A new MnII coordination polymer with a double chain structure

metal-organic papers

Acta Cryst.(2006). E62, m1453–m1455 doi:10.1107/S1600536806019647 Che and Liu _[Mn(C

8H4O4)(C19H12N4)]

m1453

Structure Reports Online

ISSN 1600-5368

A new Mn

coordination polymer with a

double-chain structure

Guang-Bo Che* and Chun-Bo Liu

Department of Chemistry, Jilin Normal University, Siping 136000, People’s Republic of China

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 292 K

Mean(C–C) = 0.004 A˚ Rfactor = 0.044 wRfactor = 0.118

Data-to-parameter ratio = 15.2

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

Received 3 May 2006 Accepted 25 May 2006

#2006 International Union of Crystallography

All rights reserved

In the title compound, poly[[(2-phenyl-1H-1,3,7,8,-tetra-azacyclopenta[l]phenanthrene)manganese(II)]- -benzene-1,3-dicarboxylato], [Mn(C8H4O4)(C19H12N4)]n, the Mn

II

atom is hexacoordinated by two N atoms from the phenanthrene ligand, and four O atoms from three different benzene-1,3-dicarboxylate (m-BDC) ligands. The MnIIatoms are bridged by the m-BDC ligands, forming a double-chain structure. Moreover, neighbouring double chains are in contact through

– interactions, generating a two-dimensional supra-molecular structure.

Comment

In recent years, metal coordination polymers have received much attention for their intriguing structural features and potential applications (Eddaoudiet al., 2002; Maet al., 2001, 2003). In general, two different types of interactions (covalent bonds and non-covalent intermolecular forces) can be used to construct varied supramolecular architectures. On this basis, a number of compounds have been prepared from one-dimen-sional covalently bonded chains, yielding extended two-dimensional or three-two-dimensional supramolecular archi-tectures through – interactions or hydrogen bonds. 1,10-Phenanthroline (phen) is an important ligand, having often been used to build novel supramolecular architectures due to its excellent coordinating ability and large conjugated system that can easily form – interactions (Chen & Liu, 2002). However, coordination polymers based on 2-phenyl-1H-1,3,7,8-tetraazacyclopenta[l]phenanthrene (L) derived from phen have not been investigated. We report here the crystal structure of [Mn(m-BDC)(L)] (m-BDC is benzene-1,3-dicarboxylate), (I), based on this ligand.

from three m-BDC ligands and two N atoms from one L ligand in a slightly distorted octahedral coordination geometry

(Fig. 1). The average Mn—O and Mn—N distances

[2.2039 (12) and 2.295 (2) A˚ , respectively] are comparable to

those observed for [Mn(bqdc)(phen)(H2O)2]n (bqdc = 2,20

-biquinoline-4,40_{-dicarboxylate) (Yeet al., 2006). Neighbouring}

MnII atoms are bridged bym-BDC ligands, forming a one-dimensional double-chain structure (Fig. 2).

Neighbouring double chains are connected by – inter-actions, generating a two-dimensional supramolecular struc-ture (Fig. 2). The – stacking distance is about 3.57 A˚ betweenLligands in the same double chain, while it is about 3.66 A˚ between adjacent double chains. It is obvious that aromatic interactions help to improve the stability of many current architectures (Noveronet al., 2002).

Experimental

The ligandLwas synthesized according to a literature method (Steck & Day, 1943). Complex (I) was prepared by adding an ethanol solution (10 ml) of L (0.5 mmol) slowly to an aqueous solution (10 ml) of MnCl22H2O (0.5 mmol) andm-H2BDC (1 mmol) while

stirring at 353 K. The resulting solution was filtered and the filtrate was left to stand in air at room temperature for several weeks, yielding pale-yellow crystals of (I) (70% yield based on Mn).

Crystal data

[Mn(C8H4O4)(C19H12N4)]

Mr= 515.38

Monoclinic,C2=c a= 15.390 (5) A˚

b= 15.935 (5) A˚

c= 18.839 (5) A˚ = 109.328 (5)

V= 4360 (2) A˚3

Z= 8

Dx= 1.570 Mg m 3

MoKradiation = 0.65 mm1

T= 292 (2) K Block, light yellow 0.330.280.21 mm

Data collection

Rigaku R-AXIS RAPID diffractometer !scans

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

Tmin= 0.804,Tmax= 0.877

18605 measured reflections 4944 independent reflections 3595 reflections withI> 2(I)

Rint= 0.041

max= 27.5

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.044

wR(F2_{) = 0.118}

S= 1.03 4944 reflections 325 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0634P)2

+ 2.055P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 1.02 e A˚

3

min=0.39 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

N1—Mn1 2.312 (2)

N2—Mn1 2.277 (2)

O1—Mn1 2.347 (2)

O2—Mn1 2.2430 (18)

O3—Mn1i

2.1211 (17)

O4—Mn1ii 2.1046 (19)

O4ii

—Mn1—O3iii

98.59 (7) O4ii—Mn1—O2 85.22 (7) O3iii

—Mn1—O2 112.13 (8)

O4ii

—Mn1—N2 84.82 (8)

O3iii—Mn1—N2 158.76 (7)

O2—Mn1—N2 89.00 (8)

O4ii

—Mn1—N1 123.62 (8)

O3iii

—Mn1—N1 89.51 (7)

O2—Mn1—N1 141.86 (7)

N2—Mn1—N1 71.50 (7)

O4ii

—Mn1—O1 141.21 (7)

O3iii

—Mn1—O1 89.82 (7)

O2—Mn1—O1 56.80 (6)

N2—Mn1—O1 100.67 (7)

N1—Mn1—O1 94.06 (7)

Symmetry codes: (i) x;yþ1;zþ1

2; (ii) xþ2;yþ1;zþ1; (iii) x;yþ1;z1

2.

metal-organic papers

m1454

8H4O4)(C19H12N4)] Acta Cryst.(2006). E62, m1453–m1455 Figure 1

The asymmetric structure together with additional atoms to complete the Mn coordination, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (A)x, 1y,1

2zfor O3A; 2x, 1y, 1zfor O4A.]

Figure 2

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 A˚ and Uiso(H)= 1.2Ueq(C). The highest

residual electron-density peak is located 1.04 A˚ from atom H2.

Data collection: PROCESS-AUTO (Rigaku, 1998); cell

refine-ment: PROCESS-AUTO; data reduction: PROCESS-AUTO;

program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:SHELXTL-Plus(Sheldrick, 1990); software used to prepare material for publication:SHELXTL-Plus.

The authors thank Jilin Normal University for supporting this work.

References

Chen, X.-M. & Liu, G.-F. (2002).Chem. Eur. J.8, 4811–4817.

Eddaoudi, M., Kim, J., O’Keeffe, M. & Yaghi, O. M. (2002).J. Am. Chem. Soc.

124, 376–377.

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

Ma, B.-Q., Gao, S., Sun, H.-L. & Xu, G.-X. (2001).J. Chem. Soc. Dalton Trans.

pp. 130–133.

Ma, J.-F., Yang, J., Zheng, G.-L., Li, L. & Liu, J.-F. (2003).Inorg. Chem.42, 7531–7534.

Noveron, J. C., Lah, M. S., Sesto, R. E. D., Arif, A. M., Miller, J. S. & Stang, P. J. (2002).J. Am. Chem. Soc.124, 6613–6625.

Rigaku (1998).PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Sheldrick, G. M. (1990).SHELXTL-Plus. Siemens Analytical X-ray

Instru-ments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Steck, E. A. & Day, A. R. (1943).J. Am. Chem. Soc.65, 452–456.

Ye, J.-W., Zhang, P., Ye, K.-Q., Zhang, H.-Y., Jiang, S.-M., Ye, L., Yang, G.-D. & Wang, Y. (2006).J. Solid State Chem.179, 438–449.

metal-organic papers

Acta Cryst.(2006). E62, m1453–m1455 Che and Liu _[Mn(C

supporting information

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Acta Cryst. (2006). E62, m1453–m1455

supporting information

Acta Cryst. (2006). E62, m1453–m1455 [https://doi.org/10.1107/S1600536806019647]

A new Mn

coordination polymer with a double-chain structure

Guang-Bo Che and Chun-Bo Liu

poly[[(2-phenyl-1H-1,3,7,8,- tetraazacyclopenta[l]phenanthrene)manganese(II)]- µ-benzene-1,3-dicarboxylato]

Crystal data

[Mn(C8H4O4)(C19H12N4)] Mr = 515.38

Monoclinic, C2/c

Hall symbol: -C 2yc

a = 15.390 (5) Å

b = 15.935 (5) Å

c = 18.839 (5) Å

β = 109.328 (5)°

V = 4360 (2) Å3 Z = 8

F(000) = 2104

Dx = 1.570 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 18605 reflections

θ = 3.4–27.4°

µ = 0.65 mm−1 T = 292 K

Block, light yellow 0.33 × 0.28 × 0.21 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Radiation source: rotor target Graphite monochromator

Detector resolution: 10.0 pixels mm-1 ω scans

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

Tmin = 0.804, Tmax = 0.877

18605 measured reflections 4944 independent reflections 3595 reflections with I > 2σ(I)

Rint = 0.041

θmax = 27.5°, θmin = 3.3° h = −19→19

k = −20→20

l = −22→23

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.044} wR(F2_{) = 0.118} S = 1.03 4944 reflections 325 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) + (0.0634P)2 + 2.055P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001 Δρmax = 1.02 e Å−3 Δρmin = −0.39 e Å−3

Special details

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Acta Cryst. (2006). E62, m1453–m1455

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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

C1 0.7972 (2) 0.25337 (18) 0.17220 (15) 0.0444 (7)

H1 0.7753 0.3051 0.1507 0.053*

C2 0.7636 (2) 0.18117 (18) 0.13070 (16) 0.0541 (8)

H2 0.7216 0.1851 0.0822 0.065*

C3 0.7927 (2) 0.10466 (18) 0.16160 (15) 0.0458 (7)

H3 0.7703 0.0559 0.1346 0.055*

C4 0.85687 (17) 0.10006 (15) 0.23441 (13) 0.0294 (5) C5 0.88930 (16) 0.17646 (15) 0.27188 (12) 0.0272 (5) C6 0.95885 (16) 0.17628 (15) 0.34628 (12) 0.0273 (5) C7 0.99598 (17) 0.10059 (16) 0.38220 (13) 0.0311 (5) C8 1.0624 (2) 0.10503 (18) 0.45380 (15) 0.0435 (7)

H8 1.0881 0.0564 0.4795 0.052*

C9 1.0888 (2) 0.18174 (19) 0.48530 (16) 0.0541 (8)

H9 1.1335 0.1859 0.5326 0.065*

C10 1.0487 (2) 0.25419 (19) 0.44656 (15) 0.0483 (7)

H10 1.0674 0.3060 0.4691 0.058*

C11 0.96138 (16) 0.02410 (15) 0.34317 (13) 0.0291 (5) C12 0.89421 (17) 0.02476 (15) 0.27339 (12) 0.0283 (5) C13 0.93155 (17) −0.10420 (16) 0.31284 (14) 0.0321 (5) C14 0.93247 (18) −0.19625 (16) 0.31426 (14) 0.0357 (6) C15 0.9880 (2) −0.23718 (19) 0.37842 (16) 0.0488 (7)

H15 1.0248 −0.2057 0.4188 0.059*

C16 0.9895 (3) −0.3234 (2) 0.38328 (19) 0.0636 (10)

H16 1.0258 −0.3499 0.4271 0.076*

C17 0.9372 (3) −0.3702 (2) 0.3230 (2) 0.0636 (10)

H17 0.9383 −0.4285 0.3259 0.076*

C18 0.8833 (3) −0.3312 (2) 0.25854 (19) 0.0598 (9)

H18 0.8485 −0.3631 0.2177 0.072*

C19 0.8806 (2) −0.24444 (19) 0.25420 (16) 0.0483 (7)

H19 0.8435 −0.2184 0.2105 0.058*

C20 0.84171 (17) 0.41410 (15) 0.41599 (12) 0.0277 (5) C21 0.80534 (16) 0.43324 (15) 0.47878 (12) 0.0272 (5) C22 0.85562 (16) 0.48345 (14) 0.53882 (11) 0.0255 (5)

H22 0.9107 0.5075 0.5389 0.031*

C23 0.82331 (16) 0.49782 (14) 0.59892 (12) 0.0255 (5) C24 0.87878 (16) 0.54917 (15) 0.66563 (12) 0.0281 (5) C25 0.74077 (18) 0.46191 (18) 0.59772 (13) 0.0369 (6)

H25 0.7193 0.4707 0.6378 0.044*

C26 0.69035 (19) 0.4133 (2) 0.53787 (15) 0.0456 (7)

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Acta Cryst. (2006). E62, m1453–m1455

C27 0.72237 (18) 0.39898 (19) 0.47794 (14) 0.0390 (6)

H27 0.6881 0.3664 0.4374 0.047*

N1 0.85880 (14) 0.25225 (13) 0.24090 (11) 0.0316 (5) N2 0.98490 (15) 0.25216 (13) 0.37894 (11) 0.0344 (5) N3 0.87488 (14) −0.05861 (13) 0.25358 (11) 0.0322 (5) N4 0.98414 (14) −0.05725 (14) 0.36733 (11) 0.0362 (5)

H4 1.0240 −0.0735 0.4089 0.043*

O1 0.78898 (13) 0.38171 (12) 0.35566 (9) 0.0388 (4) O2 0.92413 (13) 0.42863 (13) 0.42417 (10) 0.0429 (5) O3 0.85046 (12) 0.55292 (11) 0.72126 (9) 0.0345 (4) O4 0.94784 (13) 0.58707 (12) 0.66173 (10) 0.0414 (5) Mn1 0.91663 (2) 0.36874 (2) 0.314549 (17) 0.02609 (12)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Acta Cryst. (2006). E62, m1453–m1455

O2 0.0389 (11) 0.0609 (13) 0.0350 (10) −0.0098 (9) 0.0203 (8) −0.0152 (9) O3 0.0456 (11) 0.0379 (10) 0.0236 (8) −0.0053 (8) 0.0162 (7) −0.0080 (7) O4 0.0423 (11) 0.0491 (12) 0.0342 (10) −0.0163 (9) 0.0144 (8) −0.0084 (8) Mn1 0.0351 (2) 0.02436 (19) 0.01921 (18) −0.00246 (15) 0.00950 (13) −0.00069 (14)

Geometric parameters (Å, º)

C1—N1 1.328 (3) C16—H16 0.9300

C1—C2 1.391 (4) C17—C18 1.371 (5)

C1—H1 0.9300 C17—H17 0.9300

C2—C3 1.362 (4) C18—C19 1.385 (4)

C2—H2 0.9300 C18—H18 0.9300

C3—C4 1.402 (3) C19—H19 0.9300

C3—H3 0.9300 C20—O2 1.248 (3)

C4—C5 1.413 (3) C20—O1 1.267 (3)

C4—C12 1.425 (3) C20—C21 1.498 (3)

C5—N1 1.356 (3) C20—Mn1 2.639 (2)

C5—C6 1.455 (3) C21—C27 1.384 (3)

C6—N2 1.356 (3) C21—C22 1.392 (3)

C6—C7 1.408 (3) C22—C23 1.398 (3)

C7—C8 1.399 (3) C22—H22 0.9300

C7—C11 1.432 (3) C23—C25 1.387 (3)

C8—C9 1.361 (4) C23—C24 1.506 (3)

C8—H8 0.9300 C24—O4 1.245 (3)

C9—C10 1.396 (4) C24—O3 1.263 (3)

C9—H9 0.9300 C25—C26 1.376 (4)

C10—N2 1.326 (3) C25—H25 0.9300

C10—H10 0.9300 C26—C27 1.392 (4)

C11—C12 1.378 (3) C26—H26 0.9300

C11—N4 1.380 (3) C27—H27 0.9300

C12—N3 1.385 (3) N1—Mn1 2.312 (2)

C13—N4 1.311 (3) N2—Mn1 2.277 (2)

C13—N3 1.375 (3) N4—H4 0.8600

C13—C14 1.467 (4) O1—Mn1 2.347 (2)

C14—C19 1.382 (4) O2—Mn1 2.2430 (18)

C14—C15 1.391 (4) O3—Mn1i _{2.1211 (17)}

C15—C16 1.377 (4) O4—Mn1ii _{2.1046 (19)}

C15—H15 0.9300 Mn1—O4ii _{2.1047 (19)}

C16—C17 1.375 (5) Mn1—O3iii _{2.1211 (17)}

N1—C1—C2 123.3 (3) O2—C20—Mn1 58.01 (12)

N1—C1—H1 118.3 O1—C20—Mn1 62.77 (12)

C2—C1—H1 118.3 C21—C20—Mn1 174.13 (17)

C3—C2—C1 119.5 (2) C27—C21—C22 119.9 (2)

C3—C2—H2 120.3 C27—C21—C20 119.7 (2)

C1—C2—H2 120.3 C22—C21—C20 120.4 (2)

C2—C3—C4 119.4 (2) C21—C22—C23 120.1 (2)

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Acta Cryst. (2006). E62, m1453–m1455

C4—C3—H3 120.3 C23—C22—H22 120.0

C3—C4—C5 117.5 (2) C25—C23—C22 119.3 (2)

C3—C4—C12 125.6 (2) C25—C23—C24 120.1 (2)

C5—C4—C12 116.9 (2) C22—C23—C24 120.6 (2)

N1—C5—C4 122.5 (2) O4—C24—O3 124.2 (2)

N1—C5—C6 117.1 (2) O4—C24—C23 118.3 (2)

C4—C5—C6 120.3 (2) O3—C24—C23 117.5 (2)

N2—C6—C7 122.3 (2) C26—C25—C23 120.7 (2)

N2—C6—C5 116.6 (2) C26—C25—H25 119.6

C7—C6—C5 121.1 (2) C23—C25—H25 119.6

C8—C7—C6 118.1 (2) C25—C26—C27 120.1 (2)

C8—C7—C11 124.5 (2) C25—C26—H26 119.9

C6—C7—C11 117.4 (2) C27—C26—H26 119.9

C9—C8—C7 118.9 (3) C21—C27—C26 119.9 (2)

C9—C8—H8 120.5 C21—C27—H27 120.0

C7—C8—H8 120.5 C26—C27—H27 120.0

C8—C9—C10 119.9 (2) C1—N1—C5 117.7 (2)

C8—C9—H9 120.1 C1—N1—Mn1 125.67 (18)

C10—C9—H9 120.1 C5—N1—Mn1 116.56 (14)

N2—C10—C9 122.7 (3) C10—N2—C6 118.1 (2)

N2—C10—H10 118.6 C10—N2—Mn1 123.80 (18)

C9—C10—H10 118.6 C6—N2—Mn1 118.09 (15)

C12—C11—N4 110.5 (2) C13—N3—C12 105.4 (2)

C12—C11—C7 121.2 (2) C13—N4—C11 104.7 (2)

N4—C11—C7 128.3 (2) C13—N4—H4 127.6

C11—C12—N3 106.0 (2) C11—N4—H4 127.6

C11—C12—C4 123.1 (2) C20—O1—Mn1 88.53 (14)

N3—C12—C4 130.9 (2) C20—O2—Mn1 93.83 (14)

N4—C13—N3 113.3 (2) C24—O3—Mn1i _{120.84 (16)} N4—C13—C14 123.8 (2) C24—O4—Mn1ii _{162.70 (18)} N3—C13—C14 122.9 (2) O4ii_—Mn1—O3iii _{98.59 (7)} C19—C14—C15 118.3 (3) O4ii_{—Mn1—O2 85.22 (7)} C19—C14—C13 122.8 (2) O3iii_{—Mn1—O2 112.13 (8)} C15—C14—C13 119.0 (2) O4ii_{—Mn1—N2 84.82 (8)} C16—C15—C14 121.2 (3) O3iii_{—Mn1—N2 158.76 (7)}

C16—C15—H15 119.4 O2—Mn1—N2 89.00 (8)

C14—C15—H15 119.4 O4ii_{—Mn1—N1 123.62 (8)}

C17—C16—C15 119.6 (3) O3iii_{—Mn1—N1 89.51 (7)}

C17—C16—H16 120.2 O2—Mn1—N1 141.86 (7)

C15—C16—H16 120.2 N2—Mn1—N1 71.50 (7)

C18—C17—C16 120.2 (3) O4ii_{—Mn1—O1 141.21 (7)} C18—C17—H17 119.9 O3iii_{—Mn1—O1 89.82 (7)}

C16—C17—H17 119.9 O2—Mn1—O1 56.80 (6)

C17—C18—C19 120.1 (3) N2—Mn1—O1 100.67 (7)

C17—C18—H18 119.9 N1—Mn1—O1 94.06 (7)

C19—C18—H18 119.9 O4ii_{—Mn1—C20 113.23 (7)} C14—C19—C18 120.6 (3) O3iii_{—Mn1—C20 103.52 (7)}

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Acta Cryst. (2006). E62, m1453–m1455

C18—C19—H19 119.7 N2—Mn1—C20 94.18 (7)

O2—C20—O1 120.6 (2) N1—Mn1—C20 118.75 (8)

O2—C20—C21 119.7 (2) O1—Mn1—C20 28.70 (7)

O1—C20—C21 119.7 (2)