catena-Poly[copper(II)-di-μ₂-1,1-azido-copper(II)-μ₂-acetato-μ₂-1,1-azido-μ₂-(dimethyl sulfoxide)-copper(II)-di-μ₂-1,1-azido]

The title crystal structure, [Cu₃(C₂H₃O₂)₂(N₃)₄(C₂H₆OS)₂]_n, consists of one-dimensional chains in which there are two independent Cu^II ions. One of the Cu^II ions lies on a crystallographic inversion center and is in a slightly distorted octa­hedral coordination environment while the other Cu^II ion is coordinated in a distorted square-pyramidal environment.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.099
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of Tmax/Tmin expected RT(exp) is > 1.10
            Absorption corrections should be applied.
            Tmin and Tmax expected:      0.493     0.546
            RT(exp) =      1.107
PLAT057_ALERT_3_C Correction for Absorption Required   RT(exp) ...       1.12
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu2    -   O3      ..       5.24 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The crystal structure and some properties of Cu(II)-azido coordination polymers have been previously reported (Goher et al., 1999; Goher et al., 2002; Liu et al., 2007; Song et al., 2007). We report here the synthesis and crystal structure of the title one-dimensional Copper(II)-azido coordination polymer(I) (Fig. 1). In (I) one unique Cu^II atom is six-coordinated while the other is is five-coordinated. Crystallographically independent Cu^II atoms are bridged by two O atoms from acetate ligands, one µ₂-O atom from a DMSO ligand and one µ₂-N atom of an azido ion, while the symmetry related Cu^II atoms are bridged by two µ₂-N atoms from two azido ligands to from a one-dimensional polymer. In the absence of any direction specific interactions the the crystal structure is stabilized by Van der Waals interactions.

Related literature

For related literature, see: Goher et al. (1999, 2002); Liu et al. (2007); Song et al. (2007).

S2. Experimental

To a solution of Cu(OAc)₂(0.14 g, 0.6 mmol) in Dimethyl sulphoxide (3 ml) a suspension of sodium azide(0.039 g, 0.6 mmol) in the ethanol (15 ml) was added and the mixture was stirred for 2 h at 333 K. The solution was filtered after cooled and allowed to stand at room temperature without disturbing, black crystals of of the title compound were obtained after about 3 weeks.

S3. Refinement

After being located in a difference map, all H-atoms were fixed geometrically at ideal positions and allowed to ride on the parent C atoms with C—H = 0.96Å and U_iso(H)= 1.5U_eq(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures

Fig. 1. Part of the one dimensional chain of the title compound showing 30% probability displacement ellipsoids. H atoms are not included [symmetry codes: (a) -x + 1, -y + 1, -z; (b) -x + 2, -y + 2, -z].

catena-Poly[copper(II)-di-µ₂-1,1-azido-copper(II)-µ₂-acetato- µ₂-1,1-azido-µ₂-(dimethyl sulfoxide)-copper(II)-di-µ₂-1,1-azido]

Crystal data

[Cu3(C2H3O2)2(N3)4(C2H6OS)2]	Z = 1
Mr = 633.13	F(000) = 317
Triclinic, P1	Dx = 1.855 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5205 (9) Å	Cell parameters from 2542 reflections
b = 8.6624 (9) Å	θ = 2.4–27.0°
c = 9.4999 (10) Å	µ = 3.02 mm^−1
α = 90.386 (2)°	T = 293 K
β = 112.687 (1)°	Block, black
γ = 116.261 (1)°	0.30 × 0.20 × 0.20 mm
V = 566.66 (10) Å^3

Data collection

Bruker SMART-CCD diffractometer	2182 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.060
Graphite monochromator	θmax = 27.0°, θmin = 2.4°
ϕ and ω scans	h = −10→7
3467 measured reflections	k = −7→11
2404 independent reflections	l = −10→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.052P)^2 + 0.3521P] where P = (Fo^2 + 2Fc^2)/3
2404 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.65 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.81687 (5)	0.81565 (4)	−0.06003 (4)	0.03025 (14)
Cu2	0.5000	0.5000	0.0000	0.03156 (15)
C1	0.7810 (8)	1.1353 (5)	0.2360 (6)	0.0673 (12)
H1A	0.8966	1.1839	0.2199	0.101*
H1B	0.8111	1.1893	0.3382	0.101*
H1C	0.6854	1.1577	0.1586	0.101*
C2	0.4761 (7)	0.8594 (7)	0.2395 (6)	0.0707 (13)
H2A	0.4049	0.9054	0.1643	0.106*
H2B	0.5099	0.9132	0.3429	0.106*
H2C	0.3974	0.7341	0.2218	0.106*
C3	0.2979 (6)	0.5365 (6)	−0.4771 (4)	0.0630 (12)
H3A	0.2879	0.4330	−0.5259	0.095*
H3B	0.3458	0.6318	−0.5264	0.095*
H3C	0.1722	0.5130	−0.4879	0.095*
C4	0.4350 (5)	0.5860 (4)	−0.3071 (4)	0.0361 (6)
N1	1.0712 (4)	0.9551 (4)	0.1239 (3)	0.0449 (7)
N2	1.1240 (4)	0.9351 (4)	0.2578 (3)	0.0421 (6)
N3	1.1756 (6)	0.9171 (6)	0.3806 (4)	0.0691 (11)
N4	0.2460 (4)	0.4183 (3)	0.0089 (3)	0.0328 (5)
N5	0.1232 (4)	0.4496 (4)	−0.0825 (3)	0.0379 (6)
N6	0.0095 (5)	0.4816 (5)	−0.1649 (5)	0.0624 (9)
O1	0.6009 (3)	0.7171 (3)	−0.2653 (3)	0.0432 (6)
O2	0.3755 (3)	0.4928 (3)	−0.2207 (3)	0.0406 (5)
O3	0.6177 (4)	0.8295 (3)	0.0499 (3)	0.0430 (5)
S1	0.68907 (12)	0.90584 (11)	0.22039 (10)	0.0401 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0237 (2)	0.0250 (2)	0.0280 (2)	0.00378 (15)	0.00743 (15)	0.00848 (14)
Cu2	0.0225 (3)	0.0298 (3)	0.0332 (3)	0.0057 (2)	0.0115 (2)	0.0083 (2)
C1	0.080 (3)	0.0306 (19)	0.068 (3)	0.009 (2)	0.031 (2)	−0.0018 (18)
C2	0.057 (3)	0.079 (3)	0.062 (3)	0.014 (2)	0.035 (2)	−0.008 (2)
C3	0.046 (2)	0.071 (3)	0.0320 (18)	0.007 (2)	0.0030 (16)	0.0070 (17)
C4	0.0317 (15)	0.0350 (16)	0.0304 (14)	0.0103 (13)	0.0097 (12)	0.0041 (12)
N1	0.0338 (14)	0.0375 (15)	0.0345 (14)	0.0031 (12)	0.0040 (11)	0.0176 (11)
N2	0.0356 (14)	0.0370 (15)	0.0372 (15)	0.0090 (12)	0.0101 (12)	0.0122 (11)
N3	0.071 (2)	0.076 (3)	0.0393 (18)	0.026 (2)	0.0150 (17)	0.0256 (17)
N4	0.0251 (12)	0.0272 (12)	0.0428 (14)	0.0099 (10)	0.0148 (11)	0.0109 (10)
N5	0.0316 (13)	0.0317 (13)	0.0458 (15)	0.0109 (11)	0.0175 (12)	0.0118 (11)
N6	0.052 (2)	0.070 (2)	0.073 (2)	0.0381 (19)	0.0230 (18)	0.0342 (19)
O1	0.0344 (12)	0.0334 (11)	0.0305 (11)	−0.0018 (10)	0.0059 (9)	0.0056 (9)
O2	0.0282 (11)	0.0391 (12)	0.0337 (11)	0.0031 (10)	0.0094 (9)	0.0067 (9)
O3	0.0450 (13)	0.0400 (13)	0.0407 (12)	0.0177 (11)	0.0188 (11)	0.0008 (10)
S1	0.0395 (4)	0.0351 (4)	0.0384 (4)	0.0163 (4)	0.0118 (3)	0.0031 (3)

Geometric parameters (Å, º)

Cu1—O1	1.933 (2)	C2—H2B	0.9600
Cu1—N4^i	1.970 (2)	C2—H2C	0.9600
Cu1—N1	1.986 (3)	C3—C4	1.500 (4)
Cu1—N1^ii	2.002 (3)	C3—H3A	0.9600
Cu1—O3	2.351 (2)	C3—H3B	0.9600
Cu2—O2	1.936 (2)	C3—H3C	0.9600
Cu2—O2^i	1.936 (2)	C4—O2	1.245 (4)
Cu2—N4^i	1.995 (2)	C4—O1	1.259 (4)
Cu2—N4	1.995 (2)	N1—N2	1.217 (4)
Cu2—O3	2.542 (2)	N1—Cu1^ii	2.002 (3)
C1—S1	1.765 (4)	N2—N3	1.116 (4)
C1—H1A	0.9600	N4—N5	1.215 (4)
C1—H1B	0.9600	N4—Cu1^i	1.970 (2)
C1—H1C	0.9600	N5—N6	1.133 (4)
C2—S1	1.760 (5)	O3—S1	1.517 (2)
C2—H2A	0.9600
O1—Cu1—N4^i	92.49 (11)	H2A—C2—H2C	109.5
O1—Cu1—N1	166.25 (11)	H2B—C2—H2C	109.5
N4^i—Cu1—N1	98.17 (11)	C4—C3—H3A	109.5
O1—Cu1—N1^ii	89.72 (10)	C4—C3—H3B	109.5
N4^i—Cu1—N1^ii	165.71 (13)	H3A—C3—H3B	109.5
N1—Cu1—N1^ii	77.84 (12)	C4—C3—H3C	109.5
O1—Cu1—O3	91.09 (10)	H3A—C3—H3C	109.5
N4^i—Cu1—O3	87.19 (10)	H3B—C3—H3C	109.5
N1—Cu1—O3	98.06 (12)	O2—C4—O1	126.0 (3)
N1^ii—Cu1—O3	106.90 (12)	O2—C4—C3	117.2 (3)
O2—Cu2—O2^i	180.00 (15)	O1—C4—C3	116.8 (3)
O2—Cu2—N4^i	90.66 (10)	N2—N1—Cu1	129.6 (2)
O2^i—Cu2—N4^i	89.34 (10)	N2—N1—Cu1^ii	124.8 (2)
O2—Cu2—N4	89.34 (10)	Cu1—N1—Cu1^ii	102.16 (11)
O2^i—Cu2—N4	90.66 (10)	N3—N2—N1	178.7 (4)
N4^i—Cu2—N4	180.0	N5—N4—Cu1^i	122.3 (2)
S1—C1—H1A	109.5	N5—N4—Cu2	120.7 (2)
S1—C1—H1B	109.5	Cu1^i—N4—Cu2	104.04 (11)
H1A—C1—H1B	109.5	N6—N5—N4	178.3 (4)
S1—C1—H1C	109.5	C4—O1—Cu1	128.8 (2)
H1A—C1—H1C	109.5	C4—O2—Cu2	131.9 (2)
H1B—C1—H1C	109.5	S1—O3—Cu1	124.36 (14)
S1—C2—H2A	109.5	O3—S1—C2	104.30 (19)
S1—C2—H2B	109.5	O3—S1—C1	105.62 (19)
H2A—C2—H2B	109.5	C2—S1—C1	97.6 (3)
S1—C2—H2C	109.5
O1—Cu1—N1—N2	−175.2 (4)	N4^i—Cu1—O1—C4	35.2 (3)
N4^i—Cu1—N1—N2	−34.7 (4)	N1—Cu1—O1—C4	176.1 (5)
N1^ii—Cu1—N1—N2	159.2 (5)	N1^ii—Cu1—O1—C4	−158.9 (3)
O3—Cu1—N1—N2	53.6 (4)	O3—Cu1—O1—C4	−52.0 (3)
O1—Cu1—N1—Cu1^ii	25.6 (6)	O1—C4—O2—Cu2	−1.5 (6)
N4^i—Cu1—N1—Cu1^ii	166.06 (14)	C3—C4—O2—Cu2	177.6 (3)
N1^ii—Cu1—N1—Cu1^ii	0.0	N4^i—Cu2—O2—C4	−34.0 (3)
O3—Cu1—N1—Cu1^ii	−105.65 (14)	N4—Cu2—O2—C4	146.0 (3)
O2—Cu2—N4—N5	−27.1 (3)	O1—Cu1—O3—S1	−177.11 (17)
O2^i—Cu2—N4—N5	152.9 (3)	N4^i—Cu1—O3—S1	90.44 (18)
O2—Cu2—N4—Cu1^i	114.98 (12)	N1—Cu1—O3—S1	−7.41 (19)
O2^i—Cu2—N4—Cu1^i	−65.02 (12)	N1^ii—Cu1—O3—S1	−87.08 (18)
O2—C4—O1—Cu1	1.1 (5)	Cu1—O3—S1—C2	−173.7 (2)
C3—C4—O1—Cu1	−178.1 (3)	Cu1—O3—S1—C1	83.9 (2)

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