Bis(μ cantharidinato)bis­­[(1,10 phenanthroline)manganese(II)] hexa­hydrate

metal-organic papers

Acta Cryst.(2007). E63, m241–m243 doi:10.1107/S1600536806053566 Shenget al. _[Mn

2(C10H12O5)2(C12H8N2)2]6H2O

m241

Structure Reports

Online

ISSN 1600-5368

Bis(

l

-cantharidinato)bis[(1,10-phenanthroline)-manganese(II)] hexahydrate

Guo-Ding Sheng, Liang Shen,* Yin-Zhi Jin and Juan Mei

Department of Chemistry, Hangzhou Teachers College, Hangzhou, People’s Republic of China

Correspondence e-mail: shenchem@hotmail.com

Key indicators

Single-crystal X-ray study T= 298 K

Mean(C–C) = 0.002 A˚ Rfactor = 0.030 wRfactor = 0.074

Data-to-parameter ratio = 16.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 3 December 2006 Accepted 11 December 2006

#2007 International Union of Crystallography All rights reserved

The title compound {systematic name: bis( -2,3-dimethyl-7- oxobicyclo[2.2.1]heptane-2,3-dicarboxylato)bis[(1,10-phenan-throline)manganese(II)] hexahydrate}, [Mn2(C10H12O5)2

-(C12H8N2)2]6H2O, comprises centrosymmetric dinuclear

neutral molecules in which two MnIIcenters are bridged by a single carboxylate group of each of two cantharidinate ligands, together with water molecules. In the complex, each MnII _{atom is in a distorted octahedral geometry, being}

coordinated by two N atoms of one 1,10-phenanthroline ligand, three O atoms from one cantharidinate dianion and one carboxylate O atom from another cantharidinate dianion. Adjacent molecules link to each other through hydrogen bonds involving solvent water molecules and carboxylate groups, forming a three-dimensional network.

Comment

Cantharidine has long been used as a Chinese medicine (Li, 1957). In the past few decades, several studies showed that cantharidine and its derivatives presented potential antitumor capability against lung, colon and breast cancer (Cui et al., 1984; Liet al., 1984; Shimiet al., 1982). A few metal canthar-idinate complexes have been synthesized. Some platinum cantharidine complexes have shown effective antitumor activity. To our knowledge, one platinum and one copper complex with cantharidinate have been structurally char-acterized (Wanget al., 1997; Yinet al., 2003). We report here the preparation and structure of a manganese(II) complex with cantharidinate and 1,10-phenanthroline.

dinuclear molecules. A cantharidinate dianion chelates an MnIIatom by two O atoms from one carboxylate group and one bridging oxo O atom. The MnIIatom is also coordinated by two N atoms of one 1,10-phenanthroline ligand and one carboxylate O atom from another cantharidinate dianion. Each Mn site exhibits a distorted octahedral coordination, withtransbond angles ranging from 153.59 (4) to 168.22 (4) and cis angles from 73.51 (4) to 105.02 (4) _{(Table 1). The} Mn—O(carboxylate) bond distances are comparable with those in [Mn(phen)(cyclohexane-1,1-diacetato)(H2O)2]

trihy-drate (Shen et al., 2005). The Mn—O(bridging oxo) bond distance of 2.4032 (11) A˚ is much longer than those of Mn— O(carboxylate). The Mn—N bond lengths are comparable to the corresponding ones found in [Mn2(mal)(phen)3(H2O)2

Cl]-Cl (Sain et al., 2003). Cantharidinate adopts a chair confor-mation in this complex. One of the carboxylate groups behaves as a monodentate ligand, and the other carboxylate acts in a common syn–anti bridging coordination mode (Policaret al., 1999). The manganese–manganese separation is 4.441 (5) A˚ .

The hydrogen-bonding interactions (Table 2) play an important role in the solid-state structure of the title complex, (I). Adjacent molecules are linked to form a three-dimen-sional chain by hydrogen bonds between a coordinated O atom and water, and between water molecules.

Experimental

An aqueous solution (20 ml) of 2,3-dimethyl-7-oxobicyclo-[2,2,1]-heptane-2,3-dicarboxylic acid (0.214 g, 1 mmol) and Mn2(OH)2CO3 (0.102 g, 0.5 mmol) was heated to reflux temperature on a water-bath for 8 h and was then filtered. To this hot filtrate, an aqueous solution (10 ml) containing 1,10-phenanthroline (0.180 g, 1 mmol) was added. The reaction mixture was stirred at reflux temperature for 12 h. Yellow crystals were collected after cooling the reaction mixture. Yellow single crystals of (I) were obtained by recrystallizing from water.

Crystal data

[Mn2(C10H12O5)2(C12H8N2)2]6H2O

Mr= 1002.79 Monoclinic,C2=c a= 17.806 (5) A˚

b= 20.600 (5) A˚

c= 11.982 (3) A˚

= 90.812 (11)

V= 4395 (2) A˚3

Z= 4

Dx= 1.515 Mg m 3

MoKradiation

= 0.65 mm1

T= 298 (1) K Needle, yellow 0.300.150.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

!scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995)

Tmin= 0.830,Tmax= 0.937

21189 measured reflections 5033 independent reflections 3904 reflections withF2_{> 2(F}2₎

Rint= 0.029 max= 27.5

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.030

wR(F2_{) = 0.074}

S= 1.00 5033 reflections 303 parameters

H-atom parameters constrained

w= 1/[0.0003Fo 2

+(Fo 2

)]/(4Fo 2

) (/)max< 0.001

max= 0.35 e A˚ 3

min=0.34 e A˚ 3

Table 1

Selected geometric parameters (A˚ ,_).

Mn1—O1 2.1206 (11) Mn1—O3 2.1276 (10) Mn1—O4i 2.1222 (11) Mn1—O5 2.4032 (11) Mn1—N1 2.3042 (12)

Mn1—N2 2.2353 (11) O1—C13 1.2824 (18) O2—C13 1.2344 (18) O3—C20 1.2533 (16) O4—C20 1.2597 (16)

O1—Mn1—O3 95.40 (4) O1—Mn1—O4i

104.27 (4) O1—Mn1—N1 92.69 (4) O1—Mn1—N2 153.59 (4) O3—Mn1—O4i

91.41 (4) O3—Mn1—N1 159.30 (4) O3—Mn1—N2 91.27 (4) O4i

—Mn1—N1 105.02 (4) O4i

—Mn1—N2 101.08 (4) O4i

—Mn1—O5 168.22 (4) O5—Mn1—O1 78.08 (4) O5—Mn1—O3 76.85 (4) O5—Mn1—N1 86.27 (4) O5—Mn1—N2 78.63 (4) N1—Mn1—N2 73.51 (4)

Symmetry code: (i)xþ1 2;yþ

1 2;zþ1.

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O6—H601 O9i

0.91 2.04 2.949 (2) 174 O7—H701 O9i

0.90 1.91 2.809 (2) 176 O8—H801 O2 0.91 1.84 2.7466 (18) 176 O8—H802 O7ii

0.92 1.95 2.836 (2) 161 O9—H901 O1 0.91 1.87 2.7710 (17) 178 O9—H902 O8 0.92 1.95 2.772 (2) 147

Symmetry codes: (i)xþ1 2;yþ

1

2;zþ1; (ii)xþ 1 2;y

1 2;z.

All the water H atoms were located in a difference Fourier map and the remaining H atoms were placed in calculated positions, with C—H = 0.93–0.98 A˚ and O—H = 0.90–0.92 A˚. All H atoms were included in the final cycle of refinement in riding mode, withUiso(H) = 1.2Ueq(C,O).

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refine-ment:PROCESS-AUTO; data reduction:CrystalStructure(Rigaku/ Figure 1

al., 1999); program(s) used to refine structure:CRYSTALS (Better-idge et al., 2003); molecular graphics: ORTEP-3 for Windows

(Farrugia, 1997); software used to prepare material for publication:

CrystalStructure(Rigaku/MSC, 2004).

We express our gratitude to the Zhejiang Provincial Natural Science Foundation of China for financial Support through Project No. M203077. We gratefully acknowledge Professor Jian-Ming Gu for the structure analysis and advice.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999).J. Appl. Cryst.32, 115–119.

Betteridge, P. W., Carruthers, J. R., Cooper, R. L., Prout, K. & Watkin, D. J. (2003).J. Appl. Cryst.36, 1487.

Cui, Z. Y., Xu, S. Y., Wang, S. Q., Huang, D. T. & Wang, G. S. (1984).Chin. Pharm. Bull.19, 567–570.

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.

Higashi, T. (1995).ABSCOR. Rigaku Corporation, Tokyo, Japan.

Li, D. H., Li, H. K., Chang, S. K., Hao, X. G., Ma, K. S. & Wang, Z. L. (1984).

Nat. Med. J. China,18, 785–788.

Li, S. Z. (1957).Encyclopedia of Chinese Medical Herbs,40, 1528–1529. Policar, C., Lambert, F., Cesario, M. & Morgenstern-Badarau, I. (1999).Eur. J.

Inorg. Chem.pp. 2201–2207.

Rigaku (1998).PROCESS-AUTO. Version 1.06. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2004). CrystalStructure. Version 3.6.0. Rigaku/MSC, The Woodlands, Texas, USA.

Sain, S., Maji, T. K., Mostafa, G., Lu, T. H. & Chaudhuri, N. R. (2003).Inorg. Chim. Acta,351, 12–20.

Shen, L., Yan, L.-C., Jin, Z.-M. & Zhang, Y.-J. (2005).Acta Cryst.E61, m1419– m1421.

Shimi, I. R., Zaki, Z., Shoukry, S. & Medhat, A. M. (1982).Eur. J. Cancer Clin. Oncol.18, 785–789.

Wang, Y. H., Huang, Z. X. & Wu, G. (1997).Polyhedron,1, 57–59. Yin, F. L., Shen, J. & Li, R. C. (2003).Acta Chem. Sinica,4, 556–561.

metal-organic papers

Acta Cryst.(2007). E63, m241–m243 Shenget al. _[Mn

supporting information

Acta Cryst. (2007). E63, m241–m243 [https://doi.org/10.1107/S1600536806053566]

Bis(

µ

-cantharidinato)bis[(1,10-phenanthroline)manganese(II)] hexahydrate

Guo-Ding Sheng, Liang Shen, Yin-Zhi Jin and Juan Mei

bis(µ-2,3-dimethyl-7-oxobicyclo[2.2.1]heptane-2,3- dicarboxylato)bis[(1,10-phenanthroline)manganese(II)]

hexahydrate

Crystal data

[Mn2(C10H12O5)2(C12H8N2)2]·6H2O

Mr = 1002.79

Monoclinic, C2/c

Hall symbol: -C 2yc

a = 17.806 (5) Å

b = 20.600 (5) Å

c = 11.982 (3) Å

β = 90.812 (11)°

V = 4395 (2) Å3

Z = 4

F(000) = 2088.00

Dx = 1.515 Mg m−3

Mo Kα radiation, λ = 0.71075 Å Cell parameters from 17413 reflections

θ = 3.0–27.5°

µ = 0.65 mm−1

T = 298 K Needle, yellow 0.30 × 0.15 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Detector resolution: 10.00 pixels mm-1

ω scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995)

Tmin = 0.830, Tmax = 0.937

21189 measured reflections

5033 independent reflections 3904 reflections with F2 _{> 2σ(F}2₎

Rint = 0.029

θmax = 27.5°

h = −23→23

k = −26→26

l = −15→14

Refinement

Refinement on F2

R[F2 _{> 2σ(F}2_{)] = 0.030}

wR(F2_{) = 0.074}

S = 1.00 5033 reflections 303 parameters

H-atom parameters constrained

w = 1/[0.0003Fo2 + σ(Fo2)]/(4Fo2)

(Δ/σ)max < 0.001

Δρmax = 0.35 e Å−3

Δρmin = −0.34 e Å−3

Special details

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2_{. R}

-factor (gt) are based on F. The threshold expression of F2 _{> 2.0 σ(F}2_{) is used only for calculating R-factor (gt).}

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

supporting information

sup-2

Acta Cryst. (2007). E63, m241–m243

O2 0.28038 (6) 0.09050 (6) 0.38385 (9) 0.0455 (3) O3 0.17367 (6) 0.24311 (5) 0.53552 (8) 0.0299 (2) O4 0.17555 (6) 0.22806 (6) 0.35272 (8) 0.0338 (2) O5 0.13254 (6) 0.12974 (5) 0.65226 (6) 0.0281 (2) O6 0.000000 (10) 0.29861 (12) 0.250000 (10) 0.0930 (9) O7 0.000000 (10) 0.47324 (10) 0.250000 (10) 0.0642 (6) O8 0.43323 (8) 0.07894 (6) 0.36334 (12) 0.0589 (4) O9 0.43373 (8) 0.10863 (9) 0.58903 (12) 0.0714 (5) N1 0.27147 (6) 0.14483 (6) 0.82519 (10) 0.0309 (3) N2 0.16934 (6) 0.24152 (6) 0.79571 (9) 0.0282 (3) C1 0.32145 (10) 0.09838 (9) 0.84055 (13) 0.0414 (4) C2 0.33484 (11) 0.06794 (9) 0.94276 (14) 0.0473 (5) C3 0.29435 (11) 0.08682 (8) 1.03268 (13) 0.0426 (4) C4 0.24000 (9) 0.13520 (8) 1.02118 (12) 0.0329 (4) C5 0.19501 (10) 0.15837 (9) 1.11146 (12) 0.0378 (4) C6 0.14336 (10) 0.20472 (9) 1.09595 (12) 0.0375 (4) C7 0.13074 (9) 0.23361 (8) 0.98846 (12) 0.0309 (3) C8 0.07725 (10) 0.28202 (9) 0.96785 (12) 0.0389 (4) C9 0.07090 (10) 0.30905 (9) 0.86346 (13) 0.0422 (4) C10 0.11869 (10) 0.28751 (8) 0.77998 (12) 0.0359 (4) C11 0.17556 (8) 0.21388 (6) 0.89842 (11) 0.0263 (3) C12 0.23003 (8) 0.16342 (6) 0.91417 (11) 0.0272 (3) C13 0.24742 (9) 0.10079 (6) 0.47205 (12) 0.0289 (3) C14 0.16239 (9) 0.08531 (6) 0.47822 (11) 0.0267 (3) C15 0.14330 (9) 0.06695 (6) 0.60028 (11) 0.0296 (3) C16 0.06492 (10) 0.03735 (8) 0.61249 (12) 0.0372 (4) C17 0.01408 (9) 0.09706 (8) 0.59338 (12) 0.0350 (4) C18 0.07212 (8) 0.15092 (8) 0.57799 (11) 0.0269 (3) C19 0.11037 (8) 0.14838 (6) 0.46227 (10) 0.0247 (3) C20 0.15695 (8) 0.21127 (6) 0.44957 (11) 0.0251 (3) C21 0.05506 (9) 0.14505 (8) 0.36363 (12) 0.0328 (4) C22 0.14496 (10) 0.03072 (8) 0.39478 (12) 0.0387 (4)

H1 0.3494 0.0852 0.7796 0.050*

H2 0.3708 0.0353 0.9494 0.057*

H3 0.3029 0.0674 1.1018 0.051*

H5 0.2020 0.1407 1.1823 0.045*

H6 0.1150 0.2185 1.1561 0.045*

H8 0.0461 0.2959 1.0247 0.047*

H9 0.0354 0.3411 0.8487 0.051*

H10 0.1147 0.3065 0.7097 0.043*

H15 0.1827 0.0411 0.6370 0.036*

H18 0.0529 0.1941 0.5965 0.032*

H161 0.0555 0.0041 0.5567 0.045*

H162 0.0582 0.0191 0.6863 0.045*

H171 −0.0174 0.0919 0.5273 0.042*

H172 −0.0172 0.1053 0.6574 0.042*

H211 0.0189 0.1114 0.3766 0.039*

H213 0.0297 0.1860 0.3557 0.039*

H221 0.1743 −0.0069 0.4138 0.046*

H222 0.1572 0.0448 0.3209 0.046*

H223 0.0925 0.0201 0.3975 0.046*

H601 0.0230 0.3250 0.3010 0.112*

H701 0.0200 0.4481 0.3040 0.078*

H801 0.3826 0.0823 0.3665 0.071*

H802 0.4438 0.0423 0.3225 0.071*

H901 0.3835 0.1141 0.5812 0.086*

H902 0.4526 0.0941 0.5222 0.085*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-4

Acta Cryst. (2007). E63, m241–m243

Geometric parameters (Å, º)

Mn1—O1 2.1206 (11) C16—C17 1.542 (2)

Mn1—O3 2.1276 (10) C17—C18 1.529 (2)

Mn1—O4i _{2.1222 (11) C18—C19 1.5543 (18)}

Mn1—O5 2.4032 (11) C19—C20 1.547 (2)

Mn1—N1 2.3042 (12) C19—C21 1.5292 (19)

Mn1—N2 2.2353 (11) O6—H601 0.911

O1—C13 1.2824 (18) O6—H601ii _0.911

O2—C13 1.2344 (18) O7—H701 0.899

O3—C20 1.2533 (16) O7—H701ii _0.899

O4—C20 1.2597 (16) O8—H801 0.906

O5—C15 1.4495 (17) O8—H802 0.920

O5—C18 1.4535 (17) O9—H901 0.905

N1—C1 1.318 (2) O9—H902 0.923

N1—C12 1.3602 (18) C1—H1 0.930

N2—C10 1.320 (2) C2—H2 0.930

N2—C11 1.3591 (17) C3—H3 0.930

C1—C2 1.393 (2) C5—H5 0.930

C2—C3 1.362 (2) C6—H6 0.930

C3—C4 1.395 (2) C8—H8 0.930

C4—C5 1.437 (2) C9—H9 0.930

C4—C12 1.4167 (19) C10—H10 0.930

C5—C6 1.337 (2) C15—H15 0.980

C6—C7 1.434 (2) C16—H161 0.970

C7—C8 1.399 (2) C16—H162 0.970

C7—C11 1.411 (2) C17—H171 0.970

C8—C9 1.372 (2) C17—H172 0.970

C9—C10 1.395 (2) C18—H18 0.980

C11—C12 1.432 (2) C21—H211 0.960

C13—C14 1.550 (2) C21—H212 0.960

C14—C15 1.5530 (19) C21—H213 0.960

C14—C19 1.605 (2) C22—H221 0.960

C14—C22 1.534 (2) C22—H222 0.960

C15—C16 1.532 (2) C22—H223 0.960

O1···O9 2.7710 (17) C10···H9xiv _3.317

O2···O8 2.7466 (18) C10···H801i _3.206

O2···C2iii _{3.475 (2) C12···H221}xi _3.374

O4···C5iv _{3.2506 (18) C13···H2}iii _3.575

O4···C6iv _{3.1584 (17) C13···H801 2.761}

O6···O7 3.597 (3) C13···H901 2.751

O6···O9i _{2.949 (2) C15···H222}xi _3.511

O6···O9v _{2.949 (2) C16···H161}xviii _3.051

O6···C21 3.575 (2) C16···H162xiv _3.303

O6···C21ii _{3.575 (2) C16···H171}xviii _3.251

O7···O6 3.597 (3) C16···H172xiv _3.217

O7···O8vii _{2.836 (2) C16···H222}xi _3.418

O7···O9i _{2.809 (2) C16···H223}xviii _3.044

O7···O9v _{2.809 (2) C17···H161}xviii _3.008

O8···O2 2.7466 (18) C17···H162xiv _3.361

O8···O7viii _{2.836 (2) C17···H172}xiv _2.990

O8···O9 2.772 (2) C17···H223xviii _3.073

O8···C9i _{3.565 (2) C18···H172}xiv _3.461

O8···C9ix _{3.367 (2) C20···H6}iv _3.587

O8···C10i _{3.366 (2) C21···H5}iv _3.425

O9···O1 2.7710 (17) C21···H6iv _3.113

O9···O6i _{2.949 (2) C21···H6}xiv _3.391

O9···O7i _{2.809 (2) C21···H211}ii _3.224

O9···O8 2.772 (2) C21···H212ii _3.088

O9···C13 3.587 (2) C21···H213ii _3.128

N1···C6x _{3.572 (2) C22···H5}iv _3.567

N2···C5x _{3.354 (2) C22···H15}iii _3.499

C2···O2xi _{3.475 (2) C22···H162}iii _3.093

C3···C8x _{3.540 (2) C22···H171}xviii _3.531

C3···C9x _{3.438 (2) H1···O7}i _2.965

C4···C7x _{3.553 (2) H1···O9 2.793}

C4···C11x _{3.580 (2) H221···N1}iii _3.499

C5···O4xii _{3.2506 (18) H221···C1}iii _3.355

C5···N2x _{3.354 (2) H221···C2}iii _3.138

C5···C11x _{3.501 (2) H221···C3}iii _3.037

C6···O4xii _{3.1584 (17) H221···C4}iii _3.157

C6···N1x _{3.572 (2) H221···C12}iii _3.374

C6···C12x _{3.533 (2) H221···H2}iii _3.567

C7···C4x _{3.553 (2) H221···H3}iii _3.426

C7···C12x _{3.453 (2) H221···H15}iii _3.396

C8···C3x _{3.540 (2) H221···H162}iii _3.406

C9···O8i _{3.565 (2) H221···H171}xviii _3.380

C9···O8xiii _{3.367 (2) H221···H172}xviii _3.548

C9···C3x _{3.438 (2) H222···C5}iv _3.503

C10···O8i _{3.366 (2) H222···C15}iii _3.511

C11···C4x _{3.580 (2) H222···C16}iii _3.418

C11···C5x _{3.501 (2) H222···H5}iv _2.708

C12···C6x _{3.533 (2) H222···H15}iii _2.868

C12···C7x _{3.453 (2) H222···H162}iii _2.712

C13···O9 3.587 (2) H223···C16xviii _3.044

C21···O6 3.575 (2) H223···C17xviii _3.073

C21···C21ii _{3.333 (2) H223···H161}xviii _2.745

Mn1···H901 3.244 H223···H162xviii _2.965

O1···H801 3.095 H223···H162iii _2.717

O1···H901 1.867 H223···H171xviii _2.820

O1···H902 3.173 H223···H172xviii _2.980

O2···H2iii _{3.145 H601···O4 3.421}

O2···H3iv _{3.442 H601···O7 3.139}

supporting information

sup-6

Acta Cryst. (2007). E63, m241–m243

O2···H801 1.842 H601···O9v _3.276

O2···H802 3.170 H601···C8xiv _3.433

O2···H901 3.013 H601···H1i _3.095

O2···H902 3.466 H601···H6iv _3.255

O3···H901i _{3.407 H601···H6}xiv _3.340

O4···H5iv _{2.767 H601···H8}iv _3.395

O4···H6iv _{2.584 H601···H8}xiv _2.511

O4···H601 3.421 H601···H213 2.941

O4···H901i _{3.512 H601···H213}ii _3.545

O5···H172xiv _{3.131 H601···H701 2.535}

O6···H6iv _{2.872 H601···H701}ii _2.926

O6···H6xiv _{2.872 H601···H901}i _2.504

O6···H8iv _{2.833 H601···H902}i _2.725

O6···H8xiv _{2.833 H701···O6 3.165}

O6···H213 2.693 H701···O8vi _3.193

O6···H213ii _{2.693 H701···O8}vii _3.469

O6···H701 3.165 H701···O9i _1.912

O6···H701ii _{3.165 H701···O9}v _3.201

O6···H901i _{3.393 H701···C1}i _3.468

O6···H901v _{3.393 H701···H1}i _2.636

O7···H1i _{2.965 H701···H1}v _3.123

O7···H1v _{2.965 H701···H2}v _3.217

O7···H2i _{3.346 H701···H601 2.535}

O7···H2v _{3.346 H701···H601}ii _2.926

O7···H601 3.139 H701···H802vi _2.381

O7···H601ii _{3.139 H701···H802}vii _2.552

O7···H801vi _{3.384 H701···H901}i _2.533

O7···H801vii _{3.384 H701···H902}i _2.303

O7···H802vi _{1.951 H801···O1 3.095}

O7···H802vii _{1.951 H801···O2 1.842}

O7···H901i _{3.392 H801···O7}viii _3.384

O7···H901v _{3.392 H801···O9 2.857}

O7···H902i _{3.166 H801···C2}iii _3.340

O7···H902v _{3.166 H801···C10}i _3.206

O8···H2iii _{2.807 H801···C13 2.761}

O8···H9i _{3.085 H801···H2}iii _2.628

O8···H9ix _{2.462 H801···H3}iv _3.470

O8···H10i _{2.654 H801···H9}i _3.373

O8···H701viii _{3.193 H801···H9}ix _3.155

O8···H701xv _{3.469 H801···H10}i _2.467

O8···H802xvi _{3.235 H801···H901 2.654}

O8···H901 2.861 H801···H902 2.242

O8···H902 1.954 H802···O2 3.170

O9···H1 2.793 H802···O7viii _1.951

O9···H2iii _{3.577 H802···O8}xvi _3.235

O9···H8ix _{2.917 H802···O9 3.480}

O9···H9ix _{3.577 H802···C2}iii _3.328

O9···H601xvii _{3.276 H802···H2}iii _2.572

O9···H701i _{1.912 H802···H9}i _3.183

O9···H701xvii _{3.201 H802···H9}ix _2.917

O9···H801 2.857 H802···H10i _3.305

O9···H802 3.480 H802···H701viii _2.381

N1···H6x _{3.471 H802···H701}xv _2.552

N1···H221xi _{3.499 H802···H802}xvi _2.670

N2···H5x _{3.345 H802···H902 2.622}

C1···H8x _{3.579 H901···Mn1 3.244}

C1···H221xi _{3.355 H901···O1 1.867}

C1···H701i _{3.468 H901···O2 3.013}

C1···H901 3.328 H901···O3i _3.407

C2···H8x _{3.535 H901···O4}i _3.512

C2···H221xi _{3.138 H901···O6}i _3.393

C2···H801xi _{3.340 H901···O7}i _3.392

C2···H802xi _{3.328 H901···O8 2.861}

C3···H15xi _{3.540 H901···C1 3.328}

C3···H221xi _{3.037 H901···C13 2.751}

C4···H221xi _{3.157 H901···H1 2.533}

C5···H212xii _{3.054 H901···H2}iii _3.465

C5···H222xii _{3.503 H901···H8}ix _3.512

C6···H171xiv _{3.538 H901···H601}i _2.504

C6···H211xiv _{3.489 H901···H701}i _2.533

C6···H212xii _{3.013 H901···H801 2.654}

C6···H213xiv _{3.168 H902···O1 3.173}

C7···H18xiv _{3.506 H902···O2 3.466}

C7···H171xiv _{3.552 H902···O7}i _3.166

C7···H213xiv _{3.573 H902···O8 1.954}

C8···H18xiv _{3.032 H902···C8}ix _3.449

C8···H213xiv _{3.482 H902···C9}ix _3.485

C8···H601xiv _{3.433 H902···H2}xix _3.383

C8···H902xiii _{3.449 H902···H2}iii _3.156

C9···H3x _{3.416 H902···H8}ix _2.812

C9···H9xiv _{3.216 H902···H9}ix _2.891

C9···H10xiv _{3.407 H902···H601}i _2.725

C9···H18xiv _{3.275 H902···H701}i _2.303

C9···H902xiii _{3.485 H902···H801 2.242}

C10···H3x _{3.581 H902···H802 2.622}

C10···H5x _3.542

O1—Mn1—O3 95.40 (4) O5—C18—C19 101.90 (10)

O1—Mn1—O4i _{104.27 (4) C17—C18—C19 112.87 (12)}

O1—Mn1—N1 92.69 (4) C14—C19—C18 100.39 (10) O1—Mn1—N2 153.59 (4) C14—C19—C20 112.35 (11) O3—Mn1—O4i _{91.41 (4) C14—C19—C21 114.83 (11)}

supporting information

sup-8

Acta Cryst. (2007). E63, m241–m243

O4i_{—Mn1—N2 101.08 (4) O3—C20—O4 123.42 (13)}

O4i_{—Mn1—O5 168.22 (4) O3—C20—C19 118.61 (11)}

O5—Mn1—O1 78.08 (4) O4—C20—C19 117.96 (11)

O5—Mn1—O3 76.85 (4) H601—O6—H601ii _106.6

O5—Mn1—N1 86.27 (4) H701—O7—H701ii _109.5

O5—Mn1—N2 78.63 (4) H801—O8—H802 107.2

N1—Mn1—N2 73.51 (4) H901—O9—H902 108.8

Mn1—O1—C13 125.87 (9) N1—C1—H1 118.1

Mn1—O3—C20 119.31 (9) C2—C1—H1 118.1

Mn1i_{—O4—C20 117.86 (9) C1—C2—H2 120.6}

C15—O5—C18 96.08 (10) C3—C2—H2 120.6

Mn1—N1—C1 128.35 (10) C2—C3—H3 120.0

Mn1—N1—C12 113.74 (9) C4—C3—H3 120.0

C1—N1—C12 117.89 (12) C4—C5—H5 119.3

Mn1—N2—C10 125.09 (9) C6—C5—H5 119.3

Mn1—N2—C11 116.25 (9) C5—C6—H6 119.3

C10—N2—C11 118.48 (12) C7—C6—H6 119.3

N1—C1—C2 123.80 (15) C7—C8—H8 120.1

C1—C2—C3 118.75 (17) C9—C8—H8 120.1

C2—C3—C4 120.03 (15) C8—C9—H9 120.6

C3—C4—C5 123.82 (14) C10—C9—H9 120.6

C3—C4—C12 117.42 (13) N2—C10—H10 118.4

C5—C4—C12 118.75 (14) C9—C10—H10 118.4

C4—C5—C6 121.50 (14) O5—C15—H15 112.9

C5—C6—C7 121.34 (14) C14—C15—H15 112.9

C6—C7—C8 123.53 (14) C16—C15—H15 112.9

C6—C7—C11 118.96 (14) C15—C16—H161 111.4

C8—C7—C11 117.49 (13) C15—C16—H162 111.4

C7—C8—C9 119.83 (15) C17—C16—H161 111.4

C8—C9—C10 118.77 (16) C17—C16—H162 111.4

N2—C10—C9 123.27 (14) H161—C16—H162 109.5

N2—C11—C7 122.14 (13) C16—C17—H171 111.4

N2—C11—C12 118.01 (12) C16—C17—H172 111.4 C7—C11—C12 119.84 (12) C18—C17—H171 111.4

N1—C12—C4 122.10 (13) C18—C17—H172 111.4

N1—C12—C11 118.35 (12) H171—C17—H172 109.5

C4—C12—C11 119.54 (12) O5—C18—H18 113.1

O1—C13—O2 123.92 (14) C17—C18—H18 113.1

O1—C13—C14 117.23 (12) C19—C18—H18 113.1

C14—C15—C16 113.50 (12) H221—C22—H222 109.5 C15—C16—C17 101.65 (12) H221—C22—H223 109.5 C16—C17—C18 101.55 (12) H222—C22—H223 109.5 O5—C18—C17 101.77 (11)

O1—Mn1—O3—C20 16.28 (10) C5—C4—C12—N1 178.81 (14) O3—Mn1—O1—C13 −22.09 (12) C5—C4—C12—C11 −0.2 (2) O1—Mn1—O4i_—C20i _{51.85 (11) C12—C4—C5—C6 1.3 (2)}

O4i_{—Mn1—O1—C13 −114.93 (12) C4—C5—C6—C7 −0.3 (2)}

O1—Mn1—N1—C1 23.69 (14) C5—C6—C7—C8 179.74 (17) O1—Mn1—N1—C12 −154.53 (9) C5—C6—C7—C11 −2.0 (2) N1—Mn1—O1—C13 138.83 (12) C6—C7—C8—C9 177.27 (16) O1—Mn1—N2—C10 −117.50 (13) C6—C7—C11—N2 −176.56 (14) O1—Mn1—N2—C11 57.55 (15) C6—C7—C11—C12 3.1 (2) N2—Mn1—O1—C13 81.81 (15) C8—C7—C11—N2 1.8 (2) O3—Mn1—O4i_—C20i _{−44.09 (10) C8—C7—C11—C12 −178.55 (14)}

O4i_{—Mn1—O3—C20 120.76 (10) C11—C7—C8—C9 −1.0 (2)}

O3—Mn1—N1—C1 136.71 (14) C7—C8—C9—C10 −0.3 (2) O3—Mn1—N1—C12 −41.52 (17) C8—C9—C10—N2 1.0 (2) N1—Mn1—O3—C20 −96.27 (15) N2—C11—C12—N1 −1.4 (2) O3—Mn1—N2—C10 −12.65 (12) N2—C11—C12—C4 177.65 (13) O3—Mn1—N2—C11 162.40 (10) C7—C11—C12—N1 178.95 (13) N2—Mn1—O3—C20 −138.13 (10) C7—C11—C12—C4 −2.0 (2) O4i_{—Mn1—N1—C1 −81.85 (14) O1—C13—C14—C15 −27.46 (17)}

O4i_{—Mn1—N1—C12 99.92 (10) O1—C13—C14—C19 82.75 (15)}

N1—Mn1—O4i_—C20i _{148.65 (10) O1—C13—C14—C22 −150.41 (13)}

O4i_{—Mn1—N2—C10 79.03 (13) O2—C13—C14—C15 150.55 (13)}

O4i_{—Mn1—N2—C11 −105.92 (10) O2—C13—C14—C19 −99.24 (15)}

N2—Mn1—O4i_—C20i _{−135.65 (10) O2—C13—C14—C22 27.60 (18)}

N1—Mn1—N2—C10 −178.41 (13) C13—C14—C15—O5 83.87 (13) N1—Mn1—N2—C11 −3.36 (9) C13—C14—C15—C16 −168.19 (12) N2—Mn1—N1—C1 −179.21 (14) C13—C14—C19—C18 −116.63 (12) N2—Mn1—N1—C12 2.57 (9) C13—C14—C19—C20 −2.59 (14) Mn1—O1—C13—O2 132.53 (13) C13—C14—C19—C21 120.76 (13) Mn1—O1—C13—C14 −49.57 (17) C15—C14—C19—C18 −1.11 (13) Mn1—O3—C20—O4 −119.08 (13) C15—C14—C19—C20 112.92 (11) Mn1—O3—C20—C19 61.55 (15) C15—C14—C19—C21 −123.72 (12) Mn1i_{—O4—C20—O3 14.25 (19) C19—C14—C15—O5 −34.76 (13)}

Mn1i_{—O4—C20—C19 −166.39 (9) C19—C14—C15—C16 73.17 (14)}

supporting information

sup-10

Acta Cryst. (2007). E63, m241–m243

C12—N1—C1—C2 −0.9 (2) C16—C17—C18—C19 74.85 (14) Mn1—N2—C10—C9 174.67 (12) O5—C18—C19—C14 36.49 (13) Mn1—N2—C11—C7 −176.57 (11) O5—C18—C19—C20 −81.13 (13) Mn1—N2—C11—C12 3.80 (16) O5—C18—C19—C21 159.74 (11) C10—N2—C11—C7 −1.2 (2) C17—C18—C19—C14 −71.88 (13) C10—N2—C11—C12 179.19 (13) C17—C18—C19—C20 170.50 (11) C11—N2—C10—C9 −0.3 (2) C17—C18—C19—C21 51.37 (17) N1—C1—C2—C3 −0.0 (2) C14—C19—C20—O3 −90.97 (14) C1—C2—C3—C4 0.8 (2) C14—C19—C20—O4 89.64 (14) C2—C3—C4—C5 −179.65 (17) C18—C19—C20—O3 18.59 (17) C2—C3—C4—C12 −0.7 (2) C18—C19—C20—O4 −160.80 (12) C3—C4—C5—C6 −179.71 (17) C21—C19—C20—O3 141.71 (13) C3—C4—C12—N1 −0.2 (2) C21—C19—C20—O4 −37.69 (17) C3—C4—C12—C11 −179.22 (14)

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

y+1/2, −z+1/2; (viii) x+1/2, y−1/2, z; (ix) x+1/2, −y+1/2, z−1/2; (x) −x+1/2, −y+1/2, −z+2; (xi) x, −y, z+1/2; (xii) x, y, z+1; (xiii) x−1/2, −y+1/2, z+1/2; (xiv) −x, y, −z+3/2; (xv) −x+1/2, y−1/2, −z+1/2; (xvi) −x+1, y, −z+1/2; (xvii) x+1/2, −y+1/2, z+1/2; (xviii) −x, −y, −z+1; (xix) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O(6)—H(601)···O(9)i _{0.91 2.04 2.949 (2) 174}

O(7)—H(701)···O(9)i _{0.90 1.91 2.809 (2) 176}

O(8)—H(801)···O(2) 0.91 1.84 2.7466 (18) 176 O(8)—H(802)···O(7)viii _{0.92 1.95 2.836 (2) 161}

O(9)—H(901)···O(1) 0.91 1.87 2.7710 (17) 178 O(9)—H(902)···O(8) 0.92 1.95 2.772 (2) 147