Polymorphism in the nitrate salt of the [Mn(acetyl­acetonate)₂(H₂O)₂]⁺ ion

The crystallization of [Mn(acac)₂(H₂O)₂]⁺ from solutions containing excess nitrate leads to the formation of four polymorphs. All polymorphs contain two different types of complex ions, one containing essentially coplanar acac ligands and the other in which the two acac ligands together assume a chair conformation. Molecular modelling using DFT (density-functional theory) calculations shows that the coplanar conformation is the electronically stable one. The hydrogen bonding between the trans-water molecules and the nitrate ion produces a one-dimensional chain of 12-membered rings, which are further organized into a two-dimensional network via a lattice water molecule. Lattice-energy calculations have been carried out to compare the stabilities of the four polymorphs.

Computing details

For all structures, data collection: Bruker SMART; cell refinement: Bruker SMART; data reduction: Bruker SAINT; program(s) used to solve structure: Bruker SHELXTL; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

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Crystal data

C10H20MnNO10	Z = 2
Mr = 369.21	F(000) = 384
Triclinic, P1	Dx = 1.488 Mg m^−3
a = 7.7085 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.7158 (7) Å	Cell parameters from 3333 reflections
c = 15.9918 (14) Å	θ = 2.6–25.0°
α = 97.889 (1)°	µ = 0.85 mm^−1
β = 91.533 (2)°	T = 298 K
γ = 118.380 (1)°	Block, green
V = 824.28 (13) Å^3	0.24 × 0.20 × 0.20 mm

Data collection

CCD area detector diffractometer	3194 independent reflections
Radiation source: fine-focus sealed tube	2677 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
phi and ω scans	θmax = 25.9°, θmin = 1.3°
Absorption correction: empirical (using intensity measurements) sadabs	h = −9→9
Tmin = 0.823, Tmax = 0.849	k = −9→9
8507 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0573P)^2 + 0.4936P] where P = (Fo^2 + 2Fc^2)/3
3194 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.48 e Å^−3
9 restraints	Δρmin = −0.37 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.0000	0.0000	0.0000	0.04353 (18)
Mn2	0.0000	0.0000	0.5000	0.03354 (16)
O1	−0.2556 (3)	−0.1732 (3)	0.03123 (13)	0.0507 (5)
O2	−0.0175 (3)	0.2333 (3)	0.04385 (13)	0.0514 (5)
O3	0.1361 (4)	0.0080 (4)	0.12652 (14)	0.0631 (6)
H31	0.056 (5)	−0.038 (6)	0.161 (3)	0.095*
H32	0.225 (5)	0.112 (5)	0.150 (3)	0.095*
O4	−0.0797 (3)	0.1412 (3)	0.58285 (12)	0.0544 (5)
O5	−0.1226 (3)	0.0544 (3)	0.40979 (12)	0.0550 (5)
O6	0.2777 (4)	0.2763 (4)	0.49672 (15)	0.0720 (7)
H61	0.321 (7)	0.311 (7)	0.456 (2)	0.108*
H62	0.336 (6)	0.347 (6)	0.541 (2)	0.108*
N1	0.4541 (4)	0.4012 (4)	0.29868 (15)	0.0515 (6)
O7	0.5850 (5)	0.5431 (5)	0.3418 (2)	0.1466 (17)
O8	0.4553 (4)	0.3780 (4)	0.22129 (16)	0.0910 (9)
O9	0.3241 (5)	0.2830 (6)	0.3305 (2)	0.1379 (16)
C1	−0.1236 (5)	0.4467 (5)	0.1138 (2)	0.0651 (9)
H1A	−0.0176	0.5113	0.1590	0.098*
H1B	−0.2424	0.4397	0.1343	0.098*
H1C	−0.0891	0.5218	0.0681	0.098*
C2	−0.1577 (4)	0.2401 (4)	0.08276 (16)	0.0474 (6)
C3	−0.3270 (4)	0.0742 (5)	0.09698 (19)	0.0530 (7)
H3	−0.4201	0.0957	0.1258	0.064*
C4	−0.3692 (4)	−0.1220 (4)	0.07172 (17)	0.0473 (6)
C5	−0.5564 (4)	−0.2907 (5)	0.0921 (2)	0.0652 (9)
H5A	−0.6005	−0.4046	0.0478	0.098*
H5B	−0.6567	−0.2507	0.0966	0.098*
H5C	−0.5320	−0.3250	0.1450	0.098*
C6	−0.3238 (11)	0.1937 (11)	0.6556 (5)	0.075 (2)	0.50
H6A	−0.3346	0.3133	0.6537	0.090*	0.50
H6B	−0.2328	0.2179	0.7044	0.090*	0.50
C7	−0.2562 (8)	0.1335 (8)	0.5751 (4)	0.0478 (13)	0.50
C8	−0.2995 (8)	0.0582 (8)	0.4205 (4)	0.0501 (13)	0.50
C9	−0.3590 (9)	0.0993 (9)	0.4984 (4)	0.0583 (15)	0.50
H9	−0.4774	0.1039	0.4983	0.070*	0.50
C10	−0.4157 (11)	0.0365 (11)	0.3396 (5)	0.074 (2)	0.50
H10D	−0.3543	0.0112	0.2907	0.089*	0.50
H10E	−0.4268	0.1558	0.3370	0.089*	0.50
C6A	−0.0916 (11)	0.4397 (11)	0.6433 (4)	0.0674 (17)*	0.50
H6A1	−0.1149	0.5420	0.6262	0.101*	0.50
H6A2	0.0321	0.5006	0.6787	0.101*
H6A3	−0.1972	0.3595	0.6745	0.101*	0.50
C7A	−0.0833 (8)	0.3109 (8)	0.5667 (3)	0.0455 (12)*	0.50
C8A	−0.1170 (8)	0.2319 (8)	0.4118 (3)	0.0441 (12)*	0.50
C9A	−0.1032 (8)	0.3517 (9)	0.4865 (4)	0.0525 (13)*	0.50
H9A	−0.1075	0.4689	0.4828	0.063*	0.50
C10A	−0.1577 (10)	0.2775 (11)	0.3293 (4)	0.0648 (16)*	0.50
H10A	−0.0551	0.2886	0.2941	0.097*	0.50
H10B	−0.1610	0.4015	0.3381	0.097*	0.50
H10C	−0.2833	0.1722	0.3019	0.097*
O1W	0.8769 (5)	0.8320 (5)	0.23999 (16)	0.0923 (9)
H1W	0.791 (7)	0.732 (6)	0.247 (4)	0.138*
H2W	0.931 (7)	0.907 (7)	0.283 (3)	0.138*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0432 (3)	0.0345 (3)	0.0447 (3)	0.0120 (2)	0.0128 (2)	0.0063 (2)
Mn2	0.0339 (3)	0.0329 (3)	0.0361 (3)	0.0177 (2)	0.0048 (2)	0.0068 (2)
O1	0.0463 (10)	0.0399 (10)	0.0544 (11)	0.0111 (9)	0.0151 (9)	0.0084 (9)
O2	0.0533 (11)	0.0375 (10)	0.0563 (12)	0.0161 (9)	0.0185 (9)	0.0061 (8)
O3	0.0629 (14)	0.0609 (14)	0.0493 (13)	0.0172 (11)	0.0038 (10)	0.0090 (10)
O4	0.0645 (13)	0.0690 (13)	0.0457 (11)	0.0477 (11)	0.0052 (9)	−0.0002 (9)
O5	0.0739 (14)	0.0642 (13)	0.0441 (11)	0.0480 (12)	−0.0041 (9)	0.0075 (9)
O6	0.0618 (14)	0.0589 (14)	0.0523 (13)	−0.0050 (11)	0.0105 (11)	0.0079 (11)
N1	0.0518 (14)	0.0501 (14)	0.0480 (14)	0.0202 (12)	0.0096 (11)	0.0109 (11)
O7	0.126 (3)	0.109 (3)	0.079 (2)	−0.035 (2)	−0.0130 (19)	−0.0143 (19)
O8	0.0967 (19)	0.096 (2)	0.0530 (15)	0.0238 (16)	0.0181 (13)	0.0163 (14)
O9	0.121 (3)	0.126 (3)	0.076 (2)	−0.017 (2)	0.0348 (19)	0.0304 (19)
C1	0.074 (2)	0.0530 (18)	0.065 (2)	0.0291 (17)	0.0204 (17)	0.0053 (15)
C2	0.0559 (16)	0.0495 (16)	0.0350 (13)	0.0240 (14)	0.0063 (12)	0.0077 (12)
C3	0.0516 (16)	0.0559 (18)	0.0525 (17)	0.0254 (14)	0.0155 (13)	0.0127 (14)
C4	0.0406 (14)	0.0516 (16)	0.0415 (14)	0.0141 (13)	0.0052 (11)	0.0138 (12)
C5	0.0466 (17)	0.063 (2)	0.075 (2)	0.0149 (15)	0.0170 (15)	0.0231 (17)
C6	0.076 (5)	0.073 (5)	0.085 (5)	0.047 (4)	0.026 (4)	−0.003 (4)
C7	0.043 (3)	0.033 (3)	0.069 (4)	0.019 (2)	0.015 (3)	0.007 (2)
C8	0.044 (3)	0.037 (3)	0.071 (4)	0.019 (2)	−0.002 (3)	0.015 (3)
C9	0.044 (3)	0.058 (4)	0.083 (5)	0.032 (3)	0.010 (3)	0.012 (3)
C10	0.074 (5)	0.082 (5)	0.080 (5)	0.048 (4)	−0.009 (4)	0.022 (4)
O1W	0.119 (3)	0.0762 (19)	0.0470 (14)	0.0201 (17)	0.0169 (15)	0.0066 (13)

Geometric parameters (Å, º)

Mn1—O2	1.9076 (19)	O5—C8	1.392 (6)
Mn1—O2^i	1.9076 (19)	N1—O9	1.175 (3)
Mn1—O1	1.9104 (18)	N1—O7	1.182 (4)
Mn1—O1^i	1.9104 (18)	N1—O8	1.227 (3)
Mn1—O3^i	2.234 (2)	C1—C2	1.495 (4)
Mn1—O3	2.234 (2)	C2—C3	1.379 (4)
Mn2—O4	1.8983 (18)	C3—C4	1.385 (4)
Mn2—O4^ii	1.8983 (18)	C4—C5	1.496 (4)
Mn2—O5^ii	1.9026 (18)	C6—C7	1.499 (8)
Mn2—O5	1.9026 (18)	C7—C9	1.365 (9)
Mn2—O6	2.197 (2)	C8—C9	1.386 (9)
Mn2—O6^ii	2.197 (2)	C8—C10	1.497 (9)
O1—C4	1.277 (3)	C6A—C7A	1.492 (9)
O2—C2	1.280 (3)	C7A—C9A	1.383 (8)
O4—C7	1.335 (6)	C8A—C9A	1.374 (8)
O4—C7A	1.382 (6)	C8A—C10A	1.475 (8)
O5—C8A	1.346 (6)
O2—Mn1—O2^i	180.00 (15)	C7—O4—Mn2	122.8 (3)
O2—Mn1—O1	92.27 (8)	C7A—O4—Mn2	119.6 (3)
O2^i—Mn1—O1	87.73 (8)	C8A—O5—C8	63.3 (3)
O2—Mn1—O1^i	87.73 (8)	C8A—O5—Mn2	122.2 (3)
O2^i—Mn1—O1^i	92.27 (8)	C8—O5—Mn2	119.0 (3)
O1—Mn1—O1^i	180.00 (15)	O9—N1—O7	119.6 (3)
O2—Mn1—O3^i	89.68 (9)	O9—N1—O8	120.5 (3)
O2^i—Mn1—O3^i	90.32 (9)	O7—N1—O8	119.9 (3)
O1—Mn1—O3^i	90.59 (9)	O2—C2—C3	124.3 (3)
O1^i—Mn1—O3^i	89.41 (9)	O2—C2—C1	114.4 (3)
O2—Mn1—O3	90.32 (9)	C3—C2—C1	121.2 (3)
O2^i—Mn1—O3	89.68 (9)	C2—C3—C4	125.1 (3)
O1—Mn1—O3	89.41 (9)	O1—C4—C3	124.1 (2)
O1^i—Mn1—O3	90.59 (9)	O1—C4—C5	115.4 (3)
O3^i—Mn1—O3	180.00 (14)	C3—C4—C5	120.5 (3)
O4—Mn2—O4^ii	180.000 (1)	C7—C6—C10^iii	103.8 (5)
O4—Mn2—O5^ii	88.21 (8)	O4—C7—C9	122.9 (5)
O4^ii—Mn2—O5^ii	91.79 (8)	O4—C7—C6	115.8 (5)
O4—Mn2—O5	91.79 (8)	C9—C7—C6	120.8 (6)
O4^ii—Mn2—O5	88.21 (8)	C9—C8—O5	124.6 (5)
O5^ii—Mn2—O5	180.000 (1)	C9—C8—C10	120.5 (5)
O4—Mn2—O6	90.08 (10)	O5—C8—C10	114.5 (5)
O4^ii—Mn2—O6	89.92 (10)	C7—C9—C8	124.7 (5)
O5^ii—Mn2—O6	89.78 (10)	C7—C9—C9^iii	109.1 (6)
O5—Mn2—O6	90.22 (10)	C8—C9—C9^iii	109.1 (6)
O4—Mn2—O6^ii	89.92 (10)	C8—C10—C6^iii	103.8 (5)
O4^ii—Mn2—O6^ii	90.08 (10)	O4—C7A—C9A	124.7 (5)
O5^ii—Mn2—O6^ii	90.22 (10)	O4—C7A—C6A	114.5 (5)
O5—Mn2—O6^ii	89.78 (10)	C9A—C7A—C6A	120.4 (5)
O6—Mn2—O6^ii	180.00 (13)	O5—C8A—C9A	122.5 (5)
C4—O1—Mn1	127.12 (18)	O5—C8A—C10A	116.0 (5)
C2—O2—Mn1	126.97 (18)	C9A—C8A—C10A	120.9 (5)
C7—O4—C7A	62.6 (3)	C8A—C9A—C7A	124.8 (6)

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

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Crystal data

C10H18MnO6·NO3·H2O	Z = 4
Mr = 369.21	F(000) = 768
Triclinic, P1	Dx = 1.491 Mg m^−3
a = 7.902 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.238 (7) Å	Cell parameters from 4567 reflections
c = 15.966 (8) Å	θ = 2.6–26.1°
α = 86.226 (8)°	µ = 0.85 mm^−1
β = 80.642 (8)°	T = 298 K
γ = 89.990 (8)°	Diamond block, green
V = 1644.2 (14) Å^3	0.24 × 0.18 × 0.16 mm

Data collection

CCD area detector diffractometer	6520 independent reflections
Radiation source: fine-focus sealed tube	4123 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
phi and ω scans	θmax = 26.2°, θmin = 1.3°
Absorption correction: empirical (using intensity measurements) sadabs	h = −9→9
Tmin = 0.822, Tmax = 0.876	k = −16→16
17286 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0617P)^2 + 0.0075P] where P = (Fo^2 + 2Fc^2)/3
6520 reflections	(Δ/σ)max = 0.003
447 parameters	Δρmax = 0.41 e Å^−3
19 restraints	Δρmin = −0.23 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.5000	0.0000	0.0000	0.03245 (14)
Mn2	0.0000	0.5000	0.0000	0.03348 (14)
Mn3	0.0000	0.5000	0.5000	0.04283 (15)
Mn4	0.5000	0.0000	0.5000	0.04270 (15)
O1	0.4885 (2)	0.08611 (11)	0.09205 (10)	0.0419 (4)
O2	0.5510 (2)	0.11190 (11)	−0.08105 (10)	0.0424 (4)
O3	0.7765 (2)	−0.01894 (14)	0.00239 (12)	0.0460 (4)
H31	0.836 (4)	0.004 (2)	−0.0386 (16)	0.069*
H32	0.809 (4)	−0.012 (2)	0.0440 (16)	0.069*
O4	0.0559 (2)	0.40944 (12)	−0.08820 (10)	0.0435 (4)
O5	−0.0099 (2)	0.39186 (11)	0.08507 (10)	0.0434 (4)
O6	0.2757 (2)	0.51781 (14)	0.00450 (12)	0.0474 (4)
H61	0.314 (4)	0.494 (2)	0.0435 (17)	0.071*
H62	0.336 (4)	0.506 (2)	−0.0390 (16)	0.071*
O7	0.1084 (2)	0.62485 (13)	0.45571 (11)	0.0515 (4)
O8	−0.2139 (2)	0.54136 (13)	0.46795 (11)	0.0490 (4)
O9	0.0723 (3)	0.43407 (17)	0.37454 (13)	0.0610 (5)
H92	0.160 (4)	0.440 (3)	0.353 (2)	0.091*
H91	0.006 (4)	0.451 (2)	0.340 (2)	0.091*
O11	0.6066 (2)	0.12552 (13)	0.45682 (11)	0.0506 (4)
O10	0.2841 (2)	0.04096 (13)	0.46926 (11)	0.0490 (4)
O12	0.4285 (3)	0.06197 (17)	0.62732 (13)	0.0624 (6)
H122	0.497 (4)	0.050 (2)	0.662 (2)	0.094*
H121	0.338 (4)	0.050 (3)	0.649 (2)	0.094*
O13	0.0843 (3)	0.0400 (2)	0.72140 (14)	0.0908 (8)
O14	0.1919 (3)	−0.00574 (17)	0.83092 (14)	0.0862 (7)
O15	−0.0640 (3)	0.04790 (18)	0.84232 (15)	0.0889 (7)
O16	0.4174 (3)	0.46317 (19)	0.27933 (14)	0.0886 (7)
O17	0.3054 (3)	0.45294 (18)	0.16861 (15)	0.0898 (7)
O18	0.5622 (3)	0.50611 (18)	0.15915 (15)	0.0886 (7)
N1	0.0723 (3)	0.02667 (16)	0.79853 (15)	0.0513 (5)
N2	0.4277 (3)	0.47437 (16)	0.20155 (15)	0.0509 (5)
C1	0.5582 (4)	0.2174 (2)	0.17167 (17)	0.0670 (8)
H1A	0.4427	0.2311	0.1973	0.101*
H1B	0.6244	0.2791	0.1637	0.101*
H1C	0.6082	0.1695	0.2081	0.101*
C2	0.5571 (3)	0.17478 (18)	0.08784 (16)	0.0438 (6)
C3	0.6243 (3)	0.22773 (18)	0.01321 (17)	0.0535 (7)
H3	0.6809	0.2885	0.0167	0.064*
C4	0.6137 (3)	0.19710 (18)	−0.06686 (17)	0.0464 (6)
C5	0.6752 (4)	0.2647 (2)	−0.14482 (18)	0.0700 (9)
H5A	0.7575	0.2294	−0.1830	0.105*
H5B	0.7278	0.3243	−0.1289	0.105*
H5C	0.5797	0.2836	−0.1725	0.105*
C6	0.1829 (4)	0.2737 (2)	−0.16076 (19)	0.0736 (9)
H6A	0.0878	0.2621	−0.1895	0.110*
H6B	0.2366	0.2104	−0.1490	0.110*
H6C	0.2646	0.3182	−0.1962	0.110*
C7	0.1203 (3)	0.32099 (18)	−0.07912 (17)	0.0491 (6)
C8	0.1297 (3)	0.27105 (18)	−0.00121 (19)	0.0580 (7)
H8	0.1871	0.2097	−0.0012	0.070*
C9	0.0610 (3)	0.30524 (18)	0.07563 (18)	0.0481 (6)
C10	0.0618 (4)	0.2409 (2)	0.15613 (19)	0.0737 (9)
H10A	0.0849	0.2825	0.2001	0.111*
H10B	0.1492	0.1905	0.1469	0.111*
H10C	−0.0480	0.2082	0.1731	0.111*
C11	0.1628 (4)	0.7857 (2)	0.38674 (19)	0.0652 (8)
H11A	0.2108	0.8084	0.4338	0.098*
H11B	0.1016	0.8401	0.3629	0.098*
H11C	0.2533	0.7643	0.3441	0.098*
C12	0.0426 (3)	0.69896 (19)	0.41688 (15)	0.0465 (6)
C13	−0.1252 (3)	0.7007 (2)	0.40235 (17)	0.0527 (7)
H13	−0.1605	0.7580	0.3733	0.063*
C14	−0.2448 (3)	0.6237 (2)	0.42776 (15)	0.0461 (6)
C15	−0.4221 (3)	0.6338 (2)	0.40773 (19)	0.0650 (8)
H15A	−0.4283	0.6034	0.3554	0.097*
H15B	−0.4503	0.7042	0.4021	0.097*
H15C	−0.5018	0.6004	0.4528	0.097*
C16	0.0762 (3)	0.1320 (2)	0.40781 (19)	0.0650 (8)
H16A	0.0726	0.1034	0.3544	0.097*
H16B	0.0452	0.2021	0.4039	0.097*
H16C	−0.0031	0.0962	0.4517	0.097*
C17	0.2533 (3)	0.1233 (2)	0.42877 (15)	0.0457 (6)
C18	0.3722 (3)	0.2004 (2)	0.40325 (16)	0.0510 (6)
H18	0.3366	0.2576	0.3742	0.061*
C19	0.5395 (3)	0.19894 (19)	0.41765 (15)	0.0453 (6)
C20	0.6593 (4)	0.2853 (2)	0.38626 (18)	0.0632 (8)
H20A	0.7133	0.3062	0.4321	0.095*
H20B	0.5964	0.3408	0.3653	0.095*
H20C	0.7453	0.2645	0.3412	0.095*
O1W	0.8561 (3)	0.4721 (2)	0.26014 (14)	0.0903 (8)
H1W	0.922 (5)	0.474 (3)	0.218 (2)	0.135*
H2W	0.760 (4)	0.481 (3)	0.253 (3)	0.135*
O2W	0.6495 (3)	0.0157 (2)	0.73982 (14)	0.0865 (8)
H3W	0.741 (4)	0.030 (3)	0.749 (3)	0.130*
H4W	0.582 (4)	0.021 (3)	0.7845 (19)	0.130*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0333 (3)	0.0299 (3)	0.0345 (3)	−0.00275 (19)	−0.0057 (2)	−0.0035 (2)
Mn2	0.0350 (3)	0.0299 (3)	0.0359 (3)	0.0024 (2)	−0.0075 (2)	−0.0010 (2)
Mn3	0.0333 (3)	0.0511 (3)	0.0444 (3)	−0.0043 (2)	−0.0113 (2)	0.0066 (2)
Mn4	0.0333 (3)	0.0510 (3)	0.0437 (3)	−0.0044 (2)	−0.0100 (2)	0.0068 (2)
O1	0.0432 (10)	0.0404 (9)	0.0428 (10)	−0.0048 (7)	−0.0059 (7)	−0.0106 (7)
O2	0.0478 (10)	0.0352 (9)	0.0443 (10)	−0.0065 (7)	−0.0090 (8)	0.0016 (7)
O3	0.0378 (10)	0.0532 (11)	0.0480 (11)	0.0021 (8)	−0.0094 (8)	−0.0033 (9)
O4	0.0458 (10)	0.0405 (9)	0.0463 (10)	0.0056 (7)	−0.0098 (8)	−0.0119 (7)
O5	0.0437 (10)	0.0392 (9)	0.0460 (10)	0.0039 (7)	−0.0073 (8)	0.0065 (7)
O6	0.0380 (10)	0.0548 (11)	0.0502 (12)	−0.0015 (8)	−0.0100 (8)	−0.0020 (9)
O7	0.0422 (10)	0.0573 (11)	0.0553 (11)	−0.0072 (8)	−0.0142 (8)	0.0098 (9)
O8	0.0348 (9)	0.0603 (11)	0.0527 (11)	−0.0016 (8)	−0.0127 (8)	0.0043 (9)
O9	0.0506 (12)	0.0830 (14)	0.0488 (13)	−0.0021 (11)	−0.0068 (9)	−0.0044 (10)
O11	0.0401 (10)	0.0553 (11)	0.0561 (11)	−0.0089 (8)	−0.0129 (8)	0.0119 (9)
O10	0.0337 (9)	0.0608 (11)	0.0524 (11)	−0.0046 (8)	−0.0115 (8)	0.0074 (9)
O12	0.0536 (13)	0.0837 (14)	0.0488 (13)	−0.0038 (11)	−0.0047 (10)	−0.0054 (10)
O13	0.0792 (16)	0.144 (2)	0.0498 (14)	0.0050 (15)	−0.0179 (12)	0.0050 (14)
O14	0.0799 (16)	0.1095 (18)	0.0806 (16)	0.0306 (13)	−0.0427 (13)	−0.0166 (13)
O15	0.0566 (14)	0.121 (2)	0.0794 (16)	0.0055 (13)	0.0133 (12)	0.0057 (14)
O16	0.0813 (16)	0.136 (2)	0.0505 (14)	−0.0059 (14)	−0.0190 (12)	0.0015 (14)
O17	0.0795 (16)	0.1143 (19)	0.0827 (16)	−0.0327 (13)	−0.0427 (13)	0.0147 (14)
O18	0.0567 (14)	0.1189 (19)	0.0821 (16)	−0.0146 (13)	0.0143 (12)	−0.0095 (14)
N1	0.0473 (14)	0.0595 (14)	0.0475 (15)	−0.0024 (11)	−0.0090 (12)	−0.0041 (11)
N2	0.0475 (14)	0.0588 (14)	0.0478 (15)	0.0018 (11)	−0.0123 (12)	−0.0027 (11)
C1	0.072 (2)	0.0655 (19)	0.070 (2)	−0.0007 (15)	−0.0177 (16)	−0.0337 (15)
C2	0.0345 (13)	0.0411 (14)	0.0589 (17)	0.0031 (11)	−0.0121 (12)	−0.0158 (12)
C3	0.0588 (18)	0.0345 (14)	0.0685 (19)	−0.0093 (12)	−0.0120 (14)	−0.0074 (13)
C4	0.0411 (14)	0.0364 (14)	0.0609 (17)	0.0010 (11)	−0.0093 (12)	0.0048 (12)
C5	0.080 (2)	0.0490 (17)	0.076 (2)	−0.0117 (15)	−0.0084 (17)	0.0196 (15)
C6	0.070 (2)	0.0658 (19)	0.087 (2)	0.0075 (15)	−0.0041 (17)	−0.0379 (17)
C7	0.0394 (14)	0.0397 (14)	0.0690 (19)	−0.0008 (11)	−0.0068 (13)	−0.0150 (13)
C8	0.0572 (18)	0.0345 (14)	0.081 (2)	0.0108 (12)	−0.0080 (15)	−0.0017 (14)
C9	0.0352 (14)	0.0408 (14)	0.0678 (18)	−0.0047 (11)	−0.0122 (13)	0.0093 (13)
C10	0.072 (2)	0.0565 (18)	0.089 (2)	0.0026 (15)	−0.0161 (17)	0.0294 (17)
C11	0.0644 (19)	0.0669 (19)	0.0631 (19)	−0.0107 (15)	−0.0147 (15)	0.0155 (15)
C12	0.0497 (16)	0.0534 (16)	0.0366 (14)	−0.0020 (12)	−0.0086 (12)	−0.0008 (12)
C13	0.0543 (17)	0.0534 (16)	0.0532 (17)	0.0022 (13)	−0.0188 (13)	0.0015 (13)
C14	0.0423 (15)	0.0598 (17)	0.0386 (14)	0.0102 (12)	−0.0122 (11)	−0.0085 (12)
C15	0.0478 (17)	0.077 (2)	0.075 (2)	0.0091 (14)	−0.0247 (15)	−0.0067 (16)
C16	0.0479 (17)	0.076 (2)	0.074 (2)	0.0068 (14)	−0.0213 (15)	−0.0028 (16)
C17	0.0413 (15)	0.0585 (16)	0.0382 (14)	0.0069 (12)	−0.0088 (11)	−0.0051 (12)
C18	0.0512 (17)	0.0519 (16)	0.0512 (16)	0.0053 (13)	−0.0148 (13)	0.0026 (12)
C19	0.0481 (16)	0.0542 (16)	0.0333 (14)	−0.0043 (12)	−0.0073 (11)	0.0002 (12)
C20	0.0683 (19)	0.0588 (18)	0.0617 (19)	−0.0132 (14)	−0.0150 (15)	0.0129 (14)
O1W	0.0732 (16)	0.149 (2)	0.0470 (13)	−0.0064 (17)	−0.0131 (12)	0.0116 (14)
O2W	0.0785 (17)	0.135 (2)	0.0454 (13)	−0.0344 (16)	−0.0127 (12)	0.0065 (13)

Geometric parameters (Å, º)

Mn1—O2	1.8999 (16)	O5—C9	1.283 (3)
Mn1—O2^i	1.8999 (16)	O7—C12	1.281 (3)
Mn1—O1	1.9091 (16)	O8—C14	1.273 (3)
Mn1—O1^i	1.9091 (16)	O11—C19	1.283 (3)
Mn1—O3^i	2.205 (2)	O10—C17	1.274 (3)
Mn1—O3	2.205 (2)	O13—N1	1.221 (3)
Mn2—O5^ii	1.9000 (16)	O14—N1	1.214 (3)
Mn2—O5	1.9000 (16)	O15—N1	1.228 (3)
Mn2—O4	1.9067 (16)	O16—N2	1.230 (3)
Mn2—O4^ii	1.9067 (16)	O17—N2	1.215 (3)
Mn2—O6^ii	2.205 (2)	O18—N2	1.222 (3)
Mn2—O6	2.205 (2)	C1—C2	1.488 (3)
Mn3—O7	1.9014 (18)	C2—C3	1.370 (3)
Mn3—O7^iii	1.9014 (18)	C3—C4	1.382 (3)
Mn3—O8	1.9137 (18)	C4—C5	1.498 (3)
Mn3—O8^iii	1.9137 (18)	C6—C7	1.494 (3)
Mn3—O9	2.227 (2)	C7—C8	1.383 (4)
Mn3—O9^iii	2.227 (2)	C8—C9	1.364 (4)
Mn4—O11	1.8993 (18)	C9—C10	1.496 (3)
Mn4—O11^iv	1.8993 (18)	C11—C12	1.494 (4)
Mn4—O10	1.9189 (18)	C12—C13	1.382 (4)
Mn4—O10^iv	1.9189 (18)	C13—C14	1.385 (4)
Mn4—O12^iv	2.229 (2)	C14—C15	1.491 (3)
Mn4—O12	2.229 (2)	C16—C17	1.494 (3)
O1—C2	1.286 (3)	C17—C18	1.383 (4)
O2—C4	1.280 (3)	C18—C19	1.378 (3)
O4—C7	1.285 (3)	C19—C20	1.492 (4)
O2—Mn1—O2^i	180.00 (10)	O11—Mn4—O12^iv	90.17 (8)
O2—Mn1—O1	91.39 (8)	O11^iv—Mn4—O12^iv	89.83 (8)
O2^i—Mn1—O1	88.61 (8)	O10—Mn4—O12^iv	89.17 (8)
O2—Mn1—O1^i	88.61 (8)	O10^iv—Mn4—O12^iv	90.83 (8)
O2^i—Mn1—O1^i	91.39 (8)	O11—Mn4—O12	89.83 (8)
O1—Mn1—O1^i	180.00 (8)	O11^iv—Mn4—O12	90.17 (8)
O2—Mn1—O3^i	90.39 (7)	O10—Mn4—O12	90.83 (8)
O2^i—Mn1—O3^i	89.61 (7)	O10^iv—Mn4—O12	89.17 (8)
O1—Mn1—O3^i	90.99 (7)	O12^iv—Mn4—O12	180.00 (5)
O1^i—Mn1—O3^i	89.01 (7)	C2—O1—Mn1	125.60 (16)
O2—Mn1—O3	89.61 (7)	C4—O2—Mn1	125.55 (16)
O2^i—Mn1—O3	90.39 (7)	C7—O4—Mn2	125.28 (16)
O1—Mn1—O3	89.01 (7)	C9—O5—Mn2	125.93 (16)
O1^i—Mn1—O3	90.99 (7)	C12—O7—Mn3	127.25 (17)
O3^i—Mn1—O3	180.00 (10)	C14—O8—Mn3	127.27 (16)
O5^ii—Mn2—O5	180.00 (10)	C19—O11—Mn4	126.83 (16)
O5^ii—Mn2—O4	88.58 (8)	C17—O10—Mn4	126.77 (16)
O5—Mn2—O4	91.42 (8)	O14—N1—O13	121.0 (2)
O5^ii—Mn2—O4^ii	91.42 (8)	O14—N1—O15	121.1 (3)
O5—Mn2—O4^ii	88.58 (8)	O13—N1—O15	117.9 (2)
O4—Mn2—O4^ii	180.0	O17—N2—O18	121.6 (3)
O5^ii—Mn2—O6^ii	88.85 (7)	O17—N2—O16	119.6 (3)
O5—Mn2—O6^ii	91.15 (7)	O18—N2—O16	118.8 (2)
O4—Mn2—O6^ii	90.78 (7)	O1—C2—C3	124.0 (2)
O4^ii—Mn2—O6^ii	89.22 (7)	O1—C2—C1	114.6 (2)
O5^ii—Mn2—O6	91.15 (7)	C3—C2—C1	121.5 (2)
O5—Mn2—O6	88.85 (7)	C2—C3—C4	124.5 (2)
O4—Mn2—O6	89.22 (7)	O2—C4—C3	124.3 (2)
O4^ii—Mn2—O6	90.78 (7)	O2—C4—C5	114.9 (2)
O6^ii—Mn2—O6	180.0	C3—C4—C5	120.9 (2)
O7—Mn3—O7^iii	180.0	O4—C7—C8	124.0 (2)
O7—Mn3—O8	92.19 (8)	O4—C7—C6	114.4 (2)
O7^iii—Mn3—O8	87.81 (8)	C8—C7—C6	121.5 (2)
O7—Mn3—O8^iii	87.81 (8)	C9—C8—C7	124.7 (2)
O7^iii—Mn3—O8^iii	92.19 (8)	O5—C9—C8	124.1 (2)
O8—Mn3—O8^iii	180.00 (9)	O5—C9—C10	115.2 (2)
O7—Mn3—O9	90.80 (8)	C8—C9—C10	120.8 (2)
O7^iii—Mn3—O9	89.20 (8)	O7—C12—C13	124.1 (2)
O8—Mn3—O9	89.43 (8)	O7—C12—C11	114.6 (2)
O8^iii—Mn3—O9	90.57 (8)	C13—C12—C11	121.3 (2)
O7—Mn3—O9^iii	89.20 (8)	C12—C13—C14	125.1 (2)
O7^iii—Mn3—O9^iii	90.80 (8)	O8—C14—C13	124.0 (2)
O8—Mn3—O9^iii	90.57 (8)	O8—C14—C15	115.7 (2)
O8^iii—Mn3—O9^iii	89.43 (8)	C13—C14—C15	120.3 (2)
O9—Mn3—O9^iii	180.000 (1)	O10—C17—C18	124.3 (2)
O11—Mn4—O11^iv	180.0	O10—C17—C16	115.3 (2)
O11—Mn4—O10	92.40 (7)	C18—C17—C16	120.4 (2)
O11^iv—Mn4—O10	87.60 (7)	C19—C18—C17	125.0 (2)
O11—Mn4—O10^iv	87.60 (7)	O11—C19—C18	124.6 (2)
O11^iv—Mn4—O10^iv	92.40 (7)	O11—C19—C20	114.4 (2)
O10—Mn4—O10^iv	180.0	C18—C19—C20	121.0 (2)

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

(3)

Crystal data

C10H18MnO6·NO3·H2O	Z = 4
Mr = 369.21	F(000) = 768
Triclinic, p1	Dx = 1.478 Mg m^−3
a = 7.901 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.298 (7) Å	Cell parameters from 7319 reflections
c = 16.832 (8) Å	θ = 2.4–26.1°
α = 109.655 (7)°	µ = 0.84 mm^−1
β = 94.745 (8)°	T = 298 K
γ = 90.033 (8)°	Block, green
V = 1659.0 (14) Å^3	0.24 × 0.22 × 0.18 mm

Data collection

CCD area detector diffractometer	6491 independent reflections
Radiation source: fine-focus sealed tube	4461 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
phi and ω scans	θmax = 26.2°, θmin = 1.3°
Absorption correction: empirical (using intensity measurements) sadabs	h = −9→9
Tmin = 0.824, Tmax = 0.863	k = −16→16
16977 measured reflections	l = −20→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0597P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
6491 reflections	Δρmax = 0.35 e Å^−3
445 parameters	Δρmin = −0.28 e Å^−3
18 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0180 (10)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.75279 (4)	0.74868 (2)	−0.000237 (18)	0.04153 (12)
Mn2	0.5000	0.5000	0.5000	0.03243 (13)
Mn3	0.0000	0.0000	0.5000	0.03126 (13)
O1	0.98304 (18)	0.72361 (13)	0.03125 (10)	0.0482 (4)
O2	0.66697 (19)	0.64543 (13)	0.04364 (10)	0.0501 (4)
O3	0.52252 (18)	0.77454 (13)	−0.03135 (10)	0.0493 (4)
O4	0.83867 (18)	0.85204 (13)	−0.04413 (10)	0.0495 (4)
O5	0.7440 (2)	0.87548 (16)	0.12651 (11)	0.0615 (5)
H51	0.664 (3)	0.877 (3)	0.149 (2)	0.092*
H52	0.824 (3)	0.882 (2)	0.1631 (19)	0.092*
O6	0.7606 (2)	0.62055 (16)	−0.12611 (11)	0.0593 (5)
H61	0.842 (3)	0.621 (3)	−0.1485 (19)	0.089*
H62	0.683 (3)	0.619 (2)	−0.1626 (19)	0.089*
O7	0.51202 (18)	0.36555 (11)	0.41142 (9)	0.0422 (4)
O8	0.53195 (18)	0.43365 (11)	0.58466 (9)	0.0426 (4)
O9	0.7780 (2)	0.52037 (13)	0.50460 (11)	0.0467 (4)
H91	0.819 (4)	0.487 (2)	0.4626 (15)	0.070*
H92	0.835 (3)	0.516 (2)	0.5447 (15)	0.070*
O10	0.01088 (18)	0.07177 (11)	0.41931 (9)	0.0406 (3)
O11	0.03443 (18)	0.13214 (10)	0.59245 (9)	0.0399 (3)
O12	−0.2780 (2)	0.01754 (13)	0.49776 (11)	0.0458 (4)
H121	−0.334 (3)	−0.014 (2)	0.4562 (15)	0.069*
H122	−0.319 (3)	0.016 (2)	0.5390 (15)	0.069*
C1	1.2216 (3)	0.6634 (2)	0.09305 (17)	0.0633 (7)
H1A	1.2793	0.6762	0.0492	0.095*
H1B	1.2541	0.5959	0.0976	0.095*
H1C	1.2520	0.7193	0.1459	0.095*
C2	1.0345 (3)	0.66169 (18)	0.07189 (13)	0.0445 (5)
C3	0.9280 (3)	0.59715 (18)	0.09716 (14)	0.0497 (6)
H3	0.9781	0.5548	0.1261	0.060*
C4	0.7532 (3)	0.59139 (18)	0.08243 (13)	0.0442 (5)
C5	0.6488 (3)	0.5203 (2)	0.11343 (17)	0.0630 (7)
H5A	0.5889	0.5633	0.1598	0.094*
H5B	0.7220	0.4735	0.1320	0.094*
H5C	0.5686	0.4787	0.0683	0.094*
C6	0.8568 (3)	0.9774 (2)	−0.11409 (16)	0.0623 (7)
H6A	0.9284	1.0244	−0.0675	0.093*
H6B	0.7830	1.0189	−0.1382	0.093*
H6C	0.9259	0.9345	−0.1563	0.093*
C7	0.7521 (3)	0.90625 (18)	−0.08306 (13)	0.0444 (5)
C8	0.5778 (3)	0.90087 (19)	−0.09724 (14)	0.0510 (6)
H8	0.5276	0.9431	−0.1263	0.061*
C9	0.4716 (3)	0.83703 (18)	−0.07131 (13)	0.0449 (5)
C10	0.2834 (3)	0.8371 (2)	−0.09059 (17)	0.0641 (7)
H10A	0.2507	0.7828	−0.1440	0.096*
H10B	0.2515	0.9056	−0.0933	0.096*
H10C	0.2272	0.8230	−0.0468	0.096*
C11	0.6036 (4)	0.19347 (18)	0.33849 (16)	0.0724 (8)
H11A	0.4944	0.1678	0.3091	0.109*
H11B	0.6621	0.1361	0.3502	0.109*
H11C	0.6690	0.2203	0.3039	0.109*
C12	0.5808 (3)	0.28123 (16)	0.41998 (15)	0.0480 (6)
C13	0.6289 (3)	0.26950 (17)	0.49726 (16)	0.0576 (6)
H13	0.6861	0.2083	0.4969	0.069*
C14	0.5978 (3)	0.34235 (18)	0.57465 (16)	0.0484 (6)
C15	0.6389 (3)	0.3182 (2)	0.65514 (17)	0.0744 (8)
H15A	0.6940	0.3796	0.6975	0.112*
H15B	0.7130	0.2588	0.6445	0.112*
H15C	0.5359	0.3007	0.6748	0.112*
C16	0.1029 (4)	0.1928 (2)	0.35604 (16)	0.0674 (7)
H16A	0.1706	0.1405	0.3191	0.101*
H16B	0.1587	0.2618	0.3724	0.101*
H16C	−0.0064	0.1946	0.3271	0.101*
C17	0.0807 (3)	0.16402 (17)	0.43371 (14)	0.0437 (5)
C18	0.1310 (3)	0.23475 (17)	0.51398 (14)	0.0518 (6)
H18	0.1889	0.2974	0.5179	0.062*
C19	0.1011 (3)	0.21869 (16)	0.58828 (14)	0.0442 (5)
C20	0.1449 (3)	0.30406 (18)	0.67236 (15)	0.0654 (7)
H20A	0.0424	0.3309	0.6978	0.098*
H20B	0.2077	0.3612	0.6644	0.098*
H20C	0.2127	0.2747	0.7087	0.098*
N1	0.5284 (3)	0.07308 (15)	0.70145 (13)	0.0489 (5)
N2	0.9716 (3)	0.42499 (15)	0.29855 (13)	0.0499 (5)
O13	0.3920 (3)	0.09005 (16)	0.66974 (12)	0.0844 (6)
O14	0.6427 (3)	0.03064 (18)	0.65747 (13)	0.0889 (7)
O15	0.5536 (3)	0.09775 (19)	0.77890 (12)	0.0886 (7)
O16	0.8583 (3)	0.41442 (18)	0.34123 (13)	0.0874 (6)
O17	1.1104 (3)	0.46290 (18)	0.33121 (13)	0.0892 (7)
O18	0.9421 (3)	0.39658 (19)	0.22098 (12)	0.0892 (7)
O1W	0.5135 (3)	0.3984 (2)	0.23996 (13)	0.0899 (7)
H1W	0.609 (4)	0.399 (3)	0.245 (3)	0.135*
H2W	0.473 (5)	0.412 (3)	0.285 (2)	0.135*
O2W	0.0193 (3)	0.8869 (2)	0.23960 (12)	0.0852 (7)
H3W	0.119 (4)	0.911 (3)	0.248 (2)	0.128*
H4W	−0.009 (5)	0.898 (3)	0.287 (2)	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0300 (2)	0.0561 (2)	0.0425 (2)	−0.00262 (15)	−0.00017 (15)	0.02266 (17)
Mn2	0.0331 (3)	0.0297 (2)	0.0354 (3)	0.00278 (17)	0.00133 (18)	0.01249 (18)
Mn3	0.0325 (3)	0.0280 (2)	0.0323 (2)	−0.00247 (17)	0.00242 (18)	0.00906 (18)
O1	0.0301 (8)	0.0665 (10)	0.0525 (9)	−0.0004 (7)	0.0011 (7)	0.0265 (8)
O2	0.0375 (9)	0.0659 (10)	0.0538 (10)	−0.0064 (7)	−0.0010 (7)	0.0303 (8)
O3	0.0319 (8)	0.0660 (10)	0.0533 (10)	−0.0013 (7)	0.0008 (7)	0.0250 (8)
O4	0.0358 (9)	0.0680 (10)	0.0531 (9)	−0.0043 (7)	0.0000 (7)	0.0324 (8)
O5	0.0521 (12)	0.0782 (12)	0.0481 (11)	−0.0014 (10)	0.0065 (8)	0.0130 (9)
O6	0.0485 (11)	0.0771 (12)	0.0474 (11)	−0.0003 (10)	0.0029 (8)	0.0148 (9)
O7	0.0422 (9)	0.0342 (8)	0.0452 (8)	0.0022 (6)	0.0020 (7)	0.0075 (6)
O8	0.0436 (9)	0.0456 (8)	0.0444 (8)	0.0070 (7)	0.0044 (7)	0.0225 (7)
O9	0.0376 (9)	0.0535 (10)	0.0488 (10)	−0.0010 (7)	0.0020 (7)	0.0175 (8)
O10	0.0445 (9)	0.0402 (8)	0.0398 (8)	−0.0050 (6)	0.0012 (7)	0.0176 (6)
O11	0.0435 (9)	0.0332 (7)	0.0376 (8)	−0.0050 (6)	0.0027 (6)	0.0048 (6)
O12	0.0358 (9)	0.0517 (9)	0.0489 (10)	0.0018 (7)	0.0045 (7)	0.0153 (8)
C1	0.0428 (15)	0.0775 (18)	0.0693 (17)	0.0060 (13)	−0.0046 (12)	0.0267 (14)
C2	0.0398 (13)	0.0518 (13)	0.0362 (12)	0.0065 (10)	−0.0006 (10)	0.0084 (10)
C3	0.0482 (15)	0.0535 (14)	0.0490 (14)	0.0019 (11)	−0.0027 (11)	0.0211 (11)
C4	0.0505 (14)	0.0481 (13)	0.0322 (12)	−0.0035 (11)	0.0010 (10)	0.0120 (10)
C5	0.0617 (17)	0.0723 (17)	0.0653 (17)	−0.0104 (13)	−0.0008 (13)	0.0384 (14)
C6	0.0609 (17)	0.0774 (18)	0.0610 (16)	−0.0029 (13)	0.0033 (13)	0.0402 (14)
C7	0.0482 (14)	0.0509 (13)	0.0322 (12)	−0.0010 (11)	0.0012 (10)	0.0123 (10)
C8	0.0470 (15)	0.0570 (14)	0.0506 (14)	0.0016 (11)	−0.0053 (11)	0.0225 (12)
C9	0.0375 (13)	0.0526 (13)	0.0376 (12)	0.0056 (10)	−0.0011 (10)	0.0072 (10)
C10	0.0400 (14)	0.0759 (18)	0.0708 (18)	0.0050 (12)	−0.0053 (12)	0.0198 (14)
C11	0.075 (2)	0.0438 (14)	0.085 (2)	0.0077 (13)	0.0189 (15)	0.0012 (13)
C12	0.0400 (13)	0.0324 (11)	0.0674 (16)	−0.0023 (9)	0.0087 (11)	0.0105 (11)
C13	0.0596 (17)	0.0390 (13)	0.0804 (18)	0.0127 (11)	0.0095 (13)	0.0272 (13)
C14	0.0372 (13)	0.0515 (14)	0.0691 (16)	0.0010 (10)	0.0025 (11)	0.0374 (13)
C15	0.0697 (19)	0.088 (2)	0.092 (2)	0.0103 (15)	0.0031 (16)	0.0657 (18)
C16	0.079 (2)	0.0665 (17)	0.0728 (18)	−0.0036 (14)	0.0098 (15)	0.0438 (15)
C17	0.0374 (13)	0.0448 (12)	0.0588 (14)	0.0026 (10)	0.0059 (11)	0.0298 (11)
C18	0.0553 (15)	0.0372 (12)	0.0634 (16)	−0.0091 (10)	0.0046 (12)	0.0178 (11)
C19	0.0362 (12)	0.0322 (11)	0.0580 (14)	0.0002 (9)	0.0002 (10)	0.0082 (10)
C20	0.0694 (18)	0.0414 (13)	0.0673 (17)	−0.0059 (12)	0.0012 (14)	−0.0043 (12)
N1	0.0427 (12)	0.0555 (12)	0.0478 (12)	−0.0009 (9)	0.0013 (10)	0.0171 (10)
N2	0.0436 (12)	0.0558 (12)	0.0474 (12)	0.0014 (9)	0.0012 (10)	0.0143 (10)
O13	0.0642 (13)	0.0959 (15)	0.0766 (14)	0.0169 (11)	−0.0205 (11)	0.0136 (11)
O14	0.0684 (14)	0.1257 (18)	0.0790 (14)	0.0226 (12)	0.0337 (11)	0.0365 (13)
O15	0.0745 (14)	0.1332 (19)	0.0504 (12)	0.0060 (13)	−0.0073 (10)	0.0238 (12)
O16	0.0668 (14)	0.1119 (17)	0.0797 (14)	−0.0044 (11)	0.0321 (11)	0.0213 (12)
O17	0.0634 (13)	0.1283 (18)	0.0794 (14)	−0.0367 (12)	−0.0247 (11)	0.0468 (13)
O18	0.0750 (14)	0.1330 (19)	0.0488 (12)	−0.0056 (13)	−0.0056 (10)	0.0191 (12)
O1W	0.0713 (15)	0.149 (2)	0.0458 (11)	−0.0041 (15)	−0.0014 (11)	0.0301 (13)
O2W	0.0774 (15)	0.1293 (19)	0.0430 (11)	−0.0321 (14)	−0.0029 (11)	0.0234 (12)

Geometric parameters (Å, º)

Mn1—O2	1.9117 (16)	C5—H5C	0.9600
Mn1—O4	1.9132 (16)	C6—C7	1.502 (3)
Mn1—O1	1.9135 (17)	C6—H6A	0.9600
Mn1—O3	1.9149 (17)	C6—H6B	0.9600
Mn1—O6	2.234 (2)	C6—H6C	0.9600
Mn1—O5	2.237 (2)	C7—C8	1.375 (3)
Mn2—O7	1.9128 (15)	C8—C9	1.388 (3)
Mn2—O7^i	1.9128 (15)	C8—H8	0.9300
Mn2—O8	1.9129 (15)	C9—C10	1.495 (3)
Mn2—O8^i	1.9129 (15)	C10—H10A	0.9600
Mn2—O9^i	2.2050 (19)	C10—H10B	0.9600
Mn2—O9	2.2050 (19)	C10—H10C	0.9600
Mn3—O10^ii	1.9116 (15)	C11—C12	1.497 (3)
Mn3—O10	1.9116 (15)	C11—H11A	0.9600
Mn3—O11	1.9165 (15)	C11—H11B	0.9600
Mn3—O11^ii	1.9165 (15)	C11—H11C	0.9600
Mn3—O12	2.2075 (19)	C12—C13	1.384 (3)
Mn3—O12^ii	2.2075 (19)	C13—C14	1.378 (3)
O1—C2	1.282 (3)	C13—H13	0.9300
O2—C4	1.284 (3)	C14—C15	1.505 (3)
O3—C9	1.279 (3)	C15—H15A	0.9600
O4—C7	1.289 (3)	C15—H15B	0.9600
O5—H51	0.75 (3)	C15—H15C	0.9600
O5—H52	0.82 (3)	C16—C17	1.504 (3)
O6—H61	0.77 (3)	C16—H16A	0.9600
O6—H62	0.82 (3)	C16—H16B	0.9600
O7—C12	1.292 (2)	C16—H16C	0.9600
O8—C14	1.285 (3)	C17—C18	1.387 (3)
O9—H91	0.79 (2)	C18—C19	1.376 (3)
O9—H92	0.80 (2)	C18—H18	0.9300
O10—C17	1.283 (2)	C19—C20	1.500 (3)
O11—C19	1.291 (2)	C20—H20A	0.9600
O12—H121	0.78 (2)	C20—H20B	0.9600
O12—H122	0.80 (2)	C20—H20C	0.9600
C1—C2	1.490 (3)	N1—O13	1.218 (2)
C1—H1A	0.9600	N1—O14	1.230 (2)
C1—H1B	0.9600	N1—O15	1.231 (3)
C1—H1C	0.9600	N2—O17	1.214 (3)
C2—C3	1.389 (3)	N2—O16	1.229 (3)
C3—C4	1.380 (3)	N2—O18	1.233 (3)
C3—H3	0.9300	O1W—H1W	0.75 (3)
C4—C5	1.499 (3)	O1W—H2W	0.81 (3)
C5—H5A	0.9600	O2W—H3W	0.83 (3)
C5—H5B	0.9600	O2W—H4W	0.82 (3)
O2—Mn1—O4	179.99 (8)	C3—C4—C5	120.8 (2)
O2—Mn1—O1	92.14 (7)	C4—C5—H5A	109.5
O4—Mn1—O1	87.86 (7)	C4—C5—H5B	109.5
O2—Mn1—O3	88.00 (7)	H5A—C5—H5B	109.5
O4—Mn1—O3	92.00 (7)	C4—C5—H5C	109.5
O1—Mn1—O3	179.70 (7)	H5A—C5—H5C	109.5
O2—Mn1—O6	89.26 (8)	H5B—C5—H5C	109.5
O4—Mn1—O6	90.75 (8)	C7—C6—H6A	109.5
O1—Mn1—O6	90.79 (7)	C7—C6—H6B	109.5
O3—Mn1—O6	89.48 (7)	H6A—C6—H6B	109.5
O2—Mn1—O5	90.02 (8)	C7—C6—H6C	109.5
O4—Mn1—O5	89.97 (8)	H6A—C6—H6C	109.5
O1—Mn1—O5	89.18 (7)	H6B—C6—H6C	109.5
O3—Mn1—O5	90.55 (7)	O4—C7—C8	124.4 (2)
O6—Mn1—O5	179.28 (6)	O4—C7—C6	114.7 (2)
O7—Mn2—O7^i	180.000 (1)	C8—C7—C6	120.9 (2)
O7—Mn2—O8	91.38 (7)	C7—C8—C9	124.7 (2)
O7^i—Mn2—O8	88.62 (7)	C7—C8—H8	117.6
O7—Mn2—O8^i	88.62 (7)	C9—C8—H8	117.6
O7^i—Mn2—O8^i	91.38 (7)	O3—C9—C8	124.6 (2)
O8—Mn2—O8^i	180.0	O3—C9—C10	115.3 (2)
O7—Mn2—O9^i	90.87 (6)	C8—C9—C10	120.2 (2)
O7^i—Mn2—O9^i	89.13 (6)	C9—C10—H10A	109.5
O8—Mn2—O9^i	90.81 (6)	C9—C10—H10B	109.5
O8^i—Mn2—O9^i	89.19 (6)	H10A—C10—H10B	109.5
O7—Mn2—O9	89.13 (6)	C9—C10—H10C	109.5
O7^i—Mn2—O9	90.87 (6)	H10A—C10—H10C	109.5
O8—Mn2—O9	89.19 (6)	H10B—C10—H10C	109.5
O8^i—Mn2—O9	90.81 (6)	C12—C11—H11A	109.5
O9^i—Mn2—O9	180.00 (9)	C12—C11—H11B	109.5
O10^ii—Mn3—O10	180.0	H11A—C11—H11B	109.5
O10^ii—Mn3—O11	88.59 (7)	C12—C11—H11C	109.5
O10—Mn3—O11	91.41 (7)	H11A—C11—H11C	109.5
O10^ii—Mn3—O11^ii	91.41 (7)	H11B—C11—H11C	109.5
O10—Mn3—O11^ii	88.59 (7)	O7—C12—C13	124.2 (2)
O11—Mn3—O11^ii	180.0	O7—C12—C11	114.7 (2)
O10^ii—Mn3—O12	89.43 (6)	C13—C12—C11	121.1 (2)
O10—Mn3—O12	90.57 (6)	C14—C13—C12	124.5 (2)
O11—Mn3—O12	90.82 (6)	C14—C13—H13	117.8
O11^ii—Mn3—O12	89.18 (6)	C12—C13—H13	117.8
O10^ii—Mn3—O12^ii	90.57 (6)	O8—C14—C13	124.2 (2)
O10—Mn3—O12^ii	89.43 (6)	O8—C14—C15	114.8 (2)
O11—Mn3—O12^ii	89.18 (6)	C13—C14—C15	120.9 (2)
O11^ii—Mn3—O12^ii	90.82 (6)	C14—C15—H15A	109.5
O12—Mn3—O12^ii	180.0	C14—C15—H15B	109.5
C2—O1—Mn1	127.11 (14)	H15A—C15—H15B	109.5
C4—O2—Mn1	127.13 (15)	C14—C15—H15C	109.5
C9—O3—Mn1	127.08 (15)	H15A—C15—H15C	109.5
C7—O4—Mn1	127.11 (15)	H15B—C15—H15C	109.5
Mn1—O5—H51	117 (3)	C17—C16—H16A	109.5
Mn1—O5—H52	119 (2)	C17—C16—H16B	109.5
H51—O5—H52	106 (3)	H16A—C16—H16B	109.5
Mn1—O6—H61	115 (2)	C17—C16—H16C	109.5
Mn1—O6—H62	117 (2)	H16A—C16—H16C	109.5
H61—O6—H62	104 (3)	H16B—C16—H16C	109.5
C12—O7—Mn2	125.42 (15)	O10—C17—C18	124.05 (19)
C14—O8—Mn2	125.78 (14)	O10—C17—C16	115.0 (2)
Mn2—O9—H91	115 (2)	C18—C17—C16	121.0 (2)
Mn2—O9—H92	119 (2)	C19—C18—C17	124.5 (2)
H91—O9—H92	110 (3)	C19—C18—H18	117.7
C17—O10—Mn3	125.72 (14)	C17—C18—H18	117.7
C19—O11—Mn3	125.27 (14)	O11—C19—C18	124.4 (2)
Mn3—O12—H121	119 (2)	O11—C19—C20	114.7 (2)
Mn3—O12—H122	115 (2)	C18—C19—C20	121.0 (2)
H121—O12—H122	112 (3)	C19—C20—H20A	109.5
C2—C1—H1A	109.5	C19—C20—H20B	109.5
C2—C1—H1B	109.5	H20A—C20—H20B	109.5
H1A—C1—H1B	109.5	C19—C20—H20C	109.5
C2—C1—H1C	109.5	H20A—C20—H20C	109.5
H1A—C1—H1C	109.5	H20B—C20—H20C	109.5
H1B—C1—H1C	109.5	O13—N1—O14	121.3 (2)
O1—C2—C3	124.3 (2)	O13—N1—O15	120.1 (2)
O1—C2—C1	115.5 (2)	O14—N1—O15	118.7 (2)
C3—C2—C1	120.1 (2)	O17—N2—O16	121.4 (2)
C4—C3—C2	124.7 (2)	O17—N2—O18	119.8 (2)
C4—C3—H3	117.6	O16—N2—O18	118.8 (2)
C2—C3—H3	117.6	H1W—O1W—H2W	112 (4)
O2—C4—C3	124.5 (2)	H3W—O2W—H4W	103 (3)
O2—C4—C5	114.8 (2)

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

(4)

Crystal data

C10H18MnO6·NO3·H2O	F(000) = 1536
Mr = 369.21	Dx = 1.548 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.8378 (5) Å	Cell parameters from 8817 reflections
b = 12.9697 (8) Å	θ = 2.6–26.0°
c = 31.268 (2) Å	µ = 0.88 mm^−1
β = 94.690 (1)°	T = 100 K
V = 3167.9 (3) Å^3	Block, green
Z = 8	0.38 × 0.36 × 0.28 mm

Data collection

CCD area detector diffractometer	6250 independent reflections
Radiation source: fine-focus sealed tube	5448 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
phi and ω scans	θmax = 26.1°, θmin = 1.3°
Absorption correction: empirical (using intensity measurements) sadabs	h = −9→9
Tmin = 0.731, Tmax = 0.790	k = −16→16
32272 measured reflections	l = −38→38

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 2.5245P] where P = (Fo^2 + 2Fc^2)/3
6250 reflections	(Δ/σ)max = 0.001
408 parameters	Δρmax = 0.44 e Å^−3
15 restraints	Δρmin = −0.30 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.24718 (3)	0.04322 (2)	0.251429 (8)	0.01148 (9)
Mn2	0.5000	0.5000	0.0000	0.01447 (11)
Mn3	0.0000	0.0000	0.0000	0.01460 (11)
O1	0.25940 (17)	0.14778 (10)	0.20900 (4)	0.0159 (3)
O2	0.27544 (17)	0.14216 (10)	0.29665 (4)	0.0155 (3)
O3	0.23757 (17)	−0.06096 (10)	0.29452 (4)	0.0148 (3)
O4	0.21762 (17)	−0.05764 (10)	0.20640 (4)	0.0148 (3)
O5	−0.03285 (17)	0.05777 (11)	0.24895 (5)	0.0173 (3)
H51	−0.0873	0.0393	0.2268	0.021*
H52	−0.0803	0.0373	0.2697	0.021*
O6	0.52685 (17)	0.02616 (11)	0.25318 (4)	0.0166 (3)
H61	0.5706	0.0445	0.2315	0.020*
H62	0.5806	0.0465	0.2736	0.020*
O7	0.73099 (17)	0.45799 (11)	0.01553 (5)	0.0175 (3)
O8	0.40889 (17)	0.37739 (11)	0.02323 (4)	0.0180 (3)
O9	0.49359 (18)	0.57905 (12)	0.06296 (4)	0.0207 (3)
H92	0.4073	0.5703	0.0758	0.025*
H91	0.5716	0.5663	0.0794	0.025*
O10	0.23266 (17)	−0.04110 (11)	0.01405 (5)	0.0175 (3)
O11	−0.08672 (17)	−0.12474 (11)	0.02224 (4)	0.0179 (3)
O12	−0.00099 (18)	0.07147 (12)	0.06479 (5)	0.0212 (3)
H121	−0.0838	0.0649	0.0766	0.025*
H122	0.0796	0.0621	0.0809	0.025*
C1	0.3634 (3)	0.29479 (17)	0.17543 (7)	0.0230 (5)
H1A	0.4283	0.2524	0.1565	0.035*
H1B	0.4275	0.3580	0.1829	0.035*
H1C	0.2522	0.3126	0.1607	0.035*
C2	0.3364 (2)	0.23576 (15)	0.21538 (7)	0.0167 (4)
C3	0.3892 (3)	0.27532 (16)	0.25559 (7)	0.0195 (4)
H3	0.4556	0.3367	0.2569	0.023*
C4	0.3510 (2)	0.23052 (15)	0.29396 (6)	0.0165 (4)
C5	0.3901 (3)	0.28528 (17)	0.33581 (7)	0.0226 (5)
H5A	0.2834	0.3109	0.3463	0.034*
H5B	0.4668	0.3434	0.3317	0.034*
H5C	0.4454	0.2374	0.3568	0.034*
C6	0.1386 (3)	−0.20797 (17)	0.32920 (7)	0.0225 (5)
H6A	0.2504	−0.2269	0.3433	0.034*
H6B	0.0722	−0.2706	0.3221	0.034*
H6C	0.0769	−0.1649	0.3485	0.034*
C7	0.1635 (2)	−0.14924 (15)	0.28896 (6)	0.0165 (4)
C8	0.1117 (3)	−0.19120 (16)	0.24885 (7)	0.0192 (4)
H8	0.0485	−0.2538	0.2480	0.023*
C9	0.1469 (2)	−0.14684 (15)	0.21015 (7)	0.0171 (4)
C10	0.1074 (3)	−0.20362 (17)	0.16873 (7)	0.0228 (5)
H10A	0.0458	−0.1578	0.1478	0.034*
H10B	0.0361	−0.2638	0.1737	0.034*
H10C	0.2144	−0.2263	0.1575	0.034*
C11	0.9706 (3)	0.36467 (17)	0.04473 (7)	0.0216 (4)
H11A	1.0289	0.3938	0.0209	0.032*
H11B	1.0004	0.2916	0.0481	0.032*
H11C	1.0067	0.4017	0.0713	0.032*
C12	0.7806 (2)	0.37528 (16)	0.03539 (6)	0.0161 (4)
C13	0.6716 (3)	0.29892 (16)	0.04854 (6)	0.0187 (4)
H13	0.7216	0.2403	0.0628	0.022*
C14	0.4944 (3)	0.30307 (16)	0.04205 (6)	0.0155 (4)
C15	0.3865 (3)	0.21698 (17)	0.05697 (7)	0.0210 (4)
H15A	0.3165	0.2425	0.0793	0.031*
H15B	0.4607	0.1612	0.0686	0.031*
H15C	0.3117	0.1909	0.0327	0.031*
C16	0.4750 (3)	−0.12869 (17)	0.04519 (7)	0.0214 (4)
H16A	0.5330	−0.0977	0.0217	0.032*
H16B	0.5083	−0.2013	0.0484	0.032*
H16C	0.5080	−0.0918	0.0720	0.032*
C17	0.2848 (2)	−0.12140 (16)	0.03529 (6)	0.0160 (4)
C18	0.1780 (3)	−0.19780 (16)	0.04944 (6)	0.0184 (4)
H18	0.2295	−0.2544	0.0649	0.022*
C19	0.0007 (3)	−0.19636 (16)	0.04238 (6)	0.0158 (4)
C20	−0.1046 (3)	−0.28217 (17)	0.05868 (7)	0.0222 (5)
H20A	−0.1684	−0.2567	0.0822	0.033*
H20B	−0.0291	−0.3386	0.0691	0.033*
H20C	−0.1850	−0.3074	0.0354	0.033*
N1	0.2229 (2)	0.54461 (13)	0.14760 (5)	0.0169 (4)
O13	0.1938 (2)	0.54761 (13)	0.10792 (5)	0.0280 (4)
O14	0.36308 (19)	0.57525 (13)	0.16475 (5)	0.0264 (4)
O15	0.1104 (2)	0.51095 (13)	0.17017 (5)	0.0289 (4)
N2	0.7216 (2)	0.04570 (13)	0.14942 (5)	0.0170 (4)
O16	0.6993 (2)	0.05275 (13)	0.10976 (5)	0.0273 (4)
O17	0.85799 (19)	0.01015 (13)	0.16677 (5)	0.0262 (4)
O18	0.60501 (19)	0.07549 (13)	0.17196 (5)	0.0259 (4)
O1W	0.2744 (2)	0.02072 (13)	0.12086 (5)	0.0251 (3)
H2	0.2452	0.0083	0.1432	0.030*
H1	0.3669	0.0450	0.1270	0.030*
O2W	0.7660 (2)	0.52803 (14)	0.11800 (5)	0.0294 (4)
H4	0.8571	0.5291	0.1200	0.035*
H5	0.7441	0.5163	0.1414	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01146 (16)	0.00953 (16)	0.01339 (16)	−0.00099 (10)	0.00064 (11)	0.00011 (10)
Mn2	0.0100 (2)	0.0175 (2)	0.0157 (2)	−0.00061 (16)	−0.00043 (15)	0.00315 (16)
Mn3	0.0098 (2)	0.0177 (2)	0.0162 (2)	−0.00041 (16)	0.00040 (15)	0.00353 (16)
O1	0.0152 (7)	0.0143 (7)	0.0182 (7)	−0.0003 (5)	0.0013 (5)	0.0033 (5)
O2	0.0162 (7)	0.0128 (7)	0.0177 (7)	−0.0013 (5)	0.0021 (5)	−0.0018 (5)
O3	0.0171 (7)	0.0109 (7)	0.0162 (7)	−0.0015 (5)	0.0005 (5)	0.0011 (5)
O4	0.0157 (7)	0.0128 (7)	0.0159 (7)	−0.0025 (5)	0.0011 (5)	−0.0010 (5)
O5	0.0137 (7)	0.0201 (8)	0.0182 (7)	−0.0001 (6)	0.0012 (5)	−0.0005 (6)
O6	0.0133 (7)	0.0198 (7)	0.0167 (7)	−0.0004 (6)	0.0008 (5)	−0.0011 (6)
O7	0.0119 (7)	0.0212 (8)	0.0191 (7)	−0.0004 (5)	−0.0005 (5)	0.0027 (6)
O8	0.0123 (7)	0.0210 (8)	0.0205 (7)	−0.0009 (6)	0.0001 (5)	0.0040 (6)
O9	0.0157 (7)	0.0277 (8)	0.0186 (7)	−0.0009 (6)	0.0003 (6)	0.0007 (6)
O10	0.0120 (7)	0.0210 (8)	0.0194 (7)	−0.0004 (5)	0.0007 (5)	0.0034 (6)
O11	0.0130 (7)	0.0202 (8)	0.0202 (7)	−0.0014 (6)	0.0002 (5)	0.0042 (6)
O12	0.0154 (7)	0.0294 (8)	0.0186 (7)	−0.0007 (6)	0.0011 (6)	0.0007 (6)
C1	0.0225 (11)	0.0184 (11)	0.0281 (11)	−0.0007 (9)	0.0022 (9)	0.0056 (9)
C2	0.0118 (9)	0.0129 (10)	0.0255 (10)	0.0015 (7)	0.0029 (7)	0.0035 (8)
C3	0.0161 (10)	0.0146 (10)	0.0278 (11)	−0.0012 (8)	0.0016 (8)	−0.0006 (8)
C4	0.0119 (9)	0.0127 (10)	0.0246 (10)	0.0012 (7)	−0.0006 (7)	−0.0026 (8)
C5	0.0213 (11)	0.0184 (11)	0.0277 (11)	−0.0025 (9)	0.0006 (8)	−0.0062 (9)
C6	0.0224 (11)	0.0190 (11)	0.0264 (11)	−0.0009 (9)	0.0034 (8)	0.0056 (9)
C7	0.0112 (9)	0.0135 (10)	0.0252 (11)	0.0031 (7)	0.0033 (8)	0.0019 (8)
C8	0.0162 (10)	0.0131 (10)	0.0283 (11)	−0.0038 (8)	0.0026 (8)	−0.0017 (8)
C9	0.0121 (9)	0.0151 (10)	0.0238 (10)	0.0024 (8)	0.0004 (7)	−0.0025 (8)
C10	0.0228 (11)	0.0204 (11)	0.0254 (11)	−0.0026 (9)	0.0024 (8)	−0.0073 (9)
C11	0.0145 (10)	0.0237 (11)	0.0262 (11)	0.0019 (8)	−0.0010 (8)	−0.0007 (9)
C12	0.0166 (10)	0.0194 (10)	0.0120 (9)	0.0014 (8)	−0.0003 (7)	−0.0030 (8)
C13	0.0188 (10)	0.0194 (11)	0.0175 (10)	0.0023 (8)	−0.0011 (8)	0.0012 (8)
C14	0.0175 (10)	0.0178 (10)	0.0109 (9)	−0.0007 (8)	−0.0001 (7)	−0.0003 (7)
C15	0.0181 (10)	0.0223 (11)	0.0223 (11)	−0.0023 (8)	0.0003 (8)	0.0065 (9)
C16	0.0149 (10)	0.0248 (11)	0.0243 (11)	0.0007 (8)	−0.0004 (8)	0.0020 (9)
C17	0.0166 (10)	0.0194 (10)	0.0118 (9)	0.0019 (8)	0.0005 (7)	−0.0024 (8)
C18	0.0189 (10)	0.0187 (11)	0.0174 (10)	0.0021 (8)	−0.0001 (8)	0.0024 (8)
C19	0.0182 (10)	0.0178 (10)	0.0115 (9)	−0.0009 (8)	0.0021 (7)	−0.0016 (8)
C20	0.0193 (11)	0.0224 (11)	0.0247 (11)	−0.0025 (9)	0.0012 (8)	0.0055 (9)
N1	0.0141 (8)	0.0174 (9)	0.0190 (9)	0.0007 (7)	0.0001 (7)	−0.0018 (7)
O13	0.0236 (8)	0.0411 (10)	0.0184 (8)	−0.0018 (7)	−0.0039 (6)	0.0011 (7)
O14	0.0177 (8)	0.0361 (9)	0.0242 (8)	−0.0080 (7)	−0.0050 (6)	0.0044 (7)
O15	0.0215 (8)	0.0379 (10)	0.0287 (9)	−0.0080 (7)	0.0102 (6)	−0.0042 (7)
N2	0.0141 (8)	0.0182 (9)	0.0183 (9)	−0.0019 (7)	−0.0002 (7)	−0.0007 (7)
O16	0.0222 (8)	0.0430 (10)	0.0164 (8)	0.0035 (7)	−0.0008 (6)	0.0014 (7)
O17	0.0188 (8)	0.0331 (9)	0.0255 (8)	0.0080 (7)	−0.0059 (6)	−0.0035 (7)
O18	0.0195 (8)	0.0349 (9)	0.0245 (8)	0.0030 (7)	0.0084 (6)	0.0017 (7)
O1W	0.0236 (8)	0.0352 (9)	0.0164 (7)	−0.0081 (7)	0.0004 (6)	0.0032 (6)
O2W	0.0244 (8)	0.0462 (10)	0.0172 (8)	−0.0007 (7)	−0.0005 (6)	0.0060 (7)

Geometric parameters (Å, º)

Mn1—O1	1.9051 (14)	C5—H5C	0.9800
Mn1—O2	1.9089 (14)	C6—C7	1.497 (3)
Mn1—O3	1.9141 (14)	C6—H6A	0.9800
Mn1—O4	1.9218 (14)	C6—H6B	0.9800
Mn1—O5	2.1980 (14)	C6—H6C	0.9800
Mn1—O6	2.1993 (14)	C7—C8	1.397 (3)
Mn2—O8	1.9108 (14)	C8—C9	1.388 (3)
Mn2—O8^i	1.9108 (14)	C8—H8	0.9500
Mn2—O7^i	1.9149 (14)	C9—C10	1.500 (3)
Mn2—O7	1.9149 (14)	C10—H10A	0.9800
Mn2—O9	2.2238 (14)	C10—H10B	0.9800
Mn2—O9^i	2.2238 (14)	C10—H10C	0.9800
Mn3—O11^ii	1.9080 (14)	C11—C12	1.500 (3)
Mn3—O11	1.9080 (14)	C11—H11A	0.9800
Mn3—O10	1.9161 (14)	C11—H11B	0.9800
Mn3—O10^ii	1.9161 (14)	C11—H11C	0.9800
Mn3—O12^ii	2.2284 (14)	C12—C13	1.392 (3)
Mn3—O12	2.2284 (14)	C13—C14	1.389 (3)
O1—C2	1.299 (2)	C13—H13	0.9500
O2—C4	1.296 (2)	C14—C15	1.498 (3)
O3—C7	1.289 (2)	C15—H15A	0.9800
O4—C9	1.292 (2)	C15—H15B	0.9800
O5—H51	0.8204	C15—H15C	0.9800
O5—H52	0.8182	C16—C17	1.501 (3)
O6—H61	0.8184	C16—H16A	0.9800
O6—H62	0.7823	C16—H16B	0.9800
O7—C12	1.284 (2)	C16—H16C	0.9800
O8—C14	1.288 (2)	C17—C18	1.392 (3)
O9—H92	0.8221	C18—C19	1.389 (3)
O9—H91	0.7840	C18—H18	0.9500
O10—C17	1.284 (2)	C19—C20	1.499 (3)
O11—C19	1.288 (2)	C20—H20A	0.9800
O12—H121	0.7775	C20—H20B	0.9800
O12—H122	0.7842	C20—H20C	0.9800
C1—C2	1.495 (3)	N1—O13	1.244 (2)
C1—H1A	0.9800	N1—O14	1.247 (2)
C1—H1B	0.9800	N1—O15	1.253 (2)
C1—H1C	0.9800	N2—O16	1.241 (2)
C2—C3	1.389 (3)	N2—O17	1.247 (2)
C3—C4	1.388 (3)	N2—O18	1.260 (2)
C3—H3	0.9500	O1W—H2	0.7680
C4—C5	1.498 (3)	O1W—H1	0.7993
C5—H5A	0.9800	O2W—H4	0.7119
C5—H5B	0.9800	O2W—H5	0.7789
O1—Mn1—O2	91.61 (6)	C3—C4—C5	120.90 (18)
O1—Mn1—O3	179.19 (6)	C4—C5—H5A	109.5
O2—Mn1—O3	87.81 (6)	C4—C5—H5B	109.5
O1—Mn1—O4	89.10 (6)	H5A—C5—H5B	109.5
O2—Mn1—O4	179.26 (6)	C4—C5—H5C	109.5
O3—Mn1—O4	91.48 (6)	H5A—C5—H5C	109.5
O1—Mn1—O5	91.22 (6)	H5B—C5—H5C	109.5
O2—Mn1—O5	91.34 (6)	C7—C6—H6A	109.5
O3—Mn1—O5	89.36 (6)	C7—C6—H6B	109.5
O4—Mn1—O5	88.42 (6)	H6A—C6—H6B	109.5
O1—Mn1—O6	88.98 (6)	C7—C6—H6C	109.5
O2—Mn1—O6	89.66 (6)	H6A—C6—H6C	109.5
O3—Mn1—O6	90.45 (6)	H6B—C6—H6C	109.5
O4—Mn1—O6	90.57 (6)	O3—C7—C8	124.19 (18)
O5—Mn1—O6	178.97 (6)	O3—C7—C6	115.26 (18)
O8—Mn2—O8^i	180.00 (8)	C8—C7—C6	120.53 (18)
O8—Mn2—O7^i	87.61 (6)	C9—C8—C7	123.87 (19)
O8^i—Mn2—O7^i	92.39 (6)	C9—C8—H8	118.1
O8—Mn2—O7	92.39 (6)	C7—C8—H8	118.1
O8^i—Mn2—O7	87.61 (6)	O4—C9—C8	124.59 (18)
O7^i—Mn2—O7	180.00 (12)	O4—C9—C10	114.91 (18)
O8—Mn2—O9	90.64 (6)	C8—C9—C10	120.49 (18)
O8^i—Mn2—O9	89.36 (6)	C9—C10—H10A	109.5
O7^i—Mn2—O9	90.23 (6)	C9—C10—H10B	109.5
O7—Mn2—O9	89.77 (6)	H10A—C10—H10B	109.5
O8—Mn2—O9^i	89.36 (6)	C9—C10—H10C	109.5
O8^i—Mn2—O9^i	90.64 (6)	H10A—C10—H10C	109.5
O7^i—Mn2—O9^i	89.77 (6)	H10B—C10—H10C	109.5
O7—Mn2—O9^i	90.23 (6)	C12—C11—H11A	109.5
O9—Mn2—O9^i	180.00 (8)	C12—C11—H11B	109.5
O11^ii—Mn3—O11	180.00 (9)	H11A—C11—H11B	109.5
O11^ii—Mn3—O10	87.63 (6)	C12—C11—H11C	109.5
O11—Mn3—O10	92.37 (6)	H11A—C11—H11C	109.5
O11^ii—Mn3—O10^ii	92.37 (6)	H11B—C11—H11C	109.5
O11—Mn3—O10^ii	87.63 (6)	O7—C12—C13	124.65 (18)
O10—Mn3—O10^ii	180.00 (12)	O7—C12—C11	115.30 (18)
O11^ii—Mn3—O12^ii	89.63 (6)	C13—C12—C11	120.04 (18)
O11—Mn3—O12^ii	90.37 (6)	C14—C13—C12	124.06 (19)
O10—Mn3—O12^ii	91.07 (6)	C14—C13—H13	118.0
O10^ii—Mn3—O12^ii	88.93 (6)	C12—C13—H13	118.0
O11^ii—Mn3—O12	90.37 (6)	O8—C14—C13	124.92 (19)
O11—Mn3—O12	89.63 (6)	O8—C14—C15	114.48 (17)
O10—Mn3—O12	88.93 (6)	C13—C14—C15	120.59 (18)
O10^ii—Mn3—O12	91.07 (6)	C14—C15—H15A	109.5
O12^ii—Mn3—O12	180.00 (8)	C14—C15—H15B	109.5
C2—O1—Mn1	124.59 (13)	H15A—C15—H15B	109.5
C4—O2—Mn1	124.91 (13)	C14—C15—H15C	109.5
C7—O3—Mn1	125.12 (13)	H15A—C15—H15C	109.5
C9—O4—Mn1	124.74 (13)	H15B—C15—H15C	109.5
Mn1—O5—H51	117.0	C17—C16—H16A	109.5
Mn1—O5—H52	117.5	C17—C16—H16B	109.5
H51—O5—H52	109.7	H16A—C16—H16B	109.5
Mn1—O6—H61	115.8	C17—C16—H16C	109.5
Mn1—O6—H62	117.1	H16A—C16—H16C	109.5
H61—O6—H62	110.1	H16B—C16—H16C	109.5
C12—O7—Mn2	127.10 (13)	O10—C17—C18	124.59 (18)
C14—O8—Mn2	126.85 (13)	O10—C17—C16	115.24 (18)
Mn2—O9—H92	116.6	C18—C17—C16	120.16 (18)
Mn2—O9—H91	114.3	C19—C18—C17	124.01 (19)
H92—O9—H91	106.2	C19—C18—H18	118.0
C17—O10—Mn3	126.93 (13)	C17—C18—H18	118.0
C19—O11—Mn3	126.77 (13)	O11—C19—C18	124.95 (19)
Mn3—O12—H121	116.8	O11—C19—C20	114.57 (17)
Mn3—O12—H122	117.2	C18—C19—C20	120.48 (18)
H121—O12—H122	109.7	C19—C20—H20A	109.5
C2—C1—H1A	109.5	C19—C20—H20B	109.5
C2—C1—H1B	109.5	H20A—C20—H20B	109.5
H1A—C1—H1B	109.5	C19—C20—H20C	109.5
C2—C1—H1C	109.5	H20A—C20—H20C	109.5
H1A—C1—H1C	109.5	H20B—C20—H20C	109.5
H1B—C1—H1C	109.5	O13—N1—O14	120.15 (17)
O1—C2—C3	124.34 (18)	O13—N1—O15	119.54 (17)
O1—C2—C1	114.67 (18)	O14—N1—O15	120.31 (17)
C3—C2—C1	120.99 (18)	O16—N2—O17	120.52 (17)
C4—C3—C2	123.94 (19)	O16—N2—O18	119.13 (17)
C4—C3—H3	118.0	O17—N2—O18	120.35 (17)
C2—C3—H3	118.0	H2—O1W—H1	101.3
O2—C4—C3	123.95 (18)	H4—O2W—H5	102.5
O2—C4—C5	115.11 (18)

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

(5)

Crystal data

C10H22BF4MnO8	F(000) = 424
Mr = 412.03	Dx = 1.581 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 7.5897 (6) Å	Cell parameters from 4692 reflections
b = 11.8987 (10) Å	θ = 3.3–28.2°
c = 10.2350 (8) Å	µ = 0.84 mm^−1
β = 110.549 (1)°	T = 100 K
V = 865.49 (12) Å^3	Block, green
Z = 2	0.32 × 0.23 × 0.20 mm

Data collection

CCD area detector diffractometer	1067 independent reflections
Radiation source: fine-focus sealed tube	1065 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
phi and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements) sadabs	h = −10→9
Tmin = 0.776, Tmax = 0.851	k = −15→15
4915 measured reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0268P)^2 + 7.1393P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max < 0.001
1067 reflections	Δρmax = 1.35 e Å^−3
75 parameters	Δρmin = −1.10 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.050 (5)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn	0.5000	0.0000	0.0000	0.0153 (3)
O1	0.4734 (3)	0.11587 (18)	0.1210 (2)	0.0192 (5)
O2	0.1885 (4)	0.0000	−0.1068 (3)	0.0207 (7)
H31	0.1237	0.0000	−0.0623	0.025*
H32	0.1308	0.0000	−0.1934	0.025*
C1	0.3949 (5)	0.2101 (3)	0.2949 (4)	0.0259 (7)
H1A	0.5165	0.2484	0.3346	0.039*
H1B	0.3459	0.1930	0.3694	0.039*
H1C	0.3060	0.2590	0.2256	0.039*
C2	0.4198 (4)	0.1034 (3)	0.2264 (3)	0.0185 (6)
C3	0.3876 (7)	0.0000	0.2779 (5)	0.0222 (9)
H3	0.3407	0.0000	0.3526	0.027*
F1	0.0458 (12)	0.0000	0.6182 (4)	0.114 (3)
F3	0.1672 (7)	0.0949 (4)	0.5095 (5)	0.0384 (11)	0.50
B	0.0602 (17)	0.0000	0.5071 (13)	0.031 (3)	0.50
O3	0.5000	0.3486 (3)	0.0000	0.0381 (10)
H1W	0.4676	0.2963	0.0336	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0183 (5)	0.0140 (5)	0.0150 (5)	0.000	0.0074 (4)	0.000
O1	0.0225 (11)	0.0170 (11)	0.0193 (10)	−0.0006 (8)	0.0090 (8)	−0.0024 (8)
O2	0.0204 (16)	0.0261 (17)	0.0162 (15)	0.000	0.0073 (12)	0.000
C1	0.0283 (16)	0.0263 (17)	0.0259 (16)	−0.0003 (13)	0.0131 (13)	−0.0079 (13)
C2	0.0153 (13)	0.0229 (15)	0.0167 (13)	0.0010 (11)	0.0047 (11)	−0.0032 (11)
C3	0.025 (2)	0.028 (2)	0.018 (2)	0.000	0.0112 (17)	0.000
F1	0.190 (7)	0.102 (5)	0.016 (2)	0.000	−0.007 (3)	0.000
F3	0.045 (3)	0.022 (2)	0.054 (3)	0.0002 (19)	0.025 (2)	0.001 (2)
B	0.034 (6)	0.038 (6)	0.021 (5)	0.000	0.009 (6)	0.000
O3	0.035 (2)	0.0156 (17)	0.061 (3)	0.000	0.0129 (19)	0.000

Geometric parameters (Å, º)

Mn—O1	1.910 (2)	C2—C3	1.394 (4)
Mn—O1^i	1.910 (2)	C3—C2^i	1.394 (4)
Mn—O2	2.229 (3)	C3—H3	0.9500
O1—C2	1.288 (4)	F1—B	1.181 (13)
O2—H31	0.7783	F1—B^ii	1.252 (13)
O2—H32	0.8398	F3—B	1.386 (8)
C1—C2	1.494 (4)	B—F3^i	1.386 (8)
C1—H1A	0.9800	O3—H1W	0.7906
C1—H1B	0.9800	O3—H1W	0.7906
C1—H1C	0.9800
O1—Mn—O1^iii	87.62 (13)	H1B—C1—H1C	109.5
O1^iii—Mn—O1^iv	92.38 (13)	O1—C2—C3	124.6 (3)
O1^iii—Mn—O1^i	180.00 (13)	O1—C2—C1	115.1 (3)
O1—Mn—O2	89.01 (9)	C3—C2—C1	120.3 (3)
O1^iii—Mn—O2	90.99 (9)	C2^i—C3—C2	124.0 (4)
O1^iv—Mn—O2	90.99 (9)	C2^i—C3—H3	118.0
O1^i—Mn—O2	89.01 (9)	C2—C3—H3	118.0
O1—Mn—O2^iv	90.99 (9)	B^ii—B—F1	73.4 (16)
O2—Mn—O2^iv	180.0 (2)	B^ii—B—F1^ii	64.6 (15)
C2—O1—Mn	126.6 (2)	F1—B—F1^ii	138.0 (11)
Mn—O2—H31	119.5	B^ii—B—F3	125.1 (5)
Mn—O2—H32	126.0	F1—B—F3	103.5 (7)
H31—O2—H32	114.5	F1^ii—B—F3	100.4 (7)
C2—C1—H1A	109.5	B^ii—B—F3^i	125.1 (5)
C2—C1—H1B	109.5	F1—B—F3^i	103.5 (7)
H1A—C1—H1B	109.5	F1^ii—B—F3^i	100.4 (7)
C2—C1—H1C	109.5	F3—B—F3^i	109.2 (9)
H1A—C1—H1C	109.5

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