Structure cristalline, caractérisation spectroscopique, calcul DFT et analyse de surface Hirshfeld du perchlorate de p-toluidinium

A new organic perchlorate, C₇H₁₀N⁺·ClO₄⁻, was synthesized by slow evaporation at room temperature and its crystal structure was determined. This compound was characterized by powder XRD, IR, and UV–Vis spectroscopy. The DFT optimized structure at the B3LYP/6–311++G (d,p) level was compared with the experimentally determined mol­ecular structure in the solid state. Hirshfeld surface and fingerprint plots are presented and discussed.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.067
• wR factor = 0.212
• Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact O1       ..O1        .       2.80 Ang.

Alert level C
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         C1 Check
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         C2 Check
PLAT334_ALERT_2_C Small Aver. Benzene C-C Dist C1       -C5              1.37 Ang.
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00771 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.625 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT242_ALERT_2_G Low    'MainMol' Ueq as Compared to Neighbors of        Cl1 Check
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          2 Note
              Cl O4
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          3 Note
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          ! Info
PLAT931_ALERT_5_G Found Twin Law (         )[ 0 0  1  ] Est.  BASF       0.06 Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL022_ALERT_1_A There is a mismatched ~ on line 675
              extr\'emit\'e qui pointe vers l'origine et qui correspond \`a <i>d~i~</i> \~
              If you require a ~ then it should be escaped
              with a \, i.e. \~
              Otherwise there must be a matching closing ~, e.g. C~2~H~4~

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

4-Methylanilinium perchlorate

Crystal data

C7H10N^+·ClO4^−	F(000) = 432
Mr = 207.61	Dx = 1.409 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.513 (1) Å	Cell parameters from 25 reflections
b = 7.196 (5) Å	θ = 10–15°
c = 14.297 (4) Å	µ = 0.37 mm^−1
β = 90.41 (2)°	T = 293 K
V = 978.7 (7) Å^3	Plate, colorless
Z = 4	0.6 × 0.5 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	1160 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 27.0°, θmin = 2.1°
ω/2θ scans	h = −12→2
Absorption correction: ψ scan (North et al., 1968)	k = −1→9
Tmin = 0.882, Tmax = 0.998	l = −18→18
3216 measured reflections	2 standard reflections every 120 reflections
2128 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.212	w = 1/[σ^2(Fo^2) + (0.085P)^2 + 1.0514P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2128 reflections	Δρmax = 0.36 e Å^−3
129 parameters	Δρmin = −0.21 e Å^−3

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.

Refinement. Refined as a two-component twin

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

	x	y	z	Uiso*/Ueq
Cl1	0.52897 (14)	−0.29315 (14)	0.62359 (8)	0.0642 (4)
O1	0.5256 (5)	−0.1659 (6)	0.5480 (2)	0.1049 (15)
O2	0.5176 (5)	−0.1823 (6)	0.7054 (3)	0.1103 (15)
O3	0.6554 (5)	−0.3917 (7)	0.6250 (4)	0.1262 (18)
O4	0.4153 (6)	−0.4142 (7)	0.6138 (4)	0.147 (2)
N1	0.6247 (5)	0.1992 (6)	0.6276 (3)	0.0721 (11)
H1A	0.571 (6)	0.132 (8)	0.590 (4)	0.108*
H1B	0.602 (7)	0.288 (7)	0.587 (4)	0.108*
H1C	0.582 (6)	0.274 (7)	0.668 (3)	0.108*
C1	0.7767 (5)	0.1822 (6)	0.6265 (3)	0.0589 (11)
C2	1.0659 (6)	0.1509 (8)	0.6266 (4)	0.0756 (15)
C3	0.9967 (6)	0.2379 (8)	0.5552 (4)	0.0809 (15)
H3	1.0480	0.2862	0.5057	0.097*
C4	0.8528 (6)	0.2557 (8)	0.5547 (3)	0.0755 (15)
H4	0.8075	0.3174	0.5059	0.091*
C5	0.8435 (6)	0.0943 (8)	0.6986 (4)	0.0827 (16)
H5	0.7918	0.0449	0.7477	0.099*
C6	0.9870 (6)	0.0790 (9)	0.6988 (4)	0.0896 (18)
H6	1.0321	0.0193	0.7483	0.107*
C7	1.2244 (6)	0.1306 (12)	0.6272 (6)	0.120 (3)
H7A	1.2640	0.2097	0.6746	0.180*
H7B	1.2606	0.1656	0.5673	0.180*
H7C	1.2489	0.0038	0.6402	0.180*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0915 (9)	0.0434 (5)	0.0576 (6)	0.0046 (6)	−0.0020 (5)	0.0043 (6)
O1	0.179 (4)	0.069 (2)	0.067 (2)	−0.001 (3)	−0.005 (2)	0.0182 (18)
O2	0.163 (4)	0.098 (3)	0.069 (2)	0.022 (3)	0.016 (2)	−0.016 (2)
O3	0.124 (4)	0.099 (3)	0.155 (4)	0.050 (3)	−0.014 (3)	−0.011 (3)
O4	0.144 (4)	0.105 (4)	0.192 (6)	−0.052 (4)	−0.026 (4)	0.009 (4)
N1	0.071 (3)	0.059 (3)	0.086 (3)	0.002 (2)	−0.002 (2)	−0.014 (2)
C1	0.064 (3)	0.044 (2)	0.068 (3)	0.002 (2)	−0.005 (2)	−0.007 (2)
C2	0.070 (3)	0.071 (3)	0.086 (4)	0.004 (3)	0.003 (3)	−0.020 (3)
C3	0.079 (4)	0.086 (4)	0.079 (3)	−0.006 (3)	0.014 (3)	0.001 (3)
C4	0.082 (4)	0.076 (3)	0.068 (3)	0.007 (3)	−0.002 (2)	0.010 (3)
C5	0.085 (4)	0.083 (4)	0.081 (3)	−0.006 (3)	0.008 (3)	0.015 (3)
C6	0.085 (4)	0.086 (4)	0.097 (4)	0.014 (3)	−0.021 (3)	0.011 (3)
C7	0.073 (4)	0.144 (6)	0.143 (6)	0.020 (4)	−0.008 (4)	−0.050 (6)

Geometric parameters (Å, º)

Cl1—O4	1.394 (5)	C2—C6	1.380 (8)
Cl1—O3	1.396 (4)	C2—C7	1.515 (7)
Cl1—O1	1.416 (4)	C3—C4	1.375 (7)
Cl1—O2	1.421 (4)	C3—H3	0.9300
N1—C1	1.451 (6)	C4—H4	0.9300
N1—H1A	0.885 (10)	C5—C6	1.370 (8)
N1—H1B	0.887 (10)	C5—H5	0.9300
N1—H1C	0.885 (10)	C6—H6	0.9300
C1—C5	1.363 (7)	C7—H7A	0.9600
C1—C4	1.367 (7)	C7—H7B	0.9600
C2—C3	1.363 (7)	C7—H7C	0.9600
O4—Cl1—O3	110.6 (3)	C2—C3—C4	121.4 (5)
O4—Cl1—O1	108.3 (3)	C2—C3—H3	119.3
O3—Cl1—O1	110.8 (3)	C4—C3—H3	119.3
O4—Cl1—O2	111.7 (4)	C1—C4—C3	119.5 (5)
O3—Cl1—O2	110.1 (3)	C1—C4—H4	120.3
O1—Cl1—O2	105.3 (3)	C3—C4—H4	120.3
C1—N1—H1A	121 (4)	C1—C5—C6	119.8 (5)
C1—N1—H1B	107 (4)	C1—C5—H5	120.1
H1A—N1—H1B	82 (5)	C6—C5—H5	120.1
C1—N1—H1C	121 (4)	C5—C6—C2	121.0 (5)
H1A—N1—H1C	118 (6)	C5—C6—H6	119.5
H1B—N1—H1C	83 (5)	C2—C6—H6	119.5
C5—C1—C4	120.1 (5)	C2—C7—H7A	109.5
C5—C1—N1	119.3 (5)	C2—C7—H7B	109.5
C4—C1—N1	120.5 (4)	H7A—C7—H7B	109.5
C3—C2—C6	118.1 (5)	C2—C7—H7C	109.5
C3—C2—C7	121.6 (6)	H7A—C7—H7C	109.5
C6—C2—C7	120.4 (6)	H7B—C7—H7C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.89 (1)	2.26 (4)	3.011 (6)	142 (6)
N1—H1A···O1^i	0.89 (1)	2.18 (5)	2.891 (6)	137 (6)
N1—H1B···O1^i	0.89 (1)	2.44 (6)	2.891 (6)	112 (6)
N1—H1B···O3^ii	0.89 (1)	2.42 (6)	2.959 (7)	120 (5)
N1—H1C···O2^iii	0.89 (1)	2.08 (3)	2.882 (6)	150 (6)

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