PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m911.
Published online 2009 July 11. doi:  10.1107/S1600536809026269
PMCID: PMC2977342

Bis(1,10-phenanthroline-κ2 N,N′)(sulfato-κ2 O,O′)nickel(II) ethane-1,2-diol solvate

Abstract

In the title compound, [Ni(SO4)(C12H8N2)2]·C2H6O2, the coordination polyhedron around the Ni2+ ion is a distorted octahedron, with four N atoms from two phenanthroline groups and two O atoms from a bidentate sulfate ligand. The Ni2+ ion lies on a special position of site symmetry 2. Inter­molecular O—H(...)O hydrogen bonds help to stabilize the structure. The OH group of the ethane-1,2-diol solvent is disordered over two positions with equal occupancy.

Related literature

For Ni–phen complexes with chloride anions and water mol­ecules as a second ligand, see: Chen et al. (2005 [triangle]); Su & Xu (2005 [triangle]); Tang et al. (2007 [triangle]). For isostructural compounds, see: Zhong et al. (2006 [triangle]); Lu et al. (2006 [triangle]); Zhu et al. (2006a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m911-scheme1.jpg

Experimental

Crystal data

  • [Ni(SO4)(C12H8N2)2]·C2H6O2
  • M r = 577.25
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m911-efi2.jpg
  • a = 18.4551 (9) Å
  • b = 11.8839 (5) Å
  • c = 12.7526 (6) Å
  • β = 118.991 (6)°
  • V = 2446.4 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.93 mm−1
  • T = 295 K
  • 0.36 × 0.33 × 0.28 mm

Data collection

  • Oxford Diffraction Gemini S Ultra diffractometer
  • Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2009 [triangle]) T min = 0.731, T max = 0.781
  • 11586 measured reflections
  • 3010 independent reflections
  • 2467 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.106
  • S = 1.08
  • 3010 reflections
  • 183 parameters
  • 17 restraints
  • H-atom parameters constrained
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.52 e Å−3

Data collection: CrysAlisPro (Oxford Diffraction, 2009 [triangle]); cell refinement: CrysAlisPro; data reduction: CrysAlisPro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809026269/pk2166sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026269/pk2166Isup2.hkl

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

supplementary crystallographic information

Comment

Ni-phen (phen = phenanthroline) complexes with chloride-anion and water-molecule ligands have been synthesized and characterized by X-ray diffraction (Chen et al., 2005; Su & Xu, 2005; Tang et al., 2007). The title nickel complex [NiSO4(phen)2].C2H6O2, Fig. 1, is isostructural to the recently reported cobalt(II) and cadmium(II) analogs (Zhong et al., 2006; Lu et al., 2006). A twofold rotation axis passes through the Ni and S atoms, and also through the mid-point of the C—C bond of the solvent molcule. The NiII center has an octahedral geometry, with four N atoms from two phen groups and two O atoms from a bidentate sulfate ligand. The geometry of the phen and sulfate ligands are in good agreement with those reported in the two isomorphous complexes [ZnSO4(phen)2].C2H6O2 and [MnSO4(phen)2].C2H6O2 (Zhu et al., 2006a,b).

The ethane-1,2-diol solvent is disordered over two positions, and is hydrogen bonded to the sulfate ligand (Table 1).

Experimental

Green block-shaped crystals of the title compound were obtained by a procedure similar to that described previously (Zhong et al., 2006), but with NiSO4.7H2O in place of CoSO4.7H2O.

Refinement

The H atoms of phen were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The O atom of the ethane-1,2-diol solvent is disordered over two positions with site-occupancy factors of 1/2, sharing a common atom C13. The C13—C13 i (i = -x, y, -z+3/2), C13—O3 and C13—O3' distances were restrained to 1.501 (4), 1.304 (5) and 1.339 (5) Å, respectively. The H atoms of the ethane-1,2-diol were located in a difference map and then allowed to ride on their parent atoms, with C—H = 0.97 Å and O—H = 0.82 Å; Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).

Figures

Fig. 1.
The molecular structure showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. The dashed lines represent O—H···O interactions. Unlabeled atoms are related to the labelled ...

Crystal data

[Ni(SO4)(C12H8N2)2]·C2H6O2F(000) = 1192
Mr = 577.25Dx = 1.567 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6902 reflections
a = 18.4551 (9) Åθ = 3.2–30.6°
b = 11.8839 (5) ŵ = 0.93 mm1
c = 12.7526 (6) ÅT = 295 K
β = 118.991 (6)°Block, green
V = 2446.4 (2) Å30.36 × 0.33 × 0.28 mm
Z = 4

Data collection

Oxford Diffraction Gemini S Ultra diffractometer3010 independent reflections
Radiation source: fine-focus sealed tube2467 reflections with I > 2σ(I)
graphiteRint = 0.029
Detector resolution: 8.1241 pixels mm-1θmax = 28.3°, θmin = 3.2°
[var phi] and ω scansh = −24→24
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2009)k = −15→15
Tmin = 0.731, Tmax = 0.781l = −17→16
11586 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.106w = 1/[σ2(Fo2) + (0.0643P)2 + 0.296P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
3010 reflectionsΔρmax = 0.35 e Å3
183 parametersΔρmin = −0.52 e Å3
17 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0055 (6)

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 (Å2)

xyzUiso*/UeqOcc. (<1)
Ni10.00000.19859 (3)0.75000.02868 (15)
S10.0000−0.02657 (6)0.75000.02857 (19)
O2−0.05633 (9)0.05119 (13)0.65249 (13)0.0379 (4)
O10.04687 (11)−0.09628 (15)0.71006 (17)0.0479 (5)
N10.07956 (11)0.21105 (15)0.67829 (16)0.0314 (4)
N20.08892 (12)0.30656 (14)0.87419 (16)0.0331 (4)
C50.14702 (13)0.27545 (18)0.74544 (17)0.0291 (4)
C70.28779 (15)0.4016 (2)0.8974 (2)0.0438 (6)
H70.33470.44280.94810.053*
C90.22836 (17)0.4292 (2)1.0353 (2)0.0458 (6)
H90.27430.47021.08930.055*
C40.21016 (14)0.2934 (2)0.7163 (2)0.0368 (5)
C80.22400 (15)0.38596 (19)0.92872 (19)0.0368 (5)
C120.15344 (13)0.32477 (17)0.85260 (18)0.0303 (5)
C60.28132 (15)0.3577 (2)0.7956 (2)0.0454 (6)
H60.32360.36940.77690.055*
C10.07228 (15)0.1648 (2)0.5783 (2)0.0391 (5)
H10.02600.12090.53100.047*
C20.13218 (17)0.1802 (2)0.5424 (2)0.0474 (6)
H20.12500.14810.47150.057*
C30.20060 (16)0.2421 (2)0.6110 (2)0.0475 (6)
H30.24130.25060.58850.057*
C100.16452 (19)0.4099 (2)1.0571 (2)0.0507 (7)
H100.16670.43751.12680.061*
C110.09572 (16)0.3488 (2)0.9757 (2)0.0428 (6)
H110.05270.33690.99270.051*
C130.0291 (3)−0.4047 (3)0.7245 (4)0.0978 (14)
H13A0.0809−0.43510.78690.117*
H13B0.0073−0.46000.66060.117*
O30.0492 (5)−0.3177 (5)0.6817 (6)0.098 (2)0.50
H3A0.0752−0.27270.73590.147*0.50
O3'0.0850 (3)−0.3224 (4)0.7512 (6)0.0726 (17)0.50
H3'0.0792−0.29390.68910.109*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.0250 (2)0.0289 (2)0.0293 (2)0.0000.01088 (16)0.000
S10.0222 (3)0.0282 (4)0.0318 (4)0.0000.0103 (3)0.000
O20.0302 (8)0.0346 (9)0.0318 (8)−0.0013 (7)0.0014 (6)−0.0005 (6)
O10.0430 (10)0.0455 (11)0.0622 (11)0.0066 (8)0.0310 (9)−0.0055 (8)
N10.0282 (9)0.0318 (10)0.0304 (9)−0.0019 (8)0.0111 (7)−0.0032 (7)
N20.0377 (10)0.0293 (10)0.0325 (9)−0.0029 (8)0.0172 (8)−0.0026 (7)
C50.0266 (10)0.0280 (11)0.0282 (9)0.0013 (8)0.0097 (8)0.0015 (8)
C70.0300 (12)0.0428 (15)0.0448 (13)−0.0097 (10)0.0072 (10)−0.0017 (10)
C90.0495 (15)0.0406 (14)0.0351 (12)−0.0087 (12)0.0109 (11)−0.0088 (10)
C40.0307 (11)0.0397 (13)0.0387 (12)−0.0003 (10)0.0157 (9)0.0034 (9)
C80.0375 (12)0.0297 (12)0.0326 (11)−0.0042 (10)0.0088 (9)−0.0003 (9)
C120.0300 (11)0.0267 (11)0.0278 (10)−0.0001 (8)0.0091 (8)0.0013 (8)
C60.0295 (11)0.0544 (17)0.0491 (14)−0.0070 (12)0.0164 (10)0.0007 (12)
C10.0381 (12)0.0429 (13)0.0336 (11)−0.0037 (11)0.0154 (10)−0.0085 (9)
C20.0504 (15)0.0572 (17)0.0388 (13)−0.0021 (13)0.0248 (12)−0.0087 (11)
C30.0428 (14)0.0621 (18)0.0453 (13)−0.0046 (13)0.0275 (12)−0.0026 (12)
C100.0664 (18)0.0476 (16)0.0360 (12)−0.0080 (13)0.0231 (12)−0.0121 (11)
C110.0522 (15)0.0417 (14)0.0386 (12)−0.0074 (12)0.0252 (11)−0.0086 (10)
C130.111 (3)0.066 (2)0.141 (3)0.002 (2)0.081 (3)−0.002 (2)
O30.130 (5)0.087 (4)0.115 (4)0.009 (3)0.090 (4)0.017 (3)
O3'0.061 (3)0.042 (3)0.129 (5)0.017 (2)0.056 (3)0.028 (3)

Geometric parameters (Å, °)

Ni1—N1i2.0774 (18)C9—C81.418 (3)
Ni1—N12.0774 (18)C9—H90.9300
Ni1—N22.0805 (19)C4—C31.406 (3)
Ni1—N2i2.0805 (18)C4—C61.430 (3)
Ni1—O22.1077 (16)C8—C121.393 (3)
Ni1—O2i2.1077 (16)C6—H60.9300
Ni1—S12.6757 (8)C1—C21.398 (3)
S1—O1i1.4563 (17)C1—H10.9300
S1—O11.4563 (17)C2—C31.352 (4)
S1—O2i1.4926 (16)C2—H20.9300
S1—O21.4926 (16)C3—H30.9300
N1—C11.334 (3)C10—C111.392 (4)
N1—C51.355 (3)C10—H100.9300
N2—C111.337 (3)C11—H110.9300
N2—C121.363 (3)C13—O31.304 (5)
C5—C41.401 (3)C13—O3'1.339 (5)
C5—C121.438 (3)C13—C13i1.501 (4)
C7—C61.349 (4)C13—H13A0.9700
C7—C81.427 (4)C13—H13B0.9700
C7—H70.9300O3—H3A0.8200
C9—C101.355 (4)O3'—H3'0.8200
N1i—Ni1—N1171.82 (10)C8—C7—H7119.4
N1i—Ni1—N294.93 (7)C10—C9—C8119.0 (2)
N1—Ni1—N279.99 (7)C10—C9—H9120.5
N1i—Ni1—N2i79.99 (7)C8—C9—H9120.5
N1—Ni1—N2i94.93 (7)C5—C4—C3116.9 (2)
N2—Ni1—N2i103.84 (10)C5—C4—C6119.4 (2)
N1i—Ni1—O293.85 (7)C3—C4—C6123.7 (2)
N1—Ni1—O292.94 (7)C12—C8—C9117.2 (2)
N2—Ni1—O2160.60 (7)C12—C8—C7119.5 (2)
N2i—Ni1—O294.70 (6)C9—C8—C7123.3 (2)
N1i—Ni1—O2i92.94 (7)N2—C12—C8123.7 (2)
N1—Ni1—O2i93.85 (7)N2—C12—C5116.71 (19)
N2—Ni1—O2i94.70 (6)C8—C12—C5119.6 (2)
N2i—Ni1—O2i160.60 (7)C7—C6—C4120.7 (2)
O2—Ni1—O2i67.58 (8)C7—C6—H6119.7
N1i—Ni1—S194.09 (5)C4—C6—H6119.7
N1—Ni1—S194.09 (5)N1—C1—C2122.0 (2)
N2—Ni1—S1128.08 (5)N1—C1—H1119.0
N2i—Ni1—S1128.08 (5)C2—C1—H1119.0
O2—Ni1—S133.79 (4)C3—C2—C1119.9 (2)
O2i—Ni1—S133.79 (4)C3—C2—H2120.1
O1i—S1—O1110.66 (15)C1—C2—H2120.1
O1i—S1—O2i110.65 (10)C2—C3—C4119.9 (2)
O1—S1—O2i110.59 (10)C2—C3—H3120.0
O1i—S1—O2110.59 (10)C4—C3—H3120.0
O1—S1—O2110.65 (10)C9—C10—C11120.3 (2)
O2i—S1—O2103.50 (13)C9—C10—H10119.9
O1i—S1—Ni1124.67 (8)C11—C10—H10119.9
O1—S1—Ni1124.67 (8)N2—C11—C10122.8 (2)
O2i—S1—Ni151.75 (6)N2—C11—H11118.6
O2—S1—Ni151.75 (6)C10—C11—H11118.6
S1—O2—Ni194.46 (7)O3—C13—O3'35.7 (4)
C1—N1—C5118.22 (19)O3—C13—C13i126.2 (4)
C1—N1—Ni1128.76 (16)O3'—C13—C13i121.0 (4)
C5—N1—Ni1113.02 (13)O3—C13—H13A105.8
C11—N2—C12117.1 (2)O3'—C13—H13A74.5
C11—N2—Ni1129.66 (16)C13i—C13—H13A105.8
C12—N2—Ni1112.83 (14)O3—C13—H13B105.8
N1—C5—C4123.10 (19)O3'—C13—H13B131.5
N1—C5—C12117.27 (18)C13i—C13—H13B105.8
C4—C5—C12119.6 (2)H13A—C13—H13B106.2
C6—C7—C8121.2 (2)C13—O3—H3A109.5
C6—C7—H7119.4C13—O3'—H3'109.5
N1i—Ni1—S1—O1i0.87 (10)O2i—Ni1—N2—C11−82.5 (2)
N1—Ni1—S1—O1i−179.13 (10)S1—Ni1—N2—C11−88.3 (2)
N2—Ni1—S1—O1i100.39 (11)N1i—Ni1—N2—C12−177.26 (15)
N2i—Ni1—S1—O1i−79.61 (11)N1—Ni1—N2—C12−3.72 (14)
O2—Ni1—S1—O1i−89.95 (12)N2i—Ni1—N2—C12−96.38 (15)
O2i—Ni1—S1—O1i90.05 (12)O2—Ni1—N2—C1266.1 (3)
N1i—Ni1—S1—O1−179.13 (10)O2i—Ni1—N2—C1289.37 (15)
N1—Ni1—S1—O10.87 (10)S1—Ni1—N2—C1283.62 (15)
N2—Ni1—S1—O1−79.61 (11)C1—N1—C5—C4−1.6 (3)
N2i—Ni1—S1—O1100.39 (11)Ni1—N1—C5—C4178.30 (17)
O2—Ni1—S1—O190.05 (12)C1—N1—C5—C12179.8 (2)
O2i—Ni1—S1—O1−89.95 (12)Ni1—N1—C5—C12−0.3 (2)
N1i—Ni1—S1—O2i−89.18 (9)N1—C5—C4—C30.8 (3)
N1—Ni1—S1—O2i90.82 (9)C12—C5—C4—C3179.4 (2)
N2—Ni1—S1—O2i10.34 (10)N1—C5—C4—C6−176.7 (2)
N2i—Ni1—S1—O2i−169.66 (10)C12—C5—C4—C61.9 (3)
O2—Ni1—S1—O2i180.0C10—C9—C8—C12−0.4 (4)
N1i—Ni1—S1—O290.82 (9)C10—C9—C8—C7−180.0 (2)
N1—Ni1—S1—O2−89.18 (9)C6—C7—C8—C12−0.3 (4)
N2—Ni1—S1—O2−169.66 (10)C6—C7—C8—C9179.2 (3)
N2i—Ni1—S1—O210.34 (10)C11—N2—C12—C8−1.3 (3)
O2i—Ni1—S1—O2180.0Ni1—N2—C12—C8−174.28 (17)
O1i—S1—O2—Ni1118.53 (10)C11—N2—C12—C5177.7 (2)
O1—S1—O2—Ni1−118.49 (9)Ni1—N2—C12—C54.7 (2)
O2i—S1—O2—Ni10.0C9—C8—C12—N21.2 (3)
N1i—Ni1—O2—S1−91.59 (8)C7—C8—C12—N2−179.2 (2)
N1—Ni1—O2—S192.96 (8)C9—C8—C12—C5−177.8 (2)
N2—Ni1—O2—S125.2 (2)C7—C8—C12—C51.8 (3)
N2i—Ni1—O2—S1−171.85 (8)N1—C5—C12—N2−3.0 (3)
O2i—Ni1—O2—S10.0C4—C5—C12—N2178.32 (19)
N1i—Ni1—N1—C1−126.0 (2)N1—C5—C12—C8176.05 (19)
N2—Ni1—N1—C1−178.0 (2)C4—C5—C12—C8−2.6 (3)
N2i—Ni1—N1—C1−74.8 (2)C8—C7—C6—C4−0.4 (4)
O2—Ni1—N1—C120.2 (2)C5—C4—C6—C7−0.4 (4)
O2i—Ni1—N1—C187.9 (2)C3—C4—C6—C7−177.7 (3)
S1—Ni1—N1—C154.0 (2)C5—N1—C1—C20.6 (4)
N1i—Ni1—N1—C554.20 (14)Ni1—N1—C1—C2−179.27 (19)
N2—Ni1—N1—C52.17 (14)N1—C1—C2—C31.2 (4)
N2i—Ni1—N1—C5105.39 (15)C1—C2—C3—C4−1.9 (4)
O2—Ni1—N1—C5−159.64 (15)C5—C4—C3—C21.0 (4)
O2i—Ni1—N1—C5−91.93 (15)C6—C4—C3—C2178.3 (3)
S1—Ni1—N1—C5−125.80 (14)C8—C9—C10—C11−0.3 (4)
N1i—Ni1—N2—C1110.8 (2)C12—N2—C11—C100.5 (4)
N1—Ni1—N2—C11−175.6 (2)Ni1—N2—C11—C10172.17 (19)
N2i—Ni1—N2—C1191.7 (2)C9—C10—C11—N20.2 (4)
O2—Ni1—N2—C11−105.8 (3)

Symmetry codes: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3A···O10.822.152.659 (7)121
O3'—H3'···O10.822.472.763 (5)102

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2166).

References

  • Chen, J.-M., Fan, S.-R. & Zhu, L.-G. (2005). Acta Cryst. E61, m1724–m1726.
  • Lu, W.-J., Zhong, K.-L. & Zhu, Y.-M. (2006). Acta Cryst. E62, m891–m893.
  • Oxford Diffraction (2009). ABSPACK and CrysAlisPro Oxford Diffraction Ltd, Yarnton, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Su, J.-R. & Xu, D.-J. (2005). Acta Cryst. E61, m1738–m1740.
  • Tang, X.-Y., Qiu, Y.-C., Sun, F. & Yue, S.-T. (2007). Acta Cryst. E63, m2515.
  • Zhong, K.-L., Zhu, Y.-M. & Lu, W.-J. (2006). Acta Cryst. E62, m631–m633.
  • Zhu, Y.-M., Zhong, K.-L. & Lu, W.-J. (2006a). Acta Cryst. E62, m2688–m2689.
  • Zhu, Y.-M., Zhong, K.-L. & Lu, W.-J. (2006b). Acta Cryst. E62, m2725–m2726.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography