A cuboidal [Cu₄(SO₄)₄] structure supported by β-picoline ligands

A cobalt sulfate complex supported by β-picoline ligands produces a unique cuboidal tetra­mer.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.019
• wR factor = 0.046
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co1      --O3_a     .        5.7 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Co1       (II)      .       1.90 Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          3 Note
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Tetra-µ₃-sulfato-tetrakis[bis(3-methylpyridine)cobalt(II)]

Crystal data

[Co4(SO4)4(C6H7N)8]	Dx = 1.571 Mg m^−3
Mr = 1364.96	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421c	Cell parameters from 9496 reflections
a = 15.6121 (16) Å	θ = 2.9–25.7°
c = 11.8359 (13) Å	µ = 1.35 mm^−1
V = 2884.9 (7) Å^3	T = 298 K
Z = 2	BLOCK, pink
F(000) = 1400	0.24 × 0.22 × 0.20 mm

Data collection

Bruker D8 Venture CMOS diffractometer	2624 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.037
Absorption correction: multi-scan (SADABS; Bruker, 2018)	θmax = 25.7°, θmin = 2.9°
Tmin = 0.517, Tmax = 0.562	h = −19→19
54595 measured reflections	k = −19→19
2744 independent reflections	l = −14→14

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0165P)^2 + 1.2064P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.019	(Δ/σ)max = 0.001
wR(F^2) = 0.046	Δρmax = 0.16 e Å^−3
S = 1.14	Δρmin = −0.20 e Å^−3
2744 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
184 parameters	Extinction coefficient: 0.0049 (4)
0 restraints	Absolute structure: Flack x determined using 1117 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
Hydrogen site location: inferred from neighbouring sites	Absolute structure parameter: 0.007 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.64636 (2)	0.49053 (2)	0.41389 (3)	0.02066 (11)
S1	0.52522 (4)	0.64004 (4)	0.35520 (5)	0.02043 (15)
O1	0.58168 (12)	0.57205 (12)	0.30908 (15)	0.0267 (4)
O2	0.49144 (15)	0.69145 (13)	0.26473 (17)	0.0370 (5)
O3	0.45605 (11)	0.59894 (11)	0.42553 (16)	0.0240 (4)
O4	0.57304 (12)	0.69234 (11)	0.43961 (15)	0.0258 (4)
N1	0.75982 (14)	0.57112 (15)	0.4121 (2)	0.0319 (5)
N2	0.70169 (16)	0.42286 (15)	0.2775 (2)	0.0293 (5)
C1	0.82170 (19)	0.5691 (2)	0.4896 (3)	0.0400 (7)
H1	0.813680	0.534627	0.552786	0.048*
C2	0.8976 (2)	0.6156 (2)	0.4819 (3)	0.0489 (8)
C3	0.9084 (2)	0.6660 (2)	0.3863 (3)	0.0546 (10)
H3	0.958296	0.697697	0.376688	0.065*
C4	0.8451 (2)	0.6690 (2)	0.3064 (3)	0.0541 (10)
H4	0.851466	0.702977	0.242445	0.065*
C5	0.7719 (2)	0.6210 (2)	0.3218 (3)	0.0434 (8)
H5	0.729157	0.623471	0.267110	0.052*
C6	0.9650 (3)	0.6110 (3)	0.5724 (4)	0.0829 (15)
H6A	0.946445	0.572676	0.630913	0.124*
H6B	0.973938	0.667009	0.603611	0.124*
H6C	1.017567	0.590328	0.540358	0.124*
C7	0.6638 (2)	0.4183 (2)	0.1768 (3)	0.0340 (7)
H7	0.611734	0.446338	0.167140	0.041*
C8	0.6978 (2)	0.3738 (2)	0.0853 (3)	0.0422 (7)
C9	0.7741 (2)	0.3311 (2)	0.1032 (3)	0.0499 (9)
H9	0.798504	0.299413	0.045000	0.060*
C10	0.8143 (2)	0.3351 (2)	0.2062 (3)	0.0490 (9)
H10	0.865907	0.306837	0.218114	0.059*
C11	0.7766 (2)	0.3817 (2)	0.2914 (3)	0.0386 (8)
H11	0.803962	0.384829	0.361126	0.046*
C12	0.6512 (3)	0.3707 (3)	−0.0255 (3)	0.0732 (12)
H12A	0.590895	0.377919	−0.012705	0.110*
H12B	0.661205	0.316328	−0.061099	0.110*
H12C	0.671634	0.415746	−0.073630	0.110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01998 (17)	0.02203 (18)	0.01997 (16)	0.00207 (14)	0.00180 (15)	0.00176 (14)
S1	0.0216 (3)	0.0201 (3)	0.0196 (3)	0.0031 (3)	0.0031 (2)	0.0046 (3)
O1	0.0293 (10)	0.0290 (10)	0.0218 (9)	0.0075 (8)	0.0056 (8)	0.0029 (8)
O2	0.0435 (12)	0.0380 (11)	0.0297 (10)	0.0114 (11)	−0.0007 (10)	0.0133 (9)
O3	0.0227 (9)	0.0272 (9)	0.0223 (9)	−0.0037 (7)	0.0042 (8)	0.0004 (8)
O4	0.0259 (9)	0.0213 (9)	0.0301 (11)	−0.0045 (8)	0.0048 (8)	0.0015 (7)
N1	0.0281 (12)	0.0299 (12)	0.0378 (13)	−0.0040 (10)	0.0080 (12)	0.0009 (12)
N2	0.0305 (12)	0.0272 (12)	0.0301 (13)	0.0033 (11)	0.0070 (11)	0.0008 (11)
C1	0.0349 (16)	0.0417 (17)	0.0434 (18)	−0.0091 (14)	0.0040 (14)	0.0014 (14)
C2	0.0337 (16)	0.051 (2)	0.062 (2)	−0.0128 (14)	0.0054 (17)	−0.0051 (19)
C3	0.0408 (19)	0.043 (2)	0.080 (3)	−0.0156 (16)	0.0191 (18)	0.0026 (18)
C4	0.052 (2)	0.042 (2)	0.068 (3)	−0.0086 (16)	0.019 (2)	0.0151 (18)
C5	0.0396 (18)	0.0437 (19)	0.0470 (19)	−0.0036 (15)	0.0103 (16)	0.0107 (16)
C6	0.048 (2)	0.102 (4)	0.098 (4)	−0.026 (2)	−0.017 (3)	0.002 (3)
C7	0.0376 (17)	0.0333 (15)	0.0310 (15)	−0.0005 (13)	0.0067 (13)	0.0015 (13)
C8	0.061 (2)	0.0340 (16)	0.0314 (15)	−0.0070 (14)	0.0115 (17)	−0.0043 (14)
C9	0.067 (2)	0.0349 (17)	0.048 (2)	0.0039 (16)	0.0277 (18)	−0.0072 (15)
C10	0.047 (2)	0.0364 (18)	0.063 (2)	0.0135 (15)	0.0187 (18)	−0.0001 (16)
C11	0.0369 (18)	0.0342 (17)	0.045 (2)	0.0085 (14)	0.0064 (14)	0.0007 (14)
C12	0.107 (4)	0.076 (3)	0.036 (2)	−0.002 (3)	−0.002 (3)	−0.012 (2)

Geometric parameters (Å, º)

Co1—S1^i	2.7458 (7)	C3—C4	1.368 (6)
Co1—O1	2.0441 (19)	C4—H4	0.9300
Co1—O3^i	2.2037 (19)	C4—C5	1.379 (5)
Co1—O3^ii	2.1274 (18)	C5—H5	0.9300
Co1—O4^i	2.1229 (18)	C6—H6A	0.9600
Co1—N1	2.173 (2)	C6—H6B	0.9600
Co1—N2	2.114 (2)	C6—H6C	0.9600
S1—O1	1.4839 (19)	C7—H7	0.9300
S1—O2	1.438 (2)	C7—C8	1.391 (4)
S1—O3	1.5069 (18)	C8—C9	1.382 (5)
S1—O4	1.491 (2)	C8—C12	1.501 (5)
N1—C1	1.332 (4)	C9—H9	0.9300
N1—C5	1.336 (4)	C9—C10	1.371 (6)
N2—C7	1.333 (4)	C10—H10	0.9300
N2—C11	1.345 (4)	C10—C11	1.376 (5)
C1—H1	0.9300	C11—H11	0.9300
C1—C2	1.392 (4)	C12—H12A	0.9600
C2—C3	1.389 (5)	C12—H12B	0.9600
C2—C6	1.503 (5)	C12—H12C	0.9600
C3—H3	0.9300
O1—Co1—S1^i	129.94 (5)	N1—C1—H1	118.0
O1—Co1—O3^ii	94.41 (7)	N1—C1—C2	124.0 (3)
O1—Co1—O3^i	97.00 (7)	C2—C1—H1	118.0
O1—Co1—O4^i	162.52 (7)	C1—C2—C6	121.6 (4)
O1—Co1—N1	92.08 (9)	C3—C2—C1	116.9 (3)
O1—Co1—N2	92.84 (9)	C3—C2—C6	121.5 (3)
O3^i—Co1—S1^i	33.21 (5)	C2—C3—H3	120.2
O3^ii—Co1—S1^i	81.36 (5)	C4—C3—C2	119.7 (3)
O3^ii—Co1—O3^i	86.57 (8)	C4—C3—H3	120.2
O3^ii—Co1—N1	173.44 (9)	C3—C4—H4	120.4
O4^i—Co1—S1^i	32.58 (5)	C3—C4—C5	119.3 (3)
O4^i—Co1—O3^ii	83.94 (7)	C5—C4—H4	120.4
O4^i—Co1—O3^i	65.55 (7)	N1—C5—C4	122.6 (4)
O4^i—Co1—N1	90.16 (9)	N1—C5—H5	118.7
N1—Co1—S1^i	95.20 (8)	C4—C5—H5	118.7
N1—Co1—O3^i	93.61 (8)	C2—C6—H6A	109.5
N2—Co1—S1^i	136.90 (7)	C2—C6—H6B	109.5
N2—Co1—O3^i	170.11 (9)	C2—C6—H6C	109.5
N2—Co1—O3^ii	91.63 (8)	H6A—C6—H6B	109.5
N2—Co1—O4^i	104.59 (8)	H6A—C6—H6C	109.5
N2—Co1—N1	87.07 (9)	H6B—C6—H6C	109.5
O1—S1—Co1^iii	116.43 (7)	N2—C7—H7	118.2
O1—S1—O3	108.92 (10)	N2—C7—C8	123.6 (3)
O1—S1—O4	109.93 (11)	C8—C7—H7	118.2
O2—S1—Co1^iii	133.48 (9)	C7—C8—C12	120.8 (3)
O2—S1—O1	110.07 (11)	C9—C8—C7	116.8 (3)
O2—S1—O3	112.71 (12)	C9—C8—C12	122.4 (3)
O2—S1—O4	112.15 (12)	C8—C9—H9	119.7
O3—S1—Co1^iii	53.22 (7)	C10—C9—C8	120.6 (3)
O4—S1—Co1^iii	50.06 (7)	C10—C9—H9	119.7
O4—S1—O3	102.82 (11)	C9—C10—H10	120.6
S1—O1—Co1	121.04 (10)	C9—C10—C11	118.7 (3)
Co1^ii—O3—Co1^iii	124.11 (9)	C11—C10—H10	120.6
S1—O3—Co1^ii	141.48 (12)	N2—C11—C10	122.3 (3)
S1—O3—Co1^iii	93.57 (9)	N2—C11—H11	118.9
S1—O4—Co1^iii	97.36 (9)	C10—C11—H11	118.9
C1—N1—Co1	124.8 (2)	C8—C12—H12A	109.5
C1—N1—C5	117.5 (3)	C8—C12—H12B	109.5
C5—N1—Co1	117.4 (2)	C8—C12—H12C	109.5
C7—N2—Co1	121.9 (2)	H12A—C12—H12B	109.5
C7—N2—C11	118.1 (3)	H12A—C12—H12C	109.5
C11—N2—Co1	120.0 (2)	H12B—C12—H12C	109.5
Co1^iii—S1—O1—Co1	−1.75 (15)	O4—S1—O3—Co1^iii	−7.25 (10)
Co1^iii—S1—O3—Co1^ii	−168.6 (2)	N1—C1—C2—C3	−0.5 (5)
Co1—N1—C1—C2	173.9 (3)	N1—C1—C2—C6	179.7 (4)
Co1—N1—C5—C4	−174.0 (3)	N2—C7—C8—C9	1.5 (5)
Co1—N2—C7—C8	−179.4 (2)	N2—C7—C8—C12	179.5 (3)
Co1—N2—C11—C10	178.4 (2)	C1—N1—C5—C4	0.4 (5)
O1—S1—O3—Co1^iii	109.34 (9)	C1—C2—C3—C4	0.8 (5)
O1—S1—O3—Co1^ii	−59.3 (2)	C2—C3—C4—C5	−0.6 (6)
O1—S1—O4—Co1^iii	−108.29 (10)	C3—C4—C5—N1	−0.1 (6)
O2—S1—O1—Co1	176.64 (13)	C5—N1—C1—C2	−0.1 (5)
O2—S1—O3—Co1^iii	−128.20 (11)	C6—C2—C3—C4	−179.4 (4)
O2—S1—O3—Co1^ii	63.1 (2)	C7—N2—C11—C10	−0.6 (4)
O2—S1—O4—Co1^iii	128.92 (11)	C7—C8—C9—C10	−1.5 (5)
O3—S1—O1—Co1	−59.31 (15)	C8—C9—C10—C11	0.6 (5)
O3—S1—O4—Co1^iii	7.57 (11)	C9—C10—C11—N2	0.5 (5)
O4—S1—O1—Co1	52.63 (15)	C11—N2—C7—C8	−0.5 (4)
O4—S1—O3—Co1^ii	−175.90 (17)	C12—C8—C9—C10	−179.4 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4^i	0.93	2.53	3.116 (4)	121
C3—H3···O2^iv	0.93	2.46	3.135 (4)	129
C5—H5···O1	0.93	2.49	3.070 (4)	121

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