The dehydrated copper silicate Na(2)[Cu(2)Si(4)O(11)]: a three-dimensional microporous framework with a linear Si-O-Si linkage.

The structure of the title dehydrated copper silicate, disodium dicopper undeca-oxide tetra-silicate, Na(2)(Cu(2)O(11)Si(4)), was determined by single-crystal X-ray diffraction from a non-merohedral twin. It exhibits an effective three-dimensional microporous framework with the major channels, in which the Na(+) cations are placed, running along the a-axis direction and smaller channels observed along the b-axis direction. The structure is unusual in that it contains a symmetry-constrained Si-O-Si angle of 180°. The Cu centre is coordinated to five O atoms, exhibiting a slightly distorted square-pyramidal coordination geometry. The Na cation is interacting with five neighbouring O atoms, exhibiting an uncharacteristic coordination environment.

Related literature

For related literature, see: Brandão et al. (2005 ▶); Haile & Wuensch (2000 ▶); Liebau (1985 ▶); Rocha & Anderson (2000 ▶); Rocha & Lin (2005 ▶); dos Santos et al. (2005 ▶); Ananias et al. (2001 ▶, 2006 ▶); Anderson et al. (1994 ▶); Ferreira et al. (2003 ▶).

Experimental

Crystal data

Na2(Cu2O11Si4)

M = 461.44

Triclinic,

a = 5.190 (2) Å

b = 6.299 (3) Å

c = 8.196 (4) Å

α = 96.390 (7)°

β = 97.281 (7)°

γ = 100.461 (7)°

V = 258.9 (2) Å3

Z = 1

Mo Kα radiation

μ = 4.71 mm−1

T = 298 (2) K

0.28 × 0.08 × 0.04 mm

Data collection

Bruker SMART CCD 1000 diffractometer

Absorption correction: multi-scan (TWINABS; Sheldrick, 2002 ▶) T min = 0.627, T max = 0.834

1587 measured reflections

1043 independent reflections

782 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.119

S = 1.01

1043 reflections

88 parameters

Δρmax = 1.40 e Å−3

Δρmin = −1.58 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2003 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2007 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808001608/br2065sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001608/br2065Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Na2(Cu2O11Si4)	Z = 1
Mr = 461.44	F000 = 224
Triclinic, P1	Dx = 2.960 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 5.190 (2) Å	Cell parameters from 758 reflections
b = 6.299 (3) Å	θ = 8.1–58.1º
c = 8.196 (4) Å	µ = 4.71 mm−1
α = 96.390 (7)º	T = 298 (2) K
β = 97.281 (7)º	Plate, black
γ = 100.461 (7)º	0.28 × 0.08 × 0.04 mm
V = 258.9 (2) Å3

Bruker SMART CCD 1000 diffractometer	1043 independent reflections
Radiation source: fine-focus sealed tube	782 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.042
T = 298(2) K	θmax = 26.4º
ω scans	θmin = 3.9º
Absorption correction: multi-scan(TWINABS; Sheldrick, 2002)	h = −6→6
Tmin = 0.627, Tmax = 0.834	k = −7→7
1587 measured reflections	l = 0→10

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)] = 0.042	w = 1/[σ2(Fo2) + (0.0809P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.119	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 1.40 e Å−3
1043 reflections	Δρmin = −1.58 e Å−3
88 parameters	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
Cu1	0.70666 (10)	−0.10891 (9)	0.93472 (8)	0.0096 (3)
Na1	0.8700 (4)	0.3540 (3)	1.1990 (3)	0.0235 (6)
Si1	1.0175 (2)	0.1358 (2)	0.67930 (18)	0.0087 (4)
Si2	0.5954 (3)	0.3456 (2)	0.80969 (18)	0.0089 (4)
O1	1.0000	0.0000	0.5000	0.0217 (13)
O2	1.0064 (7)	−0.0190 (6)	0.8196 (5)	0.0127 (8)
O3	0.7804 (6)	0.2736 (6)	0.6719 (5)	0.0126 (8)
O4	0.2923 (6)	0.3209 (5)	0.7137 (5)	0.0144 (8)
O5	0.7200 (7)	0.5899 (6)	0.8873 (5)	0.0170 (9)
O6	0.5974 (6)	0.1760 (5)	0.9452 (5)	0.0107 (8)

	U11	U22	U33	U12	U13	U23
Cu1	0.0054 (4)	0.0083 (4)	0.0159 (4)	0.0011 (2)	0.0051 (2)	0.0018 (2)
Na1	0.0137 (11)	0.0161 (12)	0.0396 (16)	0.0021 (9)	0.0072 (10)	−0.0030 (10)
Si1	0.0048 (7)	0.0096 (7)	0.0124 (8)	0.0018 (5)	0.0034 (5)	0.0009 (5)
Si2	0.0040 (6)	0.0078 (7)	0.0155 (8)	0.0013 (5)	0.0042 (5)	0.0018 (5)
O1	0.020 (3)	0.024 (3)	0.021 (3)	0.006 (2)	0.007 (2)	−0.006 (2)
O2	0.0078 (17)	0.0137 (18)	0.018 (2)	0.0033 (13)	0.0040 (14)	0.0045 (14)
O3	0.0057 (16)	0.0169 (19)	0.018 (2)	0.0068 (14)	0.0049 (14)	0.0018 (14)
O4	0.0063 (16)	0.0140 (18)	0.023 (2)	0.0017 (14)	0.0014 (14)	0.0061 (15)
O5	0.0145 (18)	0.0100 (18)	0.028 (2)	0.0000 (14)	0.0129 (16)	0.0016 (15)
O6	0.0082 (16)	0.0111 (17)	0.016 (2)	0.0039 (13)	0.0061 (14)	0.0050 (14)

Cu1—O5i	1.909 (3)	Si1—O4iv	1.642 (4)
Cu1—O2	1.950 (4)	Si2—O5	1.583 (4)
Cu1—O6ii	1.970 (4)	Si2—O6	1.625 (4)
Cu1—O6	1.974 (3)	Si2—O4	1.639 (3)
Cu1—O2iii	2.316 (4)	Si2—O3	1.650 (4)
Cu1—Cu1ii	2.9921 (13)	Si2—Cu1ii	3.1221 (19)
Cu1—Cu1iii	3.1031 (15)	O1—Si1v	1.5991 (14)
Cu1—Si2ii	3.1221 (19)	O2—Cu1iii	2.316 (4)
Cu1—Si1	3.1673 (19)	O4—Si1vi	1.642 (4)
Si1—O2	1.588 (4)	O5—Cu1vii	1.909 (3)
Si1—O1	1.5991 (14)	O6—Cu1ii	1.970 (4)
Si1—O3	1.629 (3)
O5i—Cu1—O2	92.49 (15)	O2iii—Cu1—Si1	100.98 (10)
O5i—Cu1—O6ii	91.91 (15)	Cu1ii—Cu1—Si1	115.23 (4)
O2—Cu1—O6ii	175.60 (13)	Cu1iii—Cu1—Si1	64.33 (4)
O5i—Cu1—O6	164.27 (15)	Si2ii—Cu1—Si1	179.25 (4)
O2—Cu1—O6	94.42 (14)	O2—Si1—O1	111.33 (15)
O6ii—Cu1—O6	81.32 (16)	O2—Si1—O3	112.6 (2)
O5i—Cu1—O2iii	105.60 (16)	O1—Si1—O3	108.16 (15)
O2—Cu1—O2iii	87.05 (15)	O2—Si1—O4iv	111.48 (19)
O6ii—Cu1—O2iii	91.76 (14)	O1—Si1—O4iv	108.08 (16)
O6—Cu1—O2iii	88.87 (14)	O3—Si1—O4iv	104.92 (18)
O5i—Cu1—Cu1ii	131.06 (12)	O1—Si1—Cu1	115.96 (7)
O2—Cu1—Cu1ii	135.03 (10)	O3—Si1—Cu1	84.08 (15)
O6ii—Cu1—Cu1ii	40.70 (10)	O4iv—Si1—Cu1	129.55 (15)
O6—Cu1—Cu1ii	40.62 (10)	O5—Si2—O6	113.2 (2)
O2iii—Cu1—Cu1ii	90.41 (9)	O5—Si2—O4	111.75 (19)
O5i—Cu1—Cu1iii	103.18 (12)	O6—Si2—O4	109.3 (2)
O2—Cu1—Cu1iii	48.19 (11)	O5—Si2—O3	107.1 (2)
O6ii—Cu1—Cu1iii	130.50 (11)	O6—Si2—O3	107.00 (19)
O6—Cu1—Cu1iii	91.93 (10)	O4—Si2—O3	108.15 (19)
O2iii—Cu1—Cu1iii	38.86 (9)	O5—Si2—Cu1ii	109.62 (16)
Cu1ii—Cu1—Cu1iii	116.74 (4)	O4—Si2—Cu1ii	81.61 (15)
O5i—Cu1—Si2ii	73.75 (12)	O3—Si2—Cu1ii	134.72 (14)
O2—Cu1—Si2ii	156.11 (11)	Si1v—O1—Si1	180.0
O6ii—Cu1—Si2ii	26.72 (10)	Si1—O2—Cu1	126.8 (2)
O6—Cu1—Si2ii	103.96 (11)	Si1—O2—Cu1iii	116.29 (18)
O2iii—Cu1—Si2ii	78.31 (10)	Cu1—O2—Cu1iii	92.95 (15)
Cu1ii—Cu1—Si2ii	64.59 (4)	Si1—O3—Si2	132.7 (3)
Cu1iii—Cu1—Si2ii	115.04 (5)	Si2—O4—Si1vi	137.0 (2)
O5i—Cu1—Si1	106.73 (13)	Si2—O5—Cu1vii	152.9 (2)
O2—Cu1—Si1	23.68 (11)	Si2—O6—Cu1ii	120.24 (18)
O6ii—Cu1—Si1	153.39 (10)	Si2—O6—Cu1	130.3 (2)
O6—Cu1—Si1	75.74 (11)	Cu1ii—O6—Cu1	98.68 (16)

Table 1

Selected bond lengths (Å)

Cu1—O5i	1.909 (3)
Cu1—O2	1.950 (4)
Cu1—O6ii	1.970 (4)
Cu1—O6	1.974 (3)
Cu1—O2iii	2.316 (4)

Symmetry codes: (i) ; (ii) ; (iii) .