Anisotropic compressibility of the coordination polymer emim[Mn(btc)]

The effect of pressure on the crystal structure of a coordination polymer, emim[Mn^II(btc)] (emim = 1-ethyl,3-methyl imidazolium cation, btc = 1,3,5-benzene-tricarboxylate), was investigated with single-crystal X-ray diffraction. At 4.3 GPa the unit-cell volume had decreased by 14% compared with ambient conditions. The unit-cell contraction is highly anisotropic, with the a- and b-axes decreasing by 5.5 and 9.5%, respectively, and the c-axis compressing a mere 0.25% up to 1.7 GPa followed by a 0.2% expansion between 1.7 and 4.3 GPa. The 0.2% increase in length of the c-axis in this interval happens above the quasi-hydrostatic limit of the pressure-transmitting medium and therefore it might be a consequence of strain gradients. Under ambient conditions, two MnO₆ units are connected by two carboxylate ligands to form dimeric units. On increasing pressure, a non-bonded O atom from a bridging carboxylate group approaches the Mn atom, with the Mn-O distance decreasing from 2.866 (1) Å at 0.3 GPa to 2.482 (6) Å at 4.3 GPa, increasing the coordination environment of the Mn ion from six- to seven-coordinated.

Computing details

For all compounds, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to refine structure: XL, G.M. Sheldrick, Acta Cryst. (2008). A64, 112-122; molecular graphics: O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341.; software used to prepare material for publication: O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. (2009). 42, 339-341.

(mn6b08s1_0.3GPa)

Crystal data

C9H3MnO6·C6H11N2	Dx = 1.644 Mg m^−3
Mr = 373.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3493 reflections
a = 14.6480 (9) Å	θ = 24.7–3.2°
b = 12.4006 (10) Å	µ = 0.91 mm^−1
c = 16.6062 (10) Å	T = 296 K
V = 3016.4 (4) Å^3	Prismatic, colorless
Z = 8	0.1 × 0.08 × 0.08 mm
F(000) = 1528

Data collection

Bruker APEX-II CCD diffractometer	1748 independent reflections
Radiation source: fine-focus sealed tube	1146 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
φ and ω scans	θmax = 24.8°, θmin = 3.2°
Absorption correction: multi-scan SADABS	h = −15→16
Tmin = 0.612, Tmax = 0.745	k = −12→12
9608 measured reflections	l = −18→18

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.150	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 10.6604P] where P = (Fo^2 + 2Fc^2)/3
1748 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.39 e Å^−3
244 restraints	Δρmin = −0.39 e Å^−3

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	0.60520 (7)	0.48195 (9)	0.57808 (6)	0.0251 (4)
O5	0.7098 (3)	0.4803 (5)	0.4834 (3)	0.0505 (16)
O6	0.7001 (3)	0.6299 (5)	0.5508 (3)	0.0451 (15)
O3	0.5952 (3)	0.3443 (4)	0.6655 (3)	0.0414 (13)
O2	0.4990 (3)	0.5802 (4)	0.6262 (3)	0.0323 (13)
C6	0.3491 (4)	0.7817 (6)	0.5405 (4)	0.0263 (17)*
H6	0.3458	0.7561	0.4879	0.032*
C12	0.3454 (6)	0.2373 (9)	0.7733 (6)	0.077 (3)
H12	0.3265	0.1669	0.7831	0.092*
C10	0.3894 (8)	0.2121 (10)	0.6276 (8)	0.110 (4)
H10A	0.3318	0.1822	0.6113	0.166*
H10B	0.4321	0.1548	0.6370	0.166*
H10C	0.4122	0.2584	0.5858	0.166*
C13	0.3455 (6)	0.3178 (9)	0.8279 (7)	0.083 (3)
H13	0.3267	0.3141	0.8813	0.100*
C14	0.3902 (8)	0.5120 (10)	0.8268 (8)	0.119 (4)
H14A	0.3310	0.5457	0.8342	0.143*
H14B	0.4265	0.5578	0.7920	0.143*
N1	0.3771 (4)	0.2746 (7)	0.7018 (6)	0.072 (2)
O1	0.5232 (3)	0.3805 (4)	0.5025 (3)	0.0311 (12)
C9	0.7329 (5)	0.5753 (7)	0.4949 (5)	0.0318 (19)*
C4	0.6950 (4)	0.4109 (6)	0.8593 (4)	0.0253 (17)*
H4	0.7256	0.4737	0.8450	0.030*
C8	0.6372 (5)	0.3995 (6)	0.7173 (4)	0.0273 (18)*
C5	0.7023 (4)	0.3716 (6)	0.9373 (4)	0.0260 (17)*
C7	0.4633 (4)	0.6362 (6)	0.5710 (4)	0.0222 (16)*
O4	0.6742 (3)	0.4860 (4)	0.7007 (3)	0.0406 (14)
C15	0.4374 (9)	0.4992 (13)	0.9079 (9)	0.155 (6)
H15A	0.4968	0.4682	0.9001	0.232*
H15B	0.4017	0.4529	0.9418	0.232*
H15C	0.4435	0.5686	0.9330	0.232*
N2	0.3785 (5)	0.4046 (7)	0.7890 (6)	0.082 (2)
C11	0.3978 (6)	0.3780 (8)	0.7132 (7)	0.076 (3)
H11	0.4218	0.4241	0.6745	0.091*
C2	0.5929 (4)	0.2674 (6)	0.8252 (4)	0.0234 (17)*
H2	0.5579	0.2316	0.7869	0.028*
C1	0.4054 (4)	0.7296 (6)	0.5961 (4)	0.0212 (17)*
C3	0.6427 (4)	0.3577 (6)	0.8030 (4)	0.0249 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0291 (6)	0.0272 (8)	0.0190 (6)	0.0011 (5)	0.0027 (5)	0.0008 (6)
O5	0.060 (4)	0.040 (4)	0.052 (3)	−0.024 (3)	0.026 (3)	−0.012 (3)
O6	0.059 (4)	0.041 (4)	0.036 (3)	−0.010 (2)	0.023 (2)	−0.003 (3)
O3	0.053 (4)	0.042 (4)	0.029 (3)	−0.011 (2)	−0.007 (2)	0.007 (2)
O2	0.039 (3)	0.037 (4)	0.022 (3)	0.010 (2)	−0.003 (2)	−0.001 (2)
C12	0.048 (5)	0.061 (6)	0.120 (7)	0.003 (4)	−0.004 (5)	0.050 (4)
C10	0.099 (10)	0.097 (9)	0.135 (7)	0.009 (7)	0.005 (6)	0.021 (6)
C13	0.048 (6)	0.075 (6)	0.125 (6)	0.003 (4)	−0.004 (5)	0.041 (5)
C14	0.080 (9)	0.085 (7)	0.192 (10)	−0.010 (6)	0.004 (7)	0.008 (6)
N1	0.038 (5)	0.060 (5)	0.117 (6)	0.005 (3)	−0.001 (4)	0.047 (4)
O1	0.038 (3)	0.033 (4)	0.023 (3)	0.000 (2)	0.002 (2)	−0.005 (2)
O4	0.047 (3)	0.039 (4)	0.037 (3)	−0.010 (2)	−0.004 (2)	0.014 (3)
C15	0.092 (10)	0.193 (16)	0.179 (11)	0.039 (9)	0.005 (7)	−0.047 (9)
N2	0.039 (5)	0.071 (5)	0.137 (6)	0.000 (3)	0.003 (4)	0.033 (4)
C11	0.030 (5)	0.065 (5)	0.134 (6)	0.003 (4)	0.001 (5)	0.048 (4)

Geometric parameters (Å, º)

Mn1—O5	2.195 (5)	C14—C15	1.523 (13)
Mn1—O6	2.346 (5)	C14—N2	1.481 (12)
Mn1—O3	2.245 (5)	N1—C11	1.330 (11)
Mn1—O2	2.131 (5)	O1—C7^ii	1.253 (7)
Mn1—O1	2.145 (5)	C9—C5^iii	1.500 (9)
Mn1—C9	2.597 (8)	C4—C5	1.388 (9)
Mn1—C8	2.571 (7)	C4—C3	1.378 (9)
Mn1—O4	2.274 (5)	C8—O4	1.233 (8)
O5—C9	1.240 (9)	C8—C3	1.516 (9)
O6—C9	1.245 (8)	C5—C6^iv	1.394 (9)
O3—C8	1.260 (8)	C5—C9^v	1.500 (9)
O2—C7	1.263 (8)	C7—O1^ii	1.253 (7)
C6—C5^i	1.394 (9)	C7—C1	1.495 (9)
C6—C1	1.397 (9)	N2—C11	1.331 (11)
C12—C13	1.349 (10)	C2—C1^iv	1.388 (8)
C12—N1	1.357 (10)	C2—C3	1.387 (9)
C10—N1	1.467 (11)	C1—C2^i	1.388 (8)
C13—N2	1.346 (10)
O5—Mn1—O6	56.99 (18)	C12—N1—C10	126.6 (10)
O5—Mn1—O3	120.1 (2)	C11—N1—C12	106.3 (10)
O5—Mn1—C9	28.4 (2)	C11—N1—C10	127.0 (10)
O5—Mn1—C8	120.9 (2)	C7^ii—O1—Mn1	125.4 (4)
O5—Mn1—O4	109.4 (2)	O5—C9—Mn1	57.4 (4)
O6—Mn1—C9	28.6 (2)	O5—C9—O6	121.7 (7)
O6—Mn1—C8	112.1 (2)	O5—C9—C5^iii	119.5 (7)
O3—Mn1—O6	139.27 (19)	O6—C9—Mn1	64.4 (4)
O3—Mn1—C9	136.8 (2)	O6—C9—C5^iii	118.7 (8)
O3—Mn1—C8	29.3 (2)	C5^iii—C9—Mn1	172.2 (5)
O3—Mn1—O4	57.78 (18)	C3—C4—C5	120.6 (7)
O2—Mn1—O5	141.6 (2)	O3—C8—Mn1	60.8 (4)
O2—Mn1—O6	93.34 (19)	O3—C8—C3	118.8 (7)
O2—Mn1—O3	98.32 (19)	O4—C8—Mn1	62.2 (4)
O2—Mn1—O1	98.41 (18)	O4—C8—O3	122.3 (7)
O2—Mn1—C9	118.0 (2)	O4—C8—C3	118.9 (7)
O2—Mn1—C8	91.3 (2)	C3—C8—Mn1	171.7 (5)
O2—Mn1—O4	88.62 (18)	C6^iv—C5—C9^v	121.7 (6)
O1—Mn1—O5	88.04 (18)	C4—C5—C6^iv	119.0 (6)
O1—Mn1—O6	132.62 (18)	C4—C5—C9^v	119.3 (7)
O1—Mn1—O3	84.05 (18)	O2—C7—C1	117.3 (6)
O1—Mn1—C9	110.7 (2)	O1^ii—C7—O2	123.4 (6)
O1—Mn1—C8	113.3 (2)	O1^ii—C7—C1	119.2 (6)
O1—Mn1—O4	141.82 (19)	C8—O4—Mn1	89.2 (4)
C8—Mn1—C9	121.6 (2)	C13—N2—C14	123.9 (11)
O4—Mn1—O6	83.82 (19)	C11—N2—C13	109.3 (11)
O4—Mn1—C9	98.4 (2)	C11—N2—C14	126.8 (10)
O4—Mn1—C8	28.64 (19)	N1—C11—N2	109.1 (10)
C9—O5—Mn1	94.1 (4)	C3—C2—C1^iv	120.9 (6)
C9—O6—Mn1	87.0 (5)	C6—C1—C7	120.6 (6)
C8—O3—Mn1	89.8 (5)	C2^i—C1—C6	118.5 (7)
C7—O2—Mn1	110.1 (4)	C2^i—C1—C7	120.9 (6)
C5^i—C6—C1	120.9 (7)	C4—C3—C8	120.2 (7)
C13—C12—N1	109.6 (10)	C4—C3—C2	119.9 (6)
N2—C13—C12	105.7 (11)	C2—C3—C8	119.9 (6)
N2—C14—C15	109.5 (11)

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

(mn6b09s1_0.7GPa)

Crystal data

C9H3MnO6·C6H11N2	Dx = 1.689 Mg m^−3
Mr = 373.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3296 reflections
a = 14.3847 (6) Å	θ = 3.3–24.7°
b = 12.2888 (6) Å	µ = 0.94 mm^−1
c = 16.6029 (7) Å	T = 296 K
V = 2934.9 (2) Å^3	Prismatic, colorless
Z = 8	0.1 × 0.08 × 0.08 mm
F(000) = 1528

Data collection

Bruker APEX-II CCD diffractometer	1754 independent reflections
Radiation source: fine-focus sealed tube	1210 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
φ and ω scans	θmax = 24.7°, θmin = 3.3°
Absorption correction: multi-scan SADABS	h = −15→15
Tmin = 0.576, Tmax = 0.745	k = −12→12
9723 measured reflections	l = −18→18

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0668P)^2 + 2.8108P] where P = (Fo^2 + 2Fc^2)/3
1754 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 0.34 e Å^−3
244 restraints	Δρmin = −0.38 e Å^−3

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	1.10689 (5)	1.47768 (7)	0.92615 (4)	0.0239 (3)
O5	1.2097 (3)	1.4775 (3)	1.0225 (2)	0.0435 (11)
O6	1.2042 (3)	1.6260 (3)	0.9509 (2)	0.0408 (11)
O3	1.0985 (2)	1.3346 (3)	0.8411 (2)	0.0393 (10)
O2	1.0006 (2)	1.5740 (3)	0.8709 (2)	0.0308 (10)
C6	0.8519 (3)	1.7816 (5)	0.9556 (3)	0.0272 (14)*
H6	0.8503	1.7578	1.0088	0.033*
C12	0.8459 (5)	1.2275 (7)	0.7301 (5)	0.071 (2)
H12	0.8247	1.1569	0.7218	0.085*
C10	0.8872 (6)	1.2060 (8)	0.8768 (6)	0.095 (3)
H10A	0.8276	1.1779	0.8924	0.142*
H10B	0.9100	1.2539	0.9181	0.142*
H10C	0.9300	1.1469	0.8697	0.142*
C13	0.8485 (5)	1.3045 (7)	0.6739 (6)	0.075 (2)
H13	0.8308	1.2988	0.6202	0.091*
C14	0.8948 (6)	1.5026 (7)	0.6743 (6)	0.100 (3)
H14A	0.9363	1.5467	0.7067	0.120*
H14B	0.8351	1.5392	0.6715	0.120*
N1	0.8782 (3)	1.2661 (5)	0.8013 (4)	0.0614 (16)
O1	1.0170 (2)	1.3807 (3)	1.0007 (2)	0.0296 (9)
C9	1.2348 (4)	1.5734 (5)	1.0092 (3)	0.0297 (14)*
C4	1.1952 (3)	1.4083 (5)	0.6465 (3)	0.0271 (13)*
H4	1.2264	1.4714	0.6615	0.033*
C8	1.1407 (4)	1.3905 (5)	0.7889 (3)	0.0299 (14)*
C5	1.2005 (3)	1.3723 (5)	0.5670 (3)	0.0245 (13)*
C7	0.9664 (3)	1.6336 (5)	0.9258 (3)	0.0233 (12)*
O4	1.1794 (2)	1.4782 (3)	0.8062 (2)	0.0382 (10)
C15	0.9343 (7)	1.4901 (9)	0.5905 (6)	0.129 (4)
H15A	0.9941	1.4556	0.5936	0.193*
H15B	0.9408	1.5605	0.5662	0.193*
H15C	0.8932	1.4462	0.5586	0.193*
N2	0.8830 (4)	1.3937 (6)	0.7125 (5)	0.0704 (17)
C11	0.9011 (4)	1.3709 (6)	0.7894 (5)	0.0665 (19)
H11	0.9251	1.4185	0.8276	0.080*
C2	1.0934 (3)	1.2607 (5)	0.6794 (3)	0.0268 (13)*
H2	1.0589	1.2225	0.7174	0.032*
C1	0.9068 (3)	1.7263 (5)	0.8997 (3)	0.0244 (13)*
C3	1.1441 (3)	1.3515 (5)	0.7033 (3)	0.0223 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0279 (5)	0.0253 (6)	0.0186 (5)	0.0008 (4)	−0.0027 (3)	−0.0015 (4)
O5	0.055 (3)	0.031 (3)	0.044 (3)	−0.0195 (19)	−0.0207 (18)	0.013 (2)
O6	0.055 (3)	0.033 (3)	0.034 (2)	−0.0097 (18)	−0.0199 (18)	0.005 (2)
O3	0.050 (3)	0.040 (3)	0.029 (2)	−0.0073 (18)	0.0062 (17)	−0.0018 (19)
O2	0.036 (2)	0.035 (3)	0.021 (2)	0.0088 (16)	0.0031 (15)	−0.0002 (19)
C12	0.045 (4)	0.058 (5)	0.109 (5)	0.008 (3)	0.004 (4)	−0.045 (4)
C10	0.082 (6)	0.088 (7)	0.114 (6)	0.015 (5)	0.012 (5)	−0.011 (5)
C13	0.051 (4)	0.071 (5)	0.105 (5)	0.010 (3)	0.008 (4)	−0.043 (4)
C14	0.067 (6)	0.079 (6)	0.154 (7)	−0.002 (4)	0.003 (5)	−0.011 (5)
N1	0.034 (3)	0.050 (4)	0.099 (4)	0.002 (2)	0.004 (3)	−0.038 (3)
O1	0.035 (2)	0.031 (3)	0.023 (2)	−0.0002 (15)	−0.0031 (15)	0.0058 (19)
O4	0.042 (3)	0.037 (3)	0.035 (2)	−0.0061 (18)	0.0042 (16)	−0.010 (2)
C15	0.079 (7)	0.171 (12)	0.136 (7)	0.021 (6)	−0.010 (5)	0.029 (7)
N2	0.036 (3)	0.063 (4)	0.113 (4)	0.007 (2)	0.007 (3)	−0.028 (3)
C11	0.030 (4)	0.058 (4)	0.112 (5)	0.002 (3)	0.002 (3)	−0.040 (4)

Geometric parameters (Å, º)

Mn1—O5	2.179 (4)	C14—C15	1.510 (10)
Mn1—O6	2.335 (4)	C14—N2	1.490 (9)
Mn1—O3	2.258 (4)	N1—C11	1.343 (9)
Mn1—O2	2.140 (4)	O1—C7^ii	1.256 (6)
Mn1—O1	2.150 (4)	C9—C5^iii	1.494 (7)
Mn1—C9	2.582 (6)	C4—C5	1.393 (7)
Mn1—C8	2.564 (6)	C4—C3	1.385 (7)
Mn1—O4	2.248 (4)	C8—O4	1.247 (7)
O5—C9	1.253 (7)	C8—C3	1.502 (7)
O6—C9	1.244 (6)	C5—C6^iv	1.398 (7)
O3—C8	1.261 (6)	C5—C9^v	1.494 (7)
O2—C7	1.269 (6)	C7—O1^ii	1.256 (6)
C6—C5^i	1.398 (7)	C7—C1	1.490 (7)
C6—C1	1.395 (7)	N2—C11	1.332 (8)
C12—C13	1.329 (10)	C2—C1^iv	1.380 (7)
C12—N1	1.355 (8)	C2—C3	1.391 (7)
C10—N1	1.461 (9)	C1—C2^i	1.380 (7)
C13—N2	1.364 (8)
O5—Mn1—O6	57.63 (14)	C12—N1—C10	127.0 (8)
O5—Mn1—O3	119.65 (16)	C11—N1—C12	106.9 (7)
O5—Mn1—C9	28.95 (16)	C11—N1—C10	126.1 (7)
O5—Mn1—C8	121.56 (17)	C7^ii—O1—Mn1	121.5 (3)
O5—Mn1—O4	109.60 (15)	O5—C9—Mn1	57.4 (3)
O6—Mn1—C9	28.74 (16)	O5—C9—C5^iii	119.0 (5)
O6—Mn1—C8	111.64 (17)	O6—C9—Mn1	64.5 (3)
O3—Mn1—O6	138.58 (14)	O6—C9—O5	121.7 (5)
O3—Mn1—C9	136.60 (16)	O6—C9—C5^iii	119.2 (6)
O3—Mn1—C8	29.46 (16)	C5^iii—C9—Mn1	171.9 (4)
O2—Mn1—O5	143.14 (16)	C3—C4—C5	120.9 (5)
O2—Mn1—O6	94.12 (15)	O3—C8—Mn1	61.7 (3)
O2—Mn1—O3	97.16 (14)	O3—C8—C3	119.5 (5)
O2—Mn1—O1	97.12 (14)	O4—C8—Mn1	61.3 (3)
O2—Mn1—C9	119.05 (19)	O4—C8—O3	121.9 (5)
O2—Mn1—C8	89.19 (16)	O4—C8—C3	118.6 (5)
O2—Mn1—O4	87.15 (14)	C3—C8—Mn1	168.9 (4)
O1—Mn1—O5	89.13 (14)	C6^iv—C5—C9^v	121.3 (5)
O1—Mn1—O6	133.80 (14)	C4—C5—C6^iv	118.6 (5)
O1—Mn1—O3	84.02 (14)	C4—C5—C9^v	120.0 (5)
O1—Mn1—C9	111.95 (16)	O2—C7—C1	117.1 (5)
O1—Mn1—C8	113.18 (18)	O1^ii—C7—O2	122.9 (5)
O1—Mn1—O4	142.23 (15)	O1^ii—C7—C1	119.9 (5)
C8—Mn1—C9	121.98 (17)	C8—O4—Mn1	89.6 (3)
O4—Mn1—O6	82.82 (14)	C13—N2—C14	124.2 (8)
O4—Mn1—O3	58.23 (14)	C11—N2—C13	110.6 (8)
O4—Mn1—C9	98.09 (16)	C11—N2—C14	125.1 (7)
O4—Mn1—C8	29.10 (15)	N2—C11—N1	107.2 (7)
C9—O5—Mn1	93.7 (3)	C1^iv—C2—C3	121.2 (5)
C9—O6—Mn1	86.8 (4)	C6—C1—C7	120.3 (5)
C8—O3—Mn1	88.8 (4)	C2^i—C1—C6	118.9 (5)
C7—O2—Mn1	106.8 (3)	C2^i—C1—C7	120.8 (5)
C1—C6—C5^i	121.0 (5)	C4—C3—C8	120.1 (5)
C13—C12—N1	110.7 (8)	C4—C3—C2	119.3 (5)
C12—C13—N2	104.6 (8)	C2—C3—C8	120.6 (5)
N2—C14—C15	110.1 (8)

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y+3, −z+2; (iii) −x+5/2, −y+3, z+1/2; (iv) −x+2, y−1/2, −z+3/2; (v) −x+5/2, −y+3, z−1/2.

(mn6b10s2_1.7GPa)

Crystal data

C9H3MnO6·C6H11N2	Dx = 1.746 Mg m^−3
Mr = 373.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2758 reflections
a = 14.1985 (9) Å	θ = 3.3–23.3°
b = 12.0745 (9) Å	µ = 0.97 mm^−1
c = 16.5616 (11) Å	T = 296 K
V = 2839.3 (3) Å^3	Prismatic, colorless
Z = 8	0.1 × 0.08 × 0.08 mm
F(000) = 1528

Data collection

Bruker APEX-II CCD diffractometer	1035 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.095
φ and ω scans	θmax = 23.4°, θmin = 3.3°
Absorption correction: multi-scan SADABS	h = −14→14
Tmin = 0.588, Tmax = 0.745	k = −11→12
8467 measured reflections	l = −17→17
1539 independent reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.193	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.1159P)^2 + 2.9359P] where P = (Fo^2 + 2Fc^2)/3
1539 reflections	(Δ/σ)max = 0.005
173 parameters	Δρmax = 0.43 e Å^−3
244 restraints	Δρmin = −0.42 e Å^−3

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	0.60887 (8)	0.47342 (11)	0.56774 (7)	0.0254 (5)
O5	0.7072 (4)	0.4759 (5)	0.4676 (3)	0.0372 (16)
O6	0.7097 (4)	0.6226 (5)	0.5457 (3)	0.0376 (16)
O3	0.6019 (4)	0.3225 (5)	0.6506 (3)	0.0366 (15)
O2	0.5037 (3)	0.5668 (5)	0.6326 (3)	0.0315 (14)
C6	0.3560 (5)	0.7816 (7)	0.5487 (5)	0.027 (2)*
H6	0.3573	0.7609	0.4946	0.032*
C12	0.3471 (7)	0.2137 (10)	0.7638 (7)	0.065 (3)
H12	0.3249	0.1420	0.7715	0.078*
C10	0.3872 (8)	0.1967 (11)	0.6156 (7)	0.083 (4)
H10A	0.3255	0.1788	0.5958	0.124*
H10B	0.4225	0.1297	0.6233	0.124*
H10C	0.4190	0.2430	0.5772	0.124*
C13	0.3527 (7)	0.2914 (9)	0.8207 (7)	0.062 (3)
H13	0.3358	0.2844	0.8747	0.075*
C14	0.4016 (8)	0.4917 (10)	0.8221 (7)	0.078 (3)
H14A	0.3442	0.5347	0.8173	0.093*
H14B	0.4514	0.5315	0.7945	0.093*
N1	0.3789 (5)	0.2555 (8)	0.6930 (5)	0.056 (2)
O1	0.5094 (3)	0.3810 (5)	0.4954 (3)	0.0302 (14)
C9	0.7356 (5)	0.5718 (8)	0.4847 (5)	0.031 (2)*
C4	0.6964 (5)	0.4046 (8)	0.8465 (5)	0.029 (2)*
H4	0.7287	0.4681	0.8310	0.035*
C8	0.6456 (6)	0.3804 (8)	0.7026 (5)	0.032 (2)*
C5	0.6985 (5)	0.3701 (7)	0.9274 (4)	0.0232 (19)*
C7	0.4723 (5)	0.6313 (7)	0.5795 (5)	0.023 (2)*
O4	0.6879 (4)	0.4680 (5)	0.6838 (3)	0.0352 (15)
C15	0.4269 (9)	0.4789 (12)	0.9103 (7)	0.101 (5)
H15A	0.3815	0.4319	0.9363	0.152*
H15B	0.4269	0.5502	0.9359	0.152*
H15C	0.4884	0.4463	0.9149	0.152*
N2	0.3881 (5)	0.3832 (8)	0.7838 (6)	0.059 (2)
C11	0.4041 (6)	0.3598 (9)	0.7054 (7)	0.058 (2)
H11	0.4285	0.4081	0.6670	0.069*
C2	0.5934 (5)	0.2541 (7)	0.8135 (5)	0.030 (2)*
H2	0.5595	0.2140	0.7754	0.036*
C1	0.4095 (5)	0.7227 (7)	0.6052 (5)	0.025 (2)*
C3	0.6461 (5)	0.3442 (7)	0.7896 (4)	0.0221 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0310 (8)	0.0270 (11)	0.0183 (8)	0.0012 (6)	0.0024 (5)	0.0009 (6)
O5	0.052 (4)	0.031 (4)	0.029 (3)	−0.018 (3)	0.014 (2)	−0.009 (3)
O6	0.053 (4)	0.036 (4)	0.024 (3)	−0.008 (3)	0.014 (2)	−0.002 (3)
O3	0.050 (4)	0.042 (4)	0.018 (3)	−0.005 (3)	−0.003 (2)	0.006 (3)
O2	0.039 (3)	0.032 (4)	0.024 (3)	0.005 (2)	−0.001 (2)	0.002 (3)
C12	0.045 (6)	0.056 (6)	0.095 (6)	0.002 (4)	−0.005 (4)	0.030 (4)
C10	0.083 (9)	0.066 (9)	0.099 (6)	0.014 (6)	−0.013 (5)	0.007 (6)
C13	0.036 (5)	0.060 (6)	0.092 (5)	0.009 (4)	−0.007 (4)	0.028 (4)
C14	0.062 (8)	0.069 (7)	0.101 (7)	−0.001 (5)	0.000 (5)	0.008 (5)
N1	0.036 (4)	0.049 (5)	0.084 (5)	0.002 (3)	−0.005 (3)	0.027 (4)
O1	0.034 (3)	0.031 (4)	0.026 (3)	0.001 (2)	0.001 (2)	−0.001 (3)
O4	0.040 (3)	0.040 (5)	0.026 (3)	−0.005 (3)	−0.003 (2)	0.006 (3)
C15	0.093 (9)	0.122 (14)	0.090 (7)	0.023 (8)	0.009 (6)	−0.015 (7)
N2	0.036 (5)	0.055 (5)	0.086 (5)	0.006 (3)	−0.008 (4)	0.021 (4)
C11	0.036 (5)	0.050 (5)	0.088 (5)	0.004 (4)	−0.003 (4)	0.023 (4)

Geometric parameters (Å, º)

Mn1—O5	2.167 (5)	C14—C15	1.513 (12)
Mn1—O6	2.330 (6)	C14—N2	1.468 (12)
Mn1—O3	2.283 (6)	N1—C11	1.325 (11)
Mn1—O2	2.158 (5)	O1—C7^ii	1.276 (8)
Mn1—O1	2.163 (5)	C9—C5^iii	1.505 (11)
Mn1—C9	2.557 (8)	C4—C5	1.404 (10)
Mn1—C8	2.553 (9)	C4—C3	1.389 (11)
Mn1—O4	2.226 (5)	C8—O4	1.255 (10)
O5—C9	1.259 (10)	C8—C3	1.505 (11)
O6—C9	1.237 (9)	C5—C6^iv	1.378 (11)
O3—C8	1.270 (10)	C5—C9^v	1.505 (11)
O2—C7	1.256 (9)	C7—O1^ii	1.276 (8)
C6—C5^i	1.378 (11)	C7—C1	1.481 (11)
C6—C1	1.399 (11)	N2—C11	1.348 (11)
C12—C13	1.332 (12)	C2—C1^iv	1.399 (10)
C12—N1	1.355 (10)	C2—C3	1.379 (11)
C10—N1	1.469 (11)	C1—C2^i	1.399 (10)
C13—N2	1.362 (11)
O5—Mn1—O6	58.2 (2)	C12—N1—C10	127.0 (11)
O5—Mn1—O3	119.9 (2)	C11—N1—C12	108.0 (10)
O5—Mn1—C9	29.5 (2)	C11—N1—C10	125.0 (10)
O5—Mn1—C8	122.9 (3)	C7^ii—O1—Mn1	117.7 (5)
O5—Mn1—O4	109.7 (2)	O5—C9—Mn1	57.8 (4)
O6—Mn1—C9	28.8 (2)	O5—C9—C5^iii	119.1 (8)
O6—Mn1—C8	110.6 (3)	O6—C9—Mn1	65.3 (5)
O3—Mn1—O6	137.5 (2)	O6—C9—O5	123.0 (8)
O3—Mn1—C9	136.4 (2)	O6—C9—C5^iii	117.9 (9)
O3—Mn1—C8	29.8 (2)	C5^iii—C9—Mn1	172.9 (6)
O2—Mn1—O5	145.0 (2)	C3—C4—C5	120.3 (8)
O2—Mn1—O6	95.7 (2)	O3—C8—Mn1	63.3 (4)
O2—Mn1—O3	95.0 (2)	O3—C8—C3	119.4 (8)
O2—Mn1—O1	95.4 (2)	O4—C8—Mn1	60.7 (4)
O2—Mn1—C9	120.8 (3)	O4—C8—O3	121.9 (8)
O2—Mn1—C8	86.3 (2)	O4—C8—C3	118.6 (8)
O2—Mn1—O4	86.2 (2)	C3—C8—Mn1	164.9 (6)
O1—Mn1—O5	90.2 (2)	C6^iv—C5—C9^v	122.0 (7)
O1—Mn1—O6	135.5 (2)	C6^iv—C5—C4	119.5 (7)
O1—Mn1—O3	83.8 (2)	C4—C5—C9^v	118.5 (8)
O1—Mn1—C9	113.7 (2)	O2—C7—O1^ii	122.5 (8)
O1—Mn1—C8	113.0 (3)	O2—C7—C1	118.2 (7)
O1—Mn1—O4	142.4 (2)	O1^ii—C7—C1	119.2 (7)
C8—Mn1—C9	122.1 (3)	C8—O4—Mn1	89.9 (5)
O4—Mn1—O6	81.3 (2)	C13—N2—C14	125.5 (10)
O4—Mn1—O3	58.6 (2)	C11—N2—C13	108.9 (10)
O4—Mn1—C9	97.1 (2)	C11—N2—C14	125.6 (9)
O4—Mn1—C8	29.4 (2)	N1—C11—N2	107.7 (10)
C9—O5—Mn1	92.7 (5)	C3—C2—C1^iv	120.5 (8)
C9—O6—Mn1	85.8 (5)	C6—C1—C7	120.9 (7)
C8—O3—Mn1	87.0 (5)	C2^i—C1—C6	119.3 (8)
C7—O2—Mn1	102.7 (5)	C2^i—C1—C7	119.7 (7)
C5^i—C6—C1	120.5 (7)	C4—C3—C8	120.0 (8)
C13—C12—N1	109.3 (11)	C2—C3—C4	119.8 (7)
C12—C13—N2	106.1 (11)	C2—C3—C8	120.1 (7)
N2—C14—C15	110.9 (10)

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

(mn6b11s1_2.5GPa)

Crystal data

C9H3MnO6·C6H11N2	Dx = 1.783 Mg m^−3
Mr = 373.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2012 reflections
a = 14.150 (2) Å	θ = 3.3–23.3°
b = 11.860 (2) Å	µ = 0.99 mm^−1
c = 16.574 (2) Å	T = 296 K
V = 2781.3 (8) Å^3	Prismatic, colorless
Z = 8	0.1 × 0.08 × 0.08 mm
F(000) = 1528

Data collection

Bruker APEX-II CCD diffractometer	867 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.146
φ and ω scans	θmax = 23.5°, θmin = 3.3°
Absorption correction: multi-scan SADABS	h = −14→14
Tmin = 0.523, Tmax = 0.745	k = −11→11
6857 measured reflections	l = −17→17
1482 independent reflections

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)] = 0.089	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.252	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1059P)^2 + 27.0755P] where P = (Fo^2 + 2Fc^2)/3
1482 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.61 e Å^−3
244 restraints	Δρmin = −0.92 e Å^−3

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	0.61009 (13)	0.47072 (19)	0.56353 (10)	0.0273 (7)
O5	0.7033 (6)	0.4764 (9)	0.4601 (5)	0.037 (2)
O6	0.7123 (6)	0.6216 (9)	0.5420 (5)	0.038 (2)
O3	0.6036 (6)	0.3137 (8)	0.6452 (5)	0.034 (2)
O2	0.5082 (6)	0.5623 (8)	0.6355 (5)	0.033 (2)
C6	0.3578 (8)	0.7816 (12)	0.5527 (8)	0.029 (3)*
H6	0.3590	0.7616	0.4985	0.035*
C12	0.3480 (10)	0.2041 (14)	0.7594 (9)	0.056 (3)
H12	0.3254	0.1311	0.7662	0.067*
C10	0.3858 (11)	0.1890 (15)	0.6107 (9)	0.068 (5)
H10A	0.3244	0.1616	0.5958	0.102*
H10B	0.4289	0.1268	0.6152	0.102*
H10C	0.4082	0.2404	0.5703	0.102*
C13	0.3542 (9)	0.2821 (13)	0.8185 (10)	0.051 (3)
H13	0.3368	0.2737	0.8723	0.061*
C14	0.4052 (12)	0.4853 (15)	0.8204 (9)	0.070 (4)
H14A	0.3498	0.5318	0.8114	0.084*
H14B	0.4589	0.5227	0.7957	0.084*
N1	0.3797 (7)	0.2477 (12)	0.6888 (7)	0.055 (3)
O1	0.5045 (5)	0.3807 (9)	0.4933 (5)	0.033 (2)
C9	0.7370 (9)	0.5716 (15)	0.4791 (9)	0.040 (4)*
C4	0.6985 (9)	0.4019 (13)	0.8405 (7)	0.033 (4)*
H4	0.7332	0.4643	0.8239	0.040*
C8	0.6486 (10)	0.3723 (14)	0.6945 (9)	0.038 (4)*
C5	0.6981 (8)	0.3706 (11)	0.9214 (7)	0.019 (3)*
C7	0.4749 (9)	0.6301 (12)	0.5820 (8)	0.028 (3)*
O4	0.6932 (6)	0.4597 (9)	0.6755 (5)	0.037 (2)
C15	0.4221 (14)	0.4739 (19)	0.9096 (10)	0.095 (6)
H15A	0.3767	0.4227	0.9322	0.142*
H15B	0.4157	0.5464	0.9349	0.142*
H15C	0.4847	0.4454	0.9188	0.142*
N2	0.3914 (8)	0.3764 (11)	0.7825 (8)	0.058 (3)
C11	0.4051 (10)	0.3534 (14)	0.7044 (9)	0.057 (4)
H11	0.4289	0.4038	0.6665	0.068*
C2	0.5925 (8)	0.2485 (13)	0.8090 (8)	0.032 (3)*
H2	0.5596	0.2053	0.7715	0.039*
C1	0.4121 (8)	0.7224 (12)	0.6082 (7)	0.024 (3)*
C3	0.6467 (8)	0.3394 (12)	0.7843 (8)	0.026 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0336 (12)	0.0315 (16)	0.0167 (11)	0.0008 (10)	0.0006 (8)	0.0003 (11)
O5	0.046 (5)	0.036 (7)	0.029 (4)	−0.012 (4)	0.016 (3)	−0.004 (4)
O6	0.046 (5)	0.042 (6)	0.025 (5)	−0.007 (4)	0.009 (4)	−0.008 (4)
O3	0.042 (5)	0.044 (5)	0.015 (4)	−0.007 (4)	−0.005 (4)	0.003 (4)
O2	0.039 (5)	0.041 (6)	0.020 (4)	0.006 (4)	0.000 (3)	0.003 (4)
C12	0.043 (8)	0.056 (8)	0.069 (6)	0.002 (5)	0.002 (6)	0.015 (5)
C10	0.068 (12)	0.064 (12)	0.072 (7)	0.002 (8)	0.000 (7)	0.003 (7)
C13	0.028 (7)	0.060 (8)	0.066 (6)	0.009 (5)	−0.003 (5)	0.014 (5)
C14	0.069 (11)	0.065 (8)	0.077 (8)	0.002 (7)	0.007 (7)	−0.003 (7)
N1	0.043 (7)	0.054 (7)	0.066 (6)	−0.001 (5)	0.003 (5)	0.014 (5)
O1	0.031 (4)	0.042 (7)	0.026 (4)	−0.002 (3)	0.005 (3)	0.000 (4)
O4	0.037 (5)	0.049 (7)	0.024 (4)	−0.004 (4)	−0.003 (3)	0.001 (4)
C15	0.105 (15)	0.105 (17)	0.075 (8)	0.023 (12)	0.005 (8)	−0.015 (8)
N2	0.046 (7)	0.058 (7)	0.070 (6)	0.004 (5)	0.001 (5)	0.008 (5)
C11	0.049 (8)	0.054 (8)	0.067 (6)	0.000 (6)	0.005 (5)	0.011 (5)

Geometric parameters (Å, º)

Mn1—O5	2.164 (8)	C14—C15	1.504 (15)
Mn1—O6	2.328 (10)	C14—N2	1.449 (15)
Mn1—O3	2.304 (9)	N1—C11	1.329 (15)
Mn1—O2	2.164 (9)	O1—C7^ii	1.287 (14)
Mn1—O1	2.174 (9)	C9—C5^iii	1.492 (18)
Mn1—C9	2.572 (15)	C4—C5	1.390 (16)
Mn1—C8	2.524 (15)	C4—C3	1.398 (18)
Mn1—O4	2.201 (8)	C8—O4	1.254 (17)
O5—C9	1.266 (17)	C8—C3	1.540 (18)
O6—C9	1.249 (16)	C5—C6^iv	1.388 (18)
O3—C8	1.247 (16)	C5—C9^v	1.492 (18)
O2—C7	1.287 (15)	C7—O1^ii	1.287 (14)
C6—C5^i	1.388 (18)	C7—C1	1.477 (18)
C6—C1	1.387 (17)	N2—C11	1.337 (14)
C12—C13	1.349 (15)	C2—C1^iv	1.409 (16)
C12—N1	1.356 (14)	C2—C3	1.386 (18)
C10—N1	1.472 (14)	C1—C2^i	1.409 (16)
C13—N2	1.373 (14)
O5—Mn1—O6	58.4 (3)	C12—N1—C10	126.7 (15)
O5—Mn1—O3	121.0 (4)	C11—N1—C12	106.3 (14)
O5—Mn1—O1	90.6 (3)	C11—N1—C10	126.9 (14)
O5—Mn1—C9	29.4 (4)	C7^ii—O1—Mn1	114.4 (8)
O5—Mn1—C8	124.3 (4)	O5—C9—Mn1	57.1 (7)
O5—Mn1—O4	110.1 (3)	O5—C9—C5^iii	118.8 (13)
O6—Mn1—C9	29.0 (4)	O6—C9—Mn1	64.6 (8)
O6—Mn1—C8	110.7 (4)	O6—C9—O5	121.7 (14)
O3—Mn1—O6	137.4 (3)	O6—C9—C5^iii	119.3 (15)
O3—Mn1—C9	136.4 (4)	C5^iii—C9—Mn1	172.7 (10)
O3—Mn1—C8	29.5 (4)	C5—C4—C3	119.9 (13)
O2—Mn1—O5	145.8 (4)	O3—C8—Mn1	65.4 (8)
O2—Mn1—O6	96.5 (3)	O3—C8—O4	123.6 (13)
O2—Mn1—O3	93.1 (3)	O3—C8—C3	118.9 (13)
O2—Mn1—O1	94.8 (3)	O4—C8—Mn1	60.7 (7)
O2—Mn1—C9	122.1 (5)	O4—C8—C3	117.4 (13)
O2—Mn1—C8	84.4 (4)	C3—C8—Mn1	160.9 (10)
O2—Mn1—O4	85.5 (3)	C6^iv—C5—C9^v	120.1 (12)
O1—Mn1—O6	136.3 (3)	C6^iv—C5—C4	120.2 (12)
O1—Mn1—O3	83.7 (3)	C4—C5—C9^v	119.5 (12)
O1—Mn1—C9	114.6 (4)	O2—C7—C1	118.7 (11)
O1—Mn1—C8	112.4 (5)	O1^ii—C7—O2	121.6 (12)
O1—Mn1—O4	142.1 (4)	O1^ii—C7—C1	119.6 (12)
C8—Mn1—C9	122.2 (5)	C8—O4—Mn1	89.5 (8)
O4—Mn1—O6	80.9 (3)	C13—N2—C14	126.1 (14)
O4—Mn1—O3	58.6 (3)	C11—N2—C13	108.0 (14)
O4—Mn1—C9	96.5 (4)	C11—N2—C14	125.6 (14)
O4—Mn1—C8	29.8 (4)	N1—C11—N2	110.0 (14)
C9—O5—Mn1	93.4 (8)	C3—C2—C1^iv	118.9 (12)
C9—O6—Mn1	86.4 (9)	C6—C1—C7	120.9 (11)
C8—O3—Mn1	85.1 (9)	C6—C1—C2^i	120.6 (12)
C7—O2—Mn1	100.2 (7)	C2^i—C1—C7	118.5 (12)
C1—C6—C5^i	119.7 (12)	C4—C3—C8	120.1 (13)
C13—C12—N1	110.1 (15)	C2—C3—C4	120.4 (12)
C12—C13—N2	105.6 (14)	C2—C3—C8	119.5 (12)
N2—C14—C15	111.6 (15)

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

(mn6b12s1_3.2GPa)

Crystal data

C9H3MnO6·C6H11N2	Dx = 1.810 Mg m^−3
Mr = 373.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 1640 reflections
a = 14.138 (3) Å	θ = 3.3–21.1°
b = 11.686 (3) Å	µ = 1.00 mm^−1
c = 16.583 (3) Å	T = 296 K
V = 2739.8 (10) Å^3	Prismatic, colorless
Z = 8	0.1 × 0.08 × 0.08 mm
F(000) = 1528

Data collection

Bruker APEX-II CCD diffractometer	678 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.150
φ and ω scans	θmax = 21.1°, θmin = 3.3°
Absorption correction: multi-scan SADABS	h = −13→13
Tmin = 0.514, Tmax = 0.745	k = −10→10
5500 measured reflections	l = −15→16
1186 independent reflections

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)] = 0.105	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.248	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0001P)^2 + 93.7239P] where P = (Fo^2 + 2Fc^2)/3
1186 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.72 e Å^−3
334 restraints	Δρmin = −0.73 e Å^−3

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	0.61063 (19)	0.4686 (3)	0.56065 (17)	0.0316 (10)
O5	0.7014 (8)	0.4765 (12)	0.4552 (7)	0.037 (3)
O6	0.7133 (9)	0.6207 (11)	0.5399 (8)	0.041 (3)
O3	0.6048 (9)	0.3093 (11)	0.6414 (7)	0.038 (3)
O2	0.5111 (8)	0.5585 (11)	0.6362 (7)	0.031 (3)
C6	0.3604 (12)	0.7857 (16)	0.5568 (13)	0.036 (5)*
H6	0.3675	0.7721	0.5019	0.043*
C12	0.3475 (14)	0.1996 (19)	0.7578 (12)	0.062 (5)
H12	0.3230	0.1262	0.7642	0.074*
C10	0.3872 (17)	0.186 (2)	0.6084 (12)	0.072 (7)
H10A	0.3265	0.1548	0.5945	0.109*
H10B	0.4328	0.1250	0.6110	0.109*
H10C	0.4063	0.2402	0.5682	0.109*
C13	0.3546 (13)	0.2785 (17)	0.8173 (13)	0.054 (4)
H13	0.3375	0.2687	0.8710	0.064*
C14	0.4079 (18)	0.4853 (18)	0.8205 (13)	0.078 (7)
H14A	0.3544	0.5352	0.8101	0.093*
H14B	0.4638	0.5204	0.7973	0.093*
N1	0.3812 (10)	0.2429 (16)	0.6873 (10)	0.057 (4)
O1	0.5022 (8)	0.3798 (12)	0.4918 (7)	0.033 (3)
C9	0.7375 (15)	0.569 (2)	0.4750 (14)	0.052 (6)*
C4	0.7008 (13)	0.3996 (18)	0.8352 (11)	0.038 (6)*
H4	0.7360	0.4619	0.8173	0.045*
C8	0.6497 (15)	0.368 (2)	0.6928 (13)	0.043 (6)*
C5	0.7009 (12)	0.3674 (16)	0.9178 (10)	0.027 (5)*
C7	0.4761 (14)	0.6280 (19)	0.5856 (13)	0.041 (6)*
O4	0.6962 (9)	0.4519 (12)	0.6717 (7)	0.039 (3)
C15	0.4211 (19)	0.471 (3)	0.9109 (13)	0.104 (9)
H15A	0.3857	0.4063	0.9293	0.156*
H15B	0.3991	0.5389	0.9380	0.156*
H15C	0.4870	0.4601	0.9226	0.156*
N2	0.3918 (11)	0.3756 (15)	0.7832 (11)	0.056 (4)
C11	0.4065 (13)	0.3514 (18)	0.7044 (12)	0.058 (5)
H11	0.4309	0.4028	0.6669	0.070*
C2	0.5934 (12)	0.2430 (17)	0.8059 (11)	0.032 (5)*
H2	0.5626	0.1967	0.7686	0.039*
C1	0.4125 (11)	0.7223 (16)	0.6115 (10)	0.022 (5)*
C3	0.6472 (13)	0.3360 (18)	0.7822 (11)	0.032 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0448 (18)	0.021 (2)	0.0295 (18)	0.0011 (14)	0.0006 (14)	0.0046 (16)
O5	0.057 (6)	0.021 (7)	0.033 (5)	−0.013 (5)	0.008 (4)	−0.001 (5)
O6	0.060 (7)	0.025 (6)	0.039 (7)	−0.009 (5)	0.011 (5)	−0.003 (5)
O3	0.069 (7)	0.019 (6)	0.026 (6)	0.002 (5)	0.002 (5)	0.002 (5)
O2	0.053 (6)	0.019 (7)	0.022 (6)	0.002 (5)	−0.004 (4)	0.002 (5)
C12	0.056 (10)	0.054 (9)	0.075 (9)	0.002 (8)	0.004 (8)	0.011 (7)
C10	0.066 (16)	0.072 (15)	0.079 (10)	0.001 (12)	0.004 (9)	0.001 (9)
C13	0.039 (10)	0.050 (10)	0.072 (9)	0.014 (7)	−0.002 (7)	0.014 (7)
C14	0.084 (17)	0.060 (11)	0.089 (11)	0.002 (9)	0.001 (10)	−0.002 (8)
N1	0.044 (9)	0.052 (9)	0.074 (8)	0.006 (7)	0.001 (7)	0.012 (6)
O1	0.048 (6)	0.020 (7)	0.031 (6)	−0.004 (4)	0.004 (4)	0.001 (5)
O4	0.055 (6)	0.032 (7)	0.030 (5)	−0.001 (5)	−0.003 (4)	0.003 (5)
C15	0.11 (2)	0.11 (2)	0.088 (11)	0.016 (17)	−0.003 (11)	−0.013 (10)
N2	0.042 (9)	0.051 (9)	0.076 (8)	0.010 (6)	−0.005 (7)	0.012 (7)
C11	0.046 (11)	0.052 (9)	0.076 (8)	0.004 (7)	0.002 (7)	0.013 (7)

Geometric parameters (Å, º)

Mn1—O5	2.171 (12)	C14—C15	1.520 (18)
Mn1—O6	2.321 (13)	C14—N2	1.441 (17)
Mn1—O3	2.295 (12)	N1—C11	1.347 (17)
Mn1—O2	2.158 (12)	O1—C7^ii	1.32 (2)
Mn1—O1	2.175 (13)	C9—C5^iii	1.49 (3)
Mn1—C9	2.57 (2)	C4—C5	1.42 (2)
Mn1—C8	2.55 (2)	C4—C3	1.38 (2)
Mn1—O4	2.212 (12)	C8—O4	1.23 (2)
O5—C9	1.24 (2)	C8—C3	1.53 (3)
O6—C9	1.28 (2)	C5—C6^iv	1.36 (2)
O3—C8	1.27 (2)	C5—C9^v	1.49 (3)
O2—C7	1.27 (2)	C7—O1^ii	1.32 (2)
C6—C5^i	1.36 (2)	C7—C1	1.49 (3)
C6—C1	1.38 (2)	N2—C11	1.354 (17)
C12—C13	1.355 (17)	C2—C1^iv	1.39 (2)
C12—N1	1.360 (17)	C2—C3	1.38 (2)
C10—N1	1.472 (17)	C1—C2^i	1.39 (2)
C13—N2	1.373 (17)
O5—Mn1—O6	58.5 (5)	C12—N1—C10	128 (2)
O5—Mn1—O3	121.7 (5)	C11—N1—C12	105.3 (18)
O5—Mn1—O1	90.8 (5)	C11—N1—C10	126.7 (19)
O5—Mn1—C9	28.7 (6)	C7^ii—O1—Mn1	112.3 (12)
O5—Mn1—C8	125.8 (6)	O5—C9—Mn1	57.4 (11)
O5—Mn1—O4	110.5 (5)	O5—C9—O6	122 (2)
O6—Mn1—C9	29.8 (6)	O5—C9—C5^iii	121 (2)
O6—Mn1—C8	110.2 (6)	O6—C9—Mn1	64.3 (11)
O3—Mn1—O6	136.9 (5)	O6—C9—C5^iii	117 (2)
O3—Mn1—C9	135.8 (6)	C5^iii—C9—Mn1	171.4 (15)
O3—Mn1—C8	29.7 (5)	C3—C4—C5	118.2 (19)
O2—Mn1—O5	146.4 (5)	O3—C8—Mn1	64.0 (11)
O2—Mn1—O6	97.0 (5)	O3—C8—C3	120 (2)
O2—Mn1—O3	91.9 (5)	O4—C8—Mn1	60.3 (11)
O2—Mn1—O1	94.4 (5)	O4—C8—O3	121 (2)
O2—Mn1—C9	123.7 (7)	O4—C8—C3	119 (2)
O2—Mn1—C8	82.3 (6)	C3—C8—Mn1	160.5 (15)
O2—Mn1—O4	85.2 (4)	C6^iv—C5—C9^v	121.9 (18)
O1—Mn1—O6	136.7 (5)	C6^iv—C5—C4	119.0 (18)
O1—Mn1—O3	83.9 (5)	C4—C5—C9^v	118.8 (18)
O1—Mn1—C9	114.8 (6)	O2—C7—O1^ii	120.5 (19)
O1—Mn1—C8	112.6 (6)	O2—C7—C1	121.3 (19)
O1—Mn1—O4	141.3 (5)	O1^ii—C7—C1	118.1 (18)
C8—Mn1—C9	122.3 (7)	C8—O4—Mn1	90.9 (13)
O4—Mn1—O6	81.3 (5)	C13—N2—C14	128 (2)
O4—Mn1—O3	57.5 (5)	C11—N2—C13	106.5 (18)
O4—Mn1—C9	96.8 (6)	C11—N2—C14	125.2 (18)
O4—Mn1—C8	28.9 (5)	N1—C11—N2	111.0 (19)
C9—O5—Mn1	93.8 (13)	C3—C2—C1^iv	116.7 (18)
C9—O6—Mn1	85.9 (13)	C6—C1—C7	122.0 (17)
C8—O3—Mn1	86.2 (13)	C6—C1—C2^i	121.3 (18)
C7—O2—Mn1	100.5 (12)	C2^i—C1—C7	116.7 (17)
C5^i—C6—C1	120.9 (19)	C4—C3—C8	118.2 (19)
C13—C12—N1	110.2 (19)	C4—C3—C2	123.1 (18)
C12—C13—N2	106.9 (19)	C2—C3—C8	118.8 (18)
N2—C14—C15	110 (2)

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

(mn6b13s1_4.3GPa)

Crystal data

C9H3MnO6·C6H11N2	Dx = 1.866 Mg m^−3
Mr = 373.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 843 reflections
a = 14.140 (5) Å	θ = 3.4–13.7°
b = 11.319 (5) Å	µ = 1.03 mm^−1
c = 16.600 (6) Å	T = 296 K
V = 2656.9 (17) Å^3	Prismatic, colorless
Z = 8	0.1 × 0.08 × 0.08 mm
F(000) = 1528

Data collection

Bruker APEX-II CCD diffractometer	267 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.111
φ and ω scans	θmax = 13.9°, θmin = 3.4°
Absorption correction: multi-scan SADABS	h = −9→9
Tmin = 0.470, Tmax = 0.744	k = −7→6
1894 measured reflections	l = −10→10
372 independent reflections

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)] = 0.102	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.299	H-atom parameters constrained
S = 1.29	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
372 reflections	(Δ/σ)max < 0.001
99 parameters	Δρmax = 0.65 e Å^−3
43 restraints	Δρmin = −0.64 e Å^−3

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	0.6118 (4)	0.4661 (6)	0.5563 (4)	0.047 (5)*
O5	0.6986 (17)	0.476 (3)	0.4476 (15)	0.051 (10)*
O6	0.7158 (18)	0.619 (3)	0.537 (2)	0.064 (11)*
O3	0.6092 (16)	0.296 (2)	0.6352 (16)	0.051 (10)*
O2	0.5168 (16)	0.552 (2)	0.6356 (15)	0.038 (9)*
C6	0.362 (3)	0.790 (4)	0.561 (3)	0.049 (14)*
H6	0.3694	0.7786	0.5054	0.059*
C12	0.347 (3)	0.197 (4)	0.756 (2)	0.080 (13)*
H12	0.3228	0.1210	0.7614	0.096*
C10	0.389 (3)	0.181 (4)	0.604 (2)	0.082 (17)*
H10A	0.3283	0.1483	0.5905	0.123*
H10B	0.4355	0.1195	0.6047	0.123*
H10C	0.4062	0.2393	0.5645	0.123*
C13	0.349 (3)	0.274 (4)	0.818 (2)	0.062 (14)*
H13	0.3244	0.2660	0.8702	0.075*
C14	0.412 (3)	0.478 (4)	0.828 (3)	0.093 (19)*
H14A	0.3608	0.5320	0.8147	0.112*
H14B	0.4701	0.5127	0.8084	0.112*
N1	0.384 (2)	0.237 (3)	0.684 (2)	0.081 (13)*
O1	0.4982 (15)	0.378 (2)	0.4913 (17)	0.045 (10)*
C9	0.738 (3)	0.577 (5)	0.474 (3)	0.067 (16)*
C4	0.705 (3)	0.398 (4)	0.829 (2)	0.037 (13)*
H4	0.7472	0.4547	0.8094	0.045*
C8	0.652 (3)	0.368 (5)	0.689 (3)	0.057 (13)*
C5	0.699 (3)	0.371 (4)	0.911 (3)	0.034 (12)*
C7	0.481 (3)	0.633 (4)	0.583 (3)	0.057 (15)*
O4	0.7042 (18)	0.448 (3)	0.6632 (15)	0.054 (10)*
C15	0.418 (3)	0.468 (4)	0.918 (3)	0.11 (2)*
H15A	0.3687	0.4160	0.9370	0.169*
H15B	0.4099	0.5444	0.9418	0.169*
H15C	0.4783	0.4362	0.9328	0.169*
N2	0.396 (2)	0.368 (3)	0.785 (2)	0.081 (12)*
C11	0.414 (2)	0.345 (3)	0.707 (2)	0.069 (13)*
H11	0.4444	0.3982	0.6721	0.083*
C2	0.596 (3)	0.244 (4)	0.803 (2)	0.039 (13)*
H2	0.5666	0.1943	0.7654	0.047*
C1	0.414 (3)	0.721 (4)	0.617 (3)	0.032 (13)*
C3	0.645 (3)	0.335 (4)	0.778 (3)	0.028 (12)*

Geometric parameters (Å, º)

Mn1—O5	2.18 (3)	C14—C15	1.50 (2)
Mn1—O6	2.29 (3)	C14—N2	1.45 (2)
Mn1—O3	2.33 (3)	N1—C11	1.35 (2)
Mn1—O2	2.12 (2)	O1—Mn1^i	2.48 (2)
Mn1—O1^i	2.48 (2)	O1—C7^i	1.27 (4)
Mn1—O1	2.18 (2)	C9—C5^iii	1.50 (5)
Mn1—C9	2.57 (5)	C4—C5	1.40 (4)
Mn1—C8	2.53 (5)	C4—C3	1.40 (4)
Mn1—O4	2.21 (3)	C8—O4	1.24 (5)
O5—C9	1.34 (5)	C8—C3	1.53 (5)
O6—C9	1.19 (5)	C5—C6^iv	1.34 (5)
O3—C8	1.35 (5)	C5—C9^v	1.50 (5)
O2—C7	1.37 (4)	C7—O1^i	1.27 (4)
C6—C5^ii	1.34 (4)	C7—C1	1.48 (4)
C6—C1	1.42 (4)	N2—C11	1.36 (2)
C12—C13	1.36 (2)	C2—C1^iv	1.36 (4)
C12—N1	1.38 (2)	C2—C3	1.31 (4)
C10—N1	1.48 (2)	C1—C2^ii	1.36 (4)
C13—N2	1.37 (2)
O5—Mn1—O6	59.0 (11)	C13—C12—N1	116 (3)
O5—Mn1—O3	121.1 (10)	C12—C13—N2	102 (3)
O5—Mn1—O1^i	93.0 (9)	N2—C14—C15	115 (4)
O5—Mn1—C9	31.4 (13)	C12—N1—C10	131 (4)
O5—Mn1—C8	127.8 (12)	C11—N1—C12	101 (3)
O5—Mn1—O4	109.6 (10)	C11—N1—C10	128 (4)
O6—Mn1—O3	135.4 (10)	Mn1—O1—Mn1^i	107.1 (11)
O6—Mn1—O1^i	79.7 (8)	C7^i—O1—Mn1^i	85 (3)
O6—Mn1—C9	27.7 (12)	C7^i—O1—Mn1	111 (2)
O6—Mn1—C8	107.8 (15)	O5—C9—Mn1	58 (2)
O3—Mn1—O1^i	139.2 (8)	O5—C9—C5^iii	111 (5)
O3—Mn1—C9	135.5 (12)	O6—C9—Mn1	63 (3)
O3—Mn1—C8	32.0 (11)	O6—C9—O5	121 (5)
O2—Mn1—O5	147.9 (11)	O6—C9—C5^iii	128 (6)
O2—Mn1—O6	98.5 (11)	C5^iii—C9—Mn1	168 (4)
O2—Mn1—O3	91.1 (10)	C3—C4—C5	115 (4)
O2—Mn1—O1	92.9 (10)	O3—C8—Mn1	66 (2)
O2—Mn1—O1^i	58.3 (9)	O3—C8—C3	117 (5)
O2—Mn1—C9	123.2 (15)	O4—C8—Mn1	61 (3)
O2—Mn1—C8	78.7 (13)	O4—C8—O3	118 (5)
O2—Mn1—O4	85.3 (10)	O4—C8—C3	124 (5)
O1—Mn1—O5	91.7 (10)	C3—C8—Mn1	159 (3)
O1—Mn1—O6	138.6 (10)	C6^iv—C5—C9^v	114 (5)
O1—Mn1—O3	83.6 (11)	C6^iv—C5—C4	123 (5)
O1—Mn1—O1^i	72.9 (11)	C4—C5—C9^v	123 (5)
O1—Mn1—C9	118.0 (13)	O2—C7—C1	116 (4)
O1^i—Mn1—C9	85.2 (12)	O1^i—C7—O2	118 (4)
O1^i—Mn1—C8	136.9 (13)	O1^i—C7—C1	126 (5)
O1—Mn1—C8	113.4 (15)	C8—O4—Mn1	90 (3)
O1—Mn1—O4	142.2 (11)	C13—N2—C14	123 (4)
C8—Mn1—C9	121.4 (15)	C11—N2—C13	110 (4)
O4—Mn1—O6	78.7 (11)	C11—N2—C14	127 (4)
O4—Mn1—O3	58.7 (10)	N1—C11—N2	112 (4)
O4—Mn1—O1^i	133.8 (10)	C3—C2—C1^iv	120 (4)
O4—Mn1—C9	93.7 (13)	C6—C1—C7	116 (4)
O4—Mn1—C8	29.3 (10)	C2^ii—C1—C6	120 (4)
C9—O5—Mn1	91 (3)	C2^ii—C1—C7	124 (5)
C9—O6—Mn1	89 (4)	C4—C3—C8	114 (5)
C8—O3—Mn1	82 (3)	C2—C3—C4	123 (5)
C7—O2—Mn1	99 (3)	C2—C3—C8	122 (5)
C5^ii—C6—C1	118 (5)

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