metal-organic papers
m1204
G. O. Lloyd [Zn(C16H16N4O2)(H2O)4](NO3)2 doi:10.1107/S1600536805015291 Acta Cryst.(2005). E61, m1204–m1206 Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
catena
-Poly[[[tetraaquazinc(II)]-
l
-[(2
E
)-
N,N
000-bis-(pyridin-4-ylmethyl)but-2-enediamide]] dinitrate]
Gareth O. Lloyd
Department of Chemistry, University of Stellenbosch, Private Bag X1, Matieland, South Africa
Correspondence e-mail: gol@sun.ac.za
Key indicators
Single-crystal X-ray study
T= 100 K
Mean(C–C) = 0.003 A˚
Rfactor = 0.031
wRfactor = 0.081
Data-to-parameter ratio = 15.1
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, {[Zn(C16H16N4O2)(H2O)4](NO3)2}n, the bidentate ligand (2E)-N,N0 -bis(pyridin-4-ylmethyl)but-2-enediamide coordinates in the axial positions of the octahe-dral zinc centres to form infinite one-dimensional coordina-tion polymeric chains. In the crystal structure, O—H O and N—H O hydrogen bonds link these chains into a three-dimensional framework.
Comment
The foremost goal of crystal engineering is to tailor chemical and/or physical properties of crystalline solids, using known motifs or synthons at the molecular level. The hydrogen bond is without doubt the most used non-covalent interaction in crystal engineering. Amide groups and water are extensively used by nature to assemble small molecules into larger aggregates (Atwoodet al., 2001; Barbouret al., 1998; Kannan et al., 2003; Lloydet al., 2005; Orret al., 1998). In our pursuit of hydrogen-bonded networks that include water, the ligand (2E)-N,N0-bis(pyridin-4-ylmethyl)but-2-enediamide (Lloyd, 2005), which has dipyridyl functionality and amide groups available for hydrogen bonding, has been coordinated to metal centres and the title zinc complex, (I), was prepared.
In compound (I) (Fig. 1), this results in the formation of a one-dimensional coordination polymer (Fig. 2). The zinc metal
[image:1.610.206.532.433.563.2]Received 9 May 2005 Accepted 13 May 2005 Online 28 May 2005
Figure 1
centres are in a very slightly distorted octahedral environment, with two ligands coordinated via pyridyl groups in the two axial positions and the equatorial positions occupied by four water molecules. The two nitrate ions are each hydrogen bonded by a pair of coordinated water molecules (Figs. 2 and 3a). The amide groups of the ligand are also hydrogen bonded to the nitrate ionsviathe NH group (Fig. 3a). The last set of hydrogen bonds binds the metal centres to one another. This is accomplished by two coordinated water molecules hydrogen bonding to the C O groups of the ligand (Fig. 3a) to form membered rings. Fig. 3(b) shows how the eight-membered rings consist of two zinc ions, four coordinated water molecules and two amide groups. Adjacent strands of coordination polymer are bonded together via amide hydrogen bonding links and all these hydrogen bonds link the one-dimensional coordination polymer strands together to form the three-dimensional framework (Fig. 4).
Experimental
(2E)-N,N0-Bis(pyridin-4-ylmethyl)but-2-enediamide dihydrate was
synthesized by the reaction of 4-aminomethylpyridine with fumaryl dichloride in a 2:1 molar ratio. Crystals suitable for single-crystal X-ray diffraction analysis were grown from an equimolar solution of (2E)-N,N0-bis(pyridin-4-ylmethyl)but-2-enediamide dihydrate and
zinc nitrate hexahydrate in dimethylformamide–water (5:1).
Crystal data
[Zn(C16H16N4O2)(H2O)4](NO3)2
Mr= 557.80
Monoclinic,P21=n a= 6.506 (3) A˚
b= 9.294 (4) A˚
c= 18.822 (8) A˚ = 94.781 (6)
V= 1134.2 (9) A˚3
Z= 2
Dx= 1.633 Mg m
3
MoKradiation Cell parameters from 4749
reflections = 2.4–28.0 = 1.16 mm1
T= 100 (2) K Plate, colourless 0.190.170.08 mm
Data collection
Bruker SMART APEX CCD area-detector diffractometer !scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)
Tmin= 0.810,Tmax= 0.913
12176 measured reflections
2656 independent reflections 2273 reflections withI> 2(I)
Rint= 0.032
max= 28.2
h=8!8
k=12!12
l=24!24
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.031
wR(F2) = 0.081
S= 1.03 2656 reflections 176 parameters
H atoms treated by a mixture of independent and constrained refinement
w= 1/[2(F
o2) + (0.0482P)2
+ 0.3941P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.53 e A˚ 3
min=0.31 e A˚ 3
Table 1
Hydrogen-bonding geometry (A˚ ,).
D—H A D—H H A D A D—H A
O1W—H1W O3A 0.85 (3) 1.93 (3) 2.787 (1) 176 (3) O1W—H2W O11i
0.79 (3) 1.93 (3) 2.719 (1) 171 (3) N8—H7 O3Aii
0.88 2.12 2.921 (1) 151
O2W—H3W O2Aiii
0.81 (3) 1.91 (3) 2.719 (1) 172 (3) O2W—H4W O11iv 0.81 (3) 2.09 (3) 2.853 (1) 154 (3)
Symmetry codes: (i)1
2x;12þy;12z; (ii)12þx;32y;12þz; (iii)x;1y;z; (iv)
x1 2;
1 2y;z
1 2.
metal-organic papers
Acta Cryst.(2005). E61, m1204–m1206 G. O. Lloyd [Zn(C
[image:2.610.306.568.67.264.2]16H16N4O2)(H2O)4](NO3)2
m1205
Figure 2
The one-dimensional coordination polymer strand, showing the octahe-dral zinc metal centres and hydrogen bonding to the nitrate anions. The red dashed lines indicate hydrogen bonds.
Figure 3
(a) All the hydrogen-bonding modes found in compound (I) between the amide groups, coordinated water molecules and nitrate anions. Groups not associated with hydrogen bonding have been removed for clarity. Red dashed lines represent hydrogen bonds. (b) Eight-membered hydrogen-bonded rings found in compound (I). Red dashed lines represent O O contacts of the O—H O(amide) hydrogen bonds.
Figure 4
[image:2.610.45.292.173.361.2]All non-water H atoms were positioned geometrically (C—H = 0.95 and 0.99 A˚ , and N—H = 0.88 A˚) and constrained to ride on their parent atoms;Uiso(H) values were set at 1.2 timesUeq(C,N). Water H atoms were refined independently.
Data collection:SMART(Bruker, 2001); 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:
X-SEED(Barbour, 2001; Atwood & Barbour, 2003); software used to
prepare material for publication:X-SEED.
The author thanks the National Research Foundation of South Africa for financial support.
References
Atwood, J. L. & Barbour, L. J. (2003).Cryst. Growth Des.3, 3–8.
Atwood, J. L., Barbour, L. J., Ness, T. J., Raston, P. L. & Raston, C. L. (2001).J. Am. Chem. Soc.123, 7192–7193.
Barbour, L. J. (2001).J. Supramol.Chem.1, 189–191.
Barbour, L. J., Orr, G. W. & Atwood, J. L. (1998).Chem. Commun.393, 671– 672.
Bruker (2001).SMART. Version 5.625. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2002).SAINT.Version 6.36a. Bruker AXS Inc., Madison, Wisconsin, USA.
Kannan, R., Katti, K. K., Barbour, L. J., Barnes, C. L. & Katti, K. V. (2003).J. Am. Chem. Soc.125, 6955–6961.
Lloyd, G. O. (2005).Acta Cryst.E61, o1218–o1220.
Lloyd, G. O., Atwood, J. L. & Barbour, L. J. (2005).Chem. Commun.14, 1845– 1847.
Orr, G. W., Barbour, L. J. & Atwood, J. L. (1998).Nature(London),10, 859– 860.
Sheldrick, G. M. (1997). SADABS (Version 2.05), SHELXS97 and
SHELXL97. University of Go¨ttingen, Germany.
metal-organic papers
m1206
G. O. Lloyd [Zn(Csupporting information
sup-1
Acta Cryst. (2005). E61, m1204–m1206
supporting information
Acta Cryst. (2005). E61, m1204–m1206 [https://doi.org/10.1107/S1600536805015291]
catena
-Poly[[[tetraaquazinc(II)]-
µ
-[(2
E
)-
N,N
′
-bis(pyridin-4-ylmethyl)but-2-enediamide]] dinitrate]
Gareth O. Lloyd
catena-Poly[[[tetraaquazinc(II)]-µ-[(2E)-N,N′-bis(pyridin-4-ylmethyl)but-2- enediamide]] dinitrate]
Crystal data
[Zn(C16H16N4O2)(H2O)4](NO3)2 Mr = 557.80
Monoclinic, P21/n Hall symbol: -P 2yn a = 6.506 (3) Å b = 9.294 (4) Å c = 18.822 (8) Å β = 94.781 (6)° V = 1134.2 (9) Å3 Z = 2
F(000) = 576 Dx = 1.633 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4749 reflections θ = 2.5–28.0°
µ = 1.16 mm−1 T = 100 K Plate, colorless 0.19 × 0.17 × 0.08 mm
Data collection
Bruker APEX CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) Tmin = 0.810, Tmax = 0.913
12176 measured reflections 2656 independent reflections 2273 reflections with I > 2σ(I) Rint = 0.032
θmax = 28.2°, θmin = 2.2° h = −8→8
k = −12→12 l = −24→24
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.031 wR(F2) = 0.081 S = 1.03 2656 reflections 176 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 atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0482P)2 + 0.3941P] where P = (Fo2 + 2Fc2)/3
supporting information
sup-2
Acta Cryst. (2005). E61, m1204–m1206 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
Zn1 0.0000 0.5000 0.0000 0.01278 (10)
N1 0.0937 (2) 0.44789 (16) 0.10732 (8) 0.0140 (3)
C2 0.2688 (3) 0.3753 (2) 0.12470 (9) 0.0166 (4)
H1 0.3574 0.3559 0.0882 0.020*
C3 0.3271 (3) 0.3273 (2) 0.19277 (9) 0.0170 (4)
H2 0.4535 0.2772 0.2026 0.020*
C4 0.1985 (3) 0.35319 (19) 0.24705 (9) 0.0151 (3)
C5 0.0183 (3) 0.43114 (19) 0.22980 (9) 0.0161 (4)
H3 −0.0716 0.4538 0.2655 0.019*
C6 −0.0281 (3) 0.47514 (18) 0.16024 (10) 0.0160 (4)
H4 −0.1522 0.5273 0.1491 0.019*
C7 0.2524 (3) 0.29424 (19) 0.32083 (9) 0.0170 (4)
H6 0.1706 0.2062 0.3274 0.020*
H5 0.4001 0.2673 0.3258 0.020*
N8 0.2126 (2) 0.39790 (16) 0.37597 (8) 0.0145 (3)
H7 0.2861 0.4775 0.3786 0.017*
C9 0.0720 (3) 0.37992 (19) 0.42266 (9) 0.0142 (3)
C10 0.0614 (3) 0.50073 (18) 0.47362 (9) 0.0150 (3)
H8 0.1461 0.5826 0.4682 0.018*
O11 −0.03874 (19) 0.27043 (13) 0.42419 (7) 0.0171 (3)
O1A 0.1152 (2) 0.96608 (17) −0.17459 (8) 0.0326 (4)
O2A 0.28750 (19) 0.79493 (14) −0.11875 (7) 0.0203 (3)
O3A 0.0281 (2) 0.89557 (15) −0.07172 (7) 0.0222 (3)
N4A 0.1440 (2) 0.88572 (16) −0.12238 (8) 0.0178 (3)
O1W −0.0804 (2) 0.70838 (14) 0.03464 (7) 0.0165 (3)
H1W −0.047 (4) 0.769 (3) 0.0039 (15) 0.041 (8)*
O2W −0.2952 (2) 0.41514 (14) 0.01803 (8) 0.0169 (3)
H2W −0.189 (4) 0.736 (3) 0.0454 (13) 0.030 (7)*
H3W −0.283 (3) 0.349 (3) 0.0465 (13) 0.024 (6)*
H4W −0.370 (4) 0.386 (3) −0.0163 (14) 0.028 (6)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Zn1 0.01175 (15) 0.01575 (16) 0.01106 (15) 0.00190 (10) 0.00234 (10) −0.00025 (11)
supporting information
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Acta Cryst. (2005). E61, m1204–m1206
C2 0.0152 (8) 0.0206 (9) 0.0149 (8) 0.0020 (7) 0.0060 (7) −0.0020 (7)
C3 0.0140 (8) 0.0204 (9) 0.0168 (9) 0.0041 (7) 0.0031 (7) −0.0015 (7)
C4 0.0151 (8) 0.0159 (8) 0.0147 (8) −0.0023 (6) 0.0026 (7) −0.0021 (7)
C5 0.0163 (8) 0.0181 (9) 0.0147 (8) −0.0002 (7) 0.0054 (7) −0.0021 (7)
C6 0.0149 (8) 0.0153 (9) 0.0180 (9) 0.0016 (6) 0.0028 (7) −0.0021 (7)
C7 0.0196 (9) 0.0173 (9) 0.0146 (9) 0.0043 (7) 0.0052 (7) −0.0003 (7)
N8 0.0164 (7) 0.0155 (7) 0.0120 (7) −0.0012 (6) 0.0035 (6) −0.0005 (6)
C9 0.0143 (8) 0.0177 (8) 0.0106 (8) 0.0020 (7) 0.0005 (6) 0.0022 (7)
C10 0.0157 (8) 0.0148 (8) 0.0144 (8) −0.0003 (6) 0.0000 (7) 0.0015 (7)
O11 0.0179 (6) 0.0165 (6) 0.0176 (6) −0.0022 (5) 0.0058 (5) −0.0014 (5)
O1A 0.0347 (8) 0.0358 (8) 0.0292 (8) 0.0116 (7) 0.0147 (7) 0.0166 (7)
O2A 0.0179 (6) 0.0206 (7) 0.0232 (7) 0.0039 (5) 0.0057 (5) −0.0016 (5)
O3A 0.0195 (6) 0.0253 (7) 0.0234 (7) 0.0052 (5) 0.0112 (5) 0.0043 (6)
N4A 0.0149 (7) 0.0184 (7) 0.0205 (8) −0.0008 (6) 0.0044 (6) 0.0000 (6)
O1W 0.0154 (6) 0.0176 (6) 0.0173 (7) 0.0037 (5) 0.0056 (5) 0.0006 (5)
O2W 0.0142 (6) 0.0208 (7) 0.0157 (7) −0.0004 (5) 0.0017 (5) 0.0003 (6)
Geometric parameters (Å, º)
Zn1—N1 2.1169 (16) C7—N8 1.455 (2)
Zn1—N1i 2.1169 (16) C7—H6 0.9900
Zn1—O1W 2.1228 (15) C7—H5 0.9900
Zn1—O1Wi 2.1228 (15) N8—C9 1.331 (2)
Zn1—O2W 2.1298 (15) N8—H7 0.8800
Zn1—O2Wi 2.1298 (15) C9—O11 1.249 (2)
N1—C2 1.341 (2) C9—C10 1.482 (2)
N1—C6 1.347 (2) C10—C10ii 1.326 (4)
C2—C3 1.380 (3) C10—H8 0.9500
C2—H1 0.9500 O1A—N4A 1.236 (2)
C3—C4 1.394 (2) O2A—N4A 1.256 (2)
C3—H2 0.9500 O3A—N4A 1.2674 (19)
C4—C5 1.393 (2) O1W—H1W 0.85 (3)
C4—C7 1.507 (3) O1W—H2W 0.79 (3)
C5—C6 1.381 (3) O2W—H3W 0.81 (3)
C5—H3 0.9500 O2W—H4W 0.82 (3)
C6—H4 0.9500
N1—Zn1—N1i 180.0 C4—C5—H3 120.4
N1—Zn1—O1W 88.54 (6) N1—C6—C5 123.36 (16)
N1i—Zn1—O1W 91.46 (6) N1—C6—H4 118.3
N1—Zn1—O1Wi 91.46 (6) C5—C6—H4 118.3
N1i—Zn1—O1Wi 88.54 (6) N8—C7—C4 112.02 (14)
O1W—Zn1—O1Wi 180.00 (7) N8—C7—H6 109.2
N1—Zn1—O2W 87.43 (6) C4—C7—H6 109.2
N1i—Zn1—O2W 92.57 (6) N8—C7—H5 109.2
O1W—Zn1—O2W 92.31 (6) C4—C7—H5 109.2
O1Wi—Zn1—O2W 87.69 (6) H6—C7—H5 107.9
supporting information
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Acta Cryst. (2005). E61, m1204–m1206
N1i—Zn1—O2Wi 87.43 (6) C9—N8—H7 117.9
O1W—Zn1—O2Wi 87.69 (6) C7—N8—H7 117.9
O1Wi—Zn1—O2Wi 92.31 (6) O11—C9—N8 123.19 (16)
O2W—Zn1—O2Wi 180.00 (8) O11—C9—C10 122.98 (15)
C2—N1—C6 117.02 (15) N8—C9—C10 113.82 (15)
C2—N1—Zn1 121.28 (11) C10ii—C10—C9 122.7 (2)
C6—N1—Zn1 121.46 (12) C10ii—C10—H8 118.6
N1—C2—C3 123.47 (16) C9—C10—H8 118.6
N1—C2—H1 118.3 O1A—N4A—O2A 120.78 (15)
C3—C2—H1 118.3 O1A—N4A—O3A 119.62 (15)
C2—C3—C4 119.30 (17) O2A—N4A—O3A 119.60 (15)
C2—C3—H2 120.4 Zn1—O1W—H1W 108.4 (18)
C4—C3—H2 120.4 Zn1—O1W—H2W 128.1 (18)
C5—C4—C3 117.62 (17) H1W—O1W—H2W 104 (2)
C5—C4—C7 122.06 (15) Zn1—O2W—H3W 110.0 (16)
C3—C4—C7 120.30 (16) Zn1—O2W—H4W 118.5 (17)
C6—C5—C4 119.21 (16) H3W—O2W—H4W 107 (2)
C6—C5—H3 120.4
O1W—Zn1—N1—C2 −136.85 (14) C3—C4—C5—C6 1.9 (3)
O1Wi—Zn1—N1—C2 43.15 (14) C7—C4—C5—C6 −176.31 (16)
O2W—Zn1—N1—C2 130.76 (14) C2—N1—C6—C5 −0.6 (3)
O2Wi—Zn1—N1—C2 −49.24 (14) Zn1—N1—C6—C5 173.83 (13)
O1W—Zn1—N1—C6 48.93 (14) C4—C5—C6—N1 −0.7 (3)
O1Wi—Zn1—N1—C6 −131.07 (14) C5—C4—C7—N8 −43.1 (2)
O2W—Zn1—N1—C6 −43.46 (14) C3—C4—C7—N8 138.67 (17)
O2Wi—Zn1—N1—C6 136.54 (14) C4—C7—N8—C9 114.95 (18)
C6—N1—C2—C3 0.6 (3) C7—N8—C9—O11 0.9 (3)
Zn1—N1—C2—C3 −173.83 (14) C7—N8—C9—C10 179.84 (15)
N1—C2—C3—C4 0.7 (3) O11—C9—C10—C10ii 2.6 (3)
C2—C3—C4—C5 −1.9 (3) N8—C9—C10—C10ii −176.4 (2)
C2—C3—C4—C7 176.35 (17)
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O1W—H1W···O3A 0.85 (3) 1.93 (3) 2.787 (1) 176 (3)
O1W—H2W···O11iii 0.79 (3) 1.93 (3) 2.719 (1) 171 (3)
N8—H7···O3Aiv 0.88 2.12 2.921 (1) 151
O2W—H3W···O2Ai 0.81 (3) 1.91 (3) 2.719 (1) 172 (3)
O2W—H4W···O11v 0.81 (3) 2.09 (3) 2.853 (1) 154 (3)
