Manganese(II) chloride complexes with pyridine N-oxide (PNO) derivatives and their solid-state structures

The synthesis and structures of three manganese(II) pyridine N-oxide complexes are presented.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.031
• wR factor = 0.080
• Data-to-parameter ratio = 18.6

Structure: II

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.051
• wR factor = 0.100
• Data-to-parameter ratio = 18.8

Structure: III

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.031
• wR factor = 0.087
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          9 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  Cl1     ..       11.2 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  Cl2_a   ..        7.2 s.u.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          8 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          5 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: II


Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.440
           From the CIF: _refine_ls_abs_structure_Flack_su    0.080
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0098 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.206 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          5 Report
PLAT975_ALERT_2_C Check Calcd Residual Density  0.93A From      O2       0.74 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.55A From      O2       0.53 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.59A From      O2       0.44 eA-3
PLAT976_ALERT_2_C Check Calcd Residual Density  0.98A From      O2      -0.50 eA-3
PLAT977_ALERT_2_C Check the Negative Difference Density on     H2A      -0.39 eA-3
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT012_ALERT_1_G N.O.K. _shelx_res_checksum found in CIF ........     Please Check
PLAT033_ALERT_4_G Flack x Value Deviates > 3.0 * sigma from Zero .      0.440 Note
PLAT115_ALERT_5_G ADDSYM Detects Noncrystallographic Inversion ...        100 %
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  O2      ..        7.3 s.u.
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          5 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          4 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  10 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check




Datablock: III



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          5 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          6 Note
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.85 mm
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  Cl1     ..        5.7 s.u.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          4 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         28 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          2 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

For all structures, data collection: CrystalClearSM Expert (Rigaku, 2011); cell refinement: CrystalClearSM Expert (Rigaku, 2011); data reduction: CrystalClearSM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-poly[[aquachloridomanganese(II)]-di-µ-chlorido-[aquachloridomanganese(II)]-bis(µ-pyridine N-oxide)] (I)

Crystal data

[MnCl2(C5H5NO)(H2O)]	Z = 2
Mr = 238.96	F(000) = 238
Triclinic, P1	Dx = 1.811 Mg m^−3
a = 6.897 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.050 (1) Å	Cell parameters from 1189 reflections
c = 9.853 (3) Å	θ = 2.3–27.5°
α = 101.042 (7)°	µ = 2.06 mm^−1
β = 109.559 (10)°	T = 173 K
γ = 94.196 (6)°	Prism, clear brown
V = 438.2 (2) Å^3	0.29 × 0.18 × 0.13 mm

Data collection

Rigaku XtalLab mini CCD diffractometer	1770 reflections with I > 2σ(I)
ω scans	Rint = 0.040
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	θmax = 27.6°, θmin = 2.3°
Tmin = 0.613, Tmax = 0.765	h = −8→8
4655 measured reflections	k = −9→9
2004 independent reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + 0.444P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max = 0.001
2004 reflections	Δρmax = 0.40 e Å^−3
108 parameters	Δρmin = −0.44 e Å^−3
2 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.24478 (6)	0.51944 (6)	0.49588 (4)	0.02748 (12)
Cl1	0.21608 (12)	0.81797 (10)	0.39668 (9)	0.04150 (19)
O1	0.5727 (3)	0.6094 (3)	0.63106 (19)	0.0327 (4)
N1	0.6425 (3)	0.6894 (3)	0.7767 (2)	0.0283 (5)
C1	0.6940 (6)	0.5762 (5)	0.8731 (3)	0.0493 (8)
H1	0.681940	0.441595	0.840110	0.059*
Cl2	0.10246 (10)	0.65268 (10)	0.69397 (7)	0.03317 (16)
O2	0.2634 (4)	0.2541 (3)	0.5927 (3)	0.0447 (5)
H2A	0.146 (4)	0.218 (6)	0.594 (5)	0.081 (16)*
H2B	0.305 (7)	0.162 (5)	0.551 (5)	0.087 (16)*
C2	0.7655 (7)	0.6608 (6)	1.0222 (4)	0.0655 (11)
H2	0.802254	0.582800	1.090313	0.079*
C3	0.7826 (6)	0.8564 (6)	1.0704 (3)	0.0543 (9)
H3	0.829678	0.913307	1.171227	0.065*
C4	0.7299 (6)	0.9692 (5)	0.9693 (4)	0.0532 (9)
H4	0.742760	1.104037	1.001068	0.064*
C5	0.6577 (5)	0.8836 (5)	0.8203 (3)	0.0421 (7)
H5	0.619974	0.959566	0.750808	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0228 (2)	0.0328 (2)	0.0259 (2)	0.00479 (16)	0.00858 (16)	0.00467 (16)
Cl1	0.0478 (4)	0.0329 (4)	0.0481 (4)	0.0073 (3)	0.0188 (4)	0.0156 (3)
O1	0.0230 (9)	0.0460 (12)	0.0238 (9)	0.0052 (8)	0.0062 (8)	−0.0006 (8)
N1	0.0232 (11)	0.0371 (12)	0.0233 (10)	0.0033 (9)	0.0078 (9)	0.0052 (9)
C1	0.076 (2)	0.0386 (17)	0.0325 (15)	0.0152 (16)	0.0152 (16)	0.0124 (13)
Cl2	0.0307 (3)	0.0377 (4)	0.0267 (3)	0.0016 (3)	0.0102 (3)	−0.0016 (3)
O2	0.0553 (16)	0.0394 (13)	0.0420 (13)	0.0117 (11)	0.0186 (12)	0.0115 (10)
C2	0.094 (3)	0.073 (3)	0.0290 (16)	0.031 (2)	0.0135 (19)	0.0204 (17)
C3	0.057 (2)	0.071 (3)	0.0249 (15)	0.0074 (18)	0.0091 (15)	−0.0009 (15)
C4	0.067 (2)	0.0425 (19)	0.0391 (17)	−0.0022 (17)	0.0151 (17)	−0.0064 (15)
C5	0.054 (2)	0.0388 (17)	0.0325 (15)	0.0027 (14)	0.0149 (14)	0.0075 (13)

Geometric parameters (Å, º)

Mn1—Cl1	2.479 (2)	C1—C2	1.376 (5)
Mn1—O1	2.177 (3)	O2—H2A	0.833 (19)
Mn1—O1^i	2.182 (2)	O2—H2B	0.819 (19)
Mn1—Cl2^ii	2.5324 (19)	C2—H2	0.9300
Mn1—Cl2	2.5240 (19)	C2—C3	1.353 (5)
Mn1—O2	2.250 (3)	C3—H3	0.9300
O1—N1	1.341 (3)	C3—C4	1.364 (5)
N1—C1	1.331 (4)	C4—H4	0.9300
N1—C5	1.339 (4)	C4—C5	1.377 (4)
C1—H1	0.9300	C5—H5	0.9300
Cl1—Mn1—Cl2	93.43 (6)	C5—N1—O1	118.0 (2)
Cl1—Mn1—Cl2^ii	92.57 (6)	N1—C1—H1	120.4
O1^i—Mn1—Cl1	95.12 (8)	N1—C1—C2	119.1 (3)
O1—Mn1—Cl1	93.65 (7)	C2—C1—H1	120.4
O1—Mn1—O1^i	72.02 (10)	Mn1—Cl2—Mn1^ii	84.42 (7)
O1—Mn1—Cl2^ii	165.77 (6)	Mn1—O2—H2A	108 (3)
O1^i—Mn1—Cl2^ii	94.69 (9)	Mn1—O2—H2B	116 (3)
O1^i—Mn1—Cl2	166.32 (5)	H2A—O2—H2B	110 (4)
O1—Mn1—Cl2	96.81 (8)	C1—C2—H2	119.7
O1—Mn1—O2	86.96 (9)	C3—C2—C1	120.5 (3)
O1^i—Mn1—O2	87.46 (10)	C3—C2—H2	119.7
Cl2—Mn1—Cl2^ii	95.58 (7)	C2—C3—H3	120.4
O2—Mn1—Cl1	177.42 (7)	C2—C3—C4	119.1 (3)
O2—Mn1—Cl2^ii	87.40 (8)	C4—C3—H3	120.4
O2—Mn1—Cl2	84.01 (9)	C3—C4—H4	120.0
Mn1—O1—Mn1^i	107.98 (10)	C3—C4—C5	120.1 (3)
N1—O1—Mn1	123.78 (14)	C5—C4—H4	120.0
N1—O1—Mn1^i	126.50 (16)	N1—C5—C4	119.1 (3)
C1—N1—O1	119.9 (2)	N1—C5—H5	120.5
C1—N1—C5	122.0 (3)	C4—C5—H5	120.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···Cl1^ii	0.83 (2)	2.53 (2)	3.348 (4)	168 (4)
O2—H2B···Cl1^iii	0.82 (2)	2.52 (3)	3.232 (4)	147 (4)

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

catena-Poly[[aquachloridomanganese(II)]-di-µ-chlorido-[aquachloridomanganese(II)]-bis(µ-2-methylpyridine N-oxide)] (II)

Crystal data

[MnCl2(C6H7NO)(H2O)]	Dx = 1.811 Mg m^−3
Mr = 252.98	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, P212121	Cell parameters from 2686 reflections
a = 6.862 (2) Å	θ = 2.7–27.5°
b = 7.491 (2) Å	µ = 1.96 mm^−1
c = 18.047 (5) Å	T = 173 K
V = 927.7 (4) Å^3	Prism, colorless
Z = 4	0.2 × 0.2 × 0.1 mm
F(000) = 508

Data collection

Rigaku XtalLab mini CCD diffractometer	1800 reflections with I > 2σ(I)
ω scans	Rint = 0.051
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	θmax = 27.5°, θmin = 2.3°
Tmin = 0.563, Tmax = 0.737	h = −8→8
8438 measured reflections	k = −9→9
2109 independent reflections	l = −23→23

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.051	w = 1/[σ^2(Fo^2) + (0.004P)^2 + 2.3909P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.100	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 0.95 e Å^−3
2109 reflections	Δρmin = −0.73 e Å^−3
112 parameters	Absolute structure: Refined as an inversion twin.
0 restraints	Absolute structure parameter: 0.44 (8)
Primary atom site location: dual

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.5059 (2)	0.73290 (15)	0.50137 (7)	0.0197 (2)
Cl1	0.2537 (3)	0.6800 (2)	0.40260 (8)	0.0226 (3)
O1	0.7561 (8)	0.7085 (6)	0.42855 (19)	0.0179 (9)
N1	0.7503 (11)	0.7249 (7)	0.3544 (2)	0.0199 (11)
C1	0.7553 (14)	0.5782 (9)	0.3112 (3)	0.0276 (15)
Cl2	0.5309 (3)	0.4110 (3)	0.53742 (11)	0.0325 (5)
O2	0.4833 (8)	1.0223 (7)	0.4655 (3)	0.0265 (12)
H2A	0.546895	1.093811	0.497004	0.040*
H2B	0.358601	1.056880	0.464095	0.040*
C2	0.7532 (15)	0.6041 (10)	0.2345 (3)	0.0321 (16)
H2	0.758660	0.503891	0.202342	0.038*
C3	0.7436 (16)	0.7719 (11)	0.2056 (4)	0.0370 (18)
H3	0.740766	0.787849	0.153377	0.044*
C4	0.7378 (16)	0.9180 (10)	0.2515 (4)	0.0371 (19)
H4	0.731159	1.035141	0.231495	0.044*
C5	0.7418 (15)	0.8925 (9)	0.3261 (3)	0.0283 (16)
H5	0.738625	0.992359	0.358479	0.034*
C6	0.7629 (17)	0.4059 (10)	0.3484 (4)	0.040 (2)
H6A	0.757534	0.310158	0.311520	0.048*
H6B	0.651845	0.395059	0.382265	0.048*
H6C	0.884583	0.396660	0.376629	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0171 (4)	0.0266 (5)	0.0154 (4)	−0.0028 (5)	0.0017 (4)	−0.0008 (4)
Cl1	0.0212 (7)	0.0300 (9)	0.0167 (6)	0.0003 (10)	0.0004 (8)	−0.0069 (6)
O1	0.020 (2)	0.025 (3)	0.0089 (16)	−0.005 (3)	−0.002 (2)	−0.0013 (16)
N1	0.019 (2)	0.029 (3)	0.012 (2)	0.002 (3)	0.002 (3)	−0.001 (2)
C1	0.028 (4)	0.028 (4)	0.026 (3)	0.003 (5)	−0.001 (4)	−0.005 (3)
Cl2	0.0377 (12)	0.0234 (10)	0.0365 (11)	−0.0021 (10)	0.0037 (9)	0.0050 (8)
O2	0.015 (3)	0.048 (3)	0.016 (2)	−0.009 (3)	0.002 (2)	−0.003 (2)
C2	0.036 (4)	0.046 (5)	0.015 (3)	0.007 (6)	0.002 (4)	−0.004 (3)
C3	0.048 (5)	0.046 (5)	0.017 (3)	0.004 (6)	0.001 (4)	0.001 (3)
C4	0.060 (5)	0.027 (4)	0.024 (4)	0.002 (6)	0.003 (5)	0.005 (3)
C5	0.042 (4)	0.026 (4)	0.017 (3)	0.007 (5)	0.004 (4)	−0.002 (3)
C6	0.061 (6)	0.029 (4)	0.029 (4)	0.007 (6)	0.001 (5)	0.000 (3)

Geometric parameters (Å, º)

Mn1—Cl1^i	2.514 (3)	O2—H2B	0.8947
Mn1—Cl1	2.516 (4)	C2—H2	0.9500
Mn1—O1^ii	2.174 (5)	C2—C3	1.363 (10)
Mn1—O1	2.171 (6)	C3—H3	0.9500
Mn1—Cl2	2.503 (4)	C3—C4	1.374 (10)
Mn1—O2	2.268 (6)	C4—H4	0.9500
O1—N1	1.345 (6)	C4—C5	1.360 (9)
N1—C1	1.348 (8)	C5—H5	0.9500
N1—C5	1.357 (8)	C6—H6A	0.9800
C1—C2	1.397 (9)	C6—H6B	0.9800
C1—C6	1.456 (10)	C6—H6C	0.9800
O2—H2A	0.8951
Cl1^i—Mn1—Cl1	174.01 (5)	N1—C1—C6	117.1 (6)
O1^ii—Mn1—Cl1	84.38 (18)	C2—C1—C6	125.5 (7)
O1—Mn1—Cl1^i	84.49 (18)	Mn1—O2—H2A	110.9
O1^ii—Mn1—Cl1^i	94.57 (18)	Mn1—O2—H2B	110.5
O1—Mn1—Cl1	95.84 (18)	H2A—O2—H2B	108.1
O1—Mn1—O1^ii	173.11 (6)	C1—C2—H2	119.7
O1—Mn1—Cl2	91.26 (14)	C3—C2—C1	120.5 (7)
O1^ii—Mn1—Cl2	95.58 (14)	C3—C2—H2	119.7
O1^ii—Mn1—O2	85.39 (19)	C2—C3—H3	119.8
O1—Mn1—O2	87.78 (19)	C2—C3—C4	120.3 (6)
Cl2—Mn1—Cl1^i	91.40 (9)	C4—C3—H3	119.8
Cl2—Mn1—Cl1	94.57 (9)	C3—C4—H4	120.5
O2—Mn1—Cl1	84.34 (16)	C5—C4—C3	119.0 (7)
O2—Mn1—Cl1^i	89.71 (16)	C5—C4—H4	120.5
O2—Mn1—Cl2	178.46 (15)	N1—C5—C4	120.3 (6)
Mn1^ii—Cl1—Mn1	86.32 (13)	N1—C5—H5	119.9
Mn1—O1—Mn1^i	104.73 (19)	C4—C5—H5	119.9
N1—O1—Mn1^i	125.7 (5)	C1—C6—H6A	109.5
N1—O1—Mn1	124.9 (5)	C1—C6—H6B	109.5
O1—N1—C1	120.1 (5)	C1—C6—H6C	109.5
O1—N1—C5	117.4 (5)	H6A—C6—H6B	109.5
C1—N1—C5	122.5 (5)	H6A—C6—H6C	109.5
N1—C1—C2	117.4 (7)	H6B—C6—H6C	109.5
Mn1—O1—N1—C1	−102.4 (8)	C1—N1—C5—C4	0.0 (15)
Mn1^i—O1—N1—C1	105.6 (8)	C1—C2—C3—C4	0.7 (17)
Mn1—O1—N1—C5	78.4 (9)	C2—C3—C4—C5	0.0 (17)
Mn1^i—O1—N1—C5	−73.7 (9)	C3—C4—C5—N1	−0.3 (17)
O1—N1—C1—C2	−178.6 (8)	C5—N1—C1—C2	0.6 (14)
O1—N1—C1—C6	1.2 (13)	C5—N1—C1—C6	−179.6 (10)
O1—N1—C5—C4	179.3 (9)	C6—C1—C2—C3	179.2 (11)
N1—C1—C2—C3	−1.0 (16)

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···Cl2^iii	0.90	2.49	3.205 (7)	137
O2—H2B···Cl2^ii	0.89	2.26	3.145 (7)	169

Symmetry codes: (ii) x−1/2, −y+3/2, −z+1; (iii) x, y+1, z.

Bis(µ-3-methylpyridine N-oxide)bis[diaquadichloridomanganese(II)] (III)

Crystal data

[Mn2Cl4(C6H7NO)2(H2O)4]	Z = 1
Mr = 541.99	F(000) = 274
Triclinic, P1	Dx = 1.629 Mg m^−3
a = 7.902 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.026 (7) Å	Cell parameters from 5886 reflections
c = 9.893 (8) Å	θ = 2.8–27.5°
α = 98.033 (1)°	µ = 1.65 mm^−1
β = 99.272 (7)°	T = 173 K
γ = 113.634 (11)°	Prism, clear brown
V = 552.6 (8) Å^3	0.85 × 0.5 × 0.28 mm

Data collection

Rigaku XtalLab mini CCD diffractometer	2375 reflections with I > 2σ(I)
ω scans	Rint = 0.072
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	θmax = 27.6°, θmin = 2.8°
Tmin = 0.482, Tmax = 0.630	h = −10→10
5837 measured reflections	k = −10→10
2553 independent reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.031P)^2 + 0.023P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2553 reflections	Δρmax = 0.56 e Å^−3
135 parameters	Δρmin = −0.41 e Å^−3
4 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.27031 (3)	0.40104 (3)	0.53553 (2)	0.02936 (11)
Cl1	0.14922 (6)	0.48607 (7)	0.73553 (4)	0.04342 (14)
Cl2	0.32299 (6)	0.13672 (6)	0.60668 (6)	0.04544 (15)
O1	0.56562 (15)	0.60090 (16)	0.62683 (12)	0.0345 (3)
O2	0.2605 (2)	0.6467 (2)	0.45620 (16)	0.0443 (3)
H2A	0.355 (3)	0.710 (3)	0.436 (2)	0.055 (7)*
H2B	0.167 (3)	0.639 (3)	0.404 (2)	0.062 (8)*
O3	0.00694 (17)	0.23434 (18)	0.37696 (14)	0.0395 (3)
H3A	−0.069 (3)	0.128 (2)	0.390 (2)	0.062 (7)*
H3B	−0.054 (4)	0.288 (4)	0.352 (3)	0.081 (10)*
N1	0.62886 (17)	0.71302 (18)	0.75570 (13)	0.0294 (3)
C1	0.6561 (2)	0.8903 (2)	0.77007 (17)	0.0342 (4)
H1	0.631326	0.934009	0.690425	0.041*
C2	0.7204 (3)	1.0102 (3)	0.90084 (19)	0.0415 (4)
C3	0.7538 (3)	0.9400 (3)	1.0169 (2)	0.0568 (6)
H3	0.795802	1.016517	1.106619	0.068*
C4	0.7250 (4)	0.7571 (4)	0.9997 (2)	0.0611 (6)
H4	0.748138	0.710090	1.077885	0.073*
C5	0.6620 (3)	0.6431 (3)	0.8670 (2)	0.0472 (5)
H5	0.642729	0.519251	0.854911	0.057*
C6	0.7494 (4)	1.2087 (3)	0.9131 (3)	0.0701 (7)
H6A	0.873126	1.282752	0.900126	0.105*
H6B	0.739622	1.256760	1.004510	0.105*
H6C	0.653880	1.213706	0.842403	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02821 (16)	0.02780 (17)	0.03004 (17)	0.00959 (12)	0.00843 (11)	0.00651 (12)
Cl1	0.0471 (3)	0.0617 (3)	0.0309 (2)	0.0299 (2)	0.01431 (18)	0.0142 (2)
Cl2	0.0436 (3)	0.0349 (3)	0.0596 (3)	0.0137 (2)	0.0151 (2)	0.0236 (2)
O1	0.0326 (6)	0.0310 (6)	0.0313 (6)	0.0074 (5)	0.0091 (5)	−0.0010 (5)
O2	0.0389 (7)	0.0414 (7)	0.0584 (9)	0.0185 (6)	0.0137 (6)	0.0231 (7)
O3	0.0339 (6)	0.0322 (7)	0.0438 (7)	0.0079 (5)	0.0039 (5)	0.0080 (6)
N1	0.0295 (6)	0.0293 (7)	0.0271 (6)	0.0107 (5)	0.0061 (5)	0.0062 (5)
C1	0.0443 (9)	0.0307 (8)	0.0273 (7)	0.0159 (7)	0.0082 (6)	0.0067 (6)
C2	0.0484 (10)	0.0363 (9)	0.0336 (8)	0.0138 (8)	0.0112 (7)	0.0016 (7)
C3	0.0674 (13)	0.0598 (13)	0.0262 (9)	0.0158 (11)	0.0049 (9)	0.0014 (9)
C4	0.0766 (14)	0.0687 (15)	0.0355 (10)	0.0289 (12)	0.0028 (10)	0.0246 (10)
C5	0.0591 (11)	0.0424 (10)	0.0425 (10)	0.0236 (9)	0.0064 (9)	0.0186 (9)
C6	0.105 (2)	0.0393 (11)	0.0571 (14)	0.0257 (13)	0.0237 (14)	−0.0048 (10)

Geometric parameters (Å, º)

Mn1—Cl1	2.4602 (15)	C1—H1	0.9300
Mn1—Cl2	2.4900 (19)	C1—C2	1.381 (2)
Mn1—O1^i	2.2228 (17)	C2—C3	1.381 (3)
Mn1—O1	2.1792 (18)	C2—C6	1.500 (3)
Mn1—O2	2.246 (2)	C3—H3	0.9300
Mn1—O3	2.1704 (17)	C3—C4	1.373 (4)
O1—N1	1.3411 (19)	C4—H4	0.9300
O2—H2A	0.791 (15)	C4—C5	1.377 (3)
O2—H2B	0.802 (16)	C5—H5	0.9300
O3—H3A	0.863 (16)	C6—H6A	0.9600
O3—H3B	0.795 (17)	C6—H6B	0.9600
N1—C1	1.334 (2)	C6—H6C	0.9600
N1—C5	1.340 (2)
Cl1—Mn1—Cl2	98.31 (4)	C1—N1—O1	119.45 (13)
O1—Mn1—Cl1	95.44 (6)	C1—N1—C5	121.69 (16)
O1^i—Mn1—Cl1	165.45 (4)	C5—N1—O1	118.86 (16)
O1^i—Mn1—Cl2	89.66 (5)	N1—C1—H1	119.3
O1—Mn1—Cl2	93.11 (7)	N1—C1—C2	121.31 (16)
O1—Mn1—O1^i	71.87 (7)	C2—C1—H1	119.3
O1^i—Mn1—O2	82.07 (6)	C1—C2—C3	117.8 (2)
O1—Mn1—O2	81.64 (7)	C1—C2—C6	119.87 (19)
O2—Mn1—Cl1	89.20 (6)	C3—C2—C6	122.4 (2)
O2—Mn1—Cl2	171.24 (4)	C2—C3—H3	120.0
O3—Mn1—Cl1	101.10 (7)	C4—C3—C2	119.99 (19)
O3—Mn1—Cl2	97.13 (6)	C4—C3—H3	120.0
O3—Mn1—O1^i	89.88 (8)	C3—C4—H4	119.9
O3—Mn1—O1	159.02 (5)	C3—C4—C5	120.16 (18)
O3—Mn1—O2	85.76 (7)	C5—C4—H4	119.9
Mn1—O1—Mn1^i	108.13 (7)	N1—C5—C4	119.10 (19)
N1—O1—Mn1	124.29 (9)	N1—C5—H5	120.5
N1—O1—Mn1^i	127.41 (10)	C4—C5—H5	120.5
Mn1—O2—H2A	114.4 (17)	C2—C6—H6A	109.5
Mn1—O2—H2B	121.9 (18)	C2—C6—H6B	109.5
H2A—O2—H2B	112 (2)	C2—C6—H6C	109.5
Mn1—O3—H3A	118.3 (16)	H6A—C6—H6B	109.5
Mn1—O3—H3B	116 (2)	H6A—C6—H6C	109.5
H3A—O3—H3B	109 (3)	H6B—C6—H6C	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···Cl1^ii	0.80 (2)	2.38 (2)	3.147 (3)	161 (2)
O3—H3A···Cl2^iii	0.86 (2)	2.28 (2)	3.120 (2)	167 (2)

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