Tetra­aqua­(1,10-phenanthroline-5,6-dione-κ2N,N′)cobalt(II) dinitrate

Shi, W.-J.

doi:10.1107/S1600536809017826

metal-organic compounds

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Volume 65| Part 6| June 2009| Page m653

doi:10.1107/S1600536809017826

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Tetraaqua(1,10-phenanthroline-5,6-dione-κ²N,N′)cobalt(II) dinitrate

Wen-Juan Shi ^a ^*

^aJiangxi Key Laboratory of Surface Engineering, Jiangxi Science and Technology Normal University, Jiangxi 330013, People's Republic of China.
^*Correspondence e-mail: swjuan2000@126.com

(Received 11 May 2009; accepted 12 May 2009; online 20 May 2009)

The asymmetric unit of the title compound, [Co(C₁₂H₆N₂O₂)(H₂O)₄](NO₃)₂, consists of a Co^II complex cation with twofold rotational symmetry and two nitrate anions. The Co^II atom has a distorted octahedral geometry with the basal plane occupied by two 1,10-phenanthroline-5,6-dione N atoms and two aqua O atoms, with the other two aqua ligands in axial positions. The aqua ligands are involved in extensive hydrogen bonding to nitrate and 1,10-phenanthroline-5,6-dione O atoms.

Related literature

For related complexes of 1,10-phenanthroline-5,6-dione, see: Calderazzo et al. (1999 ); Fox et al. (1991 ); Onuegbu et al. (2007 ); Paw & Eisenberg (1997 ); Ruiz et al. (1999 ); Shavaleev et al. (2003 ). For the structures of the related phenanthroline and phendione derivatives of cobalt(II), see: Liu et al. (2008 ); Rubin-Preminger et al. (2008 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Co(C₁₂H₆N₂O₂)(H₂O)₄](NO₃)₂
M_r = 465.20
Monoclinic, C 2/c
a = 12.7978 (12) Å
b = 10.6388 (10) Å
c = 13.0989 (12) Å
β = 105.248 (2)°
V = 1720.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 295 K
0.18 × 0.14 × 0.13 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.830, T_max = 0.873
4509 measured reflections
1695 independent reflections
1549 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.138
S = 1.04
1695 reflections
132 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H2W1⋯O4	0.85	2.21	2.834 (6)	130
O2W—H2W2⋯O2ⁱ	0.85	2.14	2.957 (6)	161
O1W—H1W1⋯O1ⁱⁱ	0.85	2.00	2.793 (5)	154
O1W—H1W2⋯O3ⁱⁱⁱ	0.85	2.19	2.864 (6)	136
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+1, -z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017826/at2784sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017826/at2784Isup2.hkl

checkCIF report

Comment top

Phendione (1,10-phenanthroline-5,6-dione) is an excellent ligand that incorporates two functional groups with different coordination properties. Though phendione usually binds to metals through the imine N atoms (Onuegbu et al., 2007), in some cases both the N and O donors are used simultaneously (Calderazzo et al., 1999; Fox et al., 1991; Paw & Eisenberg, 1997; Ruiz et al., 1999; Shavaleev et al., 2003). In this paper we report the synthesis and characterization of the title compound, [CoL(H₂O)₄].(NO₃)₂ (L = 1,10-phenanthroline-5,6-dione).

The molecular structure of the title compound, shown in Fig. 1, is made up of a [CoL(H₂O)₄]²⁺ cation and two nitrate anions, which the cations have twofold rotational symmetry. The cobalt atom is coordinated to the two N atoms of a phendione ligand and four aqua ligands to form distorted octahedral geometry. The C=O bond length in the phendione ligand [1.208 (6) Å] is comparable to those observed in other complexes of phendione (Allen et al., 1987). The Co—N bond lengths [2.121 (3) Å] are similar to those values in related phenanthroline and phendione derivatives of cobalt(II) (Liu et al., 2008; Rubin-Preminger et al., 2008).

In addition to the strong O—H···O hydrogen bonds formed by the water ligands to both the nitrate and phendione O atoms, there are π-π stacking interactions between adjacent phendione ligands [perpendicular interplanar distance 3.582 (1) Å and centroid-to-centroid distance 3.823 (1) Å] (Fig. 2).

Related literature top

For related complexes of 1,10-phenanthroline-5,6-dione, see: Calderazzo et al. (1999); Fox et al. (1991); Onuegbu et al. (2007); Paw & Eisenberg (1997); Ruiz et al. (1999); Shavaleev et al. (2003). For the structures of the related phenanthroline and phendione derivatives of cobalt(II), see: Liu et al. (2008); Rubin-Preminger, Kozlov & Goldberg (2008). For bond-length data, see: Allen et al. (1987).

Experimental top

A solution of cobalt(II) nitrate hexahydrate (29.1 mg, 0.10 mmol) and phendione (21.0 mg, 0.10 mmol) in methanol (8 ml) was stirred for 2 h. After filtering, the filtrate was left at room temperature for about one week and purple, block-like crystals of the title compound appeared [yield: 18 mg (39%)].

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Hand H atoms are drawn as spheres of arbitrary radius. [Symmetry code, A: 1-x, y, 1/2-z].
	Fig. 2. Packing diagram of the title structure, showing the intermolecular O—H···O hydrogen bonds as dashed lines.

Tetraaqua(1,10-phenanthroline-5,6-dione-κ²N,N')cobalt(II) dinitrate top

Crystal data top

[Co(C₁₂H₆N₂O₂)(H₂O)₄](NO₃)₂	F(000) = 948
M_r = 465.20	D_x = 1.796 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2754 reflections
a = 12.7978 (12) Å	θ = 2.5–26.8°
b = 10.6388 (10) Å	µ = 1.08 mm⁻¹
c = 13.0989 (12) Å	T = 295 K
β = 105.248 (2)°	Block, purple
V = 1720.7 (3) Å³	0.18 × 0.14 × 0.13 mm
Z = 4

Data collection top

Bruker SMART APEX area-detector diffractometer	1695 independent reflections
Radiation source: fine-focus sealed tube	1549 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.830, T_max = 0.873	k = −5→13
4509 measured reflections	l = −16→15

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.071P)² + 5.1444P] where P = (F_o² + 2F_c²)/3
1695 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 0.68 e Å⁻³
12 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

[Co(C₁₂H₆N₂O₂)(H₂O)₄](NO₃)₂	V = 1720.7 (3) Å³
M_r = 465.20	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.7978 (12) Å	µ = 1.08 mm⁻¹
b = 10.6388 (10) Å	T = 295 K
c = 13.0989 (12) Å	0.18 × 0.14 × 0.13 mm
β = 105.248 (2)°

Data collection top

Bruker SMART APEX area-detector diffractometer	1695 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1549 reflections with I > 2σ(I)
T_min = 0.830, T_max = 0.873	R_int = 0.020
4509 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	12 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.04	Δρ_max = 0.68 e Å⁻³
1695 reflections	Δρ_min = −0.61 e Å⁻³
132 parameters

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.

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 > 2sigma(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	0.25979 (6)	0.2500	0.0379 (3)
O1W	0.5719 (3)	0.3981 (3)	0.3584 (3)	0.0621 (10)
H1W1	0.5858	0.4726	0.3425	0.075*
H1W2	0.6036	0.3829	0.4228	0.075*
O1	0.4265 (4)	−0.3399 (4)	0.1544 (5)	0.1088 (17)
O2W	0.3649 (3)	0.2686 (3)	0.3112 (3)	0.0554 (9)
H2W1	0.3018	0.2370	0.2998	0.066*
H2W2	0.3376	0.3407	0.3149	0.066*
O2	0.2233 (3)	0.0263 (4)	0.2267 (3)	0.0784 (12)
O3	0.1111 (4)	0.0285 (6)	0.0756 (4)	0.107 (2)
O4	0.1792 (4)	0.2017 (5)	0.1484 (4)	0.0996 (18)
N1	0.4417 (3)	0.1042 (3)	0.1501 (3)	0.0394 (8)
N2	0.1708 (3)	0.0851 (5)	0.1490 (3)	0.0649 (13)
C1	0.3828 (4)	0.1087 (6)	0.0491 (4)	0.0585 (12)
H1	0.3646	0.1869	0.0176	0.070*
C2	0.3481 (5)	0.0028 (7)	−0.0099 (4)	0.0761 (15)
H2	0.3086	0.0097	−0.0802	0.091*
C3	0.3716 (5)	−0.1113 (6)	0.0347 (5)	0.0735 (14)
H3	0.3470	−0.1836	−0.0040	0.088*
C4	0.4336 (4)	−0.1200 (4)	0.1406 (4)	0.0515 (11)
C5	0.4673 (3)	−0.0087 (4)	0.1946 (3)	0.0353 (8)
C6	0.4594 (3)	−0.2412 (4)	0.1964 (4)	0.0679 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0443 (5)	0.0219 (4)	0.0489 (5)	0.000	0.0149 (4)	0.000
O1W	0.094 (3)	0.0341 (16)	0.065 (2)	−0.0210 (17)	0.0333 (19)	−0.0165 (15)
O1	0.133 (4)	0.047 (2)	0.169 (4)	−0.030 (2)	0.080 (3)	−0.043 (2)
O2W	0.0501 (18)	0.0530 (19)	0.069 (2)	0.0035 (14)	0.0271 (17)	0.0139 (16)
O2	0.075 (3)	0.090 (3)	0.065 (2)	0.006 (2)	0.010 (2)	0.033 (2)
O3	0.092 (3)	0.166 (6)	0.058 (3)	−0.050 (3)	0.011 (2)	0.001 (3)
O4	0.079 (3)	0.089 (3)	0.125 (4)	−0.014 (3)	0.016 (3)	0.063 (3)
N1	0.0454 (18)	0.0375 (18)	0.0322 (16)	−0.0019 (15)	0.0046 (14)	0.0049 (14)
N2	0.048 (2)	0.092 (4)	0.054 (2)	−0.014 (2)	0.0108 (19)	0.027 (2)
C1	0.052 (2)	0.079 (3)	0.039 (2)	−0.004 (2)	0.0033 (18)	0.010 (2)
C2	0.066 (3)	0.117 (4)	0.042 (2)	−0.025 (3)	0.007 (2)	−0.015 (2)
C3	0.074 (3)	0.090 (3)	0.062 (3)	−0.036 (3)	0.028 (2)	−0.041 (2)
C4	0.060 (3)	0.047 (2)	0.057 (2)	−0.0194 (19)	0.0323 (19)	−0.0230 (18)
C5	0.0425 (19)	0.0318 (18)	0.0342 (19)	−0.0051 (15)	0.0143 (16)	−0.0032 (14)
C6	0.083 (3)	0.036 (2)	0.104 (4)	−0.012 (2)	0.059 (3)	−0.0202 (19)

Geometric parameters (Å, º) top

Co1—O1W	2.084 (3)	O4—N2	1.245 (7)
Co1—O1Wⁱ	2.084 (3)	N1—C5	1.338 (5)
Co1—O2W	2.091 (3)	N1—C1	1.340 (5)
Co1—O2Wⁱ	2.091 (3)	C1—C2	1.372 (9)
Co1—N1	2.121 (3)	C1—H1	0.9300
Co1—N1ⁱ	2.121 (3)	C2—C3	1.346 (10)
O1W—H1W1	0.8500	C2—H2	0.9300
O1W—H1W2	0.8502	C3—C4	1.408 (8)
O1—C6	1.208 (6)	C3—H3	0.9300
O2W—H2W1	0.8501	C4—C5	1.388 (6)
O2W—H2W2	0.8500	C4—C6	1.476 (7)
O2—N2	1.232 (6)	C5—C5ⁱ	1.473 (8)
O3—N2	1.218 (6)	C6—C6ⁱ	1.511 (10)

O1W—Co1—O1Wⁱ	90.1 (2)	C1—N1—Co1	126.6 (3)
O1W—Co1—O2W	88.21 (14)	O3—N2—O2	119.6 (6)
O1Wⁱ—Co1—O2W	88.18 (14)	O3—N2—O4	121.7 (5)
O1W—Co1—O2Wⁱ	88.18 (14)	O2—N2—O4	118.7 (5)
O1Wⁱ—Co1—O2Wⁱ	88.21 (14)	N1—C1—C2	122.7 (5)
O2W—Co1—O2Wⁱ	174.89 (19)	N1—C1—H1	118.7
O1W—Co1—N1	173.05 (14)	C2—C1—H1	118.7
O1Wⁱ—Co1—N1	96.32 (15)	C3—C2—C1	119.6 (5)
O2W—Co1—N1	94.55 (14)	C3—C2—H2	120.2
O2Wⁱ—Co1—N1	89.44 (13)	C1—C2—H2	120.2
O1W—Co1—N1ⁱ	96.32 (15)	C2—C3—C4	119.4 (5)
O1Wⁱ—Co1—N1ⁱ	173.05 (14)	C2—C3—H3	120.3
O2W—Co1—N1ⁱ	89.44 (13)	C4—C3—H3	120.3
O2Wⁱ—Co1—N1ⁱ	94.55 (14)	C5—C4—C3	117.7 (5)
N1—Co1—N1ⁱ	77.36 (18)	C5—C4—C6	119.6 (4)
Co1—O1W—H1W1	125.1	C3—C4—C6	122.7 (4)
Co1—O1W—H1W2	123.5	N1—C5—C4	122.4 (4)
H1W1—O1W—H1W2	110.1	N1—C5—C5ⁱ	116.1 (2)
Co1—O2W—H2W1	139.2	C4—C5—C5ⁱ	121.5 (3)
Co1—O2W—H2W2	117.1	O1—C6—C4	121.8 (5)
H2W1—O2W—H2W2	89.0	O1—C6—C6ⁱ	119.7 (4)
C5—N1—C1	118.2 (4)	C4—C6—C6ⁱ	118.0 (3)
C5—N1—Co1	115.2 (2)

O1Wⁱ—Co1—N1—C5	−176.8 (3)	C2—C3—C4—C6	177.7 (5)
O2W—Co1—N1—C5	−88.2 (3)	C1—N1—C5—C4	−1.0 (6)
O2Wⁱ—Co1—N1—C5	95.0 (3)	Co1—N1—C5—C4	178.8 (3)
N1ⁱ—Co1—N1—C5	0.2 (2)	C1—N1—C5—C5ⁱ	179.6 (4)
O1Wⁱ—Co1—N1—C1	2.9 (4)	Co1—N1—C5—C5ⁱ	−0.6 (5)
O2W—Co1—N1—C1	91.6 (4)	C3—C4—C5—N1	0.8 (6)
O2Wⁱ—Co1—N1—C1	−85.2 (4)	C6—C4—C5—N1	−176.5 (4)
N1ⁱ—Co1—N1—C1	180.0 (5)	C3—C4—C5—C5ⁱ	−179.8 (5)
C5—N1—C1—C2	−0.1 (7)	C6—C4—C5—C5ⁱ	2.9 (7)
Co1—N1—C1—C2	−179.8 (4)	C5—C4—C6—O1	175.7 (3)
N1—C1—C2—C3	1.3 (9)	C3—C4—C6—O1	−1.4 (6)
C1—C2—C3—C4	−1.5 (9)	C5—C4—C6—C6ⁱ	−12.2 (6)
C2—C3—C4—C5	0.5 (8)	C3—C4—C6—C6ⁱ	170.7 (4)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2W1···O4	0.85	2.21	2.834 (6)	130
O2W—H2W2···O2ⁱⁱ	0.85	2.14	2.957 (6)	161
O1W—H1W1···O1ⁱⁱⁱ	0.85	2.00	2.793 (5)	154
O1W—H1W2···O3^iv	0.85	2.19	2.864 (6)	136

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₆N₂O₂)(H₂O)₄](NO₃)₂
M_r	465.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	12.7978 (12), 10.6388 (10), 13.0989 (12)
β (°)	105.248 (2)
V (Å³)	1720.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.18 × 0.14 × 0.13

Data collection
Diffractometer	Bruker SMART APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.830, 0.873
No. of measured, independent and observed [I > 2σ(I)] reflections	4509, 1695, 1549
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.138, 1.04
No. of reflections	1695
No. of parameters	132
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.61

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2W1···O4	0.85	2.21	2.834 (6)	129.9
O2W—H2W2···O2ⁱ	0.85	2.14	2.957 (6)	161.2
O1W—H1W1···O1ⁱⁱ	0.85	2.00	2.793 (5)	154.2
O1W—H1W2···O3ⁱⁱⁱ	0.85	2.19	2.864 (6)	136.0

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

Acknowledgements

We thank Jiangxi Science and Technology Normal University for supporting this study.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Calderazzo, F., Marchetti, F., Pampaloni, G. & Passarelli, V. (1999). J. Chem. Soc. Dalton Trans. pp. 4389–4396. Web of Science CSD CrossRef Google Scholar
Fox, G. A., Bhattacharya, S. & Pierpont, C. G. (1991). Inorg. Chem. 30, 2895–2899. CSD CrossRef CAS Web of Science Google Scholar
Liu, G.-X., Xu, H. & Ren, X.-M. (2008). Z. Anorg. Allg. Chem. 634, 927–930. Web of Science CSD CrossRef CAS Google Scholar
Onuegbu, J., Butcher, R. J., Hosten, C., Udeochu, U. C. & Bakare, O. (2007). Acta Cryst. E63, m2309–m2310. Web of Science CSD CrossRef IUCr Journals Google Scholar
Paw, W. & Eisenberg, R. (1997). Inorg. Chem. 36, 2287–2293. CSD CrossRef PubMed CAS Web of Science Google Scholar
Rubin-Preminger, J. M., Kozlov, L. & Goldberg, I. (2008). Acta Cryst. C64, m83–m86. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ruiz, R., Caneschi, A., Gatteschi, D., Gaspar, A. B., Real, J. A., Fernandez, I. & Munoz, M. C. (1999). Inorg. Chem. Commun. 2, 521–523. Web of Science CSD CrossRef CAS Google Scholar
Shavaleev, N. M., Moorcraft, L. P., Pope, S. J. A., Bell, Z. R., Faulkner, S. & Ward, M. D. (2003). Chem. Commun. pp. 1134–1135. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar