Crystal structure and DFT study of (E)-2-chloro-4-{[2-(2,4-di­nitro­phen­yl)hydrazin-1-yl­idene]meth­yl}phenol aceto­nitrile hemisolvate

The title Schiff base compound was obtained from a condensation reaction of 4-chloro-3-hy­droxy­benzaldehyde and 2,4-di­nitro­phenyl­hydrazine. The mol­ecule is almost planar with the dihedral angle between the benzene rings being 3.70 (17)°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.057
• wR factor = 0.137
• Data-to-parameter ratio = 13.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections (too) Low ..        47% Check
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ     Please Check
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of        C14 Check
PLAT260_ALERT_2_C Large Average Ueq of Residue Including        N5      0.123 Check
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00529 Ang.
PLAT430_ALERT_2_C Short Inter D...A Contact  O5       ..O5       .       2.90 Ang.
                                            3/2-x,1/2-y,1-z  =      7_656 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......     50.142 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      8.261 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.166 Check

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT045_ALERT_1_G Calculated and Reported Z Differ by a Factor ...       0.50 Check
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT300_ALERT_4_G Atom Site Occupancy of H15A       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H15B       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H15C       Constrained at        0.5 Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

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

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

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

(E)-2-Chloro-4-{[2-(2,4-dinitrophenyl)hydrazin-1-ylidene]methyl}phenol acetonitrile hemisolvate

Crystal data

C13H9ClN4O5·0.5C2H3N	F(000) = 1464
Mr = 357.22	Dx = 1.542 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.0614 (11) Å	Cell parameters from 8879 reflections
b = 9.6960 (6) Å	θ = 1.6–27.9°
c = 26.688 (2) Å	µ = 0.28 mm^−1
β = 99.619 (7)°	T = 296 K
V = 3077.2 (4) Å^3	Plate, orange
Z = 8	0.49 × 0.28 × 0.04 mm

Data collection

Stoe IPDS 2 diffractometer	3027 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1416 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.056
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.6°
rotation method scans	h = −14→14
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −11→11
Tmin = 0.908, Tmax = 0.989	l = −32→32
8928 measured reflections

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)] = 0.057	Hydrogen site location: mixed
wR(F^2) = 0.137	H-atom parameters constrained
S = 0.93	w = 1/[σ^2(Fo^2) + (0.0568P)^2] where P = (Fo^2 + 2Fc^2)/3
3027 reflections	(Δ/σ)max < 0.001
224 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.26 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.52434 (10)	1.07475 (11)	0.57323 (4)	0.0964 (4)
O1	0.6912 (2)	1.0735 (3)	0.66391 (9)	0.0832 (8)
H1	0.733227	1.065785	0.691276	0.125*
N1	0.6314 (2)	0.5959 (3)	0.49923 (11)	0.0606 (7)
N2	0.6383 (2)	0.4785 (3)	0.47069 (11)	0.0633 (8)
H2	0.684398	0.413575	0.481954	0.076*
O4	0.6517 (2)	0.1472 (3)	0.37327 (11)	0.0926 (9)
N4	0.6512 (3)	0.2398 (3)	0.40402 (13)	0.0736 (9)
O5	0.7122 (3)	0.2383 (3)	0.44573 (11)	0.0972 (9)
O2	0.2825 (3)	0.5344 (4)	0.27290 (12)	0.1162 (12)
N3	0.3566 (3)	0.4469 (5)	0.28233 (14)	0.0906 (11)
C4	0.6977 (3)	0.7239 (3)	0.57388 (12)	0.0547 (8)
O3	0.3675 (3)	0.3539 (4)	0.25304 (12)	0.1189 (12)
C8	0.5723 (3)	0.4668 (3)	0.42510 (13)	0.0572 (9)
C7	0.6998 (3)	0.6042 (3)	0.54105 (14)	0.0620 (9)
H7	0.751146	0.533624	0.550646	0.074*
C1	0.6946 (3)	0.9554 (3)	0.63640 (13)	0.0622 (9)
C3	0.6217 (3)	0.8310 (3)	0.55996 (12)	0.0600 (9)
H3	0.571249	0.825918	0.529585	0.072*
C2	0.6210 (3)	0.9437 (3)	0.59087 (13)	0.0618 (9)
C13	0.5754 (3)	0.3556 (3)	0.39104 (13)	0.0582 (9)
C9	0.4926 (3)	0.5706 (4)	0.40833 (14)	0.0666 (9)
H9	0.486539	0.645038	0.429653	0.080*
C5	0.7703 (3)	0.7353 (4)	0.61968 (13)	0.0653 (10)
H5	0.820955	0.664350	0.629757	0.078*
C12	0.5062 (3)	0.3507 (4)	0.34458 (13)	0.0664 (10)
H12	0.510551	0.276937	0.322720	0.080*
C11	0.4313 (3)	0.4545 (4)	0.33077 (13)	0.0683 (10)
C6	0.7698 (3)	0.8491 (4)	0.65093 (13)	0.0658 (10)
H6	0.819628	0.854208	0.681488	0.079*
C10	0.4249 (3)	0.5663 (4)	0.36269 (15)	0.0724 (10)
H10	0.374492	0.637587	0.352688	0.087*
C14	0.500000	0.8470 (10)	0.250000	0.108 (2)
N5	0.500000	0.7307 (8)	0.250000	0.129 (2)
C15	0.500000	0.9945 (8)	0.250000	0.133 (3)
H15A	0.477479	1.027514	0.280695	0.200*	0.5
H15B	0.448298	1.027514	0.221207	0.200*	0.5
H15C	0.574223	1.027514	0.248098	0.200*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1112 (8)	0.0726 (7)	0.0951 (8)	0.0330 (6)	−0.0125 (6)	−0.0092 (6)
O1	0.096 (2)	0.0762 (17)	0.0716 (18)	0.0121 (15)	−0.0028 (15)	−0.0197 (14)
N1	0.0692 (19)	0.0535 (17)	0.0591 (18)	0.0024 (14)	0.0106 (17)	−0.0066 (14)
N2	0.074 (2)	0.0512 (17)	0.0631 (19)	0.0102 (14)	0.0082 (17)	−0.0038 (14)
O4	0.116 (2)	0.0702 (17)	0.0891 (19)	0.0191 (16)	0.0082 (18)	−0.0220 (16)
N4	0.089 (2)	0.063 (2)	0.068 (2)	0.0086 (18)	0.009 (2)	−0.0067 (18)
O5	0.123 (2)	0.0750 (19)	0.0822 (19)	0.0406 (17)	−0.0170 (18)	−0.0116 (15)
O2	0.086 (2)	0.166 (3)	0.089 (2)	0.016 (2)	−0.0102 (19)	0.023 (2)
N3	0.067 (2)	0.142 (4)	0.063 (2)	−0.009 (3)	0.010 (2)	0.012 (2)
C4	0.058 (2)	0.0523 (19)	0.054 (2)	−0.0033 (17)	0.0103 (18)	0.0007 (17)
O3	0.102 (2)	0.181 (4)	0.068 (2)	0.004 (2)	−0.0016 (18)	−0.029 (2)
C8	0.065 (2)	0.052 (2)	0.054 (2)	−0.0015 (17)	0.0092 (19)	0.0003 (17)
C7	0.067 (2)	0.057 (2)	0.063 (2)	0.0063 (17)	0.013 (2)	−0.0013 (18)
C1	0.067 (2)	0.061 (2)	0.059 (2)	0.0006 (19)	0.0101 (19)	−0.0087 (18)
C3	0.065 (2)	0.058 (2)	0.054 (2)	0.0043 (18)	0.0010 (18)	0.0017 (17)
C2	0.068 (2)	0.055 (2)	0.061 (2)	0.0074 (18)	0.006 (2)	0.0002 (18)
C13	0.060 (2)	0.056 (2)	0.059 (2)	0.0045 (17)	0.0111 (19)	0.0004 (17)
C9	0.070 (2)	0.060 (2)	0.071 (3)	0.009 (2)	0.015 (2)	0.0028 (19)
C5	0.060 (2)	0.071 (2)	0.064 (2)	0.0143 (19)	0.009 (2)	0.003 (2)
C12	0.075 (3)	0.071 (2)	0.055 (2)	−0.005 (2)	0.016 (2)	−0.0022 (19)
C11	0.065 (2)	0.089 (3)	0.051 (2)	−0.007 (2)	0.010 (2)	0.007 (2)
C6	0.064 (2)	0.076 (2)	0.053 (2)	0.003 (2)	−0.0012 (18)	−0.0052 (19)
C10	0.071 (3)	0.075 (2)	0.072 (3)	0.010 (2)	0.013 (2)	0.011 (2)
C14	0.090 (5)	0.123 (7)	0.110 (6)	0.000	0.012 (4)	0.000
N5	0.121 (5)	0.120 (5)	0.137 (5)	0.000	−0.001 (4)	0.000
C15	0.103 (6)	0.103 (6)	0.196 (9)	0.000	0.029 (6)	0.000

Geometric parameters (Å, º)

Cl1—C2	1.736 (3)	C3—C2	1.370 (4)
O1—C1	1.364 (4)	C3—H3	0.9300
O1—H1	0.8200	C13—C12	1.375 (5)
N1—C7	1.275 (4)	C9—C10	1.349 (5)
N1—N2	1.380 (3)	C9—H9	0.9300
N2—C8	1.343 (4)	C5—C6	1.384 (4)
N2—H2	0.8600	C5—H5	0.9300
O4—N4	1.217 (3)	C12—C11	1.362 (5)
N4—O5	1.228 (4)	C12—H12	0.9300
N4—C13	1.452 (4)	C11—C10	1.388 (5)
O2—N3	1.228 (5)	C6—H6	0.9300
N3—O3	1.215 (4)	C10—H10	0.9300
N3—C11	1.449 (5)	C14—N5	1.128 (9)
C4—C5	1.384 (4)	C14—C15	1.430 (10)
C4—C3	1.394 (4)	C15—H15A	0.9600
C4—C7	1.457 (4)	C15—H15B	0.9600
C8—C9	1.411 (5)	C15—H15C	0.9600
C8—C13	1.414 (4)	C15—H15A^i	0.9600
C7—H7	0.9300	C15—H15B^i	0.9600
C1—C2	1.384 (5)	C15—H15C^i	0.9600
C1—C6	1.385 (5)
C1—O1—H1	109.5	C4—C5—H5	119.0
C7—N1—N2	116.5 (3)	C6—C5—H5	119.0
C8—N2—N1	119.2 (3)	C11—C12—C13	119.6 (3)
C8—N2—H2	120.4	C11—C12—H12	120.2
N1—N2—H2	120.4	C13—C12—H12	120.2
O4—N4—O5	122.1 (3)	C12—C11—C10	120.9 (4)
O4—N4—C13	118.9 (3)	C12—C11—N3	119.3 (4)
O5—N4—C13	118.9 (3)	C10—C11—N3	119.8 (4)
O3—N3—O2	122.3 (4)	C5—C6—C1	119.5 (3)
O3—N3—C11	119.6 (4)	C5—C6—H6	120.2
O2—N3—C11	118.1 (4)	C1—C6—H6	120.2
C5—C4—C3	117.8 (3)	C9—C10—C11	119.4 (4)
C5—C4—C7	121.5 (3)	C9—C10—H10	120.3
C3—C4—C7	120.6 (3)	C11—C10—H10	120.3
N2—C8—C9	119.8 (3)	N5—C14—C15	180.0
N2—C8—C13	124.8 (3)	C14—C15—H15A	109.5
C9—C8—C13	115.4 (3)	C14—C15—H15B	109.5
N1—C7—C4	120.2 (3)	H15A—C15—H15B	109.5
N1—C7—H7	119.9	C14—C15—H15C	109.5
C4—C7—H7	119.9	H15A—C15—H15C	109.5
O1—C1—C2	117.9 (3)	H15B—C15—H15C	109.5
O1—C1—C6	123.4 (3)	C14—C15—H15A^i	109.471 (2)
C2—C1—C6	118.6 (3)	H15A—C15—H15A^i	141.1
C2—C3—C4	120.2 (3)	H15B—C15—H15A^i	56.3
C2—C3—H3	119.9	H15C—C15—H15A^i	56.2
C4—C3—H3	119.9	C14—C15—H15B^i	109.470 (3)
C3—C2—C1	121.8 (3)	H15A—C15—H15B^i	56.3
C3—C2—Cl1	119.5 (3)	H15B—C15—H15B^i	141.1
C1—C2—Cl1	118.8 (3)	H15C—C15—H15B^i	56.3
C12—C13—C8	121.9 (3)	H15A^i—C15—H15B^i	109.5
C12—C13—N4	116.8 (3)	C14—C15—H15C^i	109.470 (5)
C8—C13—N4	121.3 (3)	H15A—C15—H15C^i	56.3
C10—C9—C8	122.8 (4)	H15B—C15—H15C^i	56.2
C10—C9—H9	118.6	H15C—C15—H15C^i	141.1
C8—C9—H9	118.6	H15A^i—C15—H15C^i	109.5
C4—C5—C6	122.0 (3)	H15B^i—C15—H15C^i	109.5
C7—N1—N2—C8	−176.8 (3)	O4—N4—C13—C8	−179.3 (3)
N1—N2—C8—C9	−3.5 (4)	O5—N4—C13—C8	1.0 (5)
N1—N2—C8—C13	176.4 (3)	N2—C8—C9—C10	178.9 (3)
N2—N1—C7—C4	−179.4 (3)	C13—C8—C9—C10	−1.0 (5)
C5—C4—C7—N1	179.5 (3)	C3—C4—C5—C6	−0.8 (5)
C3—C4—C7—N1	−0.4 (5)	C7—C4—C5—C6	179.4 (3)
C5—C4—C3—C2	0.7 (5)	C8—C13—C12—C11	−0.7 (5)
C7—C4—C3—C2	−179.4 (3)	N4—C13—C12—C11	178.3 (3)
C4—C3—C2—C1	0.0 (5)	C13—C12—C11—C10	0.9 (5)
C4—C3—C2—Cl1	−179.1 (2)	C13—C12—C11—N3	−178.4 (3)
O1—C1—C2—C3	177.5 (3)	O3—N3—C11—C12	−5.6 (5)
C6—C1—C2—C3	−0.6 (5)	O2—N3—C11—C12	172.9 (3)
O1—C1—C2—Cl1	−3.4 (4)	O3—N3—C11—C10	175.1 (4)
C6—C1—C2—Cl1	178.5 (3)	O2—N3—C11—C10	−6.4 (5)
N2—C8—C13—C12	−179.2 (3)	C4—C5—C6—C1	0.1 (5)
C9—C8—C13—C12	0.7 (5)	O1—C1—C6—C5	−177.5 (3)
N2—C8—C13—N4	1.8 (5)	C2—C1—C6—C5	0.6 (5)
C9—C8—C13—N4	−178.3 (3)	C8—C9—C10—C11	1.3 (5)
O4—N4—C13—C12	1.7 (5)	C12—C11—C10—C9	−1.2 (5)
O5—N4—C13—C12	−178.0 (3)	N3—C11—C10—C9	178.1 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	0.86	2.01	2.619 (4)	127
O1—H1···O2^ii	0.82	2.37	3.114 (4)	152
O1—H1···O3^ii	0.82	2.25	2.998 (4)	152
N2—H2···O5^iii	0.86	2.58	3.362 (4)	152
C9—H9···Cl1^iv	0.93	2.72	3.485 (4)	140

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