Bis{methyl N^β-[4-(di­propyl­amino)­benzyl­idene]­di­thio­carb­aza­to}nickel(II)

The Schiff base ligand in the title complex, [Ni(C₁₅H₂₂N₃S₂)₂], lost a proton from its tautomeric thiol form and coordinated to Ni(II) via the mercapto S and β-N atoms. The geometry around the Ni atom is square planar with two equivalent Ni—N and Ni—S bonds. The two phenyl rings and the coordination moieties are in one plane forming an extensive electronic delocalization system. The structure is governed by C—H...S and C—H...N hydrogen bonds, leading to the formation of centrosymmetric dimers.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.060
• wR factor = 0.144
• Data-to-parameter ratio = 20.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      3
                   S1  -NI1 -S1  -C1    -29.00100.00   3.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      4
                   N1  -NI1 -N1  -C3    -83.00100.00   3.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      7
                   N1  -NI1 -N1  -N2     97.00100.00   3.555   1.555   1.555   1.555


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

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S1. Comment

There has been continuous interest in the chemistry of the metal complexes of Schiff bases containing N and S donor atoms. The thio derivatives of the Schiff bases, RCHδb NNHCSSR', are known to coordinate readily with transition metals to give stable complexes, forming a long π-conjugated system by deprotonation on complex formation (Podhye & Kauffman, 1985; Tian et al., 1996), and also have been shown to possess biological activity (Martinez & Toscano, 1995; Pérez et al., 2001) and non-linear optical (NLO) properties (Zhao et al., 1989; Tian et al., 1996). As a part of our studies on these thio-Schiff-base–metal complexes, we report the title structure (I) which is nickel(II) complexed with S-methyl-dithiocarbazate derived from 4-(dipropylamino)benzaldehyde.

In the title complex (I), the asymmetric unit consists of one half of the complex molecule. The other one half is related by an inversion center at the Ni1 atom. The nickel atom is coordinated in a distorted trans square-planar geometry. The distortion is considered from the reduction of the Ni—N—S angle to 85.98 (6)° in the chelate ring (from the ideal value of 90°). The Schiff base losses a proton from its tautomeric thiol form and acts as a singly charged bidentate ligand coordinating to Ni1 via the mercapto S and β-N atoms. The Ni1 atom is displaced by 0.284 (1) Å from the plane through N1, N2, S1, C1. All bond distances in the side chain are intermediate between a single bond and a double bond. This has been documented before (Duan et al., 1998), indicating the high electron delocalization in the π-system of the whole molecule. The mean plane defined by the N1, N2, C1, S1 and S2 makes an angle of 14.2 (1)° with the plane of the phenyl ring, whereas in the uncoordinated molecule it is 5.55 (5)° (Fun et al., 1996).

In the crystal lattice, two intramolecular C—H···S and C—H···N form closed rings of S1A—Ni1—N1—C3—H3, N2—N1—C3—C4—C5—H5, and the molecules are stacked parallel in columns along the b axis (Fig. 2).

S2. Experimental

The title compound was prepared by mixing equal volumes (25 ml) of ethanol solution of nickel acetate (1 mmol) and the ligand (2 mmol). The mixture was refluxed and stirred for 4 h. On cooling to room temperature, it yielded the crystalline complex. Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a dichloromethane solution of the complex containing ethanol.

S3. Refinement

After checking their presence in the difference map, all H-atoms were geometrically fixed and allowed to ride on the parent C atoms with C—H distances 0.93–0.97 Å and isotropic displacement parameters.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

	Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Packing diagram of the structure (I) viewed down the c axis.

Bis[methyl-N^β-(dipropylaminophenyl-methylene)-dithiocarbazato]nickel(II)

Crystal data

C30H44N6NiS4	F(000) = 716
Mr = 675.66	Dx = 1.327 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.3394 (1) Å	Cell parameters from 8192 reflections
b = 9.1468 (1) Å	θ = 1.8–28.3°
c = 15.9725 (1) Å	µ = 0.85 mm^−1
β = 110.335 (1)°	T = 293 K
V = 1690.40 (3) Å^3	Block, black
Z = 2	0.46 × 0.38 × 0.34 mm

Data collection

Siemens SMART CCD area detector diffractometer	3992 independent reflections
Radiation source: fine-focus sealed tube	2918 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
Detector resolution: 8.33 pixels mm^-1	θmax = 28.0°, θmin = 1.8°
ω scans	h = −15→16
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996)	k = −12→6
Tmin = 0.696, Tmax = 0.761	l = −20→20
11381 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.060	H-atom parameters constrained
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0713P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max = 0.001
3992 reflections	Δρmax = 0.94 e Å^−3
191 parameters	Δρmin = −0.84 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.057 (4)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Ni1	0.0000	0.0000	0.0000	0.03322 (17)
S1	0.07597 (6)	−0.17208 (9)	0.09564 (5)	0.0586 (3)
S2	0.02769 (8)	−0.24872 (10)	0.25595 (6)	0.0718 (3)
N1	−0.11607 (17)	0.01273 (19)	0.05512 (13)	0.0344 (4)
N2	−0.09958 (17)	−0.0604 (2)	0.13666 (13)	0.0393 (5)
N3	−0.5968 (2)	0.2124 (3)	0.12795 (16)	0.0546 (6)
C1	−0.0111 (2)	−0.1453 (3)	0.15804 (17)	0.0424 (6)
C2	−0.0739 (3)	−0.1897 (4)	0.3059 (2)	0.0799 (11)
H2A	−0.0604	−0.2417	0.3608	0.120*
H2B	−0.1509	−0.2091	0.2659	0.120*
H2C	−0.0648	−0.0867	0.3178	0.120*
C3	−0.2135 (2)	0.0836 (3)	0.02404 (16)	0.0373 (5)
H3	−0.2251	0.1287	−0.0306	0.045*
C4	−0.3071 (2)	0.1062 (3)	0.05703 (16)	0.0376 (5)
C5	−0.3112 (2)	0.0700 (3)	0.14163 (16)	0.0435 (6)
H5	−0.2489	0.0219	0.1827	0.052*
C6	−0.4062 (2)	0.1049 (3)	0.16443 (18)	0.0481 (6)
H6	−0.4058	0.0806	0.2210	0.058*
C7	−0.5037 (2)	0.1762 (3)	0.10453 (18)	0.0443 (6)
C8	−0.4996 (2)	0.2105 (3)	0.01970 (18)	0.0472 (6)
H8	−0.5626	0.2561	−0.0223	0.057*
C9	−0.4042 (2)	0.1776 (3)	−0.00176 (17)	0.0440 (6)
H9	−0.4038	0.2038	−0.0579	0.053*
C10	−0.5984 (3)	0.1880 (3)	0.2183 (2)	0.0532 (7)
H10A	−0.6456	0.2627	0.2318	0.064*
H10B	−0.5204	0.1978	0.2608	0.064*
C11	−0.6449 (3)	0.0395 (4)	0.2296 (2)	0.0637 (8)
H11A	−0.5938	−0.0354	0.2214	0.076*
H11B	−0.7202	0.0261	0.1839	0.076*
C12	−0.6557 (4)	0.0205 (4)	0.3214 (3)	0.0787 (11)
H12A	−0.6904	−0.0725	0.3241	0.118*
H12B	−0.7032	0.0972	0.3310	0.118*
H12C	−0.5804	0.0250	0.3667	0.118*
C13	−0.7035 (2)	0.2703 (3)	0.0624 (2)	0.0513 (7)
H13A	−0.7685	0.2371	0.0782	0.062*
H13B	−0.7123	0.2299	0.0043	0.062*
C14	−0.7077 (3)	0.4336 (3)	0.0556 (2)	0.0660 (8)
H14A	−0.6448	0.4675	0.0373	0.079*
H14B	−0.6972	0.4751	0.1138	0.079*
C15	−0.8217 (3)	0.4864 (4)	−0.0111 (3)	0.0739 (10)
H15A	−0.8199	0.5909	−0.0163	0.111*
H15B	−0.8837	0.4590	0.0090	0.111*
H15C	−0.8336	0.4427	−0.0683	0.111*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0262 (2)	0.0395 (3)	0.0365 (3)	0.00074 (16)	0.01411 (17)	−0.00199 (16)
S1	0.0503 (4)	0.0692 (5)	0.0699 (5)	0.0258 (3)	0.0383 (4)	0.0247 (4)
S2	0.0574 (5)	0.0944 (7)	0.0720 (6)	0.0304 (4)	0.0331 (4)	0.0435 (5)
N1	0.0277 (9)	0.0410 (11)	0.0353 (10)	0.0012 (7)	0.0120 (8)	−0.0019 (7)
N2	0.0354 (11)	0.0476 (12)	0.0380 (10)	0.0049 (9)	0.0165 (9)	0.0035 (9)
N3	0.0393 (12)	0.0752 (16)	0.0576 (14)	0.0142 (11)	0.0274 (11)	0.0094 (12)
C1	0.0348 (13)	0.0476 (14)	0.0476 (14)	0.0029 (10)	0.0179 (11)	0.0063 (11)
C2	0.060 (2)	0.128 (3)	0.062 (2)	0.017 (2)	0.0339 (17)	0.040 (2)
C3	0.0309 (12)	0.0472 (14)	0.0361 (12)	0.0024 (10)	0.0148 (10)	0.0004 (10)
C4	0.0291 (11)	0.0463 (14)	0.0400 (12)	0.0034 (9)	0.0153 (10)	0.0009 (10)
C5	0.0320 (12)	0.0592 (16)	0.0408 (13)	0.0085 (11)	0.0143 (10)	0.0078 (11)
C6	0.0403 (14)	0.0653 (17)	0.0443 (14)	0.0111 (12)	0.0218 (12)	0.0107 (12)
C7	0.0326 (12)	0.0519 (15)	0.0534 (15)	0.0055 (10)	0.0210 (11)	0.0036 (11)
C8	0.0343 (13)	0.0599 (17)	0.0491 (15)	0.0115 (11)	0.0164 (11)	0.0087 (12)
C9	0.0368 (13)	0.0561 (16)	0.0422 (13)	0.0099 (11)	0.0175 (11)	0.0101 (11)
C10	0.0441 (15)	0.0673 (18)	0.0572 (17)	0.0043 (13)	0.0291 (13)	−0.0042 (13)
C11	0.066 (2)	0.073 (2)	0.0588 (19)	−0.0032 (17)	0.0309 (17)	−0.0029 (16)
C12	0.089 (3)	0.089 (3)	0.068 (2)	0.003 (2)	0.040 (2)	0.0102 (18)
C13	0.0336 (13)	0.0604 (17)	0.0645 (17)	0.0040 (11)	0.0232 (13)	−0.0037 (13)
C14	0.0562 (19)	0.0607 (19)	0.080 (2)	0.0016 (15)	0.0224 (17)	−0.0140 (17)
C15	0.063 (2)	0.068 (2)	0.088 (3)	0.0190 (16)	0.023 (2)	0.0070 (17)

Geometric parameters (Å, º)

Ni1—N1^i	1.928 (2)	C6—H6	0.9300
Ni1—N1	1.928 (2)	C7—C8	1.408 (4)
Ni1—S1	2.1667 (7)	C8—C9	1.369 (3)
Ni1—S1^i	2.1667 (7)	C8—H8	0.9300
S1—C1	1.719 (2)	C9—H9	0.9300
S2—C1	1.746 (3)	C10—C11	1.509 (4)
S2—C2	1.787 (3)	C10—H10A	0.9700
N1—C3	1.303 (3)	C10—H10B	0.9700
N1—N2	1.415 (3)	C11—C12	1.528 (4)
N2—C1	1.285 (3)	C11—H11A	0.9700
N3—C7	1.367 (3)	C11—H11B	0.9700
N3—C13	1.466 (4)	C12—H12A	0.9600
N3—C10	1.468 (4)	C12—H12B	0.9600
C2—H2A	0.9600	C12—H12C	0.9600
C2—H2B	0.9600	C13—C14	1.497 (4)
C2—H2C	0.9600	C13—H13A	0.9700
C3—C4	1.441 (3)	C13—H13B	0.9700
C3—H3	0.9300	C14—C15	1.519 (5)
C4—C9	1.400 (3)	C14—H14A	0.9700
C4—C5	1.409 (3)	C14—H14B	0.9700
C5—C6	1.380 (3)	C15—H15A	0.9600
C5—H5	0.9300	C15—H15B	0.9600
C6—C7	1.410 (4)	C15—H15C	0.9600
N1^i—Ni1—N1	180.00 (8)	C7—C8—H8	119.6
N1^i—Ni1—S1	94.02 (6)	C8—C9—C4	123.0 (2)
N1—Ni1—S1	85.98 (6)	C8—C9—H9	118.5
N1^i—Ni1—S1^i	85.98 (6)	C4—C9—H9	118.5
N1—Ni1—S1^i	94.02 (6)	N3—C10—C11	112.9 (2)
S1—Ni1—S1^i	180.00 (4)	N3—C10—H10A	109.0
C1—S1—Ni1	95.79 (9)	C11—C10—H10A	109.0
C1—S2—C2	102.68 (14)	N3—C10—H10B	109.0
C3—N1—N2	113.85 (19)	C11—C10—H10B	109.0
C3—N1—Ni1	126.15 (16)	H10A—C10—H10B	107.8
N2—N1—Ni1	120.00 (14)	C10—C11—C12	112.4 (3)
C1—N2—N1	111.57 (19)	C10—C11—H11A	109.1
C7—N3—C13	121.6 (2)	C12—C11—H11A	109.1
C7—N3—C10	122.1 (2)	C10—C11—H11B	109.1
C13—N3—C10	116.2 (2)	C12—C11—H11B	109.1
N2—C1—S1	125.2 (2)	H11A—C11—H11B	107.9
N2—C1—S2	120.58 (19)	C11—C12—H12A	109.5
S1—C1—S2	114.21 (14)	C11—C12—H12B	109.5
S2—C2—H2A	109.5	H12A—C12—H12B	109.5
S2—C2—H2B	109.5	C11—C12—H12C	109.5
H2A—C2—H2B	109.5	H12A—C12—H12C	109.5
S2—C2—H2C	109.5	H12B—C12—H12C	109.5
H2A—C2—H2C	109.5	N3—C13—C14	114.4 (2)
H2B—C2—H2C	109.5	N3—C13—H13A	108.7
N1—C3—C4	133.1 (2)	C14—C13—H13A	108.7
N1—C3—H3	113.5	N3—C13—H13B	108.7
C4—C3—H3	113.5	C14—C13—H13B	108.7
C9—C4—C5	116.4 (2)	H13A—C13—H13B	107.6
C9—C4—C3	115.4 (2)	C13—C14—C15	111.6 (3)
C5—C4—C3	128.1 (2)	C13—C14—H14A	109.3
C6—C5—C4	121.1 (2)	C15—C14—H14A	109.3
C6—C5—H5	119.5	C13—C14—H14B	109.3
C4—C5—H5	119.5	C15—C14—H14B	109.3
C5—C6—C7	122.0 (2)	H14A—C14—H14B	108.0
C5—C6—H6	119.0	C14—C15—H15A	109.5
C7—C6—H6	119.0	C14—C15—H15B	109.5
N3—C7—C8	121.6 (2)	H15A—C15—H15B	109.5
N3—C7—C6	121.8 (2)	C14—C15—H15C	109.5
C8—C7—C6	116.6 (2)	H15A—C15—H15C	109.5
C9—C8—C7	120.9 (2)	H15B—C15—H15C	109.5
C9—C8—H8	119.6
N1^i—Ni1—S1—C1	170.96 (11)	C9—C4—C5—C6	−0.5 (4)
N1—Ni1—S1—C1	−9.04 (11)	C3—C4—C5—C6	177.2 (2)
S1^i—Ni1—S1—C1	−29 (100)	C4—C5—C6—C7	0.8 (4)
N1^i—Ni1—N1—C3	−83 (100)	C13—N3—C7—C8	8.5 (4)
S1—Ni1—N1—C3	−167.7 (2)	C10—N3—C7—C8	−175.0 (2)
S1^i—Ni1—N1—C3	12.3 (2)	C13—N3—C7—C6	−172.5 (3)
N1^i—Ni1—N1—N2	97 (100)	C10—N3—C7—C6	4.0 (4)
S1—Ni1—N1—N2	11.62 (15)	C5—C6—C7—N3	−179.0 (3)
S1^i—Ni1—N1—N2	−168.38 (15)	C5—C6—C7—C8	0.0 (4)
C3—N1—N2—C1	170.6 (2)	N3—C7—C8—C9	178.0 (3)
Ni1—N1—N2—C1	−8.8 (3)	C6—C7—C8—C9	−1.1 (4)
N1—N2—C1—S1	−1.3 (3)	C7—C8—C9—C4	1.4 (4)
N1—N2—C1—S2	−179.82 (17)	C5—C4—C9—C8	−0.6 (4)
Ni1—S1—C1—N2	8.6 (2)	C3—C4—C9—C8	−178.6 (2)
Ni1—S1—C1—S2	−172.86 (13)	C7—N3—C10—C11	−89.9 (3)
C2—S2—C1—N2	−3.9 (3)	C13—N3—C10—C11	86.8 (3)
C2—S2—C1—S1	177.50 (18)	N3—C10—C11—C12	−175.1 (3)
N2—N1—C3—C4	2.0 (4)	C7—N3—C13—C14	−91.2 (3)
Ni1—N1—C3—C4	−178.6 (2)	C10—N3—C13—C14	92.1 (3)
N1—C3—C4—C9	−173.4 (3)	N3—C13—C14—C15	−178.2 (3)
N1—C3—C4—C5	8.9 (5)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···S1^i	0.93	2.44	3.073 (3)	125
C5—H5···N2	0.93	2.33	2.897 (3)	119

Symmetry code: (i) −x, −y, −z.