A binuclear imino­diacetato–copper(II) complex with the N,N′-bis­(pyridin-4-ylmethyl­ene)hydrazine ligand as spacer

The centrosymmetric title compound, μ-N,N′-bis­(pyridin-4-ylmethyl­ene)hydrazine-bis­[diaqua­(imino­di­acetato)­copper(II)], [Cu₂(C₄H₅NO₄)₂(C₁₂H₁₀N₄)(H₂O)₄], features a trans-N₂O₄ donor set that defines a heavily distorted octa­hedral geometry. Coordination is provided by a tridentate imino­diacetate (ida) dianion, one end of a bidentate bridging N,N′-bis­(pyridin-4-ylmethyl­ene)hydrazine ligand, which is disposed about a centre of inversion, and two water mol­ecules. Extensive hydrogen bonding leads to a cohesive crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.116
• Data-to-parameter ratio = 18.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.35
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu     -   N1      ..       5.79 su
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.07
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Rat
              O5   -H5A     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Rat
              O5   -H5B     1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      111(4), Rep   111.0(10) ......       4.00 su-Rat
              H5A  -O5   -H5B     1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      112(3), Rep   111.0(10) ......       3.00 su-Rat
              H6A  -O6   -H6B     1.555   1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Rat
              O5   -H5A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Rat
              O5   -H5B     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.86(3), Rep   1.860(10) ......       3.00 su-Rat
              H5A  -O4      1.555   4.566
PLAT736_ALERT_1_C H...A   Calc     1.94(3), Rep   1.940(10) ......       3.00 su-Rat
              H5B  -O6      1.555   1.556

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

   8 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
   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, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: DIRDIF92 PATTY (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

µ-N,N'-bis(pyridin-4-ylmethylene)hydrazine- bis[diaqua(iminodiacetato)copper(II)]

Crystal data

[Cu2(C4H5NO4)2(C12H10N4)(H2O)4]	F(000) = 688
Mr = 671.58	Dx = 1.782 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 1612 reflections
a = 6.5799 (6) Å	θ = 3.1–24.3°
b = 27.775 (3) Å	µ = 1.78 mm^−1
c = 7.0321 (6) Å	T = 223 K
β = 103.190 (4)°	Plate, blue
V = 1251.2 (2) Å^3	0.38 × 0.08 × 0.04 mm
Z = 2

Data collection

Bruker SMART CCD diffractometer	3624 independent reflections
Radiation source: fine-focus sealed tube	2571 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
φ and ω scans	θmax = 30.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→9
Tmin = 0.729, Tmax = 0.931	k = −39→37
10424 measured reflections	l = −9→9

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0549P)^2] where P = (Fo^2 + 2Fc^2)/3
3624 reflections	(Δ/σ)max = 0.001
193 parameters	Δρmax = 1.24 e Å^−3
6 restraints	Δρmin = −0.37 e Å^−3

Special details

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	0.08677 (5)	0.147375 (12)	0.39766 (5)	0.02082 (12)
O1	−0.1394 (3)	0.09997 (7)	0.3487 (3)	0.0250 (5)
O2	−0.4587 (3)	0.08866 (8)	0.1688 (3)	0.0319 (5)
O3	0.2792 (3)	0.19522 (7)	0.3309 (3)	0.0241 (4)
O4	0.2842 (4)	0.26047 (9)	0.1499 (3)	0.0442 (7)
O5	0.1099 (4)	0.17913 (9)	0.7098 (3)	0.0386 (6)
H5A	0.017 (5)	0.1999 (11)	0.711 (6)	0.078*
H5B	0.116 (7)	0.1588 (12)	0.799 (5)	0.078*
O6	0.1365 (3)	0.11712 (8)	0.0231 (3)	0.0311 (5)
H6A	0.2656 (9)	0.1123 (11)	0.059 (6)	0.059*
H6B	0.070 (4)	0.0911 (6)	0.002 (6)	0.059*
N1	−0.1357 (4)	0.19347 (8)	0.2765 (3)	0.0229 (5)
H1	−0.1845	0.2081	0.3748	0.027*
N2	0.3047 (4)	0.10165 (8)	0.5353 (3)	0.0186 (5)
N3	0.9422 (4)	0.01922 (8)	0.9480 (3)	0.0215 (5)
C1	−0.3071 (5)	0.16572 (11)	0.1557 (4)	0.0267 (6)
H1A	−0.2935	0.1658	0.0198	0.032*
H1B	−0.4406	0.1808	0.1600	0.032*
C2	−0.3044 (4)	0.11380 (10)	0.2289 (4)	0.0218 (6)
C3	−0.0447 (5)	0.23076 (12)	0.1734 (5)	0.0351 (8)
H3A	−0.0900	0.2625	0.2085	0.042*
H3B	−0.0968	0.2265	0.0323	0.042*
C4	0.1910 (5)	0.22897 (11)	0.2218 (4)	0.0264 (7)
C5	0.2570 (4)	0.05654 (10)	0.5744 (4)	0.0242 (6)
H5	0.1197	0.0457	0.5258	0.029*
C6	0.3999 (5)	0.02525 (11)	0.6826 (4)	0.0248 (6)
H6	0.3605	−0.0063	0.7072	0.030*
C7	0.6042 (4)	0.04108 (10)	0.7552 (4)	0.0190 (5)
C8	0.6530 (4)	0.08803 (10)	0.7137 (4)	0.0216 (6)
H8	0.7892	0.0999	0.7588	0.026*
C9	0.4993 (4)	0.11674 (10)	0.6060 (4)	0.0215 (6)
H9	0.5332	0.1486	0.5808	0.026*
C10	0.7552 (4)	0.00776 (10)	0.8711 (4)	0.0230 (6)
H10	0.7112	−0.0238	0.8894	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.01395 (18)	0.01605 (18)	0.0292 (2)	0.00039 (14)	−0.00183 (13)	0.00578 (14)
O1	0.0149 (10)	0.0179 (10)	0.0387 (11)	−0.0007 (8)	−0.0012 (9)	0.0102 (9)
O2	0.0206 (11)	0.0252 (11)	0.0448 (12)	−0.0045 (9)	−0.0029 (9)	0.0020 (10)
O3	0.0205 (10)	0.0211 (10)	0.0280 (10)	−0.0051 (8)	−0.0005 (8)	0.0010 (8)
O4	0.0406 (15)	0.0441 (14)	0.0412 (13)	−0.0225 (12)	−0.0046 (11)	0.0199 (11)
O5	0.0463 (16)	0.0361 (14)	0.0344 (13)	0.0171 (12)	0.0111 (11)	0.0060 (10)
O6	0.0219 (11)	0.0226 (11)	0.0432 (13)	−0.0026 (9)	−0.0044 (10)	0.0031 (10)
N1	0.0225 (13)	0.0169 (11)	0.0266 (12)	−0.0010 (10)	0.0000 (10)	0.0021 (9)
N2	0.0149 (11)	0.0168 (11)	0.0220 (11)	0.0026 (9)	0.0002 (9)	0.0005 (9)
N3	0.0170 (12)	0.0180 (11)	0.0254 (12)	0.0039 (9)	−0.0036 (9)	0.0044 (9)
C1	0.0212 (15)	0.0227 (14)	0.0312 (15)	0.0035 (12)	−0.0046 (12)	0.0067 (12)
C2	0.0172 (14)	0.0226 (14)	0.0249 (14)	0.0014 (11)	0.0032 (11)	0.0018 (11)
C3	0.0306 (18)	0.0251 (16)	0.0454 (18)	−0.0039 (14)	−0.0003 (15)	0.0148 (14)
C4	0.0315 (17)	0.0240 (14)	0.0196 (13)	−0.0099 (13)	−0.0025 (12)	0.0008 (11)
C5	0.0159 (14)	0.0210 (14)	0.0311 (14)	0.0023 (11)	−0.0041 (11)	0.0028 (12)
C6	0.0200 (15)	0.0189 (14)	0.0322 (15)	0.0009 (11)	−0.0009 (12)	0.0041 (12)
C7	0.0138 (13)	0.0219 (13)	0.0189 (12)	0.0043 (11)	−0.0014 (10)	0.0002 (10)
C8	0.0127 (13)	0.0237 (14)	0.0251 (13)	−0.0016 (11)	−0.0025 (10)	0.0030 (11)
C9	0.0184 (14)	0.0170 (13)	0.0266 (14)	−0.0024 (11)	0.0000 (11)	0.0029 (11)
C10	0.0198 (14)	0.0181 (13)	0.0282 (14)	0.0032 (11)	−0.0008 (12)	0.0047 (11)

Geometric parameters (Å, º)

Cu—O1	1.9580 (19)	N3—N3^i	1.414 (4)
Cu—O3	1.965 (2)	N3—C10	1.267 (3)
Cu—O5	2.338 (2)	C1—C2	1.530 (4)
Cu—O6	2.854 (3)	C1—H1A	0.9800
Cu—N1	1.984 (2)	C1—H1B	0.9800
Cu—N2	1.993 (2)	C3—C4	1.511 (4)
O1—C2	1.272 (3)	C3—H3A	0.9800
O2—C2	1.225 (3)	C3—H3B	0.9800
O3—C4	1.265 (3)	C5—C6	1.375 (4)
O4—C4	1.240 (4)	C5—H5	0.9400
O5—H5A	0.84 (1)	C6—C7	1.396 (4)
O5—H5B	0.84 (1)	C6—H6	0.9400
O6—H6A	0.84 (1)	C7—C8	1.390 (4)
O6—H6B	0.84 (1)	C7—C10	1.462 (4)
N1—C1	1.467 (4)	C8—C9	1.372 (4)
N1—C3	1.468 (4)	C8—H8	0.9400
N1—H1	0.9200	C9—H9	0.9400
N2—C9	1.331 (3)	C10—H10	0.9400
N2—C5	1.335 (4)
O1—Cu—O3	156.67 (9)	C2—C1—H1A	109.5
O1—Cu—N1	84.36 (9)	N1—C1—H1B	109.5
O1—Cu—N2	95.21 (9)	C2—C1—H1B	109.5
O1—Cu—O5	107.63 (9)	H1A—C1—H1B	108.1
O1—Cu—O6	83.23 (8)	O1—C2—O2	124.8 (3)
O3—Cu—O5	93.53 (9)	O1—C2—C1	116.7 (2)
O3—Cu—O6	76.29 (7)	O2—C2—C1	118.4 (3)
O3—Cu—N1	85.04 (9)	N1—C3—C4	112.2 (2)
O3—Cu—N2	96.63 (9)	N1—C3—H3A	109.2
O5—Cu—O6	168.80 (8)	C4—C3—H3A	109.2
O5—Cu—N1	92.47 (9)	N1—C3—H3B	109.2
O5—Cu—N2	84.20 (9)	C4—C3—H3B	109.2
O6—Cu—N1	91.29 (8)	H3A—C3—H3B	107.9
O6—Cu—N2	92.25 (8)	O3—C4—O4	124.7 (3)
N1—Cu—N2	176.36 (10)	O3—C4—C3	117.8 (3)
Cu—O1—C2	114.40 (18)	O4—C4—C3	117.5 (3)
Cu—O3—C4	114.48 (19)	N2—C5—C6	122.9 (3)
Cu—O5—H5A	112 (3)	N2—C5—H5	118.5
Cu—O5—H5B	116 (3)	C6—C5—H5	118.5
H5A—O5—H5B	111 (1)	C5—C6—C7	118.9 (3)
Cu—O6—H6A	95 (3)	C5—C6—H6	120.6
Cu—O6—H6B	104 (3)	C7—C6—H6	120.6
H6A—O6—H6B	111 (1)	C8—C7—C6	117.9 (2)
C3—N1—C1	115.5 (2)	C8—C7—C10	123.4 (2)
Cu—N1—C1	107.69 (17)	C6—C7—C10	118.7 (3)
Cu—N1—C3	108.87 (19)	C9—C8—C7	119.0 (3)
C3—N1—H1	108.2	C9—C8—H8	120.5
C1—N1—H1	108.2	C7—C8—H8	120.5
Cu—N1—H1	108.2	N2—C9—C8	123.2 (3)
C9—N2—C5	118.0 (2)	N2—C9—H9	118.4
Cu—N2—C5	121.39 (19)	C8—C9—H9	118.4
Cu—N2—C9	120.33 (18)	N3—C10—C7	123.3 (3)
C10—N3—N3^i	112.7 (3)	N3—C10—H10	118.3
N1—C1—C2	110.6 (2)	C7—C10—H10	118.3
N1—C1—H1A	109.5
O3—Cu—O1—C2	−47.7 (3)	C3—N1—C1—C2	146.5 (3)
N1—Cu—O1—C2	15.6 (2)	Cu—N1—C1—C2	24.6 (3)
N2—Cu—O1—C2	−168.0 (2)	Cu—O1—C2—O2	175.1 (2)
O5—Cu—O1—C2	106.4 (2)	Cu—O1—C2—C1	−4.7 (3)
O6—Cu—O1—C2	−76.4 (2)	N1—C1—C2—O2	166.1 (3)
O1—Cu—O3—C4	53.5 (3)	N1—C1—C2—O1	−14.1 (4)
N1—Cu—O3—C4	−9.7 (2)	C1—N1—C3—C4	−132.5 (3)
N2—Cu—O3—C4	173.6 (2)	Cu—N1—C3—C4	−11.3 (3)
O5—Cu—O3—C4	−101.9 (2)	Cu—O3—C4—O4	−173.8 (2)
O6—Cu—O3—C4	82.9 (2)	Cu—O3—C4—C3	5.4 (3)
O1—Cu—N1—C3	−148.0 (2)	N1—C3—C4—O4	−176.5 (3)
O3—Cu—N1—C3	11.2 (2)	N1—C3—C4—O3	4.2 (4)
O5—Cu—N1—C3	104.5 (2)	C9—N2—C5—C6	−0.4 (4)
O6—Cu—N1—C3	−64.9 (2)	Cu—N2—C5—C6	−174.6 (2)
O1—Cu—N1—C1	−22.04 (19)	N2—C5—C6—C7	0.0 (5)
O3—Cu—N1—C1	137.2 (2)	C5—C6—C7—C8	−0.1 (4)
O5—Cu—N1—C1	−129.5 (2)	C5—C6—C7—C10	179.6 (3)
O6—Cu—N1—C1	61.03 (19)	C6—C7—C8—C9	0.7 (4)
O1—Cu—N2—C9	−179.0 (2)	C10—C7—C8—C9	−179.0 (3)
O3—Cu—N2—C9	21.2 (2)	C5—N2—C9—C8	1.1 (4)
O5—Cu—N2—C9	−71.7 (2)	Cu—N2—C9—C8	175.3 (2)
O6—Cu—N2—C9	97.6 (2)	C7—C8—C9—N2	−1.2 (4)
O1—Cu—N2—C5	−4.9 (2)	N3^i—N3—C10—C7	−179.7 (3)
O3—Cu—N2—C5	−164.8 (2)	C8—C7—C10—N3	1.9 (5)
O5—Cu—N2—C5	102.3 (2)	C6—C7—C10—N3	−177.8 (3)
O6—Cu—N2—C5	−88.3 (2)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^ii	0.92	2.17	3.073 (3)	165
O5—H5a···O4^ii	0.84 (1)	1.86 (1)	2.678 (4)	165
O5—H5b···O6^iii	0.84 (1)	1.94 (1)	2.770 (3)	174
O6—H6a···O2^iv	0.84 (1)	1.92 (1)	2.743 (3)	167
O6—H6b···N3^v	0.84 (1)	2.17 (1)	3.000 (3)	172

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