supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2008). E64, m1386    [ doi:10.1107/S1600536808032297 ]

catena-Poly[[[2,6-bis(pyrazol-1-yl-[kappa]N2)pyridine-[kappa]N1](nitrato-[kappa]2O,O')cadmium(II)]-[mu]-thiocyanato-[kappa]2N:S]

Z. N. Yang and T. T. Sun

Abstract top

In the title crystal structure, [Cd(NCS)(NO3)(C11H9N5)]n, the unique CdII ion is coordinated in a distorted pentagonal-bipyramidal environment. The axial thiocyanate ligands act in a [mu]1,3-bridging mode to connect symmetry-related CdII ions into one-dimensional chains along [010]. In addition, there are intermolecular C-H...O contacts between chains.

Comment top

Both the 2,6-bis(pyrazolyl)pyridine and thiocyanate ligands play an important role in modern coordination chemistry (Halcrow 2005; Shi et al. 2006), and our interest in complexes formed with these ligands led us to prepare the title complex and determine its crystal structure (I).

As shown in Fig. 1 the CdII ion is coordinated in a distorted pentagonal–bipyramidal environment with the 2,6-bis(pyrazolyl)pyridine and nitrate anion acting as chelating tridentate and bidentate ligands, respectively. The axial thiocyantate ligands bridge symmetry-related CdII ions [with a Cd···Cd separation of 6.1817 (10) Å] to form a one-dimensional `zigzag' chain along the b axis (Fig. 2). In addition, the crystal structure contains C—H···O and C—H···S short contacts between chains.

Related literature top

For background information, see: Halcrow (2005); Shi et al. (2006).

Experimental top

A 15 ml methanol solution containing 2,6-bis(pyrazolyl)pyridine (0.4140 g, 0.196 mmol) was added to 8 ml H2O solution of Cd(NO3)26H2O (0.0689 g, 0.200 mmol) and NaSCN (0.0324 g, 0.400 mmol), and the mixture was stirred for a few minutes. Colorless single crystals were obtained after the filtrate was allowed to stand at room temperature for a month.

Refinement top

All H atoms were placed in calculated positions with C—H = 0.93 Å and refined as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (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 top
[Figure 1] Fig. 1. View of part of the structure of (I), with displacement ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) -x + 3/2, y + 1/2, -z + 1/2; (ii) -x + 3/2, y - 1/2, -z + 1/2.]
[Figure 2] Fig. 2. Part of the one-dimensional chain of (I).
catena-Poly[[[2,6-bis(pyrazol-1-yl-κN2)pyridine-κN1](nitrato- κ2O,O')cadmium(II)]-µ-thiocyanato-κ2N:S] top
Crystal data top
[Cd(NCS)(NO3)(C11H9N5)]F(000) = 872
Mr = 443.72Dx = 1.923 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2732 reflections
a = 8.4161 (15) Åθ = 2.2–24.8°
b = 11.817 (2) ŵ = 1.59 mm−1
c = 15.631 (3) ÅT = 298 K
β = 99.673 (2)°Block, colourless
V = 1532.5 (5) Å30.18 × 0.15 × 0.11 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		3335 independent reflections
Radiation source: fine-focus sealed tube2710 reflections with I > 2σ(I)
graphiteRint = 0.034
φ and ω scansθmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→7
Tmin = 0.763, Tmax = 0.845k = −15→14
8813 measured reflectionsl = −19→19
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0324P)2]
where P = (Fo2 + 2Fc2)/3
3335 reflections(Δ/σ)max = 0.001
217 parametersΔρmax = 0.53 e Å−3
1 restraintΔρmin = −0.35 e Å−3
Crystal data top
[Cd(NCS)(NO3)(C11H9N5)]V = 1532.5 (5) Å3
Mr = 443.72Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.4161 (15) ŵ = 1.59 mm−1
b = 11.817 (2) ÅT = 298 K
c = 15.631 (3) Å0.18 × 0.15 × 0.11 mm
β = 99.673 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer		3335 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2710 reflections with I > 2σ(I)
Tmin = 0.763, Tmax = 0.845Rint = 0.034
8813 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.074Δρmax = 0.53 e Å−3
S = 1.02Δρmin = −0.35 e Å−3
3335 reflectionsAbsolute structure: ?
217 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
C10.8278 (4)0.8449 (3)0.3362 (2)0.0413 (8)
C20.3464 (4)0.7893 (3)0.1478 (2)0.0507 (9)
H20.30420.76890.19680.061*
C30.2736 (5)0.8650 (3)0.0850 (3)0.0582 (11)
H30.17690.90340.08400.070*
C40.3722 (5)0.8708 (3)0.0265 (3)0.0550 (10)
H40.35690.9151−0.02340.066*
C50.6374 (4)0.7813 (2)0.01605 (19)0.0399 (8)
C60.6570 (5)0.8277 (3)−0.0627 (2)0.0558 (10)
H60.57650.8708−0.09550.067*
C70.8005 (6)0.8073 (3)−0.0903 (2)0.0654 (12)
H70.81870.8386−0.14230.078*
C80.9175 (5)0.7420 (3)−0.0429 (2)0.0596 (11)
H81.01530.7286−0.06120.071*
C90.8833 (4)0.6968 (3)0.0337 (2)0.0428 (8)
C101.1325 (5)0.5770 (3)0.0743 (3)0.0666 (12)
H101.18040.58610.02530.080*
C111.1898 (5)0.5134 (3)0.1447 (3)0.0705 (12)
H111.28340.47010.15380.085*
C121.0793 (5)0.5266 (3)0.2001 (3)0.0633 (11)
H121.08850.49230.25430.076*
Cd10.69811 (3)0.631846 (17)0.194115 (13)0.03553 (9)
N10.9587 (4)0.5939 (2)0.16692 (19)0.0501 (7)
N20.9920 (4)0.6253 (2)0.08807 (19)0.0468 (7)
N30.7484 (3)0.7163 (2)0.06248 (15)0.0370 (6)
N40.4991 (3)0.8004 (2)0.05286 (16)0.0389 (6)
N50.4831 (3)0.7503 (2)0.12873 (16)0.0416 (6)
N60.7831 (5)0.7729 (3)0.29035 (19)0.0716 (12)
N70.6367 (3)0.5128 (2)0.34211 (16)0.0410 (6)
O10.6028 (3)0.4666 (2)0.40633 (16)0.0704 (8)
O20.7776 (3)0.5144 (2)0.32709 (14)0.0483 (6)
O30.5296 (3)0.5612 (2)0.28825 (14)0.0552 (6)
S10.89559 (11)0.94486 (6)0.40588 (5)0.0430 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.049 (2)0.0320 (17)0.0409 (17)0.0047 (15)0.0013 (15)0.0078 (14)
C20.049 (2)0.0420 (19)0.061 (2)0.0077 (17)0.0092 (18)−0.0019 (16)
C30.042 (2)0.045 (2)0.083 (3)0.0052 (17)−0.007 (2)−0.0069 (19)
C40.056 (2)0.0379 (19)0.063 (2)0.0029 (18)−0.015 (2)0.0093 (16)
C50.052 (2)0.0279 (15)0.0362 (16)−0.0140 (15)−0.0035 (15)0.0005 (13)
C60.074 (3)0.048 (2)0.0410 (19)−0.017 (2)−0.0016 (19)0.0085 (16)
C70.094 (3)0.064 (3)0.0368 (19)−0.031 (3)0.007 (2)0.0046 (18)
C80.069 (3)0.061 (2)0.055 (2)−0.026 (2)0.029 (2)−0.0149 (19)
C90.050 (2)0.0376 (18)0.0404 (17)−0.0173 (17)0.0064 (16)−0.0060 (14)
C100.047 (2)0.063 (3)0.095 (3)−0.014 (2)0.027 (2)−0.032 (2)
C110.041 (2)0.053 (2)0.115 (4)0.005 (2)0.006 (2)−0.024 (3)
C120.047 (2)0.057 (2)0.080 (3)0.010 (2)−0.007 (2)−0.010 (2)
Cd10.04344 (16)0.03132 (14)0.03132 (13)0.00301 (10)0.00483 (10)0.00214 (9)
N10.0439 (18)0.0509 (16)0.0541 (18)0.0074 (15)0.0047 (14)0.0011 (14)
N20.0382 (17)0.0452 (16)0.0589 (18)−0.0105 (13)0.0133 (14)−0.0136 (13)
N30.0421 (17)0.0308 (13)0.0372 (13)−0.0067 (12)0.0037 (12)0.0000 (11)
N40.0430 (17)0.0294 (13)0.0402 (14)−0.0014 (12)−0.0045 (12)0.0026 (11)
N50.0474 (18)0.0340 (14)0.0419 (15)−0.0001 (13)0.0032 (13)0.0025 (11)
N60.116 (3)0.0365 (17)0.0525 (18)0.0005 (18)−0.015 (2)−0.0097 (14)
N70.0462 (18)0.0433 (15)0.0339 (14)0.0003 (14)0.0076 (13)−0.0010 (12)
O10.078 (2)0.0841 (19)0.0511 (15)−0.0113 (16)0.0165 (14)0.0281 (14)
O20.0494 (15)0.0532 (15)0.0416 (11)0.0051 (12)0.0056 (11)0.0075 (9)
O30.0491 (15)0.0758 (17)0.0407 (13)0.0098 (13)0.0080 (11)0.0087 (12)
S10.0561 (6)0.0331 (4)0.0364 (4)−0.0018 (4)−0.0015 (4)−0.0006 (3)
Geometric parameters (Å, °) top
C1—N61.135 (4)C10—C111.352 (6)
C1—S11.642 (4)C10—N21.362 (5)
C2—N51.319 (4)C10—H100.9300
C2—C31.391 (5)C11—C121.383 (6)
C2—H20.9300C11—H110.9300
C3—C41.336 (6)C12—N11.325 (4)
C3—H30.9300C12—H120.9300
C4—N41.362 (4)Cd1—N62.279 (3)
C4—H40.9300Cd1—N12.346 (3)
C5—N31.327 (4)Cd1—O32.361 (2)
C5—C61.383 (4)Cd1—N52.379 (3)
C5—N41.400 (4)Cd1—N32.388 (2)
C6—C71.370 (6)Cd1—O22.495 (2)
C6—H60.9300Cd1—S1i2.7447 (9)
C7—C81.367 (5)N1—N21.360 (4)
C7—H70.9300N4—N51.352 (3)
C8—C91.385 (5)N7—O11.218 (3)
C8—H80.9300N7—O21.247 (3)
C9—N31.310 (4)N7—O31.262 (3)
C9—N21.418 (4)S1—Cd1ii2.7447 (9)
N6—C1—S1177.5 (3)O3—Cd1—N589.01 (9)
N5—C2—C3111.3 (4)N6—Cd1—N3100.47 (10)
N5—C2—H2124.3N1—Cd1—N367.50 (9)
C3—C2—H2124.3O3—Cd1—N3153.74 (9)
C4—C3—C2105.4 (4)N5—Cd1—N367.41 (9)
C4—C3—H3127.3N6—Cd1—O281.17 (9)
C2—C3—H3127.3N1—Cd1—O285.22 (9)
C3—C4—N4107.9 (3)O3—Cd1—O252.36 (8)
C3—C4—H4126.1N5—Cd1—O2139.77 (9)
N4—C4—H4126.1N3—Cd1—O2152.71 (9)
N3—C5—C6122.5 (4)N6—Cd1—S1i173.33 (8)
N3—C5—N4115.2 (3)N1—Cd1—S1i86.04 (7)
C6—C5—N4122.3 (3)O3—Cd1—S1i85.71 (6)
C7—C6—C5117.0 (4)N5—Cd1—S1i95.98 (6)
C7—C6—H6121.5N3—Cd1—S1i85.49 (6)
C5—C6—H6121.5O2—Cd1—S1i92.16 (6)
C8—C7—C6121.4 (4)C12—N1—N2105.0 (3)
C8—C7—H7119.3C12—N1—Cd1136.2 (3)
C6—C7—H7119.3N2—N1—Cd1116.9 (2)
C7—C8—C9116.8 (4)N1—N2—C10110.1 (3)
C7—C8—H8121.6N1—N2—C9119.7 (3)
C9—C8—H8121.6C10—N2—C9130.1 (4)
N3—C9—C8123.2 (3)C9—N3—C5119.0 (3)
N3—C9—N2114.0 (3)C9—N3—Cd1120.8 (2)
C8—C9—N2122.8 (3)C5—N3—Cd1120.2 (2)
C11—C10—N2107.8 (4)N5—N4—C4110.1 (3)
C11—C10—H10126.1N5—N4—C5120.2 (2)
N2—C10—H10126.1C4—N4—C5129.6 (3)
C10—C11—C12105.1 (4)C2—N5—N4105.3 (3)
C10—C11—H11127.4C2—N5—Cd1137.6 (2)
C12—C11—H11127.4N4—N5—Cd1117.0 (2)
N1—C12—C11111.9 (4)C1—N6—Cd1177.7 (3)
N1—C12—H12124.0O1—N7—O2121.5 (3)
C11—C12—H12124.0O1—N7—O3120.9 (3)
N6—Cd1—N193.43 (12)O2—N7—O3117.6 (3)
N6—Cd1—O390.12 (11)N7—O2—Cd191.99 (17)
N1—Cd1—O3136.31 (9)N7—O3—Cd198.02 (19)
N6—Cd1—N589.13 (10)C1—S1—Cd1ii99.61 (11)
N1—Cd1—N5134.53 (10)
N5—C2—C3—C4−0.1 (4)N6—Cd1—N3—C5−87.3 (2)
C2—C3—C4—N40.5 (4)N1—Cd1—N3—C5−176.7 (2)
N3—C5—C6—C7−2.4 (5)O3—Cd1—N3—C524.9 (3)
N4—C5—C6—C7177.1 (3)N5—Cd1—N3—C5−2.70 (19)
C5—C6—C7—C81.4 (5)O2—Cd1—N3—C5−178.35 (18)
C6—C7—C8—C90.6 (5)S1i—Cd1—N3—C595.7 (2)
C7—C8—C9—N3−1.8 (5)C3—C4—N4—N5−0.7 (4)
C7—C8—C9—N2178.5 (3)C3—C4—N4—C5−176.5 (3)
N2—C10—C11—C12−0.4 (4)N3—C5—N4—N5−2.6 (4)
C10—C11—C12—N10.3 (4)C6—C5—N4—N5178.0 (3)
C11—C12—N1—N2−0.1 (4)N3—C5—N4—C4172.9 (3)
C11—C12—N1—Cd1162.7 (3)C6—C5—N4—C4−6.6 (5)
N6—Cd1—N1—C1290.2 (3)C3—C2—N5—N4−0.3 (4)
O3—Cd1—N1—C12−3.6 (4)C3—C2—N5—Cd1175.3 (2)
N5—Cd1—N1—C12−177.6 (3)C4—N4—N5—C20.6 (3)
N3—Cd1—N1—C12−169.9 (4)C5—N4—N5—C2176.9 (3)
O2—Cd1—N1—C129.4 (3)C4—N4—N5—Cd1−176.07 (19)
S1i—Cd1—N1—C12−83.1 (3)C5—N4—N5—Cd10.2 (3)
N6—Cd1—N1—N2−108.5 (2)N6—Cd1—N5—C2−72.3 (3)
O3—Cd1—N1—N2157.76 (18)N1—Cd1—N5—C2−166.3 (3)
N5—Cd1—N1—N2−16.3 (3)O3—Cd1—N5—C217.8 (3)
N3—Cd1—N1—N2−8.6 (2)N3—Cd1—N5—C2−174.1 (3)
O2—Cd1—N1—N2170.7 (2)O2—Cd1—N5—C22.8 (4)
S1i—Cd1—N1—N278.2 (2)S1i—Cd1—N5—C2103.4 (3)
C12—N1—N2—C10−0.1 (4)N6—Cd1—N5—N4102.9 (2)
Cd1—N1—N2—C10−166.9 (2)N1—Cd1—N5—N49.0 (3)
C12—N1—N2—C9178.6 (3)O3—Cd1—N5—N4−166.94 (19)
Cd1—N1—N2—C911.9 (3)N3—Cd1—N5—N41.21 (18)
C11—C10—N2—N10.4 (4)O2—Cd1—N5—N4178.12 (16)
C11—C10—N2—C9−178.3 (3)S1i—Cd1—N5—N4−81.36 (19)
N3—C9—N2—N1−7.0 (4)O1—N7—O2—Cd1−177.4 (3)
C8—C9—N2—N1172.7 (3)O3—N7—O2—Cd12.5 (3)
N3—C9—N2—C10171.5 (3)N6—Cd1—O2—N795.51 (19)
C8—C9—N2—C10−8.8 (5)N1—Cd1—O2—N7−170.26 (18)
C8—C9—N3—C50.9 (4)O3—Cd1—O2—N7−1.52 (16)
N2—C9—N3—C5−179.3 (2)N5—Cd1—O2—N717.5 (2)
C8—C9—N3—Cd1178.9 (2)N3—Cd1—O2—N7−168.76 (17)
N2—C9—N3—Cd1−1.3 (3)S1i—Cd1—O2—N7−84.41 (17)
C6—C5—N3—C91.3 (4)O1—N7—O3—Cd1177.2 (3)
N4—C5—N3—C9−178.2 (3)O2—N7—O3—Cd1−2.7 (3)
C6—C5—N3—Cd1−176.8 (2)N6—Cd1—O3—N7−77.21 (19)
N4—C5—N3—Cd13.7 (3)N1—Cd1—O3—N717.9 (2)
N6—Cd1—N3—C994.7 (2)N5—Cd1—O3—N7−166.34 (18)
N1—Cd1—N3—C95.3 (2)N3—Cd1—O3—N7168.29 (17)
O3—Cd1—N3—C9−153.0 (2)O2—Cd1—O3—N71.52 (16)
N5—Cd1—N3—C9179.3 (2)S1i—Cd1—O3—N797.59 (17)
O2—Cd1—N3—C93.7 (3)N6—C1—S1—Cd1ii179 (100)
S1i—Cd1—N3—C9−82.3 (2)
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1iii0.932.503.412 (5)167
C4—H4···O2iv0.932.473.370 (4)164
C7—H7···O3v0.932.523.312 (5)143
C10—H10···S1v0.932.833.723 (4)160
Symmetry codes: (iii) −x+1/2, y+1/2, −z+1/2; (iv) x−1/2, −y+3/2, z−1/2; (v) x+1/2, −y+3/2, z−1/2.
Table 1
Selected geometric parameters (Å, °) top
Cd1—N62.279 (3)Cd1—N32.388 (2)
Cd1—N12.346 (3)Cd1—O22.495 (2)
Cd1—O32.361 (2)Cd1—S1i2.7447 (9)
Cd1—N52.379 (3)
N6—Cd1—N193.43 (12)N1—Cd1—O285.22 (9)
N6—Cd1—O390.12 (11)O3—Cd1—O252.36 (8)
N1—Cd1—O3136.31 (9)N5—Cd1—O2139.77 (9)
N6—Cd1—N589.13 (10)N3—Cd1—O2152.71 (9)
N1—Cd1—N5134.53 (10)N6—Cd1—S1i173.33 (8)
O3—Cd1—N589.01 (9)N1—Cd1—S1i86.04 (7)
N6—Cd1—N3100.47 (10)O3—Cd1—S1i85.71 (6)
N1—Cd1—N367.50 (9)N5—Cd1—S1i95.98 (6)
O3—Cd1—N3153.74 (9)N3—Cd1—S1i85.49 (6)
N5—Cd1—N367.41 (9)O2—Cd1—S1i92.16 (6)
N6—Cd1—O281.17 (9)
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1ii0.932.503.412 (5)167
C4—H4···O2iii0.932.473.370 (4)164
C7—H7···O3iv0.932.523.312 (5)143
C10—H10···S1iv0.932.833.723 (4)160
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x−1/2, −y+3/2, z−1/2; (iv) x+1/2, −y+3/2, z−1/2.
Acknowledgements top

This work was supported by the Doctor's Foundation of Binzhou University.

references
References top

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Halcrow, M. A. (2005). Coord. Chem. Rev. 249, 2880–2908.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Shi, J. M., Sun, Y. M., Liu, Z., Liu, L. D., Shi, W. & Cheng, P. (2006). Dalton Trans. pp. 376–380.