Bis(1,10-phenanthroline-κN,N')(sulfato-κO,O')cobalt(II) propane-1,3-diol solvate.

The title compound, [Co(SO(4))(C(12)H(8)N(2))(2)]·C(3)H(8)O(2), was obtained unexpectedly as a by-product during an attempt to synthesize a mixed-ligand complex of Co(II) with 1,10-phenanthroline (phen) and melamine via a solvothermal reaction. The Co(II) metal ions are in a distorted octa-hedral coordination environment formed by four N atoms from two chelating phen ligands and two O atoms from a bidentate sulfate ligand. The two chelating N(2)C(2) groups are almost perpendicular to each other [dihedral angle = 80.06 (8)°]. A twofold rotation axis passes through the Co and S atoms, and also through the central C atom of the propane-1,3-diol solvent mol-ecule. Inter-molecular O-H⋯O hydrogen bonds help to stabilize the structure.

Related literature

For related cobalt n class="Chemical">compounds with monodentate, bidentate-bridging sulfate ligands, see: Hennig et al. (1975 ▶); Li & Zhou (1987 ▶); Song et al. (2008 ▶); Zheng & Lin (2003 ▶). For related complexes with bidentate-chelating ligands, see: Lu et al. (2006 ▶); Paul et al. (2002 ▶); Wang et al. (2009 ▶). For an isostructural structure, see: Zhong et al. (2006 ▶). For a related structure, see: Chen et al. (2005 ▶). For applications of transition metal complexes of phen, see: Li et al. (2004 ▶); Wang et al. (2000 ▶).

Experimental

Crystal data

[Co(SO4)(C12n class="Species">H8N2)2]·C3H8O2

M = 591.49

Monoclinic,

a = 18.285 (4) Å

b = 12.422 (3) Å

c = 13.211 (3) Å

β = 121.82 (3)°

V = 2549.7 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.81 mm−1

T = 223 K

0.60 × 0.40 × 0.34 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (REQAB: Jan class="Chemical">cobson, 1998 ▶) T min = 0.823, T max = 1.000

7099 measured reflections

2898 independent reflections

2540 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.101

S = 1.06

2898 reflections

183 parameters

21 restraints

H atoms treated by a mixture of independent and n class="Chemical">constrained refinement

Δρmax = 0.72 e Å−3

Δρmin = −0.45 e Å−3

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003478/zq2024sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003478/zq2024Isup2.hkl

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

[Co(SO4)(C12H8N2)2]·C3H8O2	F(000) = 1220
Mr = 591.49	Dx = 1.541 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3592 reflections
a = 18.285 (4) Å	θ = 3.2–27.5°
b = 12.422 (3) Å	µ = 0.81 mm−1
c = 13.211 (3) Å	T = 223 K
β = 121.82 (3)°	Prism, red
V = 2549.7 (13) Å3	0.60 × 0.40 × 0.34 mm
Z = 4

Rigaku Mercury CCD diffractometer	2898 independent reflections
Radiation source: fine-focus sealed tube	2540 reflections with I > 2σ(I)
Graphite Monochromator	Rint = 0.021
Detector resolution: 28.5714 pixels mm-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −23→23
Absorption correction: multi-scan (REQAB: Jacobson, 1998)	k = −16→13
Tmin = 0.823, Tmax = 1.000	l = −17→14
7099 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101	w = 1/[σ2(Fo2) + (0.0616P)2 + 1.0504P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2898 reflections	Δρmax = 0.72 e Å−3
183 parameters	Δρmin = −0.45 e Å−3
21 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0057 (6)

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
Co1	0.5000	0.81835 (3)	0.2500	0.02201 (14)
S1	0.5000	1.03618 (5)	0.2500	0.02331 (17)
O1	0.44793 (9)	0.96187 (12)	0.14805 (12)	0.0329 (3)
C11	0.34382 (12)	0.68292 (14)	0.14757 (16)	0.0224 (4)
N2	0.40420 (10)	0.71189 (13)	0.12195 (14)	0.0238 (3)
C10	0.39507 (13)	0.67410 (16)	0.02169 (18)	0.0284 (4)
H10A	0.4356	0.6935	0.0028	0.034*
C8	0.26687 (13)	0.57717 (16)	−0.03144 (17)	0.0304 (4)
H8A	0.2213	0.5328	−0.0832	0.036*
O2	0.55612 (10)	1.10269 (14)	0.22920 (16)	0.0446 (4)
C6	0.21399 (13)	0.58852 (17)	0.10868 (18)	0.0310 (4)
H6A	0.1679	0.5434	0.0604	0.037*
C12	0.35267 (11)	0.72718 (15)	0.25388 (16)	0.0223 (4)
C7	0.27424 (12)	0.61511 (16)	0.07446 (17)	0.0264 (4)
C4	0.29234 (12)	0.69936 (16)	0.28497 (17)	0.0270 (4)
C9	0.32726 (14)	0.60646 (18)	−0.05671 (18)	0.0331 (4)
H9A	0.3235	0.5817	−0.1257	0.040*
C5	0.22322 (12)	0.62810 (18)	0.21042 (18)	0.0322 (5)
H5A	0.1841	0.6086	0.2319	0.039*
N1	0.41806 (10)	0.79727 (13)	0.31789 (14)	0.0250 (3)
C1	0.42581 (13)	0.84107 (17)	0.41526 (18)	0.0291 (4)
H1A	0.4706	0.8892	0.4597	0.035*
C2	0.36899 (14)	0.81726 (18)	0.45310 (19)	0.0335 (5)
H2A	0.3762	0.8491	0.5215	0.040*
C3	0.30319 (13)	0.74709 (18)	0.38888 (18)	0.0335 (5)
H3A	0.2653	0.7306	0.4135	0.040*
O3	0.56334 (16)	1.31539 (16)	0.1809 (2)	0.0659 (6)
H3B	0.5610	1.2514	0.1944	0.099*
C14	0.5000	1.4456 (3)	0.2500	0.0562 (10)
C13	0.5774 (2)	1.3764 (3)	0.2780 (3)	0.0723 (9)
H13A	0.6268	1.4227	0.3033	0.087*
H13B	0.5907	1.3286	0.3436	0.087*
H14	0.496 (3)	1.442 (4)	0.174 (2)	0.143 (19)*

	U11	U22	U33	U12	U13	U23
Co1	0.0211 (2)	0.0208 (2)	0.0239 (2)	0.000	0.01172 (16)	0.000
S1	0.0212 (3)	0.0200 (3)	0.0303 (3)	0.000	0.0146 (3)	0.000
O1	0.0315 (7)	0.0277 (8)	0.0270 (7)	0.0012 (6)	0.0068 (6)	0.0011 (6)
C11	0.0222 (9)	0.0193 (9)	0.0227 (9)	0.0027 (7)	0.0098 (7)	0.0026 (7)
N2	0.0253 (8)	0.0218 (8)	0.0254 (8)	0.0006 (6)	0.0141 (7)	0.0004 (6)
C10	0.0334 (10)	0.0272 (11)	0.0284 (10)	−0.0004 (8)	0.0189 (9)	−0.0014 (8)
C8	0.0306 (10)	0.0278 (11)	0.0241 (9)	−0.0033 (8)	0.0085 (8)	−0.0045 (8)
O2	0.0435 (9)	0.0362 (9)	0.0676 (12)	−0.0093 (8)	0.0386 (9)	0.0028 (8)
C6	0.0243 (9)	0.0314 (11)	0.0298 (10)	−0.0075 (8)	0.0092 (8)	0.0014 (8)
C12	0.0202 (8)	0.0222 (9)	0.0218 (8)	0.0026 (7)	0.0092 (7)	0.0028 (7)
C7	0.0251 (9)	0.0245 (10)	0.0247 (9)	0.0007 (8)	0.0098 (8)	0.0020 (7)
C4	0.0251 (9)	0.0291 (10)	0.0271 (9)	0.0023 (8)	0.0139 (8)	0.0045 (8)
C9	0.0397 (11)	0.0332 (11)	0.0252 (9)	0.0002 (9)	0.0162 (9)	−0.0043 (8)
C5	0.0259 (9)	0.0382 (12)	0.0328 (10)	−0.0041 (9)	0.0157 (8)	0.0046 (9)
N1	0.0249 (8)	0.0252 (8)	0.0253 (8)	0.0004 (6)	0.0135 (7)	−0.0008 (6)
C1	0.0304 (10)	0.0283 (11)	0.0270 (9)	−0.0003 (8)	0.0140 (8)	−0.0050 (8)
C2	0.0409 (12)	0.0361 (12)	0.0282 (10)	0.0029 (9)	0.0213 (10)	−0.0025 (8)
C3	0.0347 (10)	0.0419 (13)	0.0318 (10)	0.0004 (9)	0.0229 (9)	0.0030 (9)
O3	0.1116 (18)	0.0412 (11)	0.0867 (15)	−0.0012 (11)	0.0808 (15)	0.0034 (10)
C14	0.085 (3)	0.0301 (18)	0.068 (3)	0.000	0.050 (2)	0.000
C13	0.077 (2)	0.072 (2)	0.069 (2)	−0.0252 (18)	0.0392 (17)	−0.0071 (17)

Co1—N1i	2.1295 (16)	C6—C7	1.432 (3)
Co1—N1	2.1295 (16)	C6—H6A	0.9300
Co1—O1i	2.1323 (15)	C12—N1	1.355 (3)
Co1—O1	2.1323 (15)	C12—C4	1.408 (3)
Co1—N2	2.1341 (17)	C4—C3	1.410 (3)
Co1—N2i	2.1341 (17)	C4—C5	1.428 (3)
Co1—S1	2.7058 (9)	C9—H9A	0.9300
S1—O2	1.4519 (15)	C5—H5A	0.9300
S1—O2i	1.4519 (15)	N1—C1	1.334 (3)
S1—O1	1.4901 (15)	C1—C2	1.401 (3)
S1—O1i	1.4901 (15)	C1—H1A	0.9300
C11—N2	1.363 (2)	C2—C3	1.360 (3)
C11—C7	1.402 (3)	C2—H2A	0.9300
C11—C12	1.436 (3)	C3—H3A	0.9300
N2—C10	1.330 (2)	O3—C13	1.392 (3)
C10—C9	1.401 (3)	O3—H3B	0.8200
C10—H10A	0.9300	C14—C13i	1.525 (4)
C8—C9	1.361 (3)	C14—C13	1.525 (4)
C8—C7	1.414 (3)	C14—H14	0.97 (3)
C8—H8A	0.9300	C13—H13A	0.9700
C6—C5	1.356 (3)	C13—H13B	0.9700
N1i—Co1—N1	165.87 (9)	C9—C8—H8A	120.4
N1i—Co1—O1i	100.94 (6)	C7—C8—H8A	120.4
N1—Co1—O1i	90.91 (6)	C5—C6—C7	120.98 (18)
N1i—Co1—O1	90.91 (6)	C5—C6—H6A	119.5
N1—Co1—O1	100.94 (6)	C7—C6—H6A	119.5
O1i—Co1—O1	66.54 (8)	N1—C12—C4	123.01 (17)
N1i—Co1—N2	93.19 (6)	N1—C12—C11	117.63 (16)
N1—Co1—N2	77.99 (6)	C4—C12—C11	119.33 (17)
O1i—Co1—N2	157.72 (6)	C11—C7—C8	117.41 (18)
O1—Co1—N2	96.36 (6)	C11—C7—C6	119.39 (18)
N1i—Co1—N2i	77.99 (6)	C8—C7—C6	123.19 (18)
N1—Co1—N2i	93.19 (6)	C12—C4—C3	116.81 (18)
O1i—Co1—N2i	96.36 (6)	C12—C4—C5	119.71 (18)
O1—Co1—N2i	157.72 (6)	C3—C4—C5	123.45 (18)
N2—Co1—N2i	103.42 (9)	C8—C9—C10	119.69 (19)
N1i—Co1—S1	97.06 (5)	C8—C9—H9A	120.2
N1—Co1—S1	97.06 (5)	C10—C9—H9A	120.2
O1i—Co1—S1	33.27 (4)	C6—C5—C4	120.73 (18)
O1—Co1—S1	33.27 (4)	C6—C5—H5A	119.6
N2—Co1—S1	128.29 (5)	C4—C5—H5A	119.6
N2i—Co1—S1	128.29 (5)	C1—N1—C12	118.30 (16)
O2—S1—O2i	110.64 (15)	C1—N1—Co1	127.99 (14)
O2—S1—O1	111.10 (9)	C12—N1—Co1	113.67 (12)
O2i—S1—O1	110.18 (9)	N1—C1—C2	122.42 (19)
O2—S1—O1i	110.18 (9)	N1—C1—H1A	118.8
O2i—S1—O1i	111.10 (9)	C2—C1—H1A	118.8
O1—S1—O1i	103.45 (12)	C3—C2—C1	119.41 (19)
O2—S1—Co1	124.68 (7)	C3—C2—H2A	120.3
O2i—S1—Co1	124.68 (7)	C1—C2—H2A	120.3
O1—S1—Co1	51.72 (6)	C2—C3—C4	120.05 (18)
O1i—S1—Co1	51.72 (6)	C2—C3—H3A	120.0
S1—O1—Co1	95.01 (7)	C4—C3—H3A	120.0
N2—C11—C7	123.19 (17)	C13—O3—H3B	109.5
N2—C11—C12	116.97 (16)	C13i—C14—C13	111.4 (3)
C7—C11—C12	119.82 (17)	C13i—C14—H14	100 (3)
C10—N2—C11	117.47 (17)	C13—C14—H14	77 (3)
C10—N2—Co1	128.88 (13)	O3—C13—C14	112.8 (2)
C11—N2—Co1	113.62 (12)	O3—C13—H13A	109.0
N2—C10—C9	123.06 (18)	C14—C13—H13A	109.0
N2—C10—H10A	118.5	O3—C13—H13B	109.0
C9—C10—H10A	118.5	C14—C13—H13B	109.0
C9—C8—C7	119.17 (19)	H13A—C13—H13B	107.8
N1i—Co1—S1—O2	−9.86 (10)	C11—N2—C10—C9	−0.4 (3)
N1—Co1—S1—O2	170.14 (10)	Co1—N2—C10—C9	−178.16 (15)
O1i—Co1—S1—O2	89.33 (12)	N2—C11—C12—N1	2.5 (3)
O1—Co1—S1—O2	−90.67 (12)	C7—C11—C12—N1	−176.19 (17)
N2—Co1—S1—O2	−109.61 (10)	N2—C11—C12—C4	−179.60 (17)
N2i—Co1—S1—O2	70.39 (10)	C7—C11—C12—C4	1.7 (3)
N1i—Co1—S1—O2i	170.14 (10)	N2—C11—C7—C8	−1.0 (3)
N1—Co1—S1—O2i	−9.86 (10)	C12—C11—C7—C8	177.62 (17)
O1i—Co1—S1—O2i	−90.67 (12)	N2—C11—C7—C6	179.73 (18)
O1—Co1—S1—O2i	89.33 (12)	C12—C11—C7—C6	−1.7 (3)
N2—Co1—S1—O2i	70.39 (10)	C9—C8—C7—C11	0.8 (3)
N2i—Co1—S1—O2i	−109.61 (10)	C9—C8—C7—C6	−179.9 (2)
N1i—Co1—S1—O1	80.81 (9)	C5—C6—C7—C11	0.1 (3)
N1—Co1—S1—O1	−99.19 (9)	C5—C6—C7—C8	−179.1 (2)
O1i—Co1—S1—O1	180.0	N1—C12—C4—C3	−0.9 (3)
N2—Co1—S1—O1	−18.94 (9)	C11—C12—C4—C3	−178.66 (17)
N2i—Co1—S1—O1	161.06 (9)	N1—C12—C4—C5	177.55 (18)
N1i—Co1—S1—O1i	−99.19 (9)	C11—C12—C4—C5	−0.2 (3)
N1—Co1—S1—O1i	80.81 (9)	C7—C8—C9—C10	−0.5 (3)
O1—Co1—S1—O1i	180.0	N2—C10—C9—C8	0.3 (3)
N2—Co1—S1—O1i	161.06 (9)	C7—C6—C5—C4	1.4 (3)
N2i—Co1—S1—O1i	−18.94 (9)	C12—C4—C5—C6	−1.3 (3)
O2—S1—O1—Co1	118.19 (9)	C3—C4—C5—C6	177.0 (2)
O2i—S1—O1—Co1	−118.83 (9)	C4—C12—N1—C1	0.6 (3)
O1i—S1—O1—Co1	0.0	C11—C12—N1—C1	178.38 (17)
N1i—Co1—O1—S1	−101.54 (8)	C4—C12—N1—Co1	178.28 (14)
N1—Co1—O1—S1	86.20 (8)	C11—C12—N1—Co1	−3.9 (2)
O1i—Co1—O1—S1	0.0	N1i—Co1—N1—C1	128.19 (17)
N2—Co1—O1—S1	165.15 (7)	O1i—Co1—N1—C1	−19.01 (17)
N2i—Co1—O1—S1	−42.22 (19)	O1—Co1—N1—C1	−85.28 (18)
C7—C11—N2—C10	0.7 (3)	N2—Co1—N1—C1	−179.54 (18)
C12—C11—N2—C10	−177.90 (17)	N2i—Co1—N1—C1	77.41 (18)
C7—C11—N2—Co1	178.87 (14)	S1—Co1—N1—C1	−51.81 (17)
C12—C11—N2—Co1	0.2 (2)	N1i—Co1—N1—C12	−49.27 (13)
N1i—Co1—N2—C10	−14.97 (17)	O1i—Co1—N1—C12	163.52 (13)
N1—Co1—N2—C10	176.18 (18)	O1—Co1—N1—C12	97.25 (14)
O1i—Co1—N2—C10	114.64 (19)	N2—Co1—N1—C12	2.99 (13)
O1—Co1—N2—C10	76.30 (17)	N2i—Co1—N1—C12	−100.06 (14)
N2i—Co1—N2—C10	−93.38 (17)	S1—Co1—N1—C12	130.73 (13)
S1—Co1—N2—C10	86.62 (17)	C12—N1—C1—C2	−0.1 (3)
N1i—Co1—N2—C11	167.15 (13)	Co1—N1—C1—C2	−177.43 (15)
N1—Co1—N2—C11	−1.71 (12)	N1—C1—C2—C3	−0.1 (3)
O1i—Co1—N2—C11	−63.2 (2)	C1—C2—C3—C4	−0.3 (3)
O1—Co1—N2—C11	−101.58 (13)	C12—C4—C3—C2	0.7 (3)
N2i—Co1—N2—C11	88.74 (13)	C5—C4—C3—C2	−177.6 (2)
S1—Co1—N2—C11	−91.26 (13)	C13i—C14—C13—O3	64.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O2	0.82	1.92	2.737 (3)	179

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O2	0.82	1.92	2.737 (3)	179