Ethyl­enediammonium tetra­aqua­bis(pyridine-3,5-dicarboxyl­ato-κN)cuprate(II) dihydrate

In the title compound, (C₂H₁₀N₂)[Cu(C₇H₃NO₄)₂(H₂O)₄]·2H₂O, the Cu^II ion occupies a special position on an inversion center and has an elongated octa­hedral geometry with the pyridine-3,5-dicarboxyl­ate ligands in trans positions. The ethyl­enediammonium cation is also in a special position on an inversion center located at the mid-point of the C—C bond. Multiple crystallographically independent hydrogen bonds form a three-dimensional network in the crystal structure. π–π Inter­actions between aromatic rings of the pyridine-3,5-dicarboxyl­ate ligand are observed. The electron-spin resonance (ESR) spectrum is in agreement with an elongated octa­hedral geometry.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.029
• wR factor = 0.069
• Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu     -   O6      ..       6.66 su

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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

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Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: X-SEED (Version 2.0; Barbour, 2001); software used to prepare material for publication: SHELXTL and enCIFer (Allen et al., 2004).

Ethylenediammonium tetraaquabis(pyridine-3,5-dicarboxylato-κN)copper(II) dihydrate

Crystal data

(C2H10N2)[Cu(C7H3NO4)2(H2O)4]·2H2O	Z = 1
Mr = 563.96	F(000) = 293
Triclinic, P1	Dx = 1.653 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.870 (1) Å	Cell parameters from 3572 reflections
b = 8.476 (1) Å	θ = 2.6–25.4°
c = 10.987 (1) Å	µ = 1.04 mm^−1
α = 77.574 (2)°	T = 294 K
β = 74.588 (2)°	Prism, blue
γ = 67.865 (1)°	0.20 × 0.13 × 0.04 mm
V = 566.55 (12) Å^3

Data collection

Bruker SMART APEX CCD diffractometer	2073 independent reflections
Radiation source: fine-focus sealed tube	1882 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 0.661 pixels mm^-1	θmax = 25.4°, θmin = 1.9°
ω scans	h = −8→8
Absorption correction: analytrical (Sheldrick, 2000)	k = −10→10
Tmin = 0.817, Tmax = 0.958	l = −13→13
4800 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0357P)^2] where P = (Fo^2 + 2Fc^2)/3
2073 reflections	(Δ/σ)max < 0.001
169 parameters	Δρmax = 0.37 e Å^−3
3 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. Selected IR data (cm^-1, KBr pellets): 3503 (m), 3437 (m), 3100 (m), 2960 (m), 2910 (m), 3072 (m), 3035 (m), 2972 (m), 2795 (m), 2577 (w), 1711 (w), 1700 (s, COO^-), 1582 (s), 1480 (m), 1432 (w), 1390 (s), 1300 (d), 1131 (w), 1210 (m), 1170 (m), 940 (w), 766 (m), 750 (m), 700 (m), 560 (w), 511 (w).

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.

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

	x	y	z	Uiso*/Ueq
Cu	0.5000	0.5000	0.5000	0.02722 (13)
O1	0.7886 (3)	0.06461 (18)	0.13781 (13)	0.0386 (4)
O2	0.8160 (3)	−0.19806 (17)	0.23504 (13)	0.0389 (4)
O3	0.8708 (2)	−0.31862 (17)	0.70174 (14)	0.0367 (4)
O4	0.7163 (3)	−0.09359 (19)	0.80747 (14)	0.0470 (4)
O5	0.2402 (2)	0.46258 (17)	0.60306 (15)	0.0431 (4)
H5A	0.1234	0.5437	0.6238	0.065*
H5B	0.2328	0.3714	0.6516	0.065*
N1	0.6356 (2)	0.24741 (19)	0.48379 (15)	0.0246 (4)
C2	0.6815 (3)	0.1874 (2)	0.37300 (18)	0.0245 (4)
H2	0.6588	0.2659	0.3003	0.029*
C3	0.7615 (3)	0.0134 (2)	0.36104 (18)	0.0245 (4)
C4	0.7993 (3)	−0.1017 (2)	0.46989 (18)	0.0245 (4)
H4	0.8555	−0.2191	0.4652	0.029*
C5	0.7538 (3)	−0.0421 (2)	0.58488 (18)	0.0235 (4)
C6	0.6707 (3)	0.1339 (2)	0.58808 (18)	0.0248 (4)
H6	0.6382	0.1748	0.6657	0.030*
C7	0.7919 (3)	−0.0433 (2)	0.23450 (19)	0.0279 (4)
C8	0.7832 (3)	−0.1607 (2)	0.70853 (19)	0.0273 (4)
C9	0.9226 (3)	0.4520 (3)	0.0202 (2)	0.0342 (5)
H9A	0.8448	0.4697	0.1066	0.041*
H9B	0.8195	0.4949	−0.0349	0.041*
N2	1.0391 (3)	0.2668 (2)	0.01366 (17)	0.0323 (4)
H2A	1.132 (3)	0.230 (3)	0.058 (2)	0.049*
H2B	1.090 (4)	0.246 (3)	−0.0623 (16)	0.049*
H2C	0.952 (3)	0.214 (3)	0.043 (2)	0.049*
O6	0.3544 (3)	0.5454 (2)	0.29936 (18)	0.0571 (5)
H6A	0.2709	0.4900	0.3055	0.086*
H6B	0.3696	0.6068	0.2277	0.086*
O7	0.5713 (3)	0.2142 (2)	−0.07924 (17)	0.0618 (5)
H7A	0.6018	0.1858	−0.0057	0.093*
H7B	0.5969	0.1247	−0.1123	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0327 (2)	0.01446 (18)	0.0300 (2)	−0.00753 (14)	0.00087 (14)	−0.00385 (14)
O1	0.0600 (10)	0.0330 (8)	0.0267 (8)	−0.0232 (7)	−0.0094 (7)	0.0027 (7)
O2	0.0656 (10)	0.0253 (8)	0.0265 (8)	−0.0202 (7)	−0.0010 (7)	−0.0063 (6)
O3	0.0422 (9)	0.0202 (7)	0.0366 (8)	−0.0039 (6)	−0.0034 (7)	0.0009 (6)
O4	0.0719 (11)	0.0306 (8)	0.0265 (8)	−0.0017 (8)	−0.0129 (8)	−0.0040 (7)
O5	0.0365 (8)	0.0188 (7)	0.0587 (10)	−0.0080 (6)	0.0100 (7)	−0.0008 (7)
N1	0.0282 (9)	0.0171 (8)	0.0275 (9)	−0.0076 (6)	−0.0040 (7)	−0.0032 (7)
C2	0.0280 (10)	0.0200 (9)	0.0234 (10)	−0.0082 (8)	−0.0034 (8)	−0.0010 (8)
C3	0.0245 (10)	0.0212 (10)	0.0270 (10)	−0.0090 (8)	−0.0031 (8)	−0.0023 (8)
C4	0.0251 (10)	0.0179 (9)	0.0301 (11)	−0.0069 (7)	−0.0045 (8)	−0.0048 (8)
C5	0.0221 (9)	0.0207 (9)	0.0268 (10)	−0.0072 (7)	−0.0042 (8)	−0.0022 (8)
C6	0.0295 (10)	0.0210 (9)	0.0240 (10)	−0.0091 (8)	−0.0033 (8)	−0.0047 (8)
C7	0.0311 (11)	0.0255 (10)	0.0270 (11)	−0.0116 (8)	−0.0019 (8)	−0.0044 (9)
C8	0.0259 (10)	0.0231 (10)	0.0301 (11)	−0.0058 (8)	−0.0061 (8)	−0.0014 (9)
C9	0.0424 (13)	0.0262 (11)	0.0324 (12)	−0.0108 (9)	−0.0067 (10)	−0.0031 (9)
N2	0.0481 (12)	0.0240 (9)	0.0260 (10)	−0.0144 (8)	−0.0068 (8)	−0.0024 (8)
O6	0.0775 (13)	0.0377 (9)	0.0711 (12)	−0.0265 (9)	−0.0397 (10)	0.0060 (9)
O7	0.0963 (15)	0.0413 (10)	0.0453 (10)	−0.0159 (10)	−0.0242 (10)	−0.0020 (8)

Geometric parameters (Å, º)

Cu—N1	2.0140 (15)	C4—C5	1.376 (3)
Cu—N1^i	2.0140 (15)	C4—H4	0.9300
Cu—O5	1.9409 (14)	C5—C6	1.386 (2)
Cu—O5^i	1.9409 (14)	C5—C8	1.518 (3)
Cu—O6	2.5545 (16)	C6—H6	0.9300
O1—C7	1.243 (2)	C9—N2	1.477 (3)
O2—C7	1.257 (2)	C9—C9^ii	1.495 (4)
O3—C8	1.253 (2)	C9—H9A	0.9700
O4—C8	1.233 (2)	C9—H9B	0.9700
O5—H5A	0.8500	N2—H2A	0.833 (16)
O5—H5B	0.8500	N2—H2B	0.843 (16)
N1—C2	1.335 (2)	N2—H2C	0.836 (16)
N1—C6	1.339 (2)	O6—H6A	0.8500
C2—C3	1.389 (3)	O6—H6B	0.8501
C2—H2	0.9300	O7—H7A	0.8500
C3—C4	1.386 (3)	O7—H7B	0.8500
C3—C7	1.505 (3)
N1—Cu—N1^i	180.0	C6—C5—C8	118.80 (17)
O5—Cu—N1	90.02 (6)	N1—C6—C5	122.61 (17)
O5^i—Cu—N1	89.98 (6)	N1—C6—H6	118.7
O5—Cu—N1^i	89.98 (6)	C5—C6—H6	118.7
O5^i—Cu—N1^i	90.02 (6)	O1—C7—O2	124.59 (18)
N1—Cu—O6	89.10 (6)	O1—C7—C3	118.56 (17)
N1^i—Cu—O6	90.90 (6)	O2—C7—C3	116.84 (17)
O5—Cu—O5^i	180.000 (1)	O4—C8—O3	125.51 (19)
O5—Cu—O6	89.80 (6)	O4—C8—C5	117.11 (17)
O5^i—Cu—O6	90.20 (6)	O3—C8—C5	117.37 (17)
Cu—O5—H5A	123.4	N2—C9—C9^ii	110.0 (2)
Cu—O5—H5B	126.1	N2—C9—H9A	109.7
H5A—O5—H5B	108.1	C9^ii—C9—H9A	109.7
C2—N1—C6	118.21 (16)	N2—C9—H9B	109.7
C2—N1—Cu	122.17 (13)	C9^ii—C9—H9B	109.7
C6—N1—Cu	119.52 (12)	H9A—C9—H9B	108.2
N1—C2—C3	123.20 (17)	C9—N2—H2A	110.3 (17)
N1—C2—H2	118.4	C9—N2—H2B	111.5 (17)
C3—C2—H2	118.4	H2A—N2—H2B	113 (2)
C4—C3—C2	117.58 (17)	C9—N2—H2C	108.7 (17)
C4—C3—C7	122.64 (17)	H2A—N2—H2C	108 (2)
C2—C3—C7	119.69 (17)	H2B—N2—H2C	105 (2)
C5—C4—C3	120.01 (17)	Cu—O6—H6A	114.1
C5—C4—H4	120.0	Cu—O6—H6B	133.2
C3—C4—H4	120.0	H6A—O6—H6B	112.7
C4—C5—C6	118.38 (17)	H7A—O7—H7B	109.8
C4—C5—C8	122.79 (17)
O5—Cu—N1—C2	112.62 (16)	C3—C4—C5—C6	−0.1 (3)
O5^iii—Cu—N1—C2	176.58 (13)	C3—C4—C5—C8	177.65 (17)
N1^iii—Cu—N1—C2	166.22 (13)	C2—N1—C6—C5	0.4 (3)
O6—Cu—N1—C2	22.82 (16)	Cu—N1—C6—C5	176.80 (14)
O5—Cu—N1—C6	−63.56 (16)	C4—C5—C6—N1	−0.7 (3)
O5^iii—Cu—N1—C6	0.40 (19)	C8—C5—C6—N1	−178.61 (16)
N1^iii—Cu—N1—C6	−9.96 (19)	C4—C3—C7—O1	−168.58 (18)
O6—Cu—N1—C6	−153.36 (16)	C2—C3—C7—O1	15.0 (3)
C6—N1—C2—C3	0.7 (3)	C4—C3—C7—O2	12.5 (3)
Cu—N1—C2—C3	−175.53 (14)	C2—C3—C7—O2	−163.87 (18)
N1—C2—C3—C4	−1.5 (3)	C4—C5—C8—O4	−172.55 (19)
N1—C2—C3—C7	175.05 (17)	C6—C5—C8—O4	5.2 (3)
C2—C3—C4—C5	1.2 (3)	C4—C5—C8—O3	6.5 (3)
C7—C3—C4—C5	−175.28 (17)	C6—C5—C8—O3	−175.69 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O3^iv	0.85	1.79	2.6289 (19)	167
O5—H5B···O2^v	0.85	1.78	2.6289 (19)	172
O6—H6A···O3^v	0.85	2.05	2.890 (2)	167
O6—H6B···O7^vi	0.85	2.04	2.875 (2)	166
O7—H7A···O1	0.85	2.14	2.947 (2)	159
O7—H7B···O4^vii	0.85	2.01	2.851 (2)	169
N2—H2A···O4^viii	0.83 (2)	1.94 (2)	2.738 (2)	159 (2)
N2—H2B···O2^ix	0.84 (2)	1.92 (2)	2.757 (2)	176 (2)
N2—H2C···O1	0.84 (2)	1.96 (2)	2.780 (2)	168 (2)

Symmetry codes: (iv) x−1, y+1, z; (v) −x+1, −y, −z+1; (vi) −x+1, −y+1, −z; (vii) x, y, z−1; (viii) −x+2, −y, −z+1; (ix) −x+2, −y, −z.