Di-μ-chlorido-bis­{aqua­chlorido[3-ethyl-4-phenyl-5-(2-pyrid­yl)-4H-1,2,4-triazole-κ2N1,N5]manganese(II)}

Wang, Z.; Gong, I.; Liu, C.; Zhang, X.

doi:10.1107/S1600536808044103

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page m157

doi:10.1107/S1600536808044103

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Di-μ-chlorido-bis{aquachlorido[3-ethyl-4-phenyl-5-(2-pyridyl)-4H-1,2,4-triazole-κ²N¹,N⁵]manganese(II)}

Zuoxiang Wang,^a ^* Ixaoning Gong,^a Chunyi Liu ^b and Xiaoming Zhang ^a

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China, and ^bJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: wangzx0908@yahoo.com.cn

(Received 15 December 2008; accepted 29 December 2008; online 8 January 2009)

In the centrosymmetric dinuclear title compound, [Mn₂Cl₄(C₁₅H₁₄N₄)₂(H₂O)₂], the Mn^II atom is coordinated by an N,N′-bidentate ligand, a water molecule, a terminal chloride ion and two bridging chloride ions in a distorted MnN₂OCl₃ octahedral geometry. The Mn⋯Mn separation is 3.6563 (9) Å. In the crystal structure, O—H⋯N and O—H⋯Cl hydrogen bonds help to establish the packing.

Related literature

For background, see: Klingele et al. (2005 ), Kume et al. (2006 ).

Experimental

Crystal data

[Mn₂Cl₄(C₁₅H₁₄N₄)₂(H₂O)₂]
M_r = 788.32
Monoclinic, P 2₁ /c
a = 9.9369 (15) Å
b = 8.9369 (13) Å
c = 19.642 (3) Å
β = 103.323 (2)°
V = 1697.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.10 mm⁻¹
T = 293 (2) K
0.32 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.72, T_max = 0.77
8811 measured reflections
3329 independent reflections
2364 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.105
S = 1.02
3329 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Mn1—O1	2.273 (2)
Mn1—N2	2.280 (3)
Mn1—N1	2.344 (3)
Mn1—Cl2	2.4544 (11)
Mn1—Cl1	2.5252 (11)
Mn1—Cl1ⁱ	2.5387 (11)

Mn1—Cl1—Mn1ⁱ	92.45 (4)
Symmetry code: (i) -x+1, -y+2, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl2ⁱⁱ	0.85	2.28	3.122 (3)	170
O1—H1C⋯N3ⁱⁱ	0.85	2.12	2.875 (4)	148
Symmetry code: (ii) -x+1, -y+1, -z+1.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808044103/hb2883sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808044103/hb2883Isup2.hkl

checkCIF report

Comment top

The 1,2,4-triazole ring can act as a bidentate ligand in coordination chemistry (e.g. Klingele et al., 2005; Kume et al. 2006). We report here the synthesis and crystal structure analysis of the title compound, (I).

The structure of (I) is shown in Fig.1. The title compound is a centrosymmetric dinuclear maganese(II) complex bridged by two chloride ions (Table 1). The dihedral angle between the triazole and pyridine rings is 9.42 (24)°, and that between the triazole and benzene rings is 80.53 (12)°. In the crystal, O—H···N and O—H···Cl hydrogen bonds (Table 2) help to establish the packing.

Related literature top

For background, see: Klingele et al. (2005); Kume et al. (2006).

Experimental top

To a warm solution of 0.501 g of 3-ethyl-4-phenyl-5-(2-pyridyl)-1,2,4-triazole (2.0 mmol) in 10 ml ethanol, 0.792 g of manganese(II) chloride tetrahydrate (4.0 mmol) in 10 ml water was added. The filtrate was left to stand at room temperature for several days, and pale yellow blocks of (I) were collected.

Computing details top

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

Figures top

Fig. 1. The molecular structure of (I) with Displacement ellipsoids shown at the 30% probability level and H atoms omitted for clarity. Mn1A and the unlabelled atoms are generated by the symmetry operation (1–x, 2–y, 1–z).

Di-µ-chlorido-bis{aquachlorido[3-ethyl-4-phenyl-5-(2-pyridyl)-4H- 1,2,4-triazole-κ²N¹,N⁵]manganese(II)} top

Crystal data top

[Mn₂Cl₄(C₁₅H₁₄N₄)₂(H₂O)₂]	F(000) = 804
M_r = 788.32	D_x = 1.542 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4766 reflections
a = 9.9369 (15) Å	θ = 2.5–28.0°
b = 8.9369 (13) Å	µ = 1.10 mm⁻¹
c = 19.642 (3) Å	T = 293 K
β = 103.323 (2)°	Block, pale yellow
V = 1697.3 (4) Å³	0.32 × 0.26 × 0.24 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	3329 independent reflections
Radiation source: sealed tube	2364 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→8
T_min = 0.72, T_max = 0.77	k = −11→10
8811 measured reflections	l = −24→24

Refinement top

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.04P)² + 0.95P] where P = (F_o² + 2F_c²)/3
3329 reflections	(Δ/σ)_max < 0.001
209 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Mn₂Cl₄(C₁₅H₁₄N₄)₂(H₂O)₂]	V = 1697.3 (4) Å³
M_r = 788.32	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.9369 (15) Å	µ = 1.10 mm⁻¹
b = 8.9369 (13) Å	T = 293 K
c = 19.642 (3) Å	0.32 × 0.26 × 0.24 mm
β = 103.323 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	3329 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2364 reflections with I > 2σ(I)
T_min = 0.72, T_max = 0.77	R_int = 0.045
8811 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.02	Δρ_max = 0.35 e Å⁻³
3329 reflections	Δρ_min = −0.44 e Å⁻³
209 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.52358 (6)	0.80195 (6)	0.52295 (3)	0.03231 (16)
Cl1	0.32636 (10)	0.98690 (10)	0.50448 (4)	0.0327 (2)
Cl2	0.46719 (10)	0.68828 (10)	0.40606 (4)	0.0340 (2)
C1	0.5362 (4)	0.9652 (4)	0.67503 (19)	0.0356 (9)
H1	0.4723	1.0295	0.6477	0.043*
C2	0.5739 (4)	0.9897 (5)	0.7457 (2)	0.0416 (10)
H2	0.5393	1.0715	0.7654	0.050*
C3	0.6643 (4)	0.8909 (5)	0.78734 (19)	0.0404 (10)
H3	0.6896	0.9038	0.8356	0.049*
C4	0.7167 (4)	0.7719 (4)	0.75560 (18)	0.0365 (9)
H4	0.7757	0.7025	0.7825	0.044*
C5	0.6801 (3)	0.7581 (4)	0.68393 (18)	0.0263 (7)
C6	0.7326 (4)	0.6459 (4)	0.64299 (19)	0.0324 (8)
C7	0.8480 (4)	0.4695 (4)	0.60588 (18)	0.0335 (8)
C8	0.9328 (5)	0.3335 (5)	0.60667 (19)	0.0438 (10)
H8A	1.0122	0.3415	0.6459	0.053*
H8B	0.8786	0.2488	0.6159	0.053*
C9	0.9834 (4)	0.2988 (5)	0.5451 (2)	0.0422 (10)
H9A	0.9074	0.2977	0.5047	0.063*
H9B	1.0272	0.2024	0.5506	0.063*
H9C	1.0492	0.3734	0.5390	0.063*
C10	0.8737 (4)	0.4760 (4)	0.73627 (18)	0.0368 (9)
C11	1.0054 (4)	0.5134 (5)	0.77226 (18)	0.0390 (9)
H11	1.0620	0.5727	0.7517	0.047*
C12	1.0518 (4)	0.4594 (5)	0.84098 (19)	0.0397 (10)
H12	1.1397	0.4835	0.8670	0.048*
C13	0.9654 (4)	0.3702 (5)	0.86918 (19)	0.0420 (10)
H13	0.9960	0.3335	0.9144	0.050*
C14	0.8336 (5)	0.3345 (5)	0.83126 (19)	0.0421 (10)
H14	0.7758	0.2764	0.8517	0.051*
C15	0.7878 (5)	0.3844 (5)	0.7637 (2)	0.0443 (10)
H15	0.7012	0.3570	0.7372	0.053*
N1	0.5877 (3)	0.8514 (3)	0.64330 (14)	0.0303 (7)
N2	0.7055 (3)	0.6526 (3)	0.57301 (15)	0.0322 (7)
N3	0.7784 (3)	0.5400 (3)	0.55068 (15)	0.0329 (7)
N4	0.8223 (3)	0.5325 (3)	0.66508 (14)	0.0313 (7)
O1	0.3944 (3)	0.6254 (3)	0.56175 (12)	0.0321 (6)
H1A	0.4420	0.5461	0.5721	0.039*
H1C	0.3228	0.6062	0.5299	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0361 (3)	0.0276 (3)	0.0307 (3)	0.0000 (2)	0.0025 (2)	0.0027 (2)
Cl1	0.0357 (5)	0.0278 (4)	0.0319 (4)	−0.0004 (4)	0.0022 (4)	0.0028 (3)
Cl2	0.0396 (5)	0.0281 (5)	0.0320 (4)	0.0000 (4)	0.0033 (4)	0.0023 (3)
C1	0.044 (2)	0.0233 (18)	0.039 (2)	0.0110 (16)	0.0080 (17)	−0.0013 (16)
C2	0.043 (2)	0.040 (2)	0.044 (2)	0.0019 (18)	0.0136 (19)	−0.0123 (18)
C3	0.040 (2)	0.054 (3)	0.0277 (18)	0.002 (2)	0.0079 (17)	−0.0088 (18)
C4	0.039 (2)	0.039 (2)	0.0292 (18)	0.0055 (18)	0.0043 (16)	0.0020 (16)
C5	0.0177 (15)	0.0252 (17)	0.0346 (17)	−0.0063 (13)	0.0027 (14)	0.0008 (14)
C6	0.037 (2)	0.0271 (18)	0.0341 (19)	0.0037 (16)	0.0110 (17)	0.0057 (15)
C7	0.039 (2)	0.0322 (19)	0.0292 (18)	0.0090 (17)	0.0079 (16)	−0.0013 (15)
C8	0.061 (3)	0.041 (2)	0.031 (2)	0.021 (2)	0.0134 (19)	0.0053 (17)
C9	0.040 (2)	0.045 (2)	0.042 (2)	0.0178 (19)	0.0108 (18)	0.0159 (19)
C10	0.045 (2)	0.035 (2)	0.0272 (17)	0.0145 (18)	0.0007 (17)	0.0003 (16)
C11	0.047 (2)	0.043 (2)	0.0253 (17)	0.0156 (19)	0.0036 (18)	−0.0038 (16)
C12	0.041 (2)	0.045 (2)	0.0313 (19)	0.0245 (19)	0.0045 (18)	0.0087 (17)
C13	0.047 (3)	0.047 (2)	0.0293 (19)	0.024 (2)	0.0044 (18)	0.0118 (17)
C14	0.049 (3)	0.043 (2)	0.0313 (19)	0.0236 (19)	0.0022 (18)	0.0072 (16)
C15	0.042 (2)	0.052 (3)	0.038 (2)	0.007 (2)	0.0074 (19)	0.0102 (19)
N1	0.0344 (17)	0.0319 (16)	0.0232 (14)	0.0032 (13)	0.0036 (13)	0.0050 (12)
N2	0.0368 (18)	0.0262 (16)	0.0313 (16)	0.0005 (13)	0.0029 (14)	0.0041 (12)
N3	0.0374 (18)	0.0287 (16)	0.0303 (15)	0.0047 (14)	0.0027 (13)	0.0028 (12)
N4	0.0355 (17)	0.0337 (16)	0.0224 (14)	0.0055 (14)	0.0019 (13)	0.0034 (12)
O1	0.0367 (14)	0.0260 (13)	0.0330 (13)	−0.0022 (11)	0.0066 (11)	0.0033 (10)

Geometric parameters (Å, º) top

Mn1—O1	2.273 (2)	C7—C8	1.477 (5)
Mn1—N2	2.280 (3)	C8—C9	1.447 (5)
Mn1—N1	2.344 (3)	C8—H8A	0.9700
Mn1—Cl2	2.4544 (11)	C8—H8B	0.9700
Mn1—Cl1	2.5252 (11)	C9—H9A	0.9600
Mn1—Cl1ⁱ	2.5387 (11)	C9—H9B	0.9600
Cl1—Mn1ⁱ	2.5387 (11)	C9—H9C	0.9600
C1—N1	1.353 (5)	C10—C11	1.377 (6)
C1—C2	1.369 (5)	C10—C15	1.379 (6)
C1—H1	0.9300	C10—N4	1.463 (4)
C2—C3	1.385 (6)	C11—C12	1.407 (5)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.393 (5)	C12—C13	1.378 (6)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.376 (5)	C13—C14	1.387 (6)
C4—H4	0.9300	C13—H13	0.9300
C5—N1	1.356 (4)	C14—C15	1.374 (5)
C5—C6	1.455 (5)	C14—H14	0.9300
C6—N2	1.340 (5)	C15—H15	0.9300
C6—N4	1.354 (5)	N2—N3	1.370 (4)
C7—N3	1.306 (4)	O1—H1A	0.8500
C7—N4	1.368 (4)	O1—H1C	0.8500

O1—Mn1—N2	84.37 (10)	C9—C8—H8B	107.7
O1—Mn1—N1	80.58 (10)	C7—C8—H8B	107.7
N2—Mn1—N1	70.80 (10)	H8A—C8—H8B	107.1
O1—Mn1—Cl2	90.09 (7)	C8—C9—H9A	109.5
N2—Mn1—Cl2	98.54 (8)	C8—C9—H9B	109.5
N1—Mn1—Cl2	166.35 (8)	H9A—C9—H9B	109.5
O1—Mn1—Cl1	91.32 (7)	C8—C9—H9C	109.5
N2—Mn1—Cl1	163.18 (8)	H9A—C9—H9C	109.5
N1—Mn1—Cl1	92.47 (8)	H9B—C9—H9C	109.5
Cl2—Mn1—Cl1	97.71 (3)	C11—C10—C15	122.9 (4)
O1—Mn1—Cl1ⁱ	172.57 (7)	C11—C10—N4	119.2 (4)
N2—Mn1—Cl1ⁱ	94.62 (8)	C15—C10—N4	117.8 (4)
N1—Mn1—Cl1ⁱ	92.13 (8)	C10—C11—C12	118.2 (4)
Cl2—Mn1—Cl1ⁱ	97.34 (4)	C10—C11—H11	120.9
Cl1—Mn1—Cl1ⁱ	87.55 (4)	C12—C11—H11	120.9
Mn1—Cl1—Mn1ⁱ	92.45 (4)	C13—C12—C11	119.1 (4)
N1—C1—C2	122.9 (3)	C13—C12—H12	120.4
N1—C1—H1	118.6	C11—C12—H12	120.4
C2—C1—H1	118.6	C12—C13—C14	121.1 (4)
C1—C2—C3	119.1 (4)	C12—C13—H13	119.4
C1—C2—H2	120.5	C14—C13—H13	119.4
C3—C2—H2	120.5	C15—C14—C13	120.3 (4)
C2—C3—C4	118.7 (3)	C15—C14—H14	119.8
C2—C3—H3	120.6	C13—C14—H14	119.8
C4—C3—H3	120.6	C14—C15—C10	118.3 (4)
C5—C4—C3	119.2 (4)	C14—C15—H15	120.9
C5—C4—H4	120.4	C10—C15—H15	120.9
C3—C4—H4	120.4	C1—N1—C5	117.9 (3)
N1—C5—C4	122.0 (3)	C1—N1—Mn1	124.2 (2)
N1—C5—C6	112.3 (3)	C5—N1—Mn1	117.9 (2)
C4—C5—C6	125.7 (3)	C6—N2—N3	107.5 (3)
N2—C6—N4	108.9 (3)	C6—N2—Mn1	114.8 (2)
N2—C6—C5	121.6 (3)	N3—N2—Mn1	135.8 (2)
N4—C6—C5	129.2 (3)	C7—N3—N2	107.8 (3)
N3—C7—N4	109.9 (3)	C6—N4—C7	105.9 (3)
N3—C7—C8	126.7 (3)	C6—N4—C10	128.6 (3)
N4—C7—C8	123.2 (3)	C7—N4—C10	125.3 (3)
C9—C8—C7	118.3 (3)	Mn1—O1—H1A	109.5
C9—C8—H8A	107.7	Mn1—O1—H1C	109.5
C7—C8—H8A	107.7	H1A—O1—H1C	109.5

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl2ⁱⁱ	0.85	2.28	3.122 (3)	170
O1—H1C···N3ⁱⁱ	0.85	2.12	2.875 (4)	148

Symmetry code: (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Mn₂Cl₄(C₁₅H₁₄N₄)₂(H₂O)₂]
M_r	788.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.9369 (15), 8.9369 (13), 19.642 (3)
β (°)	103.323 (2)
V (Å³)	1697.3 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.10
Crystal size (mm)	0.32 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.72, 0.77
No. of measured, independent and observed [I > 2σ(I)] reflections	8811, 3329, 2364
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.105, 1.02
No. of reflections	3329
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.44

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Mn1—O1	2.273 (2)	Mn1—Cl2	2.4544 (11)
Mn1—N2	2.280 (3)	Mn1—Cl1	2.5252 (11)
Mn1—N1	2.344 (3)	Mn1—Cl1ⁱ	2.5387 (11)

Mn1—Cl1—Mn1ⁱ	92.45 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl2ⁱⁱ	0.85	2.28	3.122 (3)	170
O1—H1C···N3ⁱⁱ	0.85	2.12	2.875 (4)	148

Symmetry code: (ii) −x+1, −y+1, −z+1.

Acknowledgements

The authors are grateful to Jingye Pharmachemical Pilot Plant for financial assistance through project No. 8507041056.

References

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