Bis(2-amino­pyridine-κN¹)bis­(N,N′-dimethyl­formamide-κO)(sulfato-κ²O,O′)copper(II)

In the title compound, [Cu(SO₄)(C₅H₆N₂)₂(C₃H₇NO)₂], the coordination geometry around the Cu^II atom is distorted octa­hedral, involving two O atoms from a bidentate sulfate anion, two N atoms from two 2-amino­pyridine ligands and two O atoms from two N,N′-dimethyl­formamide mol­ecules. The Cu and S atoms are located on a crystallographic twofold rotation axis. A one-dimensional chain structure is built via hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.028
• wR factor = 0.079
• Data-to-parameter ratio = 19.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        500 Ang.
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O1      ..       5.85 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.26

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

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

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S1. Comment

The title compound was obtained as the product of an attempted synthesis of an open-framework compound of copper(II) using 2-aminopyridine as structure-directing agent.

As shown in Fig. 1, the coordination polyhedron around the Cu^II atom is a distorted octahedron, comprising two O atoms from a bidentate sulfate anion, two N atoms from two 2-aminopyridine molecules and two O atoms from two N,N'-dimethylformamide (DMF) molecules. The bond distances are similar to those in the literature (Hagrman et al., 1998). There is a weak Cu1—O3 interaction of 2.589 (2)Å (Table 1). The molecules are connected by intermolecular hydrogen-bonding interactions (Table 2), resulting in a one-dimentional supramolecular structure (Fig. 2).

Related literature

The bond distances are similar to those reported in the literature (Hagrman et al., 1998).

S2. Experimental

Typically, CuSO₄.5H₂O (0.125 g, 0.5 mmol) was dispersed into DMF (10 ml) with stirring, then 2-aminopyridine (0.285 g, 0.3 mmol) was added to the above reaction mixture with stirring. The mixture with pH value of 5 was transferred into a 18 ml Teflon-lined stainless steel autoclave and heated at 353 K for 3 d. After cooling to room temperature, green block-shaped crystals of the title compound were obtained; they were filtered and washed thoroughly with deionized water and dried at room temperature.

S3. Refinement

All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å and U_iso(H) = 1.2U_eq(C,N), and U_iso(H) = 1.5U_eq(C) for CH₃ groups.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x, y, 3/2 - z.]
	Fig. 2. One-dimensional structure built up via hydrogen-bonding interactions in the title compound.

Bis(2-aminopyridine-κN¹)bis(N,N'-dimethylformamide-κO)(sulfato- κ²O,O')copper(II)

Crystal data

[Cu(SO4)(C5H6N2)2(C3H7NO)2]	F(000) = 1028
Mr = 494.03	Dx = 1.491 Mg m^−3
Monoclinic, C2/c	Melting point: not measured K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 11.528 (5) Å	Cell parameters from 2666 reflections
b = 18.156 (5) Å	θ = 2.1–28.3°
c = 10.828 (5) Å	µ = 1.13 mm^−1
β = 103.801 (5)°	T = 293 K
V = 2200.9 (15) Å^3	Block, blue
Z = 4	0.19 × 0.15 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2666 independent reflections
Radiation source: fine-focus sealed tube	2222 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→10
Tmin = 0.814, Tmax = 0.877	k = −23→24
6718 measured reflections	l = −14→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.079	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0417P)^2 + 0.588P] where P = (Fo^2 + 2Fc^2)/3
2666 reflections	(Δ/σ)max < 0.001
139 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.23305 (15)	0.10448 (9)	0.86610 (17)	0.0350 (4)
C2	0.32604 (18)	0.05410 (12)	0.8644 (2)	0.0531 (5)
H2	0.3957	0.0550	0.9289	0.064*
C3	0.3138 (2)	0.00471 (13)	0.7693 (3)	0.0659 (7)
H3	0.3755	−0.0278	0.7670	0.079*
C4	0.2086 (2)	0.00265 (12)	0.6749 (2)	0.0636 (6)
H4	0.1983	−0.0316	0.6093	0.076*
C5	0.12116 (19)	0.05163 (10)	0.68049 (18)	0.0461 (4)
H5	0.0505	0.0499	0.6175	0.055*
C6	0.1553 (2)	0.15450 (15)	0.3507 (2)	0.0672 (6)
H6A	0.1303	0.1484	0.2630	0.101*
H6B	0.1240	0.1169	0.3912	0.101*
H6C	0.2383	0.1530	0.3750	0.101*
C7	0.1560 (2)	0.29009 (15)	0.3324 (2)	0.0623 (6)
H7A	0.1346	0.2874	0.2441	0.093*
H7B	0.2387	0.2933	0.3600	0.093*
H7C	0.1213	0.3316	0.3592	0.093*
C8	0.04146 (17)	0.22969 (12)	0.46322 (18)	0.0437 (4)
H8	0.0197	0.2768	0.4830	0.052*
N1	0.13161 (12)	0.10318 (7)	0.77361 (13)	0.0326 (3)
N2	0.24550 (13)	0.15442 (9)	0.95966 (16)	0.0451 (4)
H2A	0.1890	0.1852	0.9602	0.054*
H2B	0.3100	0.1556	1.0191	0.054*
N3	0.11426 (14)	0.22427 (10)	0.38583 (15)	0.0461 (4)
O1	0.10372 (10)	0.26717 (6)	0.76849 (12)	0.0368 (3)
O2	0.01014 (11)	0.36464 (7)	0.86254 (12)	0.0442 (3)
O3	0.00034 (14)	0.17725 (8)	0.51108 (14)	0.0532 (4)
S1	0.0000	0.31992 (3)	0.7500	0.02985 (13)
Cu1	0.0000	0.177216 (14)	0.7500	0.03053 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0330 (8)	0.0314 (8)	0.0415 (9)	0.0056 (7)	0.0110 (7)	0.0099 (7)
C2	0.0419 (10)	0.0495 (12)	0.0673 (14)	0.0179 (9)	0.0121 (10)	0.0141 (10)
C3	0.0659 (15)	0.0486 (12)	0.0899 (18)	0.0290 (11)	0.0316 (13)	0.0091 (12)
C4	0.0897 (17)	0.0407 (11)	0.0663 (15)	0.0180 (12)	0.0302 (14)	−0.0085 (10)
C5	0.0590 (11)	0.0357 (9)	0.0436 (10)	0.0062 (8)	0.0124 (9)	−0.0049 (8)
C6	0.0670 (15)	0.0732 (16)	0.0676 (16)	0.0154 (13)	0.0286 (13)	−0.0051 (12)
C7	0.0502 (12)	0.0835 (17)	0.0540 (13)	−0.0139 (12)	0.0139 (10)	0.0161 (12)
C8	0.0419 (10)	0.0525 (11)	0.0377 (10)	0.0039 (9)	0.0117 (8)	0.0025 (8)
N1	0.0354 (7)	0.0274 (7)	0.0354 (7)	0.0047 (5)	0.0090 (6)	0.0014 (5)
N2	0.0373 (8)	0.0498 (9)	0.0421 (8)	0.0074 (7)	−0.0023 (7)	−0.0039 (7)
N3	0.0438 (9)	0.0569 (10)	0.0407 (9)	0.0010 (8)	0.0165 (7)	0.0055 (7)
O1	0.0250 (5)	0.0303 (6)	0.0537 (8)	0.0004 (4)	0.0064 (5)	−0.0001 (5)
O2	0.0506 (7)	0.0354 (7)	0.0422 (7)	0.0043 (6)	0.0022 (6)	−0.0077 (5)
O3	0.0549 (8)	0.0605 (9)	0.0497 (8)	−0.0010 (7)	0.0234 (7)	0.0091 (6)
S1	0.0272 (3)	0.0246 (3)	0.0349 (3)	0.000	0.0019 (2)	0.000
Cu1	0.02611 (15)	0.02407 (15)	0.03997 (18)	0.000	0.00507 (12)	0.000

Geometric parameters (Å, º)

C1—N2	1.342 (2)	C7—H7B	0.9300
C1—N1	1.346 (2)	C7—H7C	0.9300
C1—C2	1.413 (2)	C8—O3	1.232 (2)
C2—C3	1.347 (3)	C8—N3	1.324 (2)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.388 (4)	N1—Cu1	1.9972 (14)
C3—H3	0.9300	N2—H2A	0.8600
C4—C5	1.356 (3)	N2—H2B	0.8600
C4—H4	0.9300	O1—S1	1.5076 (13)
C5—N1	1.360 (2)	O1—Cu1	2.0056 (13)
C5—H5	0.9300	O2—S1	1.4457 (13)
C6—N3	1.435 (3)	O3—Cu1	2.589 (2)
C6—H6A	0.9300	S1—O2^i	1.4457 (13)
C6—H6B	0.9300	S1—O1^i	1.5076 (13)
C6—H6C	0.9300	Cu1—N1^i	1.9972 (14)
C7—N3	1.458 (3)	Cu1—O1^i	2.0056 (13)
C7—H7A	0.9300	Cu1—O3^i	2.589 (2)
N2—C1—N1	119.40 (15)	O3^i—Cu1—N1	93.10 (6)
N2—C1—C2	120.18 (17)	O3^i—Cu1—N1^i	86.89 (6)
N1—C1—C2	120.42 (17)	O3—Cu1—O1	87.47 (6)
C3—C2—C1	120.0 (2)	O3^i—Cu1—O1	92.47 (5)
C3—C2—H2	120.0	O3—Cu1—O1^i	92.47 (5)
C1—C2—H2	120.0	O3—Cu1—O3^i	179.99 (6)
C2—C3—C4	119.6 (2)	O3^i—Cu1—O1^i	87.47 (6)
C2—C3—H3	120.2	N3—C8—H8	117.5
C4—C3—H3	120.2	C1—N1—C5	118.11 (15)
C5—C4—C3	118.5 (2)	C1—N1—Cu1	125.59 (11)
C5—C4—H4	120.7	C5—N1—Cu1	115.99 (12)
C3—C4—H4	120.7	C1—N2—H2A	120.0
N1—C5—C4	123.3 (2)	C1—N2—H2B	120.0
N1—C5—H5	118.4	H2A—N2—H2B	120.0
C4—C5—H5	118.4	C8—N3—C6	122.20 (19)
N3—C6—H6A	109.5	C8—N3—C7	120.6 (2)
N3—C6—H6B	109.5	C6—N3—C7	117.20 (19)
H6A—C6—H6B	109.5	S1—O1—Cu1	93.96 (6)
N3—C6—H6C	109.5	O2—S1—O2^i	111.66 (11)
H6A—C6—H6C	109.5	O2—S1—O1	110.05 (7)
H6B—C6—H6C	109.5	O2^i—S1—O1	111.77 (7)
N3—C7—H7A	109.5	O2—S1—O1^i	111.77 (7)
N3—C7—H7B	109.5	O2^i—S1—O1^i	110.05 (7)
H7A—C7—H7B	109.5	O1—S1—O1^i	101.11 (10)
N3—C7—H7C	109.5	N1^i—Cu1—N1	95.40 (8)
H7A—C7—H7C	109.5	N1^i—Cu1—O1	167.79 (5)
H7B—C7—H7C	109.5	N1—Cu1—O1	96.81 (6)
O3—C8—N3	125.1 (2)	N1^i—Cu1—O1^i	96.81 (6)
O3—C8—H8	117.5	N1—Cu1—O1^i	167.79 (5)
O3—Cu1—N1	86.89 (6)	O1—Cu1—O1^i	70.97 (7)
O3—Cu1—N1^i	93.10 (6)
N2—C1—C2—C3	−179.1 (2)	C5—N1—Cu1—O1^i	−126.5 (2)
N1—C1—C2—C3	0.5 (3)	C1—N1—Cu1—S1	47.13 (15)
C1—C2—C3—C4	−1.4 (4)	C5—N1—Cu1—S1	−126.28 (12)
C2—C3—C4—C5	0.9 (4)	S1—O1—Cu1—N1^i	0.2 (3)
C3—C4—C5—N1	0.5 (3)	S1—O1—Cu1—N1	−179.95 (6)
N2—C1—N1—C5	−179.56 (16)	S1—O1—Cu1—O1^i	0.0
C2—C1—N1—C5	0.9 (2)	O2—S1—Cu1—N1^i	91.32 (8)
N2—C1—N1—Cu1	7.2 (2)	O2^i—S1—Cu1—N1^i	−88.68 (8)
C2—C1—N1—Cu1	−172.40 (13)	O1—S1—Cu1—N1^i	−179.94 (8)
C4—C5—N1—C1	−1.4 (3)	O1^i—S1—Cu1—N1^i	0.06 (8)
C4—C5—N1—Cu1	172.55 (17)	O2—S1—Cu1—N1	−88.68 (8)
O3—C8—N3—C6	−1.1 (3)	O2^i—S1—Cu1—N1	91.32 (8)
O3—C8—N3—C7	178.8 (2)	O1—S1—Cu1—N1	0.06 (8)
Cu1—O1—S1—O2	118.29 (7)	O1^i—S1—Cu1—N1	−179.94 (8)
Cu1—O1—S1—O2^i	−117.04 (7)	O2—S1—Cu1—O1	−88.75 (9)
Cu1—O1—S1—O1^i	0.0	O2^i—S1—Cu1—O1	91.25 (9)
C1—N1—Cu1—N1^i	−132.87 (15)	O1^i—S1—Cu1—O1	180.0
C5—N1—Cu1—N1^i	53.72 (12)	O2—S1—Cu1—O1^i	91.25 (9)
C1—N1—Cu1—O1	47.16 (14)	O2^i—S1—Cu1—O1^i	−88.75 (9)
C5—N1—Cu1—O1	−126.24 (13)	O1—S1—Cu1—O1^i	180.0
C1—N1—Cu1—O1^i	47.0 (3)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.55	3.087 (2)	121
N2—H2A···O3^i	0.86	2.28	2.955 (2)	135
N2—H2B···O2^ii	0.86	2.19	3.029 (2)	164

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