Crystal structure of di-chlorido-{N (1)-phenyl-N (4)-[(quinolin-2-yl-κN)methylidene]benzene-1,4-diamine-κN (4)}mercury(II).

In the mononuclear title complex, [HgCl2(C22H17N3)], synthesized from the quinoline-derived Schiff base N (1)-phenyl-N (4)-[(quinolin-2-yl)methyl-idene]benzene-1,4-di-amine (PQMBD) and HgCl2, the coordination sphere around the Hg(2+) atom is distorted tetra-hedral, comprising two Cl atoms [Hg-Cl = 2.3487 (14) and 2.4490 (15) Å] and two N atom donors from the PQMBD ligand, viz. the quinolyl and the imine N atom [Hg-N = 2.270 (4) and 2.346 (4) Å, respectively]. The dihedral angle between the two benzene rings attached to the amino group is 43.7 (3)°. In the crystal, N-H⋯Cl and C-H⋯Cl hydrogen bonds, as well as π-π stacking inter-actions between one phenyl ring and the pyridine ring of the quinoline moiety of an adjacent mol-ecule [centroid-to-centroid separation = 3.617 (4) Å] are observed, resulting in a three-dimensional network.

Related literature

For the haza­rds of mercury in organisms, see: Mandal et al. (2012 ▸). For reports of n class="Chemical">quinolyl derivatives of Schiff bases, see: Motswainyana et al. (2013 ▸); Das et al. (2013 ▸); Song et al. (2011 ▸); Jursic et al. (2002 ▸). For background to related Schiff base–metal complexes, see: Faizi & Hussain (2014 ▸); Faizi et al. (2014 ▸); Moroz et al. (2012 ▸). For related Hg-containing structures, see: Marjani et al. (2009 ▸); Faizi & Sen (2014 ▸), and for related Schiff base complexes, see: Penkova et al. (2009 ▸, 2010 ▸); Strotmeyer et al. (2003 ▸); Petrusenko et al. (1997 ▸). The amino group of the title compound is separated from the chelating unit which makes this complex a possible precursor for further functionalization, eventually yielding binuclear compounds as reported by Fritsky et al. (1998 ▸, 2006 ▸) and Kanderal et al. (2005 ▸).

Experimental

Crystal data

[HgCl2(C22H17n class="Chemical">N3)]

M = 594.88

Monoclinic,

a = 29.265 (5) Å

b = 7.5671 (13) Å

c = 18.811 (3) Å

β = 99.271 (7)°

V = 4111.4 (12) Å3

Z = 8

Mo Kα radiation

μ = 7.76 mm−1

T = 100 K

0.18 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▸) T min = 0.336, T max = 0.511

22545 measured reflections

5133 independent reflections

3182 reflections with I > 2σ(I)

R int = 0.059

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.087

S = 1.00

5133 reflections

253 parameters

H-atom parameters constrained

Δρmax = 0.99 e Å−3

Δρmin = −0.56 e Å−3

Data collection: SMART (Bruker, 2003 ▸); cell refinement: SAINT (Bruker, 2003 ▸); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015001620/wm5117sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015001620/wm5117Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015001620/wm5117fig1.tif

The mol­ecular structure and the atom-numbering scheme of the title complex, with non-H atoms drawn as displacement ellipsoids at the 40% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015001620/wm5117fig2.tif

N—H⋯Cl n class="Chemical">hydrogen bonds between adjacent mol­ecules as viewed along [010].

Click here for additional data file.

. DOI: 10.1107/S2056989015001620/wm5117fig3.tif

The packing of mol­ecules in the title compound, showing inter­molecular inter­actions as dashed lines.

CCDC reference: 1045457

Additional supporting information: crystallographic information; 3D view; checkCIF report

[HgCl2(C22H17N3)]	F(000) = 2272
Mr = 594.88	Dx = 1.922 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7479 reflections
a = 29.265 (5) Å	θ = 2.8–24.6°
b = 7.5671 (13) Å	µ = 7.76 mm−1
c = 18.811 (3) Å	T = 100 K
β = 99.271 (7)°	Block, colourless
V = 4111.4 (12) Å3	0.18 × 0.15 × 0.10 mm
Z = 8

Bruker SMART APEX CCD diffractometer	5133 independent reflections
Radiation source: fine-focus sealed tube	3182 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
ω scans	θmax = 28.4°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −38→38
Tmin = 0.336, Tmax = 0.511	k = −10→9
22545 measured reflections	l = −25→25

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0374P)2 + 1.5818P] where P = (Fo2 + 2Fc2)/3
5133 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.99 e Å−3
0 restraints	Δρmin = −0.56 e Å−3

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.

	x	y	z	Uiso*/Ueq
N1	0.42861 (15)	0.2191 (5)	0.5298 (2)	0.0396 (10)
N2	0.50810 (14)	0.2420 (6)	0.4703 (2)	0.0389 (10)
N3	0.65162 (17)	0.3036 (7)	0.3095 (2)	0.0603 (14)
H3A	0.6410	0.3037	0.2641	0.072*
C11	0.54666 (17)	0.2526 (7)	0.4348 (2)	0.0373 (12)
C10	0.50915 (18)	0.2791 (7)	0.5369 (3)	0.0422 (13)
H10	0.5369	0.3144	0.5644	0.051*
C17	0.6984 (2)	0.3274 (7)	0.3265 (3)	0.0507 (14)
C12	0.59004 (18)	0.3146 (7)	0.4656 (2)	0.0431 (13)
H12	0.5952	0.3467	0.5140	0.052*
C1	0.3891 (2)	0.2106 (7)	0.5581 (3)	0.0475 (14)
C16	0.5400 (2)	0.2029 (7)	0.3633 (3)	0.0509 (15)
H16	0.5115	0.1588	0.3418	0.061*
C9	0.46781 (18)	0.2673 (7)	0.5702 (3)	0.0392 (12)
C15	0.5752 (2)	0.2181 (8)	0.3236 (3)	0.0572 (16)
H15	0.5697	0.1861	0.2753	0.069*
C13	0.62510 (18)	0.3293 (7)	0.4263 (3)	0.0447 (13)
H13	0.6537	0.3729	0.4481	0.054*
C6	0.3892 (2)	0.2468 (8)	0.6324 (3)	0.0479 (14)
C7	0.4309 (2)	0.2985 (7)	0.6737 (3)	0.0543 (15)
H7	0.4319	0.3271	0.7220	0.065*
C8	0.4699 (2)	0.3076 (8)	0.6443 (3)	0.0559 (16)
H8	0.4978	0.3400	0.6722	0.067*
C14	0.61872 (19)	0.2795 (7)	0.3533 (3)	0.0469 (14)
Hg1	0.432753 (8)	0.18401 (3)	0.411137 (10)	0.05198 (10)
Cl2	0.40186 (6)	0.4552 (2)	0.35050 (7)	0.0702 (5)
Cl1	0.41693 (5)	−0.0647 (2)	0.33652 (7)	0.0593 (4)
C2	0.3473 (2)	0.1623 (7)	0.5149 (3)	0.0553 (15)
H2	0.3471	0.1343	0.4667	0.066*
C4	0.3076 (2)	0.1986 (8)	0.6148 (4)	0.0699 (19)
H4	0.2798	0.1988	0.6327	0.084*
C3	0.3070 (2)	0.1557 (8)	0.5420 (3)	0.0656 (18)
H3	0.2795	0.1233	0.5129	0.079*
C5	0.3471 (2)	0.2397 (9)	0.6601 (3)	0.0624 (17)
H5	0.3465	0.2628	0.7085	0.075*
C18	0.7240 (2)	0.2570 (9)	0.3877 (3)	0.0632 (17)
H18	0.7096	0.1968	0.4210	0.076*
C19	0.7715 (3)	0.2770 (13)	0.3989 (4)	0.098 (3)
H19	0.7890	0.2272	0.4396	0.118*
C22	0.7218 (3)	0.4179 (9)	0.2794 (3)	0.0700 (19)
H22	0.7050	0.4696	0.2384	0.084*
C21	0.7680 (3)	0.4324 (11)	0.2915 (5)	0.091 (3)
H21	0.7826	0.4886	0.2573	0.110*
C20	0.7937 (3)	0.3686 (15)	0.3512 (5)	0.115 (4)
H20	0.8256	0.3856	0.3602	0.138*

	U11	U22	U33	U12	U13	U23
N1	0.046 (3)	0.040 (3)	0.033 (2)	0.002 (2)	0.0060 (19)	0.0038 (18)
N2	0.043 (3)	0.040 (2)	0.033 (2)	−0.003 (2)	0.0032 (18)	−0.0005 (18)
N3	0.050 (3)	0.101 (4)	0.030 (2)	0.000 (3)	0.007 (2)	0.001 (2)
C11	0.039 (3)	0.041 (3)	0.034 (3)	0.001 (2)	0.011 (2)	−0.006 (2)
C10	0.045 (3)	0.044 (3)	0.034 (3)	0.003 (2)	−0.002 (2)	0.007 (2)
C17	0.053 (4)	0.056 (4)	0.046 (3)	0.003 (3)	0.015 (3)	−0.004 (3)
C12	0.050 (3)	0.050 (3)	0.029 (2)	−0.002 (3)	0.003 (2)	−0.002 (2)
C1	0.055 (4)	0.040 (3)	0.047 (3)	0.009 (3)	0.008 (3)	0.008 (2)
C16	0.048 (3)	0.064 (4)	0.039 (3)	−0.007 (3)	0.000 (2)	−0.014 (3)
C9	0.048 (3)	0.038 (3)	0.033 (3)	0.007 (2)	0.007 (2)	0.000 (2)
C15	0.055 (4)	0.085 (5)	0.030 (3)	−0.009 (3)	0.002 (3)	−0.013 (3)
C13	0.037 (3)	0.058 (4)	0.037 (3)	−0.005 (3)	0.000 (2)	−0.007 (3)
C6	0.057 (4)	0.048 (3)	0.042 (3)	0.006 (3)	0.015 (3)	0.009 (3)
C7	0.070 (4)	0.061 (4)	0.034 (3)	0.002 (3)	0.015 (3)	−0.003 (3)
C8	0.060 (4)	0.071 (4)	0.034 (3)	−0.001 (3)	0.000 (3)	0.003 (3)
C14	0.046 (3)	0.058 (4)	0.037 (3)	0.005 (3)	0.007 (2)	0.000 (3)
Hg1	0.05736 (16)	0.05833 (16)	0.03782 (13)	−0.00317 (12)	0.00037 (9)	−0.00853 (11)
Cl2	0.1027 (13)	0.0504 (9)	0.0476 (8)	0.0032 (9)	−0.0178 (8)	−0.0030 (7)
Cl1	0.0732 (10)	0.0508 (9)	0.0524 (8)	−0.0083 (8)	0.0053 (7)	−0.0122 (7)
C2	0.052 (4)	0.064 (4)	0.052 (3)	−0.002 (3)	0.012 (3)	0.000 (3)
C4	0.066 (4)	0.078 (5)	0.073 (5)	0.007 (4)	0.032 (4)	−0.001 (4)
C3	0.049 (4)	0.078 (5)	0.070 (4)	0.003 (3)	0.011 (3)	0.007 (4)
C5	0.069 (5)	0.068 (4)	0.058 (4)	0.009 (4)	0.034 (4)	0.010 (3)
C18	0.051 (4)	0.087 (5)	0.052 (4)	0.003 (4)	0.010 (3)	0.009 (3)
C19	0.057 (5)	0.174 (9)	0.062 (4)	0.006 (5)	0.006 (4)	−0.022 (5)
C22	0.082 (5)	0.076 (5)	0.061 (4)	0.009 (4)	0.040 (4)	0.008 (4)
C21	0.094 (6)	0.097 (6)	0.098 (6)	−0.031 (5)	0.061 (5)	−0.025 (5)
C20	0.069 (6)	0.179 (10)	0.107 (7)	−0.036 (6)	0.045 (5)	−0.069 (7)

N1—C9	1.322 (6)	C13—H13	0.9300
N1—C1	1.349 (7)	C6—C7	1.394 (8)
N1—Hg1	2.270 (4)	C6—C5	1.413 (8)
N2—C10	1.279 (6)	C7—C8	1.347 (8)
N2—C11	1.402 (6)	C7—H7	0.9300
N2—Hg1	2.346 (4)	C8—H8	0.9300
N3—C17	1.367 (7)	Hg1—Cl1	2.3487 (14)
N3—C14	1.377 (7)	Hg1—Cl2	2.4490 (15)
N3—H3A	0.8600	C2—C3	1.359 (8)
C11—C16	1.380 (6)	C2—H2	0.9300
C11—C12	1.389 (7)	C4—C5	1.358 (9)
C10—C9	1.453 (7)	C4—C3	1.403 (8)
C10—H10	0.9300	C4—H4	0.9300
C17—C22	1.385 (8)	C3—H3	0.9300
C17—C18	1.375 (8)	C5—H5	0.9300
C12—C13	1.362 (7)	C18—C19	1.381 (9)
C12—H12	0.9300	C18—H18	0.9300
C1—C2	1.404 (8)	C19—C20	1.375 (12)
C1—C6	1.425 (7)	C19—H19	0.9300
C16—C15	1.370 (8)	C22—C21	1.340 (9)
C16—H16	0.9300	C22—H22	0.9300
C9—C8	1.418 (7)	C21—C20	1.338 (11)
C15—C14	1.385 (7)	C21—H21	0.9300
C15—H15	0.9300	C20—H20	0.9300
C13—C14	1.409 (7)
C9—N1—C1	120.4 (4)	C6—C7—H7	119.7
C9—N1—Hg1	114.8 (3)	C7—C8—C9	119.1 (5)
C1—N1—Hg1	124.5 (4)	C7—C8—H8	120.4
C10—N2—C11	124.0 (4)	C9—C8—H8	120.4
C10—N2—Hg1	112.2 (3)	C15—C14—N3	119.3 (5)
C11—N2—Hg1	123.5 (3)	C15—C14—C13	116.8 (5)
C17—N3—C14	130.3 (5)	N3—C14—C13	123.6 (5)
C17—N3—H3A	114.8	N1—Hg1—N2	72.96 (15)
C14—N3—H3A	114.8	N1—Hg1—Cl1	130.14 (11)
C16—C11—C12	118.3 (5)	N2—Hg1—Cl1	120.86 (11)
C16—C11—N2	116.8 (5)	N1—Hg1—Cl2	106.60 (11)
C12—C11—N2	124.9 (4)	N2—Hg1—Cl2	108.21 (11)
N2—C10—C9	121.3 (5)	Cl1—Hg1—Cl2	111.75 (5)
N2—C10—H10	119.4	C3—C2—C1	121.4 (6)
C9—C10—H10	119.4	C3—C2—H2	119.3
N3—C17—C22	119.6 (5)	C1—C2—H2	119.3
N3—C17—C18	122.4 (5)	C5—C4—C3	122.7 (6)
C22—C17—C18	118.0 (6)	C5—C4—H4	118.7
C13—C12—C11	121.2 (4)	C3—C4—H4	118.7
C13—C12—H12	119.4	C2—C3—C4	118.9 (6)
C11—C12—H12	119.4	C2—C3—H3	120.6
N1—C1—C2	120.5 (5)	C4—C3—H3	120.6
N1—C1—C6	120.8 (5)	C4—C5—C6	118.8 (6)
C2—C1—C6	118.7 (5)	C4—C5—H5	120.6
C15—C16—C11	120.5 (5)	C6—C5—H5	120.6
C15—C16—H16	119.7	C19—C18—C17	119.0 (6)
C11—C16—H16	119.7	C19—C18—H18	120.5
N1—C9—C8	121.4 (5)	C17—C18—H18	120.5
N1—C9—C10	118.3 (4)	C18—C19—C20	121.7 (8)
C8—C9—C10	120.3 (5)	C18—C19—H19	119.2
C16—C15—C14	122.1 (5)	C20—C19—H19	119.2
C16—C15—H15	118.9	C21—C22—C17	121.4 (7)
C14—C15—H15	118.9	C21—C22—H22	119.3
C12—C13—C14	121.0 (5)	C17—C22—H22	119.3
C12—C13—H13	119.5	C22—C21—C20	121.9 (7)
C14—C13—H13	119.5	C22—C21—H21	119.0
C7—C6—C5	122.9 (5)	C20—C21—H21	119.0
C7—C6—C1	117.6 (5)	C21—C20—C19	118.0 (8)
C5—C6—C1	119.4 (6)	C21—C20—H20	121.0
C8—C7—C6	120.6 (5)	C19—C20—H20	121.0
C8—C7—H7	119.7
C10—N2—C11—C16	178.2 (5)	C16—C15—C14—N3	−175.4 (6)
Hg1—N2—C11—C16	−8.8 (7)	C16—C15—C14—C13	−1.1 (9)
C10—N2—C11—C12	−4.2 (8)	C17—N3—C14—C15	−165.2 (6)
Hg1—N2—C11—C12	168.9 (4)	C17—N3—C14—C13	20.9 (10)
C11—N2—C10—C9	179.3 (5)	C12—C13—C14—C15	0.9 (8)
Hg1—N2—C10—C9	5.6 (6)	C12—C13—C14—N3	174.9 (5)
C14—N3—C17—C22	−153.7 (6)	C9—N1—Hg1—N2	5.3 (3)
C14—N3—C17—C18	29.6 (10)	C1—N1—Hg1—N2	178.8 (4)
C16—C11—C12—C13	1.1 (8)	C9—N1—Hg1—Cl1	121.6 (3)
N2—C11—C12—C13	−176.5 (5)	C1—N1—Hg1—Cl1	−64.9 (4)
C9—N1—C1—C2	178.9 (5)	C9—N1—Hg1—Cl2	−99.2 (3)
Hg1—N1—C1—C2	5.8 (7)	C1—N1—Hg1—Cl2	74.3 (4)
C9—N1—C1—C6	−2.3 (8)	C10—N2—Hg1—N1	−5.6 (3)
Hg1—N1—C1—C6	−175.5 (4)	C11—N2—Hg1—N1	−179.4 (4)
C12—C11—C16—C15	−1.3 (8)	C10—N2—Hg1—Cl1	−132.7 (3)
N2—C11—C16—C15	176.6 (5)	C11—N2—Hg1—Cl1	53.5 (4)
C1—N1—C9—C8	1.3 (7)	C10—N2—Hg1—Cl2	96.7 (4)
Hg1—N1—C9—C8	175.1 (4)	C11—N2—Hg1—Cl2	−77.1 (4)
C1—N1—C9—C10	−178.3 (5)	N1—C1—C2—C3	−178.9 (5)
Hg1—N1—C9—C10	−4.6 (6)	C6—C1—C2—C3	2.3 (8)
N2—C10—C9—N1	−0.9 (8)	C1—C2—C3—C4	0.1 (9)
N2—C10—C9—C8	179.5 (5)	C5—C4—C3—C2	−2.7 (10)
C11—C16—C15—C14	1.3 (10)	C3—C4—C5—C6	2.7 (10)
C11—C12—C13—C14	−1.0 (8)	C7—C6—C5—C4	175.9 (6)
N1—C1—C6—C7	2.8 (8)	C1—C6—C5—C4	−0.1 (9)
C2—C1—C6—C7	−178.5 (5)	N3—C17—C18—C19	175.8 (6)
N1—C1—C6—C5	178.9 (5)	C22—C17—C18—C19	−0.9 (10)
C2—C1—C6—C5	−2.3 (8)	C17—C18—C19—C20	1.4 (12)
C5—C6—C7—C8	−178.2 (6)	N3—C17—C22—C21	−174.9 (6)
C1—C6—C7—C8	−2.2 (9)	C18—C17—C22—C21	1.9 (10)
C6—C7—C8—C9	1.3 (9)	C17—C22—C21—C20	−3.5 (13)
N1—C9—C8—C7	−0.8 (8)	C22—C21—C20—C19	3.8 (14)
C10—C9—C8—C7	178.9 (5)	C18—C19—C20—C21	−2.8 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl2i	0.86	2.58	3.363 (4)	151
C10—H10···Cl2ii	0.93	2.81	3.679 (7)	157
C20—H20···Cl1iii	0.93	2.80	3.692 (11)	160

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H3ACl2i	0.86	2.58	3.363(4)	151
C10H10Cl2ii	0.93	2.81	3.679(7)	157
C20H20Cl1iii	0.93	2.80	3.692(11)	160

Symmetry codes: (i) ; (ii) ; (iii) .