metal-organic papers
Acta Cryst.(2005). E61, m1105–m1107 doi:10.1107/S1600536805014017 Hu and Zhu [Mn(C
9H8O4)(C12H8N2)(H2O)]H2O
m1105
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
catena
-Poly[[[aqua(1,10-phenanthroline)-manganese(II)]-
l
-
endo
-norbornene-
cis
-5,6-dicarboxylato] monohydrate]
Mao-Lin Hua* and Nan-Wen Zhub
a
Department of Chemistry and Materials Science, Wenzhou Normal College, Wenzhou 325027, People’s Republic of China, and
bSchool of Environmental Science and
Engineering, Shanghai Jiao Tong University, Shanghai 200240, People’s Republic of China
Correspondence e-mail: hu403cn@yahoo.com.cn
Key indicators Single-crystal X-ray study
T= 298 K
Mean(C–C) = 0.004 A˚
Rfactor = 0.040
wRfactor = 0.099
Data-to-parameter ratio = 12.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
In the title compound, {[Mn(endc)(phen)(H2O)]H2O}n[phen is 1,10-phenanthroline (C12H8N2) and endc is the endo -norbornene-cis-5,6-dicarboxylate anion (C9H8O4)], each Mn
II
ion is surrounded by two N atoms from a phen ligand, four O atoms from water molecules and two carboxylate groups of two endc anions, with one endc carboxylate group coordi-nating in a monodentate fashion and the other in a chelating fashion, forming a distorted MnO4N2 octahedron. The endc anions act as bridges between MnIIions, resulting in a zigzag chain structure along the [010] axis.
Comment
Carboxylate anions can coordinate to metal ions in versatile binding modes, such as monodentate, chelating bidentate, bridging bidentate and bridging tridentate, generating varied and sometimes surprising molecular architectures (Zhang et al., 1990). Numerous complexes with carboxylate anions have been extensively studied (Hu et al., 2003, 2004; Wang et al., 2003), but only three Mn complexes including endo -norbor-nene-cis-5,6-dicarboxylate anions (endc) have been char-acterized to date (Hartunget al., 1993; Devereuxet al., 1995; Baumeister & Hartung, 1997). Thus, we have selected the Mn– endc–phen system (phen is 1,10-phenanthroline) in order to extend this research and we present here the crystal structure of the title compound, namely [Mn(endc)(phen)(H2O)]H2O, (I).
In the polymeric structure of (I), the Mn centre possesses a distorted octahedral geometry (Fig. 1 and Table 1). The equatorial plane consists of one phen N atom, one carboxylate
O atom from an endc anion and two carboxylate O atoms from another symmetry-related endc anion, while the two axial sites are occupied by an aqua O atom and the other phen N atom. The equatorial plane N2/O1/O3i/O4i [symmetry code: (i) 1x, y1
2, 1
2z] is seriously distorted, with an r.m.s. deviation of 0.233 A˚ . The interaxial O5—Mn1—N1 angle [160.44 (7)] is also distorted.
The two carboxylate functionalities of each endc anion show different coordination modes: one is chelating bidentate, the other is monodentate. Moreover, each endc anion acts as a bridge to link two adjacent MnII ions, with an Mn Mni separation of 5.6983 (10) A˚ [symmetry code: (i) 1x,y1
2, 1
2z], forming a zigzag chain structure along the [010] axis (Fig. 2).
In the crystal structure, O—H O hydrogen-bond inter-actions strengthen the above-mentioned zigzag chains (Table 2).
Experimental
The title compound was synthesized by the hydrothermal method using a mixture of 1,10-phenanthroline (2 mmol, 0.36 g), MnCl22H2O (1 mmol, 0.16 g),endo-norbornene-cis-5,6-dicarboxylic
acid (1 mmol, 0.18 g) and water (20 ml) in a 30 ml Teflon-lined stainless steel reactor. The solution was heated to 432 K for 4 d. After slow cooling of the reaction system to room temperature, pink block crystals of (I) were collected and washed with distilled water.
Crystal data
[Mn(C9H8O4)(C12H8N2)(H2O)] -H2O
Mr= 451.33 Monoclinic, P21=c
a= 10.941 (3) A˚
b= 9.135 (2) A˚
c= 20.013 (4) A˚ = 103.605 (4) V= 1944.1 (8) A˚3
Z= 4
Dx= 1.542 Mg m
3 MoKradiation Cell parameters from 4067
reflections = 2.5–24.9
= 0.72 mm1
T= 298 (2) K Block, pink
0.270.230.21 mm
Data collection
Bruker APEX CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Bruker, 2002)
Tmin= 0.829,Tmax= 0.863 9928 measured reflections
3501 independent reflections 3002 reflections withI> 2(I)
Rint= 0.020 max= 25.3
h=13!9
k=9!10
l=24!23
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.040
wR(F2) = 0.099
S= 1.07 3501 reflections 271 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0491P)2 + 0.9627P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.32 e A˚
3
min=0.25 e A˚
3
Table 1
Selected geometric parameters (A˚ ,).
Mn1—O1 2.0992 (16) Mn1—O5 2.1384 (18) Mn1—O3i 2.2165 (17) Mn1—N2 2.2633 (19)
Mn1—O4i
2.3015 (16) Mn1—N1 2.3045 (19) Mn1—Mn1i 5.6983 (10)
O1—Mn1—O5 86.91 (7) O1—Mn1—O3i
98.63 (6) O5—Mn1—O3i
108.27 (7) O1—Mn1—N2 104.11 (7) O5—Mn1—N2 88.88 (8) O3i
—Mn1—N2 152.23 (7) O1—Mn1—O4i 153.64 (6) O5—Mn1—O4i 89.91 (7) O3i —Mn1—O4i 57.73 (6) N2—Mn1—O4i 101.98 (6) O1—Mn1—N1 103.44 (6) O5—Mn1—N1 160.44 (7) O3i
—Mn1—N1 86.83 (7) N2—Mn1—N1 72.62 (7) O4i
—Mn1—N1 87.83 (6)
Symmetry code: (i) 1x;y1 2;
1 2z.
Table 2
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O5—H5A O2 0.82 1.91 2.666 (2) 152 O5—H5B O3ii
0.82 1.87 2.677 (2) 169 O6—H6A O2 0.82 2.06 2.773 (4) 145
Symmetry code: (ii)x;y1;z.
metal-organic papers
m1106
Hu and Zhu [Mn(C [image:2.610.47.293.73.290.2]9H8O4)(C12H8N2)(H2O)]H2O Acta Cryst.(2005). E61, m1105–m1107
Figure 1
The coordination environment of the MnIIion in (I), with the atom
numbering for the asymmetric unit, showing displacement ellipsoids at the 30% probability level. Unlabelled atoms are related by the symmetry operator (1x;y1
[image:2.610.46.295.360.508.2]2; 1 2z).
Figure 2
Water H atoms were found in difference maps and regularized using the restraints O—H = 0.820 (1) A˚ and H H = 1.39 (1) A˚ . In the final cycles of refinement, these H atoms were constrained to ride on their parent O atoms, with Uiso(H) = 1.2Ueq(parent atom). H
atoms bonded to C atoms were positioned geometrically and allowed to ride on their parent atoms at distances of Csp2—H = 0.93 A˚ with Uiso(H) = 1.2Ueq(parent atom), Csp
3
—H = 0.97 A˚ withUiso(H) =
1.5Ueq(parent atom) for methylene H, and Csp 3
—H = 0.98 A˚ with Uiso(H) = 1.5Ueq(parent atom) for methine H.
Data collection:SMART(Bruker, 2002); cell refinement:SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication:SHELXL97.
This work was supported by the Wenzhou Technology Project Foundation of China (grant No. S2004A004), the Zhejiang Provincial Natural Science Foundation of China
(grant No. Y404118) and the National Natural Science Foundation of China (grant No. 20471043).
References
Baumeister, U. & Hartung, H. (1997).Acta Cryst.C53, 1246–1248.
Bruker (2002).SADABS (Version 2.03), SAINT (Version 6.02), SMART
(Version 5.62) andSHELXTL(Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.
Devereux, M., Curran, M., McCann, M., Casey, M. T. & McKee, V. (1995).
Polyhedron,14, 2247–2253.
Hartung, H., Baumeister, U., Kaplonek, R. & Fechtel, G. (1993).Z. Anorg. Allg. Chem.619, 1196–1202.
Hu, M.-L., Xiao, H.-P., Wang, S. & Li, X.-H. (2003).Acta Cryst.C59, m454– m455.
Hu, M.-L., Yuan, J.-X., Xiao, H.-P. & Chen, F. (2004).Acta Cryst.C60, m235– 237.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 (Release 97-2). University of Go¨ttingen, Germany.
Wang, M., Xia, J., Jin, L., Cai, G. & Lu, S. (2003).J. Mol. Struct.655, 443– 449.
Zhang, D. L., Huang, C. H. & Xu, G. X. (1990).Chin. J. Chem . 8, 529– 535.
metal-organic papers
Acta Cryst.(2005). E61, m1105–m1107 Hu and Zhu [Mn(C
supporting information
sup-1
Acta Cryst. (2005). E61, m1105–m1107
supporting information
Acta Cryst. (2005). E61, m1105–m1107 [https://doi.org/10.1107/S1600536805014017]
catena
-Poly[[[aqua(1,10-phenanthroline)manganese(II)]-
µ
-
endo
-norbornene-cis
-5,6-dicarboxylato] monohydrate]
Mao-Lin Hu and Nan-Wen Zhu
catena-Poly[[[aqua(1,10-phenanthroline)manganese(II)]-µ-endo-norbornene- cis-5,6-dicarboxylato]
monohydrate]
Crystal data
[Mn(C9H8O4)(C12H8N2)(H2O)]·H2O
Mr = 451.33
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 10.941 (3) Å
b = 9.135 (2) Å
c = 20.013 (4) Å
β = 103.605 (4)°
V = 1944.1 (8) Å3
Z = 4
F(000) = 932
Dx = 1.542 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4067 reflections
θ = 2.5–24.9°
µ = 0.72 mm−1
T = 298 K Block, pink
0.27 × 0.23 × 0.21 mm
Data collection
Bruker APEX CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2002)
Tmin = 0.829, Tmax = 0.863
9928 measured reflections 3501 independent reflections 3002 reflections with I > 2σ(I)
Rint = 0.020
θmax = 25.3°, θmin = 1.9°
h = −13→9
k = −9→10
l = −24→23
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.040
wR(F2) = 0.099
S = 1.07 3501 reflections 271 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0491P)2 + 0.9627P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.32 e Å−3
supporting information
sup-2
Acta Cryst. (2005). E61, m1105–m1107
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Mn1 0.54328 (3) 0.25324 (4) 0.173606 (17) 0.03121 (13) O1 0.67961 (15) 0.41325 (17) 0.21165 (8) 0.0351 (4) O2 0.79614 (16) 0.32338 (18) 0.30950 (9) 0.0427 (4) O3 0.60661 (16) 0.83219 (17) 0.27767 (8) 0.0368 (4) O4 0.63046 (15) 0.61386 (16) 0.32313 (8) 0.0361 (4) O5 0.65970 (19) 0.10364 (19) 0.24268 (9) 0.0565 (5) H5A 0.7103 0.1486 0.2723 0.068* H5B 0.6354 0.0255 0.2551 0.068* O6 0.9932 (5) 0.1852 (5) 0.4001 (3) 0.236 (3) H6A 0.9576 0.2213 0.3631 0.283* H6B 0.9565 0.1962 0.4310 0.283* N1 0.42814 (18) 0.3548 (2) 0.07296 (9) 0.0336 (4) N2 0.60989 (18) 0.1488 (2) 0.08592 (9) 0.0326 (4) C1 0.9014 (3) 0.7807 (3) 0.33231 (16) 0.0486 (7)
H1 0.8990 0.8878 0.3344 0.058*
C2 0.9013 (3) 0.7027 (3) 0.39818 (15) 0.0520 (7)
H2 0.8748 0.7410 0.4355 0.062*
C3 0.9453 (2) 0.5704 (3) 0.39358 (14) 0.0482 (7)
H3 0.9544 0.4978 0.4269 0.058*
C4 0.9785 (2) 0.5565 (3) 0.32502 (13) 0.0426 (6)
H4 1.0399 0.4802 0.3219 0.051*
C5 0.8544 (2) 0.5534 (2) 0.26790 (12) 0.0338 (5)
H5 0.8801 0.5547 0.2242 0.041*
C6 0.7968 (2) 0.7077 (2) 0.27458 (12) 0.0347 (5)
H6 0.7913 0.7613 0.2315 0.042*
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Acta Cryst. (2005). E61, m1105–m1107
H12 0.2591 0.4957 −0.0981 0.056* C13 0.3983 (2) 0.3567 (3) −0.05095 (12) 0.0391 (6) C14 0.4386 (3) 0.3027 (3) −0.10956 (13) 0.0492 (7) H14 0.4007 0.3384 −0.1530 0.059* C15 0.5299 (3) 0.2018 (3) −0.10306 (13) 0.0473 (7) H15 0.5539 0.1684 −0.1420 0.057* C16 0.5906 (2) 0.1450 (3) −0.03712 (12) 0.0383 (6) C17 0.6855 (2) 0.0385 (3) −0.02794 (14) 0.0457 (6) H17 0.7119 0.0019 −0.0656 0.055* C18 0.7384 (2) −0.0108 (3) 0.03668 (14) 0.0460 (6) H18 0.8009 −0.0820 0.0437 0.055* C19 0.6976 (2) 0.0470 (3) 0.09217 (13) 0.0409 (6) H19 0.7341 0.0119 0.1359 0.049* C20 0.5559 (2) 0.1972 (2) 0.02186 (11) 0.0324 (5) C21 0.4581 (2) 0.3058 (2) 0.01486 (11) 0.0325 (5)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-4
Acta Cryst. (2005). E61, m1105–m1107
C21 0.0391 (13) 0.0278 (11) 0.0292 (12) −0.0102 (10) 0.0052 (10) 0.0000 (9)
Geometric parameters (Å, º)
Mn1—O1 2.0992 (16) C4—C5 1.556 (3)
Mn1—O5 2.1384 (18) C4—H4 0.9800
Mn1—O3i 2.2165 (17) C5—C8 1.522 (3)
Mn1—N2 2.2633 (19) C5—C6 1.563 (3)
Mn1—O4i 2.3015 (16) C5—H5 0.9800
Mn1—N1 2.3045 (19) C6—C9 1.513 (3)
Mn1—Mn1i 5.6983 (10) C6—H6 0.9800
O1—C8 1.270 (3) C7—H7A 0.9700
O2—C8 1.243 (3) C7—H7B 0.9700
O3—C9 1.274 (3) C10—C11 1.391 (3)
O3—Mn1ii 2.2165 (17) C10—H10 0.9300
O4—C9 1.240 (3) C11—C12 1.361 (4)
O4—Mn1ii 2.3015 (16) C11—H11 0.9300
O5—H5A 0.8200 C12—C13 1.403 (4)
O5—H5B 0.8200 C12—H12 0.9300
O6—H6A 0.8200 C13—C21 1.404 (3)
O6—H6B 0.8200 C13—C14 1.434 (4)
N1—C10 1.323 (3) C14—C15 1.343 (4)
N1—C21 1.356 (3) C14—H14 0.9300
N2—C19 1.322 (3) C15—C16 1.428 (4)
N2—C20 1.354 (3) C15—H15 0.9300
C1—C2 1.499 (4) C16—C17 1.403 (4)
C1—C7 1.538 (4) C16—C20 1.406 (3)
C1—C6 1.571 (3) C17—C18 1.363 (4)
C1—H1 0.9800 C17—H17 0.9300
C2—C3 1.312 (4) C18—C19 1.394 (4)
C2—H2 0.9300 C18—H18 0.9300
C3—C4 1.505 (4) C19—H19 0.9300
C3—H3 0.9300 C20—C21 1.441 (3)
C4—C7 1.542 (4)
O1—Mn1—O5 86.91 (7) C1—C6—H6 108.5 O1—Mn1—O3i 98.63 (6) C1—C7—C4 92.9 (2)
O5—Mn1—O3i 108.27 (7) C1—C7—H7A 113.1
O1—Mn1—N2 104.11 (7) C4—C7—H7A 113.1 O5—Mn1—N2 88.88 (8) C1—C7—H7B 113.1 O3i—Mn1—N2 152.23 (7) C4—C7—H7B 113.1
O1—Mn1—O4i 153.64 (6) H7A—C7—H7B 110.5
O5—Mn1—O4i 89.91 (7) O2—C8—O1 124.8 (2)
O3i—Mn1—O4i 57.73 (6) O2—C8—C5 120.2 (2)
N2—Mn1—O4i 101.98 (6) O1—C8—C5 114.80 (19)
supporting information
sup-5
Acta Cryst. (2005). E61, m1105–m1107
N2—Mn1—N1 72.62 (7) N1—C10—C11 123.7 (2) O4i—Mn1—N1 87.83 (6) N1—C10—H10 118.2
C10—N1—C21 117.5 (2) C11—C10—H10 118.2 C10—N1—Mn1 127.39 (16) C12—C11—C10 119.1 (3) C21—N1—Mn1 115.10 (15) C12—C11—H11 120.5 C19—N2—C20 117.7 (2) C10—C11—H11 120.5 C19—N2—Mn1 125.63 (16) C11—C12—C13 119.5 (2) C20—N2—Mn1 116.63 (15) C11—C12—H12 120.2 C2—C1—C7 100.5 (2) C13—C12—H12 120.2 C2—C1—C6 107.1 (2) C12—C13—C21 117.4 (2) C7—C1—C6 100.4 (2) C12—C13—C14 123.4 (2) C2—C1—H1 115.6 C21—C13—C14 119.2 (2) C7—C1—H1 115.6 C15—C14—C13 121.4 (2)
C6—C1—H1 115.6 C15—C14—H14 119.3
C3—C2—C1 107.4 (3) C13—C14—H14 119.3 C3—C2—H2 126.3 C14—C15—C16 120.8 (2)
C1—C2—H2 126.3 C14—C15—H15 119.6
C2—C3—C4 108.3 (3) C16—C15—H15 119.6 C2—C3—H3 125.9 C17—C16—C20 117.6 (2) C4—C3—H3 125.9 C17—C16—C15 122.8 (2) C3—C4—C7 100.0 (2) C20—C16—C15 119.6 (2) C3—C4—C5 108.4 (2) C18—C17—C16 119.3 (2) C7—C4—C5 99.2 (2) C18—C17—H17 120.3
C3—C4—H4 115.7 C16—C17—H17 120.3
C7—C4—H4 115.7 C17—C18—C19 119.1 (2)
C5—C4—H4 115.7 C17—C18—H18 120.5
C8—C5—C4 117.55 (19) C19—C18—H18 120.5 C8—C5—C6 118.22 (18) N2—C19—C18 123.5 (2) C4—C5—C6 102.72 (18) N2—C19—H19 118.2
C8—C5—H5 105.7 C18—C19—H19 118.2
C4—C5—H5 105.7 N2—C20—C16 122.7 (2) C6—C5—H5 105.7 N2—C20—C21 117.8 (2) C9—C6—C5 117.98 (18) C16—C20—C21 119.5 (2) C9—C6—C1 110.9 (2) N1—C21—C13 122.8 (2) C5—C6—C1 101.96 (19) N1—C21—C20 117.8 (2) C9—C6—H6 108.5 C13—C21—C20 119.3 (2) C5—C6—H6 108.5
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O5—H5A···O2 0.82 1.91 2.666 (2) 152 O5—H5B···O3iii 0.82 1.87 2.677 (2) 169
O6—H6A···O2 0.82 2.06 2.773 (4) 145
