0.268 (4)	0.4054 (14)	0.030 (8)*
H10	−0.0601 (17)	0.644 (4)	0.6156 (13)	0.033 (8)*
H4	0.5598 (16)	0.241 (5)	0.4491 (14)	0.043 (9)*
H3	0.4244 (15)	0.264 (4)	0.4530 (13)	0.024 (7)*
H11	−0.1288 (19)	0.685 (5)	0.5212 (16)	0.048 (9)*
H5	0.628 (2)	0.193 (5)	0.3552 (18)	0.065 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0339 (2)	0.0265 (2)	0.01404 (15)	−0.00014 (19)	0.0046 (2)	−0.0021 (2)
Cl2	0.0349 (3)	0.0370 (3)	0.0142 (2)	0.0039 (2)	−0.0042 (2)	0.0027 (3)
Cl3	0.0369 (3)	0.0357 (3)	0.0135 (2)	−0.0016 (2)	0.0051 (2)	−0.00025 (17)
O7	0.0223 (7)	0.0158 (6)	0.0189 (6)	−0.0004 (5)	−0.0060 (5)	−0.0012 (5)
O6	0.0223 (7)	0.0187 (7)	0.0216 (7)	0.0002 (5)	−0.0035 (6)	0.0027 (5)
O1	0.0299 (8)	0.0169 (6)	0.0206 (7)	−0.0003 (5)	0.0096 (6)	0.0020 (5)
O2	0.0284 (8)	0.0170 (7)	0.0256 (8)	0.0007 (5)	0.0066 (6)	−0.0012 (5)
O4	0.0335 (9)	0.0205 (7)	0.0271 (8)	0.0015 (6)	−0.0108 (6)	−0.0045 (6)
O8	0.0342 (9)	0.0177 (6)	0.0306 (8)	−0.0018 (6)	−0.0079 (7)	0.0053 (6)
O3	0.0222 (8)	0.0343 (9)	0.0286 (8)	0.0048 (6)	0.0137 (6)	0.0082 (6)
O5	0.0239 (8)	0.0330 (8)	0.0290 (8)	0.0039 (6)	−0.0144 (7)	−0.0030 (6)
O9	0.0235 (8)	0.0303 (8)	0.0297 (9)	0.0012 (6)	−0.0149 (6)	−0.0050 (6)
N6	0.0145 (7)	0.0177 (7)	0.0178 (7)	−0.0001 (5)	0.0007 (6)	−0.0013 (5)
N4	0.0136 (7)	0.0204 (7)	0.0148 (7)	−0.0001 (5)	0.0010 (5)	0.0022 (5)
N5	0.0161 (8)	0.0222 (8)	0.0136 (7)	−0.0007 (6)	−0.0013 (6)	0.0005 (5)
N1	0.0182 (8)	0.0196 (8)	0.0128 (7)	0.0006 (6)	0.0023 (6)	−0.0011 (5)
N2	0.0162 (7)	0.0157 (7)	0.0149 (7)	0.0002 (5)	−0.0012 (6)	0.0004 (5)
N3	0.0164 (7)	0.0193 (7)	0.0145 (7)	0.0005 (5)	0.0019 (6)	0.0024 (6)
C8	0.0157 (8)	0.0141 (7)	0.0157 (8)	0.0007 (6)	−0.0005 (6)	−0.0012 (6)
C15	0.0245 (9)	0.0206 (9)	0.0202 (9)	0.0032 (7)	−0.0066 (9)	−0.0012 (8)
C14	0.0138 (8)	0.0155 (7)	0.0155 (7)	0.0000 (6)	0.0006 (6)	0.0003 (6)
C18	0.0225 (11)	0.0211 (10)	0.0411 (14)	−0.0010 (7)	0.0139 (9)	0.0011 (8)
C1	0.0199 (9)	0.0166 (8)	0.0187 (8)	0.0004 (6)	0.0045 (7)	0.0004 (6)
C2	0.0171 (9)	0.0168 (8)	0.0169 (8)	−0.0002 (6)	0.0023 (6)	0.0013 (6)
C13	0.0216 (10)	0.0177 (8)	0.0184 (8)	−0.0006 (6)	0.0063 (7)	−0.0002 (6)
C6	0.0220 (11)	0.0217 (10)	0.0403 (13)	0.0008 (8)	0.0114 (10)	−0.0010 (8)
C3	0.0251 (10)	0.0263 (9)	0.0212 (9)	−0.0029 (8)	−0.0047 (10)	0.0016 (9)
C7	0.0205 (9)	0.0215 (9)	0.0191 (9)	0.0024 (7)	−0.0044 (7)	−0.0024 (6)
C4	0.0241 (11)	0.0307 (11)	0.0418 (15)	−0.0033 (8)	−0.0123 (11)	0.0006 (11)
C9	0.0228 (10)	0.0215 (9)	0.0239 (10)	−0.0010 (7)	0.0065 (8)	0.0004 (7)
C17	0.0162 (10)	0.0230 (10)	0.0621 (19)	−0.0014 (7)	0.0003 (11)	0.0009 (11)
C10	0.0214 (11)	0.0269 (10)	0.0436 (15)	−0.0020 (8)	0.0114 (10)	−0.0014 (9)
C5	0.0156 (10)	0.0301 (12)	0.0586 (19)	−0.0005 (8)	0.0005 (11)	0.0031 (11)
C16	0.0241 (10)	0.0225 (10)	0.0447 (13)	0.0021 (7)	−0.0131 (12)	−0.0034 (10)
C12	0.0237 (11)	0.0299 (11)	0.0363 (13)	0.0041 (8)	−0.0125 (10)	−0.0054 (9)
C11	0.0158 (10)	0.0287 (12)	0.0598 (19)	0.0000 (8)	0.0006 (11)	−0.0057 (11)

Geometric parameters (Å, º)

Cl1—C1	1.733 (2)	C15—C16	1.391 (3)
Cl2—C7	1.731 (2)	C15—H15	0.90 (3)
Cl3—C13	1.729 (2)	C14—C13	1.385 (3)
O7—N6	1.276 (2)	C18—C17	1.386 (4)
O6—N5	1.263 (2)	C18—C13	1.390 (3)
O1—N4	1.278 (2)	C18—H18	0.95 (3)
O2—N4	1.248 (2)	C1—C2	1.387 (3)
O4—N5	1.261 (2)	C1—C6	1.389 (3)
O8—N6	1.250 (2)	C2—C3	1.390 (3)
O3—N4	1.227 (2)	C6—C5	1.392 (4)
O5—N5	1.231 (2)	C6—H6	0.94 (3)
O9—N6	1.230 (2)	C3—C4	1.388 (3)
N1—C2	1.453 (2)	C3—H3	0.92 (3)
N1—H1C	0.82 (3)	C7—C12	1.390 (3)
N1—H1A	0.85 (3)	C4—C5	1.374 (5)
N1—H1B	0.89 (3)	C4—H4	0.92 (3)
N2—C8	1.459 (2)	C9—C10	1.390 (3)
N2—H2B	0.87 (3)	C9—H9	0.91 (3)
N2—H2C	0.94 (3)	C17—C16	1.382 (5)
N2—H2A	0.88 (3)	C17—H17	0.95 (3)
N3—C14	1.458 (2)	C10—C11	1.385 (4)
N3—H3A	0.87 (2)	C10—H10	0.93 (3)
N3—H3C	0.87 (4)	C5—H5	0.99 (4)
N3—H3B	0.84 (3)	C16—H16	0.92 (3)
C8—C7	1.386 (3)	C12—C11	1.387 (4)
C8—C9	1.387 (3)	C12—H12	0.91 (3)
C15—C14	1.388 (3)	C11—H11	1.01 (3)
O9—N6—O8	122.19 (17)	C6—C1—Cl1	120.45 (17)
O9—N6—O7	120.04 (16)	C1—C2—C3	120.1 (2)
O8—N6—O7	117.76 (16)	C1—C2—N1	119.72 (18)
O3—N4—O2	122.24 (16)	C3—C2—N1	120.17 (18)
O3—N4—O1	120.35 (16)	C14—C13—C18	120.0 (2)
O2—N4—O1	117.41 (16)	C14—C13—Cl3	119.43 (15)
O5—N5—O4	121.30 (17)	C18—C13—Cl3	120.56 (17)
O5—N5—O6	121.10 (17)	C1—C6—C5	118.9 (2)
O4—N5—O6	117.60 (16)	C1—C6—H6	121.0 (16)
C2—N1—H1C	110.4 (19)	C5—C6—H6	120.0 (16)
C2—N1—H1A	110.6 (18)	C4—C3—C2	119.2 (3)
H1C—N1—H1A	112 (3)	C4—C3—H3	121.9 (17)
C2—N1—H1B	110.7 (18)	C2—C3—H3	118.9 (17)
H1C—N1—H1B	105 (3)	C8—C7—C12	120.2 (2)
H1A—N1—H1B	108 (3)	C8—C7—Cl2	119.20 (15)
C8—N2—H2B	109.8 (17)	C12—C7—Cl2	120.65 (18)
C8—N2—H2C	106.9 (17)	C5—C4—C3	120.6 (3)
H2B—N2—H2C	110 (2)	C5—C4—H4	123.0 (19)
C8—N2—H2A	110.6 (18)	C3—C4—H4	116.4 (19)
H2B—N2—H2A	113 (2)	C8—C9—C10	119.5 (2)
H2C—N2—H2A	107 (2)	C8—C9—H9	118.8 (17)
C14—N3—H3A	111.0 (17)	C10—C9—H9	121.6 (17)
C14—N3—H3C	109.3 (19)	C16—C17—C18	120.7 (2)
H3A—N3—H3C	105 (3)	C16—C17—H17	123 (2)
C14—N3—H3B	112.3 (16)	C18—C17—H17	116 (2)
H3A—N3—H3B	108 (2)	C11—C10—C9	119.9 (3)
H3C—N3—H3B	111 (2)	C11—C10—H10	123.2 (18)
C7—C8—C9	120.41 (19)	C9—C10—H10	116.9 (18)
C7—C8—N2	119.77 (17)	C4—C5—C6	120.7 (2)
C9—C8—N2	119.81 (18)	C4—C5—H5	123 (2)
C14—C15—C16	119.2 (3)	C6—C5—H5	117 (2)
C14—C15—H15	120.9 (18)	C17—C16—C15	120.1 (3)
C16—C15—H15	119.8 (18)	C17—C16—H16	123.0 (19)
C13—C14—C15	120.61 (19)	C15—C16—H16	117 (2)
C13—C14—N3	119.79 (17)	C11—C12—C7	119.3 (2)
C15—C14—N3	119.60 (18)	C11—C12—H12	124.2 (17)
C17—C18—C13	119.4 (2)	C7—C12—H12	116.5 (17)
C17—C18—H18	123.9 (16)	C10—C11—C12	120.7 (2)
C13—C18—H18	116.7 (16)	C10—C11—H11	122 (2)
C2—C1—C6	120.5 (2)	C12—C11—H11	117 (2)
C2—C1—Cl1	119.01 (16)
C16—C15—C14—C13	−0.3 (3)	N2—C8—C7—C12	178.84 (19)
C16—C15—C14—N3	−179.66 (17)	C9—C8—C7—Cl2	−179.67 (16)
C6—C1—C2—C3	−0.6 (3)	N2—C8—C7—Cl2	−0.8 (3)
Cl1—C1—C2—C3	179.67 (16)	C2—C3—C4—C5	0.5 (3)
C6—C1—C2—N1	179.05 (18)	C7—C8—C9—C10	0.2 (3)
Cl1—C1—C2—N1	−0.7 (2)	N2—C8—C9—C10	−178.62 (19)
C15—C14—C13—C18	0.3 (3)	C13—C18—C17—C16	0.4 (3)
N3—C14—C13—C18	179.74 (17)	C8—C9—C10—C11	0.0 (3)
C15—C14—C13—Cl3	−178.85 (14)	C3—C4—C5—C6	−0.5 (4)
N3—C14—C13—Cl3	0.6 (2)	C1—C6—C5—C4	−0.1 (3)
C17—C18—C13—C14	−0.4 (3)	C18—C17—C16—C15	−0.4 (3)
C17—C18—C13—Cl3	178.75 (16)	C14—C15—C16—C17	0.3 (3)
C2—C1—C6—C5	0.6 (3)	C8—C7—C12—C11	−0.5 (3)
Cl1—C1—C6—C5	−179.66 (17)	Cl2—C7—C12—C11	179.15 (19)
C1—C2—C3—C4	0.0 (3)	C9—C10—C11—C12	−0.6 (4)
N1—C2—C3—C4	−179.58 (19)	C7—C12—C11—C10	0.8 (4)
C9—C8—C7—C12	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O4	0.82 (3)	1.98 (3)	2.800 (2)	173 (3)
N1—H1A···O6^i	0.85 (3)	1.99 (3)	2.825 (2)	169 (3)
N1—H1B···O1	0.89 (3)	1.99 (3)	2.858 (2)	166 (3)
N1—H1B···O2	0.89 (3)	2.43 (3)	3.095 (2)	132 (2)
N2—H2B···O1	0.87 (3)	1.93 (3)	2.799 (2)	174 (3)
N2—H2A···O2^ii	0.88 (3)	1.96 (3)	2.821 (2)	166 (3)
N2—H2C···O7	0.94 (3)	1.90 (3)	2.823 (2)	166 (2)
N2—H2C···O8	0.94 (3)	2.53 (3)	3.185 (2)	127 (2)
N3—H3B···O7	0.84 (3)	1.95 (3)	2.793 (2)	175 (2)
N3—H3A···O8^i	0.87 (2)	1.96 (3)	2.819 (2)	171 (3)
N3—H3C···O6^iii	0.87 (4)	2.08 (3)	2.904 (2)	159 (2)
N3—H3C···O4^iii	0.87 (4)	2.34 (3)	3.038 (2)	138 (2)

Symmetry codes: (i) x, y−1, z; (ii) x−1/2, −y+3/2, z; (iii) −x+1/2, y−1/2, z+1/2.