metal-organic compounds
Tetra-μ-acetato-κ8O:O′-bis[(N-ethylpyrimidin-2-amine)copper(II)](Cu—Cu)
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: edward.tiekink@gmail.com
In the centrosymmetric title molecule, [Cu2(CH3COO)4(C6H9N3)2], each of the four acetate groups bridges a pair of CuII atoms [Cu—Cu = 2.6540 (4) Å]. The distorted octahedral geometry of the metal atom is completed by an N-donor atom of the N-ethylpyrimidin-2-amine ligand: an intramolecular N—H⋯O hydrogen links its N—H group to an acetate carboxylate O atom. In the crystal, C—H⋯O interactions link the molecules into a supramolecular chain along the b axis.
Related literature
For related examples of tetrakisacetatobis[(substituted 2-aminopyridyl)copper(II)] complexes, see: Fairuz et al. (2010a,b).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536810034033/hb5613sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810034033/hb5613Isup2.hkl
Copper acetate (0.1 g, 0.5 mmol) was dissolved in acetonitrile (15 ml) and mixed with a solution of N-(pyrimidin-2-yl)ethylamine (0.2 g, 1.1 mmol) dissolved in acetonitrile (15 ml). The blue precipitate that formed was recrystallized from acetonitrile to yield blue prisms of (I).
Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the
in the riding model approximation, with Uiso(H) set to 1.2 to 1.5Uequiv(C). The N-bound H-atom was located in a difference Fourier map and was refined with a distance restraint of N–H 0.86±0.01 Å; the Uiso value was freely refinedIn continuation of on-going structural studies of tetrakisacetatobis[(substituted 2-aminopyridyl)copper] complexes (Fairuz et al., 2010a, 2010b), the title complex, (I), was investigated.
The binuclear copper(II) complex, Fig. 1, is situated about a centre of inversion and features two Cu atoms bridged by four acetate groups. The Cu–O bond distances lie in a narrow range of 1.953 (1) to 1.978 (2) Å, Table 1. The coordination environment for each Cu atom is completed by an N atom derived from the N-ethylpyrimidin-2-amine ligand and the second Cu atom [Cu···Cui = 2.6540 (4) Å for i: 1 - x, 1 - y, 1 - z]. The resulting hexa-coordinated geometry is based on an octahedron. An intramolecular N3–H···O1 interaction contributes to the stability of the dinuclear molecule, Table 2. The N-heterocycle is effectively planar as seen in the C8–N3–C9–C10 torsion angle of -166.6 (2) °. In the crystal packing, the presence of C–H···O interactions connect dinuclear molecules into supramolecular chains along the b axis, Fig. 2 and Table 2.
For related examples of tetrakisacetatobis[(substituted 2-aminopyridyl)copper] complexes, see: Fairuz et al. (2010a,b).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Cu2(C2H3O2)4(C6H9N3)2] | Z = 1 |
Mr = 609.58 | F(000) = 314 |
Triclinic, P1 | Dx = 1.550 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8488 (6) Å | Cell parameters from 3508 reflections |
b = 8.5114 (7) Å | θ = 2.5–28.2° |
c = 10.2999 (8) Å | µ = 1.68 mm−1 |
α = 98.404 (1)° | T = 293 K |
β = 92.698 (1)° | Prism, blue |
γ = 105.599 (1)° | 0.40 × 0.35 × 0.10 mm |
V = 652.92 (9) Å3 |
Bruker SMART APEX CCD diffractometer | 2969 independent reflections |
Radiation source: fine-focus sealed tube | 2669 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω scans | θmax = 27.5°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.613, Tmax = 0.746 | k = −11→11 |
6208 measured reflections | l = −13→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.051P)2 + 0.1167P] where P = (Fo2 + 2Fc2)/3 |
2969 reflections | (Δ/σ)max = 0.001 |
170 parameters | Δρmax = 0.28 e Å−3 |
1 restraint | Δρmin = −0.25 e Å−3 |
[Cu2(C2H3O2)4(C6H9N3)2] | γ = 105.599 (1)° |
Mr = 609.58 | V = 652.92 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.8488 (6) Å | Mo Kα radiation |
b = 8.5114 (7) Å | µ = 1.68 mm−1 |
c = 10.2999 (8) Å | T = 293 K |
α = 98.404 (1)° | 0.40 × 0.35 × 0.10 mm |
β = 92.698 (1)° |
Bruker SMART APEX CCD diffractometer | 2969 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2669 reflections with I > 2σ(I) |
Tmin = 0.613, Tmax = 0.746 | Rint = 0.018 |
6208 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 1 restraint |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.28 e Å−3 |
2969 reflections | Δρmin = −0.25 e Å−3 |
170 parameters |
x | y | z | Uiso*/Ueq | ||
Cu | 0.60458 (3) | 0.58733 (2) | 0.42299 (2) | 0.02818 (9) | |
O1 | 0.3830 (2) | 0.5272 (2) | 0.30471 (15) | 0.0479 (4) | |
O2 | 0.2102 (2) | 0.3821 (2) | 0.43330 (16) | 0.0491 (4) | |
O3 | 0.5310 (2) | 0.77124 (17) | 0.51727 (16) | 0.0474 (4) | |
O4 | 0.3551 (2) | 0.62484 (18) | 0.64537 (16) | 0.0473 (4) | |
N1 | 0.7898 (2) | 0.7417 (2) | 0.30101 (17) | 0.0328 (3) | |
N2 | 0.8689 (3) | 0.8709 (2) | 0.11294 (19) | 0.0473 (4) | |
N3 | 0.5862 (3) | 0.7135 (2) | 0.12539 (18) | 0.0435 (4) | |
H3 | 0.513 (3) | 0.648 (2) | 0.165 (2) | 0.048 (7)* | |
C1 | 0.2361 (3) | 0.4432 (2) | 0.3307 (2) | 0.0364 (4) | |
C2 | 0.0792 (3) | 0.4133 (4) | 0.2317 (3) | 0.0585 (7) | |
H2A | 0.0917 | 0.5081 | 0.1889 | 0.088* | |
H2B | −0.0277 | 0.3946 | 0.2758 | 0.088* | |
H2C | 0.0736 | 0.3180 | 0.1672 | 0.088* | |
C3 | 0.4244 (3) | 0.7560 (2) | 0.6037 (2) | 0.0361 (4) | |
C4 | 0.3760 (4) | 0.9086 (3) | 0.6633 (3) | 0.0595 (7) | |
H4A | 0.3991 | 0.9880 | 0.6044 | 0.089* | |
H4B | 0.4457 | 0.9552 | 0.7459 | 0.089* | |
H4C | 0.2522 | 0.8799 | 0.6775 | 0.089* | |
C5 | 0.9529 (3) | 0.8135 (3) | 0.3561 (2) | 0.0497 (6) | |
H5 | 0.9836 | 0.7926 | 0.4389 | 0.060* | |
C6 | 1.0798 (3) | 0.9180 (4) | 0.2965 (3) | 0.0650 (8) | |
H6 | 1.1928 | 0.9706 | 0.3381 | 0.078* | |
C7 | 1.0308 (3) | 0.9397 (3) | 0.1740 (3) | 0.0566 (6) | |
H7 | 1.1151 | 1.0064 | 0.1302 | 0.068* | |
C8 | 0.7529 (3) | 0.7767 (2) | 0.18107 (19) | 0.0342 (4) | |
C9 | 0.5238 (4) | 0.7487 (3) | 0.0013 (2) | 0.0564 (6) | |
H9A | 0.5716 | 0.6922 | −0.0707 | 0.068* | |
H9B | 0.5645 | 0.8666 | 0.0000 | 0.068* | |
C10 | 0.3254 (4) | 0.6923 (4) | −0.0163 (3) | 0.0754 (9) | |
H10A | 0.2848 | 0.7136 | −0.0996 | 0.113* | |
H10B | 0.2785 | 0.7513 | 0.0534 | 0.113* | |
H10C | 0.2855 | 0.5759 | −0.0140 | 0.113* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.02719 (13) | 0.02865 (14) | 0.02816 (14) | 0.00393 (9) | 0.00634 (9) | 0.00911 (9) |
O1 | 0.0309 (7) | 0.0684 (10) | 0.0392 (8) | −0.0011 (7) | −0.0011 (6) | 0.0225 (7) |
O2 | 0.0326 (7) | 0.0646 (10) | 0.0454 (9) | −0.0021 (7) | −0.0016 (6) | 0.0253 (8) |
O3 | 0.0602 (10) | 0.0330 (7) | 0.0548 (10) | 0.0145 (7) | 0.0295 (8) | 0.0149 (7) |
O4 | 0.0601 (10) | 0.0336 (7) | 0.0526 (9) | 0.0139 (7) | 0.0292 (8) | 0.0122 (7) |
N1 | 0.0319 (8) | 0.0309 (8) | 0.0339 (8) | 0.0039 (6) | 0.0071 (6) | 0.0077 (6) |
N2 | 0.0493 (11) | 0.0492 (10) | 0.0452 (10) | 0.0069 (8) | 0.0209 (9) | 0.0206 (9) |
N3 | 0.0444 (10) | 0.0495 (10) | 0.0344 (9) | 0.0033 (8) | 0.0042 (8) | 0.0178 (8) |
C1 | 0.0308 (9) | 0.0396 (10) | 0.0367 (10) | 0.0061 (8) | −0.0001 (8) | 0.0081 (8) |
C2 | 0.0364 (11) | 0.0801 (18) | 0.0541 (15) | 0.0041 (11) | −0.0089 (10) | 0.0223 (13) |
C3 | 0.0414 (10) | 0.0314 (9) | 0.0367 (10) | 0.0108 (8) | 0.0080 (8) | 0.0068 (8) |
C4 | 0.0823 (18) | 0.0381 (12) | 0.0678 (17) | 0.0253 (12) | 0.0358 (14) | 0.0144 (11) |
C5 | 0.0410 (12) | 0.0578 (14) | 0.0434 (12) | −0.0030 (10) | 0.0060 (10) | 0.0171 (11) |
C6 | 0.0387 (12) | 0.0742 (18) | 0.0664 (18) | −0.0164 (12) | 0.0095 (12) | 0.0203 (14) |
C7 | 0.0510 (14) | 0.0589 (15) | 0.0581 (15) | 0.0006 (11) | 0.0247 (12) | 0.0254 (12) |
C8 | 0.0419 (11) | 0.0298 (9) | 0.0325 (10) | 0.0094 (8) | 0.0137 (8) | 0.0080 (7) |
C9 | 0.0632 (16) | 0.0740 (17) | 0.0362 (12) | 0.0191 (13) | 0.0054 (11) | 0.0222 (11) |
C10 | 0.0622 (17) | 0.116 (3) | 0.0530 (16) | 0.0251 (17) | −0.0021 (13) | 0.0323 (17) |
Cu—O1 | 1.978 (2) | C2—H2A | 0.9600 |
Cu—O2i | 1.963 (2) | C2—H2B | 0.9600 |
Cu—O3 | 1.955 (1) | C2—H2C | 0.9600 |
Cu—O4i | 1.953 (1) | C3—C4 | 1.504 (3) |
Cu—N1 | 2.246 (2) | C4—H4A | 0.9600 |
Cu—Cui | 2.6540 (4) | C4—H4B | 0.9600 |
O1—C1 | 1.247 (2) | C4—H4C | 0.9600 |
O2—C1 | 1.246 (3) | C5—C6 | 1.378 (3) |
O3—C3 | 1.247 (2) | C5—H5 | 0.9300 |
O4—C3 | 1.250 (2) | C6—C7 | 1.355 (4) |
N1—C5 | 1.321 (3) | C6—H6 | 0.9300 |
N1—C8 | 1.349 (3) | C7—H7 | 0.9300 |
N2—C7 | 1.331 (3) | C9—C10 | 1.494 (4) |
N2—C8 | 1.340 (3) | C9—H9A | 0.9700 |
N3—C8 | 1.338 (3) | C9—H9B | 0.9700 |
N3—C9 | 1.448 (3) | C10—H10A | 0.9600 |
N3—H3 | 0.85 (1) | C10—H10B | 0.9600 |
C1—C2 | 1.502 (3) | C10—H10C | 0.9600 |
O4i—Cu—O3 | 167.23 (6) | H2B—C2—H2C | 109.5 |
O4i—Cu—O2i | 88.86 (8) | O3—C3—O4 | 125.51 (18) |
O3—Cu—O2i | 89.53 (8) | O3—C3—C4 | 117.20 (18) |
O4i—Cu—O1 | 89.76 (8) | O4—C3—C4 | 117.29 (18) |
O3—Cu—O1 | 88.95 (7) | C3—C4—H4A | 109.5 |
O2i—Cu—O1 | 166.94 (6) | C3—C4—H4B | 109.5 |
O4i—Cu—N1 | 97.38 (6) | H4A—C4—H4B | 109.5 |
O3—Cu—N1 | 95.36 (6) | C3—C4—H4C | 109.5 |
O2i—Cu—N1 | 93.54 (6) | H4A—C4—H4C | 109.5 |
O1—Cu—N1 | 99.52 (6) | H4B—C4—H4C | 109.5 |
O4i—Cu—Cui | 83.74 (4) | N1—C5—C6 | 123.0 (2) |
O3—Cu—Cui | 83.49 (4) | N1—C5—H5 | 118.5 |
O2i—Cu—Cui | 84.07 (5) | C6—C5—H5 | 118.5 |
O1—Cu—Cui | 82.87 (5) | C7—C6—C5 | 116.3 (2) |
N1—Cu—Cui | 177.35 (4) | C7—C6—H6 | 121.9 |
C1—O1—Cu | 124.63 (14) | C5—C6—H6 | 121.9 |
C1—O2—Cui | 123.95 (14) | N2—C7—C6 | 123.7 (2) |
C3—O3—Cu | 123.73 (13) | N2—C7—H7 | 118.2 |
C3—O4—Cui | 123.48 (13) | C6—C7—H7 | 118.2 |
C5—N1—C8 | 115.85 (17) | N3—C8—N2 | 116.97 (19) |
C5—N1—Cu | 115.99 (14) | N3—C8—N1 | 117.50 (17) |
C8—N1—Cu | 128.08 (13) | N2—C8—N1 | 125.53 (19) |
C7—N2—C8 | 115.5 (2) | N3—C9—C10 | 109.8 (2) |
C8—N3—C9 | 123.88 (19) | N3—C9—H9A | 109.7 |
C8—N3—H3 | 118.0 (17) | C10—C9—H9A | 109.7 |
C9—N3—H3 | 118.1 (17) | N3—C9—H9B | 109.7 |
O2—C1—O1 | 124.4 (2) | C10—C9—H9B | 109.7 |
O2—C1—C2 | 117.62 (19) | H9A—C9—H9B | 108.2 |
O1—C1—C2 | 117.9 (2) | C9—C10—H10A | 109.5 |
C1—C2—H2A | 109.5 | C9—C10—H10B | 109.5 |
C1—C2—H2B | 109.5 | H10A—C10—H10B | 109.5 |
H2A—C2—H2B | 109.5 | C9—C10—H10C | 109.5 |
C1—C2—H2C | 109.5 | H10A—C10—H10C | 109.5 |
H2A—C2—H2C | 109.5 | H10B—C10—H10C | 109.5 |
O4i—Cu—O1—C1 | 84.62 (19) | Cui—O2—C1—C2 | −177.97 (16) |
O3—Cu—O1—C1 | −82.68 (19) | Cu—O1—C1—O2 | −2.0 (3) |
O2i—Cu—O1—C1 | 0.7 (4) | Cu—O1—C1—C2 | 178.01 (16) |
N1—Cu—O1—C1 | −177.93 (18) | Cu—O3—C3—O4 | 2.6 (3) |
Cui—Cu—O1—C1 | 0.90 (18) | Cu—O3—C3—C4 | −177.68 (17) |
O4i—Cu—O3—C3 | −2.8 (4) | Cui—O4—C3—O3 | −2.2 (3) |
O2i—Cu—O3—C3 | −85.53 (19) | Cui—O4—C3—C4 | 178.11 (17) |
O1—Cu—O3—C3 | 81.49 (18) | C8—N1—C5—C6 | −0.1 (3) |
N1—Cu—O3—C3 | −179.05 (18) | Cu—N1—C5—C6 | −177.0 (2) |
Cui—Cu—O3—C3 | −1.45 (17) | N1—C5—C6—C7 | −2.4 (4) |
O4i—Cu—N1—C5 | −93.37 (16) | C8—N2—C7—C6 | 0.3 (4) |
O3—Cu—N1—C5 | 85.80 (16) | C5—C6—C7—N2 | 2.3 (4) |
O2i—Cu—N1—C5 | −4.07 (16) | C9—N3—C8—N2 | −3.6 (3) |
O1—Cu—N1—C5 | 175.63 (16) | C9—N3—C8—N1 | 175.8 (2) |
Cui—Cu—N1—C5 | 21.6 (10) | C7—N2—C8—N3 | 176.3 (2) |
O4i—Cu—N1—C8 | 90.11 (16) | C7—N2—C8—N1 | −3.1 (3) |
O3—Cu—N1—C8 | −90.72 (16) | C5—N1—C8—N3 | −176.44 (19) |
O2i—Cu—N1—C8 | 179.42 (16) | Cu—N1—C8—N3 | 0.1 (3) |
O1—Cu—N1—C8 | −0.89 (17) | C5—N1—C8—N2 | 3.0 (3) |
Cui—Cu—N1—C8 | −154.9 (8) | Cu—N1—C8—N2 | 179.51 (15) |
Cui—O2—C1—O1 | 2.0 (3) | C8—N3—C9—C10 | −166.6 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1 | 0.85 (1) | 2.04 (1) | 2.871 (2) | 164 (2) |
C4—H4a···O3ii | 0.96 | 2.51 | 3.458 (3) | 171 |
Symmetry code: (ii) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C2H3O2)4(C6H9N3)2] |
Mr | 609.58 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.8488 (6), 8.5114 (7), 10.2999 (8) |
α, β, γ (°) | 98.404 (1), 92.698 (1), 105.599 (1) |
V (Å3) | 652.92 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.68 |
Crystal size (mm) | 0.40 × 0.35 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.613, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6208, 2969, 2669 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.080, 1.02 |
No. of reflections | 2969 |
No. of parameters | 170 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.25 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Cu—O1 | 1.978 (2) | Cu—O4i | 1.953 (1) |
Cu—O2i | 1.963 (2) | Cu—N1 | 2.246 (2) |
Cu—O3 | 1.955 (1) | Cu—Cui | 2.6540 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1 | 0.85 (1) | 2.043 (12) | 2.871 (2) | 164 (2) |
C4—H4a···O3ii | 0.96 | 2.51 | 3.458 (3) | 171 |
Symmetry code: (ii) −x+1, −y+2, −z+1. |
Footnotes
‡Additional correspondence author, e-mail: zana@um.edu.my.
Acknowledgements
Z. Abdullah thanks the Ministry of Higher Education for a research grant (FS143/2008 C). The authors are also grateful to the University of Malaya for support of the crystallographic facility.
References
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Fairuz, Z. A., Aiyub, Z., Abdullah, Z., Ng, S. W. & Tiekink, E. R. T. (2010b). Acta Cryst. E66, m1077–m1078. Web of Science CSD CrossRef IUCr Journals Google Scholar
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In continuation of on-going structural studies of tetrakisacetatobis[(substituted 2-aminopyridyl)copper] complexes (Fairuz et al., 2010a, 2010b), the title complex, (I), was investigated.
The binuclear copper(II) complex, Fig. 1, is situated about a centre of inversion and features two Cu atoms bridged by four acetate groups. The Cu–O bond distances lie in a narrow range of 1.953 (1) to 1.978 (2) Å, Table 1. The coordination environment for each Cu atom is completed by an N atom derived from the N-ethylpyrimidin-2-amine ligand and the second Cu atom [Cu···Cui = 2.6540 (4) Å for i: 1 - x, 1 - y, 1 - z]. The resulting hexa-coordinated geometry is based on an octahedron. An intramolecular N3–H···O1 interaction contributes to the stability of the dinuclear molecule, Table 2. The N-heterocycle is effectively planar as seen in the C8–N3–C9–C10 torsion angle of -166.6 (2) °. In the crystal packing, the presence of C–H···O interactions connect dinuclear molecules into supramolecular chains along the b axis, Fig. 2 and Table 2.