Di­ammonium tetra­thio­cyanato­cobaltate(II) tetrahydrate

The Co atom of the title compound, (NH₄)₂[Co(SCN)₄]·4H₂O, is located on a special position of site symmetry , whereas all atoms of the SCN ligand lie on general positions. As a result, the anions possess crystallographic symmetry. The ammonium cations are located on a twofold rotation axis parallel to c. The four water mol­ecules occupy general positions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](N-C) = 0.008 Å
• H-atom completeness 1%
• R factor = 0.054
• wR factor = 0.177
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......         O1

Author Response: The H atoms could not be located.

Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  N2     ..  N2       =       2.68 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  N2     ..  N2       =       2.68 Ang.

Alert level C
CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as
            calculated from the _atom_site* data lies outside
            the range 0.99 <> 1.01
           From the CIF: _cell_formula_units_Z                    2
           From the CIF: _chemical_formula_weight           391.33
           TEST: Calculate formula weight from _atom_site_*
           atom     mass    num     sum
           C        12.01    4.00   48.04
           H         1.01    0.00    0.00
           Co       58.93    1.00   58.93
           N        14.01    6.00   84.04
           O        16.00    4.00   64.00
           S        32.07    4.00  128.26
           Calculated formula weight              383.28
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.99
PLAT040_ALERT_1_C No H-atoms in this Carbon Containing Compound ..          ?
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT043_ALERT_1_C Check Reported Molecular Weight ................     391.33
PLAT044_ALERT_1_C Calculated and Reported Dx Differ ..............          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.60

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C4 H8 Co1 N6 O4 S4
            Atom count from _chemical_formula_moiety:C4 H16 Co1 N6 O4 S4
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C4 H8 Co1 N6 O4 S4
            Atom count from the _atom_site data:  C4 Co1 N6 O4 S4
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    2
           From the CIF: _chemical_formula_sum  C4 H8 Co N6 O4 S4
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C          8.00      8.00    0.00
           H         16.00      0.00   16.00
           Co         2.00      2.00    0.00
           N         12.00     12.00    0.00
           O          8.00      8.00    0.00
           S          8.00      8.00    0.00
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.22
           From the CIF: _reflns_number_total                882
           Count of symmetry unique reflns          536
           Completeness (_total/calc)            164.55%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       346
           Fraction of Friedel pairs measured     0.646
           Are heavy atom types Z>Si present          yes

   1 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

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

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Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: PLATON (Spek, 1990).

Diammonium tetrathiocyanatocobaltate(II) tetrahydrate

Crystal data

(NH4)2[Co(SCN)4]·4H2O	Dx = 1.628 Mg m^−3
Mr = 391.33	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421c	Cell parameters from 6680 reflections
Hall symbol: P -4 2n	θ = 3.7–27.0°
a = 12.2050 (16) Å	µ = 1.61 mm^−1
c = 5.3588 (7) Å	T = 100 K
V = 798.26 (18) Å^3	Plate, blue
Z = 2	0.37 × 0.13 × 0.04 mm
F(000) = 394

Data collection

Stoe IPDS II two-circle diffractometer	882 independent reflections
Radiation source: fine-focus sealed tube	729 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 27.2°, θmin = 4.2°
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995)	h = −15→13
Tmin = 0.587, Tmax = 0.938	k = −15→15
5438 measured reflections	l = −6→6

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.054	w = 1/[σ^2(Fo^2) + (0.1367P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.177	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.95 e Å^−3
882 reflections	Δρmin = −0.37 e Å^−3
44 parameters	Absolute structure: Flack (1983), 351 Friedel pairs
0 restraints	Absolute structure parameter: 0.02 (7)
Primary atom site location: structure-invariant direct methods

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
Co1	0.5000	0.5000	0.0000	0.0451 (4)
N1	0.5480 (4)	0.3801 (4)	0.2196 (9)	0.0481 (11)
C1	0.5714 (5)	0.3251 (5)	0.3912 (12)	0.0499 (13)
S1	0.60884 (16)	0.24747 (17)	0.6240 (3)	0.0663 (6)
O1	0.7943 (3)	0.3749 (3)	0.9965 (10)	0.0506 (9)
N2	0.0000	0.5000	0.961 (5)	0.161 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0540 (6)	0.0540 (6)	0.0273 (6)	0.000	0.000	0.000
N1	0.056 (3)	0.054 (3)	0.034 (2)	0.006 (2)	−0.0010 (19)	0.000 (2)
C1	0.053 (3)	0.058 (3)	0.039 (3)	0.007 (3)	0.005 (3)	0.000 (3)
S1	0.0789 (11)	0.0798 (12)	0.0401 (8)	0.0270 (9)	0.0085 (8)	0.0138 (8)
O1	0.058 (2)	0.0379 (17)	0.056 (2)	0.0095 (15)	−0.005 (2)	0.001 (2)
N2	0.093 (10)	0.116 (12)	0.27 (3)	0.013 (7)	0.000	0.000

Geometric parameters (Å, º)

Co1—N1^i	1.967 (5)	Co1—N1	1.967 (5)
Co1—N1^ii	1.967 (5)	N1—C1	1.174 (8)
Co1—N1^iii	1.967 (5)	C1—S1	1.632 (7)
N1^i—Co1—N1^ii	110.97 (15)	N1^ii—Co1—N1	106.5 (3)
N1^i—Co1—N1^iii	106.5 (3)	N1^iii—Co1—N1	110.97 (15)
N1^ii—Co1—N1^iii	110.97 (15)	C1—N1—Co1	165.1 (5)
N1^i—Co1—N1	110.97 (15)	N1—C1—S1	177.6 (6)

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