Bis[S-benzyl 3-(furan-2-yl­methyl­idene)di­thio­carbazato-κ2N3,S]copper(II): crystal structure and Hirshfeld surface analysis

Yusof, E.N.M.; Nasri, N.M.; Ravoof, T.B.S.A.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989019006145

Bis[S-benzyl 3-(furan-2-ylmethylidene)dithiocarbazato-κ²N³,S]copper(II): crystal structure and Hirshfeld surface analysis

E. N. M. Yusof, N. M. Nasri, T. B. S. A. Ravoof, M. M. Jotani and E. R. T. Tiekink

The title Cu^II dithiocarbazate complex features a square-planar trans-N₂S₂ donor set for the metal atom (site symmetry $\overline{1}$ ). Supramolecular layers parallel to ( $\overline{1}$ 02) are found in the crystal, being sustained by π–π(furyl) and C—H

π interactions.

Keywords: crystal structure; copper; dithiocarbazato; Hirshfeld surface analysis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989019006145/hb7822sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019006145/hb7822Isup2.hkl Contains datablock I

CCDC reference: 1913482

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Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.004 Å
R factor = 0.040
wR factor = 0.111
Data-to-parameter ratio = 17.1

checkCIF/PLATON results

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Datablock: I


Alert level G
PLAT398_ALERT_2_G Deviating  C-O-C    Angle From 120 for O1             106.7 Degree
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
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        415 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

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

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

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis[S-benzyl 3-(furan-2-ylmethylidene)dithiocarbazato-κ²N³,S]copper(II) top

Crystal data top

[Cu(C₁₃H₁₁N₂OS₂)₂]	F(000) = 630
M_r = 614.25	D_x = 1.590 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.3515 (7) Å	Cell parameters from 1956 reflections
b = 5.0151 (3) Å	θ = 2.4–28.7°
c = 16.7186 (8) Å	µ = 1.21 mm⁻¹
β = 94.618 (4)°	T = 100 K
V = 1282.98 (11) Å³	Prism, dark-brown
Z = 2	0.30 × 0.20 × 0.10 mm

Data collection top

Agilent Xcalibur Eos Gemini diffractometer	2898 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2382 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 16.1952 pixels mm^-1	θ_max = 28.8°, θ_min = 2.4°
ω scans	h = −19→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −5→6
T_min = 0.744, T_max = 1.000	l = −22→20
5864 measured 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0542P)² + 1.1451P] where P = (F_o² + 2F_c²)/3
2898 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.61 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
Cu	0.5000	0.5000	0.5000	0.01942 (15)
S1	0.40280 (4)	0.46830 (15)	0.39759 (4)	0.02392 (18)
S2	0.22892 (4)	0.71156 (14)	0.37681 (4)	0.02121 (18)
O1	0.42829 (12)	1.2573 (4)	0.69781 (11)	0.0240 (4)
N1	0.34226 (13)	0.8207 (4)	0.49969 (13)	0.0186 (5)
N2	0.42578 (13)	0.7729 (4)	0.53831 (13)	0.0168 (5)
C1	0.32893 (16)	0.6845 (5)	0.43470 (16)	0.0185 (5)
C2	0.17122 (17)	0.9561 (6)	0.43348 (17)	0.0221 (6)
H2A	0.1756	0.9075	0.4911	0.027*
H2B	0.1976	1.1347	0.4281	0.027*
C3	0.07652 (17)	0.9609 (5)	0.40095 (16)	0.0192 (6)
C4	0.04586 (19)	1.1481 (6)	0.34526 (17)	0.0255 (6)
H4	0.0848	1.2774	0.3268	0.031*
C5	−0.0419 (2)	1.1495 (6)	0.31570 (18)	0.0299 (7)
H5	−0.0623	1.2800	0.2775	0.036*
C6	−0.09871 (18)	0.9637 (6)	0.34150 (17)	0.0236 (6)
H6	−0.1583	0.9647	0.3212	0.028*
C7	−0.06860 (19)	0.7743 (6)	0.39746 (19)	0.0301 (7)
H7	−0.1076	0.6453	0.4160	0.036*
C8	0.01881 (19)	0.7741 (6)	0.42627 (19)	0.0321 (7)
H8	0.0393	0.6426	0.4642	0.039*
C9	0.44368 (17)	0.9293 (6)	0.59946 (15)	0.0192 (5)
H9	0.4991	0.9036	0.6280	0.023*
C10	0.39017 (17)	1.1365 (5)	0.62925 (15)	0.0188 (5)
C11	0.37208 (19)	1.4495 (6)	0.71860 (17)	0.0250 (6)
H11	0.3819	1.5641	0.7637	0.030*
C12	0.30047 (19)	1.4555 (6)	0.66655 (17)	0.0246 (6)
H12	0.2518	1.5715	0.6685	0.030*
C13	0.31160 (18)	1.2562 (5)	0.60850 (17)	0.0224 (6)
H13	0.2721	1.2137	0.5637	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0141 (2)	0.0252 (3)	0.0192 (3)	−0.00134 (18)	0.00266 (17)	−0.00100 (19)
S1	0.0163 (3)	0.0344 (4)	0.0207 (3)	0.0034 (3)	−0.0001 (3)	−0.0076 (3)
S2	0.0153 (3)	0.0256 (4)	0.0222 (3)	0.0000 (3)	−0.0016 (2)	−0.0025 (3)
O1	0.0217 (10)	0.0322 (11)	0.0178 (9)	0.0049 (8)	0.0005 (7)	−0.0047 (8)
N1	0.0126 (10)	0.0229 (12)	0.0202 (11)	0.0010 (9)	0.0013 (8)	0.0005 (9)
N2	0.0106 (10)	0.0216 (11)	0.0186 (10)	−0.0031 (8)	0.0027 (8)	0.0015 (9)
C1	0.0140 (12)	0.0192 (13)	0.0224 (13)	−0.0040 (10)	0.0020 (10)	0.0024 (11)
C2	0.0168 (13)	0.0239 (14)	0.0251 (14)	−0.0007 (11)	−0.0019 (10)	−0.0021 (11)
C3	0.0163 (12)	0.0223 (14)	0.0187 (13)	0.0023 (10)	−0.0002 (10)	−0.0046 (11)
C4	0.0253 (14)	0.0257 (15)	0.0251 (14)	−0.0018 (12)	−0.0008 (11)	0.0018 (12)
C5	0.0298 (16)	0.0312 (16)	0.0276 (15)	0.0017 (13)	−0.0052 (12)	0.0073 (13)
C6	0.0195 (13)	0.0282 (15)	0.0225 (14)	0.0060 (11)	−0.0018 (11)	−0.0057 (12)
C7	0.0193 (14)	0.0341 (17)	0.0366 (17)	−0.0021 (12)	0.0012 (12)	0.0086 (14)
C8	0.0232 (14)	0.0346 (17)	0.0376 (17)	0.0006 (13)	−0.0030 (12)	0.0166 (14)
C9	0.0137 (12)	0.0264 (14)	0.0176 (12)	−0.0014 (10)	0.0018 (10)	0.0006 (11)
C10	0.0184 (12)	0.0225 (14)	0.0158 (12)	−0.0050 (11)	0.0032 (10)	0.0014 (11)
C11	0.0291 (15)	0.0280 (15)	0.0184 (13)	0.0017 (12)	0.0052 (11)	−0.0007 (12)
C12	0.0231 (14)	0.0230 (14)	0.0280 (15)	0.0028 (11)	0.0045 (11)	−0.0004 (12)
C13	0.0211 (13)	0.0213 (14)	0.0245 (14)	0.0000 (11)	−0.0007 (11)	−0.0017 (11)

Geometric parameters (Å, º) top

Cu—S1	2.1845 (7)	C4—C5	1.397 (4)
Cu—N2	1.923 (2)	C4—H4	0.9500
Cu—N2ⁱ	1.923 (2)	C5—C6	1.369 (4)
Cu—S1ⁱ	2.1845 (7)	C5—H5	0.9500
C1—S1	1.720 (3)	C6—C7	1.386 (4)
C1—S2	1.753 (2)	C6—H6	0.9500
S2—C2	1.823 (3)	C7—C8	1.389 (4)
O1—C11	1.358 (3)	C7—H7	0.9500
O1—C10	1.384 (3)	C8—H8	0.9500
N1—N2	1.409 (3)	C9—C10	1.438 (4)
C1—N1	1.286 (3)	C9—H9	0.9500
C9—N2	1.300 (3)	C10—C13	1.367 (4)
C2—C3	1.511 (3)	C11—C12	1.346 (4)
C2—H2A	0.9900	C11—H11	0.9500
C2—H2B	0.9900	C12—C13	1.413 (4)
C3—C8	1.379 (4)	C12—H12	0.9500
C3—C4	1.378 (4)	C13—H13	0.9500

N2—Cu—N2ⁱ	180.00 (11)	C6—C5—C4	120.4 (3)
S1—Cu—N2	85.83 (6)	C6—C5—H5	119.8
N2ⁱ—Cu—S1	94.17 (6)	C4—C5—H5	119.8
S1ⁱ—Cu—N2	94.18 (6)	C5—C6—C7	119.5 (3)
N2ⁱ—Cu—S1ⁱ	85.82 (6)	C5—C6—H6	120.2
S1—Cu—S1ⁱ	180.0	C7—C6—H6	120.2
C1—S1—Cu	95.74 (9)	C6—C7—C8	119.7 (3)
C1—S2—C2	101.88 (12)	C6—C7—H7	120.2
C11—O1—C10	106.7 (2)	C8—C7—H7	120.2
C1—N1—N2	112.0 (2)	C3—C8—C7	121.3 (3)
C9—N2—N1	112.6 (2)	C3—C8—H8	119.4
C9—N2—Cu	126.72 (18)	C7—C8—H8	119.4
N1—N2—Cu	120.67 (16)	N2—C9—C10	128.2 (2)
S1—C1—S2	115.03 (15)	N2—C9—H9	115.9
S1—C1—N1	125.08 (19)	C10—C9—H9	115.9
S2—C1—N1	119.9 (2)	C13—C10—O1	108.9 (2)
C3—C2—S2	108.50 (18)	C13—C10—C9	138.3 (2)
C3—C2—H2A	110.0	O1—C10—C9	112.8 (2)
S2—C2—H2A	110.0	C12—C11—O1	110.7 (2)
C3—C2—H2B	110.0	C12—C11—H11	124.7
S2—C2—H2B	110.0	O1—C11—H11	124.7
H2A—C2—H2B	108.4	C11—C12—C13	106.9 (3)
C8—C3—C4	118.5 (3)	C11—C12—H12	126.6
C8—C3—C2	120.1 (2)	C13—C12—H12	126.6
C4—C3—C2	121.4 (3)	C10—C13—C12	106.8 (2)
C3—C4—C5	120.6 (3)	C10—C13—H13	126.6
C3—C4—H4	119.7	C12—C13—H13	126.6
C5—C4—H4	119.7

C1—N1—N2—C9	173.3 (2)	C5—C6—C7—C8	−0.4 (5)
C1—N1—N2—Cu	−6.9 (3)	C4—C3—C8—C7	−0.7 (5)
N2—N1—C1—S1	0.0 (3)	C2—C3—C8—C7	179.9 (3)
N2—N1—C1—S2	179.76 (17)	C6—C7—C8—C3	0.7 (5)
Cu—S1—C1—N1	5.3 (2)	N1—N2—C9—C10	−0.8 (4)
Cu—S1—C1—S2	−174.52 (13)	Cu—N2—C9—C10	179.4 (2)
C2—S2—C1—N1	1.1 (3)	C11—O1—C10—C13	0.4 (3)
C2—S2—C1—S1	−179.07 (15)	C11—O1—C10—C9	179.1 (2)
C1—S2—C2—C3	−168.47 (19)	N2—C9—C10—C13	−4.3 (6)
S2—C2—C3—C8	82.6 (3)	N2—C9—C10—O1	177.5 (2)
S2—C2—C3—C4	−96.8 (3)	C10—O1—C11—C12	0.0 (3)
C8—C3—C4—C5	0.5 (4)	O1—C11—C12—C13	−0.4 (3)
C2—C3—C4—C5	179.9 (3)	O1—C10—C13—C12	−0.6 (3)
C3—C4—C5—C6	−0.2 (5)	C9—C10—C13—C12	−178.8 (3)
C4—C5—C6—C7	0.2 (5)	C11—C12—C13—C10	0.6 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the (C3–C8) ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cg1ⁱⁱ	0.95	2.96	3.646 (3)	131

Symmetry code: (ii) −x, y+1/2, −z+1/2.

Summary of short interatomic contacts (Å) in (I) top

Contact	Distance	Symmetry operation
H8···H8	2.11	-x, 1 - y, 1 - z
H5···C4	2.66	-x, 1/2 + y, 1/2 - z
H2B···S2	2.97	x, 1 + y, z
C9···C11	3.364 (4)	x, -1 + y, z

Notes: (a) The interatomic distances are calculated in Crystal Explorer (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) top

Contact	Percentage contribution
H···H	36.2
C···H/H···C	23.0
S···H/H···S	17.5
O···H/H···O	5.1
C···N/N···C	3.3
S···O/O···S	2.9
N···H/H···N	2.8
Cu···C/C···Cu	2.7
C···C	2.6
C···S/S···C	1.3
N···S/S···N	1.2
O···O	0.5
N···O/O···N	0.3
N···N	0.3
Cu···N/N···Cu	0.2
Cu···H/H···Cu	0.1
Cu···O/O···Cu	0.1

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

Contact	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
Cu···Cg(furyl)ⁱ +
Cg(chelate)···Cg(furyl)ⁱ +
C9···C11ⁱ +
S2···H2Bⁱ	5.02	-23.2	-9.4	-154.4	97.6	-89.7
Cg(phenyl)···Cg(phenyl)ⁱⁱ	16.15	-6.3	-3.3	-50.9	28.3	-31.5
S1···H11ⁱⁱⁱ	11.25	-12.0	-2.6	-10.6	5.2	-19.2
C5—H5···Cg(phenyl)^iv	17.06	-6.2	-2.1	-20.6	13.8	-15.1
H8···H8^v	15.35	0.7	-0.9	-15.6	7.9	-7.5

Notes: Symmetry operations: (i) x, -1 + y, z; (ii) -x, 2 - y, 1 - z; (iii) x, 3/2 - y, 1/2 + z; (iv) -x, 1/2 + y, 1/2 - z; (v) -x, 1 - y, 1 - z.

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Bis[S-benzyl 3-(furan-2-yl­methyl­idene)di­thio­carbazato-κ2N3,S]copper(II): crystal structure and Hirshfeld surface analysis

Supporting information

Key indicators

checkCIF/PLATON results

Bis[S-benzyl 3-(furan-2-ylmethylidene)dithiocarbazato-κ²N³,S]copper(II): crystal structure and Hirshfeld surface analysis