Tri­aqua(2,2′-bi­pyridine)(thio­phene-2,5-di­carboxyl­ato)­manganese(II) 4,4′-bi­pyridine hemisolvate trihydrate

Sun, X.-Z.; Ye, B.-H.

doi:10.1107/S1600536804012619

Triaqua(2,2'-bipyridine)(thiophene-2,5-dicarboxylato)manganese(II) 4,4'-bipyridine hemisolvate trihydrate

The title compound, [Mn(C₆H₂O₄S)(C₁₀H₈N₂)(H₂O)₃]·0.5C₁₀H₈N₂·3H₂O or [Mn(tdc)(bpy)(H₂O)₃]·3H₂O·0.5(bpyn) (tdc is thiophene-2,5-dicarboxylate, bpy is 2,2'-bipyridine and bpyn is 4,4'-bipyridine), crystallizes in space group P $\overline 1$ . Complex molecules are linked into one-dimensional chains, running along the b axis, by hydrogen bonds between the coordinated aqua ligands and uncoordinated carboxylate groups of tdc. Double-stranded chains consist of two of the one-dimensional chains and uncoordinated centrosymmetric bpyn molecules, connected by hydrogen bonds between N atoms of the bpyn molecules and coordinated aqua ligands. These double chains are further assembled into layers parallel to the ab plane, which extend into three-dimensional networks via hydrogen bonds between the coordinated and uncoordinated water molecules, and O atoms of tdc.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804012619/cv6316sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536804012619/cv6316Isup2.hkl Contains datablock I

CCDC reference: 242293

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.048
wR factor = 0.139
Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        C19

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: r3m software (Siemens, 1990); cell refinement: r3m software; data reduction: r3m software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXL97.

Triaqua(2,2'-bipyridine)(thiophene-2,5-dicarboxylato)manganese 4,4'-bipyridine hemisolvate trihydrate top

Crystal data top

[Mn(C₆H₂O₄S)(C₁₀H₈N₂)(H₂O)₃]·0.5C₁₀H₈N₂·3H2O	Z = 2
M_r = 567.45	F(000) = 588
Triclinic, P1	D_x = 1.462 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.172 (3) Å	Cell parameters from 25 reflections
b = 12.014 (7) Å	θ = 2–28°
c = 12.597 (8) Å	µ = 0.65 mm⁻¹
α = 75.150 (1)°	T = 293 K
β = 73.950 (1)°	Block, pale green
γ = 86.79 (1)°	0.51 × 0.43 × 0.36 mm
V = 1289.3 (12) Å³

Data collection top

Siemens r3m diffractometer	5369 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.053
Graphite monochromator	θ_max = 28.0°, θ_min = 2.1°
ω scan	h = 0→12
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −15→15
T_min = 0.733, T_max = 0.800	l = −15→16
6573 measured reflections	2 standard reflections every 200 reflections
6198 independent reflections	intensity decay: none

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.088P)² + 0.5664P] where P = (F_o² + 2F_c²)/3
6198 reflections	(Δ/σ)_max = 0.001
337 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

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	0.26609 (3)	0.11949 (2)	0.26332 (3)	0.03350 (11)
S1	0.13381 (6)	−0.29640 (4)	0.32183 (5)	0.03581 (14)
C1	0.0634 (2)	−0.52595 (16)	0.34884 (17)	0.0325 (4)
C2	0.0073 (2)	−0.40915 (16)	0.35952 (16)	0.0308 (4)
C3	−0.1384 (2)	−0.37494 (17)	0.3980 (2)	0.0379 (4)
H3A	−0.2225	−0.4240	0.4216	0.046*
C4	−0.1475 (2)	−0.25700 (17)	0.3979 (2)	0.0390 (5)
H4A	−0.2380	−0.2203	0.4222	0.047*
C5	−0.0087 (2)	−0.20310 (16)	0.35824 (17)	0.0320 (4)
C6	0.0265 (2)	−0.07953 (16)	0.34426 (17)	0.0331 (4)
C7	0.1564 (3)	0.2094 (2)	0.0343 (3)	0.0526 (6)
H7A	0.0617	0.2078	0.0862	0.063*
C8	0.1681 (4)	0.2543 (3)	−0.0800 (3)	0.0629 (7)
H8A	0.0827	0.2805	−0.1047	0.075*
C9	0.3080 (4)	0.2595 (3)	−0.1564 (3)	0.0705 (9)
H9A	0.3200	0.2919	−0.2337	0.085*
C10	0.4320 (4)	0.2157 (3)	−0.1169 (2)	0.0653 (8)
H10A	0.5276	0.2171	−0.1677	0.078*
C11	0.4116 (3)	0.16995 (19)	−0.0010 (2)	0.0401 (5)
C12	0.5390 (2)	0.12150 (18)	0.04776 (18)	0.0369 (4)
C13	0.6839 (3)	0.1122 (2)	−0.0211 (2)	0.0507 (6)
H13A	0.7035	0.1334	−0.1002	0.061*
C14	0.7978 (3)	0.0712 (3)	0.0292 (3)	0.0607 (7)
H14A	0.8956	0.0649	−0.0158	0.073*
C15	0.7670 (3)	0.0395 (3)	0.1460 (3)	0.0610 (7)
H15A	0.8432	0.0133	0.1816	0.073*
C16	0.6196 (3)	0.0477 (2)	0.2088 (2)	0.0506 (6)
H16A	0.5976	0.0244	0.2879	0.061*
C17	0.7183 (3)	0.3657 (3)	0.1658 (2)	0.0625 (7)
H17A	0.6808	0.3253	0.2415	0.075*
C18	0.8632 (3)	0.4115 (3)	0.1322 (2)	0.0576 (7)
H18A	0.9207	0.4007	0.1842	0.069*
C19	0.9225 (2)	0.47371 (19)	0.02058 (18)	0.0376 (4)
C20	0.8289 (3)	0.4849 (3)	−0.0510 (2)	0.0582 (7)
H20A	0.8620	0.5267	−0.1267	0.070*
C21	0.6864 (3)	0.4337 (3)	−0.0098 (3)	0.0642 (8)
H21A	0.6273	0.4404	−0.0603	0.077*
N1	0.2748 (2)	0.16791 (16)	0.07422 (17)	0.0406 (4)
N2	0.5065 (2)	0.08749 (16)	0.16233 (16)	0.0379 (4)
N3	0.6289 (2)	0.3754 (2)	0.0976 (2)	0.0552 (5)
O1	0.20460 (18)	−0.53679 (13)	0.31611 (15)	0.0430 (4)
O2	−0.03369 (18)	−0.60434 (12)	0.37046 (14)	0.0403 (3)
O3	0.16028 (19)	−0.04420 (13)	0.29065 (16)	0.0469 (4)
O4	−0.07977 (19)	−0.01843 (13)	0.38401 (16)	0.0465 (4)
O5	0.3163 (2)	0.05771 (15)	0.42945 (14)	0.0451 (4)
H5B	0.2437	0.0529	0.4895	0.068 (10)*
H5C	0.3945	0.0963	0.4297	0.117 (17)*
O6	0.04589 (19)	0.19252 (14)	0.31809 (18)	0.0531 (5)
H6B	−0.0158	0.1379	0.3584	0.094 (13)*
H6C	0.0206	0.2525	0.3428	0.051 (8)*
O7	0.3535 (2)	0.28717 (14)	0.24810 (18)	0.0561 (5)
H7B	0.4303	0.3146	0.1933	0.082 (12)*
H7C	0.3032	0.3435	0.2681	0.087 (12)*
O8	0.4604 (2)	0.54419 (19)	0.35695 (19)	0.0623 (5)
H8B	0.3834	0.5165	0.3469	0.079 (12)*
H8C	0.5097	0.4852	0.3802	0.075 (11)*
O9	0.3505 (2)	0.63232 (15)	0.54676 (18)	0.0539 (4)
H9B	0.2547	0.6226	0.5692	0.085 (12)*
H9C	0.3864	0.6148	0.4834	0.105 (16)*
O10	0.4654 (3)	0.8490 (2)	0.5090 (3)	0.0852 (8)
H10B	0.4091	0.8964	0.4765	0.125 (19)*
H10C	0.4112	0.7879	0.5374	0.113 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.03089 (17)	0.02409 (16)	0.04160 (19)	−0.00074 (11)	−0.00017 (12)	−0.01165 (12)
S1	0.0337 (3)	0.0244 (2)	0.0453 (3)	−0.00129 (18)	−0.0020 (2)	−0.01078 (19)
C1	0.0421 (10)	0.0247 (9)	0.0323 (9)	0.0039 (7)	−0.0102 (8)	−0.0103 (7)
C2	0.0378 (10)	0.0231 (8)	0.0318 (9)	−0.0018 (7)	−0.0078 (7)	−0.0087 (7)
C3	0.0351 (10)	0.0254 (9)	0.0543 (12)	−0.0045 (7)	−0.0094 (9)	−0.0135 (8)
C4	0.0345 (10)	0.0262 (9)	0.0564 (13)	0.0012 (8)	−0.0079 (9)	−0.0156 (9)
C5	0.0378 (10)	0.0209 (8)	0.0361 (9)	0.0004 (7)	−0.0073 (8)	−0.0078 (7)
C6	0.0390 (10)	0.0223 (8)	0.0365 (10)	−0.0038 (7)	−0.0059 (8)	−0.0087 (7)
C7	0.0453 (13)	0.0482 (13)	0.0679 (17)	0.0103 (10)	−0.0178 (12)	−0.0201 (12)
C8	0.0673 (18)	0.0562 (16)	0.0745 (19)	0.0096 (14)	−0.0390 (16)	−0.0134 (14)
C9	0.075 (2)	0.080 (2)	0.0540 (16)	−0.0060 (17)	−0.0276 (15)	0.0016 (15)
C10	0.0533 (16)	0.084 (2)	0.0481 (14)	−0.0119 (15)	−0.0107 (12)	0.0010 (14)
C11	0.0393 (11)	0.0360 (10)	0.0432 (11)	−0.0037 (8)	−0.0078 (9)	−0.0096 (9)
C12	0.0352 (10)	0.0328 (10)	0.0393 (10)	−0.0014 (8)	−0.0024 (8)	−0.0112 (8)
C13	0.0418 (12)	0.0562 (14)	0.0453 (12)	0.0002 (10)	0.0052 (10)	−0.0158 (11)
C14	0.0335 (12)	0.0723 (19)	0.0671 (18)	0.0068 (12)	0.0020 (11)	−0.0197 (14)
C15	0.0416 (13)	0.0724 (19)	0.0690 (18)	0.0157 (13)	−0.0165 (12)	−0.0193 (15)
C16	0.0461 (13)	0.0565 (15)	0.0462 (13)	0.0134 (11)	−0.0106 (10)	−0.0122 (11)
C17	0.0552 (16)	0.0729 (19)	0.0459 (14)	−0.0208 (14)	0.0004 (12)	−0.0018 (13)
C18	0.0544 (15)	0.0709 (18)	0.0412 (13)	−0.0197 (13)	−0.0127 (11)	0.0010 (12)
C19	0.0344 (10)	0.0398 (11)	0.0359 (10)	0.0004 (8)	−0.0059 (8)	−0.0085 (8)
C20	0.0437 (13)	0.083 (2)	0.0428 (13)	−0.0121 (13)	−0.0130 (11)	−0.0022 (13)
C21	0.0427 (14)	0.087 (2)	0.0629 (17)	−0.0099 (14)	−0.0179 (12)	−0.0129 (15)
N1	0.0384 (9)	0.0348 (9)	0.0488 (10)	0.0038 (7)	−0.0091 (8)	−0.0144 (8)
N2	0.0347 (9)	0.0360 (9)	0.0401 (9)	0.0043 (7)	−0.0035 (7)	−0.0121 (7)
N3	0.0386 (10)	0.0576 (13)	0.0650 (14)	−0.0094 (9)	−0.0029 (10)	−0.0177 (11)
O1	0.0401 (8)	0.0340 (8)	0.0559 (9)	0.0054 (6)	−0.0072 (7)	−0.0200 (7)
O2	0.0448 (8)	0.0244 (7)	0.0565 (9)	0.0014 (6)	−0.0143 (7)	−0.0178 (6)
O3	0.0419 (8)	0.0269 (7)	0.0637 (10)	−0.0073 (6)	0.0041 (7)	−0.0158 (7)
O4	0.0432 (9)	0.0247 (7)	0.0632 (10)	−0.0034 (6)	0.0036 (7)	−0.0149 (7)
O5	0.0439 (9)	0.0443 (9)	0.0443 (9)	−0.0018 (7)	−0.0039 (7)	−0.0146 (7)
O6	0.0381 (8)	0.0273 (7)	0.0849 (13)	−0.0017 (6)	0.0068 (8)	−0.0231 (8)
O7	0.0412 (9)	0.0321 (8)	0.0847 (13)	−0.0081 (7)	0.0120 (9)	−0.0261 (8)
O8	0.0555 (11)	0.0564 (12)	0.0803 (14)	0.0020 (9)	−0.0219 (10)	−0.0232 (10)
O9	0.0477 (10)	0.0446 (10)	0.0730 (13)	−0.0039 (8)	−0.0147 (9)	−0.0220 (9)
O10	0.0790 (16)	0.0434 (11)	0.148 (3)	−0.0024 (11)	−0.0596 (17)	−0.0184 (13)

Geometric parameters (Å, º) top

Mn1—O3	2.1470 (18)	C13—C14	1.372 (4)
Mn1—O7	2.153 (2)	C13—H13A	0.9300
Mn1—O6	2.1601 (17)	C14—C15	1.373 (4)
Mn1—O5	2.200 (2)	C14—H14A	0.9300
Mn1—N1	2.282 (3)	C15—C16	1.377 (4)
Mn1—N2	2.2874 (19)	C15—H15A	0.9300
S1—C5	1.716 (2)	C16—N2	1.336 (3)
S1—C2	1.717 (2)	C16—H16A	0.9300
C1—O1	1.256 (3)	C17—N3	1.323 (4)
C1—O2	1.258 (3)	C17—C18	1.378 (4)
C1—C2	1.493 (3)	C17—H17A	0.9300
C2—C3	1.368 (3)	C18—C19	1.384 (3)
C3—C4	1.415 (3)	C18—H18A	0.9300
C3—H3A	0.9300	C19—C20	1.386 (3)
C4—C5	1.366 (3)	C19—C19ⁱ	1.489 (4)
C4—H4A	0.9300	C20—C21	1.381 (4)
C5—C6	1.493 (3)	C20—H20A	0.9300
C6—O4	1.256 (3)	C21—N3	1.327 (4)
C6—O3	1.263 (3)	C21—H21A	0.9300
C7—N1	1.340 (3)	O5—H5B	0.8498
C7—C8	1.378 (4)	O5—H5C	0.8765
C7—H7A	0.9300	O6—H6B	0.8484
C8—C9	1.368 (5)	O6—H6C	0.8519
C8—H8A	0.9300	O7—H7B	0.8499
C9—C10	1.389 (4)	O7—H7C	0.8499
C9—H9A	0.9300	O8—H8B	0.8500
C10—C11	1.385 (4)	O8—H8C	0.8500
C10—H10A	0.9300	O9—H9B	0.8500
C11—N1	1.344 (3)	O9—H9C	0.8500
C11—C12	1.489 (3)	O10—H10B	0.8499
C12—N2	1.346 (3)	O10—H10C	0.8500
C12—C13	1.389 (3)

O3—Mn1—O7	174.49 (6)	N2—C12—C11	116.52 (19)
O3—Mn1—O6	90.01 (7)	C13—C12—C11	121.9 (2)
O7—Mn1—O6	85.05 (7)	C14—C13—C12	119.0 (2)
O3—Mn1—O5	88.97 (7)	C14—C13—H13A	120.5
O7—Mn1—O5	89.43 (8)	C12—C13—H13A	120.5
O6—Mn1—O5	99.35 (8)	C13—C14—C15	119.9 (2)
O3—Mn1—N1	92.15 (7)	C13—C14—H14A	120.1
O7—Mn1—N1	90.73 (8)	C15—C14—H14A	120.1
O6—Mn1—N1	95.17 (8)	C14—C15—C16	117.8 (3)
O5—Mn1—N1	165.44 (7)	C14—C15—H15A	121.1
O3—Mn1—N2	100.38 (7)	C16—C15—H15A	121.1
O7—Mn1—N2	84.98 (7)	N2—C16—C15	123.6 (2)
O6—Mn1—N2	163.57 (7)	N2—C16—H16A	118.2
O5—Mn1—N2	93.58 (7)	C15—C16—H16A	118.2
N1—Mn1—N2	71.94 (7)	N3—C17—C18	124.5 (3)
C5—S1—C2	91.91 (10)	N3—C17—H17A	117.8
O1—C1—O2	125.40 (18)	C18—C17—H17A	117.8
O1—C1—C2	116.78 (18)	C17—C18—C19	119.6 (2)
O2—C1—C2	117.80 (18)	C17—C18—H18A	120.2
C3—C2—C1	128.89 (18)	C19—C18—H18A	120.2
C3—C2—S1	111.21 (15)	C18—C19—C20	116.2 (2)
C1—C2—S1	119.90 (16)	C18—C19—C19ⁱ	122.1 (3)
C2—C3—C4	112.83 (18)	C20—C19—C19ⁱ	121.7 (2)
C2—C3—H3A	123.6	C21—C20—C19	119.9 (2)
C4—C3—H3A	123.6	C21—C20—H20A	120.1
C5—C4—C3	112.49 (19)	C19—C20—H20A	120.1
C5—C4—H4A	123.8	N3—C21—C20	123.9 (3)
C3—C4—H4A	123.8	N3—C21—H21A	118.1
C4—C5—C6	127.91 (18)	C20—C21—H21A	118.1
C4—C5—S1	111.56 (15)	C7—N1—C11	118.3 (2)
C6—C5—S1	120.53 (16)	C7—N1—Mn1	123.64 (17)
O4—C6—O3	125.27 (18)	C11—N1—Mn1	117.35 (15)
O4—C6—C5	117.59 (18)	C16—N2—C12	117.9 (2)
O3—C6—C5	117.11 (18)	C16—N2—Mn1	124.60 (16)
N1—C7—C8	123.2 (3)	C12—N2—Mn1	117.14 (14)
N1—C7—H7A	118.4	C17—N3—C21	116.0 (2)
C8—C7—H7A	118.4	C6—O3—Mn1	129.93 (14)
C9—C8—C7	118.5 (3)	Mn1—O5—H5B	118.1
C9—C8—H8A	120.8	Mn1—O5—H5C	109.4
C7—C8—H8A	120.8	H5B—O5—H5C	112.2
C8—C9—C10	119.2 (3)	Mn1—O6—H6B	108.1
C8—C9—H9A	120.4	Mn1—O6—H6C	130.8
C10—C9—H9A	120.4	H6B—O6—H6C	109.1
C11—C10—C9	119.2 (3)	Mn1—O7—H7B	119.2
C11—C10—H10A	120.4	Mn1—O7—H7C	127.0
C9—C10—H10A	120.4	H7B—O7—H7C	107.6
N1—C11—C10	121.5 (2)	H8B—O8—H8C	104.1
N1—C11—C12	116.1 (2)	H9B—O9—H9C	110.6
C10—C11—C12	122.4 (2)	H10B—O10—H10C	103.4
N2—C12—C13	121.6 (2)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O4ⁱⁱ	0.85	1.84	2.679 (3)	170
O5—H5C···O10ⁱⁱⁱ	0.88	1.89	2.725 (3)	158
O6—H6B···O4	0.85	1.92	2.676 (3)	148
O6—H6C···O2^iv	0.85	1.86	2.699 (3)	170
O7—H7B···N3	0.85	1.95	2.778 (3)	166
O7—H7C···O1^iv	0.85	1.80	2.651 (3)	176
O8—H8B···O1^iv	0.85	1.96	2.810 (3)	176
O8—H8C···O9ⁱⁱⁱ	0.85	2.07	2.900 (3)	167
O9—H9B···O2ⁱⁱ	0.85	1.96	2.810 (3)	176
O9—H9C···O8	0.85	1.94	2.775 (3)	169
O10—H10B···O5^iv	0.85	2.08	2.872 (3)	154
O10—H10C···O9	0.85	1.95	2.740 (3)	155

Symmetry codes: (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z.

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Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

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Tri­aqua(2,2'-bi­pyridine)(thio­phene-2,5-di­carboxyl­ato)­manganese(II) 4,4'-bi­pyridine hemisolvate trihydrate

Supporting information

Key indicators

checkCIF/PLATON results

Triaqua(2,2'-bipyridine)(thiophene-2,5-dicarboxylato)manganese(II) 4,4'-bipyridine hemisolvate trihydrate