The synthesis and structures of three manganese(II) pyridine N-oxide complexes are presented.
Supporting information
CCDC references: 1570001; 1570000; 1569999
Key indicators
Structure: I
- Single-crystal X-ray study
- T = 173 K
- Mean (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 (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 (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
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)
top
Crystal data top
[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) Å3 | 0.29 × 0.18 × 0.13 mm |
Data collection top
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 top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + 0.444P] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Mn1—Cl1 | 2.479 (2) | C1—C2 | 1.376 (5) |
Mn1—O1 | 2.177 (3) | O2—H2A | 0.833 (19) |
Mn1—O1i | 2.182 (2) | O2—H2B | 0.819 (19) |
Mn1—Cl2ii | 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—Cl2ii | 92.57 (6) | N1—C1—H1 | 120.4 |
O1i—Mn1—Cl1 | 95.12 (8) | N1—C1—C2 | 119.1 (3) |
O1—Mn1—Cl1 | 93.65 (7) | C2—C1—H1 | 120.4 |
O1—Mn1—O1i | 72.02 (10) | Mn1—Cl2—Mn1ii | 84.42 (7) |
O1—Mn1—Cl2ii | 165.77 (6) | Mn1—O2—H2A | 108 (3) |
O1i—Mn1—Cl2ii | 94.69 (9) | Mn1—O2—H2B | 116 (3) |
O1i—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) |
O1i—Mn1—O2 | 87.46 (10) | C3—C2—H2 | 119.7 |
Cl2—Mn1—Cl2ii | 95.58 (7) | C2—C3—H3 | 120.4 |
O2—Mn1—Cl1 | 177.42 (7) | C2—C3—C4 | 119.1 (3) |
O2—Mn1—Cl2ii | 87.40 (8) | C4—C3—H3 | 120.4 |
O2—Mn1—Cl2 | 84.01 (9) | C3—C4—H4 | 120.0 |
Mn1—O1—Mn1i | 107.98 (10) | C3—C4—C5 | 120.1 (3) |
N1—O1—Mn1 | 123.78 (14) | C5—C4—H4 | 120.0 |
N1—O1—Mn1i | 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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···Cl1ii | 0.83 (2) | 2.53 (2) | 3.348 (4) | 168 (4) |
O2—H2B···Cl1iii | 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)
top
Crystal data top
[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) Å3 | Prism, colorless |
Z = 4 | 0.2 × 0.2 × 0.1 mm |
F(000) = 508 | |
Data collection top
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 top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.004P)2 + 2.3909P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Mn1—Cl1i | 2.514 (3) | O2—H2B | 0.8947 |
Mn1—Cl1 | 2.516 (4) | C2—H2 | 0.9500 |
Mn1—O1ii | 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 | | |
| | | |
Cl1i—Mn1—Cl1 | 174.01 (5) | N1—C1—C6 | 117.1 (6) |
O1ii—Mn1—Cl1 | 84.38 (18) | C2—C1—C6 | 125.5 (7) |
O1—Mn1—Cl1i | 84.49 (18) | Mn1—O2—H2A | 110.9 |
O1ii—Mn1—Cl1i | 94.57 (18) | Mn1—O2—H2B | 110.5 |
O1—Mn1—Cl1 | 95.84 (18) | H2A—O2—H2B | 108.1 |
O1—Mn1—O1ii | 173.11 (6) | C1—C2—H2 | 119.7 |
O1—Mn1—Cl2 | 91.26 (14) | C3—C2—C1 | 120.5 (7) |
O1ii—Mn1—Cl2 | 95.58 (14) | C3—C2—H2 | 119.7 |
O1ii—Mn1—O2 | 85.39 (19) | C2—C3—H3 | 119.8 |
O1—Mn1—O2 | 87.78 (19) | C2—C3—C4 | 120.3 (6) |
Cl2—Mn1—Cl1i | 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—Cl1i | 89.71 (16) | C5—C4—H4 | 120.5 |
O2—Mn1—Cl2 | 178.46 (15) | N1—C5—C4 | 120.3 (6) |
Mn1ii—Cl1—Mn1 | 86.32 (13) | N1—C5—H5 | 119.9 |
Mn1—O1—Mn1i | 104.73 (19) | C4—C5—H5 | 119.9 |
N1—O1—Mn1i | 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) |
Mn1i—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) |
Mn1i—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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···Cl2iii | 0.90 | 2.49 | 3.205 (7) | 137 |
O2—H2B···Cl2ii | 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)
top
Crystal data top
[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) Å3 | 0.85 × 0.5 × 0.28 mm |
Data collection top
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 top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.031P)2 + 0.023P] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Mn1—Cl1 | 2.4602 (15) | C1—H1 | 0.9300 |
Mn1—Cl2 | 2.4900 (19) | C1—C2 | 1.381 (2) |
Mn1—O1i | 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) |
O1i—Mn1—Cl1 | 165.45 (4) | C5—N1—O1 | 118.86 (16) |
O1i—Mn1—Cl2 | 89.66 (5) | N1—C1—H1 | 119.3 |
O1—Mn1—Cl2 | 93.11 (7) | N1—C1—C2 | 121.31 (16) |
O1—Mn1—O1i | 71.87 (7) | C2—C1—H1 | 119.3 |
O1i—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—O1i | 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—Mn1i | 108.13 (7) | N1—C5—C4 | 119.10 (19) |
N1—O1—Mn1 | 124.29 (9) | N1—C5—H5 | 120.5 |
N1—O1—Mn1i | 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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2B···Cl1ii | 0.80 (2) | 2.38 (2) | 3.147 (3) | 161 (2) |
O3—H3A···Cl2iii | 0.86 (2) | 2.28 (2) | 3.120 (2) | 167 (2) |
Symmetry codes: (ii) −x, −y+1, −z+1; (iii) −x, −y, −z+1. |