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The crystal structure of the title compound, (C2H7N4O)2[CoCl4(H2O)2], contains a molecular network of (C2H7N4O)+ cations and trans-[Co(H2O)2Cl4]2− octahedral anions (Co site symmetry 2/m). An extensive network of N—H...Cl, N—H...(Cl,Cl), N—H...O, O—H...O and O—H...Cl hydrogen bonds results in a structure with a three-dimensional hydrogen-bond network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012406/wn6167sup1.cif
Contains datablocks I, cbs29

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012406/wn6167Isup2.hkl
Contains datablock I

CCDC reference: 217372

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](Co-O) = 0.001 Å
  • R factor = 0.027
  • wR factor = 0.068
  • Data-to-parameter ratio = 29.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The title compound, (I), arose as a side product during our synthetic investigations of organically templated cobalt phosphate networks (Cowley & Chippindale, 1999). It is isostructural with (C2H7N4O)2[CuCl4(H2O)2] (Begley et al., 1988) and (C2H7N4O)2[MnCl4(H2O)2] (Bremner & Harrison, 2003).

In (I), Co1 (site symmetry 2/m) has flattened, trans, octahedral coordination by two O (water) atoms and four Cl atoms. The cis bond angles lie between 84.64 (3) and 95.36 (3)°. The Co—O bond distance of 2.1000 (9) Å and the average Co—Cl separation of 2.4695 (4) Å correlate reasonably well with the ionic radius (IR) sums for the species involved [dIR(Co—O) = 2.09 Å and dIR(Co—Cl) = 2.56 Å], assuming the presence of high-spin Co2+ (Shannon, 1976). The [CuCl4(H2O)2]2− grouping in (C2H7N4O)2[CuCl4(H2O)2] (Begley et al., 1988) is much more distorted, with a Cu—O distance of 1.992 (3) Å and Cu—Cl bond lengths of 2.305 (1) and 2.791 (1) Å, which can be ascribed to a typical Jahn–Teller distortion for the d9 Cu2+ species.

The 1-carbamoylguanidinium (guanylurea) cation has normal geometrical parameters [dav(N—C) = 1.339 (3) Å], indicating significant delocalization of electrons over the non-hydrogen skeleton (Zaman & Darlow, 1986; Begley et al., 1988) and is essentially planar (for the non-H atoms, the r.m.s. deviation from the least-squares plane = 0.029 Å). A very acute (θ = 129°) intramolecular N4—H9···O2 hydrogen bond is present, which is typical for (C2H7N4O)+ (Bremner & Harrison, 2002).

The component species in (I) interact by way of an extensive hydrogen-bonding network (Table 2). The N—H···Cl hydrogen bonds to chloride ion acceptors involving H5 and H6 are bifurcated [dav(H···Cl) = 2.72 Å, dav(N···Cl) = 3.398 (2) Å and θav(N—H···Cl) = 138°], which is a characteristic `synthon' bonding motif for these species (Brammer et al., 2001). In this case, the pairs of chloride ions occupy an octahedral edge, with Cl1···Cl2 and Cl1i···Cl2ii [symmetry codes: (i) 1/2 − x, 1/2 + y, 1/2 − z; (ii) 1/2 + x, 3/2 − y, 1/2 + z] separations of 3.4662 (5) and 3.5190 (5) Å for the interactions involving H5 and H6, respectively. The hydrogen bonds involving H3, H7 and H8 are simple N—H···Cl links [dav(H···Cl) = 2.52 Å dav(N···Cl) = 3.329 (2) Å and θav(N—H···Cl) = 159°]. Overall, Cl1 accepts three and Cl2 accepts five hydrogen bonds.

The hydrogen-bonding scheme in (I) results in stacks of alternating [Co(H2O)2Cl4]2− octahedra and pairs of 1-carbamoylguanidinium species propagating along [010] (Fig. 2), which are held together by the O1—H1···O2i, N1—H3···Cl1iii, N3—H6···Cl2iv, and N4—H8···Cl2iv bonds (see Table 2 for the acceptor-atom symmetry codes). There may be pseudo ππ-stacking interactions involving the parallel 1-carbamoylguanidinium pairs, with resulting short contact distances of C1···N4vi = 3.346 (2) Å and C2···O2vi = 3.364 (2) Å [symmetry code: (vi) 1 − x, 1 − y, 1 − z].

The stacks are fused into (101) pseudo-sheets by way of the N1—H4···O1, N2—H5···(Cl1, Cl2), N3—H6···Cl1v, and N3—H7···Cl2 bonds, which in turn are crosslinked by the O1—H2···Cl2ii bonds (symmetry codes as in Table 2), resulting in a three-dimensional structure.

Experimental top

10 ml of 1 M CoCl2 solution, 10 ml of 1M H3PO4 solution and 0.5 g dicyandiamide were mixed together in a plastic bottle and heated to 353 K for 24 h, resulting in a purple solution. The solution was cooled to room temperature, and rod-like crystals of (I) grew as the solvent slowly evaporated. The dicyandiamide was transformed to guanylurea by slow acid hydrolysis.

Refinement top

The H atoms attached to atom O1 were located in difference maps and refined by riding in their as-found positions. The other H atoms were placed in idealized locations [d(N—H) = 0.86 Å] and refined by riding on their parent atom, with Uiso(H) = 1.2Ueq(parent atom) in all cases.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Component species of (I) (50% displacement ellipsoids, arbitrary spheres for the H atoms and hydrogen bonds indicated by dashed lines). [Symmetry code: (i) −x, 1 − y, −z.]
[Figure 2] Fig. 2. Detail of (I), showing an [010] stack of alternating cation pairs and anions. Colour key: Co(H2O)2Cl4 octahedra purple, Cl atoms green, C atoms blue, N atoms yellow, and H atoms grey (all radii arbitrary). The intramolecular H···O, other H···O, H···Cl portions of the hydrogen bonds and the pseudo-ππ-stacking contacts (see text) are coloured light blue, orange, yellow, and purple, respectively.
[Figure 3] Fig. 3. Unit-cell packing in (I), viewed down [010]. Colour key as in Fig. 2 (pseudo-ππ-stacking contacts have been omitted for clarity).
(I) top
Crystal data top
(C2H7N4O)2[CoCl4(H2O)2]F(000) = 450
Mr = 443.00Dx = 1.818 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.3488 (3) ÅCell parameters from 3083 reflections
b = 11.3392 (5) Åθ = 2.6–32.4°
c = 11.5436 (5) ŵ = 1.75 mm1
β = 103.1180 (1)°T = 293 K
V = 809.34 (6) Å3Block, purple
Z = 20.26 × 0.19 × 0.13 mm
Data collection top
Bruker SMART1000 CCD
diffractometer
2914 independent reflections
Radiation source: fine-focus sealed tube2160 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scansθmax = 32.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 89
Tmin = 0.650, Tmax = 0.810k = 1717
7802 measured reflectionsl = 1617
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)] = 0.027Hydrogen site location: difmap (O-H) and geom (N-H)
wR(F2) = 0.068H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.0356P)2]
where P = (Fo2 + 2Fc2)/3
2914 reflections(Δ/σ)max < 0.001
98 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
(C2H7N4O)2[CoCl4(H2O)2]V = 809.34 (6) Å3
Mr = 443.00Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.3488 (3) ŵ = 1.75 mm1
b = 11.3392 (5) ÅT = 293 K
c = 11.5436 (5) Å0.26 × 0.19 × 0.13 mm
β = 103.1180 (1)°
Data collection top
Bruker SMART1000 CCD
diffractometer
2914 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
2160 reflections with I > 2σ(I)
Tmin = 0.650, Tmax = 0.810Rint = 0.019
7802 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.068H-atom parameters constrained
S = 0.96Δρmax = 0.37 e Å3
2914 reflectionsΔρmin = 0.29 e Å3
98 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
xyzUiso*/Ueq
Co10.00000.50000.00000.02519 (8)
Cl10.00034 (6)0.49559 (3)0.21078 (3)0.03329 (9)
Cl20.31559 (6)0.63849 (3)0.04533 (3)0.03150 (9)
O10.23677 (16)0.36722 (8)0.02831 (9)0.0288 (2)
H10.22650.29890.00040.035*
H20.34520.39450.00250.035*
O20.70085 (19)0.35117 (9)0.44223 (10)0.0409 (3)
N10.4719 (2)0.29772 (10)0.27020 (12)0.0394 (3)
H30.49090.22360.28430.047*
H40.38580.32110.20560.047*
N20.5279 (2)0.49248 (9)0.31399 (12)0.0306 (3)
H50.42880.50410.25060.037*
N30.5648 (2)0.69217 (10)0.32110 (12)0.0398 (3)
H60.61970.75630.35480.048*
H70.47140.69510.25430.048*
N40.7651 (2)0.58169 (11)0.47313 (11)0.0372 (3)
H80.82240.64450.50860.045*
H90.80090.51370.50440.045*
C10.5749 (2)0.37577 (12)0.34769 (13)0.0301 (3)
C20.6237 (2)0.58962 (12)0.37173 (13)0.0286 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.02434 (14)0.02235 (12)0.02850 (14)0.00140 (9)0.00516 (10)0.00021 (10)
Cl10.0347 (2)0.03586 (18)0.03060 (18)0.00071 (14)0.01009 (15)0.00024 (14)
Cl20.02900 (17)0.02758 (15)0.03733 (19)0.00376 (13)0.00631 (13)0.00077 (14)
O10.0291 (5)0.0225 (4)0.0360 (5)0.0002 (4)0.0100 (4)0.0018 (4)
O20.0451 (6)0.0284 (5)0.0408 (6)0.0001 (5)0.0077 (5)0.0070 (4)
N10.0484 (8)0.0255 (6)0.0380 (7)0.0015 (5)0.0035 (6)0.0025 (5)
N20.0304 (6)0.0242 (5)0.0329 (6)0.0013 (4)0.0018 (5)0.0025 (5)
N30.0536 (8)0.0245 (6)0.0366 (7)0.0025 (5)0.0002 (6)0.0008 (5)
N40.0386 (7)0.0290 (6)0.0384 (7)0.0001 (5)0.0028 (6)0.0019 (5)
C10.0287 (7)0.0262 (6)0.0347 (8)0.0001 (5)0.0059 (6)0.0033 (5)
C20.0282 (7)0.0265 (6)0.0316 (7)0.0009 (5)0.0078 (6)0.0009 (5)
Geometric parameters (Å, º) top
Co1—O12.1000 (9)N1—H40.8600
Co1—O1i2.1000 (9)N2—C21.3577 (17)
Co1—Cl12.4332 (4)N2—C11.3926 (16)
Co1—Cl1i2.4332 (4)N2—H50.8600
Co1—Cl2i2.5057 (3)N3—C21.3170 (17)
Co1—Cl22.5057 (3)N3—H60.8600
O1—H10.8362N3—H70.8600
O1—H20.8667N4—C21.3066 (19)
O2—C11.2297 (18)N4—H80.8600
N1—C11.3212 (19)N4—H90.8600
N1—H30.8600
O1—Co1—O1i180.0C1—N1—H3120.0
O1—Co1—Cl189.51 (3)C1—N1—H4120.0
O1i—Co1—Cl190.49 (3)H3—N1—H4120.0
O1—Co1—Cl1i90.49 (3)C2—N2—C1126.17 (13)
O1i—Co1—Cl1i89.51 (3)C2—N2—H5116.9
Cl1—Co1—Cl1i180.0C1—N2—H5116.9
O1—Co1—Cl2i95.36 (3)C2—N3—H6120.0
O1i—Co1—Cl2i84.64 (3)C2—N3—H7120.0
Cl1—Co1—Cl2i90.869 (12)H6—N3—H7120.0
Cl1i—Co1—Cl2i89.131 (12)C2—N4—H8120.0
O1—Co1—Cl284.64 (3)C2—N4—H9120.0
O1i—Co1—Cl295.36 (3)H8—N4—H9120.0
Cl1—Co1—Cl289.131 (12)O2—C1—N1124.84 (13)
Cl1i—Co1—Cl290.869 (12)O2—C1—N2121.23 (13)
Cl2i—Co1—Cl2180.000 (12)N1—C1—N2113.93 (13)
Co1—O1—H1127.9N4—C2—N3121.77 (14)
Co1—O1—H2106.7N4—C2—N2121.61 (13)
H1—O1—H2101.3N3—C2—N2116.62 (13)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2ii0.841.822.6587 (13)179
O1—H2···Cl2iii0.872.373.1465 (10)149
N1—H3···Cl1iv0.862.593.4349 (12)170
N1—H4···O10.862.122.9586 (17)166
N2—H5···Cl10.862.663.2905 (14)132
N2—H5···Cl20.862.773.5040 (13)144
N3—H6···Cl2v0.862.563.3245 (14)148
N3—H6···Cl1vi0.862.873.4749 (12)129
N3—H7···Cl20.862.483.2743 (15)155
N4—H8···Cl2v0.862.503.2778 (13)151
N4—H9···O20.862.032.6571 (16)129
Symmetry codes: (ii) x1/2, y+1/2, z1/2; (iii) x+1, y+1, z; (iv) x+1/2, y1/2, z+1/2; (v) x+1/2, y+3/2, z+1/2; (vi) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula(C2H7N4O)2[CoCl4(H2O)2]
Mr443.00
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.3488 (3), 11.3392 (5), 11.5436 (5)
β (°) 103.1180 (1)
V3)809.34 (6)
Z2
Radiation typeMo Kα
µ (mm1)1.75
Crystal size (mm)0.26 × 0.19 × 0.13
Data collection
DiffractometerBruker SMART1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.650, 0.810
No. of measured, independent and
observed [I > 2σ(I)] reflections
7802, 2914, 2160
Rint0.019
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.068, 0.96
No. of reflections2914
No. of parameters98
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.29

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999), SHELXL97.

Selected bond lengths (Å) top
Co1—O12.1000 (9)N2—C21.3577 (17)
Co1—Cl12.4332 (4)N2—C11.3926 (16)
Co1—Cl22.5057 (3)N3—C21.3170 (17)
O2—C11.2297 (18)N4—C21.3066 (19)
N1—C11.3212 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.841.822.6587 (13)179
O1—H2···Cl2ii0.872.373.1465 (10)149
N1—H3···Cl1iii0.862.593.4349 (12)170
N1—H4···O10.862.122.9586 (17)166
N2—H5···Cl10.862.663.2905 (14)132
N2—H5···Cl20.862.773.5040 (13)144
N3—H6···Cl2iv0.862.563.3245 (14)148
N3—H6···Cl1v0.862.873.4749 (12)129
N3—H7···Cl20.862.483.2743 (15)155
N4—H8···Cl2iv0.862.503.2778 (13)151
N4—H9···O20.862.032.6571 (16)129
Symmetry codes: (i) x1/2, y+1/2, z1/2; (ii) x+1, y+1, z; (iii) x+1/2, y1/2, z+1/2; (iv) x+1/2, y+3/2, z+1/2; (v) x+1/2, y+1/2, z+1/2.
 

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