Diammine(2,2′-bipyridine)­bis(thio­cyan­ato­-κN)cobalt(III) diamminetetra­kis(thio­cyanato­-κN)chromate(III) aceto­nitrile disolvate

Semenaka, V.V.; Nesterova, O.V.; Kokozay, V.N.; Zybatyuk, R.I.; Shishkin, O.V.

doi:10.1107/S1600536811024998

Diammine(2,2′-bipyridine)bis(thiocyanato-κN)cobalt(III) diamminetetrakis(thiocyanato-κN)chromate(III) acetonitrile disolvate

V. V. Semenaka, O. V. Nesterova, V. N. Kokozay, R. I. Zybatyuk and O. V. Shishkin

The new heterometallic title complex, [Co(NCS)₂(C₁₀H₈N₂)(NH₃)₂][Cr(NCS)₄(NH₃)₂]·2CH₃CN, has been prepared using the open-air reaction of cobalt powder, Reineckes salt and 2,2′-bipyridine (dpy) in acetonitrile. The crystal structure consists of discrete cationic [Co(NCS)₂(NH₃)₂(dpy)]⁺ and anionic [Cr(NCS)₄(NH₃)₂]⁻ building blocks, both with 2 symmetry, and acetonitrile solvent molecules, which are linked together by N—H

N hydrogen bonds, forming extended supramolecular chains. Furthermore, N—H

S, C—H

S and C—H

N hydrogen bonds interlink neighbouring chains into a three-dimensional framework. The Co atom is in an elongated octahedral coordination environment with two N atoms from the dpy ligands and two NCS-groups in the equatorial plane and with two NH₃ molecules at the axial positions. The Cr^III ion is octahedraly coordinated by two NH₃ molecules at the axial positions and four NCS-groups in the equatorial plane. Intensity statistics indicated non-merohedral twinning with the twin matrix [100; 0 $\overline{1}$ 0; $\overline{1}$ 0 $\overline{1}$ ]. The refined ratio of the twin components is 0.530 (1):0.470 (1).

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811024998/ff2017sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811024998/ff2017Isup2.hkl Contains datablock I
	Chemdraw file https://doi.org/10.1107/S1600536811024998/ff2017Isup4.cdx Supplementary material

CCDC reference: 840994

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R factor = 0.038
wR factor = 0.084
Data-to-parameter ratio = 28.4

checkCIF/PLATON results

No syntax errors found



Alert level B
            Crystal system given = monoclinic
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S2     --  C7      ..        7.6 su

Alert level C
CELLV02_ALERT_1_C  The supplied cell volume s.u. differs from that
            calculated from the cell parameter s.u.'s by > 2
            Calculated cell volume su =      16.79
            Cell volume su given      =      13.00
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  C1      ..        6.5 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S3     --  C8      ..        5.9 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          C9
PLAT420_ALERT_2_C D-H Without Acceptor       N6     -   H6B    ...          ?
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         12
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        615

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instruction_details found in CIF          ?
PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ...          4 Units
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          !
PLAT931_ALERT_5_G Check Twin Law ( 0 0  1)[       ] Estimated BASF       0.47

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

Direct synthesis of coordination compounds, which employs metal powders or metal oxides as starting materials, has been proved to be an efficient route to obtain novel heterometallic complexes (Kokozay & Shevchenko, 2005). Recently, it has been shown that use of anionic complexes as a source of metalloligands (Reineckes salt, (NH)₄[Cr(NCS)₄(NH₃)₂]^.H₂O, was taken as a representative example) in direct synthesis of Cu/Cr heterometallic compounds with amines and Schiff-base ligands Nikitina et al. (2009) has yielded a broad range of complexes with various polymeric and ionic crystal structures. In the present work, we report that the reaction of cobalt powder, Reineckes salt and 2,2'-bipyridine (dpy) in acetonitrile solution has afforded a single crystals of the novel heterometallic Co/Cr compound. In crystal structure of the complex cationic [Co(NCS)₂(NH₃)₂(dpy)]⁺ and anionic [Cr(NCS)₄(NH₃)₂]^- building blocks as well as acetonitrile molecules are joined together forming three-dimensional supramolecular framework assisted by numerous N—H···N, N—H..S and C—H···S hydrogen bonds (Fig. 1). The Co atoms are in elongated octahedral coordination environment with two nitrogen atoms from dpy ligand and two NCS-groups in the equatorial plane and with two nitrogen atoms of NH₃ molecules at the axial positions. The bond lengths of Co–N are in a narrow range: Co(1)–N(1) = 1.9237 (15) Å; Co(1)–N(2) = 1.8957 (16) Å; Co(1)–N(3) = 1.9586 (14) Å, the cis bond angles range from 83.17 (9)° to 93.55 (6)°, while the trans bond angles are 176.61 (7)° and 176.63 (10). The Cr^III ions have N6 donor set formed by two NH₃ molecules at the axial positions and four NCS-groups in the equatorial plane. The axial Cr–N bond lengths are 2.0711 (15) Å. The thiocyanate groups are almost linear with angles N(4)–C(7)–S(21) = 178.51 (18)° and N(5)–C(8)–S(3) = 178.40 (20)°.

Related literature top

For background to direct synthesis, see: Kokozay & Shevchenko (2005). For background to heterometallic complexes based on an anion of Reineckes salt, see: Zhang et al. (2001); Cucos et al. (2006); Cherkasova et al. (2003); Nikitina et al. (2009); Kolotilov et al. (2010).

Experimental top

Cobalt powder (0.074 g, 1.25 mmol), NH₄[Cr(NCS)₄(NH₃)₂]^.H₂O (0.443 g, 1.25 mmol), NH₄NCS (0.190 g, 2.5 mmol), dpy (0.195 g, 1.25 mmol) and acetonitrile (15 ml) were heated to 50–60° and stirred magnetically until total dissolution of the cobalt was observed (5 h). The resulting blue solution was slowly evaporated at room temperature until dark-brown crystals suitable for crystallographic study were formed. The crystals were filtered off, washed with dry PrⁱOH and finally dried in vacuo at room temperature. Yield: 0.34 g. Anal. Calc. for C₂₀H₂₆CoCrN₁₄S₆: Co, 7.70; Cr, 6.79; C, 31.37; H, 3.39; N, 26.61; S, 25.12. Found: Co, 7.5; Cr, 6.8; C, 31.5; H, 3.4; N, 26.2; S 25.0%. IR (KBr, cm^-1): 3350(br), 3131(sh), 3022(sh), 2120(sh), 2082(vs), 2035(sh), 2008(sh), 1736(w), 1639(sh), 1607(m), 1579(sh), 1547(sh), 1500(w), 1565(sh) 1442(m), 1421(sh), 1310(sh), 1291(sh), 1275(m) 1229(sh), 1156(w), 1102(w), 1078(w), 1037(w), 794(sh), 749(w), 659(m), 613(m), 574(w), 509(m), 500(sh), 473(sh), 421(w), 412(w). The compound is sparingly soluble in dmso and dmf, insoluble in water and it is indefinitely stable in air.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction 2010); cell refinement: CrysAlis PRO (Oxford Diffraction 2010); data reduction: CrysAlis PRO (Oxford Diffraction 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The structure of [Co(NCS)₂(NH₃)₂(dpy)][Cr(NCS)₄(NH₃)₂]^.2CH₃CN with displacement ellipsoids drawn at 50% probability level. Hydrogen bonds ar drawn as dashed lines. [Symmetry codes: (i) x, 1-x, -0.5+z; (ii) 1-x, y, 0.5-z]

Diammine(2,2'-bipyridine)bis(thiocyanato-κN)cobalt(III) diamminetetrakis(thiocyanato-κN)chromate(III) acetonitrile disolvate top

Crystal data top

[Co(NCS)₂(C₁₀H₈N₂)(NH₃)₂][Cr(NCS)₄(NH₃)₂]·2C₂H₃N	F(000) = 782
M_r = 765.90	D_x = 1.466 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.7107 Å
a = 13.2923 (7) Å	Cell parameters from 6460 reflections
b = 10.7155 (3) Å	θ = 2.9–32.0°
c = 13.8745 (7) Å	µ = 1.19 mm⁻¹
β = 118.592 (6)°	T = 100 K
V = 1735.21 (13) Å³	Block, brown
Z = 2	0.32 × 0.08 × 0.07 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	5538 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4555 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 16.1827 pixels mm^-1	θ_max = 32.0°, θ_min = 2.9°
ω scans	h = −19→19
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −15→15
T_min = 0.913, T_max = 1.000	l = −20→19
15857 measured reflections

Refinement top

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0393P)² + 0.0897P] where P = (F_o² + 2F_c²)/3
5538 reflections	(Δ/σ)_max < 0.001
195 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Co(NCS)₂(C₁₀H₈N₂)(NH₃)₂][Cr(NCS)₄(NH₃)₂]·2C₂H₃N	V = 1735.21 (13) Å³
M_r = 765.90	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 13.2923 (7) Å	µ = 1.19 mm⁻¹
b = 10.7155 (3) Å	T = 100 K
c = 13.8745 (7) Å	0.32 × 0.08 × 0.07 mm
β = 118.592 (6)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	5538 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	4555 reflections with I > 2σ(I)
T_min = 0.913, T_max = 1.000	R_int = 0.037
15857 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.02	Δρ_max = 0.63 e Å⁻³
5538 reflections	Δρ_min = −0.45 e Å⁻³
195 parameters

Special details top

Experimental. CrysAlisPro, Oxford Diffraction (2010), Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.37302 (4)	0.2500	0.01545 (9)
Cr1	1.0000	0.60863 (5)	0.7500	0.01985 (11)
S1	0.63132 (7)	0.70219 (5)	0.50113 (5)	0.02427 (13)
S2	0.77446 (6)	0.93976 (6)	0.77738 (5)	0.02889 (15)
S3	0.76313 (6)	0.31039 (6)	0.79923 (5)	0.03010 (15)
N1	0.55064 (19)	0.49821 (16)	0.35953 (14)	0.0207 (4)
N2	0.55107 (18)	0.23884 (15)	0.35489 (13)	0.0166 (3)
N3	0.35074 (16)	0.37847 (16)	0.24572 (19)	0.0200 (3)
H3A	0.3215	0.4570	0.2283	0.024*
H3B	0.3592	0.3571	0.3127	0.024*
H3C	0.3021	0.3239	0.1942	0.024*
N4	0.89869 (17)	0.74301 (18)	0.75553 (19)	0.0241 (4)
N5	0.89681 (18)	0.47780 (18)	0.7556 (2)	0.0255 (4)
N6	0.9113 (2)	0.60481 (18)	0.58032 (15)	0.0256 (4)
H6A	0.9004	0.5242	0.5568	0.031*
H6B	0.9523	0.6458	0.5532	0.031*
H6C	0.8421	0.6428	0.5563	0.031*
N7	0.1244 (3)	0.6759 (2)	0.50204 (19)	0.0399 (6)
C1	0.5829 (2)	0.58425 (18)	0.41771 (16)	0.0173 (4)
C2	0.5294 (2)	0.12311 (18)	0.31030 (15)	0.0184 (4)
C3	0.5631 (2)	0.01704 (19)	0.37534 (17)	0.0223 (4)
H3	0.5474	−0.0636	0.3430	0.027*
C4	0.6201 (3)	0.0306 (2)	0.48808 (18)	0.0239 (4)
H4	0.6441	−0.0408	0.5343	0.029*
C5	0.6417 (2)	0.1487 (2)	0.53293 (16)	0.0224 (4)
H5	0.6813	0.1592	0.6104	0.027*
C6	0.6057 (2)	0.25133 (19)	0.46479 (16)	0.0200 (4)
H6	0.6197	0.3325	0.4961	0.024*
C7	0.84805 (19)	0.8257 (2)	0.76460 (18)	0.0201 (4)
C8	0.8414 (2)	0.4067 (2)	0.77314 (18)	0.0221 (5)
C9	0.0976 (3)	0.7692 (3)	0.4594 (2)	0.0387 (6)
C10	0.0669 (4)	0.8930 (4)	0.4081 (3)	0.0722 (13)
H10A	−0.0165	0.9034	0.3724	0.108*
H10B	0.0930	0.9007	0.3532	0.108*
H10C	0.1036	0.9574	0.4644	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0162 (3)	0.01328 (18)	0.01519 (18)	0.000	0.0061 (2)	0.000
Cr1	0.0194 (3)	0.0213 (3)	0.0185 (2)	0.000	0.0089 (3)	0.000
S1	0.0297 (4)	0.0188 (2)	0.0256 (3)	−0.0041 (3)	0.0143 (3)	−0.0073 (2)
S2	0.0309 (3)	0.0248 (3)	0.0281 (3)	0.0080 (3)	0.0117 (3)	0.0012 (2)
S3	0.0362 (4)	0.0268 (3)	0.0304 (3)	−0.0103 (3)	0.0184 (3)	−0.0061 (2)
N1	0.0233 (11)	0.0172 (8)	0.0203 (8)	−0.0005 (9)	0.0093 (9)	−0.0012 (7)
N2	0.0158 (9)	0.0164 (7)	0.0151 (7)	0.0005 (8)	0.0054 (8)	0.0011 (6)
N3	0.0195 (10)	0.0200 (8)	0.0208 (9)	−0.0005 (7)	0.0099 (9)	−0.0014 (9)
N4	0.0242 (11)	0.0261 (9)	0.0218 (9)	0.0000 (8)	0.0108 (9)	−0.0016 (10)
N5	0.0229 (11)	0.0273 (10)	0.0266 (10)	−0.0007 (8)	0.0122 (10)	0.0013 (10)
N6	0.0259 (11)	0.0289 (10)	0.0205 (9)	0.0005 (10)	0.0099 (9)	−0.0026 (7)
N7	0.0356 (15)	0.0469 (15)	0.0336 (12)	−0.0052 (14)	0.0136 (13)	−0.0113 (11)
C1	0.0152 (10)	0.0174 (9)	0.0186 (9)	0.0020 (9)	0.0076 (10)	0.0033 (7)
C2	0.0211 (11)	0.0180 (9)	0.0168 (9)	−0.0004 (9)	0.0095 (10)	−0.0012 (7)
C3	0.0287 (13)	0.0149 (9)	0.0201 (10)	−0.0011 (11)	0.0091 (11)	−0.0008 (8)
C4	0.0286 (13)	0.0204 (10)	0.0191 (9)	0.0019 (11)	0.0085 (11)	0.0053 (8)
C5	0.0241 (12)	0.0254 (10)	0.0147 (9)	−0.0002 (12)	0.0069 (11)	0.0007 (8)
C6	0.0196 (11)	0.0186 (9)	0.0183 (9)	−0.0013 (11)	0.0064 (10)	−0.0031 (8)
C7	0.0193 (11)	0.0236 (10)	0.0139 (11)	−0.0040 (9)	0.0051 (9)	0.0020 (9)
C8	0.0221 (11)	0.0220 (11)	0.0187 (13)	0.0028 (9)	0.0069 (10)	−0.0029 (8)
C9	0.0253 (15)	0.0644 (19)	0.0212 (12)	−0.0008 (16)	0.0069 (12)	−0.0024 (13)
C10	0.044 (2)	0.104 (3)	0.062 (2)	0.026 (2)	0.0195 (19)	0.045 (2)

Geometric parameters (Å, º) top

Co1—N1	1.8929 (17)	N3—H3C	0.9100
Co1—N1ⁱ	1.8929 (17)	N4—C7	1.155 (3)
Co1—N2ⁱ	1.9236 (16)	N5—C8	1.164 (3)
Co1—N2	1.9236 (16)	N6—H6A	0.9100
Co1—N3ⁱ	1.9572 (17)	N6—H6B	0.9100
Co1—N3	1.9571 (17)	N6—H6C	0.9100
Cr1—N4	1.9979 (19)	N7—C9	1.130 (4)
Cr1—N4ⁱⁱ	1.9980 (19)	C2—C2ⁱ	1.469 (4)
Cr1—N5ⁱⁱ	1.9884 (19)	C2—C3	1.386 (3)
Cr1—N5	1.988 (2)	C3—H3	0.9500
Cr1—N6	2.0682 (18)	C3—C4	1.381 (3)
Cr1—N6ⁱⁱ	2.0682 (18)	C4—H4	0.9500
S1—C1	1.624 (2)	C4—C5	1.378 (3)
S2—C7	1.627 (2)	C5—H5	0.9500
S3—C8	1.624 (3)	C5—C6	1.378 (3)
N1—C1	1.164 (3)	C6—H6	0.9500
N2—C2	1.354 (3)	C9—C10	1.467 (5)
N2—C6	1.346 (3)	C10—H10A	0.9800
N3—H3A	0.9100	C10—H10B	0.9800
N3—H3B	0.9100	C10—H10C	0.9800

N1ⁱ—Co1—N1	89.74 (11)	H3A—N3—H3B	109.5
N1ⁱ—Co1—N2ⁱ	93.51 (7)	H3A—N3—H3C	109.5
N1—Co1—N2ⁱ	176.59 (8)	H3B—N3—H3C	109.5
N1ⁱ—Co1—N2	176.59 (8)	C7—N4—Cr1	174.5 (2)
N1—Co1—N2	93.51 (7)	C8—N5—Cr1	170.8 (2)
N1—Co1—N3	88.23 (9)	Cr1—N6—H6A	109.5
N1ⁱ—Co1—N3ⁱ	88.23 (9)	Cr1—N6—H6B	109.5
N1ⁱ—Co1—N3	89.34 (9)	Cr1—N6—H6C	109.5
N1—Co1—N3ⁱ	89.35 (9)	H6A—N6—H6B	109.5
N2—Co1—N2ⁱ	83.26 (10)	H6A—N6—H6C	109.5
N2ⁱ—Co1—N3ⁱ	91.77 (9)	H6B—N6—H6C	109.5
N2—Co1—N3ⁱ	90.79 (9)	N1—C1—S1	178.3 (2)
N2ⁱ—Co1—N3	90.79 (9)	N2—C2—C2ⁱ	113.66 (10)
N2—Co1—N3	91.77 (9)	N2—C2—C3	121.47 (17)
N3—Co1—N3ⁱ	176.58 (10)	C3—C2—C2ⁱ	124.86 (12)
N4—Cr1—N4ⁱⁱ	87.77 (11)	C2—C3—H3	120.6
N4—Cr1—N6ⁱⁱ	89.90 (9)	C4—C3—C2	118.82 (19)
N4ⁱⁱ—Cr1—N6ⁱⁱ	91.73 (9)	C4—C3—H3	120.6
N4—Cr1—N6	91.73 (9)	C3—C4—H4	120.3
N4ⁱⁱ—Cr1—N6	89.90 (9)	C5—C4—C3	119.4 (2)
N5—Cr1—N4	90.94 (8)	C5—C4—H4	120.3
N5ⁱⁱ—Cr1—N4ⁱⁱ	90.94 (8)	C4—C5—H5	120.2
N5ⁱⁱ—Cr1—N4	178.72 (8)	C4—C5—C6	119.60 (18)
N5—Cr1—N4ⁱⁱ	178.72 (8)	C6—C5—H5	120.2
N5ⁱⁱ—Cr1—N5	90.34 (11)	N2—C6—C5	121.32 (18)
N5ⁱⁱ—Cr1—N6ⁱⁱ	90.12 (9)	N2—C6—H6	119.3
N5—Cr1—N6ⁱⁱ	88.28 (10)	C5—C6—H6	119.3
N5ⁱⁱ—Cr1—N6	88.28 (10)	N4—C7—S2	178.6 (2)
N5—Cr1—N6	90.12 (10)	N5—C8—S3	178.5 (2)
N6ⁱⁱ—Cr1—N6	177.73 (11)	N7—C9—C10	177.5 (4)
C1—N1—Co1	171.81 (19)	C9—C10—H10A	109.5
C2—N2—Co1	114.71 (13)	C9—C10—H10B	109.5
C6—N2—Co1	125.92 (14)	C9—C10—H10C	109.5
C6—N2—C2	119.36 (17)	H10A—C10—H10B	109.5
Co1—N3—H3A	109.5	H10A—C10—H10C	109.5
Co1—N3—H3B	109.5	H10B—C10—H10C	109.5
Co1—N3—H3C	109.5

Co1—N2—C2—C2ⁱ	0.0 (4)	N3ⁱ—Co1—N2—C6	87.5 (2)
Co1—N2—C2—C3	178.6 (2)	N3—Co1—N2—C6	−90.2 (2)
Co1—N2—C6—C5	−178.1 (2)	C2—N2—C6—C5	1.1 (4)
N1—Co1—N2—C2	178.9 (2)	C2ⁱ—C2—C3—C4	178.5 (4)
N1—Co1—N2—C6	−1.8 (2)	C2—C3—C4—C5	0.1 (5)
N2ⁱ—Co1—N2—C2	0.00 (16)	C3—C4—C5—C6	0.4 (5)
N2ⁱ—Co1—N2—C6	179.2 (3)	C4—C5—C6—N2	−1.0 (4)
N2—C2—C3—C4	0.0 (5)	C6—N2—C2—C2ⁱ	−179.3 (3)
N3ⁱ—Co1—N2—C2	−91.7 (2)	C6—N2—C2—C3	−0.6 (4)
N3—Co1—N2—C2	90.6 (2)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···S3ⁱⁱⁱ	0.91	2.69	3.591 (2)	173
N3—H3B···S1ⁱⁱⁱ	0.91	2.60	3.513 (2)	176
N3—H3C···N7^iv	0.91	2.58	3.330 (4)	140
N6—H6A···N7ⁱⁱⁱ	0.91	2.26	3.172 (3)	179
N6—H6C···S1	0.91	2.61	3.498 (3)	167
C4—H4···S1^v	0.95	2.78	3.523 (2)	135
C5—H5···S3	0.95	2.82	3.681 (2)	151
C6—H6···N1	0.95	2.43	2.940 (3)	113

Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x, −y+1, z−1/2; (v) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₁₀H₈N₂)(NH₃)₂][Cr(NCS)₄(NH₃)₂]·2C₂H₃N
M_r	765.90
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	100
a, b, c (Å)	13.2923 (7), 10.7155 (3), 13.8745 (7)
β (°)	118.592 (6)
V (Å³)	1735.21 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.19
Crystal size (mm)	0.32 × 0.08 × 0.07

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.913, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15857, 5538, 4555
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.084, 1.02
No. of reflections	5538
No. of parameters	195
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.45

Computer programs: CrysAlis PRO (Oxford Diffraction 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Co1—N1	1.8929 (17)	Cr1—N4	1.9979 (19)
Co1—N2	1.9236 (16)	Cr1—N5	1.988 (2)
Co1—N3	1.9571 (17)	Cr1—N6	2.0682 (18)