Bis[μ-N-(2-oxidobenzyl-idene)pyridine-2-carbohydrazidato]bis-[chlorido(methanol-κO)erbium(III)].

In the binuclear title complex, [Er(2)(C(13)H(9)N(3)O(2))(2)Cl(2)(CH(3)OH)(2)], the entire mol-ecule is generated by the application of inversion symmetry. Each Er(III) ion is seven-coordinated by two O atoms and one N atom from one N-(2-oxidobenzyl-idene)pyridine-2-carbohydrazidate (L(2-)) ligand, one O atom and one N atom from the symmetry-related L(2-) ligand, one O atom of a methanol mol-ecule and one chloride anion. The coordination geometry is based on a pseudo-penta-gonal bipyramid. Linear supra-molecular chains along [010] are formed in the crystal packing through O-H⋯Cl hydrogen bonds.

Related literature

For complexes containing salicyl­aldehyde-2-pyridine­carboxyl-hydrazone and related ligands, see: Guo et al. (2011a ▶,b ▶); Bai et al. (2005 ▶, 2006 ▶); Wu et al. (2004 ▶); Milway et al. (2003 ▶). For the mechanism of the hydrolysis of salicyl­aldehyde thio­semicarbazone, see: Narang & Aggarwal (1974 ▶).

Experimental

Crystal data

[Er2(C13H9N3O2)2Cl2(CH4O)2]

M = 947.97

Monoclinic,

a = 9.5810 (4) Å

b = 7.0906 (3) Å

c = 22.3504 (8) Å

β = 96.920 (3)°

V = 1507.31 (10) Å3

Z = 2

Mo Kα radiation

μ = 5.76 mm−1

T = 128 K

0.15 × 0.13 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2000 ▶) T min = 0.479, T max = 0.545

14182 measured reflections

3732 independent reflections

2931 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.059

S = 0.99

3732 reflections

200 parameters

H-atom parameters constrained

Δρmax = 1.25 e Å−3

Δρmin = −0.71 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812013979/tk5069sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812013979/tk5069Isup2.hkl

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

[Er2(C13H9N3O2)2Cl2(CH4O)2]	F(000) = 908
Mr = 947.97	Dx = 2.089 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4466 reflections
a = 9.5810 (4) Å	θ = 2.7–28.1°
b = 7.0906 (3) Å	µ = 5.76 mm−1
c = 22.3504 (8) Å	T = 128 K
β = 96.920 (3)°	Block, yellow
V = 1507.31 (10) Å3	0.15 × 0.13 × 0.12 mm
Z = 2

Bruker SMART CCD diffractometer	3732 independent reflections
Radiation source: fine-focus sealed tube	2931 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ scans and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker 2000)	h = −12→11
Tmin = 0.479, Tmax = 0.545	k = −9→9
14182 measured reflections	l = −29→29

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0299P)2] where P = (Fo2 + 2Fc2)/3
3732 reflections	(Δ/σ)max = 0.004
200 parameters	Δρmax = 1.25 e Å−3
0 restraints	Δρmin = −0.71 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
Er1	0.372121 (17)	0.91591 (3)	0.432040 (7)	0.02740 (6)
O2	0.5836 (3)	1.0615 (4)	0.46548 (11)	0.0323 (6)
O3	0.2988 (3)	1.2290 (5)	0.42893 (15)	0.0526 (8)
H7	0.3591	1.3150	0.4521	0.063*
C5	0.6425 (4)	1.0757 (5)	0.36561 (16)	0.0289 (8)
Cl1	0.48595 (13)	0.58790 (16)	0.42195 (5)	0.0476 (3)
N1	0.5108 (3)	1.0104 (5)	0.34970 (14)	0.0282 (7)
O1	0.1993 (3)	0.8698 (4)	0.36235 (12)	0.0386 (7)
C14	0.0511 (4)	0.7742 (6)	0.46482 (18)	0.0366 (9)
H14	−0.0122	0.7498	0.4935	0.044*
C8	0.0727 (4)	0.7952 (5)	0.35398 (17)	0.0306 (9)
C6	0.6814 (4)	1.1036 (5)	0.43082 (17)	0.0287 (8)
N3	0.1753 (3)	0.8294 (5)	0.48577 (14)	0.0308 (7)
N4	0.8066 (3)	1.1581 (5)	0.45048 (14)	0.0344 (8)
C1	0.4695 (4)	0.9753 (6)	0.29156 (18)	0.0343 (9)
H1	0.3765	0.9309	0.2802	0.041*
C4	0.7340 (4)	1.1077 (6)	0.32293 (18)	0.0373 (10)
H4	0.8257	1.1559	0.3347	0.045*
C10	−0.1348 (5)	0.6619 (7)	0.3905 (2)	0.0435 (11)
H10	−0.1858	0.6313	0.4230	0.052*
C12	−0.1223 (5)	0.6715 (7)	0.2860 (2)	0.0440 (11)
H12	−0.1625	0.6447	0.2459	0.053*
C9	−0.0018 (4)	0.7457 (6)	0.40305 (17)	0.0332 (8)
C3	0.6899 (5)	1.0688 (6)	0.26356 (19)	0.0413 (10)
H3	0.7513	1.0886	0.2338	0.050*
C13	0.0074 (4)	0.7590 (6)	0.29574 (18)	0.0366 (9)
H13	0.0532	0.7954	0.2621	0.044*
C2	0.5561 (5)	1.0008 (7)	0.24736 (18)	0.0393 (10)
H2	0.5241	0.9721	0.2065	0.047*
C11	−0.1934 (5)	0.6230 (7)	0.3332 (2)	0.0499 (12)
H11	−0.2825	0.5629	0.3262	0.060*
C7	0.1756 (6)	1.3080 (8)	0.3970 (3)	0.0722 (17)
H7A	0.1078	1.2075	0.3850	0.108*
H7B	0.2000	1.3728	0.3609	0.108*
H7C	0.1341	1.3985	0.4229	0.108*

	U11	U22	U33	U12	U13	U23
Er1	0.02276 (9)	0.03156 (11)	0.02796 (10)	−0.00645 (8)	0.00334 (6)	−0.00213 (8)
O2	0.0269 (13)	0.0435 (18)	0.0273 (14)	−0.0087 (12)	0.0062 (10)	−0.0013 (12)
O3	0.0461 (19)	0.0366 (19)	0.073 (2)	0.0010 (15)	−0.0021 (15)	−0.0050 (17)
C5	0.0294 (18)	0.027 (2)	0.0304 (19)	−0.0045 (16)	0.0041 (15)	0.0008 (17)
Cl1	0.0544 (7)	0.0371 (6)	0.0535 (7)	0.0029 (5)	0.0145 (5)	0.0048 (5)
N1	0.0286 (16)	0.0276 (17)	0.0285 (17)	−0.0043 (13)	0.0038 (13)	−0.0008 (14)
O1	0.0266 (14)	0.054 (2)	0.0347 (16)	−0.0102 (13)	0.0012 (11)	−0.0015 (13)
C14	0.0283 (19)	0.042 (3)	0.040 (2)	−0.0070 (18)	0.0065 (16)	−0.003 (2)
C8	0.0251 (18)	0.032 (2)	0.034 (2)	0.0003 (15)	−0.0017 (15)	−0.0056 (17)
C6	0.0285 (19)	0.031 (2)	0.0273 (19)	−0.0042 (16)	0.0040 (14)	−0.0006 (16)
N3	0.0264 (16)	0.0361 (19)	0.0299 (17)	−0.0075 (14)	0.0033 (13)	−0.0026 (14)
N4	0.0288 (17)	0.046 (2)	0.0289 (18)	−0.0093 (15)	0.0066 (14)	−0.0029 (15)
C1	0.035 (2)	0.038 (3)	0.029 (2)	−0.0038 (17)	0.0004 (16)	0.0010 (18)
C4	0.032 (2)	0.045 (3)	0.035 (2)	−0.0083 (19)	0.0059 (16)	0.003 (2)
C10	0.035 (2)	0.048 (3)	0.046 (3)	−0.012 (2)	0.0013 (19)	−0.002 (2)
C12	0.036 (2)	0.047 (3)	0.046 (3)	−0.003 (2)	−0.0083 (19)	−0.011 (2)
C9	0.0263 (18)	0.036 (2)	0.036 (2)	−0.0036 (18)	0.0003 (15)	−0.0054 (19)
C3	0.041 (2)	0.049 (3)	0.036 (2)	0.002 (2)	0.0135 (18)	0.005 (2)
C13	0.033 (2)	0.040 (2)	0.036 (2)	0.0003 (19)	0.0012 (16)	−0.006 (2)
C2	0.044 (2)	0.047 (3)	0.026 (2)	0.000 (2)	−0.0002 (18)	0.0001 (19)
C11	0.037 (2)	0.050 (3)	0.060 (3)	−0.018 (2)	−0.007 (2)	−0.005 (2)
C7	0.069 (4)	0.058 (4)	0.088 (4)	0.019 (3)	0.003 (3)	0.013 (3)

Er1—O1	2.157 (3)	C6—N4	1.286 (5)
Er1—O2i	2.284 (3)	N3—N4i	1.417 (4)
Er1—O2	2.316 (3)	N4—N3i	1.417 (4)
Er1—O3	2.327 (3)	C1—C2	1.376 (6)
Er1—N3	2.433 (3)	C1—H1	0.9500
Er1—N1	2.488 (3)	C4—C3	1.371 (6)
Er1—Cl1	2.5901 (12)	C4—H4	0.9500
O2—C6	1.320 (4)	C10—C11	1.362 (6)
O2—Er1i	2.284 (3)	C10—C9	1.403 (5)
O3—C7	1.419 (6)	C10—H10	0.9500
O3—H7	0.9500	C12—C11	1.369 (7)
C5—N1	1.351 (5)	C12—C13	1.382 (6)
C5—C4	1.390 (5)	C12—H12	0.9500
C5—C6	1.474 (5)	C3—C2	1.377 (6)
N1—C1	1.335 (5)	C3—H3	0.9500
O1—C8	1.316 (4)	C13—H13	0.9500
C14—N3	1.286 (5)	C2—H2	0.9500
C14—C9	1.427 (5)	C11—H11	0.9500
C14—H14	0.9500	C7—H7A	0.9800
C8—C13	1.398 (5)	C7—H7B	0.9800
C8—C9	1.423 (5)	C7—H7C	0.9800
O1—Er1—O2i	140.21 (10)	O1—C8—C13	120.5 (4)
O1—Er1—O2	149.99 (10)	O1—C8—C9	122.0 (3)
O2i—Er1—O2	66.16 (10)	C13—C8—C9	117.5 (3)
O1—Er1—O3	85.42 (12)	N4—C6—O2	124.5 (3)
O2i—Er1—O3	88.97 (11)	N4—C6—C5	119.5 (3)
O2—Er1—O3	80.42 (11)	O2—C6—C5	115.9 (3)
O1—Er1—N3	75.24 (10)	C14—N3—N4i	112.4 (3)
O2i—Er1—N3	65.42 (10)	C14—N3—Er1	129.4 (3)
O2—Er1—N3	130.77 (10)	N4i—N3—Er1	118.2 (2)
O3—Er1—N3	90.34 (11)	C6—N4—N3i	111.0 (3)
O1—Er1—N1	86.47 (10)	N1—C1—C2	122.7 (4)
O2i—Er1—N1	132.20 (10)	N1—C1—H1	118.6
O2—Er1—N1	66.06 (9)	C2—C1—H1	118.6
O3—Er1—N1	84.69 (11)	C3—C4—C5	119.0 (4)
N3—Er1—N1	161.38 (11)	C3—C4—H4	120.5
O1—Er1—Cl1	95.50 (9)	C5—C4—H4	120.5
O2i—Er1—Cl1	96.94 (7)	C11—C10—C9	122.4 (4)
O2—Er1—Cl1	93.86 (7)	C11—C10—H10	118.8
O3—Er1—Cl1	169.37 (9)	C9—C10—H10	118.8
N3—Er1—Cl1	100.15 (8)	C11—C12—C13	120.8 (4)
N1—Er1—Cl1	84.80 (8)	C11—C12—H12	119.6
O1—Er1—Er1i	167.32 (8)	C13—C12—H12	119.6
O2i—Er1—Er1i	33.34 (6)	C10—C9—C8	118.5 (4)
O2—Er1—Er1i	32.82 (6)	C10—C9—C14	117.5 (4)
O3—Er1—Er1i	83.65 (8)	C8—C9—C14	123.9 (3)
N3—Er1—Er1i	98.39 (7)	C4—C3—C2	119.6 (4)
N1—Er1—Er1i	98.87 (7)	C4—C3—H3	120.2
Cl1—Er1—Er1i	96.43 (3)	C2—C3—H3	120.2
C6—O2—Er1i	120.9 (2)	C12—C13—C8	121.5 (4)
C6—O2—Er1	124.5 (2)	C12—C13—H13	119.3
Er1i—O2—Er1	113.84 (10)	C8—C13—H13	119.3
C7—O3—Er1	128.4 (3)	C1—C2—C3	118.7 (4)
C7—O3—H7	115.8	C1—C2—H2	120.7
Er1—O3—H7	115.8	C3—C2—H2	120.7
N1—C5—C4	121.5 (4)	C10—C11—C12	119.2 (4)
N1—C5—C6	115.0 (3)	C10—C11—H11	120.4
C4—C5—C6	123.5 (3)	C12—C11—H11	120.4
C1—N1—C5	118.5 (3)	O3—C7—H7A	109.5
C1—N1—Er1	123.2 (3)	O3—C7—H7B	109.5
C5—N1—Er1	117.6 (2)	H7A—C7—H7B	109.5
C8—O1—Er1	141.0 (2)	O3—C7—H7C	109.5
N3—C14—C9	126.9 (4)	H7A—C7—H7C	109.5
N3—C14—H14	116.5	H7B—C7—H7C	109.5
C9—C14—H14	116.5

D—H···A	D—H	H···A	D···A	D—H···A
O3—H7···Cl1ii	0.95	2.42	3.128 (4)	131

Table 1

Selected bond lengths (Å)

Er1—O1	2.157 (3)
Er1—O2i	2.284 (3)
Er1—O2	2.316 (3)
Er1—O3	2.327 (3)
Er1—N3	2.433 (3)
Er1—N1	2.488 (3)
Er1—Cl1	2.5901 (12)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H7⋯Cl1ii	0.95	2.42	3.128 (4)	131

Symmetry code: (ii) .