(C4H12N2)[Zn2(PO4)(HPO4)(H2PO4)], a layered zinc phosphate with inter­calated N methyl­propane 1,3 diaminium cations

metal-organic papers

m1354

4H14N2)[Zn2(PO4)(HPO4)(H2PO4)] doi:10.1107/S1600536805018908 Acta Cryst.(2005). E61, m1354–m1356

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

(C

H

N

)[Zn

(PO

)(HPO

)(H

PO

)], a layered

zinc phosphate with intercalated

N

-methylpropane-1,3-diaminium cations

Natasˇa Zabukovec Logar,a* Nevenka Rajic´,bDjordje

Stojakovic´,bSanja S˘ajic´,bAmalija Golobicˇcand Vencˇeslav Kaucˇicˇa

a_{National Institute of Chemistry, Hajdrihova 19,}

1000 Ljubljana, Slovenia,b_{Faculty of}

Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Beograd, Serbia and Montenegro, andc_{Faculty of Chemistry and}

Chemical Technology, University of Ljubljana, Asˇkercˇeva 5, 1000 Ljubljana, Slovenia

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 295 K

Mean(C–C) = 0.009 A˚

Rfactor = 0.028

wRfactor = 0.086

Data-to-parameter ratio = 14.5

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

The title compound, catena-poly[[N -methylpropane-1,3-diaminium [-phosphato-(-hydrogen phosphato)( -dihy-drogen phosphato)dizincate(II)]], {(C4H14N2)[Zn2(PO4

)(H-PO4)(H2PO4)]}n, consists of macroanionic [Zn2(PO4)(HPO4

)-(H2PO4)] 2

layers and intercalated (C4H12N2) 2+

cations. The layers are built up from ZnO4 and PO4/HPO4/H2PO4

tetra-hedra that result in small channels of approximate diameter 3.7 A˚ within the layers. Framework-to-framework O—H O and template-to-framework N—H O hydrogen bonds are important in stabilizing the structure.

Comment

Zinc phosphates have become an important class of open-framework materials due to their large structural variety and capability of forming chain, layer and framework structures (Raoet al., 2001; Natarajan, 2002; Norquist & O’Hare, 2004). Generally, these solids have been synthesized through a synthetic route requiring hydrothermal conditions and the presence of organic amines which act as templates.

The title compound, (I) (Fig. 1), has been obtained in the presence of a 3-methylaminopropylamine (MPA) template. In the asymmetric unit of (I), there are two crystallographically distinct Zn atoms and three P atoms, all of them being tetra-hedrally coordinated. The Zn—O distances (Table 1) are in the range 1.911 (3)–1.965 (4) A˚ , in accordance with literature values (Harrison, 2001; Guo et al., 2005). All of the P—O distances that lie in the range 1.499 (4)–1.547 (3) A˚ corre-spond to P—O—Zn bridges, whereas those in the 1.560 (4)–

Received 26 May 2005 Accepted 14 June 2005 Online 24 June 2005

Figure 1

1.566 (4) A˚ range were assigned to the terminal P—OH groups (Guo et al., 2005). In addition, P3—O7 is an unpro-tonated terminal bond with a length of 1.545 (4) A˚ , which is greater than the typical P O distance. The P3—O7 bond may be lengthened because O7 accepts a short strong hydrogen bond (Table 2) from an O8—H8 grouping in an adjacent layer. Overall, this results in the presence of phosphate, hydrogen phosphate and dihydrogen phosphate groups in (I). The four-membered rings (i.e. four tetrahedral centres), as primary building units of the structure of (I), are formed by a link of the —Zn1—O6—P3—O1—Zn2—O2—P2—O5— atoms. Neighbouring rings are connected by two oxygen bridges (P3—O9—Zn1 and Zn2—O10—P2). Such a ring connection gives rise to a channel of about 3.7 A˚ diameter. Adjacent columns are linked into a layer by the Zn1—O3—P1—O4— Zn2 bridges. The negative charge of the zinc phosphate layers is compensated by diprotonated diamine molecules, which lie between the layers parallel to the ring channels. The proto-nated diamine molecules interact with the zinc phosphate layers through N—H O hydrogen bonds (Table 2) with N O separations from 2.823 (6) to 3.089 (5) A˚ . The inter-layer O—H O hydrogen bonds result in O O separations ranging from 2.480 (5) to 2.580 (5) A˚ .

Very recently a similar zinc phosphate structure was reported by Jensenet al.(2005). The use of a different organic amine, namelyN,N0_{-dimethylethylendiamine, in that synthesis}

led to a structure with very similar unit-cell dimensions and the same inorganic zinc phosphate layers, but a different arrangement of organic cations and consequently a higher structural symmetry (space groupP2/n).

Experimental

A mixture having a relative molar composition of Zn(OAc)2:

5.5H3PO4:2MPA:100H2O, where Zn(OAc)2is zinc acetate dihydrate

(Aldrich) and MPA is a 98% 3-methylaminopropylamine solution (Fluka) was prepared by successive additions of phosphoric acid and MPA to a solution of zinc acetate in water with vigorous stirring. Crystallization, which was performed hydrothermally at 437 K for 2 d, gave parallelepiped-shaped crystals of (I).

Crystal data

(C4H14N2)[Zn2(PO4)(HPO4

)-(H2PO4)]

Mr= 508.85 Monoclinic,Pn a= 11.8920 (2) A˚

b= 5.1318 (1) A˚

c= 12.3063 (2) A˚

= 98.125 (1) V= 743.48 (2) A˚3

Z= 2

Dx= 2.273 Mg m3

MoKradiation Cell parameters from 1860

reflections

= 2.6–27.5

= 3.61 mm1

T= 295 (2) K Prism, colourless 0.20.20.05 mm

Data collection

Nonius KappaCCD area-detector diffractometer

’and!scans

Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)

Tmin= 0.490,Tmax= 0.835

3295 measured reflections

3108 independent reflections 3029 reflections withI> 2(I)

Rint= 0.014 max= 27.5

h=15!15

k=6!6

l=15!15

Refinement

Refinement onF2

R[F2_{> 2(F}2_{)] = 0.028}

wR(F2) = 0.087

S= 1.19 3108 reflections 214 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0502P)2

+ 0.3227P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001 max= 0.64 e A˚

3 min=0.93 e A˚

3

Absolute structure: Flack (1983), 1399 Friedel pairs

Flack parameter: 0.44 (1)

Table 1

Selected geometric parameters (A˚ ,_).

Zn1—O9i 1.911 (3) Zn1—O5 1.927 (4) Zn1—O3 1.946 (3) Zn1—O6 1.960 (3) Zn2—O1 1.926 (4) Zn2—O10ii

1.928 (3) Zn2—O4 1.963 (3) Zn2—O2 1.965 (3) P1—O3iii

1.499 (4) P1—O4 1.518 (3)

P1—O12 1.560 (4) P1—O11 1.566 (4) P2—O10 1.522 (3) P2—O5 1.525 (3) P2—O2 1.547 (3) P2—O8 1.563 (4) P3—O1 1.517 (4) P3—O9 1.525 (3) P3—O6 1.540 (4) P3—O7 1.545 (4) P3—O1—Zn2 131.9 (2)

P2—O2—Zn2 121.39 (19) P1iv—O3—Zn1 136.9 (3) P1—O4—Zn2 130.0 (2) P2—O5—Zn1 130.9 (2) P3—O6—Zn1 124.30 (18) P2—O8—H8 109.5

P3—O9—Zn1ii

133.9 (2) P2—O10—Zn2i

132.3 (2) N1—C1—C2 112.8 (5) C3—C2—C1 112.8 (5) C2—C3—N2 113.1 (5) C4—N2—C3 113.5 (4)

Symmetry codes: (i) x;yþ1;z; (ii) x;y1;z; (iii) x1 2;y;zþ

1 2; (iv)

xþ1 2;y;z

1 2.

metal-organic papers

Acta Cryst.(2005). E61, m1354–m1356 Logaret al. _(C

4H14N2)[Zn2(PO4)(HPO4)(H2PO4)]

m1355

Figure 2

Polyhedral view of (I), showing zinc–phosphate layers (ZnO4tetrahedra

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O8—H8 O7v

0.82 1.66 2.480 (5) 176 O11—H11 O6vi

0.82 1.76 2.567 (5) 169 O12—H12 O2ii

0.82 1.77 2.580 (5) 167 N1—H1A O7vii

0.89 1.96 2.823 (6) 164 N1—H1B O10viii 0.89 2.25 3.085 (5) 155 N2—H2D O4iv

0.90 2.08 2.938 (5) 159

Symmetry codes: (ii) x;y1;z; (iv) xþ1 2;y;z

1 2; (v) xþ

1 2;y;zþ

1 2; (vi)

x1

2;y1;zþ 1

2; (vii)x;y;z; (viii)x 1

2;yþ1;z 1 2.

The possible centrosymmetric space groupP2/nwas not selected for the refinement because it causes statistical disorder of the non-symmetricN-methylpropane-1,3-diaminium molecules and poorerR factors. We emphasize again that the space group P2/nwas deter-mined in a recently published structure refinement of a similar zinc phosphate, where a symmetric organic molecule, viz. CH3NHCH2CH2NHCH3, was used in the synthesis (Jensen et al.,

2005). H atoms were included at calculated positions (C—H = 0.96– 0.97 A˚ , N—H = 0.89–0.90 A˚ and O—H = 0.82 A˚) and modelled as riding on their attached O, C or N atoms. The value of the Flack parameter indicates an inversion twin.

Data collection: COLLECT (Hooft, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97

(Sheldrick, 1997); program(s) used to refine structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP3 for Windows (Farrugia, 1997) and ATOMS (Dowty, 2004); software used to prepare material for publication:WinGX(Farrugia, 1999).

This work is partially financed by the Slovenian Ministry of Higher Education, Science and Technology (project No. P1– 0021) and the Ministry of Science and Technology of Serbia (project No. OI 1603).

References

Hooft, R. W. W. (2000). COLLECT. Bruker–Nonius BV, Delft, The Netherlands.

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838. Flack, H. D. (1983).Acta Cryst.A39, 876–881.

Guo, G.-S., Wei, Y.-G., Li, J., Wang, Y. & Guo, H.-Y. (2005).Acta Cryst.C61, m87–m89.

Harrison, W. T. A. (2001).Acta Cryst.E57, i72–i74.

Jensen, T. R., Gerentes, N., Jepsen, J., Hazell, R. G. & Jakobsen, H. J. (2005).

Inorg. Chem.44, 658–665.

Natarajan, S. (2002).Inorg. Chem.41, 5530–5537.

Norquist, A. J. & O’Hare, D. (2004).J. Am. Chem. Soc.126, 6673–6679. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,

Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Rao, C. N. R., Natarajan, S., Choudhury, A., Neeraj, S. & Vaidhyanathan, R. (2001).Acta Cryst.B57, 1–12.

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

metal-organic papers

m1356

supporting information

sup-1 Acta Cryst. (2005). E61, m1354–m1356

supporting information

Acta Cryst. (2005). E61, m1354–m1356 [https://doi.org/10.1107/S1600536805018908]

(C

H

N

)[Zn

(PO

)(HPO

)(H

PO

)], a layered zinc phosphate with intercalated

N

-methylpropane-1,3-diaminium cations

Nata

š

a Zabukovec Logar, Nevenka Raji

ć

, Djordje Stojakovi

ć

, Sanja

Š

aji

ć

, Amalija Golobi

č

and

Ven

č

eslav Kau

č

i

č

(I)

Crystal data

C4H14N22+·H3O12P3Zn22−

Mr = 508.85 Monoclinic, Pn Hall symbol: P -2yac a = 11.8920 (2) Å b = 5.1318 (1) Å c = 12.3063 (2) Å β = 98.125 (1)° V = 743.48 (2) Å3

Z = 2 F(000) = 512

Dx = 2.273 Mg m−3

Melting point: structure decomposes befor melting K

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1860 reflections θ = 2.6–27.5°

µ = 3.61 mm−1

T = 295 K Prism, colourless 0.2 × 0.2 × 0.05 mm

Data collection

Nonius KappaCCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan

(DENZO-SMN; Otwinowski & Minor, 1997) Tmin = 0.490, Tmax = 0.835

3295 measured reflections 3108 independent reflections 3029 reflections with I > 2σ(I) Rint = 0.014

θmax = 27.5°, θmin = 2.6°

h = −15→15 k = −6→6 l = −15→15

Refinement

Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.028}

wR(F2_{) = 0.087}

S = 1.19 3108 reflections 214 parameters 2 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) + (0.0502P)2 + 0.3227P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001 Δρmax = 0.64 e Å−3 Δρmin = −0.93 e Å−3

Absolute structure: Flack (1983), racemic twin, 1399 Friedel pairs

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sup-2 Acta Cryst. (2005). E61, m1354–m1356

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 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

Zn1 0.24869 (3) 0.18524 (7) 0.24710 (3) 0.01519 (13) Zn2 0.09146 (3) −0.20501 (7) 0.44526 (3) 0.01475 (13) P1 −0.08139 (13) −0.43124 (15) 0.59410 (12) 0.01723 (16) P2 0.23758 (10) 0.28419 (19) 0.49751 (10) 0.0139 (2) P3 0.09990 (10) −0.30706 (15) 0.19427 (10) 0.0130 (2) O1 0.0437 (3) −0.2051 (5) 0.2891 (3) 0.0232 (8) O2 0.1224 (3) 0.1484 (6) 0.5032 (3) 0.0199 (7) O3 0.3871 (3) 0.2732 (7) 0.1877 (3) 0.0257 (7) O4 −0.0549 (3) −0.2757 (7) 0.4959 (3) 0.0243 (7) O5 0.2944 (3) 0.1748 (5) 0.4036 (3) 0.0218 (7) O6 0.2140 (3) −0.1673 (5) 0.1910 (3) 0.0197 (7) O7 0.0189 (3) −0.2508 (9) 0.0873 (3) 0.0226 (7) O8 0.3149 (3) 0.2200 (7) 0.6077 (3) 0.0215 (7)

H8 0.3818 0.2251 0.5983 0.083 (6)*

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sup-3 Acta Cryst. (2005). E61, m1354–m1356

H4B 0.3848 −0.2221 −0.2808 0.083 (6)* H4C 0.2913 −0.3790 −0.2308 0.083 (6)* N2 0.3017 (4) −0.0026 (8) −0.1809 (3) 0.0364 (9) H2C 0.3102 0.1214 −0.2308 0.083 (6)* H2D 0.3411 0.0477 −0.1165 0.083 (6)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Zn1 0.0158 (3) 0.0139 (2) 0.0165 (3) −0.00030 (14) 0.00468 (19) 0.00010 (15) Zn2 0.0130 (3) 0.0155 (2) 0.0162 (3) −0.00038 (16) 0.00349 (18) −0.00041 (17) P1 0.0167 (3) 0.0178 (4) 0.0188 (3) 0.0015 (4) 0.0081 (2) 0.0013 (4) P2 0.0131 (6) 0.0122 (5) 0.0164 (6) 0.0012 (3) 0.0025 (5) −0.0006 (3) P3 0.0113 (6) 0.0144 (5) 0.0133 (6) 0.0016 (3) 0.0018 (4) 0.0000 (3) O1 0.019 (2) 0.0321 (18) 0.0190 (18) 0.0050 (11) 0.0051 (14) −0.0030 (11) O2 0.0166 (16) 0.0160 (11) 0.0284 (19) −0.0033 (12) 0.0074 (14) −0.0034 (11) O3 0.0180 (18) 0.0325 (17) 0.0288 (19) 0.0015 (12) 0.0115 (14) 0.0074 (14) O4 0.0215 (19) 0.0259 (16) 0.0277 (19) −0.0001 (12) 0.0115 (14) 0.0096 (13) O5 0.0204 (19) 0.0310 (17) 0.0144 (16) 0.0088 (11) 0.0043 (13) −0.0019 (10) O6 0.0167 (17) 0.0129 (12) 0.030 (2) −0.0009 (10) 0.0065 (14) −0.0101 (10) O7 0.0217 (19) 0.0297 (13) 0.0159 (17) 0.0030 (14) 0.0009 (13) 0.0030 (13) O8 0.0158 (17) 0.0290 (17) 0.0183 (17) 0.0015 (12) −0.0021 (12) 0.0041 (12) O9 0.0203 (16) 0.0096 (13) 0.041 (2) 0.0002 (10) 0.0020 (14) −0.0002 (11) O10 0.0196 (17) 0.0131 (14) 0.0397 (19) −0.0008 (10) 0.0017 (14) 0.0025 (11) O11 0.0287 (19) 0.0292 (15) 0.027 (2) −0.0110 (14) 0.0096 (15) 0.0004 (13) O12 0.0288 (19) 0.0405 (19) 0.0196 (17) 0.0149 (14) 0.0091 (14) 0.0041 (13) N1 0.024 (2) 0.0335 (18) 0.030 (2) −0.0041 (14) 0.0034 (15) −0.0059 (15) C1 0.028 (3) 0.124 (7) 0.024 (3) −0.013 (3) 0.008 (2) −0.013 (3) C2 0.029 (3) 0.107 (6) 0.067 (4) −0.021 (3) 0.014 (3) −0.057 (4) C3 0.036 (3) 0.039 (3) 0.068 (4) −0.006 (2) −0.014 (2) 0.001 (3) C4 0.047 (3) 0.029 (2) 0.035 (3) −0.001 (2) 0.007 (2) 0.001 (2) N2 0.036 (2) 0.038 (2) 0.036 (2) −0.0057 (16) 0.0084 (15) −0.0062 (17)

Geometric parameters (Å, º)

Zn1—O9i _{1.911 (3) O11—H11 0.8200}

Zn1—O5 1.927 (4) O12—H12 0.8200

Zn1—O3 1.946 (3) N1—C1 1.465 (7)

Zn1—O6 1.960 (3) N1—H1A 0.8900

Zn2—O1 1.926 (4) N1—H1B 0.8900

Zn2—O10ii _{1.928 (3) N1—H1C 0.8900}

Zn2—O4 1.963 (3) C1—C2 1.518 (9)

Zn2—O2 1.965 (3) C1—H1D 0.9700

P1—O3iii _{1.499 (4) C1—H1E 0.9700}

P1—O4 1.518 (3) C2—C3 1.452 (9)

P1—O12 1.560 (4) C2—H2A 0.9700

P1—O11 1.566 (4) C2—H2B 0.9700

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sup-4 Acta Cryst. (2005). E61, m1354–m1356

P2—O5 1.525 (3) C3—H3A 0.9700

P2—O2 1.547 (3) C3—H3B 0.9700

P2—O8 1.563 (4) C4—N2 1.492 (7)

P3—O1 1.517 (4) C4—H4A 0.9600

P3—O9 1.525 (3) C4—H4B 0.9600

P3—O6 1.540 (4) C4—H4C 0.9600

P3—O7 1.545 (4) N2—H2C 0.9000

O8—H8 0.8200 N2—H2D 0.9000

O9i_{—Zn1—O5 115.08 (14) P1—O11—H11 109.5} O9i_{—Zn1—O3 115.87 (15) P1—O12—H12 109.5} O5—Zn1—O3 104.36 (16) C1—N1—H1A 109.5 O9i_{—Zn1—O6 107.62 (14) C1—N1—H1B 109.5} O5—Zn1—O6 109.99 (13) H1A—N1—H1B 109.5 O3—Zn1—O6 103.25 (15) C1—N1—H1C 109.5 O1—Zn2—O10ii _{113.17 (15) H1A—N1—H1C 109.5} O1—Zn2—O4 99.63 (16) H1B—N1—H1C 109.5 O10ii_{—Zn2—O4 121.41 (14) N1—C1—C2 112.8 (5)} O1—Zn2—O2 112.11 (13) N1—C1—H1D 109.0 O10ii_{—Zn2—O2 109.12 (14) C2—C1—H1D 109.0} O4—Zn2—O2 100.62 (14) N1—C1—H1E 109.0 O3iii_{—P1—O4 115.45 (15) C2—C1—H1E 109.0} O3iii_{—P1—O12 105.4 (2) H1D—C1—H1E 107.8} O4—P1—O12 110.2 (2) C3—C2—C1 112.8 (5) O3iii_{—P1—O11 112.3 (2) C3—C2—H2A 109.0}

O4—P1—O11 105.1 (2) C1—C2—H2A 109.0

O12—P1—O11 108.18 (16) C3—C2—H2B 109.0 O10—P2—O5 112.11 (19) C1—C2—H2B 109.0

O10—P2—O2 110.6 (2) H2A—C2—H2B 107.8

O5—P2—O2 111.0 (2) C2—C3—N2 113.1 (5)

O10—P2—O8 108.4 (2) C2—C3—H3A 109.0

O5—P2—O8 108.1 (2) N2—C3—H3A 109.0

O2—P2—O8 106.4 (2) C2—C3—H3B 109.0

O1—P3—O9 113.01 (19) N2—C3—H3B 109.0

O1—P3—O6 110.16 (19) H3A—C3—H3B 107.8

O9—P3—O6 109.27 (18) N2—C4—H4A 109.5

O1—P3—O7 107.6 (2) N2—C4—H4B 109.5

O9—P3—O7 107.1 (2) H4A—C4—H4B 109.5

O6—P3—O7 109.6 (2) N2—C4—H4C 109.5

P3—O1—Zn2 131.9 (2) H4A—C4—H4C 109.5

P2—O2—Zn2 121.39 (19) H4B—C4—H4C 109.5 P1iv_{—O3—Zn1 136.9 (3) C4—N2—C3 113.5 (4)}

P1—O4—Zn2 130.0 (2) C4—N2—H2C 108.9

P2—O5—Zn1 130.9 (2) C3—N2—H2C 108.9

P3—O6—Zn1 124.30 (18) C4—N2—H2D 108.9

P2—O8—H8 109.5 C3—N2—H2D 108.9

supporting information

sup-5 Acta Cryst. (2005). E61, m1354–m1356

O9—P3—O1—Zn2 61.8 (3) O10—P2—O5—Zn1 −59.7 (3) O6—P3—O1—Zn2 −60.8 (3) O2—P2—O5—Zn1 64.6 (3) O7—P3—O1—Zn2 179.8 (3) O8—P2—O5—Zn1 −179.1 (2) O10ii_{—Zn2—O1—P3 −11.3 (3) O9}i_{—Zn1—O5—P2 7.7 (3)} O4—Zn2—O1—P3 −141.6 (3) O3—Zn1—O5—P2 135.8 (3) O2—Zn2—O1—P3 112.7 (2) O6—Zn1—O5—P2 −114.0 (3) O10—P2—O2—Zn2 150.3 (2) O1—P3—O6—Zn1 −27.2 (3) O5—P2—O2—Zn2 25.2 (3) O9—P3—O6—Zn1 −152.0 (2) O8—P2—O2—Zn2 −92.2 (3) O7—P3—O6—Zn1 91.0 (3) O1—Zn2—O2—P2 −82.5 (3) O9i_{—Zn1—O6—P3 −43.9 (3)} O10ii_{—Zn2—O2—P2 43.7 (3) O5—Zn1—O6—P3 82.1 (3)} O4—Zn2—O2—P2 172.4 (2) O3—Zn1—O6—P3 −167.0 (2) O9i_{—Zn1—O3—P1}iv _{−16.6 (4) O1—P3—O9—Zn1}ii _{−99.8 (3)} O5—Zn1—O3—P1iv _{−144.2 (3) O6—P3—O9—Zn1}ii _{23.2 (4)} O6—Zn1—O3—P1iv _{100.8 (4) O7—P3—O9—Zn1}ii _{141.9 (3)} O3iii_{—P1—O4—Zn2 106.5 (3) O5—P2—O10—Zn2}i _{104.5 (3)} O12—P1—O4—Zn2 −12.8 (4) O2—P2—O10—Zn2i _{−19.9 (4)} O11—P1—O4—Zn2 −129.1 (3) O8—P2—O10—Zn2i _{−136.2 (3)} O1—Zn2—O4—P1 145.4 (3) N1—C1—C2—C3 127.5 (7) O10ii_{—Zn2—O4—P1 20.6 (4) C1—C2—C3—N2 167.6 (6)} O2—Zn2—O4—P1 −99.7 (3) C2—C3—N2—C4 167.8 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O8—H8···O7v _{0.82 1.66 2.480 (5) 176}

O11—H11···O6vi _{0.82 1.76 2.567 (5) 169} O12—H12···O2ii _{0.82 1.77 2.580 (5) 167}

N1—H1A···O7 0.89 1.96 2.823 (6) 164

N1—H1B···O10vii _{0.89 2.25 3.085 (5) 155} N2—H2D···O4iv _{0.90 2.08 2.938 (5) 159}