Crystal structure, Hirshfeld surface analysis and computational study of bis­(2-{[(2,6-di­chloro­benzyl­idene)hydrazinyl­idene]meth­yl}phenolato)cobalt(II) and of the copper(II) analogue

Manawar, R.B.; Mamtora, M.J.; Shah, M.K.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989019016529

Crystal structure, Hirshfeld surface analysis and computational study of bis(2-{[(2,6-dichlorobenzylidene)hydrazinylidene]methyl}phenolato)cobalt(II) and of the copper(II) analogue

R. B. Manawar, M. J. Mamtora, M. K. Shah, M. M. Jotani and E. R. T. Tiekink

Distinct coordination geometries are found in the crystals of the title Co^II (trigonal bipyramidal) and Cu^II (square-planar) complexes, each defined by a N₂S₂ donor set derived from two chelating Schiff base anions.

Keywords: crystal structure; Schiff base complex; cobalt; copper; Hirshfeld surface analysis; computational chemistry.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989019016529/hb7872sup1.cif Contains datablocks I, II, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019016529/hb7872Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019016529/hb7872IIsup3.hkl Contains datablock II

CCDC references: 1891529; 1970822

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.004 Å
R factor = 0.045
wR factor = 0.112
Data-to-parameter ratio = 19.8

Structure: II

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.004 Å
R factor = 0.033
wR factor = 0.093
Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full value Low .      0.961 Why?
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         89 Report

Alert level G
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.007 Degree
PLAT794_ALERT_5_G Tentative Bond Valency for Co        (II)      .       1.94 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        106 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          5 Info

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

   1 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
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: II


Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full value Low .      0.961 Why?
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         89 Report

Alert level G
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          4 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        103 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          8 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 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
   3 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

Computing details top

For both structures, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2/SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(2-{[(2,6-dichlorobenzylidene)hydrazinylidene]methyl}phenolato)cobalt(II) (I) top

Crystal data top

[Co(C₁₄H₉Cl₂N₂O)₂]	Z = 2
M_r = 643.19	F(000) = 650
Triclinic, P1	D_x = 1.577 Mg m⁻³
a = 8.8137 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4801 (12) Å	Cell parameters from 5585 reflections
c = 15.0785 (17) Å	θ = 2.3–22.4°
α = 85.684 (7)°	µ = 1.06 mm⁻¹
β = 77.984 (7)°	T = 296 K
γ = 84.965 (7)°	Block, red
V = 1354.7 (3) Å³	0.35 × 0.30 × 0.30 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4590 reflections with I > 2σ(I)
Radiation source: X-ray tube	R_int = 0.102
ω and φ scan	θ_max = 28.8°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→11
T_min = 0.631, T_max = 0.746	k = −14→14
45690 measured reflections	l = −20→20
6959 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.031P)² + 0.0591P] where P = (F_o² + 2F_c²)/3
6959 reflections	(Δ/σ)_max = 0.001
352 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Co	0.44734 (4)	0.27310 (3)	0.68541 (2)	0.03428 (11)
Cl1	0.88398 (11)	−0.08192 (9)	0.85762 (6)	0.0821 (3)
Cl2	0.45007 (10)	0.29954 (8)	0.98752 (6)	0.0675 (2)
Cl3	0.79790 (9)	0.73174 (7)	0.69395 (6)	0.0643 (2)
Cl4	0.96728 (8)	0.23680 (7)	0.60664 (6)	0.0566 (2)
O1	0.48493 (19)	0.28424 (16)	0.55684 (12)	0.0386 (4)
O2	0.25211 (19)	0.24964 (17)	0.76315 (12)	0.0441 (4)
N1	0.6051 (2)	0.12543 (18)	0.69189 (13)	0.0310 (4)
N2	0.6554 (2)	0.0714 (2)	0.77036 (14)	0.0411 (5)
N3	0.4754 (2)	0.43864 (19)	0.73568 (14)	0.0352 (5)
N4	0.6127 (2)	0.5040 (2)	0.71934 (17)	0.0470 (6)
C1	0.5601 (3)	0.1984 (2)	0.50173 (16)	0.0320 (5)
C2	0.6504 (3)	0.0906 (2)	0.53011 (16)	0.0328 (5)
C3	0.7307 (3)	0.0055 (3)	0.46435 (18)	0.0424 (6)
H3	0.788970	−0.065835	0.483233	0.051*
C4	0.7258 (3)	0.0241 (3)	0.37463 (19)	0.0496 (7)
H4	0.780924	−0.032128	0.332457	0.060*
C5	0.6353 (3)	0.1305 (3)	0.34809 (19)	0.0488 (7)
H5	0.629642	0.144282	0.287166	0.059*
C6	0.5546 (3)	0.2148 (3)	0.40882 (17)	0.0403 (6)
H6	0.495089	0.284277	0.388505	0.048*
C7	0.6684 (3)	0.0616 (2)	0.62082 (17)	0.0355 (6)
H7	0.732456	−0.011148	0.630792	0.043*
C8	0.6244 (3)	0.1407 (3)	0.83673 (17)	0.0394 (6)
H8	0.574799	0.221594	0.828883	0.047*
C9	0.6609 (3)	0.1035 (2)	0.92574 (17)	0.0377 (6)
C10	0.7686 (3)	0.0031 (3)	0.94344 (19)	0.0467 (7)
C11	0.7896 (4)	−0.0315 (3)	1.0308 (2)	0.0573 (8)
H11	0.860799	−0.099067	1.041003	0.069*
C12	0.7048 (4)	0.0344 (4)	1.1022 (2)	0.0646 (9)
H12	0.717869	0.010093	1.160909	0.078*
C13	0.6007 (4)	0.1359 (3)	1.0883 (2)	0.0588 (8)
H13	0.544591	0.180895	1.136912	0.071*
C14	0.5809 (3)	0.1697 (3)	1.00133 (19)	0.0448 (7)
C15	0.1585 (3)	0.3409 (3)	0.80467 (17)	0.0397 (6)
C16	0.2042 (3)	0.4638 (3)	0.81575 (18)	0.0410 (6)
C17	0.0932 (3)	0.5554 (3)	0.8613 (2)	0.0575 (8)
H17	0.123982	0.635619	0.869447	0.069*
C18	−0.0578 (4)	0.5289 (4)	0.8936 (2)	0.0671 (10)
H18	−0.130212	0.591163	0.921242	0.081*
C19	−0.1010 (3)	0.4085 (4)	0.8846 (2)	0.0649 (9)
H19	−0.203286	0.389479	0.907762	0.078*
C20	0.0023 (3)	0.3155 (3)	0.84240 (19)	0.0523 (8)
H20	−0.030665	0.234560	0.838523	0.063*
C21	0.3586 (3)	0.5031 (3)	0.78469 (19)	0.0440 (7)
H21	0.377708	0.582955	0.801210	0.053*
C22	0.7287 (3)	0.4444 (2)	0.67455 (18)	0.0374 (6)
H22	0.712804	0.364115	0.657169	0.045*
C23	0.8864 (3)	0.4856 (2)	0.64614 (16)	0.0333 (5)
C24	0.9300 (3)	0.6101 (2)	0.64938 (19)	0.0414 (6)
C25	1.0819 (3)	0.6408 (3)	0.6154 (2)	0.0511 (7)
H25	1.108921	0.724006	0.618188	0.061*
C26	1.1928 (3)	0.5492 (3)	0.5775 (2)	0.0525 (8)
H26	1.293927	0.571199	0.553932	0.063*
C27	1.1554 (3)	0.4260 (3)	0.57441 (18)	0.0453 (7)
H27	1.230392	0.363795	0.549057	0.054*
C28	1.0048 (3)	0.3955 (3)	0.60946 (18)	0.0384 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.03317 (18)	0.0346 (2)	0.0336 (2)	0.00280 (14)	−0.00453 (14)	−0.00479 (15)
Cl1	0.1017 (7)	0.0828 (6)	0.0679 (6)	0.0502 (5)	−0.0448 (5)	−0.0328 (5)
Cl2	0.0717 (5)	0.0700 (6)	0.0533 (5)	0.0181 (4)	−0.0018 (4)	−0.0142 (4)
Cl3	0.0601 (5)	0.0356 (4)	0.1007 (7)	0.0009 (3)	−0.0221 (4)	−0.0150 (4)
Cl4	0.0460 (4)	0.0380 (4)	0.0810 (6)	0.0041 (3)	−0.0014 (4)	−0.0129 (4)
O1	0.0414 (9)	0.0376 (10)	0.0348 (10)	0.0096 (8)	−0.0074 (8)	−0.0044 (8)
O2	0.0387 (9)	0.0430 (11)	0.0459 (12)	−0.0004 (8)	0.0022 (8)	−0.0058 (9)
N1	0.0356 (10)	0.0300 (11)	0.0274 (11)	−0.0004 (8)	−0.0075 (9)	−0.0003 (9)
N2	0.0546 (13)	0.0363 (13)	0.0329 (13)	0.0050 (10)	−0.0137 (10)	−0.0005 (10)
N3	0.0302 (10)	0.0345 (12)	0.0393 (13)	0.0028 (9)	−0.0046 (9)	−0.0045 (10)
N4	0.0381 (12)	0.0387 (13)	0.0618 (16)	−0.0019 (10)	−0.0005 (11)	−0.0162 (12)
C1	0.0331 (12)	0.0312 (13)	0.0321 (14)	−0.0049 (10)	−0.0069 (10)	−0.0014 (11)
C2	0.0374 (13)	0.0315 (13)	0.0303 (13)	−0.0020 (10)	−0.0076 (10)	−0.0059 (11)
C3	0.0452 (15)	0.0403 (16)	0.0414 (16)	0.0036 (12)	−0.0086 (12)	−0.0087 (13)
C4	0.0596 (17)	0.0513 (18)	0.0366 (16)	0.0003 (14)	−0.0036 (13)	−0.0166 (14)
C5	0.0617 (18)	0.0576 (19)	0.0302 (15)	−0.0106 (15)	−0.0126 (13)	−0.0062 (14)
C6	0.0453 (14)	0.0424 (16)	0.0347 (15)	−0.0019 (12)	−0.0131 (12)	−0.0010 (12)
C7	0.0407 (13)	0.0293 (13)	0.0357 (15)	0.0045 (10)	−0.0085 (11)	−0.0031 (11)
C8	0.0463 (14)	0.0368 (15)	0.0349 (15)	0.0065 (12)	−0.0112 (12)	−0.0034 (12)
C9	0.0461 (14)	0.0375 (15)	0.0306 (14)	−0.0059 (12)	−0.0096 (11)	−0.0010 (12)
C10	0.0574 (17)	0.0446 (17)	0.0423 (17)	0.0006 (13)	−0.0195 (14)	−0.0087 (13)
C11	0.076 (2)	0.0532 (19)	0.0510 (19)	−0.0012 (16)	−0.0361 (17)	0.0022 (16)
C12	0.083 (2)	0.079 (2)	0.0371 (18)	−0.015 (2)	−0.0227 (17)	0.0032 (17)
C13	0.074 (2)	0.070 (2)	0.0328 (17)	−0.0076 (18)	−0.0091 (15)	−0.0092 (16)
C14	0.0535 (16)	0.0464 (17)	0.0349 (15)	−0.0098 (13)	−0.0069 (12)	−0.0034 (13)
C15	0.0344 (13)	0.0524 (17)	0.0295 (14)	−0.0004 (12)	−0.0033 (11)	0.0037 (12)
C16	0.0372 (13)	0.0466 (16)	0.0343 (15)	0.0073 (12)	0.0004 (11)	−0.0030 (12)
C17	0.0498 (17)	0.0564 (19)	0.056 (2)	0.0133 (14)	0.0064 (14)	−0.0076 (16)
C18	0.0467 (17)	0.076 (3)	0.065 (2)	0.0186 (17)	0.0105 (15)	−0.0072 (19)
C19	0.0350 (15)	0.097 (3)	0.055 (2)	0.0029 (17)	0.0038 (14)	0.0023 (19)
C20	0.0389 (15)	0.064 (2)	0.0497 (19)	−0.0041 (14)	−0.0014 (13)	0.0016 (15)
C21	0.0416 (14)	0.0365 (15)	0.0509 (18)	0.0043 (12)	−0.0035 (12)	−0.0081 (13)
C22	0.0348 (13)	0.0298 (14)	0.0482 (16)	0.0003 (10)	−0.0097 (11)	−0.0057 (12)
C23	0.0348 (12)	0.0344 (14)	0.0317 (14)	−0.0014 (10)	−0.0110 (10)	0.0014 (11)
C24	0.0452 (15)	0.0350 (15)	0.0491 (17)	−0.0046 (11)	−0.0215 (13)	0.0001 (12)
C25	0.0534 (17)	0.0454 (17)	0.061 (2)	−0.0170 (14)	−0.0232 (15)	0.0048 (15)
C26	0.0381 (15)	0.068 (2)	0.0531 (19)	−0.0158 (14)	−0.0116 (13)	0.0036 (16)
C27	0.0345 (13)	0.0602 (19)	0.0405 (16)	0.0005 (13)	−0.0077 (12)	−0.0025 (14)
C28	0.0365 (13)	0.0405 (15)	0.0387 (15)	−0.0001 (11)	−0.0114 (11)	0.0014 (12)

Geometric parameters (Å, º) top

Co—O2	1.8937 (17)	C9—C14	1.406 (4)
Co—O1	1.8940 (17)	C10—C11	1.385 (4)
Co—N1	1.9988 (19)	C11—C12	1.371 (4)
Co—N3	1.999 (2)	C11—H11	0.9300
Cl1—C10	1.723 (3)	C12—C13	1.376 (4)
Cl2—C14	1.733 (3)	C12—H12	0.9300
Cl3—C24	1.725 (3)	C13—C14	1.375 (4)
Cl4—C28	1.729 (3)	C13—H13	0.9300
O1—C1	1.310 (3)	C15—C20	1.416 (3)
O2—C15	1.313 (3)	C15—C16	1.414 (4)
N1—C7	1.304 (3)	C16—C17	1.416 (4)
N1—N2	1.411 (3)	C16—C21	1.431 (3)
N2—C8	1.251 (3)	C17—C18	1.363 (4)
N3—C21	1.303 (3)	C17—H17	0.9300
N3—N4	1.410 (3)	C18—C19	1.374 (5)
N4—C22	1.247 (3)	C18—H18	0.9300
C1—C6	1.409 (3)	C19—C20	1.371 (4)
C1—C2	1.416 (3)	C19—H19	0.9300
C2—C3	1.417 (3)	C20—H20	0.9300
C2—C7	1.417 (3)	C21—H21	0.9300
C3—C4	1.361 (4)	C22—C23	1.461 (3)
C3—H3	0.9300	C22—H22	0.9300
C4—C5	1.396 (4)	C23—C28	1.397 (3)
C4—H4	0.9300	C23—C24	1.399 (3)
C5—C6	1.366 (4)	C24—C25	1.388 (4)
C5—H5	0.9300	C25—C26	1.374 (4)
C6—H6	0.9300	C25—H25	0.9300
C7—H7	0.9300	C26—C27	1.367 (4)
C8—C9	1.461 (3)	C26—H26	0.9300
C8—H8	0.9300	C27—C28	1.379 (3)
C9—C10	1.402 (4)	C27—H27	0.9300

O2—Co—O1	125.33 (8)	C11—C12—H12	119.5
O2—Co—N1	113.82 (8)	C13—C12—H12	119.5
O1—Co—N1	94.06 (7)	C14—C13—C12	119.0 (3)
O2—Co—N3	94.60 (8)	C14—C13—H13	120.5
O1—Co—N3	112.12 (8)	C12—C13—H13	120.5
N1—Co—N3	119.03 (8)	C13—C14—C9	122.7 (3)
C1—O1—Co	127.34 (15)	C13—C14—Cl2	117.0 (2)
C15—O2—Co	125.37 (16)	C9—C14—Cl2	120.3 (2)
C7—N1—N2	111.4 (2)	O2—C15—C20	118.7 (3)
C7—N1—Co	121.70 (16)	O2—C15—C16	124.1 (2)
N2—N1—Co	126.78 (15)	C20—C15—C16	117.2 (2)
C8—N2—N1	114.8 (2)	C15—C16—C17	119.4 (2)
C21—N3—N4	112.1 (2)	C15—C16—C21	124.2 (2)
C21—N3—Co	121.09 (17)	C17—C16—C21	116.4 (3)
N4—N3—Co	126.71 (15)	C18—C17—C16	121.6 (3)
C22—N4—N3	114.3 (2)	C18—C17—H17	119.2
O1—C1—C6	118.8 (2)	C16—C17—H17	119.2
O1—C1—C2	123.5 (2)	C17—C18—C19	118.9 (3)
C6—C1—C2	117.7 (2)	C17—C18—H18	120.6
C3—C2—C7	116.8 (2)	C19—C18—H18	120.6
C3—C2—C1	118.9 (2)	C18—C19—C20	121.9 (3)
C7—C2—C1	124.4 (2)	C18—C19—H19	119.0
C4—C3—C2	122.6 (3)	C20—C19—H19	119.0
C4—C3—H3	118.7	C19—C20—C15	120.9 (3)
C2—C3—H3	118.7	C19—C20—H20	119.5
C3—C4—C5	117.7 (3)	C15—C20—H20	119.5
C3—C4—H4	121.1	N3—C21—C16	126.8 (3)
C5—C4—H4	121.1	N3—C21—H21	116.6
C6—C5—C4	122.1 (3)	C16—C21—H21	116.6
C6—C5—H5	119.0	N4—C22—C23	127.7 (2)
C4—C5—H5	119.0	N4—C22—H22	116.1
C5—C6—C1	121.1 (3)	C23—C22—H22	116.1
C5—C6—H6	119.5	C28—C23—C24	116.2 (2)
C1—C6—H6	119.5	C28—C23—C22	118.2 (2)
N1—C7—C2	127.3 (2)	C24—C23—C22	125.6 (2)
N1—C7—H7	116.4	C25—C24—C23	120.9 (3)
C2—C7—H7	116.4	C25—C24—Cl3	117.3 (2)
N2—C8—C9	124.5 (2)	C23—C24—Cl3	121.8 (2)
N2—C8—H8	117.7	C26—C25—C24	120.5 (3)
C9—C8—H8	117.7	C26—C25—H25	119.7
C10—C9—C14	116.0 (2)	C24—C25—H25	119.7
C10—C9—C8	125.2 (2)	C27—C26—C25	120.4 (3)
C14—C9—C8	118.8 (2)	C27—C26—H26	119.8
C11—C10—C9	121.7 (3)	C25—C26—H26	119.8
C11—C10—Cl1	116.5 (2)	C26—C27—C28	118.9 (3)
C9—C10—Cl1	121.8 (2)	C26—C27—H27	120.5
C12—C11—C10	119.7 (3)	C28—C27—H27	120.5
C12—C11—H11	120.2	C27—C28—C23	123.1 (2)
C10—C11—H11	120.2	C27—C28—Cl4	116.4 (2)
C11—C12—C13	121.0 (3)	C23—C28—Cl4	120.48 (19)

O2—Co—O1—C1	−108.33 (19)	C12—C13—C14—Cl2	−179.2 (2)
N1—Co—O1—C1	14.8 (2)	C10—C9—C14—C13	−2.7 (4)
N3—Co—O1—C1	138.45 (19)	C8—C9—C14—C13	175.8 (3)
O1—Co—O2—C15	−99.8 (2)	C10—C9—C14—Cl2	177.6 (2)
N1—Co—O2—C15	146.13 (19)	C8—C9—C14—Cl2	−3.9 (3)
N3—Co—O2—C15	21.5 (2)	Co—O2—C15—C20	164.92 (18)
C7—N1—N2—C8	166.6 (2)	Co—O2—C15—C16	−16.2 (4)
Co—N1—N2—C8	−17.3 (3)	O2—C15—C16—C17	179.6 (3)
C21—N3—N4—C22	178.3 (2)	C20—C15—C16—C17	−1.4 (4)
Co—N3—N4—C22	−6.0 (3)	O2—C15—C16—C21	−1.3 (4)
Co—O1—C1—C6	169.84 (16)	C20—C15—C16—C21	177.6 (2)
Co—O1—C1—C2	−11.6 (3)	C15—C16—C17—C18	−1.1 (4)
O1—C1—C2—C3	−178.2 (2)	C21—C16—C17—C18	179.7 (3)
C6—C1—C2—C3	0.3 (3)	C16—C17—C18—C19	2.6 (5)
O1—C1—C2—C7	1.0 (4)	C17—C18—C19—C20	−1.5 (5)
C6—C1—C2—C7	179.5 (2)	C18—C19—C20—C15	−1.2 (5)
C7—C2—C3—C4	−178.5 (2)	O2—C15—C20—C19	−178.5 (3)
C1—C2—C3—C4	0.7 (4)	C16—C15—C20—C19	2.5 (4)
C2—C3—C4—C5	−1.2 (4)	N4—N3—C21—C16	−178.3 (2)
C3—C4—C5—C6	0.6 (4)	Co—N3—C21—C16	5.7 (4)
C4—C5—C6—C1	0.4 (4)	C15—C16—C21—N3	6.4 (4)
O1—C1—C6—C5	177.8 (2)	C17—C16—C21—N3	−174.5 (3)
C2—C1—C6—C5	−0.8 (4)	N3—N4—C22—C23	179.7 (2)
N2—N1—C7—C2	−177.2 (2)	N4—C22—C23—C28	169.5 (3)
Co—N1—C7—C2	6.5 (3)	N4—C22—C23—C24	−12.9 (4)
C3—C2—C7—N1	−179.5 (2)	C28—C23—C24—C25	1.7 (4)
C1—C2—C7—N1	1.3 (4)	C22—C23—C24—C25	−176.0 (2)
N1—N2—C8—C9	178.1 (2)	C28—C23—C24—Cl3	−179.22 (19)
N2—C8—C9—C10	17.7 (4)	C22—C23—C24—Cl3	3.1 (4)
N2—C8—C9—C14	−160.7 (3)	C23—C24—C25—C26	0.1 (4)
C14—C9—C10—C11	2.5 (4)	Cl3—C24—C25—C26	−179.0 (2)
C8—C9—C10—C11	−175.9 (3)	C24—C25—C26—C27	−1.2 (4)
C14—C9—C10—Cl1	−176.4 (2)	C25—C26—C27—C28	0.2 (4)
C8—C9—C10—Cl1	5.2 (4)	C26—C27—C28—C23	1.8 (4)
C9—C10—C11—C12	−0.8 (5)	C26—C27—C28—Cl4	−177.9 (2)
Cl1—C10—C11—C12	178.2 (3)	C24—C23—C28—C27	−2.7 (4)
C10—C11—C12—C13	−1.0 (5)	C22—C23—C28—C27	175.1 (2)
C11—C12—C13—C14	0.9 (5)	C24—C23—C28—Cl4	176.99 (19)
C12—C13—C14—C9	1.1 (4)	C22—C23—C28—Cl4	−5.2 (3)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C27—H27···O1ⁱ	0.93	2.35	3.114 (3)	140
C25—H25···Cg3ⁱⁱ	0.93	2.86	3.647 (3)	143

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

Bis(2-{[(2,6-dichlorobenzylidene)hydrazinylidene]methyl}phenolato)copper(II) (II) top

Crystal data top

[Cu(C₁₄H₉Cl₂N₂O)₂]	Z = 1
M_r = 647.80	F(000) = 327
Triclinic, P1	D_x = 1.626 Mg m⁻³
a = 8.1300 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5072 (11) Å	Cell parameters from 3126 reflections
c = 9.7386 (13) Å	θ = 4.9–56.5°
α = 83.240 (4)°	µ = 1.26 mm⁻¹
β = 87.646 (3)°	T = 296 K
γ = 81.533 (4)°	Block, dark-brown
V = 661.39 (14) Å³	0.35 × 0.35 × 0.30 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2708 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.021
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 28.3°, θ_min = 3.3°
T_min = 0.637, T_max = 0.714	h = −5→10
5554 measured reflections	k = −11→11
3090 independent reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0461P)² + 0.2934P] where P = (F_o² + 2F_c²)/3
3090 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu	0.500000	0.500000	0.500000	0.02898 (11)
Cl1	0.31832 (11)	0.73971 (12)	0.01621 (8)	0.0830 (3)
Cl2	−0.14142 (7)	0.45455 (7)	0.33048 (7)	0.05364 (17)
O1	0.5954 (2)	0.30738 (17)	0.59863 (16)	0.0435 (4)
N1	0.4436 (2)	0.37945 (19)	0.34549 (16)	0.0293 (3)
N2	0.3392 (2)	0.4457 (2)	0.23415 (17)	0.0352 (4)
C1	0.6593 (3)	0.1736 (2)	0.5513 (2)	0.0338 (4)
C2	0.6301 (3)	0.1364 (2)	0.4182 (2)	0.0325 (4)
C3	0.7051 (3)	−0.0117 (3)	0.3762 (3)	0.0439 (5)
H3	0.684470	−0.036821	0.288672	0.053*
C4	0.8071 (3)	−0.1183 (3)	0.4617 (3)	0.0519 (6)
H4	0.857619	−0.214233	0.432071	0.062*
C5	0.8345 (3)	−0.0824 (3)	0.5923 (3)	0.0519 (6)
H5	0.903270	−0.155502	0.650883	0.062*
C6	0.7625 (3)	0.0588 (3)	0.6378 (3)	0.0459 (5)
H6	0.782038	0.079204	0.726963	0.055*
C7	0.5198 (3)	0.2392 (2)	0.3251 (2)	0.0321 (4)
H7	0.500996	0.201827	0.242030	0.038*
C8	0.2031 (2)	0.5217 (2)	0.2710 (2)	0.0327 (4)
H8	0.179795	0.526076	0.364870	0.039*
C9	0.0790 (3)	0.6043 (2)	0.1705 (2)	0.0338 (4)
C10	0.1164 (3)	0.7083 (3)	0.0554 (2)	0.0456 (5)
C11	−0.0074 (4)	0.7920 (3)	−0.0292 (3)	0.0597 (7)
H11	0.019998	0.861210	−0.105066	0.072*
C12	−0.1692 (4)	0.7730 (3)	−0.0015 (3)	0.0676 (9)
H12	−0.251592	0.830675	−0.058269	0.081*
C13	−0.2130 (3)	0.6699 (3)	0.1091 (3)	0.0589 (7)
H13	−0.323355	0.655485	0.126954	0.071*
C14	−0.0872 (3)	0.5881 (2)	0.1931 (2)	0.0392 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.02975 (19)	0.02729 (17)	0.02922 (18)	−0.00160 (12)	−0.00773 (12)	−0.00101 (12)
Cl1	0.0648 (5)	0.1185 (7)	0.0567 (4)	−0.0217 (5)	0.0044 (3)	0.0361 (4)
Cl2	0.0335 (3)	0.0511 (3)	0.0743 (4)	−0.0079 (2)	0.0011 (3)	0.0025 (3)
O1	0.0645 (11)	0.0280 (7)	0.0364 (8)	0.0034 (7)	−0.0205 (7)	−0.0033 (6)
N1	0.0274 (8)	0.0338 (8)	0.0264 (7)	−0.0031 (6)	−0.0058 (6)	−0.0014 (6)
N2	0.0360 (9)	0.0415 (9)	0.0273 (8)	−0.0016 (7)	−0.0089 (7)	−0.0033 (7)
C1	0.0346 (11)	0.0265 (9)	0.0404 (10)	−0.0063 (8)	−0.0087 (8)	0.0015 (7)
C2	0.0301 (10)	0.0297 (9)	0.0377 (10)	−0.0056 (7)	0.0007 (8)	−0.0025 (7)
C3	0.0474 (14)	0.0369 (11)	0.0465 (12)	−0.0020 (9)	0.0044 (10)	−0.0079 (9)
C4	0.0484 (14)	0.0331 (11)	0.0702 (17)	0.0059 (10)	0.0038 (12)	−0.0057 (11)
C5	0.0471 (14)	0.0335 (11)	0.0700 (17)	0.0039 (10)	−0.0135 (12)	0.0067 (11)
C6	0.0529 (14)	0.0336 (10)	0.0498 (13)	−0.0026 (9)	−0.0207 (11)	0.0037 (9)
C7	0.0328 (10)	0.0357 (9)	0.0287 (9)	−0.0066 (8)	0.0001 (7)	−0.0061 (7)
C8	0.0304 (10)	0.0414 (10)	0.0268 (9)	−0.0068 (8)	−0.0060 (7)	−0.0016 (7)
C9	0.0350 (11)	0.0352 (10)	0.0317 (10)	−0.0016 (8)	−0.0095 (8)	−0.0068 (8)
C10	0.0534 (15)	0.0507 (13)	0.0318 (10)	−0.0051 (11)	−0.0099 (9)	−0.0014 (9)
C11	0.084 (2)	0.0506 (14)	0.0422 (13)	−0.0036 (13)	−0.0263 (13)	0.0042 (11)
C12	0.077 (2)	0.0517 (15)	0.0713 (18)	0.0100 (14)	−0.0474 (16)	−0.0024 (13)
C13	0.0419 (15)	0.0499 (14)	0.085 (2)	0.0029 (11)	−0.0289 (13)	−0.0106 (13)
C14	0.0370 (12)	0.0330 (10)	0.0482 (12)	−0.0006 (8)	−0.0126 (9)	−0.0088 (9)

Geometric parameters (Å, º) top

Cu—O1	1.8776 (14)	C4—H4	0.9300
Cu—O1ⁱ	1.8776 (14)	C5—C6	1.371 (3)
Cu—N1	2.0211 (16)	C5—H5	0.9300
Cu—N1ⁱ	2.0211 (16)	C6—H6	0.9300
Cl1—C10	1.722 (3)	C7—H7	0.9300
Cl2—C14	1.737 (2)	C8—C9	1.476 (3)
O1—C1	1.306 (2)	C8—H8	0.9300
N1—C7	1.294 (2)	C9—C14	1.384 (3)
N1—N2	1.416 (2)	C9—C10	1.396 (3)
N2—C8	1.258 (3)	C10—C11	1.385 (3)
C1—C6	1.411 (3)	C11—C12	1.361 (5)
C1—C2	1.407 (3)	C11—H11	0.9300
C2—C3	1.415 (3)	C12—C13	1.376 (5)
C2—C7	1.428 (3)	C12—H12	0.9300
C3—C4	1.365 (3)	C13—C14	1.387 (3)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.377 (4)

O1—Cu—O1ⁱ	180.00 (10)	C5—C6—H6	119.5
O1—Cu—N1	90.28 (6)	C1—C6—H6	119.5
O1ⁱ—Cu—N1	89.72 (6)	N1—C7—C2	126.18 (18)
O1—Cu—N1ⁱ	89.72 (6)	N1—C7—H7	116.9
O1ⁱ—Cu—N1ⁱ	90.28 (6)	C2—C7—H7	116.9
N1—Cu—N1ⁱ	180.0	N2—C8—C9	122.34 (18)
C1—O1—Cu	128.77 (13)	N2—C8—H8	118.8
C7—N1—N2	111.28 (16)	C9—C8—H8	118.8
C7—N1—Cu	123.02 (13)	C14—C9—C10	116.3 (2)
N2—N1—Cu	124.88 (12)	C14—C9—C8	119.63 (19)
C8—N2—N1	113.85 (16)	C10—C9—C8	124.0 (2)
O1—C1—C6	118.78 (19)	C11—C10—C9	121.3 (3)
O1—C1—C2	123.59 (18)	C11—C10—Cl1	117.8 (2)
C6—C1—C2	117.63 (19)	C9—C10—Cl1	120.87 (18)
C1—C2—C3	119.48 (19)	C12—C11—C10	120.1 (3)
C1—C2—C7	122.47 (18)	C12—C11—H11	120.0
C3—C2—C7	117.97 (19)	C10—C11—H11	120.0
C4—C3—C2	121.2 (2)	C11—C12—C13	121.1 (2)
C4—C3—H3	119.4	C11—C12—H12	119.4
C2—C3—H3	119.4	C13—C12—H12	119.4
C3—C4—C5	119.3 (2)	C14—C13—C12	117.9 (3)
C3—C4—H4	120.3	C14—C13—H13	121.1
C5—C4—H4	120.3	C12—C13—H13	121.1
C6—C5—C4	121.4 (2)	C13—C14—C9	123.3 (2)
C6—C5—H5	119.3	C13—C14—Cl2	118.0 (2)
C4—C5—H5	119.3	C9—C14—Cl2	118.66 (16)
C5—C6—C1	121.0 (2)

N1—Cu—O1—C1	25.25 (19)	C1—C2—C7—N1	4.8 (3)
N1ⁱ—Cu—O1—C1	−154.75 (19)	C3—C2—C7—N1	−178.5 (2)
C7—N1—N2—C8	141.33 (19)	N1—N2—C8—C9	178.03 (18)
Cu—N1—N2—C8	−48.8 (2)	N2—C8—C9—C14	134.7 (2)
Cu—O1—C1—C6	163.39 (17)	N2—C8—C9—C10	−49.5 (3)
Cu—O1—C1—C2	−17.0 (3)	C14—C9—C10—C11	1.1 (3)
O1—C1—C2—C3	179.9 (2)	C8—C9—C10—C11	−174.8 (2)
C6—C1—C2—C3	−0.5 (3)	C14—C9—C10—Cl1	179.69 (17)
O1—C1—C2—C7	−3.5 (3)	C8—C9—C10—Cl1	3.8 (3)
C6—C1—C2—C7	176.1 (2)	C9—C10—C11—C12	−0.4 (4)
C1—C2—C3—C4	−0.9 (3)	Cl1—C10—C11—C12	−179.1 (2)
C7—C2—C3—C4	−177.7 (2)	C10—C11—C12—C13	−0.8 (4)
C2—C3—C4—C5	1.4 (4)	C11—C12—C13—C14	1.2 (4)
C3—C4—C5—C6	−0.6 (4)	C12—C13—C14—C9	−0.5 (4)
C4—C5—C6—C1	−0.9 (4)	C12—C13—C14—Cl2	−178.6 (2)
O1—C1—C6—C5	−179.0 (2)	C10—C9—C14—C13	−0.6 (3)
C2—C1—C6—C5	1.4 (4)	C8—C9—C14—C13	175.5 (2)
N2—N1—C7—C2	−177.83 (19)	C10—C9—C14—Cl2	177.47 (16)
Cu—N1—C7—C2	12.1 (3)	C8—C9—C14—Cl2	−6.4 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Selected geometric parameters (Å, °) for (I) and (II)^a top

Parameter	(I): M = Co^II	(II): M = Cu^II
M—O1	1.8940 (17)	1.8776 (14)
M—O2	1.8937 (17)	1.8776 (14)^a
M—N1	1.9988 (19)	2.0211 (16)
M—N3	1.999 (2)	2.0211 (16)^a
N1—N2	1.411 (3)	1.416 (2)
N3—N4	1.410 (3)	1.416 (2)^a
C7—N1	1.304 (3)	1.294 (2)
C8—N2	1.251 (3)	1.258 (3)
C21—N3	1.303 (3)	1.294 (2)^a
C22—N4	1.247 (3)	1.258 (3)^a

O1—Co—O2	125.33 (8)	180^a
O1—Co—N1	94.06 (7)	90.28 (6)
O1—Co—N3	112.12 (8)	89.72 (6)
O2—Co—N1	113.82 (8)	89.72 (6)^a
O2—Co—N3	94.60 (8)	90.28 (6)^a
N1—Co—N3	119.03 (8)	180^a

Notes: (a) The Cu^II atom in (II) lies on a centre of inversion so O2 is equivalent to O1, N3 to N1, etc. and are related by the symmetry operation 1 - x, 1 - y, 1 - z.

Summary of short interatomic contacts (Å) in (I) and (II)^a top

Contact	Distance	Symmetry operation
(I)
Cl1···Cl3	3.4993 (13)	x, -1 + y, z
Cl3···H7	2.70	x, 1 + y, z
Cl4···H3	2.74	2 - x, - y, 1 - z
C1···H26	2.71	2 - x, 1 - y, 1 - z
C6···H26	2.76	2 - x, 1 - y, 1 - z
Co···C27	3.558 (3)	-1 + x, y, z
Co···H27	3.08	-1 + x, y, z
H5···H12	2.23	x, y, -1 + z
H5···H13	2.30	x, y, -1 + z
(II)
Cl1···H7	2.81	1 - x, 1 - y, -z
C5···C7	3.378 (3)	1 - x, -y, 1 - z
Cu···Cl2	3.2858 (7)	1 + x, y, z

Notes: (a) The interatomic distances are calculated in Crystal Explorer 17 (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values.

Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) and (II) top

Contact		Percentage contribution
	(I)	(II)
H···H	26.2	30.5
O···H/H···O	7.9	4.2
C···H/H···C	16.7	14.5
Cl···H/H···Cl	25.8	24.9
C···C	12.0	9.8
N···H/H··· N	5.5	6.2
Cl···Cl	2.2	0.4
C···O/O···C	0.5	0.3
C···N/N···C	0.5	1.3
Cl···O/O···Cl	0.2	0.4
C···Cl/Cl···C	1.9	3.9
Cl···N/N···Cl	0.2	1.6
M···H/H···M	0.4	0.1
M···Cl/Cl···M	0.0	1.9

Summary of interaction energies (kJ mol^-1) calculated for (I) top

Contact	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
H27···Coⁱ +	8.81	-21.7	-6.7	-71.3	41.6	-57.0
C27···Coⁱ +
C27—H27···O1ⁱ +
Cg(C15–C20)···Cg(C23–C28)ⁱ
Cg(C9–C14) ···Cg(C9–C14)ⁱⁱ	9.60	-29.6	-7.6	-71.9	32.5	-73.5
Cg(C1–C6) ···Cg(C1–C6)ⁱⁱⁱ	10.19	-23.4	-5.5	-58.3	29.4	-56.0
Cl4···H3^iv +	10.54	-12.7	-1.2	-26.4	19.8	-21.4
Cl1···Cl3^iv
Cl3···H7^v	10.48	-3.9	-1.3	-14.8	13.4	-7.3
C1···H26^vi +	9.86	-37.0	-8.0	-84.1	48.4	-79.5
C6···H26^vi +
C25–H25···Cg(C1–C6)^vi +
Cg(C23–C28)···Cg(C23–C28)^vi

Symmetry codes: (i) 1 + x, y, z; (ii) 1 - x, - y, 2 - z; (iii) 1 - x, - y, 1 - z; (iv) 2 - x, - y, 1 - z; (v) x, 1 + y, z; (vi) 2 - x, 1 - y, 1 - z.

Summary of interaction energies (kJ mol^-1) calculated for (II) top

Contact	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
Cg(C9–C14)···Cg(C9–C14)ⁱ	12.94	-0.7	-3.0	-44.5	14.8	-30.8
Cu···Cl2ⁱⁱ	8.13	-33.0	-5.6	-64.1	44.4	-59.0
Cl1···H7ⁱⁱⁱ	9.74	-3.7	-2.5	-25.7	15.4	-16.0
C5···C7^iv +	8.51	-14.4	-4.7	-68.5	36.8	-49.6
Cg(C1–C6)···Cg(C1–C6)^iv

Symmetry codes: (i) - x, 1 - y, - z; (ii) 1 + x, y, z; (iii) 1 - x, 1 - y, -z; (iv) 1 - x, - y, 1 - z.

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Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

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Crystal structure, Hirshfeld surface analysis and computational study of bis­(2-{[(2,6-di­chloro­benzyl­idene)hydrazinyl­idene]meth­yl}phenolato)cobalt(II) and of the copper(II) analogue

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Crystal structure, Hirshfeld surface analysis and computational study of bis(2-{[(2,6-dichlorobenzylidene)hydrazinylidene]methyl}phenolato)cobalt(II) and of the copper(II) analogue