Crystal structure and Hirshfeld surface analysis of 4-{2,2-di­chloro-1-[(E)-(4-fluoro­phen­yl)diazen­yl]ethen­yl}-N,N-di­methyl­aniline

The dihedral angle between the two aromatic rings of the title compound is 64.12 (14)°. The crystal structure is stabilized by a short Cl...H contact, C—Cl...π and van der Waals inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.034
• wR factor = 0.084
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00407 Ang.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         21 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          8 Note

Alert level G
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          4 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          2 Info

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   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

---

Computing details

Data collection: APEX3 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXT2016/6 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

4-{2,2-Dichloro-1-[(E)-(4-fluorophenyl)diazenyl]ethenyl}-N,N-dimethylaniline

Crystal data

C16H14Cl2FN3	Dx = 1.413 Mg m^−3
Mr = 338.20	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 6056 reflections
a = 6.0730 (3) Å	θ = 2.8–26.4°
b = 15.9782 (9) Å	µ = 0.42 mm^−1
c = 16.3860 (7) Å	T = 296 K
V = 1590.03 (14) Å^3	Block, orange
Z = 4	0.27 × 0.24 × 0.17 mm
F(000) = 696

Data collection

Bruker APEXII PHOTON 100 detector diffractometer	2696 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θmax = 26.4°, θmin = 2.5°
Tmin = 0.887, Tmax = 0.944	h = −7→7
12082 measured reflections	k = −19→19
3215 independent reflections	l = −20→20

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0431P)^2 + 0.1514P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.084	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.13 e Å^−3
3215 reflections	Δρmin = −0.22 e Å^−3
201 parameters	Absolute structure: Flack x determined using 1002 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013).
0 restraints	Absolute structure parameter: −0.02 (2)

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
C1	0.4252 (4)	0.61833 (16)	0.56623 (16)	0.0443 (6)
C2	0.5620 (5)	0.68715 (18)	0.55987 (18)	0.0509 (7)
H2A	0.540332	0.725536	0.517976	0.061*
C3	0.7298 (5)	0.6994 (2)	0.61488 (17)	0.0573 (8)
H3A	0.823241	0.745307	0.610610	0.069*
C4	0.7553 (5)	0.6416 (2)	0.67653 (18)	0.0594 (8)
C5	0.6205 (6)	0.5739 (2)	0.6855 (2)	0.0673 (9)
H5A	0.641740	0.536178	0.728082	0.081*
C6	0.4535 (5)	0.56267 (19)	0.63053 (18)	0.0574 (8)
H6A	0.358152	0.517491	0.636245	0.069*
C7	−0.0179 (4)	0.53364 (16)	0.45205 (16)	0.0439 (6)
C8	−0.0207 (4)	0.58320 (16)	0.37493 (15)	0.0421 (6)
C9	−0.1979 (4)	0.63333 (18)	0.35356 (16)	0.0465 (6)
H9A	−0.319781	0.635689	0.387856	0.056*
C10	−0.1976 (4)	0.67976 (18)	0.28261 (16)	0.0470 (7)
H10A	−0.319254	0.712725	0.270104	0.056*
C11	−0.0185 (4)	0.67833 (17)	0.22914 (15)	0.0419 (6)
C12	0.1597 (5)	0.62650 (17)	0.25034 (16)	0.0463 (6)
H12A	0.280540	0.622891	0.215669	0.056*
C13	0.1577 (5)	0.58098 (17)	0.32175 (17)	0.0473 (6)
H13A	0.278742	0.547916	0.334730	0.057*
C14	−0.1613 (5)	0.47174 (16)	0.46824 (16)	0.0469 (6)
C15	−0.1744 (6)	0.7909 (2)	0.14541 (19)	0.0624 (8)
H15A	−0.174793	0.828007	0.191458	0.094*
H15B	−0.318008	0.766689	0.138916	0.094*
H15C	−0.136230	0.821563	0.097069	0.094*
C16	0.1532 (6)	0.7139 (2)	0.09817 (19)	0.0666 (8)
H16A	0.162051	0.655738	0.083877	0.100*
H16B	0.292048	0.732038	0.119880	0.100*
H16C	0.118356	0.746158	0.050458	0.100*
Cl1	−0.16032 (15)	0.41361 (5)	0.55620 (5)	0.0677 (3)
Cl2	−0.36345 (14)	0.44180 (5)	0.40139 (5)	0.0680 (3)
F1	0.9220 (4)	0.65309 (16)	0.73030 (13)	0.0957 (8)
N1	0.2619 (4)	0.60931 (14)	0.50431 (14)	0.0477 (5)
N2	0.1433 (4)	0.54576 (14)	0.51363 (13)	0.0469 (5)
N3	−0.0159 (4)	0.72557 (16)	0.15854 (14)	0.0554 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0531 (15)	0.0378 (14)	0.0420 (13)	0.0006 (11)	−0.0011 (12)	−0.0018 (11)
C2	0.0671 (18)	0.0421 (15)	0.0436 (14)	−0.0075 (13)	0.0032 (14)	0.0000 (12)
C3	0.0676 (19)	0.0562 (17)	0.0480 (16)	−0.0201 (15)	0.0029 (15)	−0.0036 (14)
C4	0.0617 (18)	0.070 (2)	0.0468 (15)	−0.0164 (16)	−0.0090 (15)	0.0004 (15)
C5	0.079 (2)	0.065 (2)	0.0583 (18)	−0.0209 (17)	−0.0234 (17)	0.0185 (15)
C6	0.0655 (18)	0.0480 (17)	0.0588 (17)	−0.0192 (15)	−0.0148 (15)	0.0152 (14)
C7	0.0430 (13)	0.0427 (14)	0.0461 (14)	0.0082 (11)	−0.0043 (12)	−0.0006 (11)
C8	0.0433 (13)	0.0398 (14)	0.0433 (13)	0.0034 (11)	−0.0052 (12)	−0.0006 (11)
C9	0.0409 (14)	0.0550 (16)	0.0436 (14)	0.0078 (12)	0.0017 (12)	−0.0020 (12)
C10	0.0421 (14)	0.0513 (15)	0.0474 (15)	0.0121 (12)	−0.0034 (13)	0.0028 (12)
C11	0.0416 (14)	0.0435 (15)	0.0406 (14)	0.0010 (11)	−0.0047 (12)	−0.0043 (11)
C12	0.0384 (13)	0.0517 (15)	0.0486 (14)	0.0059 (12)	0.0035 (13)	−0.0033 (12)
C13	0.0392 (13)	0.0478 (14)	0.0547 (15)	0.0077 (12)	−0.0061 (13)	−0.0012 (12)
C14	0.0453 (14)	0.0438 (14)	0.0515 (14)	0.0037 (12)	−0.0048 (13)	−0.0001 (11)
C15	0.0624 (19)	0.0655 (19)	0.0591 (18)	0.0090 (16)	−0.0018 (17)	0.0153 (15)
C16	0.0647 (19)	0.075 (2)	0.0595 (18)	0.0020 (18)	0.0144 (18)	0.0095 (16)
Cl1	0.0720 (5)	0.0627 (5)	0.0683 (5)	−0.0060 (4)	0.0004 (5)	0.0197 (4)
Cl2	0.0576 (4)	0.0620 (5)	0.0845 (5)	−0.0089 (4)	−0.0209 (4)	0.0044 (4)
F1	0.0914 (16)	0.1181 (18)	0.0777 (13)	−0.0488 (14)	−0.0399 (12)	0.0172 (13)
N1	0.0566 (14)	0.0415 (12)	0.0450 (12)	−0.0009 (11)	−0.0058 (11)	0.0018 (10)
N2	0.0506 (12)	0.0449 (12)	0.0454 (11)	−0.0031 (11)	−0.0081 (11)	0.0016 (10)
N3	0.0568 (15)	0.0634 (16)	0.0461 (12)	0.0129 (12)	0.0076 (12)	0.0089 (11)

Geometric parameters (Å, º)

C1—C2	1.382 (4)	C10—C11	1.397 (4)
C1—C6	1.389 (4)	C10—H10A	0.9300
C1—N1	1.426 (3)	C11—N3	1.381 (3)
C2—C3	1.374 (4)	C11—C12	1.406 (4)
C2—H2A	0.9300	C12—C13	1.378 (4)
C3—C4	1.377 (4)	C12—H12A	0.9300
C3—H3A	0.9300	C13—H13A	0.9300
C4—F1	1.354 (3)	C14—Cl2	1.713 (3)
C4—C5	1.365 (4)	C14—Cl1	1.715 (3)
C5—C6	1.369 (4)	C15—N3	1.436 (4)
C5—H5A	0.9300	C15—H15A	0.9600
C6—H6A	0.9300	C15—H15B	0.9600
C7—C14	1.344 (4)	C15—H15C	0.9600
C7—N2	1.419 (3)	C16—N3	1.438 (4)
C7—C8	1.491 (4)	C16—H16A	0.9600
C8—C9	1.387 (4)	C16—H16B	0.9600
C8—C13	1.391 (4)	C16—H16C	0.9600
C9—C10	1.379 (4)	N1—N2	1.255 (3)
C9—H9A	0.9300
C2—C1—C6	119.5 (3)	N3—C11—C10	121.7 (2)
C2—C1—N1	116.4 (2)	N3—C11—C12	121.3 (2)
C6—C1—N1	124.1 (2)	C10—C11—C12	117.0 (2)
C3—C2—C1	120.6 (3)	C13—C12—C11	120.9 (3)
C3—C2—H2A	119.7	C13—C12—H12A	119.5
C1—C2—H2A	119.7	C11—C12—H12A	119.5
C2—C3—C4	118.0 (3)	C12—C13—C8	121.7 (2)
C2—C3—H3A	121.0	C12—C13—H13A	119.1
C4—C3—H3A	121.0	C8—C13—H13A	119.1
F1—C4—C5	119.0 (3)	C7—C14—Cl2	122.9 (2)
F1—C4—C3	118.1 (3)	C7—C14—Cl1	124.2 (2)
C5—C4—C3	122.9 (3)	Cl2—C14—Cl1	112.87 (16)
C4—C5—C6	118.5 (3)	N3—C15—H15A	109.5
C4—C5—H5A	120.8	N3—C15—H15B	109.5
C6—C5—H5A	120.8	H15A—C15—H15B	109.5
C5—C6—C1	120.5 (3)	N3—C15—H15C	109.5
C5—C6—H6A	119.8	H15A—C15—H15C	109.5
C1—C6—H6A	119.8	H15B—C15—H15C	109.5
C14—C7—N2	114.0 (2)	N3—C16—H16A	109.5
C14—C7—C8	123.4 (2)	N3—C16—H16B	109.5
N2—C7—C8	122.5 (2)	H16A—C16—H16B	109.5
C9—C8—C13	117.5 (2)	N3—C16—H16C	109.5
C9—C8—C7	122.0 (2)	H16A—C16—H16C	109.5
C13—C8—C7	120.6 (2)	H16B—C16—H16C	109.5
C10—C9—C8	121.5 (3)	N2—N1—C1	113.2 (2)
C10—C9—H9A	119.2	N1—N2—C7	114.8 (2)
C8—C9—H9A	119.2	C11—N3—C15	121.0 (2)
C9—C10—C11	121.4 (2)	C11—N3—C16	120.9 (2)
C9—C10—H10A	119.3	C15—N3—C16	118.0 (2)
C11—C10—H10A	119.3
C6—C1—C2—C3	2.2 (4)	N3—C11—C12—C13	178.6 (3)
N1—C1—C2—C3	−177.5 (2)	C10—C11—C12—C13	−1.4 (4)
C1—C2—C3—C4	−0.6 (4)	C11—C12—C13—C8	1.1 (4)
C2—C3—C4—F1	179.3 (3)	C9—C8—C13—C12	−0.1 (4)
C2—C3—C4—C5	−0.7 (5)	C7—C8—C13—C12	−179.7 (3)
F1—C4—C5—C6	−179.6 (3)	N2—C7—C14—Cl2	−177.0 (2)
C3—C4—C5—C6	0.4 (6)	C8—C7—C14—Cl2	0.6 (4)
C4—C5—C6—C1	1.2 (5)	N2—C7—C14—Cl1	2.1 (3)
C2—C1—C6—C5	−2.5 (5)	C8—C7—C14—Cl1	179.6 (2)
N1—C1—C6—C5	177.1 (3)	C2—C1—N1—N2	−179.9 (2)
C14—C7—C8—C9	63.2 (4)	C6—C1—N1—N2	0.4 (4)
N2—C7—C8—C9	−119.4 (3)	C1—N1—N2—C7	−178.6 (2)
C14—C7—C8—C13	−117.3 (3)	C14—C7—N2—N1	−172.0 (2)
N2—C7—C8—C13	60.1 (3)	C8—C7—N2—N1	10.4 (3)
C13—C8—C9—C10	−0.4 (4)	C10—C11—N3—C15	13.1 (4)
C7—C8—C9—C10	179.1 (3)	C12—C11—N3—C15	−166.9 (3)
C8—C9—C10—C11	0.0 (4)	C10—C11—N3—C16	−170.4 (3)
C9—C10—C11—N3	−179.1 (3)	C12—C11—N3—C16	9.6 (4)
C9—C10—C11—C12	0.9 (4)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—Cl1···Cg1^i	1.72 (1)	3.93 (1)	3.882 (3)	76 (1)

Symmetry code: (i) x−1, y, z.