fac-Tri­aqua­(1,10-phenanthroline-κ2N,N′)(sulfato-κO)cobalt(II): crystal structure, Hirshfeld surface analysis and computational study

Setifi, Z.; Kwong, H.C.; Tiekink, E.R.T.; Maris, T.; Setifi, F.

doi:10.1107/S2056989020006271

fac-Triaqua(1,10-phenanthroline-κ²N,N′)(sulfato-κO)cobalt(II): crystal structure, Hirshfeld surface analysis and computational study

Z. Setifi, H. C. Kwong, E. R. T. Tiekink, T. Maris and F. Setifi

The Co^II atom in the title complex is octahedrally coordinated within an N₂O₄ donor set defined by two N-atom donors of the 1,10-phenanthroline ligand, sulfate-O and three aqua-O atoms, the latter occupying an octahedral face. In the crystal, supramolecular layers parallel to (110) are sustained by aqua-O—H

O(sulfate) hydrogen bonding.

Keywords: crystal structure; cobalt(II); hydrogen bonding; Hirshfeld surface analysis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989020006271/hb7911sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989020006271/hb7911Isup2.hkl Contains datablock I

CCDC reference: 2002737

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.003 Å
R factor = 0.017
wR factor = 0.046
Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          4 Report
PLAT915_ALERT_3_C No Flack x Check Done: Low Friedel Pair Coverage         90 %

Alert level G
ABSMU01_ALERT_1_G  Calculation of _exptl_absorpt_correction_mu
                not performed for this radiation type.
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          9 Note
PLAT033_ALERT_4_G Flack x Value Deviates > 3.0 * sigma from Zero .      0.010 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co       --O1W      .        5.7 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Co        (II)      .       1.83 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          6 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          4 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          2 Info

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

   1 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
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

fac-Triaqua(1,10-phenanthroline-κ²N,N')(sulfato-κO)cobalt(II) top

Crystal data top

[Co(SO₄)(C₁₂H₈N₂)(H₂O)₃]	D_x = 1.776 Mg m⁻³
M_r = 389.24	Ga Kα radiation, λ = 1.34139 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9840 reflections
a = 7.9732 (4) Å	θ = 4.0–60.7°
b = 9.5589 (4) Å	µ = 7.61 mm⁻¹
c = 19.0955 (9) Å	T = 150 K
V = 1455.36 (12) Å³	Prism, light-pink
Z = 4	0.08 × 0.08 × 0.05 mm
F(000) = 796

Data collection top

Bruker Venture Metaljet diffractometer	3202 independent reflections
Radiation source: Metal Jet, Gallium Liquid Metal Jet Source	3126 reflections with I > 2σ(I)
Helios MX Mirror Optics monochromator	R_int = 0.033
Detector resolution: 10.24 pixels mm^-1	θ_max = 60.6°, θ_min = 4.5°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −12→12
T_min = 0.064, T_max = 0.155	l = −24→24
25223 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.017	w = 1/[σ²(F_o²) + (0.0202P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.046	(Δ/σ)_max = 0.001
S = 0.99	Δρ_max = 0.51 e Å⁻³
3202 reflections	Δρ_min = −0.58 e Å⁻³
227 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.0057 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 1194 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.0101 (17)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co	0.63811 (3)	0.53373 (3)	0.31720 (2)	0.02111 (9)
S1	0.24258 (5)	0.56910 (4)	0.27630 (2)	0.02212 (11)
O1	0.40704 (16)	0.63702 (14)	0.29351 (7)	0.0239 (3)
O2	0.17822 (17)	0.49545 (15)	0.33775 (7)	0.0291 (3)
O3	0.26932 (17)	0.46986 (15)	0.21777 (7)	0.0289 (3)
O4	0.12543 (18)	0.68089 (14)	0.25463 (7)	0.0290 (3)
O1W	0.60122 (18)	0.42633 (14)	0.22184 (7)	0.0267 (3)
H1W	0.5005 (18)	0.431 (3)	0.2097 (13)	0.040*
H2W	0.607 (3)	0.3405 (14)	0.2144 (14)	0.040*
O2W	0.77952 (18)	0.68717 (15)	0.26762 (8)	0.0296 (3)
H3W	0.768 (4)	0.7735 (15)	0.2743 (14)	0.044*
H4W	0.8839 (17)	0.673 (3)	0.2607 (15)	0.044*
O3W	0.85965 (17)	0.41650 (15)	0.32821 (7)	0.0281 (3)
H5W	0.874 (4)	0.353 (2)	0.2999 (12)	0.042*
H6W	0.9583 (19)	0.440 (3)	0.3324 (14)	0.042*
N1	0.6414 (2)	0.64091 (16)	0.41532 (8)	0.0252 (3)
N2	0.5377 (2)	0.37822 (16)	0.38651 (8)	0.0240 (3)
C1	0.6826 (3)	0.7733 (2)	0.42840 (11)	0.0307 (4)
H1	0.716162	0.831005	0.390391	0.037*
C2	0.6788 (3)	0.8312 (2)	0.49569 (12)	0.0349 (5)
H2	0.706310	0.926898	0.502638	0.042*
C3	0.6351 (3)	0.7487 (2)	0.55149 (12)	0.0357 (5)
H3	0.634774	0.786001	0.597609	0.043*
C4	0.5906 (3)	0.6081 (2)	0.53970 (11)	0.0311 (4)
C5	0.5383 (3)	0.5154 (3)	0.59456 (11)	0.0374 (5)
H5	0.537335	0.547683	0.641615	0.045*
C6	0.4904 (3)	0.3828 (3)	0.58034 (11)	0.0394 (5)
H6	0.456658	0.323326	0.617613	0.047*
C7	0.4897 (3)	0.3302 (2)	0.50992 (11)	0.0315 (4)
C8	0.4422 (3)	0.1926 (2)	0.49259 (12)	0.0358 (5)
H8	0.410012	0.128509	0.528178	0.043*
C9	0.4430 (3)	0.1523 (2)	0.42371 (12)	0.0350 (5)
H9	0.411464	0.059775	0.411121	0.042*
C10	0.4904 (3)	0.2480 (2)	0.37212 (11)	0.0290 (4)
H10	0.488688	0.218795	0.324580	0.035*
C11	0.5388 (2)	0.4191 (2)	0.45479 (10)	0.0251 (4)
C12	0.5919 (2)	0.5600 (2)	0.46986 (10)	0.0258 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.02084 (13)	0.02088 (13)	0.02160 (13)	−0.00016 (10)	0.00033 (10)	0.00127 (10)
S1	0.0203 (2)	0.0203 (2)	0.0258 (2)	−0.00016 (15)	−0.00058 (17)	−0.00105 (15)
O1	0.0203 (6)	0.0225 (6)	0.0291 (6)	−0.0006 (5)	−0.0005 (5)	−0.0017 (5)
O2	0.0262 (6)	0.0301 (7)	0.0311 (7)	−0.0029 (6)	0.0008 (5)	0.0037 (5)
O3	0.0282 (6)	0.0279 (6)	0.0306 (7)	−0.0006 (6)	−0.0015 (6)	−0.0074 (6)
O4	0.0235 (6)	0.0256 (6)	0.0378 (7)	0.0016 (6)	−0.0023 (6)	0.0027 (5)
O1W	0.0273 (7)	0.0240 (6)	0.0287 (7)	0.0042 (5)	−0.0013 (6)	−0.0016 (5)
O2W	0.0244 (7)	0.0244 (6)	0.0399 (8)	0.0008 (6)	0.0046 (6)	0.0047 (6)
O3W	0.0221 (6)	0.0250 (6)	0.0371 (7)	0.0012 (6)	−0.0018 (6)	−0.0011 (5)
N1	0.0242 (7)	0.0253 (7)	0.0259 (7)	0.0006 (7)	−0.0010 (7)	0.0000 (6)
N2	0.0225 (7)	0.0251 (8)	0.0242 (7)	−0.0003 (6)	0.0009 (6)	0.0010 (6)
C1	0.0318 (11)	0.0275 (9)	0.0329 (10)	−0.0025 (8)	−0.0020 (8)	−0.0001 (8)
C2	0.0354 (11)	0.0292 (10)	0.0402 (11)	−0.0022 (9)	−0.0043 (9)	−0.0074 (8)
C3	0.0365 (11)	0.0404 (11)	0.0302 (10)	−0.0001 (10)	−0.0014 (10)	−0.0109 (8)
C4	0.0296 (10)	0.0363 (10)	0.0273 (9)	0.0006 (8)	−0.0011 (8)	−0.0032 (8)
C5	0.0423 (12)	0.0468 (12)	0.0231 (9)	−0.0016 (10)	0.0031 (8)	−0.0016 (9)
C6	0.0461 (13)	0.0474 (13)	0.0247 (10)	−0.0035 (11)	0.0058 (10)	0.0064 (9)
C7	0.0314 (10)	0.0347 (10)	0.0286 (9)	−0.0023 (9)	0.0038 (8)	0.0045 (8)
C8	0.0386 (12)	0.0341 (11)	0.0348 (11)	−0.0053 (10)	0.0064 (9)	0.0084 (9)
C9	0.0381 (11)	0.0270 (9)	0.0400 (11)	−0.0056 (9)	0.0029 (9)	0.0024 (9)
C10	0.0289 (10)	0.0288 (9)	0.0293 (10)	−0.0023 (8)	0.0015 (8)	−0.0021 (8)
C11	0.0234 (8)	0.0277 (9)	0.0244 (8)	0.0003 (7)	0.0011 (7)	0.0008 (7)
C12	0.0236 (8)	0.0285 (9)	0.0253 (9)	0.0011 (7)	−0.0005 (7)	−0.0006 (7)

Geometric parameters (Å, º) top

Co—O1	2.1386 (13)	C1—C2	1.399 (3)
Co—O1W	2.1110 (14)	C1—H1	0.9500
Co—O2W	2.0782 (15)	C2—C3	1.371 (3)
Co—O3W	2.1024 (14)	C2—H2	0.9500
Co—N1	2.1356 (15)	C3—C4	1.408 (3)
Co—N2	2.1453 (16)	C3—H3	0.9500
S1—O1	1.4997 (13)	C4—C12	1.411 (3)
S1—O2	1.4616 (14)	C4—C5	1.434 (3)
S1—O3	1.4813 (14)	C5—C6	1.351 (4)
S1—O4	1.4784 (14)	C5—H5	0.9500
O1W—H1W	0.837 (12)	C6—C7	1.436 (3)
O1W—H2W	0.834 (13)	C6—H6	0.9500
O2W—H3W	0.840 (13)	C7—C11	1.409 (3)
O2W—H4W	0.853 (12)	C7—C8	1.408 (3)
O3W—H5W	0.822 (12)	C8—C9	1.371 (3)
O3W—H6W	0.822 (13)	C8—H8	0.9500
N1—C1	1.331 (3)	C9—C10	1.397 (3)
N1—C12	1.356 (2)	C9—H9	0.9500
N2—C10	1.329 (3)	C10—H10	0.9500
N2—C11	1.361 (2)	C11—C12	1.441 (3)

O2W—Co—O3W	88.05 (6)	N1—C1—C2	122.9 (2)
O2W—Co—O1W	91.48 (6)	N1—C1—H1	118.6
O3W—Co—O1W	86.80 (6)	C2—C1—H1	118.6
O2W—Co—N1	93.13 (6)	C3—C2—C1	119.5 (2)
O3W—Co—N1	99.08 (6)	C3—C2—H2	120.3
O2W—Co—O1	92.59 (6)	C1—C2—H2	120.3
O1—Co—O3W	172.31 (5)	C2—C3—C4	119.26 (19)
O1W—Co—O1	85.53 (5)	C2—C3—H3	120.4
N1—Co—O1	88.54 (6)	C4—C3—H3	120.4
O1W—Co—N1	172.65 (6)	C3—C4—C12	117.42 (19)
O2W—Co—N2	166.55 (6)	C3—C4—C5	123.1 (2)
O3W—Co—N2	83.25 (6)	C12—C4—C5	119.4 (2)
O1W—Co—N2	98.23 (6)	C6—C5—C4	121.0 (2)
N1—Co—N2	78.21 (6)	C6—C5—H5	119.5
O1—Co—N2	97.41 (6)	C4—C5—H5	119.5
O2—S1—O4	110.56 (8)	C5—C6—C7	121.2 (2)
O2—S1—O3	110.35 (8)	C5—C6—H6	119.4
O4—S1—O3	110.04 (8)	C7—C6—H6	119.4
O2—S1—O1	109.85 (8)	C11—C7—C8	117.58 (19)
O4—S1—O1	107.51 (8)	C11—C7—C6	119.2 (2)
O3—S1—O1	108.47 (8)	C8—C7—C6	123.3 (2)
S1—O1—Co	126.85 (8)	C9—C8—C7	119.13 (19)
Co—O1W—H1W	110.3 (18)	C9—C8—H8	120.4
Co—O1W—H2W	128.2 (19)	C7—C8—H8	120.4
H1W—O1W—H2W	93 (3)	C8—C9—C10	119.6 (2)
Co—O2W—H3W	125 (2)	C8—C9—H9	120.2
Co—O2W—H4W	119 (2)	C10—C9—H9	120.2
H3W—O2W—H4W	106 (3)	N2—C10—C9	123.01 (19)
Co—O3W—H5W	117 (2)	N2—C10—H10	118.5
Co—O3W—H6W	132 (2)	C9—C10—H10	118.5
H5W—O3W—H6W	97 (3)	N2—C11—C7	122.72 (18)
C1—N1—C12	118.04 (17)	N2—C11—C12	117.50 (16)
C1—N1—Co	128.58 (14)	C7—C11—C12	119.78 (18)
C12—N1—Co	113.38 (12)	N1—C12—C4	122.85 (18)
C10—N2—C11	117.96 (16)	N1—C12—C11	117.73 (16)
C10—N2—Co	128.85 (14)	C4—C12—C11	119.43 (18)
C11—N2—Co	112.92 (12)

O2—S1—O1—Co	67.05 (11)	C10—N2—C11—C7	−1.0 (3)
O4—S1—O1—Co	−172.59 (9)	Co—N2—C11—C7	−175.48 (16)
O3—S1—O1—Co	−53.64 (11)	C10—N2—C11—C12	179.40 (17)
C12—N1—C1—C2	0.7 (3)	Co—N2—C11—C12	4.9 (2)
Co—N1—C1—C2	179.75 (16)	C8—C7—C11—N2	1.7 (3)
N1—C1—C2—C3	1.7 (3)	C6—C7—C11—N2	−178.4 (2)
C1—C2—C3—C4	−1.6 (3)	C8—C7—C11—C12	−178.70 (19)
C2—C3—C4—C12	−0.7 (3)	C6—C7—C11—C12	1.2 (3)
C2—C3—C4—C5	−178.1 (2)	C1—N1—C12—C4	−3.3 (3)
C3—C4—C5—C6	177.4 (2)	Co—N1—C12—C4	177.58 (15)
C12—C4—C5—C6	0.0 (4)	C1—N1—C12—C11	176.72 (17)
C4—C5—C6—C7	−0.2 (4)	Co—N1—C12—C11	−2.4 (2)
C5—C6—C7—C11	−0.4 (4)	C3—C4—C12—N1	3.2 (3)
C5—C6—C7—C8	179.5 (2)	C5—C4—C12—N1	−179.3 (2)
C11—C7—C8—C9	−1.1 (3)	C3—C4—C12—C11	−176.74 (19)
C6—C7—C8—C9	179.0 (2)	C5—C4—C12—C11	0.8 (3)
C7—C8—C9—C10	−0.1 (4)	N2—C11—C12—N1	−1.7 (3)
C11—N2—C10—C9	−0.3 (3)	C7—C11—C12—N1	178.67 (18)
Co—N2—C10—C9	173.15 (16)	N2—C11—C12—C4	178.26 (17)
C8—C9—C10—N2	0.9 (4)	C7—C11—C12—C4	−1.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O3	0.84 (2)	1.89 (2)	2.680 (2)	158 (2)
O1W—H2W···O1ⁱ	0.83 (1)	1.95 (1)	2.7818 (19)	172 (2)
O2W—H3W···O3ⁱⁱ	0.84 (2)	1.91 (2)	2.744 (2)	175 (3)
O2W—H4W···O4ⁱⁱⁱ	0.85 (1)	1.93 (1)	2.770 (2)	167 (3)
O3W—H5W···O4ⁱ	0.82 (2)	1.95 (2)	2.7548 (19)	168 (3)
O3W—H6W···O2ⁱⁱⁱ	0.82 (2)	1.84 (2)	2.6560 (19)	178 (3)
C3—H3···O2^iv	0.95	2.45	3.252 (3)	142

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

A summary of short interatomic contacts (Å) in (I)^a top

Contact	Distance	Symmetry operation
H2W···O1^b	1.81	-x + 1, y - 1/2, -z + 1/2
H3W···O3^b	1.76	-x + 1, y + 1/2, -z + 1/2
H4W···O4^b	1.81	x + 1, y, z
H5W···O4^b	1.79	-x + 1, y - 1/2, -z + 1/2
H6W···O2^b	1.67	x + 1, y, z
H1···O3	2.33	-x + 1, y + 1/2, -z + 1/2
H3···O2	2.35	x + 1/2, -y + 3/2, - z + 1
H6···O3W	2.51	x - 1/2, -y + 1/2, - z + 1
H10···O1	2.40	-x + 1, y - 1/2, - z + 1/2

Notes: (a) The interatomic distances are calculated in Crystal Explorer 17 (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values; (b) these interactions correspond to conventional hydrogen bonds.

A summary of interaction energies (kJ mol^-1) calculated for (I) top

Contact	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
O1W—H2W···O1ⁱ +	6.78	-330.8	-116.8	-49.6	180.1	-368.1
O3W—H5W···O4ⁱ +
O2W—H3W···O3ⁱⁱ +
C10—H10···O1ⁱ
O3W—H6W···O2ⁱⁱⁱ +	7.97	-198.3	-63.8	-16.4	121.0	-196.4
O2W—H4W···O4ⁱⁱⁱ
C5—H5···O3^v +	10.47	-46.2	-19.3	-9.8	7.8	-66.8
C6—H6···O4^v
C3—H3···O2^iv	7.64	-17.3	-30.2	-42.3	35.3	-55.7
C6—H6···O3W^vi	8.03	-2.3	-13.7	-37.7	24.0	-30.6

Symmetry operations: (i) -x + 1, y - 1/2, -z + 1/2; (ii) - x + 1, y + 1/2, - z + 1/2; (iii) x + 1, y, z; (iv) x + 1/2, -y + 3/2, -z + 1; (v) -x + 1/2, - y + 1, z + 1/2; (vi) x – 1/2, -y + 1/2, -z + 1.

Percentage contributions to intermolecular contacts on the Hirshfeld surface calculated for (I) top

Contact		Percentage contribution
	(I), M = Co	IJOQAA, M = Zn	RACWUO, M = Cd	XATNAH, M = Mn
H···H	28.6	30.1	27.6	27.2
H···O/O···H	44.5	43.3	45.8	45.9
H···C/C···H	19.5	19.1	19.2	19.1
C···C	5.7	5.7	5.2	5.6
Others	1.7	1.8	2.2	2.2

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fac-Tri­aqua­(1,10-phenanthroline-κ2N,N′)(sulfato-κO)cobalt(II): crystal structure, Hirshfeld surface analysis and computational study

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fac-Triaqua(1,10-phenanthroline-κ²N,N′)(sulfato-κO)cobalt(II): crystal structure, Hirshfeld surface analysis and computational study