catena-Poly[[[2-(pyridin-2-yldisulfan­yl)pyridine-κ²N,S]copper(I)]-μ_1,5-dicyanamido]

In the title compound, [Cu(C₂N₃)(C₁₀H₈N₂S₂)]_n, the Cu^I atoms are connected by bridging dicyanamide ligands, forming chains parallel to [100]. Each Cu^I atom displays a tetra­hedral coordination environment, formed by one S atom and three N atoms from one 2-(pyridin-2-yldisulfan­yl)pyridine and two dicyanamide ligands. The crystal structure is stabilized by C—H...N hydrogen bonds, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.028
• wR factor = 0.081
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    --  S1      ..      49.45 su
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          1

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         29
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          3
PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc)          1
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         51

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu1     .......       2.00

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

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

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S1. Comment

Metal-organic compounds have attracted much attention because of their diverse structures (Eddaoudi et al., 2001). Flexible ligands can play different roles in constructing metal-organic frameworks (Xu et al., 2009). The title compound, {C₁₂H₈CuN₅S₂}_n, is constructed by two kinds of flexible ligands: briding dicyanamide ligands and chelate 2-(pyridin-2-yldisulfanyl)pyridine ligands. In this paper, the crystal structure of the title compound is presented. As illustrated in Fig. 1, the Cu atoms are connected by briding dicyanamide ligands, forming a serrate chain. Each Cu atom displays a tetrahedral coordination environment, formed by one S atom and three N atoms from one 2-(pyridin-2-yldisulfanyl)pyridine and two dicyanamide ligands, where the Cu—S and average Cu—N bonds are 2.472 (1) and 1.969 Å, respectively. The crystal structure is stabilized by C—H···N hydrogen bonds [H9···N3ⁱⁱⁱ = 2.53 Å, C9···N3ⁱⁱⁱ = 3.453 (3) Å, and C9—H9···N3ⁱⁱⁱ = 171°] between the central N atom of the dicyanamide and one H atom of a pyridine ring, forming a three-dimensional network [symmetry code: (iii) x + 1, y - 1, z].

Related literature

For potential applications of metal-organic frameworks, see: Eddaoudi et al. (2001). For metal-organic frameworks constructed from flexible ligands, see: Xu et al. (2009). For related structures, see: Mal et al. (2006); Schlueter et al. (2007); Sen et al. (2007).

S2. Experimental

CuN(CN)₂ (0.4 mmol) and NaN(CN)₂ (1.2 mmol) were added into 2 ml DMF with thorough stir for 6 minutes. After filtration, the colorless filtrate was carefully laid on the surface with the solution of bis(2-pyridyl)disulfide (0.5 mmol) in 5 ml i-PrOH. Colorless crystals were obtained after 3 weeks.

S3. Refinement

The H atoms were positioned geometrically and refined with a riding model, with C—H = 0.93 Å and U_iso = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of a portion of the title compound, with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted [symmetry code: (i) x+1, y, z].

catena-Poly[[[2-(pyridin-2-yldisulfanyl)pyridine- κ²N,S]copper(I)]-µ_1,5-dicyanamido]

Crystal data

[Cu(C2N3)(C10H8N2S2)]	Z = 2
Mr = 349.92	F(000) = 352
Triclinic, P1	Dx = 1.671 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6294 (15) Å	Cell parameters from 3088 reflections
b = 9.5964 (19) Å	θ = 3.0–28.9°
c = 10.202 (2) Å	µ = 1.87 mm^−1
α = 84.19 (3)°	T = 293 K
β = 80.63 (3)°	Block, colourless
γ = 70.93 (3)°	0.20 × 0.16 × 0.12 mm
V = 695.6 (2) Å^3

Data collection

Bruker APEXII CCD diffractometer	2669 independent reflections
Radiation source: fine-focus sealed tube	2301 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
Tmin = 0.893, Tmax = 1.000	k = −11→11
6615 measured reflections	l = −12→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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0478P)^2 + 0.0204P] where P = (Fo^2 + 2Fc^2)/3
2669 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.29 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	−0.03943 (3)	0.83530 (3)	0.16964 (3)	0.05693 (13)
S1	−0.00326 (7)	0.67390 (7)	0.37486 (5)	0.05609 (17)
S2	0.11161 (9)	0.47767 (7)	0.28919 (5)	0.06255 (18)
N1	−0.3026 (2)	0.9293 (2)	0.16879 (19)	0.0580 (5)
N2	0.1131 (2)	0.9633 (2)	0.17961 (19)	0.0599 (5)
N3	−0.6377 (2)	1.0592 (2)	0.2077 (2)	0.0694 (6)
N4	0.3589 (3)	0.6469 (2)	0.38308 (18)	0.0610 (5)
N5	0.1249 (2)	0.65814 (18)	0.06703 (15)	0.0464 (4)
C1	−0.4605 (3)	0.9840 (2)	0.1839 (2)	0.0489 (5)
C2	0.2361 (3)	1.0016 (2)	0.1905 (2)	0.0480 (5)
C3	0.1841 (3)	0.7106 (2)	0.43562 (18)	0.0452 (4)
C4	0.1311 (3)	0.8103 (3)	0.5330 (2)	0.0612 (6)
H4	0.0059	0.8499	0.5684	0.073*
C5	0.2682 (4)	0.8504 (3)	0.5770 (2)	0.0709 (7)
H5	0.2372	0.9197	0.6414	0.085*
C6	0.4516 (4)	0.7863 (3)	0.5242 (2)	0.0692 (7)
H6	0.5475	0.8109	0.5519	0.083*
C7	0.4889 (3)	0.6858 (3)	0.4302 (2)	0.0695 (7)
H7	0.6136	0.6409	0.3963	0.083*
C8	0.1811 (3)	0.5212 (2)	0.11824 (18)	0.0462 (5)
C9	0.2919 (4)	0.4027 (2)	0.0454 (2)	0.0627 (6)
H9	0.3245	0.3078	0.0850	0.075*
C10	0.3528 (4)	0.4264 (3)	−0.0852 (2)	0.0681 (7)
H10	0.4289	0.3484	−0.1362	0.082*
C11	0.2996 (4)	0.5682 (3)	−0.1403 (2)	0.0660 (6)
H11	0.3402	0.5877	−0.2292	0.079*
C12	0.1868 (3)	0.6795 (2)	−0.0633 (2)	0.0568 (5)
H12	0.1505	0.7748	−0.1019	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03597 (17)	0.0595 (2)	0.0745 (2)	−0.01273 (13)	−0.00278 (13)	−0.01572 (14)
S1	0.0434 (3)	0.0798 (4)	0.0469 (3)	−0.0244 (3)	0.0007 (2)	−0.0063 (3)
S2	0.0847 (4)	0.0645 (4)	0.0502 (3)	−0.0423 (3)	−0.0082 (3)	0.0048 (3)
N1	0.0393 (10)	0.0623 (11)	0.0748 (12)	−0.0157 (9)	−0.0099 (8)	−0.0125 (9)
N2	0.0394 (10)	0.0572 (11)	0.0836 (13)	−0.0155 (9)	−0.0067 (9)	−0.0086 (10)
N3	0.0382 (10)	0.0433 (10)	0.1278 (17)	−0.0077 (8)	−0.0184 (10)	−0.0154 (11)
N4	0.0464 (10)	0.0763 (13)	0.0606 (10)	−0.0187 (9)	0.0016 (8)	−0.0213 (10)
N5	0.0448 (9)	0.0463 (9)	0.0459 (9)	−0.0120 (7)	−0.0051 (7)	−0.0025 (7)
C1	0.0433 (12)	0.0430 (10)	0.0654 (12)	−0.0170 (9)	−0.0154 (10)	−0.0011 (9)
C2	0.0353 (10)	0.0381 (10)	0.0647 (12)	−0.0040 (8)	−0.0064 (9)	−0.0028 (9)
C3	0.0450 (11)	0.0532 (11)	0.0357 (9)	−0.0147 (9)	−0.0049 (8)	0.0008 (9)
C4	0.0542 (13)	0.0674 (14)	0.0528 (11)	−0.0058 (11)	−0.0028 (10)	−0.0145 (11)
C5	0.0843 (18)	0.0700 (15)	0.0601 (13)	−0.0197 (14)	−0.0148 (12)	−0.0186 (12)
C6	0.0719 (16)	0.0802 (17)	0.0667 (14)	−0.0325 (14)	−0.0237 (13)	−0.0036 (13)
C7	0.0453 (12)	0.0879 (18)	0.0762 (15)	−0.0188 (12)	−0.0066 (11)	−0.0184 (14)
C8	0.0496 (11)	0.0484 (11)	0.0467 (10)	−0.0227 (9)	−0.0093 (9)	−0.0022 (9)
C9	0.0802 (17)	0.0417 (11)	0.0665 (14)	−0.0190 (11)	−0.0118 (12)	−0.0030 (11)
C10	0.0834 (18)	0.0525 (13)	0.0635 (14)	−0.0162 (12)	0.0008 (12)	−0.0167 (11)
C11	0.0817 (17)	0.0652 (15)	0.0466 (11)	−0.0200 (13)	0.0006 (11)	−0.0081 (11)
C12	0.0596 (13)	0.0518 (12)	0.0520 (11)	−0.0108 (10)	−0.0056 (10)	0.0024 (10)

Geometric parameters (Å, º)

Cu1—N1	1.9143 (18)	C3—C4	1.369 (3)
Cu1—N2	1.967 (2)	C4—C5	1.377 (4)
Cu1—N5	2.0244 (18)	C4—H4	0.9300
Cu1—S1	2.4720 (10)	C5—C6	1.373 (4)
S1—C3	1.792 (2)	C5—H5	0.9300
S1—S2	2.0207 (11)	C6—C7	1.361 (4)
S2—C8	1.787 (2)	C6—H6	0.9300
N1—C1	1.138 (3)	C7—H7	0.9300
N2—C2	1.138 (3)	C8—C9	1.378 (3)
N3—C2^i	1.298 (3)	C9—C10	1.360 (3)
N3—C1	1.303 (3)	C9—H9	0.9300
N4—C3	1.319 (3)	C10—C11	1.375 (3)
N4—C7	1.337 (3)	C10—H10	0.9300
N5—C8	1.322 (3)	C11—C12	1.359 (3)
N5—C12	1.356 (3)	C11—H11	0.9300
C2—N3^ii	1.298 (3)	C12—H12	0.9300
N1—Cu1—N2	117.16 (8)	C6—C5—C4	118.9 (2)
N1—Cu1—N5	126.58 (8)	C6—C5—H5	120.6
N2—Cu1—N5	107.60 (7)	C4—C5—H5	120.6
N1—Cu1—S1	106.75 (7)	C7—C6—C5	118.1 (2)
N2—Cu1—S1	104.29 (6)	C7—C6—H6	121.0
N5—Cu1—S1	87.90 (5)	C5—C6—H6	121.0
C3—S1—S2	105.95 (8)	N4—C7—C6	124.6 (2)
C3—S1—Cu1	102.35 (7)	N4—C7—H7	117.7
S2—S1—Cu1	98.20 (4)	C6—C7—H7	117.7
C8—S2—S1	105.52 (8)	N5—C8—C9	123.48 (18)
C1—N1—Cu1	172.06 (19)	N5—C8—S2	121.22 (16)
C2—N2—Cu1	161.63 (17)	C9—C8—S2	115.29 (16)
C2^i—N3—C1	120.23 (19)	C10—C9—C8	119.1 (2)
C3—N4—C7	115.9 (2)	C10—C9—H9	120.5
C8—N5—C12	116.52 (18)	C8—C9—H9	120.5
C8—N5—Cu1	124.88 (13)	C9—C10—C11	118.6 (2)
C12—N5—Cu1	118.59 (14)	C9—C10—H10	120.7
N1—C1—N3	173.2 (2)	C11—C10—H10	120.7
N2—C2—N3^ii	173.5 (2)	C12—C11—C10	119.2 (2)
N4—C3—C4	124.4 (2)	C12—C11—H11	120.4
N4—C3—S1	119.92 (16)	C10—C11—H11	120.4
C4—C3—S1	115.61 (16)	N5—C12—C11	123.1 (2)
C3—C4—C5	118.1 (2)	N5—C12—H12	118.5
C3—C4—H4	120.9	C11—C12—H12	118.5
C5—C4—H4	120.9

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N3^iii	0.93	2.53	3.453 (3)	171

Symmetry code: (iii) x+1, y−1, z.