Enantiopure and racemic alanine as bridging ligands in Ca and Mn chain polymers

Under accelerated and controlled evaporation, chain polymers crystallize from aqueous solutions of Ca^II and Mn^II halides with enantiopure L-alanine or racemic DL-alanine. In all ten solids thus obtained zwitterionic amino acid ligands bridge neighbouring cations. The exclusively O-donor-based coordination sphere around the metal cations is completed by aqua ligands; the halides remain uncoordinated and act as counter-anions for the cationic strands. Despite the differences in ionic radii and electronic structure between the main group and the transition metal cation, their derivatives with L-alanine share a common structure type. In contrast, the solids derived from DL-alanine differ and adopt structures depending on the metal cation and the halide. Homochiral chains of either chirality or heterochiral chains with different arrangements of crystallographic inversion centres along the polymer strands are encountered. On average, the six-coordinated Ca^II cations, devoid of any ligand field effect, show more pronounced deviation from idealized octahedral geometry than the d-block cation Mn^II.

S1. Experimental

S1.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

S2. Results and discussion

Computing details

For all compounds, program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013).

Figures

(1)

Crystal data

C9H23CaN3O7·2(Br)	Z = 2
Mr = 485.20	F(000) = 488
Monoclinic, P21	Dx = 1.771 Mg m^−3
a = 4.8971 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 15.812 (3) Å	µ = 4.77 mm^−1
c = 11.773 (2) Å	T = 100 K
β = 93.746 (3)°	Needle, colourless
V = 909.7 (3) Å^3	0.30 × 0.06 × 0.03 mm

Data collection

Bruker APEX CCD diffractometer	3731 independent reflections
Radiation source: microsource	3445 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.074
ω scans	θmax = 26.4°, θmin = 1.7°
Absorption correction: multi-scan SADABS	h = −6→6
Tmin = 0.455, Tmax = 0.745	k = −19→19
10950 measured reflections	l = −14→14

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.039P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.099	(Δ/σ)max = 0.003
S = 1.02	Δρmax = 0.67 e Å^−3
3731 reflections	Δρmin = −0.67 e Å^−3
235 parameters	Absolute structure: Flack x determined using 1513 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
38 restraints	Absolute structure parameter: −0.007 (13)

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.

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

	x	y	z	Uiso*/Ueq
Ca1	0.9046 (3)	0.75000 (11)	0.06889 (14)	0.0095 (3)
Br1	0.62601 (18)	0.64760 (5)	0.46238 (6)	0.0198 (2)
Br2	0.80165 (16)	0.36363 (4)	0.32036 (6)	0.0151 (2)
O1	0.2738 (11)	0.6854 (3)	0.1640 (5)	0.0134 (12)
O2	0.6857 (11)	0.6305 (3)	0.1400 (5)	0.0142 (13)
C1	0.4435 (16)	0.6270 (5)	0.1705 (6)	0.0115 (17)
C2	0.3493 (15)	0.5403 (5)	0.2125 (7)	0.0106 (16)
H2A	0.5010	0.5137	0.2611	0.013*
C3	0.274 (2)	0.4832 (6)	0.1114 (8)	0.023 (2)
H3A	0.2091	0.4287	0.1386	0.034*
H3B	0.4361	0.4741	0.0680	0.034*
H3C	0.1299	0.5100	0.0623	0.034*
N1	0.1083 (15)	0.5528 (5)	0.2812 (6)	0.0133 (14)
H1N	0.136 (19)	0.585 (5)	0.344 (5)	0.016*
H2N	−0.028 (13)	0.577 (5)	0.239 (6)	0.016*
H3N	0.066 (19)	0.502 (3)	0.306 (7)	0.016*
O3	0.5333 (10)	0.7620 (4)	−0.0654 (4)	0.0115 (12)
O4	0.1190 (11)	0.7043 (3)	−0.0977 (5)	0.0126 (12)
C4	0.3632 (17)	0.7164 (5)	−0.1203 (6)	0.0129 (17)
C5	0.4584 (17)	0.6686 (5)	−0.2224 (6)	0.0129 (17)
H5A	0.3022	0.6632	−0.2810	0.015*
C6	0.5589 (19)	0.5813 (5)	−0.1876 (7)	0.0180 (18)
H6A	0.6286	0.5525	−0.2535	0.027*
H6B	0.4073	0.5486	−0.1595	0.027*
H6C	0.7057	0.5862	−0.1273	0.027*
N2	0.6828 (15)	0.7171 (5)	−0.2713 (6)	0.0130 (14)
H4N	0.844 (11)	0.714 (6)	−0.232 (7)	0.016*
H5N	0.714 (18)	0.693 (5)	−0.338 (5)	0.016*
H6N	0.643 (18)	0.771 (3)	−0.289 (7)	0.016*
O5	0.7518 (12)	0.8303 (4)	0.2094 (5)	0.0161 (12)
O6	0.3726 (11)	0.8859 (3)	0.2718 (4)	0.0135 (12)
C7	0.6146 (15)	0.8613 (5)	0.2845 (6)	0.0128 (15)
C8	0.7586 (15)	0.8745 (5)	0.4012 (6)	0.0120 (16)
H8A	0.6298	0.8603	0.4609	0.014*
C9	0.8480 (19)	0.9678 (6)	0.4150 (7)	0.0189 (19)
H9A	0.9778	0.9734	0.4815	0.028*
H9B	0.6872	1.0032	0.4254	0.028*
H9C	0.9356	0.9862	0.3466	0.028*
N3	1.0034 (14)	0.8185 (4)	0.4153 (6)	0.0137 (14)
H7N	1.079 (18)	0.826 (6)	0.486 (4)	0.016*
H8N	0.957 (18)	0.764 (3)	0.406 (7)	0.016*
H9N	1.118 (15)	0.834 (5)	0.362 (6)	0.016*
O1W	1.1758 (12)	0.8728 (4)	0.0495 (5)	0.0159 (13)
H1W	1.241 (19)	0.880 (6)	0.109 (6)	0.019*
H2W	1.292 (17)	0.856 (7)	0.018 (7)	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0084 (7)	0.0084 (7)	0.0115 (6)	−0.0002 (6)	−0.0014 (5)	0.0000 (6)
Br1	0.0271 (5)	0.0175 (4)	0.0147 (4)	−0.0089 (4)	0.0005 (3)	−0.0022 (3)
Br2	0.0176 (4)	0.0105 (4)	0.0165 (4)	−0.0022 (3)	−0.0040 (3)	0.0009 (3)
O1	0.010 (3)	0.007 (3)	0.023 (3)	0.001 (2)	−0.005 (2)	0.004 (2)
O2	0.008 (3)	0.015 (3)	0.019 (3)	−0.002 (2)	−0.001 (2)	0.003 (2)
C1	0.012 (4)	0.012 (4)	0.009 (4)	−0.002 (3)	−0.003 (3)	0.002 (3)
C2	0.007 (4)	0.008 (4)	0.017 (4)	0.000 (3)	−0.002 (3)	0.001 (3)
C3	0.027 (5)	0.017 (5)	0.026 (5)	−0.007 (4)	0.005 (4)	−0.005 (4)
N1	0.012 (4)	0.010 (3)	0.018 (4)	0.001 (3)	0.000 (3)	0.003 (3)
O3	0.011 (3)	0.011 (3)	0.012 (2)	0.002 (2)	−0.004 (2)	−0.002 (2)
O4	0.007 (3)	0.015 (3)	0.015 (3)	−0.002 (2)	−0.001 (2)	−0.003 (2)
C4	0.016 (4)	0.013 (4)	0.008 (3)	0.005 (3)	−0.003 (3)	0.003 (3)
C5	0.015 (4)	0.008 (4)	0.015 (4)	−0.002 (3)	−0.001 (3)	0.000 (3)
C6	0.023 (5)	0.010 (4)	0.021 (4)	−0.002 (4)	−0.001 (4)	0.001 (3)
N2	0.012 (4)	0.016 (4)	0.011 (3)	−0.001 (3)	−0.001 (3)	−0.003 (3)
O5	0.015 (3)	0.019 (3)	0.015 (3)	−0.001 (2)	0.002 (2)	−0.008 (2)
O6	0.011 (3)	0.013 (3)	0.016 (3)	0.000 (2)	−0.001 (2)	−0.001 (2)
C7	0.013 (4)	0.006 (3)	0.020 (4)	−0.003 (4)	0.004 (3)	0.000 (3)
C8	0.006 (3)	0.014 (4)	0.016 (4)	0.003 (3)	0.001 (3)	−0.003 (3)
C9	0.023 (5)	0.016 (4)	0.018 (4)	0.000 (4)	−0.006 (4)	−0.008 (4)
N3	0.008 (4)	0.012 (4)	0.021 (4)	−0.001 (3)	0.002 (3)	0.001 (3)
O1W	0.017 (3)	0.014 (3)	0.016 (3)	−0.002 (3)	−0.002 (2)	−0.003 (3)

Geometric parameters (Å, º)

Ca1—O5	2.251 (6)	C4—C5	1.519 (11)
Ca1—O1^i	2.302 (5)	C5—N2	1.487 (10)
Ca1—O3	2.338 (5)	C5—C6	1.514 (11)
Ca1—O2	2.353 (6)	C5—H5A	1.0000
Ca1—O1W	2.372 (6)	C6—H6A	0.9800
Ca1—O4^i	2.396 (6)	C6—H6B	0.9800
Ca1—H1W	2.66 (10)	C6—H6C	0.9800
Ca1—H2W	2.63 (10)	N2—H4N	0.89 (3)
O1—C1	1.242 (9)	N2—H5N	0.90 (3)
O1—Ca1^ii	2.302 (5)	N2—H6N	0.89 (3)
O2—C1	1.262 (9)	O5—C7	1.246 (9)
C1—C2	1.538 (11)	O6—C7	1.247 (9)
C2—N1	1.487 (10)	C7—C8	1.518 (10)
C2—C3	1.520 (12)	C8—N3	1.491 (10)
C2—H2A	1.0000	C8—C9	1.545 (12)
C3—H3A	0.9800	C8—H8A	1.0000
C3—H3B	0.9800	C9—H9A	0.9800
C3—H3C	0.9800	C9—H9B	0.9800
N1—H1N	0.90 (3)	C9—H9C	0.9800
N1—H2N	0.89 (3)	N3—H7N	0.90 (3)
N1—H3N	0.89 (3)	N3—H8N	0.90 (3)
O3—C4	1.249 (9)	N3—H9N	0.90 (3)
O4—C4	1.257 (10)	O1W—H1W	0.76 (6)
O4—Ca1^ii	2.396 (6)	O1W—H2W	0.75 (6)
O5—Ca1—O1^i	100.4 (2)	H2N—N1—H3N	113 (8)
O5—Ca1—O3	99.8 (2)	C4—O3—Ca1	140.0 (5)
O1^i—Ca1—O3	156.4 (2)	C4—O4—Ca1^ii	127.0 (5)
O5—Ca1—O2	90.6 (2)	O3—C4—O4	126.1 (7)
O1^i—Ca1—O2	80.36 (19)	O3—C4—C5	117.9 (7)
O3—Ca1—O2	87.3 (2)	O4—C4—C5	115.9 (7)
O5—Ca1—O1W	79.9 (2)	N2—C5—C6	109.9 (7)
O1^i—Ca1—O1W	89.0 (2)	N2—C5—C4	108.8 (6)
O3—Ca1—O1W	106.5 (2)	C6—C5—C4	110.6 (6)
O2—Ca1—O1W	164.3 (2)	N2—C5—H5A	109.2
O5—Ca1—O4^i	162.9 (2)	C6—C5—H5A	109.2
O1^i—Ca1—O4^i	83.8 (2)	C4—C5—H5A	109.2
O3—Ca1—O4^i	80.45 (19)	C5—C6—H6A	109.5
O2—Ca1—O4^i	106.5 (2)	C5—C6—H6B	109.5
O1W—Ca1—O4^i	83.7 (2)	H6A—C6—H6B	109.5
O5—Ca1—H1W	70.5 (19)	C5—C6—H6C	109.5
O1^i—Ca1—H1W	78 (2)	H6A—C6—H6C	109.5
O3—Ca1—H1W	120.1 (18)	H6B—C6—H6C	109.5
O2—Ca1—H1W	148.3 (16)	C5—N2—H4N	115 (6)
O1W—Ca1—H1W	16.0 (15)	C5—N2—H5N	108 (6)
O4^i—Ca1—H1W	94.5 (18)	H4N—N2—H5N	104 (8)
O5—Ca1—H2W	95.1 (17)	C5—N2—H6N	115 (6)
O1^i—Ca1—H2W	81 (2)	H4N—N2—H6N	111 (8)
O3—Ca1—H2W	110 (2)	H5N—N2—H6N	104 (8)
O2—Ca1—H2W	161 (2)	C7—O5—Ca1	164.6 (6)
O1W—Ca1—H2W	16.3 (17)	O5—C7—O6	126.2 (7)
O4^i—Ca1—H2W	69.0 (17)	O5—C7—C8	117.2 (7)
H1W—Ca1—H2W	26 (3)	O6—C7—C8	116.6 (7)
C1—O1—Ca1^ii	149.5 (5)	N3—C8—C7	110.0 (6)
C1—O2—Ca1	126.5 (5)	N3—C8—C9	109.6 (6)
O1—C1—O2	125.9 (7)	C7—C8—C9	109.8 (7)
O1—C1—C2	118.0 (7)	N3—C8—H8A	109.2
O2—C1—C2	116.0 (7)	C7—C8—H8A	109.2
N1—C2—C3	110.2 (7)	C9—C8—H8A	109.2
N1—C2—C1	108.8 (6)	C8—C9—H9A	109.5
C3—C2—C1	109.9 (6)	C8—C9—H9B	109.5
N1—C2—H2A	109.3	H9A—C9—H9B	109.5
C3—C2—H2A	109.3	C8—C9—H9C	109.5
C1—C2—H2A	109.3	H9A—C9—H9C	109.5
C2—C3—H3A	109.5	H9B—C9—H9C	109.5
C2—C3—H3B	109.5	C8—N3—H7N	108 (6)
H3A—C3—H3B	109.5	C8—N3—H8N	111 (6)
C2—C3—H3C	109.5	H7N—N3—H8N	109 (8)
H3A—C3—H3C	109.5	C8—N3—H9N	107 (6)
H3B—C3—H3C	109.5	H7N—N3—H9N	112 (8)
C2—N1—H1N	116 (6)	H8N—N3—H9N	110 (8)
C2—N1—H2N	110 (6)	Ca1—O1W—H1W	104 (8)
H1N—N1—H2N	106 (8)	Ca1—O1W—H2W	102 (8)
C2—N1—H3N	106 (6)	H1W—O1W—H2W	103 (10)
H1N—N1—H3N	106 (8)

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

(2)

Crystal data

C9H23CaN3O7·2(I)	Z = 2
Mr = 579.18	F(000) = 560
Monoclinic, P21	Dx = 1.981 Mg m^−3
a = 4.9164 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 16.416 (3) Å	µ = 3.53 mm^−1
c = 12.039 (2) Å	T = 100 K
β = 92.435 (3)°	Needle, colourless
V = 970.8 (3) Å^3	0.20 × 0.04 × 0.03 mm

Data collection

Bruker APEX CCD diffractometer	3955 independent reflections
Radiation source: microsource	3580 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.063
ω scans	θmax = 26.4°, θmin = 2.5°
Absorption correction: multi-scan SADABS	h = −6→6
Tmin = 0.554, Tmax = 0.745	k = −20→20
11583 measured reflections	l = −15→15

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.014P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.065	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.71 e Å^−3
3955 reflections	Δρmin = −0.61 e Å^−3
235 parameters	Absolute structure: Flack x determined using 1553 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
50 restraints	Absolute structure parameter: −0.04 (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.

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

	x	y	z	Uiso*/Ueq
I1	0.77508 (13)	0.36750 (3)	0.32244 (5)	0.01822 (16)
I2	0.62059 (14)	0.64888 (4)	0.45882 (5)	0.02179 (17)
Ca1	0.9183 (4)	0.75002 (12)	0.06479 (17)	0.0120 (4)
O1W	1.1891 (13)	0.8687 (5)	0.0436 (5)	0.0167 (14)
H1W	1.303 (17)	0.849 (6)	0.001 (7)	0.020*
H2W	1.271 (18)	0.880 (6)	0.104 (6)	0.020*
O1	0.2805 (13)	0.6869 (4)	0.1558 (5)	0.0165 (15)
O2	0.6910 (13)	0.6334 (4)	0.1296 (5)	0.0182 (16)
C1	0.4470 (19)	0.6301 (5)	0.1596 (7)	0.013 (2)
C2	0.348 (2)	0.5470 (6)	0.1982 (8)	0.016 (2)
H2	0.4967	0.5207	0.2449	0.019*
C3	0.279 (3)	0.4925 (6)	0.0994 (9)	0.028 (3)
H3A	0.2159	0.4395	0.1258	0.041*
H3B	0.4413	0.4848	0.0561	0.041*
H3C	0.1349	0.5179	0.0525	0.041*
N1	0.1079 (17)	0.5577 (5)	0.2663 (7)	0.0126 (18)
H1N	−0.034 (13)	0.581 (5)	0.221 (6)	0.015*
H2N	0.174 (17)	0.584 (5)	0.332 (5)	0.015*
H3N	0.058 (18)	0.505 (3)	0.291 (7)	0.015*
O3	0.5575 (15)	0.7602 (5)	−0.0660 (6)	0.0160 (14)
O4	0.1440 (14)	0.7032 (4)	−0.0950 (6)	0.0174 (16)
C4	0.389 (2)	0.7165 (6)	−0.1182 (8)	0.016 (2)
C5	0.4883 (19)	0.6697 (5)	−0.2183 (8)	0.014 (2)
H5	0.3378	0.6665	−0.2766	0.017*
C6	0.578 (2)	0.5832 (6)	−0.1856 (9)	0.021 (2)
H6A	0.6433	0.5549	−0.2510	0.032*
H6B	0.4238	0.5534	−0.1566	0.032*
H6C	0.7256	0.5860	−0.1282	0.032*
N2	0.7248 (18)	0.7148 (5)	−0.2641 (7)	0.0144 (18)
H4N	0.648 (18)	0.766 (3)	−0.283 (8)	0.017*
H5N	0.744 (19)	0.703 (6)	−0.341 (3)	0.017*
H6N	0.882 (13)	0.717 (6)	−0.215 (7)	0.017*
O5	0.7670 (14)	0.8290 (4)	0.2022 (6)	0.0193 (16)
O6	0.3879 (13)	0.8871 (4)	0.2589 (5)	0.0196 (16)
N3	1.0119 (18)	0.8253 (5)	0.4015 (7)	0.018 (2)
H7N	0.950 (19)	0.770 (3)	0.399 (8)	0.022*
H8N	1.129 (17)	0.841 (5)	0.344 (6)	0.022*
H9N	1.092 (18)	0.838 (6)	0.473 (4)	0.022*
C7	0.6250 (19)	0.8623 (6)	0.2739 (7)	0.016 (2)
C8	0.7610 (18)	0.8762 (6)	0.3884 (7)	0.0135 (19)
H8	0.6318	0.8605	0.4467	0.016*
C9	0.837 (2)	0.9659 (6)	0.4028 (9)	0.027 (3)
H9A	0.9469	0.9729	0.4721	0.041*
H9B	0.6714	0.9987	0.4057	0.041*
H9C	0.9429	0.9835	0.3399	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0214 (4)	0.0132 (3)	0.0198 (3)	−0.0021 (3)	−0.0029 (3)	0.0015 (3)
I2	0.0281 (4)	0.0218 (3)	0.0155 (3)	−0.0075 (3)	0.0017 (3)	−0.0027 (3)
Ca1	0.0118 (9)	0.0129 (9)	0.0113 (9)	0.0008 (8)	−0.0005 (7)	−0.0001 (7)
O1W	0.018 (4)	0.019 (3)	0.013 (3)	−0.002 (4)	0.002 (3)	−0.004 (4)
O1	0.016 (4)	0.013 (3)	0.021 (4)	0.006 (3)	0.001 (3)	0.002 (3)
O2	0.013 (4)	0.019 (4)	0.022 (4)	0.001 (3)	−0.003 (3)	0.001 (3)
C1	0.016 (5)	0.014 (5)	0.010 (5)	0.001 (4)	−0.002 (4)	0.001 (4)
C2	0.015 (5)	0.014 (5)	0.018 (5)	0.000 (4)	0.002 (4)	0.002 (4)
C3	0.035 (7)	0.023 (7)	0.025 (6)	−0.007 (5)	0.002 (5)	0.001 (5)
N1	0.006 (4)	0.016 (4)	0.016 (5)	−0.001 (3)	0.003 (3)	0.002 (3)
O3	0.019 (4)	0.018 (3)	0.011 (3)	−0.004 (3)	−0.003 (3)	−0.001 (3)
O4	0.014 (4)	0.021 (4)	0.017 (4)	0.001 (3)	0.002 (3)	−0.005 (3)
C4	0.017 (6)	0.016 (5)	0.014 (5)	0.004 (4)	0.001 (4)	0.010 (4)
C5	0.013 (5)	0.016 (5)	0.015 (5)	−0.002 (4)	0.007 (4)	0.001 (4)
C6	0.026 (6)	0.011 (5)	0.026 (6)	−0.001 (5)	0.002 (5)	0.000 (4)
N2	0.017 (5)	0.018 (4)	0.009 (4)	−0.007 (4)	0.002 (4)	−0.001 (4)
O5	0.014 (4)	0.023 (4)	0.021 (4)	0.000 (3)	0.001 (3)	−0.007 (3)
O6	0.015 (4)	0.020 (4)	0.024 (4)	0.003 (3)	0.001 (3)	−0.001 (3)
N3	0.018 (5)	0.015 (5)	0.022 (5)	0.004 (4)	−0.001 (4)	0.000 (4)
C7	0.024 (6)	0.011 (4)	0.013 (5)	−0.006 (5)	0.000 (4)	−0.002 (4)
C8	0.013 (3)	0.017 (4)	0.011 (3)	0.003 (3)	0.005 (3)	−0.002 (3)
C9	0.034 (6)	0.019 (5)	0.027 (5)	−0.001 (4)	−0.008 (5)	−0.016 (4)

Geometric parameters (Å, º)

Ca1—O5	2.253 (7)	O3—C4	1.245 (12)
Ca1—O1^i	2.298 (7)	O4—C4	1.267 (11)
Ca1—O3	2.327 (7)	O4—Ca1^ii	2.388 (7)
Ca1—O2	2.365 (7)	C4—C5	1.527 (12)
Ca1—O1W	2.380 (8)	C5—N2	1.503 (12)
Ca1—O4^i	2.388 (7)	C5—C6	1.534 (13)
O1—C1	1.241 (10)	O5—C7	1.258 (11)
O1—Ca1^ii	2.298 (7)	O6—C7	1.241 (11)
O2—C1	1.269 (10)	N3—C8	1.492 (12)
C1—C2	1.528 (12)	C7—C8	1.523 (12)
C2—N1	1.477 (12)	C8—C9	1.527 (14)
C2—C3	1.515 (14)
O5—Ca1—O1^i	100.5 (3)	O2—C1—C2	116.2 (8)
O5—Ca1—O3	100.9 (3)	N1—C2—C3	110.4 (8)
O1^i—Ca1—O3	155.2 (3)	N1—C2—C1	109.6 (8)
O5—Ca1—O2	92.8 (2)	C3—C2—C1	110.6 (8)
O1^i—Ca1—O2	81.1 (2)	C4—O3—Ca1	140.5 (7)
O3—Ca1—O2	85.6 (2)	C4—O4—Ca1^ii	126.9 (6)
O5—Ca1—O1W	79.1 (2)	O3—C4—O4	127.3 (9)
O1^i—Ca1—O1W	89.7 (2)	O3—C4—C5	117.3 (9)
O3—Ca1—O1W	106.4 (3)	O4—C4—C5	115.2 (9)
O2—Ca1—O1W	166.5 (2)	N2—C5—C4	108.7 (7)
O5—Ca1—O4^i	162.9 (3)	N2—C5—C6	109.4 (8)
O1^i—Ca1—O4^i	82.0 (2)	C4—C5—C6	111.2 (8)
O3—Ca1—O4^i	81.1 (3)	C7—O5—Ca1	164.6 (6)
O2—Ca1—O4^i	104.3 (2)	O6—C7—O5	126.0 (9)
O1W—Ca1—O4^i	84.0 (2)	O6—C7—C8	117.1 (8)
C1—O1—Ca1^ii	148.5 (6)	O5—C7—C8	116.8 (8)
C1—O2—Ca1	126.5 (6)	N3—C8—C7	109.9 (8)
O1—C1—O2	126.0 (9)	N3—C8—C9	109.2 (8)
O1—C1—C2	117.7 (8)	C7—C8—C9	110.1 (8)

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

(3)

Crystal data

C9H23MnN3O7·2(Br)	Z = 2
Mr = 500.06	F(000) = 498
Monoclinic, P21	Dx = 1.905 Mg m^−3
a = 4.7809 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 15.7146 (13) Å	µ = 5.38 mm^−1
c = 11.6246 (10) Å	T = 100 K
β = 93.581 (1)°	Block, colourless
V = 871.65 (13) Å^3	0.19 × 0.15 × 0.07 mm

Data collection

Bruker APEX CCD diffractometer	4600 independent reflections
Radiation source: microsource	4269 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.046
ω scans	θmax = 29.0°, θmin = 2.2°
Absorption correction: multi-scan SADABS	h = −6→6
Tmin = 0.486, Tmax = 0.746	k = −21→21
12613 measured reflections	l = −15→15

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[σ^2(Fo^2) + (0.020P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.059	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 0.46 e Å^−3
4600 reflections	Δρmin = −0.35 e Å^−3
234 parameters	Absolute structure: Flack x determined using 1890 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
12 restraints	Absolute structure parameter: −0.028 (7)

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.

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

	x	y	z	Uiso*/Ueq
Mn1	0.90766 (15)	0.74999 (5)	0.06999 (6)	0.00787 (14)
Br1	0.79653 (10)	0.36550 (3)	0.31414 (4)	0.01299 (11)
Br2	0.61843 (10)	0.64821 (3)	0.46537 (4)	0.01540 (12)
O1	0.2712 (7)	0.6937 (2)	0.1663 (3)	0.0106 (7)
O2	0.6911 (6)	0.6388 (2)	0.1310 (3)	0.0121 (7)
C1	0.4438 (9)	0.6349 (3)	0.1655 (4)	0.0092 (9)
C2	0.3558 (10)	0.5469 (3)	0.2053 (4)	0.0106 (9)
H2	0.5147	0.5206	0.2528	0.013*
C3	0.2774 (11)	0.4897 (3)	0.1029 (4)	0.0175 (11)
H3A	0.2214	0.4337	0.1305	0.026*
H3B	0.4390	0.4834	0.0557	0.026*
H3C	0.1211	0.5152	0.0563	0.026*
N1	0.1096 (9)	0.5568 (3)	0.2780 (4)	0.0109 (8)
H1N	0.054 (11)	0.504 (2)	0.296 (4)	0.013*
H2N	−0.029 (8)	0.588 (3)	0.242 (4)	0.013*
H3N	0.160 (11)	0.585 (3)	0.345 (3)	0.013*
O3	0.5479 (7)	0.7651 (2)	−0.0571 (3)	0.0093 (7)
O4	0.1248 (7)	0.7031 (2)	−0.0831 (3)	0.0110 (7)
C4	0.3735 (9)	0.7172 (3)	−0.1103 (4)	0.0085 (9)
C5	0.4672 (10)	0.6687 (3)	−0.2145 (4)	0.0102 (9)
H5	0.3050	0.6643	−0.2729	0.012*
C6	0.5648 (11)	0.5800 (3)	−0.1821 (5)	0.0171 (11)
H6A	0.6228	0.5503	−0.2508	0.026*
H6B	0.4113	0.5486	−0.1495	0.026*
H6C	0.7239	0.5834	−0.1248	0.026*
N2	0.6946 (9)	0.7180 (3)	−0.2655 (4)	0.0115 (8)
H4N	0.649 (11)	0.7744 (19)	−0.277 (5)	0.014*
H5N	0.723 (11)	0.691 (3)	−0.334 (3)	0.014*
H6N	0.855 (8)	0.717 (3)	−0.223 (4)	0.014*
O5	0.7764 (7)	0.8219 (2)	0.2086 (3)	0.0146 (7)
O6	0.3859 (7)	0.8844 (2)	0.2654 (3)	0.0129 (7)
C7	0.6313 (9)	0.8570 (3)	0.2812 (4)	0.0117 (9)
C8	0.7722 (9)	0.8727 (3)	0.4010 (4)	0.0105 (9)
H8	0.6375	0.8590	0.4608	0.013*
C9	0.8616 (11)	0.9657 (3)	0.4131 (5)	0.0183 (11)
H9A	0.9819	0.9729	0.4838	0.027*
H9B	0.6950	1.0017	0.4167	0.027*
H9C	0.9652	0.9822	0.3465	0.027*
N3	1.0218 (9)	0.8160 (3)	0.4166 (4)	0.0123 (8)
H7N	0.949 (11)	0.763 (2)	0.417 (5)	0.015*
H8N	1.101 (10)	0.826 (4)	0.490 (3)	0.015*
H9N	1.136 (10)	0.828 (3)	0.361 (4)	0.015*
O1W	1.1545 (7)	0.8656 (2)	0.0490 (3)	0.0117 (6)
H1W	1.286 (8)	0.856 (4)	0.010 (4)	0.014*
H2W	1.228 (10)	0.872 (4)	0.113 (3)	0.014*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0065 (3)	0.0092 (3)	0.0079 (3)	0.0002 (3)	0.0002 (2)	−0.0001 (3)
Br1	0.0143 (2)	0.0112 (2)	0.0131 (2)	−0.0020 (2)	−0.00191 (17)	0.00100 (19)
Br2	0.0193 (3)	0.0161 (3)	0.0107 (2)	−0.0058 (2)	0.00069 (18)	−0.0016 (2)
O1	0.0096 (16)	0.0095 (17)	0.0126 (17)	0.0012 (13)	−0.0001 (13)	0.0012 (14)
O2	0.0076 (15)	0.0122 (18)	0.0165 (17)	−0.0020 (14)	0.0018 (13)	0.0030 (15)
C1	0.006 (2)	0.015 (3)	0.007 (2)	−0.0010 (18)	−0.0027 (16)	0.0025 (18)
C2	0.006 (2)	0.013 (2)	0.013 (2)	0.0000 (18)	0.0029 (17)	0.0028 (19)
C3	0.022 (3)	0.013 (3)	0.017 (3)	−0.003 (2)	0.003 (2)	−0.004 (2)
N1	0.009 (2)	0.011 (2)	0.013 (2)	−0.0027 (16)	0.0011 (16)	0.0008 (17)
O3	0.0090 (16)	0.0113 (17)	0.0075 (16)	0.0001 (13)	−0.0010 (12)	−0.0008 (13)
O4	0.0082 (16)	0.0160 (18)	0.0088 (16)	−0.0020 (13)	0.0000 (13)	−0.0030 (13)
C4	0.009 (2)	0.009 (2)	0.008 (2)	0.0033 (17)	−0.0011 (17)	0.0028 (17)
C5	0.009 (2)	0.012 (2)	0.009 (2)	−0.0021 (18)	0.0002 (17)	−0.0042 (18)
C6	0.020 (3)	0.013 (3)	0.018 (3)	−0.002 (2)	0.004 (2)	−0.002 (2)
N2	0.010 (2)	0.016 (2)	0.0084 (19)	−0.0006 (17)	0.0011 (16)	−0.0006 (17)
O5	0.0093 (16)	0.022 (2)	0.0131 (17)	−0.0026 (15)	0.0044 (14)	−0.0088 (15)
O6	0.0111 (16)	0.0129 (18)	0.0145 (17)	−0.0002 (13)	−0.0011 (13)	−0.0004 (13)
C7	0.011 (2)	0.008 (2)	0.015 (2)	−0.0044 (19)	0.0015 (18)	0.001 (2)
C8	0.009 (2)	0.014 (2)	0.008 (2)	0.001 (2)	−0.0025 (16)	0.000 (2)
C9	0.020 (3)	0.013 (2)	0.021 (3)	0.000 (2)	−0.006 (2)	−0.003 (2)
N3	0.012 (2)	0.014 (2)	0.011 (2)	0.0000 (17)	0.0007 (16)	−0.0007 (17)
O1W	0.0111 (16)	0.0136 (16)	0.0104 (16)	−0.0001 (16)	−0.0005 (12)	0.0008 (16)

Geometric parameters (Å, º)

Mn1—O5	2.097 (3)	C5—N2	1.488 (6)
Mn1—O2	2.173 (3)	C5—C6	1.511 (7)
Mn1—O1W	2.189 (4)	C5—H5	1.0000
Mn1—O1^i	2.194 (3)	C6—H6A	0.9800
Mn1—O3	2.209 (3)	C6—H6B	0.9800
Mn1—O4^i	2.241 (3)	C6—H6C	0.9800
O1—C1	1.239 (6)	N2—H4N	0.92 (3)
O1—Mn1^ii	2.194 (3)	N2—H5N	0.92 (3)
O2—C1	1.274 (5)	N2—H6N	0.89 (3)
C1—C2	1.526 (6)	O5—C7	1.253 (5)
C2—N1	1.499 (6)	O6—C7	1.253 (5)
C2—C3	1.521 (7)	C7—C8	1.529 (6)
C2—H2	1.0000	C8—N3	1.492 (6)
C3—H3A	0.9800	C8—C9	1.526 (7)
C3—H3B	0.9800	C8—H8	1.0000
C3—H3C	0.9800	C9—H9A	0.9800
N1—H1N	0.91 (3)	C9—H9B	0.9800
N1—H2N	0.91 (3)	C9—H9C	0.9800
N1—H3N	0.91 (3)	N3—H7N	0.91 (3)
O3—C4	1.257 (5)	N3—H8N	0.92 (3)
O4—C4	1.269 (6)	N3—H9N	0.89 (3)
O4—Mn1^ii	2.241 (3)	O1W—H1W	0.81 (3)
C4—C5	1.522 (6)	O1W—H2W	0.81 (3)
O5—Mn1—O2	90.64 (14)	N2—C5—C6	111.0 (4)
O5—Mn1—O1W	80.07 (13)	N2—C5—C4	108.4 (4)
O2—Mn1—O1W	167.29 (13)	C6—C5—C4	111.4 (4)
O5—Mn1—O1^i	95.19 (13)	N2—C5—H5	108.7
O2—Mn1—O1^i	83.55 (12)	C6—C5—H5	108.7
O1W—Mn1—O1^i	88.64 (12)	C4—C5—H5	108.7
O5—Mn1—O3	101.43 (13)	C5—C6—H6A	109.5
O2—Mn1—O3	86.44 (12)	C5—C6—H6B	109.5
O1W—Mn1—O3	103.80 (13)	H6A—C6—H6B	109.5
O1^i—Mn1—O3	160.67 (12)	C5—C6—H6C	109.5
O5—Mn1—O4^i	164.57 (13)	H6A—C6—H6C	109.5
O2—Mn1—O4^i	104.37 (13)	H6B—C6—H6C	109.5
O1W—Mn1—O4^i	84.54 (12)	C5—N2—H4N	113 (3)
O1^i—Mn1—O4^i	83.18 (12)	C5—N2—H5N	105 (3)
O3—Mn1—O4^i	83.35 (11)	H4N—N2—H5N	111 (5)
C1—O1—Mn1^ii	143.4 (3)	C5—N2—H6N	113 (4)
C1—O2—Mn1	127.7 (3)	H4N—N2—H6N	107 (5)
O1—C1—O2	126.8 (4)	H5N—N2—H6N	108 (5)
O1—C1—C2	118.5 (4)	C7—O5—Mn1	163.7 (3)
O2—C1—C2	114.7 (4)	O6—C7—O5	127.3 (4)
N1—C2—C3	109.8 (4)	O6—C7—C8	115.7 (4)
N1—C2—C1	108.6 (4)	O5—C7—C8	117.0 (4)
C3—C2—C1	110.9 (4)	N3—C8—C9	110.1 (4)
N1—C2—H2	109.2	N3—C8—C7	108.5 (4)
C3—C2—H2	109.2	C9—C8—C7	110.1 (4)
C1—C2—H2	109.2	N3—C8—H8	109.4
C2—C3—H3A	109.5	C9—C8—H8	109.4
C2—C3—H3B	109.5	C7—C8—H8	109.4
H3A—C3—H3B	109.5	C8—C9—H9A	109.5
C2—C3—H3C	109.5	C8—C9—H9B	109.5
H3A—C3—H3C	109.5	H9A—C9—H9B	109.5
H3B—C3—H3C	109.5	C8—C9—H9C	109.5
C2—N1—H1N	107 (3)	H9A—C9—H9C	109.5
C2—N1—H2N	112 (3)	H9B—C9—H9C	109.5
H1N—N1—H2N	113 (5)	C8—N3—H7N	105 (3)
C2—N1—H3N	111 (3)	C8—N3—H8N	107 (3)
H1N—N1—H3N	108 (5)	H7N—N3—H8N	107 (5)
H2N—N1—H3N	106 (5)	C8—N3—H9N	108 (4)
C4—O3—Mn1	136.8 (3)	H7N—N3—H9N	117 (5)
C4—O4—Mn1^ii	128.9 (3)	H8N—N3—H9N	114 (5)
O3—C4—O4	125.8 (4)	Mn1—O1W—H1W	111 (4)
O3—C4—C5	118.2 (4)	Mn1—O1W—H2W	101 (4)
O4—C4—C5	115.9 (4)	H1W—O1W—H2W	103 (5)

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

(4)

Crystal data

C9H23MnN3O7·2(I)	Z = 2
Mr = 594.04	F(000) = 570
Monoclinic, P21	Dx = 2.130 Mg m^−3
a = 4.7932 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 16.261 (5) Å	µ = 4.08 mm^−1
c = 11.894 (4) Å	T = 100 K
β = 92.255 (6)°	Needle, colourless
V = 926.3 (5) Å^3	0.12 × 0.04 × 0.04 mm

Data collection

Bruker APEX CCD diffractometer	3762 independent reflections
Radiation source: microsource	3371 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.069
ω scans	θmax = 26.4°, θmin = 2.5°
Absorption correction: multi-scan SADABS	h = −5→5
Tmin = 0.588, Tmax = 0.745	k = −20→20
10911 measured reflections	l = −14→14

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.042P)^2 + 0.6P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.099	(Δ/σ)max = 0.014
S = 1.01	Δρmax = 1.59 e Å^−3
3762 reflections	Δρmin = −1.04 e Å^−3
235 parameters	Absolute structure: Flack x determined using 1417 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
30 restraints	Absolute structure parameter: −0.03 (4)

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.

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

	x	y	z	Uiso*/Ueq
Mn1	0.9199 (5)	0.74999 (13)	0.06440 (18)	0.0125 (4)
I1	0.76587 (17)	0.37006 (5)	0.31903 (7)	0.0167 (2)
I2	0.61347 (18)	0.64837 (5)	0.46242 (7)	0.0185 (2)
O1W	1.167 (2)	0.8625 (7)	0.0408 (8)	0.017 (2)
H2W	1.23 (3)	0.866 (11)	0.108 (5)	0.020*
H1W	1.29 (2)	0.838 (8)	0.004 (11)	0.020*
O1	0.2765 (19)	0.6959 (5)	0.1573 (8)	0.016 (2)
O2	0.6941 (18)	0.6409 (6)	0.1214 (8)	0.015 (2)
C1	0.450 (3)	0.6381 (8)	0.1546 (11)	0.017 (3)
C2	0.357 (3)	0.5515 (8)	0.1927 (12)	0.012 (3)
H2	0.5123	0.5251	0.2385	0.014*
C3	0.281 (4)	0.4975 (9)	0.0913 (12)	0.024 (3)
H3A	0.2415	0.4415	0.1167	0.035*
H3B	0.4375	0.4963	0.0406	0.035*
H3C	0.1156	0.5200	0.0513	0.035*
N1	0.737 (2)	0.7153 (7)	−0.2601 (10)	0.014 (2)
H1N	0.894 (18)	0.708 (9)	−0.214 (10)	0.017*
H2N	0.68 (3)	0.768 (3)	−0.272 (12)	0.017*
H3N	0.75 (3)	0.692 (9)	−0.330 (6)	0.017*
O3	0.571 (2)	0.7637 (6)	−0.0602 (8)	0.0145 (19)
O4	0.1481 (19)	0.7036 (6)	−0.0846 (7)	0.0127 (19)
C4	0.396 (3)	0.7169 (8)	−0.1107 (10)	0.011 (3)
C5	0.498 (3)	0.6700 (8)	−0.2133 (12)	0.018 (3)
H5	0.3427	0.6674	−0.2719	0.022*
C6	0.582 (3)	0.5826 (8)	−0.1801 (12)	0.019 (3)
H6A	0.6473	0.5534	−0.2461	0.028*
H6B	0.4208	0.5538	−0.1508	0.028*
H6C	0.7326	0.5846	−0.1219	0.028*
N2	0.107 (3)	0.5610 (7)	0.2631 (10)	0.016 (2)
H4N	0.03 (3)	0.510 (4)	0.268 (12)	0.019*
H5N	0.01 (3)	0.599 (7)	0.220 (10)	0.019*
H6N	0.14 (3)	0.589 (8)	0.329 (7)	0.019*
O5	0.790 (2)	0.8190 (6)	0.1996 (8)	0.018 (2)
O6	0.4015 (18)	0.8845 (6)	0.2518 (7)	0.016 (2)
C7	0.644 (3)	0.8565 (8)	0.2698 (11)	0.016 (3)
C8	0.771 (2)	0.8721 (9)	0.3869 (11)	0.016 (3)
H8	0.6355	0.8566	0.4451	0.019*
C9	0.852 (3)	0.9633 (9)	0.3997 (13)	0.024 (3)
H9A	0.9408	0.9724	0.4743	0.035*
H9B	0.6846	0.9975	0.3910	0.035*
H9C	0.9835	0.9781	0.3418	0.035*
N3	1.028 (3)	0.8214 (8)	0.4007 (11)	0.019 (3)
H7N	1.07 (3)	0.826 (10)	0.477 (4)	0.023*
H8N	1.17 (2)	0.842 (8)	0.356 (11)	0.023*
H9N	1.01 (3)	0.766 (2)	0.392 (12)	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0096 (9)	0.0112 (10)	0.0170 (10)	0.0005 (8)	0.0013 (7)	−0.0004 (8)
I1	0.0164 (5)	0.0110 (4)	0.0227 (5)	−0.0013 (4)	−0.0009 (3)	0.0011 (4)
I2	0.0197 (5)	0.0162 (4)	0.0197 (5)	−0.0042 (4)	0.0009 (3)	−0.0017 (4)
O1W	0.017 (5)	0.014 (5)	0.020 (5)	0.001 (5)	0.001 (4)	−0.001 (5)
O1	0.013 (5)	0.009 (5)	0.026 (5)	0.003 (4)	0.004 (4)	0.002 (4)
O2	0.011 (5)	0.012 (5)	0.023 (5)	−0.001 (4)	0.003 (4)	0.000 (4)
C1	0.018 (7)	0.009 (7)	0.023 (7)	−0.004 (6)	0.003 (6)	−0.002 (6)
C2	0.005 (6)	0.010 (7)	0.021 (7)	−0.002 (5)	0.005 (5)	0.003 (5)
C3	0.035 (9)	0.014 (8)	0.021 (8)	−0.003 (7)	0.003 (7)	0.001 (6)
N1	0.010 (6)	0.012 (6)	0.020 (6)	0.001 (5)	−0.004 (5)	−0.001 (5)
O3	0.012 (5)	0.010 (4)	0.021 (5)	−0.001 (4)	0.000 (4)	−0.005 (4)
O4	0.012 (5)	0.015 (5)	0.012 (5)	0.005 (4)	0.003 (4)	−0.004 (4)
C4	0.009 (7)	0.013 (7)	0.011 (6)	0.003 (5)	0.003 (5)	0.003 (5)
C5	0.012 (7)	0.019 (8)	0.023 (8)	−0.002 (6)	0.002 (6)	−0.004 (6)
C6	0.020 (8)	0.010 (7)	0.026 (8)	0.002 (6)	0.002 (6)	−0.004 (6)
N2	0.017 (7)	0.010 (6)	0.020 (6)	−0.002 (5)	0.001 (5)	0.001 (5)
O5	0.013 (5)	0.019 (5)	0.022 (5)	−0.001 (4)	0.005 (4)	0.000 (4)
O6	0.012 (5)	0.015 (5)	0.020 (5)	−0.001 (4)	0.002 (4)	0.001 (4)
C7	0.011 (5)	0.017 (6)	0.020 (5)	−0.008 (4)	0.003 (4)	0.002 (5)
C8	0.008 (5)	0.017 (5)	0.023 (5)	0.001 (5)	0.001 (4)	0.002 (5)
C9	0.029 (8)	0.015 (7)	0.025 (7)	0.000 (6)	−0.013 (6)	−0.008 (6)
N3	0.018 (7)	0.016 (6)	0.022 (7)	0.005 (5)	0.005 (5)	0.004 (5)

Geometric parameters (Å, º)

Mn1—O5	2.077 (10)	O4—C4	1.259 (15)
Mn1—O1^i	2.183 (9)	O4—Mn1^ii	2.249 (9)
Mn1—O2	2.199 (10)	C4—C5	1.536 (18)
Mn1—O3	2.202 (10)	C5—C6	1.52 (2)
Mn1—O1W	2.202 (11)	C5—H5	1.0000
Mn1—O4^i	2.249 (9)	C6—H6A	0.9800
O1W—H2W	0.84 (3)	C6—H6B	0.9800
O1W—H1W	0.84 (3)	C6—H6C	0.9800
O1—C1	1.256 (16)	N2—H4N	0.92 (3)
O1—Mn1^ii	2.183 (9)	N2—H5N	0.92 (3)
O2—C1	1.252 (16)	N2—H6N	0.92 (3)
C1—C2	1.549 (18)	O5—C7	1.268 (16)
C2—N2	1.496 (18)	O6—C7	1.258 (16)
C2—C3	1.52 (2)	C7—C8	1.520 (18)
C2—H2	1.0000	C8—N3	1.485 (18)
C3—H3A	0.9800	C8—C9	1.54 (2)
C3—H3B	0.9800	C8—H8	1.0000
C3—H3C	0.9800	C9—H9A	0.9800
N1—C5	1.488 (18)	C9—H9B	0.9800
N1—H1N	0.92 (3)	C9—H9C	0.9800
N1—H2N	0.91 (3)	N3—H7N	0.92 (3)
N1—H3N	0.92 (3)	N3—H8N	0.92 (3)
O3—C4	1.265 (16)	N3—H9N	0.91 (3)
O5—Mn1—O1^i	94.5 (4)	O4—C4—O3	126.9 (12)
O5—Mn1—O2	91.8 (4)	O4—C4—C5	116.3 (11)
O1^i—Mn1—O2	84.5 (3)	O3—C4—C5	116.8 (11)
O5—Mn1—O3	103.0 (4)	N1—C5—C6	111.0 (12)
O1^i—Mn1—O3	160.1 (4)	N1—C5—C4	108.9 (11)
O2—Mn1—O3	85.4 (4)	C6—C5—C4	110.2 (11)
O5—Mn1—O1W	80.1 (4)	N1—C5—H5	108.9
O1^i—Mn1—O1W	89.2 (4)	C6—C5—H5	108.9
O2—Mn1—O1W	169.3 (4)	C4—C5—H5	108.9
O3—Mn1—O1W	103.1 (4)	C5—C6—H6A	109.5
O5—Mn1—O4^i	164.0 (4)	C5—C6—H6B	109.5
O1^i—Mn1—O4^i	82.4 (4)	H6A—C6—H6B	109.5
O2—Mn1—O4^i	103.5 (3)	C5—C6—H6C	109.5
O3—Mn1—O4^i	83.3 (3)	H6A—C6—H6C	109.5
O1W—Mn1—O4^i	84.1 (3)	H6B—C6—H6C	109.5
Mn1—O1W—H2W	96 (10)	C2—N2—H4N	107 (9)
Mn1—O1W—H1W	93 (10)	C2—N2—H5N	100 (9)
H2W—O1W—H1W	108 (10)	H4N—N2—H5N	116 (10)
C1—O1—Mn1^ii	142.6 (9)	C2—N2—H6N	114 (9)
C1—O2—Mn1	127.2 (9)	H4N—N2—H6N	117 (10)
O2—C1—O1	127.5 (13)	H5N—N2—H6N	102 (10)
O2—C1—C2	114.1 (12)	C7—O5—Mn1	163.8 (9)
O1—C1—C2	118.4 (12)	O6—C7—O5	126.4 (12)
N2—C2—C3	109.3 (12)	O6—C7—C8	115.5 (12)
N2—C2—C1	108.3 (11)	O5—C7—C8	118.1 (12)
C3—C2—C1	110.7 (11)	N3—C8—C7	108.1 (11)
N2—C2—H2	109.5	N3—C8—C9	108.6 (11)
C3—C2—H2	109.5	C7—C8—C9	109.9 (11)
C1—C2—H2	109.5	N3—C8—H8	110.1
C2—C3—H3A	109.5	C7—C8—H8	110.1
C2—C3—H3B	109.5	C9—C8—H8	110.1
H3A—C3—H3B	109.5	C8—C9—H9A	109.5
C2—C3—H3C	109.5	C8—C9—H9B	109.5
H3A—C3—H3C	109.5	H9A—C9—H9B	109.5
H3B—C3—H3C	109.5	C8—C9—H9C	109.5
C5—N1—H1N	110 (9)	H9A—C9—H9C	109.5
C5—N1—H2N	107 (10)	H9B—C9—H9C	109.5
H1N—N1—H2N	117 (10)	C8—N3—H7N	101 (10)
C5—N1—H3N	103 (10)	C8—N3—H8N	110 (10)
H1N—N1—H3N	113 (10)	H7N—N3—H8N	115 (10)
H2N—N1—H3N	106 (10)	C8—N3—H9N	119 (10)
C4—O3—Mn1	136.9 (9)	H7N—N3—H9N	102 (10)
C4—O4—Mn1^ii	129.0 (8)	H8N—N3—H9N	110 (10)

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

(5)

Crystal data

C6H18CaN2O6·2(Cl)·H2O	F(000) = 720
Mr = 343.22	Dx = 1.518 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
a = 23.347 (7) Å	µ = 0.80 mm^−1
b = 8.702 (3) Å	T = 100 K
c = 7.391 (2) Å	Needle, colourless
V = 1501.5 (8) Å^3	0.20 × 0.08 × 0.04 mm
Z = 4

Data collection

Bruker APEX CCD diffractometer	1545 independent reflections
Radiation source: microsource	1164 reflections with I > 2σ(I)
Multi-layer optics monochromator	Rint = 0.129
ω scans	θmax = 26.4°, θmin = 2.5°
Absorption correction: multi-scan SADABS	h = −29→29
Tmin = 0.571, Tmax = 0.745	k = −10→10
16504 measured reflections	l = −9→9

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.025P)^2 + 0.6P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.002
1545 reflections	Δρmax = 0.34 e Å^−3
102 parameters	Δρmin = −0.31 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.

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

	x	y	z	Uiso*/Ueq
Ca1	0.5000	0.59494 (8)	0.2500	0.01290 (19)
Cl1	0.68892 (3)	0.73248 (7)	0.05715 (9)	0.01771 (18)
O1	0.59104 (7)	0.4699 (2)	0.2517 (3)	0.0224 (5)
O2	0.53781 (8)	0.3579 (2)	0.0429 (2)	0.0208 (4)
C1	0.58538 (11)	0.3843 (3)	0.1180 (4)	0.0160 (6)
C2	0.63906 (11)	0.3070 (3)	0.0425 (4)	0.0164 (6)
H2	0.6427	0.3342	−0.0885	0.020*
C3	0.63797 (12)	0.1331 (3)	0.0599 (4)	0.0225 (6)
H3A	0.6727	0.0899	0.0053	0.034*
H3B	0.6042	0.0924	−0.0025	0.034*
H3C	0.6364	0.1047	0.1881	0.034*
N1	0.68928 (9)	0.3709 (3)	0.1413 (3)	0.0165 (5)
H1A	0.6865 (11)	0.353 (3)	0.264 (2)	0.020*
H1B	0.6908 (11)	0.475 (2)	0.125 (4)	0.020*
H1C	0.7220 (9)	0.324 (3)	0.096 (4)	0.020*
O1W	0.55648 (8)	0.8059 (2)	0.1368 (3)	0.0250 (5)
H3E	0.5900 (8)	0.793 (3)	0.117 (4)	0.030*
H3D	0.5480 (13)	0.892 (2)	0.175 (4)	0.030*
O2W	0.5000	1.0793 (3)	0.2500	0.0352 (8)
H4	0.4958 (15)	1.137 (3)	0.160 (3)	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0082 (4)	0.0166 (4)	0.0139 (4)	0.000	0.0001 (3)	0.000
Cl1	0.0119 (3)	0.0200 (3)	0.0212 (4)	−0.0023 (3)	−0.0005 (3)	−0.0010 (3)
O1	0.0129 (10)	0.0248 (10)	0.0296 (12)	0.0022 (8)	0.0019 (9)	−0.0079 (9)
O2	0.0107 (10)	0.0335 (11)	0.0181 (10)	−0.0006 (8)	−0.0015 (8)	0.0061 (9)
C1	0.0136 (14)	0.0177 (13)	0.0166 (14)	−0.0002 (11)	0.0018 (11)	0.0090 (11)
C2	0.0142 (14)	0.0198 (14)	0.0152 (14)	0.0008 (10)	−0.0008 (11)	−0.0001 (11)
C3	0.0201 (15)	0.0185 (14)	0.0290 (17)	0.0016 (11)	−0.0021 (13)	−0.0002 (13)
N1	0.0099 (11)	0.0185 (12)	0.0212 (13)	0.0002 (9)	0.0009 (11)	0.0002 (11)
O1W	0.0126 (10)	0.0196 (10)	0.0426 (14)	−0.0007 (9)	0.0077 (10)	−0.0007 (10)
O2W	0.055 (2)	0.0203 (17)	0.0306 (19)	0.000	0.0203 (18)	0.000

Geometric parameters (Å, º)

Ca1—O2^i	2.3732 (19)	O2—Ca1^ii	2.3732 (19)
Ca1—O2^ii	2.3732 (19)	C1—C2	1.528 (4)
Ca1—O1^iii	2.3880 (18)	C2—N1	1.489 (3)
Ca1—O1	2.3880 (18)	C2—C3	1.519 (3)
Ca1—O1W	2.410 (2)	C2—H2	1.0000
Ca1—O1W^iii	2.410 (2)	C3—H3A	0.9800
Ca1—O2	2.716 (2)	C3—H3B	0.9800
Ca1—O2^iii	2.716 (2)	C3—H3C	0.9800
Ca1—C1^iii	2.879 (3)	N1—H1A	0.922 (17)
Ca1—C1	2.879 (3)	N1—H1B	0.917 (17)
Ca1—Ca1^ii	4.0479 (12)	N1—H1C	0.927 (17)
Ca1—Ca1^iv	4.0479 (12)	O1W—H3E	0.805 (17)
O1—C1	1.245 (3)	O1W—H3D	0.825 (17)
O2—C1	1.263 (3)	O2W—H4	0.840 (17)
O2^i—Ca1—O2^ii	160.10 (10)	O1W—Ca1—Ca1^ii	89.66 (6)
O2^i—Ca1—O1^iii	114.50 (7)	O1W^iii—Ca1—Ca1^ii	128.89 (6)
O2^ii—Ca1—O1^iii	75.10 (6)	O2—Ca1—Ca1^ii	34.46 (4)
O2^i—Ca1—O1	75.10 (6)	O2^iii—Ca1—Ca1^ii	101.81 (5)
O2^ii—Ca1—O1	114.50 (7)	C1^iii—Ca1—Ca1^ii	92.83 (6)
O1^iii—Ca1—O1	125.78 (9)	C1—Ca1—Ca1^ii	55.29 (6)
O2^i—Ca1—O1W	88.93 (7)	O2^i—Ca1—Ca1^iv	40.36 (5)
O2^ii—Ca1—O1W	75.84 (7)	O2^ii—Ca1—Ca1^iv	154.57 (5)
O1^iii—Ca1—O1W	146.33 (7)	O1^iii—Ca1—Ca1^iv	79.56 (5)
O1—Ca1—O1W	82.07 (7)	O1—Ca1—Ca1^iv	79.00 (5)
O2^i—Ca1—O1W^iii	75.84 (7)	O1W—Ca1—Ca1^iv	128.89 (6)
O2^ii—Ca1—O1W^iii	88.93 (7)	O1W^iii—Ca1—Ca1^iv	89.66 (6)
O1^iii—Ca1—O1W^iii	82.07 (7)	O2—Ca1—Ca1^iv	101.81 (5)
O1—Ca1—O1W^iii	146.33 (7)	O2^iii—Ca1—Ca1^iv	34.46 (4)
O1W—Ca1—O1W^iii	80.77 (10)	C1^iii—Ca1—Ca1^iv	55.29 (6)
O2^i—Ca1—O2	121.63 (6)	C1—Ca1—Ca1^iv	92.83 (6)
O2^ii—Ca1—O2	74.81 (7)	Ca1^ii—Ca1—Ca1^iv	131.82 (4)
O1^iii—Ca1—O2	86.58 (6)	C1—O1—Ca1	100.03 (16)
O1—Ca1—O2	50.77 (6)	C1—O2—Ca1^ii	134.18 (17)
O1W—Ca1—O2	101.83 (7)	C1—O2—Ca1	84.27 (16)
O1W^iii—Ca1—O2	162.15 (7)	Ca1^ii—O2—Ca1	105.19 (7)
O2^i—Ca1—O2^iii	74.81 (7)	O1—C1—O2	123.5 (2)
O2^ii—Ca1—O2^iii	121.63 (6)	O1—C1—C2	117.8 (2)
O1^iii—Ca1—O2^iii	50.77 (6)	O2—C1—C2	118.8 (2)
O1—Ca1—O2^iii	86.58 (6)	O1—C1—Ca1	54.78 (13)
O1W—Ca1—O2^iii	162.15 (7)	O2—C1—Ca1	69.85 (15)
O1W^iii—Ca1—O2^iii	101.83 (7)	C2—C1—Ca1	166.44 (18)
O2—Ca1—O2^iii	81.18 (8)	N1—C2—C3	110.1 (2)
O2^i—Ca1—C1^iii	93.36 (7)	N1—C2—C1	107.6 (2)
O2^ii—Ca1—C1^iii	99.30 (7)	C3—C2—C1	113.2 (2)
O1^iii—Ca1—C1^iii	25.20 (7)	N1—C2—H2	108.6
O1—Ca1—C1^iii	108.93 (8)	C3—C2—H2	108.6
O1W—Ca1—C1^iii	168.99 (7)	C1—C2—H2	108.6
O1W^iii—Ca1—C1^iii	89.35 (7)	C2—C3—H3A	109.5
O2—Ca1—C1^iii	86.13 (7)	C2—C3—H3B	109.5
O2^iii—Ca1—C1^iii	25.88 (6)	H3A—C3—H3B	109.5
O2^i—Ca1—C1	99.30 (7)	C2—C3—H3C	109.5
O2^ii—Ca1—C1	93.36 (7)	H3A—C3—H3C	109.5
O1^iii—Ca1—C1	108.93 (8)	H3B—C3—H3C	109.5
O1—Ca1—C1	25.20 (7)	C2—N1—H1A	111.4 (17)
O1W—Ca1—C1	89.35 (7)	C2—N1—H1B	109.5 (16)
O1W^iii—Ca1—C1	168.99 (7)	H1A—N1—H1B	107 (2)
O2—Ca1—C1	25.88 (6)	C2—N1—H1C	107.9 (18)
O2^iii—Ca1—C1	86.13 (7)	H1A—N1—H1C	110 (2)
C1^iii—Ca1—C1	100.88 (11)	H1B—N1—H1C	111 (2)
O2^i—Ca1—Ca1^ii	154.57 (5)	Ca1—O1W—H3E	119 (2)
O2^ii—Ca1—Ca1^ii	40.36 (5)	Ca1—O1W—H3D	116 (2)
O1^iii—Ca1—Ca1^ii	79.00 (5)	H3E—O1W—H3D	115 (3)
O1—Ca1—Ca1^ii	79.56 (5)

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

(6)

Crystal data

C9H23CaN3O7·2(Br)	F(000) = 976
Mr = 485.20	Dx = 1.779 Mg m^−3
Orthorhombic, Pc21n	Mo Kα radiation, λ = 0.71073 Å
a = 4.8727 (5) Å	µ = 4.79 mm^−1
b = 16.0701 (17) Å	T = 100 K
c = 23.129 (2) Å	Needle, colourless
V = 1811.1 (3) Å^3	0.50 × 0.09 × 0.07 mm
Z = 4

Data collection

Bruker APEX CCD diffractometer	3739 independent reflections
Radiation source: microsource	3450 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.060
ω scans	θmax = 26.5°, θmin = 2.2°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −6→6
Tmin = 0.437, Tmax = 0.745	k = −20→20
20251 measured reflections	l = −29→28

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.028	w = 1/[σ^2(Fo^2) + (0.020P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.062	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 1.06 e Å^−3
3739 reflections	Δρmin = −0.30 e Å^−3
234 parameters	Absolute structure: Flack x determined using 1545 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
38 restraints	Absolute structure parameter: 0.004 (6)

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.

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

	x	y	z	Uiso*/Ueq
Ca1	0.9085 (2)	0.75000 (6)	0.03355 (4)	0.0096 (2)
Br1	0.57417 (12)	0.65284 (4)	0.23125 (2)	0.02133 (15)
Br2	0.75563 (10)	0.36823 (4)	0.16347 (2)	0.01238 (12)
O5	0.7433 (7)	0.8303 (2)	0.10495 (16)	0.0144 (8)
O6	0.3528 (7)	0.8887 (2)	0.13480 (16)	0.0137 (8)
O1W	1.1826 (7)	0.8715 (3)	0.02281 (15)	0.0133 (8)
H1W	1.237 (11)	0.878 (4)	0.0532 (19)	0.016*
H2W	1.314 (9)	0.859 (4)	0.008 (2)	0.016*
N3	0.9651 (10)	0.8216 (3)	0.2085 (2)	0.0139 (10)
H9N	1.082 (10)	0.834 (4)	0.1796 (19)	0.017*
H7N	1.045 (12)	0.830 (4)	0.2435 (15)	0.017*
H8N	0.925 (12)	0.7672 (19)	0.210 (3)	0.017*
C9	0.7680 (13)	0.9621 (4)	0.2169 (3)	0.0200 (13)
H9C	0.8926	0.9846	0.1876	0.024*
H9A	0.8538	0.9664	0.2551	0.024*
H9B	0.5961	0.9937	0.2166	0.024*
C8	0.7081 (10)	0.8714 (4)	0.2036 (2)	0.0131 (10)
H8A	0.5711	0.8499	0.2322	0.016*
C7	0.5909 (10)	0.8621 (3)	0.1428 (2)	0.0126 (11)
O4	0.1499 (8)	0.7049 (2)	−0.05102 (16)	0.0135 (8)
O3	0.5612 (7)	0.7625 (2)	−0.03518 (15)	0.0123 (8)
C4	0.3979 (11)	0.7181 (3)	−0.0636 (2)	0.0106 (11)
C5	0.5094 (11)	0.6740 (3)	−0.1170 (2)	0.0114 (11)
H5A	0.3634	0.6718	−0.1474	0.014*
C6	0.5979 (13)	0.5859 (4)	−0.1017 (3)	0.0198 (13)
H6C	0.7363	0.5879	−0.0710	0.024*
H6A	0.6759	0.5590	−0.1360	0.024*
H6B	0.4384	0.5542	−0.0883	0.024*
N2	0.7484 (9)	0.7226 (3)	−0.1392 (2)	0.0118 (10)
H5N	0.792 (11)	0.700 (4)	−0.1735 (16)	0.014*
H6N	0.724 (11)	0.7780 (18)	−0.142 (3)	0.014*
H4N	0.881 (9)	0.718 (4)	−0.113 (2)	0.014*
N1	0.0739 (10)	0.5555 (3)	0.1412 (2)	0.0134 (10)
H2N	−0.062 (9)	0.578 (3)	0.120 (2)	0.016*
H3N	−0.015 (11)	0.510 (3)	0.153 (2)	0.016*
H1N	0.095 (12)	0.591 (3)	0.1719 (18)	0.016*
C1	0.4265 (12)	0.6279 (3)	0.0851 (2)	0.0122 (11)
C2	0.3281 (11)	0.5436 (3)	0.1058 (2)	0.0116 (11)
H2A	0.4736	0.5170	0.1300	0.014*
C3	0.2614 (13)	0.4877 (4)	0.0546 (3)	0.0215 (13)
H3A	0.1986	0.4334	0.0687	0.032*
H3B	0.4261	0.4802	0.0308	0.032*
H3C	0.1164	0.5134	0.0313	0.032*
O1	0.2600 (7)	0.6863 (2)	0.08266 (16)	0.0133 (8)
O2	0.6762 (7)	0.6311 (2)	0.06906 (16)	0.0137 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0092 (5)	0.0100 (5)	0.0097 (5)	0.0005 (4)	0.0002 (4)	0.0002 (4)
Br1	0.0315 (3)	0.0188 (3)	0.0137 (3)	−0.0106 (3)	−0.0023 (2)	−0.0011 (2)
Br2	0.0130 (2)	0.0112 (2)	0.0130 (2)	−0.0009 (2)	0.0007 (2)	0.0008 (2)
O5	0.012 (2)	0.0183 (19)	0.0125 (19)	0.0013 (16)	0.0015 (16)	−0.0042 (16)
O6	0.0122 (19)	0.014 (2)	0.0153 (19)	0.0006 (15)	0.0012 (16)	−0.0010 (15)
O1W	0.012 (2)	0.0174 (19)	0.0102 (18)	−0.0015 (19)	−0.0001 (14)	−0.001 (2)
N3	0.013 (3)	0.016 (2)	0.012 (2)	−0.001 (2)	−0.002 (2)	−0.001 (2)
C9	0.025 (4)	0.015 (3)	0.020 (3)	0.000 (2)	−0.006 (3)	−0.006 (2)
C8	0.012 (3)	0.015 (3)	0.012 (2)	0.001 (3)	0.000 (2)	−0.002 (3)
C7	0.014 (3)	0.010 (2)	0.013 (3)	−0.003 (3)	0.003 (2)	0.000 (2)
O4	0.010 (2)	0.018 (2)	0.0126 (19)	0.0009 (15)	−0.0006 (16)	−0.0019 (15)
O3	0.012 (2)	0.0126 (19)	0.0117 (18)	0.0007 (16)	−0.0012 (16)	−0.0010 (15)
C4	0.010 (3)	0.010 (2)	0.012 (3)	0.004 (2)	0.000 (2)	0.003 (2)
C5	0.007 (3)	0.015 (3)	0.012 (2)	−0.0006 (19)	0.002 (2)	−0.003 (2)
C6	0.021 (3)	0.011 (3)	0.027 (3)	−0.001 (2)	0.007 (3)	−0.005 (2)
N2	0.012 (3)	0.014 (2)	0.009 (2)	0.000 (2)	0.0017 (19)	−0.0019 (19)
N1	0.012 (2)	0.013 (2)	0.015 (2)	−0.002 (2)	0.003 (2)	0.0030 (19)
C1	0.011 (3)	0.016 (3)	0.010 (2)	−0.003 (2)	−0.004 (2)	−0.003 (2)
C2	0.005 (3)	0.010 (3)	0.019 (3)	0.000 (2)	0.000 (2)	0.002 (2)
C3	0.025 (4)	0.018 (3)	0.020 (3)	−0.005 (3)	0.002 (3)	−0.004 (3)
O1	0.0090 (19)	0.0127 (19)	0.018 (2)	0.0012 (15)	−0.0039 (16)	0.0032 (15)
O2	0.0089 (19)	0.015 (2)	0.0173 (19)	−0.0008 (14)	0.0015 (15)	0.0046 (16)

Geometric parameters (Å, º)

Ca1—O5	2.245 (4)	O3—C4	1.254 (6)
Ca1—O1^i	2.296 (4)	C4—C5	1.524 (7)
Ca1—O3	2.331 (4)	C5—N2	1.493 (7)
Ca1—O2	2.367 (4)	C5—C6	1.521 (8)
Ca1—O1W	2.379 (4)	C5—H5A	1.0000
Ca1—O4^i	2.395 (4)	C6—H6C	0.9800
Ca1—H1W	2.64 (6)	C6—H6A	0.9800
Ca1—H2W	2.71 (6)	C6—H6B	0.9800
O5—C7	1.257 (6)	N2—H5N	0.90 (3)
O6—C7	1.250 (6)	N2—H6N	0.90 (3)
O1W—H1W	0.76 (4)	N2—H4N	0.89 (3)
O1W—H2W	0.75 (4)	N1—C2	1.497 (7)
N3—C8	1.491 (7)	N1—H2N	0.90 (3)
N3—H9N	0.90 (3)	N1—H3N	0.90 (3)
N3—H7N	0.91 (3)	N1—H1N	0.91 (3)
N3—H8N	0.90 (3)	C1—O1	1.242 (7)
C9—C8	1.518 (8)	C1—O2	1.273 (7)
C9—H9C	0.9800	C1—C2	1.515 (7)
C9—H9A	0.9800	C2—C3	1.522 (8)
C9—H9B	0.9800	C2—H2A	1.0000
C8—C7	1.526 (7)	C3—H3A	0.9800
C8—H8A	1.0000	C3—H3B	0.9800
O4—C4	1.261 (6)	C3—H3C	0.9800
O4—Ca1^ii	2.395 (4)	O1—Ca1^ii	2.296 (4)
O5—Ca1—O1^i	99.20 (14)	O6—C7—O5	125.8 (5)
O5—Ca1—O3	101.06 (13)	O6—C7—C8	116.8 (4)
O1^i—Ca1—O3	156.57 (14)	O5—C7—C8	117.4 (4)
O5—Ca1—O2	92.13 (14)	C4—O4—Ca1^ii	127.4 (3)
O1^i—Ca1—O2	79.94 (13)	C4—O3—Ca1	140.3 (3)
O3—Ca1—O2	87.64 (13)	O3—C4—O4	125.7 (5)
O5—Ca1—O1W	78.83 (14)	O3—C4—C5	117.6 (5)
O1^i—Ca1—O1W	89.93 (14)	O4—C4—C5	116.8 (5)
O3—Ca1—O1W	105.43 (13)	N2—C5—C6	110.2 (4)
O2—Ca1—O1W	165.24 (13)	N2—C5—C4	108.3 (4)
O5—Ca1—O4^i	161.98 (14)	C6—C5—C4	110.2 (4)
O1^i—Ca1—O4^i	84.41 (13)	N2—C5—H5A	109.4
O3—Ca1—O4^i	79.97 (13)	C6—C5—H5A	109.4
O2—Ca1—O4^i	105.90 (13)	C4—C5—H5A	109.4
O1W—Ca1—O4^i	83.54 (13)	C5—C6—H6C	109.5
O5—Ca1—H1W	69.1 (12)	C5—C6—H6A	109.5
O1^i—Ca1—H1W	79.1 (13)	H6C—C6—H6A	109.5
O3—Ca1—H1W	119.3 (12)	C5—C6—H6B	109.5
O2—Ca1—H1W	149.0 (10)	H6C—C6—H6B	109.5
O1W—Ca1—H1W	16.3 (10)	H6A—C6—H6B	109.5
O4^i—Ca1—H1W	94.5 (12)	C5—N2—H5N	106 (4)
O5—Ca1—H2W	92.9 (11)	C5—N2—H6N	116 (4)
O1^i—Ca1—H2W	81.6 (13)	H5N—N2—H6N	111 (6)
O3—Ca1—H2W	108.9 (13)	C5—N2—H4N	107 (4)
O2—Ca1—H2W	161.4 (12)	H5N—N2—H4N	113 (5)
O1W—Ca1—H2W	15.3 (11)	H6N—N2—H4N	104 (5)
O4^i—Ca1—H2W	70.0 (11)	C2—N1—H2N	111 (4)
H1W—Ca1—H2W	24.9 (17)	C2—N1—H3N	117 (4)
C7—O5—Ca1	163.4 (4)	H2N—N1—H3N	98 (5)
Ca1—O1W—H1W	102 (5)	C2—N1—H1N	114 (4)
Ca1—O1W—H2W	108 (5)	H2N—N1—H1N	105 (5)
H1W—O1W—H2W	100 (6)	H3N—N1—H1N	109 (5)
C8—N3—H9N	111 (4)	O1—C1—O2	125.5 (5)
C8—N3—H7N	111 (4)	O1—C1—C2	118.9 (5)
H9N—N3—H7N	111 (6)	O2—C1—C2	115.5 (5)
C8—N3—H8N	110 (4)	N1—C2—C1	108.7 (4)
H9N—N3—H8N	113 (5)	N1—C2—C3	108.9 (4)
H7N—N3—H8N	101 (5)	C1—C2—C3	110.5 (5)
C8—C9—H9C	109.5	N1—C2—H2A	109.6
C8—C9—H9A	109.5	C1—C2—H2A	109.6
H9C—C9—H9A	109.5	C3—C2—H2A	109.6
C8—C9—H9B	109.5	C2—C3—H3A	109.5
H9C—C9—H9B	109.5	C2—C3—H3B	109.5
H9A—C9—H9B	109.5	H3A—C3—H3B	109.5
N3—C8—C9	109.8 (4)	C2—C3—H3C	109.5
N3—C8—C7	109.4 (4)	H3A—C3—H3C	109.5
C9—C8—C7	110.6 (5)	H3B—C3—H3C	109.5
N3—C8—H8A	109.0	C1—O1—Ca1^ii	147.9 (3)
C9—C8—H8A	109.0	C1—O2—Ca1	126.2 (3)
C7—C8—H8A	109.0

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

(7)

Crystal data

C15H41Ca2N5O13·4(I)·2(H2O)	Z = 4
Mr = 1123.32	F(000) = 2168
Monoclinic, P21/c	Dx = 2.096 Mg m^−3
a = 22.842 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.3609 (13) Å	µ = 3.85 mm^−1
c = 18.807 (3) Å	T = 100 K
β = 97.734 (3)°	Needle, colourless
V = 3559.1 (10) Å^3	0.18 × 0.06 × 0.05 mm

Data collection

Bruker APEX CCD diffractometer	7339 independent reflections
Radiation source: microsource	5475 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.103
ω scans	θmax = 26.5°, θmin = 0.9°
Absorption correction: multi-scan SADABS	h = −28→28
Tmin = 0.570, Tmax = 0.755	k = −10→10
41724 measured reflections	l = −23→23

Refinement

Refinement on F^2	15 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.030P)^2 + 1.P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
7339 reflections	Δρmax = 2.00 e Å^−3
420 parameters	Δρmin = −1.46 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.

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

	x	y	z	Uiso*/Ueq
I1	0.56851 (2)	0.72857 (5)	0.65183 (2)	0.01631 (12)
I2	0.57243 (2)	0.67891 (5)	0.90174 (2)	0.01641 (12)
I3	0.94569 (2)	0.78083 (6)	0.84436 (2)	0.01830 (12)
I4	0.92274 (2)	0.70133 (6)	0.60187 (3)	0.02210 (12)
Ca1	0.74407 (5)	0.18112 (15)	0.87017 (7)	0.0102 (3)
Ca2	0.74623 (5)	0.14511 (16)	0.62740 (7)	0.0112 (3)
O1	0.65489 (18)	0.1027 (5)	0.6691 (2)	0.0155 (10)
O2	0.67798 (18)	0.0319 (5)	0.7843 (2)	0.0114 (10)
C1	0.6428 (3)	0.0827 (7)	0.7322 (3)	0.0092 (13)
C21	0.5805 (3)	0.1316 (8)	0.7443 (3)	0.0123 (14)
H21	0.5515	0.0845	0.7054	0.015*
C31	0.5728 (3)	0.3104 (8)	0.7442 (4)	0.0176 (15)
H31A	0.6015	0.3578	0.7817	0.026*
H31B	0.5327	0.3365	0.7536	0.026*
H31C	0.5790	0.3534	0.6974	0.026*
N1	0.5690 (2)	0.0647 (7)	0.8150 (3)	0.0144 (12)
H1A	0.5342 (17)	0.101 (8)	0.828 (3)	0.017*
H1B	0.597 (2)	0.109 (7)	0.849 (3)	0.017*
H1C	0.567 (3)	−0.042 (3)	0.806 (4)	0.017*
O3	0.7303 (2)	0.4169 (5)	0.6533 (3)	0.0193 (11)
O4	0.7239 (2)	0.3555 (5)	0.7678 (2)	0.0171 (11)
C4	0.7256 (3)	0.4535 (8)	0.7174 (4)	0.0120 (14)
C51	0.7267 (3)	0.6332 (8)	0.7358 (3)	0.0128 (14)
H51	0.7082	0.6957	0.6933	0.015*
C6	0.7906 (3)	0.6847 (8)	0.7556 (4)	0.0178 (15)
H6A	0.8091	0.6196	0.7958	0.027*
H6B	0.7919	0.7976	0.7696	0.027*
H6C	0.8119	0.6700	0.7142	0.027*
N2	0.6932 (2)	0.6602 (7)	0.7979 (3)	0.0157 (13)
H2A	0.702 (3)	0.589 (7)	0.835 (3)	0.024*
H2B	0.6532 (11)	0.652 (8)	0.781 (3)	0.024*
H2C	0.701 (3)	0.757 (5)	0.822 (3)	0.024*
O5	0.81341 (19)	0.0801 (5)	0.7249 (2)	0.0150 (10)
O6	0.83890 (19)	0.1560 (6)	0.8381 (2)	0.0208 (11)
C7	0.8493 (3)	0.1333 (8)	0.7746 (3)	0.0137 (14)
C8	0.9106 (3)	0.1805 (8)	0.7590 (4)	0.0180 (16)
H8	0.9405	0.1496	0.8006	0.022*
C9	0.9122 (4)	0.3603 (9)	0.7485 (5)	0.033 (2)
H9A	0.8856	0.3897	0.7051	0.050*
H9B	0.9526	0.3936	0.7434	0.050*
H9C	0.8995	0.4139	0.7902	0.050*
N3	0.9235 (2)	0.0956 (7)	0.6937 (3)	0.0158 (13)
H3A	0.899 (2)	0.119 (8)	0.653 (2)	0.019*
H3B	0.919 (3)	−0.013 (3)	0.700 (4)	0.019*
H3C	0.9596 (16)	0.109 (8)	0.678 (3)	0.019*
O7	0.80765 (19)	0.3368 (5)	0.4822 (2)	0.0158 (10)
O8	0.83607 (18)	0.1996 (5)	0.5826 (2)	0.0147 (10)
C10	0.6444 (3)	0.2134 (8)	0.4760 (4)	0.0129 (14)
C11	0.5822 (3)	0.2203 (8)	0.4946 (3)	0.0118 (14)
H11	0.5538	0.2041	0.4499	0.014*
C12	0.5705 (3)	0.3822 (9)	0.5265 (4)	0.0213 (17)
H12A	0.5979	0.3987	0.5707	0.032*
H12B	0.5298	0.3857	0.5376	0.032*
H12C	0.5762	0.4666	0.4920	0.032*
N4	0.5729 (2)	0.0928 (7)	0.5467 (3)	0.0139 (12)
H4A	0.576 (3)	−0.009 (4)	0.530 (3)	0.017*
H4B	0.5378 (17)	0.097 (8)	0.566 (3)	0.017*
H4C	0.599 (2)	0.104 (8)	0.588 (2)	0.017*
O9	0.65355 (19)	0.2840 (5)	0.4195 (2)	0.0155 (10)
O10	0.68299 (18)	0.1427 (5)	0.5188 (2)	0.0130 (10)
C13	0.8450 (3)	0.2738 (8)	0.5270 (4)	0.0125 (14)
C14	0.9102 (3)	0.2781 (7)	0.5145 (3)	0.0116 (14)
H14	0.9355	0.3030	0.5608	0.014*
C15	0.9296 (3)	0.1189 (8)	0.4858 (4)	0.0249 (18)
H15A	0.9716	0.1241	0.4803	0.037*
H15B	0.9064	0.0971	0.4390	0.037*
H15C	0.9232	0.0332	0.5194	0.037*
N5	0.9182 (2)	0.4066 (7)	0.4607 (3)	0.0149 (13)
H5A	0.9559 (14)	0.395 (8)	0.450 (3)	0.018*
H5B	0.917 (3)	0.506 (4)	0.481 (3)	0.018*
H5C	0.894 (2)	0.385 (8)	0.419 (2)	0.018*
O1W	0.8337 (2)	0.7023 (6)	0.9426 (2)	0.0208 (11)
H1W	0.8639	0.7234	0.9162	0.025*
H2W	0.8573	0.7277	0.9847	0.025*
O2W	0.6958 (2)	−0.3676 (6)	0.5441 (2)	0.0203 (11)
H4W	0.7073	−0.4394	0.5805	0.024*
H3W	0.6567	−0.3325	0.5462	0.024*
O3W	0.7674 (2)	−0.1157 (5)	0.5881 (2)	0.0208 (11)
H5W	0.7430	−0.2002	0.5734	0.025*
H6W	0.8046	−0.1595	0.5914	0.025*
O4W	0.7501 (2)	0.4650 (5)	0.9161 (2)	0.0183 (11)
H7W	0.7780	0.5446	0.9252	0.022*
H8W	0.7279	0.4294	0.9506	0.022*
O5W	0.73759 (18)	−0.0974 (5)	0.9098 (2)	0.0140 (10)
H9W	0.7695	−0.1643	0.9204	0.017*
H10W	0.7237	−0.1092	0.9532	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0147 (2)	0.0159 (2)	0.0186 (3)	−0.00246 (18)	0.00305 (18)	0.00132 (19)
I2	0.0167 (2)	0.0167 (2)	0.0171 (3)	0.00184 (18)	0.00670 (18)	0.00420 (19)
I3	0.0135 (2)	0.0228 (3)	0.0193 (3)	0.00161 (18)	0.00484 (18)	−0.0049 (2)
I4	0.0335 (3)	0.0172 (3)	0.0154 (3)	0.0019 (2)	0.0026 (2)	−0.0007 (2)
Ca1	0.0107 (6)	0.0129 (7)	0.0071 (7)	−0.0020 (5)	0.0013 (5)	0.0000 (5)
Ca2	0.0123 (7)	0.0135 (7)	0.0083 (7)	0.0016 (5)	0.0025 (5)	−0.0008 (5)
O1	0.011 (2)	0.024 (3)	0.011 (3)	−0.0035 (19)	0.0008 (19)	−0.002 (2)
O2	0.010 (2)	0.012 (2)	0.012 (2)	−0.0007 (18)	−0.0013 (18)	0.0014 (19)
C1	0.014 (3)	0.006 (3)	0.008 (3)	−0.005 (2)	0.004 (3)	−0.004 (2)
C21	0.014 (3)	0.018 (4)	0.005 (3)	0.001 (3)	0.003 (3)	0.000 (3)
C31	0.019 (4)	0.021 (4)	0.014 (4)	0.005 (3)	0.008 (3)	0.001 (3)
N1	0.010 (3)	0.017 (3)	0.016 (3)	−0.003 (2)	0.005 (2)	−0.002 (3)
O3	0.024 (3)	0.018 (3)	0.018 (3)	0.002 (2)	0.010 (2)	0.000 (2)
O4	0.023 (3)	0.013 (3)	0.015 (3)	0.002 (2)	0.002 (2)	0.001 (2)
C4	0.010 (3)	0.011 (3)	0.015 (4)	0.001 (3)	0.004 (3)	−0.003 (3)
C51	0.019 (4)	0.012 (3)	0.007 (3)	0.002 (3)	0.003 (3)	0.003 (3)
C6	0.012 (3)	0.019 (4)	0.023 (4)	−0.001 (3)	0.004 (3)	−0.004 (3)
N2	0.015 (3)	0.018 (3)	0.015 (3)	−0.002 (3)	0.003 (2)	−0.005 (2)
O5	0.014 (2)	0.022 (3)	0.008 (2)	−0.003 (2)	0.0003 (19)	0.003 (2)
O6	0.016 (3)	0.037 (3)	0.010 (3)	0.001 (2)	0.003 (2)	−0.001 (2)
C7	0.010 (3)	0.021 (4)	0.011 (4)	0.003 (3)	0.005 (3)	0.000 (3)
C8	0.013 (3)	0.026 (4)	0.015 (4)	−0.002 (3)	0.002 (3)	−0.006 (3)
C9	0.036 (5)	0.025 (5)	0.040 (5)	−0.006 (4)	0.014 (4)	−0.005 (4)
N3	0.010 (3)	0.021 (3)	0.017 (3)	−0.003 (3)	0.005 (2)	0.000 (3)
O7	0.013 (2)	0.022 (3)	0.011 (3)	0.003 (2)	−0.0014 (19)	0.000 (2)
O8	0.013 (2)	0.019 (3)	0.013 (3)	0.0019 (19)	0.0033 (19)	0.002 (2)
C10	0.013 (3)	0.012 (3)	0.014 (4)	−0.002 (3)	0.005 (3)	−0.003 (3)
C11	0.009 (3)	0.018 (4)	0.008 (3)	0.002 (3)	0.002 (3)	0.003 (3)
C12	0.016 (4)	0.025 (4)	0.025 (4)	0.004 (3)	0.009 (3)	−0.001 (3)
N4	0.010 (3)	0.018 (3)	0.014 (3)	0.000 (2)	0.003 (2)	0.001 (3)
O9	0.017 (2)	0.018 (3)	0.012 (3)	0.002 (2)	0.0053 (19)	0.004 (2)
O10	0.011 (2)	0.018 (3)	0.010 (2)	0.0033 (19)	−0.0008 (18)	0.0026 (19)
C13	0.014 (3)	0.009 (3)	0.014 (4)	0.000 (3)	0.001 (3)	−0.006 (3)
C14	0.011 (3)	0.013 (3)	0.009 (4)	−0.003 (3)	−0.004 (3)	0.000 (3)
C15	0.026 (4)	0.018 (4)	0.034 (5)	0.004 (3)	0.017 (3)	0.002 (3)
N5	0.012 (3)	0.017 (3)	0.015 (3)	−0.005 (3)	−0.001 (2)	−0.001 (3)
O1W	0.019 (3)	0.029 (3)	0.015 (3)	−0.004 (2)	0.003 (2)	−0.001 (2)
O2W	0.016 (3)	0.026 (3)	0.019 (3)	−0.001 (2)	0.004 (2)	0.003 (2)
O3W	0.022 (3)	0.016 (3)	0.024 (3)	−0.002 (2)	0.001 (2)	−0.003 (2)
O4W	0.022 (3)	0.016 (3)	0.018 (3)	−0.009 (2)	0.005 (2)	−0.001 (2)
O5W	0.019 (2)	0.017 (3)	0.007 (2)	0.0035 (19)	0.0017 (19)	0.0032 (19)

Geometric parameters (Å, º)

Ca1—O6	2.335 (5)	C8—N3	1.482 (9)
Ca1—O9^i	2.395 (5)	C8—C9	1.518 (10)
Ca1—O7^i	2.398 (4)	C8—H8	1.0000
Ca1—O2	2.405 (4)	C9—H9A	0.9800
Ca1—O4	2.410 (5)	C9—H9B	0.9800
Ca1—O5W	2.456 (4)	C9—H9C	0.9800
Ca1—O4W	2.523 (5)	N3—H3A	0.92 (2)
Ca1—C7	3.214 (6)	N3—H3B	0.92 (2)
Ca1—H8W	2.6233	N3—H3C	0.92 (2)
Ca2—O5	2.292 (4)	O7—C13	1.233 (7)
Ca2—O10	2.338 (4)	O8—C13	1.255 (8)
Ca2—O1	2.353 (4)	C10—O10	1.258 (7)
Ca2—O3	2.362 (5)	C10—O9	1.258 (8)
Ca2—O8	2.365 (4)	C10—C11	1.509 (8)
Ca2—O3W	2.373 (5)	C11—N4	1.482 (8)
Ca2—C4	3.155 (6)	C11—C12	1.519 (9)
O1—C1	1.264 (7)	C11—H11	1.0000
O2—C1	1.255 (7)	C12—H12A	0.9800
C1—C21	1.528 (8)	C12—H12B	0.9800
C21—N1	1.498 (8)	C12—H12C	0.9800
C21—C31	1.506 (9)	N4—H4A	0.91 (2)
C21—H21	1.0000	N4—H4B	0.92 (2)
C31—H31A	0.9800	N4—H4C	0.92 (2)
C31—H31B	0.9800	C13—C14	1.541 (9)
C31—H31C	0.9800	C14—N5	1.503 (8)
N1—H1A	0.92 (2)	C14—C15	1.525 (9)
N1—H1B	0.92 (2)	C14—H14	1.0000
N1—H1C	0.91 (2)	C15—H15A	0.9800
O3—C4	1.264 (8)	C15—H15B	0.9800
O4—C4	1.257 (8)	C15—H15C	0.9800
C4—C51	1.541 (9)	N5—H5A	0.91 (2)
C51—N2	1.498 (8)	N5—H5B	0.92 (2)
C51—C6	1.518 (9)	N5—H5C	0.91 (2)
C51—H51	1.0000	O1W—H1W	0.9200
C6—H6A	0.9800	O1W—H2W	0.9200
C6—H6B	0.9800	O2W—H4W	0.9222
C6—H6C	0.9800	O2W—H3W	0.9464
N2—H2A	0.92 (2)	O3W—H5W	0.9200
N2—H2B	0.93 (2)	O3W—H6W	0.9200
N2—H2C	0.93 (2)	O4W—H7W	0.9206
O5—C7	1.239 (7)	O4W—H8W	0.9255
O6—C7	1.263 (8)	O5W—H9W	0.9200
C7—C8	1.522 (9)	O5W—H10W	0.9200
O6—Ca1—O9^i	172.01 (16)	C51—C6—H6B	109.5
O6—Ca1—O7^i	75.43 (16)	H6A—C6—H6B	109.5
O9^i—Ca1—O7^i	96.88 (16)	C51—C6—H6C	109.5
O6—Ca1—O2	107.47 (16)	H6A—C6—H6C	109.5
O9^i—Ca1—O2	79.99 (15)	H6B—C6—H6C	109.5
O7^i—Ca1—O2	143.97 (16)	C51—N2—H2A	115 (4)
O6—Ca1—O4	86.12 (16)	C51—N2—H2B	107 (4)
O9^i—Ca1—O4	98.81 (16)	H2A—N2—H2B	108 (6)
O7^i—Ca1—O4	140.20 (16)	C51—N2—H2C	116 (5)
O2—Ca1—O4	75.05 (15)	H2A—N2—H2C	100 (6)
O6—Ca1—O5W	95.11 (17)	H2B—N2—H2C	110 (6)
O9^i—Ca1—O5W	84.69 (15)	C7—O5—Ca2	145.2 (5)
O7^i—Ca1—O5W	74.23 (15)	C7—O6—Ca1	123.8 (4)
O2—Ca1—O5W	69.74 (14)	O5—C7—O6	125.3 (6)
O4—Ca1—O5W	143.44 (15)	O5—C7—C8	118.7 (6)
O6—Ca1—O4W	99.37 (17)	O6—C7—C8	115.9 (6)
O9^i—Ca1—O4W	76.33 (15)	O5—C7—Ca1	89.9 (4)
O7^i—Ca1—O4W	76.07 (15)	C8—C7—Ca1	148.4 (4)
O2—Ca1—O4W	135.90 (15)	N3—C8—C9	110.8 (6)
O4—Ca1—O4W	72.54 (15)	N3—C8—C7	109.0 (5)
O5W—Ca1—O4W	142.30 (15)	C9—C8—C7	108.7 (6)
O6—Ca1—C7	19.06 (16)	N3—C8—H8	109.4
O9^i—Ca1—C7	168.84 (16)	C9—C8—H8	109.4
O7^i—Ca1—C7	94.24 (16)	C7—C8—H8	109.4
O2—Ca1—C7	90.51 (16)	C8—C9—H9A	109.5
O4—Ca1—C7	72.87 (16)	C8—C9—H9B	109.5
O5W—Ca1—C7	97.58 (16)	H9A—C9—H9B	109.5
O4W—Ca1—C7	107.32 (17)	C8—C9—H9C	109.5
O6—Ca1—H8W	115.3	H9A—C9—H9C	109.5
O9^i—Ca1—H8W	59.0	H9B—C9—H9C	109.5
O7^i—Ca1—H8W	70.0	C8—N3—H3A	115 (4)
O2—Ca1—H8W	132.3	C8—N3—H3B	109 (4)
O4—Ca1—H8W	87.4	H3A—N3—H3B	104 (6)
O5W—Ca1—H8W	123.8	C8—N3—H3C	119 (4)
O4W—Ca1—H8W	20.6	H3A—N3—H3C	101 (6)
C7—Ca1—H8W	126.5	H3B—N3—H3C	106 (6)
O5—Ca2—O10	164.83 (17)	C13—O7—Ca1^ii	148.8 (4)
O5—Ca2—O1	103.04 (16)	C13—O8—Ca2	129.6 (4)
O10—Ca2—O1	79.57 (15)	O10—C10—O9	125.4 (6)
O5—Ca2—O3	99.71 (17)	O10—C10—C11	118.0 (6)
O10—Ca2—O3	95.40 (16)	O9—C10—C11	116.5 (6)
O1—Ca2—O3	84.73 (16)	N4—C11—C10	110.4 (5)
O5—Ca2—O8	79.11 (16)	N4—C11—C12	109.4 (5)
O10—Ca2—O8	98.86 (16)	C10—C11—C12	110.3 (5)
O1—Ca2—O8	177.13 (17)	N4—C11—H11	108.9
O3—Ca2—O8	93.06 (16)	C10—C11—H11	108.9
O5—Ca2—O3W	83.61 (16)	C12—C11—H11	108.9
O10—Ca2—O3W	81.23 (16)	C11—C12—H12A	109.5
O1—Ca2—O3W	101.09 (17)	C11—C12—H12B	109.5
O3—Ca2—O3W	172.56 (17)	H12A—C12—H12B	109.5
O8—Ca2—O3W	80.97 (16)	C11—C12—H12C	109.5
O5—Ca2—C4	84.09 (17)	H12A—C12—H12C	109.5
O10—Ca2—C4	110.90 (16)	H12B—C12—H12C	109.5
O1—Ca2—C4	74.96 (16)	C11—N4—H4A	114 (4)
O3—Ca2—C4	20.77 (16)	C11—N4—H4B	116 (4)
O8—Ca2—C4	103.51 (17)	H4A—N4—H4B	107 (6)
O3W—Ca2—C4	165.84 (17)	C11—N4—H4C	111 (4)
C1—O1—Ca2	130.4 (4)	H4A—N4—H4C	108 (6)
C1—O2—Ca1	128.8 (4)	H4B—N4—H4C	100 (6)
O2—C1—O1	125.5 (6)	C10—O9—Ca1^ii	129.4 (4)
O2—C1—C21	119.0 (5)	C10—O10—Ca2	148.4 (4)
O1—C1—C21	115.5 (5)	O7—C13—O8	127.3 (6)
N1—C21—C31	109.7 (5)	O7—C13—C14	118.7 (6)
N1—C21—C1	108.2 (5)	O8—C13—C14	114.0 (5)
C31—C21—C1	112.2 (5)	N5—C14—C15	108.5 (5)
N1—C21—H21	108.9	N5—C14—C13	109.1 (5)
C31—C21—H21	108.9	C15—C14—C13	111.5 (5)
C1—C21—H21	108.9	N5—C14—H14	109.2
C21—C31—H31A	109.5	C15—C14—H14	109.2
C21—C31—H31B	109.5	C13—C14—H14	109.2
H31A—C31—H31B	109.5	C14—C15—H15A	109.5
C21—C31—H31C	109.5	C14—C15—H15B	109.5
H31A—C31—H31C	109.5	H15A—C15—H15B	109.5
H31B—C31—H31C	109.5	C14—C15—H15C	109.5
C21—N1—H1A	113 (4)	H15A—C15—H15C	109.5
C21—N1—H1B	107 (4)	H15B—C15—H15C	109.5
H1A—N1—H1B	103 (6)	C14—N5—H5A	106 (4)
C21—N1—H1C	102 (4)	C14—N5—H5B	111 (4)
H1A—N1—H1C	111 (6)	H5A—N5—H5B	106 (6)
H1B—N1—H1C	123 (6)	C14—N5—H5C	108 (4)
C4—O3—Ca2	117.7 (4)	H5A—N5—H5C	106 (6)
C4—O4—Ca1	167.0 (4)	H5B—N5—H5C	119 (6)
O4—C4—O3	125.2 (6)	H1W—O1W—H2W	91.4
O4—C4—C51	117.9 (6)	H4W—O2W—H3W	110.3
O3—C4—C51	116.7 (6)	Ca2—O3W—H5W	131.3
O4—C4—Ca2	83.9 (4)	Ca2—O3W—H6W	124.8
C51—C4—Ca2	156.6 (4)	H5W—O3W—H6W	103.4
N2—C51—C6	110.0 (5)	Ca1—O4W—H7W	138.5
N2—C51—C4	109.1 (5)	Ca1—O4W—H8W	85.8
C6—C51—C4	108.6 (5)	H7W—O4W—H8W	122.2
N2—C51—H51	109.7	Ca1—O5W—H9W	124.3
C6—C51—H51	109.7	Ca1—O5W—H10W	114.3
C4—C51—H51	109.7	H9W—O5W—H10W	95.7
C51—C6—H6A	109.5

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

(8)

Crystal data

C6H18MnN2O6·2(Cl)·2(H2O)	Z = 2
Mr = 376.09	F(000) = 390
Monoclinic, P21/c	Dx = 1.567 Mg m^−3
a = 4.7294 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 19.101 (4) Å	µ = 1.19 mm^−1
c = 9.0705 (17) Å	T = 100 K
β = 103.395 (3)°	Needle, colourless
V = 797.1 (3) Å^3	0.40 × 0.07 × 0.07 mm

Data collection

Bruker APEX-II CCD diffractometer	1637 independent reflections
Radiation source: microsource	1419 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.069
ω scans	θmax = 26.5°, θmin = 2.5°
Absorption correction: multi-scan SADABS	h = −5→5
Tmin = 0.565, Tmax = 0.745	k = −23→23
9455 measured reflections	l = −11→11

Refinement

Refinement on F^2	5 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.030P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
1637 reflections	Δρmax = 0.41 e Å^−3
110 parameters	Δρmin = −0.28 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.

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

	x	y	z	Uiso*/Ueq
Cl1	1.14813 (11)	0.74272 (3)	0.51100 (5)	0.01587 (15)
Mn2	0.5000	0.5000	0.5000	0.00991 (14)
O1	0.8297 (3)	0.57126 (7)	0.46174 (15)	0.0121 (3)
O2	1.1996 (3)	0.56861 (7)	0.34688 (15)	0.0129 (3)
C1	0.9515 (4)	0.58773 (10)	0.3584 (2)	0.0107 (4)
C2	0.7897 (4)	0.63498 (10)	0.2301 (2)	0.0130 (4)
H2	0.9310	0.6685	0.2022	0.016*
C3	0.6497 (5)	0.59220 (12)	0.0918 (2)	0.0214 (5)
H3A	0.5091	0.5596	0.1179	0.032*
H3B	0.7998	0.5658	0.0571	0.032*
H3C	0.5497	0.6236	0.0108	0.032*
N1	0.5649 (4)	0.67528 (9)	0.28562 (19)	0.0124 (4)
H1A	0.455 (4)	0.7014 (10)	0.206 (2)	0.015*
H1B	0.657 (5)	0.7030 (10)	0.369 (2)	0.015*
H1C	0.432 (4)	0.6477 (10)	0.319 (2)	0.015*
O1W	0.4853 (3)	0.56036 (8)	0.70187 (17)	0.0162 (3)
H3D	0.344 (4)	0.5809 (11)	0.715 (3)	0.019*
H3E	0.631 (4)	0.5837 (11)	0.728 (3)	0.019*
O2W	0.9933 (4)	0.63929 (8)	0.76154 (17)	0.0200 (4)
H4B	1.042 (5)	0.6679 (11)	0.836 (2)	0.024*
H4A	0.995 (5)	0.6641 (11)	0.685 (2)	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0181 (3)	0.0150 (3)	0.0133 (3)	−0.0032 (2)	0.0011 (2)	−0.00158 (19)
Mn2	0.0095 (3)	0.0104 (2)	0.0098 (2)	0.00046 (16)	0.00209 (18)	0.00158 (16)
O1	0.0110 (7)	0.0136 (7)	0.0116 (7)	−0.0014 (6)	0.0028 (6)	0.0012 (6)
O2	0.0113 (8)	0.0142 (7)	0.0135 (7)	0.0018 (6)	0.0037 (6)	0.0030 (6)
C1	0.0104 (11)	0.0097 (9)	0.0110 (10)	−0.0026 (8)	0.0001 (8)	−0.0032 (8)
C2	0.0115 (11)	0.0146 (10)	0.0129 (10)	0.0020 (8)	0.0029 (8)	0.0014 (8)
C3	0.0245 (13)	0.0257 (12)	0.0120 (11)	0.0058 (10)	0.0004 (9)	−0.0011 (9)
N1	0.0113 (9)	0.0129 (9)	0.0126 (9)	0.0013 (7)	0.0020 (7)	0.0029 (7)
O1W	0.0135 (8)	0.0176 (8)	0.0176 (8)	−0.0001 (6)	0.0040 (7)	−0.0051 (6)
O2W	0.0237 (9)	0.0215 (8)	0.0143 (8)	−0.0036 (7)	0.0033 (7)	−0.0023 (6)

Geometric parameters (Å, º)

Mn2—O1^i	2.1577 (14)	C2—H2	1.0000
Mn2—O1	2.1577 (14)	C3—H3A	0.9800
Mn2—O1W^i	2.1785 (15)	C3—H3B	0.9800
Mn2—O1W	2.1785 (15)	C3—H3C	0.9800
Mn2—O2^ii	2.1795 (14)	N1—H1A	0.930 (15)
Mn2—O2^iii	2.1795 (14)	N1—H1B	0.946 (15)
O1—C1	1.249 (2)	N1—H1C	0.922 (15)
O2—C1	1.256 (2)	O1W—H3D	0.808 (17)
O2—Mn2^iv	2.1795 (14)	O1W—H3E	0.810 (18)
C1—C2	1.530 (3)	O2W—H4B	0.856 (18)
C2—N1	1.492 (3)	O2W—H4A	0.839 (18)
C2—C3	1.515 (3)
O1^i—Mn2—O1	180.00 (5)	N1—C2—C1	108.53 (16)
O1^i—Mn2—O1W^i	88.07 (5)	C3—C2—C1	110.94 (16)
O1—Mn2—O1W^i	91.93 (5)	N1—C2—H2	109.0
O1^i—Mn2—O1W	91.93 (5)	C3—C2—H2	109.0
O1—Mn2—O1W	88.07 (5)	C1—C2—H2	109.0
O1W^i—Mn2—O1W	180.0	C2—C3—H3A	109.5
O1^i—Mn2—O2^ii	95.35 (5)	C2—C3—H3B	109.5
O1—Mn2—O2^ii	84.65 (5)	H3A—C3—H3B	109.5
O1W^i—Mn2—O2^ii	85.74 (5)	C2—C3—H3C	109.5
O1W—Mn2—O2^ii	94.26 (5)	H3A—C3—H3C	109.5
O1^i—Mn2—O2^iii	84.65 (5)	H3B—C3—H3C	109.5
O1—Mn2—O2^iii	95.35 (5)	C2—N1—H1A	109.2 (14)
O1W^i—Mn2—O2^iii	94.26 (5)	C2—N1—H1B	109.0 (14)
O1W—Mn2—O2^iii	85.74 (5)	H1A—N1—H1B	113.1 (18)
O2^ii—Mn2—O2^iii	180.0	C2—N1—H1C	114.1 (13)
C1—O1—Mn2	139.10 (12)	H1A—N1—H1C	105.0 (19)
C1—O2—Mn2^iv	127.23 (13)	H1B—N1—H1C	106 (2)
O1—C1—O2	126.27 (18)	Mn2—O1W—H3D	125.0 (17)
O1—C1—C2	118.88 (18)	Mn2—O1W—H3E	110.0 (17)
O2—C1—C2	114.84 (17)	H3D—O1W—H3E	112 (2)
N1—C2—C3	110.42 (17)	H4B—O2W—H4A	103 (2)

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

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Crystal data

C6H18MnN2O6·2(Br)·2(H2O)	Z = 2
Mr = 465.01	F(000) = 462
Monoclinic, P21/c	Dx = 1.846 Mg m^−3
a = 4.7592 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 19.571 (2) Å	µ = 5.59 mm^−1
c = 9.1998 (11) Å	T = 100 K
β = 102.450 (2)°	Needle, colourless
V = 836.72 (18) Å^3	0.30 × 0.07 × 0.07 mm

Data collection

Bruker APEX-II CCD diffractometer	2500 independent reflections
Radiation source: microsource	2207 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.043
ω scans	θmax = 30.8°, θmin = 2.5°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −6→6
Tmin = 0.507, Tmax = 0.746	k = −27→27
12568 measured reflections	l = −13→13

Refinement

Refinement on F^2	5 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.062	w = 1/[σ^2(Fo^2) + (0.025P)^2 + 0.5P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2500 reflections	Δρmax = 0.83 e Å^−3
110 parameters	Δρmin = −0.43 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.

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

	x	y	z	Uiso*/Ueq
Br1	1.15542 (5)	0.74336 (2)	0.50714 (2)	0.01593 (7)
Mn1	0.5000	0.5000	0.5000	0.00944 (10)
O1	0.8292 (3)	0.56913 (7)	0.46041 (16)	0.0115 (3)
O2	1.2030 (3)	0.56632 (7)	0.34946 (16)	0.0126 (3)
C1	0.9536 (4)	0.58471 (10)	0.3589 (2)	0.0107 (4)
C2	0.7976 (4)	0.63027 (11)	0.2311 (2)	0.0133 (4)
H2	0.9384	0.6632	0.2038	0.016*
C3	0.6662 (5)	0.58766 (12)	0.0954 (2)	0.0208 (5)
H3A	0.5347	0.5538	0.1226	0.031*
H3B	0.8194	0.5642	0.0590	0.031*
H3C	0.5597	0.6175	0.0170	0.031*
N1	0.5703 (4)	0.66897 (9)	0.2837 (2)	0.0126 (3)
H1A	0.475 (5)	0.6959 (11)	0.212 (2)	0.015*
H1B	0.651 (5)	0.6954 (11)	0.361 (2)	0.015*
H1C	0.445 (5)	0.6410 (11)	0.312 (3)	0.015*
O1W	0.4823 (3)	0.55852 (8)	0.69944 (18)	0.0166 (3)
H3D	0.351 (5)	0.5763 (13)	0.714 (3)	0.020*
H3E	0.610 (5)	0.5800 (13)	0.718 (3)	0.020*
O2W	0.9919 (4)	0.63300 (9)	0.75833 (19)	0.0207 (4)
H4A	0.984 (6)	0.6528 (14)	0.688 (3)	0.025*
H4B	1.048 (6)	0.6569 (14)	0.820 (3)	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.01858 (12)	0.01419 (11)	0.01396 (11)	−0.00378 (8)	0.00117 (8)	−0.00216 (7)
Mn1	0.00871 (19)	0.0086 (2)	0.0109 (2)	0.00049 (15)	0.00185 (15)	0.00159 (15)
O1	0.0104 (7)	0.0106 (7)	0.0134 (7)	−0.0006 (5)	0.0022 (6)	0.0013 (5)
O2	0.0101 (7)	0.0127 (7)	0.0152 (7)	0.0019 (5)	0.0031 (6)	0.0031 (5)
C1	0.0114 (9)	0.0078 (8)	0.0120 (9)	−0.0005 (7)	0.0005 (7)	−0.0018 (7)
C2	0.0114 (9)	0.0149 (9)	0.0134 (10)	0.0022 (8)	0.0023 (8)	0.0024 (7)
C3	0.0239 (12)	0.0231 (11)	0.0134 (10)	0.0054 (9)	−0.0007 (9)	−0.0019 (8)
N1	0.0109 (8)	0.0119 (8)	0.0143 (9)	0.0014 (6)	0.0010 (7)	0.0037 (7)
O1W	0.0149 (8)	0.0157 (8)	0.0194 (8)	−0.0006 (6)	0.0043 (7)	−0.0043 (6)
O2W	0.0238 (9)	0.0221 (9)	0.0155 (9)	−0.0044 (7)	0.0026 (7)	−0.0042 (6)

Geometric parameters (Å, º)

Mn1—O1^i	2.1595 (14)	C2—H2	1.0000
Mn1—O1	2.1595 (14)	C3—H3A	0.9800
Mn1—O1W^i	2.1799 (16)	C3—H3B	0.9800
Mn1—O1W	2.1799 (16)	C3—H3C	0.9800
Mn1—O2^ii	2.1811 (14)	N1—H1A	0.890 (17)
Mn1—O2^iii	2.1811 (14)	N1—H1B	0.899 (17)
O1—C1	1.247 (2)	N1—H1C	0.886 (17)
O2—C1	1.261 (2)	O1W—H3D	0.752 (19)
O2—Mn1^iv	2.1811 (14)	O1W—H3E	0.73 (2)
C1—C2	1.534 (3)	O2W—H4A	0.75 (2)
C2—N1	1.485 (3)	O2W—H4B	0.74 (2)
C2—C3	1.519 (3)
O1^i—Mn1—O1	180.00 (6)	N1—C2—C1	108.25 (16)
O1^i—Mn1—O1W^i	88.50 (6)	C3—C2—C1	110.88 (17)
O1—Mn1—O1W^i	91.50 (6)	N1—C2—H2	109.1
O1^i—Mn1—O1W	91.50 (6)	C3—C2—H2	109.1
O1—Mn1—O1W	88.50 (6)	C1—C2—H2	109.1
O1W^i—Mn1—O1W	180.0	C2—C3—H3A	109.5
O1^i—Mn1—O2^ii	94.90 (5)	C2—C3—H3B	109.5
O1—Mn1—O2^ii	85.10 (5)	H3A—C3—H3B	109.5
O1W^i—Mn1—O2^ii	85.16 (6)	C2—C3—H3C	109.5
O1W—Mn1—O2^ii	94.84 (6)	H3A—C3—H3C	109.5
O1^i—Mn1—O2^iii	85.10 (5)	H3B—C3—H3C	109.5
O1—Mn1—O2^iii	94.90 (5)	C2—N1—H1A	110.6 (16)
O1W^i—Mn1—O2^iii	94.84 (6)	C2—N1—H1B	109.5 (16)
O1W—Mn1—O2^iii	85.16 (6)	H1A—N1—H1B	108 (2)
O2^ii—Mn1—O2^iii	180.0	C2—N1—H1C	111.1 (16)
C1—O1—Mn1	139.35 (13)	H1A—N1—H1C	108 (2)
C1—O2—Mn1^iv	128.09 (13)	H1B—N1—H1C	109 (2)
O1—C1—O2	126.02 (19)	Mn1—O1W—H3D	125 (2)
O1—C1—C2	119.12 (17)	Mn1—O1W—H3E	109 (2)
O2—C1—C2	114.86 (17)	H3D—O1W—H3E	112 (3)
N1—C2—C3	110.36 (17)	H4A—O2W—H4B	106 (3)

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

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Crystal data

C6H18MnN2O6·2(I)·2(H2O)	F(000) = 534
Mr = 558.99	Dx = 2.062 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.794 (3) Å	Cell parameters from 265 reflections
b = 20.114 (11) Å	θ = 2.4–18.2°
c = 9.482 (5) Å	µ = 4.19 mm^−1
β = 100.047 (10)°	T = 100 K
V = 900.3 (9) Å^3	Needle, colourless
Z = 2	0.23 × 0.04 × 0.02 mm

Data collection

Bruker APEX CCD diffractometer	3312 independent reflections
Radiation source: microsource	2231 reflections with I > 2σ(I)
Multilayer optics monochromator	θmax = 26.4°, θmin = 2.4°
ω scans	h = −5→5
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	k = 0→25
Tmin = 0.327, Tmax = 0.745	l = 0→11
3312 measured reflections

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.143	w = 1/[σ^2(Fo^2) + (0.060P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3312 reflections	Δρmax = 1.07 e Å^−3
111 parameters	Δρmin = −1.76 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. Refined as a 2-component twin.

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

	x	y	z	Uiso*/Ueq
I1	1.16518 (16)	0.74663 (3)	0.50202 (7)	0.0201 (2)
Mn1	0.5000	0.5000	0.5000	0.0156 (5)
O1	0.8296 (15)	0.5664 (3)	0.4572 (7)	0.0158 (16)
O2	1.2155 (15)	0.5634 (3)	0.3541 (7)	0.0165 (16)
C1	0.963 (2)	0.5804 (4)	0.3597 (11)	0.015 (2)
C2	0.815 (2)	0.6226 (5)	0.2343 (11)	0.018 (2)
H2	0.9558	0.6551	0.2083	0.021*
C3	0.711 (3)	0.5799 (5)	0.1055 (11)	0.023 (2)
H3A	0.5604	0.5504	0.1264	0.034*
H3B	0.8677	0.5532	0.0825	0.034*
H3C	0.6358	0.6083	0.0236	0.034*
N1	0.584 (2)	0.6600 (4)	0.2804 (10)	0.0172 (19)
H1A	0.48 (2)	0.684 (4)	0.207 (8)	0.021*
H1B	0.65 (2)	0.689 (4)	0.355 (8)	0.021*
H1C	0.439 (17)	0.631 (4)	0.290 (11)	0.021*
O3	0.4664 (18)	0.5568 (4)	0.6922 (9)	0.024 (2)
H3D	0.333 (19)	0.581 (5)	0.696 (13)	0.028*
H3E	0.57 (2)	0.588 (5)	0.700 (12)	0.028*
O4	0.9751 (19)	0.6267 (4)	0.7476 (8)	0.025 (2)
H4B	0.96 (3)	0.651 (5)	0.814 (6)	0.030*
H4A	0.96 (3)	0.651 (5)	0.678 (6)	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0220 (4)	0.0186 (4)	0.0193 (4)	−0.0021 (3)	0.0023 (3)	−0.0029 (3)
Mn1	0.0135 (12)	0.0159 (11)	0.0177 (11)	−0.0003 (10)	0.0034 (10)	0.0022 (9)
O1	0.018 (4)	0.015 (3)	0.015 (4)	−0.001 (3)	0.002 (3)	0.003 (3)
O2	0.014 (4)	0.016 (4)	0.022 (4)	0.001 (3)	0.010 (3)	0.003 (3)
C1	0.016 (6)	0.009 (5)	0.022 (6)	−0.001 (5)	0.004 (5)	0.000 (4)
C2	0.012 (6)	0.016 (5)	0.027 (6)	0.002 (4)	0.006 (5)	0.001 (4)
C3	0.026 (7)	0.026 (6)	0.016 (5)	0.004 (5)	0.001 (5)	0.001 (4)
N1	0.013 (5)	0.014 (4)	0.023 (5)	0.001 (4)	0.002 (5)	0.001 (4)
O3	0.023 (5)	0.012 (4)	0.037 (5)	0.001 (3)	0.008 (4)	−0.003 (3)
O4	0.033 (5)	0.028 (5)	0.015 (4)	−0.007 (4)	0.007 (4)	−0.002 (3)

Geometric parameters (Å, º)

Mn1—O1^i	2.161 (7)	C2—H2	1.0000
Mn1—O1	2.161 (7)	C3—H3A	0.9800
Mn1—O2^ii	2.177 (7)	C3—H3B	0.9800
Mn1—O2^iii	2.177 (7)	C3—H3C	0.9800
Mn1—O3^i	2.180 (8)	N1—H1A	0.93 (5)
Mn1—O3	2.180 (8)	N1—H1B	0.93 (5)
O1—C1	1.243 (12)	N1—H1C	0.93 (5)
O2—C1	1.270 (12)	O3—H3D	0.81 (7)
O2—Mn1^iv	2.177 (7)	O3—H3E	0.80 (7)
C1—C2	1.530 (13)	O4—H4B	0.81 (5)
C2—N1	1.467 (13)	O4—H4A	0.81 (5)
C2—C3	1.507 (13)
O1^i—Mn1—O1	180.0 (3)	N1—C2—C1	108.9 (8)
O1^i—Mn1—O2^ii	85.2 (3)	C3—C2—C1	110.9 (8)
O1—Mn1—O2^ii	94.8 (3)	N1—C2—H2	108.4
O1^i—Mn1—O2^iii	94.8 (3)	C3—C2—H2	108.4
O1—Mn1—O2^iii	85.2 (3)	C1—C2—H2	108.4
O2^ii—Mn1—O2^iii	180.0	C2—C3—H3A	109.5
O1^i—Mn1—O3^i	89.8 (3)	C2—C3—H3B	109.5
O1—Mn1—O3^i	90.2 (3)	H3A—C3—H3B	109.5
O2^ii—Mn1—O3^i	95.5 (3)	C2—C3—H3C	109.5
O2^iii—Mn1—O3^i	84.5 (3)	H3A—C3—H3C	109.5
O1^i—Mn1—O3	90.2 (3)	H3B—C3—H3C	109.5
O1—Mn1—O3	89.8 (3)	C2—N1—H1A	113 (7)
O2^ii—Mn1—O3	84.5 (3)	C2—N1—H1B	112 (7)
O2^iii—Mn1—O3	95.5 (3)	H1A—N1—H1B	108 (9)
O3^i—Mn1—O3	180.0	C2—N1—H1C	109 (7)
C1—O1—Mn1	140.0 (6)	H1A—N1—H1C	94 (9)
C1—O2—Mn1^iv	128.9 (6)	H1B—N1—H1C	119 (9)
O1—C1—O2	126.0 (9)	Mn1—O3—H3D	121 (9)
O1—C1—C2	118.5 (9)	Mn1—O3—H3E	110 (9)
O2—C1—C2	115.6 (9)	H3D—O3—H3E	92 (10)
N1—C2—C3	111.8 (9)	H4B—O4—H4A	106 (9)

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