Dibromido{N'-[1-(pyridin-2-yl)ethyl-idene]picolinohydrazide-κ(2)N',O}cadmium.

The title compound, [CdBr(2)(C(13)H(12)N(4)O)], was obtained from the reaction of Cd(NO(3))(2)·4H(2)O with meth-yl(pyridin-2-yl)methanone picolinoylhydrazone and sodium bromide. The Cd(2+) cation is ligated by one O atom and two N atoms of the tridentate ligand and two bromide anions, forming a Br(2)CdN(2)O polyhedron with a distorted trigonal-bipyramidal coordination geometry. In the crystal, non-classical C-H⋯Br hydrogen bonds are observed. In addition, π-π stacking inter-actions [centroid-centroid distance = 3.7455 (19) Å] contribute to the stabilization of the crystal structure.

Related literature

For related complexes with similar tridentate ligands, see: Kasuga et al. (2001 ▶); Chen et al. (2005 ▶); Datta et al. (2011 ▶).

Experimental

Crystal data

[CdBr2(C13n class="Species">H12N4O)]

M = 512.48

Monoclinic,

a = 8.1336 (3) Å

b = 13.6111 (5) Å

c = 14.6102 (5) Å

β = 90.550 (1)°

V = 1617.38 (10) Å3

Z = 4

Mo Kα radiation

μ = 6.29 mm−1

T = 296 K

0.32 × 0.18 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.267, T max = 0.365

15317 measured reflections

3874 independent reflections

2859 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.062

S = 1.02

3874 reflections

195 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.54 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812023185/vm2176sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023185/vm2176Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[CdBr2(C13H12N4O)]	F(000) = 976
Mr = 512.48	Dx = 2.105 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 545 reflections
a = 8.1336 (3) Å	θ = 4.2–18.3°
b = 13.6111 (5) Å	µ = 6.29 mm−1
c = 14.6102 (5) Å	T = 296 K
β = 90.550 (1)°	Prism, colourless
V = 1617.38 (10) Å3	0.32 × 0.18 × 0.16 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	3874 independent reflections
Radiation source: fine-focus sealed tube	2859 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 28.1°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.267, Tmax = 0.365	k = −17→18
15317 measured reflections	l = −19→18

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0245P)2 + 0.5132P] where P = (Fo2 + 2Fc2)/3
3874 reflections	(Δ/σ)max = 0.001
195 parameters	Δρmax = 0.47 e Å−3
1 restraint	Δρmin = −0.54 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
Cd1	0.32238 (3)	0.16938 (2)	0.27655 (2)	0.0429 (1)
Br1	0.04606 (5)	0.15378 (3)	0.35202 (3)	0.0626 (1)
Br2	0.42596 (5)	0.34049 (2)	0.23982 (3)	0.0550 (1)
O1	0.2555 (3)	0.10824 (15)	0.12175 (14)	0.0493 (8)
N1	0.5195 (3)	0.12698 (18)	0.38976 (17)	0.0438 (9)
N2	0.4511 (3)	0.02135 (16)	0.24438 (15)	0.0370 (8)
N3	0.4106 (3)	−0.02318 (18)	0.16427 (17)	0.0401 (8)
N4	0.3565 (3)	−0.11450 (19)	0.01147 (18)	0.0495 (10)
C1	0.5632 (5)	0.1867 (2)	0.4579 (2)	0.0555 (11)
C2	0.6781 (5)	0.1618 (3)	0.5230 (2)	0.0585 (11)
C3	0.7498 (4)	0.0712 (3)	0.5186 (2)	0.0585 (14)
C4	0.7079 (4)	0.0090 (2)	0.4477 (2)	0.0487 (11)
C5	0.5925 (4)	0.0390 (2)	0.3832 (2)	0.0385 (9)
C6	0.5464 (3)	−0.0217 (2)	0.3021 (2)	0.0377 (9)
C7	0.6137 (5)	−0.1226 (2)	0.2915 (2)	0.0577 (11)
C8	0.3114 (4)	0.0268 (2)	0.1050 (2)	0.0392 (9)
C9	0.2810 (4)	−0.0274 (2)	0.01743 (19)	0.0381 (9)
C10	0.1844 (4)	0.0113 (2)	−0.0505 (2)	0.0473 (11)
C11	0.1592 (4)	−0.0425 (2)	−0.1296 (2)	0.0523 (11)
C12	0.2361 (5)	−0.1319 (2)	−0.1370 (2)	0.0543 (11)
C13	0.3333 (5)	−0.1652 (2)	−0.0658 (2)	0.0569 (13)
H1	0.51340	0.24800	0.46140	0.0660*
H2	0.70680	0.20560	0.56930	0.0700*
H3	0.82590	0.05170	0.56290	0.0700*
H3N	0.434 (4)	−0.0819 (15)	0.150 (2)	0.056 (10)*
H4	0.75670	−0.05260	0.44310	0.0580*
H7A	0.54530	−0.15920	0.24990	0.0860*
H7B	0.61610	−0.15480	0.34990	0.0860*
H7C	0.72320	−0.11890	0.26780	0.0860*
H10	0.13630	0.07280	−0.04360	0.0570*
H11	0.09200	−0.01880	−0.17650	0.0630*
H12	0.22280	−0.16960	−0.18970	0.0650*
H13	0.38510	−0.22580	−0.07180	0.0680*

	U11	U22	U33	U12	U13	U23
Cd1	0.0474 (1)	0.0383 (1)	0.0428 (1)	0.0045 (1)	−0.0051 (1)	−0.0016 (1)
Br1	0.0532 (2)	0.0726 (3)	0.0622 (2)	−0.0011 (2)	0.0063 (2)	0.0021 (2)
Br2	0.0638 (2)	0.0413 (2)	0.0598 (2)	−0.0049 (2)	−0.0091 (2)	0.0024 (2)
O1	0.0616 (15)	0.0432 (13)	0.0429 (12)	0.0105 (11)	−0.0085 (11)	−0.0083 (10)
N1	0.0503 (16)	0.0397 (14)	0.0412 (15)	−0.0023 (12)	−0.0086 (12)	0.0021 (11)
N2	0.0393 (14)	0.0367 (13)	0.0350 (14)	−0.0022 (11)	−0.0031 (11)	−0.0016 (10)
N3	0.0476 (15)	0.0354 (14)	0.0373 (14)	−0.0005 (12)	−0.0045 (11)	−0.0063 (11)
N4	0.0654 (19)	0.0394 (15)	0.0436 (16)	0.0006 (13)	−0.0089 (13)	−0.0043 (12)
C1	0.075 (2)	0.0403 (18)	0.051 (2)	−0.0047 (17)	−0.0117 (18)	−0.0030 (15)
C2	0.071 (2)	0.061 (2)	0.0433 (19)	−0.0144 (19)	−0.0141 (17)	−0.0057 (16)
C3	0.056 (2)	0.073 (3)	0.046 (2)	−0.0134 (18)	−0.0175 (17)	0.0083 (17)
C4	0.0471 (19)	0.0505 (19)	0.0483 (19)	−0.0019 (15)	−0.0065 (15)	0.0107 (15)
C5	0.0371 (16)	0.0401 (16)	0.0381 (16)	−0.0056 (13)	−0.0025 (13)	0.0074 (13)
C6	0.0359 (16)	0.0361 (16)	0.0411 (17)	−0.0045 (13)	0.0005 (13)	0.0033 (13)
C7	0.065 (2)	0.0458 (19)	0.062 (2)	0.0137 (17)	−0.0072 (18)	−0.0003 (17)
C8	0.0396 (16)	0.0418 (17)	0.0362 (16)	−0.0092 (14)	−0.0016 (13)	0.0004 (13)
C9	0.0384 (16)	0.0383 (16)	0.0376 (16)	−0.0058 (13)	0.0000 (13)	−0.0005 (12)
C10	0.0495 (19)	0.0458 (18)	0.0464 (19)	0.0008 (15)	−0.0065 (15)	−0.0043 (15)
C11	0.056 (2)	0.057 (2)	0.0437 (19)	−0.0102 (17)	−0.0101 (16)	0.0044 (15)
C12	0.069 (2)	0.053 (2)	0.0408 (19)	−0.0194 (18)	−0.0046 (17)	−0.0082 (15)
C13	0.075 (3)	0.0397 (18)	0.056 (2)	−0.0021 (17)	−0.0054 (19)	−0.0107 (16)

Cd1—Br1	2.5218 (5)	C5—C6	1.490 (4)
Cd1—Br2	2.5359 (4)	C6—C7	1.487 (4)
Cd1—O1	2.466 (2)	C8—C9	1.495 (4)
Cd1—N1	2.364 (2)	C9—C10	1.366 (4)
Cd1—N2	2.321 (2)	C10—C11	1.382 (4)
O1—C8	1.224 (4)	C11—C12	1.373 (4)
N1—C1	1.331 (4)	C12—C13	1.377 (5)
N1—C5	1.341 (4)	C1—H1	0.9300
N2—N3	1.356 (3)	C2—H2	0.9300
N2—C6	1.282 (4)	C3—H3	0.9300
N3—C8	1.360 (4)	C4—H4	0.9300
N4—C9	1.338 (4)	C7—H7A	0.9600
N4—C13	1.335 (4)	C7—H7B	0.9600
N3—H3N	0.85 (2)	C7—H7C	0.9600
C1—C2	1.370 (5)	C10—H10	0.9300
C2—C3	1.366 (6)	C11—H11	0.9300
C3—C4	1.378 (4)	C12—H12	0.9300
C4—C5	1.385 (4)	C13—H13	0.9300
Br1—Cd1—Br2	117.98 (2)	O1—C8—N3	123.0 (3)
Br1—Cd1—O1	100.54 (6)	O1—C8—C9	124.0 (3)
Br1—Cd1—N1	105.95 (6)	C8—C9—C10	121.4 (3)
Br1—Cd1—N2	114.91 (6)	N4—C9—C8	114.9 (3)
Br2—Cd1—O1	100.76 (5)	N4—C9—C10	123.8 (3)
Br2—Cd1—N1	98.50 (6)	C9—C10—C11	118.9 (3)
Br2—Cd1—N2	127.09 (6)	C10—C11—C12	118.1 (3)
O1—Cd1—N1	134.55 (8)	C11—C12—C13	119.4 (3)
O1—Cd1—N2	67.49 (8)	N4—C13—C12	123.0 (3)
N1—Cd1—N2	68.01 (8)	N1—C1—H1	118.00
Cd1—O1—C8	114.21 (19)	C2—C1—H1	119.00
Cd1—N1—C1	123.3 (2)	C1—C2—H2	121.00
Cd1—N1—C5	117.77 (19)	C3—C2—H2	121.00
C1—N1—C5	118.9 (3)	C2—C3—H3	120.00
Cd1—N2—N3	117.17 (17)	C4—C3—H3	120.00
Cd1—N2—C6	122.33 (18)	C3—C4—H4	120.00
N3—N2—C6	120.3 (2)	C5—C4—H4	120.00
N2—N3—C8	117.6 (2)	C6—C7—H7A	109.00
C9—N4—C13	116.9 (3)	C6—C7—H7B	109.00
C8—N3—H3N	117 (2)	C6—C7—H7C	109.00
N2—N3—H3N	126 (2)	H7A—C7—H7B	109.00
N1—C1—C2	123.0 (3)	H7A—C7—H7C	109.00
C1—C2—C3	118.7 (3)	H7B—C7—H7C	109.00
C2—C3—C4	119.2 (3)	C9—C10—H10	121.00
C3—C4—C5	119.4 (3)	C11—C10—H10	121.00
N1—C5—C4	120.8 (3)	C10—C11—H11	121.00
C4—C5—C6	122.8 (3)	C12—C11—H11	121.00
N1—C5—C6	116.4 (3)	C11—C12—H12	120.00
N2—C6—C7	125.1 (3)	C13—C12—H12	120.00
C5—C6—C7	120.3 (2)	N4—C13—H13	119.00
N2—C6—C5	114.6 (2)	C12—C13—H13	119.00
N3—C8—C9	113.0 (2)
Br1—Cd1—O1—C8	−107.6 (2)	Cd1—N2—C6—C7	170.9 (2)
Br2—Cd1—O1—C8	131.0 (2)	Cd1—N2—N3—C8	6.6 (3)
N1—Cd1—O1—C8	17.6 (3)	Cd1—N2—C6—C5	−11.0 (3)
N2—Cd1—O1—C8	5.2 (2)	N3—N2—C6—C7	−3.4 (4)
Br1—Cd1—N1—C1	−76.1 (3)	N3—N2—C6—C5	174.8 (2)
Br2—Cd1—N1—C1	46.4 (3)	N2—N3—C8—O1	−1.5 (4)
O1—Cd1—N1—C1	160.7 (2)	N2—N3—C8—C9	177.5 (2)
N2—Cd1—N1—C1	173.0 (3)	C9—N4—C13—C12	−0.5 (5)
Br1—Cd1—N1—C5	105.4 (2)	C13—N4—C9—C8	−179.7 (3)
Br2—Cd1—N1—C5	−132.2 (2)	C13—N4—C9—C10	−0.4 (5)
O1—Cd1—N1—C5	−17.9 (3)	N1—C1—C2—C3	−0.8 (6)
N2—Cd1—N1—C5	−5.6 (2)	C1—C2—C3—C4	1.8 (5)
Br1—Cd1—N2—N3	85.55 (18)	C2—C3—C4—C5	−0.9 (5)
Br2—Cd1—N2—N3	−92.50 (19)	C3—C4—C5—N1	−1.0 (5)
O1—Cd1—N2—N3	−5.94 (17)	C3—C4—C5—C6	177.0 (3)
N1—Cd1—N2—N3	−176.5 (2)	N1—C5—C6—N2	5.2 (4)
Br1—Cd1—N2—C6	−88.8 (2)	C4—C5—C6—C7	5.3 (4)
Br2—Cd1—N2—C6	93.1 (2)	C4—C5—C6—N2	−172.9 (3)
O1—Cd1—N2—C6	179.7 (2)	N1—C5—C6—C7	−176.6 (3)
N1—Cd1—N2—C6	9.2 (2)	O1—C8—C9—N4	178.4 (3)
Cd1—O1—C8—C9	177.1 (2)	N3—C8—C9—C10	−179.9 (3)
Cd1—O1—C8—N3	−4.0 (4)	O1—C8—C9—C10	−1.0 (5)
Cd1—N1—C5—C6	2.6 (3)	N3—C8—C9—N4	−0.6 (4)
Cd1—N1—C1—C2	−179.7 (3)	N4—C9—C10—C11	1.4 (5)
C1—N1—C5—C4	2.0 (4)	C8—C9—C10—C11	−179.3 (3)
C1—N1—C5—C6	−176.1 (3)	C9—C10—C11—C12	−1.5 (5)
C5—N1—C1—C2	−1.1 (5)	C10—C11—C12—C13	0.7 (5)
Cd1—N1—C5—C4	−179.3 (2)	C11—C12—C13—N4	0.3 (6)
C6—N2—N3—C8	−178.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7C···Br2i	0.96	2.91	3.810 (4)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7C⋯Br2i	0.96	2.91	3.810 (4)	157

Symmetry code: (i) .