catena-Poly[[bis­(dimethyl­formamide-κO)cadmium]-bis­(μ-4-nitro­phenyl­cyanamido-κ2N1:N3)]

Chiniforoshan, H.; Jazestani, M.; Notash, B.

doi:10.1107/S1600536812001924

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page m232

doi:10.1107/S1600536812001924

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catena-Poly[[bis(dimethylformamide-κO)cadmium]-bis(μ-4-nitrophenylcyanamido-κ²N¹:N³)]

Hossein Chiniforoshan,^a ^* Mehdi Jazestani ^a and Behrouz Notash ^b

^aDepartment of Chemistry, Isfahan University of Technology, Isfahan 84456-38111, Iran, and ^bDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: chinif@cc.iut.ac.ir

(Received 5 December 2011; accepted 16 January 2012; online 4 February 2012)

In the title coordination polymer, [Cd(C₇H₄N₃O₂)₂(C₃H₇NO)₂]_n, the Cd^II atom, lying on an inversion center, is six-coordinated in a distorted N₄O₂ octahedral geometry. The N atoms of the 4-nitrophenylcyanamide anions form the equatorial plane and the O atoms of the dimethylformamide molecules occupy the axial positions. The anions act as bridging ligands, connecting the Cd atoms into a one-dimensional coordination polymer along [100].

Related literature

For background to phenylcyanamide ligands and their complexes, see: Crutchley (2001 ). For polynuclear complexes of phenylcyanamide ligands, see: Ainscough et al. (1991 ); Chiniforoshan et al. (2009 , 2010 ); Escuer et al. (2004 ). For the preparation of 4-nitro-phenylcyanamide used in the synthesis of the title compound, see: Crutchley & Naklicki (1989 ).

Experimental

Crystal data

[Cd(C₇H₄N₃O₂)₂(C₃H₇NO)₂]
M_r = 582.87
Triclinic, $[P \overline 1]$
a = 5.6070 (11) Å
b = 9.811 (2) Å
c = 11.679 (2) Å
α = 67.44 (3)°
β = 81.93 (3)°
γ = 84.28 (3)°
V = 586.7 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 298 K
0.45 × 0.10 × 0.08 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002 ) T_min = 0.887, T_max = 0.923
6589 measured reflections
3150 independent reflections
3038 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.114
S = 1.11
3150 reflections
162 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N1ⁱ	2.287 (3)
Cd1—O3	2.347 (3)
Cd1—N2	2.383 (3)
Symmetry code: (i) -x+1, -y+2, -z.

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812001924/hy2496sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001924/hy2496Isup2.hkl

checkCIF report

Comment top

Phenylcyanmide ligands can act as monodentate, bidentate and also as bridging ligands (Crutchley, 2001). In the bridging mode, the cyanamido group (NCN) is coordinated in an end-to-end mode, forming polynuclear complexes (Ainscough et al., 1991; Chiniforoshan et al., 2009, 2010; Escuer et al., 2004).

Following our work with this family of ligands, we report here the synthesis and crystal structure of a cadmium(II) coordination polymer of 4-nitro-phenylcyanamide ligand (Crutchley & Naklicki, 1989). The asymmetric unit of the title compound is shown in Fig. 1. In the title compound, the Cd^II atom lies on an inversion center and has a distorted octahedral geometry (Fig. 2, Table 1). The coordination environment consists of four N atoms from 4-nitro-phenylcyanamide ligands in the equatorial plane and two O atoms from DMF molecules in the axial positions. The one-dimensional structure of the title compound is shown in Fig. 2.

Related literature top

For background to phenylcyanamide ligands and their complexes, see: Crutchley (2001). For polynuclear complexes of phenylcyanamide ligands, see: Ainscough et al. (1991); Chiniforoshan et al. (2009, 2010); Escuer et al. (2004). For the preparation of 4-nitro-phenylcyanamide used in the synthesis of the title compound, see: Crutchley & Naklicki (1989).

Experimental top

4-Nitrophenylcynamide (Crutchley & Naklicki, 1989) (0.163 g, 1 mmol) was dissolved in methanol (25 ml) and was added slowly to a solution of cadmium(II) acetate (0.133 g, 0.5 mmol) in methanol (25 ml). The mixture was stirred for 3 hrs. The resulting solid was filtered off. Yellow needles of the title compound were obtained by n-hexane diffusion into a DMF solution of the title compound after 4 weeks.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at 50% probability level.
	Fig. 2. The one-dimensional polymeric structure of the title compound. [Symmetry codes: (i) 1-x, 2-y, -z; (ii) -1+x, y, z; (iii) -x, 2-y, -z; (iv) 1+x, y, z.]

catena-Poly[[bis(dimethylformamide-κO)cadmium]-bis(µ-4- nitrophenylcyanamido-κ²N¹:N³)] top

Crystal data top

[Cd(C₇H₄N₃O₂)₂(C₃H₇NO)₂]	Z = 1
M_r = 582.87	F(000) = 294
Triclinic, P1	D_x = 1.650 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6070 (11) Å	Cell parameters from 3150 reflections
b = 9.811 (2) Å	θ = 2.3–29.2°
c = 11.679 (2) Å	µ = 0.98 mm⁻¹
α = 67.44 (3)°	T = 298 K
β = 81.93 (3)°	Needle, yellow
γ = 84.28 (3)°	0.45 × 0.10 × 0.08 mm
V = 586.7 (2) Å³

Data collection top

Stoe IPDS 2T diffractometer	3150 independent reflections
Radiation source: fine-focus sealed tube	3038 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ω scans	θ_max = 29.2°, θ_min = 2.3°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)	h = −7→7
T_min = 0.887, T_max = 0.923	k = −13→13
6589 measured reflections	l = −15→16

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0672P)² + 0.308P] where P = (F_o² + 2F_c²)/3
3150 reflections	(Δ/σ)_max < 0.001
162 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −0.89 e Å⁻³

Crystal data top

[Cd(C₇H₄N₃O₂)₂(C₃H₇NO)₂]	γ = 84.28 (3)°
M_r = 582.87	V = 586.7 (2) Å³
Triclinic, P1	Z = 1
a = 5.6070 (11) Å	Mo Kα radiation
b = 9.811 (2) Å	µ = 0.98 mm⁻¹
c = 11.679 (2) Å	T = 298 K
α = 67.44 (3)°	0.45 × 0.10 × 0.08 mm
β = 81.93 (3)°

Data collection top

Stoe IPDS 2T diffractometer	3150 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)	3038 reflections with I > 2σ(I)
T_min = 0.887, T_max = 0.923	R_int = 0.066
6589 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.11	Δρ_max = 0.82 e Å⁻³
3150 reflections	Δρ_min = −0.89 e Å⁻³
162 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cd1	0.0000	1.0000	0.0000	0.03092 (12)
O1	−0.1591 (9)	0.2034 (5)	0.4718 (4)	0.0897 (14)
O2	0.1354 (7)	0.1984 (4)	0.5719 (3)	0.0705 (10)
O3	0.0654 (5)	1.1593 (3)	0.0984 (3)	0.0493 (6)
N1	0.6524 (5)	0.9163 (3)	0.1262 (3)	0.0404 (6)
N2	0.2627 (5)	0.8176 (3)	0.1293 (3)	0.0362 (5)
N3	0.0180 (6)	0.2570 (4)	0.4842 (3)	0.0511 (8)
N4	0.3441 (5)	1.1798 (4)	0.2129 (3)	0.0417 (6)
C1	0.2102 (5)	0.6769 (3)	0.2158 (3)	0.0326 (6)
C2	0.3446 (6)	0.6018 (4)	0.3172 (3)	0.0392 (7)
H2	0.4765	0.6457	0.3264	0.047*
C3	0.2838 (7)	0.4640 (4)	0.4033 (3)	0.0437 (7)
H3	0.3748	0.4149	0.4694	0.052*
C4	0.0864 (6)	0.4002 (4)	0.3899 (3)	0.0387 (7)
C5	−0.0458 (6)	0.4682 (4)	0.2903 (4)	0.0446 (8)
H5	−0.1761	0.4225	0.2818	0.053*
C6	0.0172 (6)	0.6057 (4)	0.2026 (4)	0.0413 (7)
H6	−0.0697	0.6511	0.1344	0.050*
C7	0.4701 (5)	0.8656 (4)	0.1296 (3)	0.0338 (6)
C8	0.1668 (6)	1.1147 (4)	0.1947 (4)	0.0412 (7)
H8	0.1137	1.0288	0.2590	0.049*
C9	0.4414 (9)	1.3125 (5)	0.1153 (5)	0.0584 (10)
H9A	0.6050	1.2913	0.0873	0.088*
H9B	0.4371	1.3892	0.1476	0.088*
H9C	0.3461	1.3444	0.0466	0.088*
C10	0.4716 (9)	1.1095 (6)	0.3235 (5)	0.0598 (11)
H10A	0.3882	1.0246	0.3806	0.090*
H10B	0.4778	1.1784	0.3631	0.090*
H10C	0.6327	1.0793	0.2994	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01969 (14)	0.03075 (16)	0.03821 (18)	−0.00441 (9)	−0.00930 (10)	−0.00556 (12)
O1	0.092 (3)	0.066 (2)	0.089 (3)	−0.048 (2)	−0.027 (2)	0.011 (2)
O2	0.073 (2)	0.0528 (18)	0.0584 (19)	−0.0116 (16)	−0.0145 (16)	0.0133 (15)
O3	0.0510 (14)	0.0441 (14)	0.0569 (16)	−0.0031 (11)	−0.0226 (12)	−0.0175 (12)
N1	0.0274 (11)	0.0406 (14)	0.0439 (15)	−0.0065 (10)	−0.0072 (10)	−0.0035 (12)
N2	0.0253 (11)	0.0335 (13)	0.0425 (14)	−0.0060 (9)	−0.0082 (10)	−0.0037 (11)
N3	0.0499 (17)	0.0391 (16)	0.0529 (18)	−0.0092 (13)	−0.0037 (14)	−0.0038 (14)
N4	0.0381 (13)	0.0435 (15)	0.0451 (15)	−0.0046 (11)	−0.0100 (11)	−0.0159 (13)
C1	0.0256 (12)	0.0321 (14)	0.0362 (14)	−0.0014 (10)	−0.0073 (10)	−0.0072 (11)
C2	0.0347 (14)	0.0401 (16)	0.0398 (16)	−0.0078 (12)	−0.0126 (12)	−0.0075 (13)
C3	0.0431 (17)	0.0400 (17)	0.0389 (17)	−0.0069 (13)	−0.0139 (13)	−0.0003 (13)
C4	0.0380 (15)	0.0302 (14)	0.0436 (17)	−0.0045 (11)	−0.0024 (13)	−0.0092 (13)
C5	0.0341 (15)	0.0359 (16)	0.059 (2)	−0.0078 (12)	−0.0133 (14)	−0.0081 (15)
C6	0.0332 (14)	0.0350 (15)	0.0507 (19)	−0.0046 (11)	−0.0181 (13)	−0.0052 (14)
C7	0.0256 (12)	0.0349 (14)	0.0340 (14)	0.0007 (10)	−0.0073 (10)	−0.0045 (11)
C8	0.0410 (16)	0.0386 (16)	0.0467 (18)	−0.0055 (13)	−0.0073 (13)	−0.0172 (14)
C9	0.059 (2)	0.054 (2)	0.060 (2)	−0.0214 (19)	−0.0045 (19)	−0.015 (2)
C10	0.056 (2)	0.072 (3)	0.056 (2)	0.001 (2)	−0.0242 (19)	−0.024 (2)

Geometric parameters (Å, º) top

Cd1—N1ⁱ	2.287 (3)	C2—C3	1.381 (5)
Cd1—O3	2.347 (3)	C2—H2	0.9300
Cd1—N2	2.383 (3)	C3—C4	1.380 (5)
O1—N3	1.219 (5)	C3—H3	0.9300
O2—N3	1.214 (5)	C4—C5	1.377 (5)
O3—C8	1.238 (5)	C5—C6	1.388 (5)
N1—C7	1.170 (4)	C5—H5	0.9300
N1—Cd1ⁱⁱ	2.287 (3)	C6—H6	0.9300
N2—C7	1.299 (4)	C8—H8	0.9300
N2—C1	1.392 (4)	C9—H9A	0.9600
N3—C4	1.461 (4)	C9—H9B	0.9600
N4—C8	1.316 (4)	C9—H9C	0.9600
N4—C9	1.456 (5)	C10—H10A	0.9600
N4—C10	1.460 (5)	C10—H10B	0.9600
C1—C6	1.401 (4)	C10—H10C	0.9600
C1—C2	1.409 (4)

N1ⁱ—Cd1—N1ⁱⁱⁱ	180.000 (1)	C3—C2—H2	119.5
N1ⁱ—Cd1—O3	86.19 (12)	C1—C2—H2	119.5
N1ⁱⁱⁱ—Cd1—O3	93.81 (12)	C4—C3—C2	119.2 (3)
N1ⁱ—Cd1—O3^iv	93.81 (12)	C4—C3—H3	120.4
N1ⁱⁱⁱ—Cd1—O3^iv	86.19 (12)	C2—C3—H3	120.4
O3—Cd1—O3^iv	180.00 (10)	C5—C4—C3	121.5 (3)
N1ⁱ—Cd1—N2^iv	95.72 (10)	C5—C4—N3	119.8 (3)
N1ⁱⁱⁱ—Cd1—N2^iv	84.28 (10)	C3—C4—N3	118.7 (3)
O3—Cd1—N2^iv	90.74 (10)	C4—C5—C6	119.4 (3)
O3^iv—Cd1—N2^iv	89.26 (10)	C4—C5—H5	120.3
N1ⁱ—Cd1—N2	84.28 (10)	C6—C5—H5	120.3
N1ⁱⁱⁱ—Cd1—N2	95.72 (10)	C5—C6—C1	120.8 (3)
O3—Cd1—N2	89.26 (10)	C5—C6—H6	119.6
O3^iv—Cd1—N2	90.74 (10)	C1—C6—H6	119.6
N2^iv—Cd1—N2	180.0	N1—C7—N2	176.4 (3)
C8—O3—Cd1	121.5 (2)	O3—C8—N4	124.9 (4)
C7—N1—Cd1ⁱⁱ	142.5 (3)	O3—C8—H8	117.6
C7—N2—C1	116.9 (3)	N4—C8—H8	117.6
C7—N2—Cd1	113.9 (2)	N4—C9—H9A	109.5
C1—N2—Cd1	128.50 (19)	N4—C9—H9B	109.5
O2—N3—O1	123.1 (4)	H9A—C9—H9B	109.5
O2—N3—C4	119.1 (3)	N4—C9—H9C	109.5
O1—N3—C4	117.7 (4)	H9A—C9—H9C	109.5
C8—N4—C9	120.7 (3)	H9B—C9—H9C	109.5
C8—N4—C10	120.8 (4)	N4—C10—H10A	109.5
C9—N4—C10	117.9 (4)	N4—C10—H10B	109.5
N2—C1—C6	119.5 (3)	H10A—C10—H10B	109.5
N2—C1—C2	122.5 (3)	N4—C10—H10C	109.5
C6—C1—C2	118.0 (3)	H10A—C10—H10C	109.5
C3—C2—C1	121.1 (3)	H10B—C10—H10C	109.5

N1ⁱ—Cd1—O3—C8	−96.1 (3)	C6—C1—C2—C3	−1.9 (5)
N1ⁱⁱⁱ—Cd1—O3—C8	83.9 (3)	C1—C2—C3—C4	−0.7 (6)
N2^iv—Cd1—O3—C8	168.2 (3)	C2—C3—C4—C5	2.5 (6)
N2—Cd1—O3—C8	−11.8 (3)	C2—C3—C4—N3	−177.6 (4)
N1ⁱ—Cd1—N2—C7	35.1 (3)	O2—N3—C4—C5	−179.7 (4)
N1ⁱⁱⁱ—Cd1—N2—C7	−144.9 (3)	O1—N3—C4—C5	−1.2 (6)
O3—Cd1—N2—C7	−51.2 (3)	O2—N3—C4—C3	0.4 (6)
O3^iv—Cd1—N2—C7	128.8 (3)	O1—N3—C4—C3	178.9 (5)
N1ⁱ—Cd1—N2—C1	−155.1 (3)	C3—C4—C5—C6	−1.5 (6)
N1ⁱⁱⁱ—Cd1—N2—C1	24.9 (3)	N3—C4—C5—C6	178.6 (4)
O3—Cd1—N2—C1	118.6 (3)	C4—C5—C6—C1	−1.2 (6)
O3^iv—Cd1—N2—C1	−61.4 (3)	N2—C1—C6—C5	−177.2 (3)
C7—N2—C1—C6	−165.8 (3)	C2—C1—C6—C5	2.9 (5)
Cd1—N2—C1—C6	24.6 (5)	Cd1—O3—C8—N4	131.9 (3)
C7—N2—C1—C2	14.0 (5)	C9—N4—C8—O3	−1.7 (6)
Cd1—N2—C1—C2	−155.5 (3)	C10—N4—C8—O3	−172.6 (4)
N2—C1—C2—C3	178.2 (3)

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

Experimental details

Crystal data
Chemical formula	[Cd(C₇H₄N₃O₂)₂(C₃H₇NO)₂]
M_r	582.87
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.6070 (11), 9.811 (2), 11.679 (2)
α, β, γ (°)	67.44 (3), 81.93 (3), 84.28 (3)
V (Å³)	586.7 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.98
Crystal size (mm)	0.45 × 0.10 × 0.08

Data collection
Diffractometer	Stoe IPDS 2T diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.887, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	6589, 3150, 3038
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.114, 1.11
No. of reflections	3150
No. of parameters	162
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.89

Computer programs: X-AREA (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cd1—N1ⁱ	2.287 (3)	Cd1—N2	2.383 (3)
Cd1—O3	2.347 (3)

Symmetry code: (i) −x+1, −y+2, −z.

Acknowledgements

The authors acknowledge financial support from Isfahan University of Technology.

References

Ainscough, E. W., Baker, E. N., Brader, M. L. & Brodie, A. M. (1991). J. Chem. Soc. Dalton Trans. pp. 1243–1249. CSD CrossRef Web of Science Google Scholar
Chiniforoshan, H., Jalilpour, S., Shirinfar, B. & Khavasi, H. R. (2009). Acta Cryst. E65, m386. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chiniforoshan, H., Shirinfar, B., Jalilpour, S. & Khavasi, H. R. (2010). Acta Cryst. E66, m331. Web of Science CSD CrossRef IUCr Journals Google Scholar
Crutchley, R. J. (2001). Coord. Chem. Rev. 219, 125–155. Web of Science CrossRef Google Scholar
Crutchley, R. J. & Naklicki, M. L. (1989). Inorg. Chem. 28, 1955–1958. CrossRef CAS Web of Science Google Scholar
Escuer, A., Mautner, F. A., Sanz, N. & Vicente, R. (2004). Polyhedron, 23, 1409–1417. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2002). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar

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