Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101000919/bm1427sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101000919/bm1427Isup2.hkl |
For related literature, see: Adams & Raynor (1965); Chertanova & Pascard (1996); Ferrari et al. (1965); Hand & Prout (1966); Hathaway (1987); Jeffrey (1997); Palmer (1954); Prout & Powell (1961); Traube & Passarge (1913).
Chromous hydrazine sulfate was prepared by reacting chromous acetate with hydrazine sulfate in dilute sulfuric acid (Adams & Raynor, 1965) and was crystallized from the reaction medium.
The H atoms were located in the difference map and were refined with unconstrained isotropic displacement parameters, but with a fixed N—H distance of 0.88 Å. When the determination was carried out, the diffractometer was incapable of collecting cusp data, and so we report a comparatively low completeness of possible data. The somewhat low reflections/parameters ratio is caused by the refinement of parameters for the H atoms.
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 1999) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Cr(N2H5)2(SO4)2] | Z = 1 |
Mr = 310.24 | F(000) = 158 |
Triclinic, P1 | Dx = 2.366 Mg m−3 |
a = 7.2662 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 5.4568 (5) Å | Cell parameters from 1336 reflections |
c = 5.7092 (6) Å | θ = 3.6–26.0° |
α = 97.596 (2)° | µ = 1.83 mm−1 |
β = 91.830 (2)° | T = 100 K |
γ = 103.493 (2)° | Rectangular prism, blue |
V = 217.73 (3) Å3 | 0.35 × 0.10 × 0.10 mm |
Nonius KappaCCD area-detector diffractometer | 786 independent reflections |
Radiation source: fine-focus sealed tube | 751 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 9.09 pixels mm-1 | θmax = 26.0°, θmin = 3.6° |
2° ϕ frames scans | h = −8→8 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −6→6 |
Tmin = 0.567, Tmax = 0.838 | l = −6→7 |
1336 measured reflections |
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)] = 0.025 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.074 | All H-atom parameters refined |
S = 1.18 | w = 1/[σ2(Fo2) + 0.4661P] where P = (Fo2 + 2Fc2)/3 |
786 reflections | (Δ/σ)max < 0.001 |
91 parameters | Δρmax = 0.32 e Å−3 |
5 restraints | Δρmin = −0.58 e Å−3 |
[Cr(N2H5)2(SO4)2] | γ = 103.493 (2)° |
Mr = 310.24 | V = 217.73 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.2662 (3) Å | Mo Kα radiation |
b = 5.4568 (5) Å | µ = 1.83 mm−1 |
c = 5.7092 (6) Å | T = 100 K |
α = 97.596 (2)° | 0.35 × 0.10 × 0.10 mm |
β = 91.830 (2)° |
Nonius KappaCCD area-detector diffractometer | 786 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 751 reflections with I > 2σ(I) |
Tmin = 0.567, Tmax = 0.838 | Rint = 0.021 |
1336 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 5 restraints |
wR(F2) = 0.074 | All H-atom parameters refined |
S = 1.18 | Δρmax = 0.32 e Å−3 |
786 reflections | Δρmin = −0.58 e Å−3 |
91 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cr | 0.0000 | 0.0000 | 0.0000 | 0.0069 (2) | |
S | 0.22578 (9) | 0.65572 (12) | 0.25201 (10) | 0.0043 (2) | |
O1 | 0.1197 (3) | 0.8620 (4) | 0.2695 (3) | 0.0065 (4) | |
O2 | 0.0916 (3) | 0.4063 (4) | 0.2378 (3) | 0.0096 (4) | |
O3 | 0.3545 (3) | 0.7047 (4) | 0.4685 (3) | 0.0070 (4) | |
O4 | 0.3390 (3) | 0.6709 (4) | 0.0417 (3) | 0.0071 (4) | |
N1 | 0.2575 (3) | 0.0712 (5) | −0.1781 (4) | 0.0069 (5) | |
N2 | 0.2794 (3) | 0.2740 (5) | −0.3238 (4) | 0.0082 (5) | |
H1 | 0.269 (5) | −0.062 (4) | −0.277 (5) | 0.009 (8)* | |
H2 | 0.365 (3) | 0.120 (7) | −0.090 (6) | 0.025 (10)* | |
H3 | 0.284 (5) | 0.420 (3) | −0.234 (5) | 0.015 (9)* | |
H4 | 0.390 (2) | 0.291 (7) | −0.387 (5) | 0.013 (8)* | |
H5 | 0.183 (3) | 0.253 (7) | −0.427 (4) | 0.012 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr | 0.0063 (4) | 0.0084 (4) | 0.0069 (3) | 0.0027 (3) | 0.0009 (2) | 0.0028 (2) |
S | 0.0050 (4) | 0.0040 (4) | 0.0043 (3) | 0.0020 (3) | −0.0002 (2) | 0.0008 (2) |
O1 | 0.0081 (9) | 0.0060 (11) | 0.0071 (9) | 0.0052 (8) | −0.0003 (7) | 0.0013 (7) |
O2 | 0.0105 (9) | 0.0054 (11) | 0.0112 (9) | −0.0015 (8) | −0.0006 (7) | 0.0016 (7) |
O3 | 0.0073 (9) | 0.0090 (10) | 0.0052 (9) | 0.0030 (8) | −0.0018 (7) | 0.0015 (7) |
O4 | 0.0078 (9) | 0.0097 (11) | 0.0047 (9) | 0.0037 (8) | 0.0021 (7) | 0.0007 (7) |
N1 | 0.0086 (11) | 0.0053 (13) | 0.0071 (11) | 0.0015 (10) | 0.0011 (8) | 0.0024 (8) |
N2 | 0.0088 (11) | 0.0077 (14) | 0.0082 (11) | 0.0014 (10) | −0.0015 (8) | 0.0034 (9) |
Cr—O1i | 2.0535 (17) | S—O1 | 1.5006 (18) |
Cr—O1ii | 2.0535 (17) | S—O2 | 1.468 (2) |
Cr—O2 | 2.3791 (19) | S—O3 | 1.4820 (18) |
Cr—O2iii | 2.3791 (19) | S—O4 | 1.4775 (18) |
Cr—N1iii | 2.138 (2) | O1—Criv | 2.0535 (17) |
Cr—N1 | 2.138 (2) | N1—N2 | 1.453 (3) |
O1i—Cr—O1ii | 180.00 (9) | N1iii—Cr—O2iii | 91.50 (8) |
O1i—Cr—N1iii | 87.09 (8) | N1—Cr—O2iii | 88.50 (8) |
O1ii—Cr—N1iii | 92.91 (8) | O2—Cr—O2iii | 180.00 (11) |
O1i—Cr—N1 | 92.91 (8) | O2—S—O4 | 111.29 (11) |
O1ii—Cr—N1 | 87.09 (8) | O2—S—O3 | 110.22 (11) |
N1iii—Cr—N1 | 180.00 (17) | O4—S—O3 | 109.46 (11) |
O1i—Cr—O2 | 86.73 (7) | O2—S—O1 | 109.79 (11) |
O1ii—Cr—O2 | 93.27 (7) | O4—S—O1 | 108.87 (10) |
N1iii—Cr—O2 | 88.50 (8) | O3—S—O1 | 107.10 (10) |
N1—Cr—O2 | 91.50 (8) | S—O1—Criv | 128.35 (11) |
O1i—Cr—O2iii | 93.27 (7) | S—O2—Cr | 141.90 (11) |
O1ii—Cr—O2iii | 86.73 (7) | N2—N1—Cr | 115.17 (16) |
O2—S—O1—Criv | −85.92 (16) | O1ii—Cr—O2—S | −70.81 (19) |
O4—S—O1—Criv | 36.14 (17) | N1iii—Cr—O2—S | −163.64 (19) |
O3—S—O1—Criv | 154.40 (13) | N1—Cr—O2—S | 16.36 (19) |
O4—S—O2—Cr | 4.5 (2) | O1i—Cr—N1—N2 | −152.83 (17) |
O3—S—O2—Cr | −117.15 (17) | O1ii—Cr—N1—N2 | 27.17 (17) |
O1—S—O2—Cr | 125.10 (17) | O2—Cr—N1—N2 | −66.04 (18) |
O1i—Cr—O2—S | 109.19 (19) | O2iii—Cr—N1—N2 | 113.96 (18) |
Symmetry codes: (i) x, y−1, z; (ii) −x, −y+1, −z; (iii) −x, −y, −z; (iv) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3v | 0.88 (3) | 2.01 (3) | 2.872 (3) | 164 (3) |
N1—H2···O4vi | 0.88 (3) | 2.18 (2) | 2.970 (3) | 150 (3) |
N2—H3···O4 | 0.88 (3) | 1.91 (2) | 2.746 (3) | 158 (3) |
N2—H4···O3vi | 0.88 (3) | 1.92 (2) | 2.792 (3) | 168 (3) |
N2—H5···O2vii | 0.88 (3) | 2.32 (2) | 3.061 (3) | 142 (3) |
N2—H5···O1ii | 0.88 (3) | 2.38 (3) | 2.858 (3) | 114 (2) |
N2—H5···O1v | 0.88 (3) | 2.51 (3) | 3.004 (3) | 117 (3) |
Symmetry codes: (ii) −x, −y+1, −z; (v) x, y−1, z−1; (vi) −x+1, −y+1, −z; (vii) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Cr(N2H5)2(SO4)2] |
Mr | 310.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.2662 (3), 5.4568 (5), 5.7092 (6) |
α, β, γ (°) | 97.596 (2), 91.830 (2), 103.493 (2) |
V (Å3) | 217.73 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.83 |
Crystal size (mm) | 0.35 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.567, 0.838 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1336, 786, 751 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.074, 1.18 |
No. of reflections | 786 |
No. of parameters | 91 |
No. of restraints | 5 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.32, −0.58 |
Computer programs: COLLECT (Hooft, 1998), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 1999) and ORTEP-3 (Farrugia, 1997), SHELXL97.
Cr—O1i | 2.0535 (17) | S—O2 | 1.468 (2) |
Cr—O2 | 2.3791 (19) | S—O3 | 1.4820 (18) |
Cr—N1 | 2.138 (2) | S—O4 | 1.4775 (18) |
S—O1 | 1.5006 (18) | N1—N2 | 1.453 (3) |
O1i—Cr—N1 | 92.91 (8) | O2—S—O1 | 109.79 (11) |
O1i—Cr—O2 | 86.73 (7) | O4—S—O1 | 108.87 (10) |
N1—Cr—O2 | 91.50 (8) | O3—S—O1 | 107.10 (10) |
O2—S—O4 | 111.29 (11) | S—O1—Crii | 128.35 (11) |
O2—S—O3 | 110.22 (11) | S—O2—Cr | 141.90 (11) |
O4—S—O3 | 109.46 (11) | N2—N1—Cr | 115.17 (16) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3iii | 0.88 (3) | 2.01 (3) | 2.872 (3) | 164 (3) |
N1—H2···O4iv | 0.88 (3) | 2.18 (2) | 2.970 (3) | 150 (3) |
N2—H3···O4 | 0.88 (3) | 1.91 (2) | 2.746 (3) | 158 (3) |
N2—H4···O3iv | 0.88 (3) | 1.92 (2) | 2.792 (3) | 168 (3) |
N2—H5···O2v | 0.88 (3) | 2.32 (2) | 3.061 (3) | 142 (3) |
N2—H5···O1vi | 0.88 (3) | 2.38 (3) | 2.858 (3) | 114 (2) |
N2—H5···O1iii | 0.88 (3) | 2.51 (3) | 3.004 (3) | 117 (3) |
Symmetry codes: (iii) x, y−1, z−1; (iv) −x+1, −y+1, −z; (v) x, y, z−1; (vi) −x, −y+1, −z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Chromous hydrazine sulfate, (I), was originally reported by Traube & Passarge (1913) and is unusual in that it is an air-stable complex of chromium(II). Although often encountered as a preparative experiment in undergraduate practical courses (Adams & Raynor, 1965; Palmer, 1954), the structure of chromous hydrazine sulfate has never been determined, as it is usually obtained as a microcrystalline solid unsuitable for single-crystal X-ray diffraction. The structure of zinc hydrazine sulfate, (II), has been reported and shows chains of zinc(II) cations with bridging sulfate anions and coordinated hydrazinium cations. Both compounds are best formulated as [M(N2H5)2(SO4)2] (Prout & Powell, 1961). The cell dimensions of a number of metal hydrazine sulfates including the CrII complex were reported and it was suggested that the compounds were all of the same structural type (Hand & Prout, 1966).
On one occasion, we were fortunate enough to obtain good-quality crystals of chromous hydrazine sulfate from a preparation carried out in a practical class. The sample was prepared by reacting chromous acetate with hydrazine sulfate in dilute sulfuric acid (Adams & Raynor, 1965). The original formulation of Traube & Passarge (1913) without water of crystallization is confirmed by our crystallographic study. Both Adams & Raynor (1965) and Palmer (1954) formulated the compound as a hydrate. The present crystal is triclinic with dimensions close to those reported previously (Hand & Prout, 1966).
The structure of chromous hydrazine sulfate is very similar to that of the analogous zinc compound and consists of chains of chromium(II) cations linked by sulfate anions (Fig. 1). The chains are parallel to the b axis and the Cr—Cr distance is the same as the b-cell dimension, i.e. 5.4568 (5) Å. Selected geometric parameters are given in Table 1. The structure is centrosymmetric, with the chromium(II) ion on a centre of symmetry, and the asymmetric unit is one half a formula unit, i.e. 1/2 × [Cr(N2H5)2(SO4)2]. As with the zinc analogue, there is pronounced asymmetry in the Cr—O distances to the sulfate ion, 2.0535 (17) and 2.3791 (19) Å. Asymmetry of this type is not unusual (Hathaway, 1987). Each chromium(II) ion is also coordinated to two hydrazinium (N2H5+) cations. We have used the same choice of axes as Prout & Powell (1961), and labelled the atoms in a corresponding manner, except that O1 and O2 have been interchanged, so that Cr—O1 remains the `short' metal–oxygen bond in both structures, and have given symmetry equivalent coordinates for N1 and N2 to achieve connectivity within the asymmetric unit.
The structure determination was carried out at 100 K and all th H atoms were experimentally located and their positions refined, see Table 2. A l l five H atoms are involved in hydrogen bonding to O atoms of the sulfate groups. Fig. 1 shows the hydrogen bonding within the chromium/sulfate chains and Fig. 2 shows the hydrogen bonding between the chains. While atoms H1 to H4 are only involved in interaction with one O atom, H5 has interactions with O1 within the chain and with O1 and O2 from an adjacent chain. Atom H5 is therefore involved in hydrogen bonding to three O atoms in what has been described as a four-centre bonding (Jeffrey, 1997). The hydrogen bonding in (I) is similar to that suggested for (II), although there is no H atom linking N1 and O4 of the same chain. The N—H···O distances are close to those previously observed for N—H hydrogen bonds to the O atoms of sulfate groups (Chertanova & Pascard, 1996).
Since the structure of (II) was initially reported, several structures of the general formula [Zn(N2H4)2X2], in which X is a monovalent anion, have been investigated. In contrast to the sulfate, the complexes with mononegative anions have unprotonated bridging hydrazine molecules with the anions completing pseudo-octahedral geometry at the metal (Ferrari et al., 1965, and references therein).