Chlorido{1-[2-(methyl­sulfan­yl)phenyl­diazen­yl]naphtholato-κ³O,N,S}nickel(II)

The Ni atom in the title compound, [Ni(C₁₇H₁₉N₂S)Cl], is tetra­coordinated by a naphtholate O atom, a diazene N atom, a Cl atom and an S atom in an approximately square-planar geometry. The crystal packing is stabilized by one inter­molecular C—H...Cl inter­action and two inter­molecular π–π inter­actions; the centroid-to-centroid distances are 3.745 (3) and 3.744 (3) Å, and the corresponding perpendicular distances are 3.528 and 3.541 Å, respectively.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.045
• wR factor = 0.113
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............      24.99 Deg.

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT128_ALERT_4_C Non-standard setting of Space group Pna21   ....    Pn21a
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           24.99
           From the CIF: _reflns_number_total               2728
           Count of symmetry unique reflns         1436
           Completeness (_total/calc)            189.97%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1292
           Fraction of Friedel pairs measured     0.900
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.50
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

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

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S1. Comment

Due to their potential biological activities, square planar Ni(II) complexes of various tridentate ONS ligands have been the subject of recent studies (Ali et al. 2002). Some of them have also been found to catalyse important reactions related to CO-dehydrogenase and silane alcoholosis (Lu et al., 1993; Barber et al., 1992). Against this background, we report here the crystal structure of (I).

The molecular structure of the title compound, (I), is shown in Fig. 1, with the atom numbering scheme. The nickel atom along with donor set of four atoms lie nearly in a plane. Selected bond lengths, bond angles and torsion angles are listed in Table 1. The packing arrangement of (I) is shown in Fig. 2. The N=N bond length 1.286 (5) is slightly greater than that in the free azoarenes (Das et al., 2006). Two nearly planar fragment in the molecular structure of (I) may be identified: the nickel atom, diazene unit, the chlorine atom and the naphtholato unit (A), the sulfur atom and the phenyl moiety (B). The dehedral angle between the planes A/B is 4.15 (16)°. The crystal packing is stabilized by one intermolecular C—H···Clⁱ [Symmetry code: (i) x, y, -1 + z.] interaction (Fig. 3; Table 2) and two intermolecular π—π interactions (Bagchi et al., 2007); the Cg3-Cg4ⁱⁱ and Cg4-Cg3ⁱⁱⁱ [Symmetry codes: (ii) x, y, 1 + z; (iii) x, y, -1 + z. Cg3 and Cg4 are the centroids of C1—C10 and C5—C9 rings respectively.] distances are 3.745 (3) and 3.744 (3) Å (Fig. 4); the corresponding perpendicular distances are 3.528 and 3.541 Å respectively. No C—H···π(arene) interaction is present in (I).

Related literature

For related literature, see: Ali et al. (2002); Bagchi et al. (2007); Das et al. (2006); Barber et al. (1992); Lu et al. (1993).

S2. Experimental

The title compound was synthesized by boiling 1-{2-(methylsulfanyl)phenyldiazenyl}naphthol and NiCl₂, 2H₂O in aqueous ethanol on water bath for one hour. The resulting precipitate was recrystallized from dichloromethane–hexane(1:4 v/v) producing crystals suitable for X-ray crystallography. Yield: 65%.

S3. Refinement

H atoms were included at calculated positions as riding atoms with C—H set to 0.93 Å for (aromatic) and 0.96 Å for (CH₃) H atoms, with U_iso(H) = 1.2U_eq(C) (1.5U_eq for methyl group).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

	Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The molecular arrangement of (I) in the ab plane.
	Fig. 3. The intra molecular C—H···Cl interaction in (I) shown by dotted line [Symmetry code: (i) x, y, -1 + z.].
	Fig. 4. The inter molecular π—π interaction for (I), indicated by the dotted line. [Symmetry codes: (ii) x, y, 1 + z; (iii) x, y, -1 + z. Cg3 & Cg4 are the centroids of C1—C10 & C5—C9 rings respectively.], H atoms are omitted for clarity.

Chlorido{1-[2-(methylsulfanyl)phenyldiazenyl]naphtholato-κ³O,N,S}nickel(II)

Crystal data

[Ni(C17H19N2S)Cl]	F(000) = 792
Mr = 387.51	Dx = 1.665 Mg m^−3
Orthorhombic, Pn21a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2ac -2n	Cell parameters from 2728 reflections
a = 28.717 (4) Å	θ = 1.4–25.0°
b = 11.5393 (14) Å	µ = 1.57 mm^−1
c = 4.6660 (6) Å	T = 293 K
V = 1546.2 (3) Å^3	Block, brown
Z = 4	0.42 × 0.30 × 0.19 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2728 independent reflections
Radiation source: fine-focus sealed tube	2579 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −34→34
Tmin = 0.581, Tmax = 0.744	k = −13→13
13677 measured reflections	l = −5→5

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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0638P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.19	(Δ/σ)max = 0.001
2728 reflections	Δρmax = 0.64 e Å^−3
209 parameters	Δρmin = −0.51 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1292 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (2)

Special details

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	0.56150 (2)	0.00129 (5)	0.28733 (11)	0.03227 (19)
S1	0.54404 (5)	0.18260 (11)	0.2816 (3)	0.0355 (3)
O1	0.57767 (14)	−0.1511 (3)	0.3416 (8)	0.0424 (9)
C12	0.58366 (17)	0.2283 (5)	0.0137 (10)	0.0347 (11)
C2	0.61100 (19)	−0.2046 (5)	0.2164 (10)	0.0359 (12)
C1	0.64243 (17)	−0.1529 (4)	0.0188 (11)	0.0328 (11)
C11	0.61433 (15)	0.1454 (4)	−0.0855 (10)	0.0284 (10)
N1	0.64058 (13)	−0.0413 (3)	−0.0621 (8)	0.0315 (9)
C8	0.7118 (2)	−0.1748 (5)	−0.3035 (12)	0.0465 (14)
H8	0.7099	−0.0971	−0.3552	0.056*
C3	0.6169 (2)	−0.3253 (5)	0.2821 (12)	0.0470 (14)
H3	0.5963	−0.3608	0.4083	0.056*
C16	0.64729 (18)	0.1740 (5)	−0.2918 (11)	0.0390 (12)
H16	0.6678	0.1184	−0.3621	0.047*
C4	0.6514 (2)	−0.3882 (5)	0.1664 (11)	0.0472 (15)
H4	0.6542	−0.4658	0.2174	0.057*
C14	0.6185 (2)	0.3707 (5)	−0.2884 (11)	0.0488 (15)
H14	0.6200	0.4462	−0.3576	0.059*
C10	0.67968 (17)	−0.2211 (5)	−0.1069 (11)	0.0344 (11)
C15	0.64898 (19)	0.2874 (5)	−0.3907 (12)	0.0408 (13)
H15	0.6710	0.3077	−0.5280	0.049*
C9	0.68426 (19)	−0.3401 (5)	−0.0339 (12)	0.0408 (13)
N2	0.60954 (13)	0.0300 (3)	0.0295 (8)	0.0270 (9)
C17	0.4890 (2)	0.2028 (5)	0.1036 (14)	0.0492 (15)
H17A	0.4859	0.2823	0.0462	0.074*
H17B	0.4642	0.1830	0.2322	0.074*
H17C	0.4876	0.1539	−0.0625	0.074*
C5	0.7201 (2)	−0.4051 (6)	−0.1506 (12)	0.0472 (14)
H5	0.7233	−0.4823	−0.0975	0.057*
C13	0.58585 (19)	0.3419 (4)	−0.0849 (11)	0.0391 (12)
H13	0.5655	0.3977	−0.0140	0.047*
C7	0.7461 (2)	−0.2437 (5)	−0.4200 (15)	0.0557 (16)
H7	0.7666	−0.2127	−0.5541	0.067*
C6	0.7505 (2)	−0.3591 (5)	−0.3389 (13)	0.0548 (16)
H6	0.7742	−0.4045	−0.4146	0.066*
Cl1	0.50075 (5)	−0.02334 (13)	0.5684 (4)	0.0566 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0357 (3)	0.0281 (3)	0.0330 (3)	−0.0016 (3)	0.0049 (2)	0.0013 (4)
S1	0.0442 (8)	0.0305 (7)	0.0318 (7)	0.0008 (6)	0.0014 (5)	−0.0027 (6)
O1	0.042 (2)	0.030 (2)	0.054 (2)	0.0021 (17)	0.0135 (19)	0.0033 (17)
C12	0.041 (3)	0.032 (2)	0.031 (3)	−0.004 (2)	−0.004 (2)	0.003 (2)
C2	0.039 (3)	0.034 (3)	0.035 (3)	0.000 (2)	0.001 (2)	0.002 (2)
C1	0.030 (3)	0.030 (3)	0.038 (3)	−0.002 (2)	0.000 (2)	0.002 (2)
C11	0.025 (2)	0.029 (2)	0.031 (3)	−0.002 (2)	−0.009 (2)	0.006 (2)
N1	0.030 (2)	0.030 (2)	0.035 (2)	0.0012 (17)	−0.0033 (18)	0.0008 (17)
C8	0.045 (3)	0.040 (3)	0.055 (4)	0.002 (3)	0.014 (3)	0.002 (3)
C3	0.054 (4)	0.034 (3)	0.053 (3)	0.001 (3)	0.008 (3)	0.012 (3)
C16	0.032 (3)	0.038 (3)	0.047 (3)	−0.002 (2)	0.000 (2)	0.005 (2)
C4	0.066 (4)	0.031 (3)	0.045 (3)	0.006 (3)	0.002 (3)	0.008 (2)
C14	0.069 (4)	0.034 (3)	0.043 (3)	−0.005 (3)	−0.007 (3)	0.010 (3)
C10	0.030 (3)	0.038 (3)	0.035 (3)	0.001 (2)	−0.002 (2)	0.004 (2)
C15	0.039 (3)	0.041 (3)	0.042 (3)	−0.009 (2)	0.001 (2)	0.012 (2)
C9	0.047 (3)	0.033 (3)	0.042 (3)	0.005 (2)	−0.001 (2)	−0.003 (2)
N2	0.023 (2)	0.028 (2)	0.030 (2)	−0.0004 (17)	−0.0031 (16)	0.0012 (16)
C17	0.043 (3)	0.055 (4)	0.050 (3)	0.012 (3)	−0.001 (3)	−0.013 (3)
C5	0.050 (4)	0.036 (3)	0.056 (3)	0.014 (3)	−0.004 (3)	0.002 (3)
C13	0.050 (3)	0.022 (3)	0.045 (3)	0.008 (2)	−0.001 (3)	0.002 (2)
C7	0.046 (3)	0.051 (4)	0.070 (4)	0.002 (3)	0.021 (3)	0.009 (3)
C6	0.049 (4)	0.051 (4)	0.064 (4)	0.009 (3)	0.010 (3)	−0.013 (3)
Cl1	0.0605 (9)	0.0400 (8)	0.0694 (10)	−0.0014 (6)	0.0323 (7)	0.0028 (7)

Geometric parameters (Å, º)

Ni1—O1	1.836 (4)	C3—H3	0.9300
Ni1—N2	1.860 (4)	C16—C15	1.388 (8)
Ni1—S1	2.1516 (14)	C16—H16	0.9300
Ni1—Cl1	2.2009 (15)	C4—C9	1.439 (8)
S1—C12	1.771 (5)	C4—H4	0.9300
S1—C17	1.800 (6)	C14—C13	1.374 (8)
O1—C2	1.280 (6)	C14—C15	1.386 (8)
C12—C11	1.380 (7)	C14—H14	0.9300
C12—C13	1.391 (7)	C10—C9	1.421 (7)
C2—C1	1.421 (7)	C15—H15	0.9300
C2—C3	1.437 (8)	C9—C5	1.385 (8)
C1—N1	1.343 (6)	C17—H17A	0.9600
C1—C10	1.452 (7)	C17—H17B	0.9600
C11—C16	1.390 (7)	C17—H17C	0.9600
C11—N2	1.442 (6)	C5—C6	1.346 (8)
N1—N2	1.286 (5)	C5—H5	0.9300
C8—C7	1.379 (8)	C13—H13	0.9300
C8—C10	1.407 (8)	C7—C6	1.390 (8)
C8—H8	0.9300	C7—H7	0.9300
C3—C4	1.341 (8)	C6—H6	0.9300
O1—Ni1—N2	94.14 (16)	C9—C4—H4	118.8
O1—Ni1—S1	172.66 (13)	C13—C14—C15	120.0 (5)
N2—Ni1—S1	89.52 (12)	C13—C14—H14	120.0
O1—Ni1—Cl1	89.69 (12)	C15—C14—H14	120.0
N2—Ni1—Cl1	175.02 (12)	C8—C10—C9	117.6 (5)
S1—Ni1—Cl1	87.04 (6)	C8—C10—C1	122.7 (5)
C12—S1—C17	101.5 (3)	C9—C10—C1	119.7 (5)
C12—S1—Ni1	98.54 (19)	C14—C15—C16	121.2 (5)
C17—S1—Ni1	109.6 (2)	C14—C15—H15	119.4
C2—O1—Ni1	126.0 (3)	C16—C15—H15	119.4
C11—C12—C13	120.9 (5)	C5—C9—C10	119.8 (5)
C11—C12—S1	116.2 (4)	C5—C9—C4	122.3 (5)
C13—C12—S1	122.9 (4)	C10—C9—C4	117.9 (5)
O1—C2—C1	124.7 (5)	N1—N2—C11	113.7 (4)
O1—C2—C3	117.3 (5)	N1—N2—Ni1	127.9 (3)
C1—C2—C3	118.0 (5)	C11—N2—Ni1	118.4 (3)
N1—C1—C2	124.0 (5)	S1—C17—H17A	109.5
N1—C1—C10	115.8 (5)	S1—C17—H17B	109.5
C2—C1—C10	120.2 (5)	H17A—C17—H17B	109.5
C12—C11—C16	120.2 (5)	S1—C17—H17C	109.5
C12—C11—N2	117.0 (4)	H17A—C17—H17C	109.5
C16—C11—N2	122.8 (4)	H17B—C17—H17C	109.5
N2—N1—C1	123.2 (4)	C6—C5—C9	121.6 (6)
C7—C8—C10	120.4 (6)	C6—C5—H5	119.2
C7—C8—H8	119.8	C9—C5—H5	119.2
C10—C8—H8	119.8	C14—C13—C12	119.2 (5)
C4—C3—C2	121.8 (5)	C14—C13—H13	120.4
C4—C3—H3	119.1	C12—C13—H13	120.4
C2—C3—H3	119.1	C8—C7—C6	120.6 (6)
C15—C16—C11	118.5 (5)	C8—C7—H7	119.7
C15—C16—H16	120.7	C6—C7—H7	119.7
C11—C16—H16	120.7	C5—C6—C7	119.8 (5)
C3—C4—C9	122.5 (5)	C5—C6—H6	120.1
C3—C4—H4	118.8	C7—C6—H6	120.1
N2—Ni1—S1—C12	5.10 (19)	C2—C1—C10—C8	180.0 (5)
Cl1—Ni1—S1—C12	−171.29 (17)	N1—C1—C10—C9	−179.9 (5)
N2—Ni1—S1—C17	110.7 (3)	C2—C1—C10—C9	0.7 (7)
Cl1—Ni1—S1—C17	−65.7 (2)	C13—C14—C15—C16	0.2 (9)
N2—Ni1—O1—C2	−2.0 (4)	C11—C16—C15—C14	−0.3 (8)
Cl1—Ni1—O1—C2	174.8 (4)	C8—C10—C9—C5	1.5 (8)
C17—S1—C12—C11	−117.6 (4)	C1—C10—C9—C5	−179.2 (5)
Ni1—S1—C12—C11	−5.4 (4)	C8—C10—C9—C4	−179.8 (5)
C17—S1—C12—C13	65.3 (5)	C1—C10—C9—C4	−0.4 (8)
Ni1—S1—C12—C13	177.5 (4)	C3—C4—C9—C5	179.3 (6)
Ni1—O1—C2—C1	2.3 (7)	C3—C4—C9—C10	0.6 (9)
Ni1—O1—C2—C3	−177.9 (4)	C1—N1—N2—C11	179.9 (4)
O1—C2—C1—N1	−0.6 (8)	C1—N1—N2—Ni1	0.6 (6)
C3—C2—C1—N1	179.6 (5)	C12—C11—N2—N1	−176.9 (4)
O1—C2—C1—C10	178.8 (5)	C16—C11—N2—N1	4.5 (6)
C3—C2—C1—C10	−1.0 (7)	C12—C11—N2—Ni1	2.5 (5)
C13—C12—C11—C16	−1.6 (8)	C16—C11—N2—Ni1	−176.1 (4)
S1—C12—C11—C16	−178.8 (4)	O1—Ni1—N2—N1	0.7 (4)
C13—C12—C11—N2	179.8 (4)	S1—Ni1—N2—N1	174.3 (4)
S1—C12—C11—N2	2.6 (6)	O1—Ni1—N2—C11	−178.6 (3)
C2—C1—N1—N2	−0.9 (8)	S1—Ni1—N2—C11	−5.0 (3)
C10—C1—N1—N2	179.7 (4)	C10—C9—C5—C6	−1.7 (9)
O1—C2—C3—C4	−178.6 (5)	C4—C9—C5—C6	179.6 (6)
C1—C2—C3—C4	1.2 (8)	C15—C14—C13—C12	−0.7 (8)
C12—C11—C16—C15	1.0 (8)	C11—C12—C13—C14	1.4 (8)
N2—C11—C16—C15	179.6 (4)	S1—C12—C13—C14	178.4 (4)
C2—C3—C4—C9	−1.0 (9)	C10—C8—C7—C6	−1.9 (10)
C7—C8—C10—C9	0.3 (9)	C9—C5—C6—C7	0.1 (10)
C7—C8—C10—C1	−179.0 (5)	C8—C7—C6—C5	1.7 (10)
N1—C1—C10—C8	−0.6 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17C···Cl1^i	0.96	2.70	3.628 (6)	163

Symmetry code: (i) x, y, z−1.