Poly­[[dicopper(I)-tri-μ-4,4′-bipyridyl] diperchlorate dihydrate]

The title compound, {[Cu₂(C₁₀H₈N₂)₃](ClO₄)₂·2H₂O}_n, forms a three-dimensional network containing one-dimensional nanoporous channels, accommodating guest water mol­ecules and perchlorate anions. The network consists of [Cu₂(4,4′-bipyridyl)₃]²⁺ cations containing trigonal planar Cu^I centers bonded to three 4,4′-bipyridyl groups.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in solvent or counterion
• R factor = 0.053
• wR factor = 0.169
• Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.72
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        Cl1
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................       8.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.719
            Tmax scaled      0.719 Tmin scaled      0.538

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

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

---

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens,1994); data reduction: SAINT and XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Poly[[dicopper(I)-tri-µ-4,4'-bipyridyl] diperchlorate dihydrate]

Crystal data

[Cu2(C10H8N2)3](ClO4)2·2H2O	F(000) = 6752
Mr = 830.56	Dx = 1.654 Mg m^−3
Orthorhombic, Fddd	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -F 2uv 2vw	Cell parameters from 200 reflections
a = 18.7770 (8) Å	θ = 1.5–25.0°
b = 23.3593 (13) Å	µ = 1.50 mm^−1
c = 30.4231 (16) Å	T = 293 K
V = 13344.1 (12) Å^3	Prism, yellow
Z = 16	0.56 × 0.40 × 0.22 mm

Data collection

SMART CCD area-detector diffractometer	2938 independent reflections
Radiation source: fine-focus sealed tube	2014 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
φ and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→12
Tmin = 0.538, Tmax = 0.719	k = −19→27
7804 measured reflections	l = −35→35

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.169	w = 1/[σ^2(Fo^2) + (0.089P)^2 + 84.2861P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.004
2938 reflections	Δρmax = 0.62 e Å^−3
241 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00015 (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	Occ. (<1)
Cu1	0.23583 (4)	0.36023 (3)	0.12145 (2)	0.0559 (3)
N1	0.2878 (2)	0.40542 (18)	0.16730 (14)	0.0478 (10)
N2	0.4371 (2)	0.58827 (17)	0.32842 (14)	0.0490 (10)
N3	0.2292 (2)	0.27642 (18)	0.12170 (13)	0.0497 (11)
C1	0.3266 (3)	0.4513 (2)	0.15647 (17)	0.0531 (13)
H1	0.3336	0.4590	0.1268	0.064*
C2	0.3564 (3)	0.4875 (2)	0.18631 (18)	0.0517 (13)
H2	0.3822	0.5191	0.1767	0.062*
C3	0.2809 (3)	0.3951 (2)	0.21022 (18)	0.0518 (13)
H3	0.2555	0.3628	0.2187	0.062*
C4	0.3090 (3)	0.4291 (2)	0.24246 (17)	0.0489 (13)
H4	0.3019	0.4200	0.2719	0.059*
C5	0.3484 (3)	0.4774 (2)	0.23094 (16)	0.0431 (11)
C6	0.3795 (2)	0.5151 (2)	0.26475 (17)	0.0434 (11)
C7	0.4042 (3)	0.4946 (2)	0.30455 (17)	0.0534 (13)
H7	0.4020	0.4557	0.3107	0.064*
C8	0.4321 (3)	0.5315 (2)	0.33479 (17)	0.0546 (13)
H8	0.4484	0.5166	0.3613	0.066*
C9	0.3856 (3)	0.5741 (2)	0.25745 (18)	0.0500 (13)
H9	0.3709	0.5898	0.2309	0.060*
C10	0.4136 (3)	0.6085 (2)	0.28969 (18)	0.0522 (13)
H10	0.4164	0.6477	0.2845	0.063*
C11	0.2499 (3)	0.2454 (2)	0.08708 (18)	0.0580 (14)
H11	0.2644	0.2644	0.0618	0.070*
C12	0.2506 (3)	0.1863 (2)	0.08723 (18)	0.0562 (14)
H12	0.2651	0.1664	0.0623	0.067*
C13	0.2077 (3)	0.2476 (2)	0.15745 (18)	0.0549 (13)
H13	0.1918	0.2684	0.1816	0.066*
C14	0.2079 (3)	0.1889 (2)	0.15999 (17)	0.0522 (13)
H14	0.1935	0.1709	0.1857	0.063*
C15	0.2296 (3)	0.1568 (2)	0.12447 (16)	0.0444 (12)
Cl1	0.3750	0.3750	0.02855 (6)	0.0610 (5)
O1	0.3227 (7)	0.4218 (5)	0.0195 (4)	0.123 (4)	0.50
O2	0.3258 (6)	0.3438 (5)	0.0079 (3)	0.203 (5)
O3	0.3750	0.3750	0.0733 (2)	0.151 (4)
Cl2	0.77566 (13)	0.1250	0.1250	0.0644 (6)
O4	0.7344 (5)	0.1631 (4)	0.1024 (3)	0.183 (4)
O5	0.8155 (6)	0.0955 (5)	0.0973 (3)	0.239 (5)
O1W	0.3346 (5)	0.5398 (4)	0.0138 (3)	0.124 (3)
H1WA	0.338 (5)	0.549 (4)	0.037 (3)	0.10 (3)*
H1WB	0.325 (5)	0.506 (4)	0.016 (3)	0.11 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0744 (5)	0.0384 (4)	0.0550 (5)	0.0011 (3)	−0.0118 (3)	−0.0004 (3)
N1	0.056 (3)	0.042 (2)	0.046 (3)	0.004 (2)	−0.006 (2)	−0.0053 (19)
N2	0.055 (3)	0.039 (2)	0.053 (3)	−0.0049 (19)	−0.006 (2)	0.0002 (19)
N3	0.061 (3)	0.039 (2)	0.049 (3)	0.000 (2)	−0.013 (2)	0.0001 (19)
C1	0.061 (3)	0.050 (3)	0.049 (3)	−0.002 (3)	−0.001 (3)	−0.002 (2)
C2	0.052 (3)	0.045 (3)	0.058 (3)	−0.007 (2)	0.000 (3)	−0.001 (3)
C3	0.054 (3)	0.042 (3)	0.060 (4)	0.002 (2)	−0.004 (3)	−0.002 (2)
C4	0.056 (3)	0.046 (3)	0.045 (3)	0.001 (2)	−0.003 (2)	−0.002 (2)
C5	0.044 (3)	0.040 (3)	0.045 (3)	0.006 (2)	−0.002 (2)	−0.004 (2)
C6	0.038 (3)	0.043 (3)	0.050 (3)	−0.001 (2)	−0.001 (2)	−0.005 (2)
C7	0.067 (3)	0.039 (3)	0.055 (3)	−0.004 (3)	−0.007 (3)	0.000 (2)
C8	0.069 (4)	0.046 (3)	0.049 (3)	−0.010 (3)	−0.010 (3)	0.001 (2)
C9	0.053 (3)	0.044 (3)	0.053 (3)	0.002 (2)	−0.009 (2)	0.001 (2)
C10	0.061 (3)	0.037 (3)	0.058 (3)	−0.002 (2)	−0.008 (3)	0.001 (2)
C11	0.083 (4)	0.046 (3)	0.045 (3)	0.005 (3)	0.003 (3)	0.003 (2)
C12	0.077 (4)	0.044 (3)	0.047 (3)	0.004 (3)	0.005 (3)	−0.006 (2)
C13	0.074 (4)	0.041 (3)	0.050 (3)	−0.001 (3)	−0.001 (3)	−0.008 (2)
C14	0.068 (3)	0.044 (3)	0.045 (3)	−0.004 (3)	0.001 (3)	0.001 (2)
C15	0.050 (3)	0.036 (3)	0.046 (3)	−0.003 (2)	−0.002 (2)	0.002 (2)
Cl1	0.0707 (13)	0.0704 (12)	0.0420 (11)	−0.0053 (11)	0.000	0.000
O1	0.119 (9)	0.103 (9)	0.147 (10)	0.039 (7)	−0.001 (8)	0.045 (8)
O2	0.237 (10)	0.251 (11)	0.122 (6)	−0.147 (9)	−0.029 (6)	−0.006 (6)
O3	0.182 (9)	0.223 (12)	0.050 (4)	0.058 (8)	0.000	0.000
Cl2	0.0903 (16)	0.0514 (11)	0.0516 (11)	0.000	0.000	0.0024 (9)
O4	0.221 (9)	0.144 (7)	0.183 (8)	0.045 (6)	−0.054 (7)	0.059 (6)
O5	0.252 (12)	0.243 (11)	0.222 (10)	0.039 (9)	0.111 (9)	−0.092 (8)
O1W	0.192 (8)	0.097 (5)	0.083 (5)	−0.026 (5)	0.003 (5)	0.019 (4)

Geometric parameters (Å, º)

Cu1—N3	1.962 (4)	C1—H1	0.93
Cu1—N2^i	1.999 (4)	C9—C10	1.373 (7)
Cu1—N1	2.003 (4)	C9—H9	0.93
N3—C11	1.336 (6)	C7—C8	1.365 (7)
N3—C13	1.342 (6)	C7—H7	0.93
C6—C7	1.382 (7)	C12—H12	0.93
C6—C9	1.401 (7)	C2—H2	0.93
C6—C5	1.474 (7)	Cl1—O2	1.335 (7)
C15—C14	1.378 (7)	Cl1—O2^iii	1.335 (7)
C15—C12	1.383 (7)	Cl1—O3	1.361 (8)
C15—C15^ii	1.484 (9)	Cl1—O1^iii	1.496 (10)
N1—C3	1.334 (7)	Cl1—O1	1.496 (10)
N1—C1	1.338 (7)	Cl2—O5^ii	1.320 (7)
C4—C3	1.368 (7)	Cl2—O5	1.320 (7)
C4—C5	1.394 (7)	Cl2—O4^ii	1.366 (7)
C4—H4	0.93	Cl2—O4	1.366 (7)
C5—C2	1.386 (7)	O1W—H1WB	0.81 (8)
C13—C14	1.373 (7)	O1W—H1WA	0.74 (8)
C13—H13	0.93	N2—C8	1.343 (6)
C11—C12	1.381 (7)	N2—C10	1.344 (6)
C11—H11	0.93	N2—Cu1^iv	1.999 (4)
C14—H14	0.93	C10—H10	0.93
C3—H3	0.93	C8—H8	0.93
C1—C2	1.361 (7)
N3—Cu1—N2^i	125.03 (17)	C10—C9—H9	120.2
N3—Cu1—N1	123.65 (17)	C6—C9—H9	120.2
N2^i—Cu1—N1	111.21 (17)	C8—C7—C6	120.1 (5)
C11—N3—C13	117.0 (4)	C8—C7—H7	120.0
C11—N3—Cu1	121.3 (4)	C6—C7—H7	120.0
C13—N3—Cu1	121.5 (3)	C11—C12—C15	119.9 (5)
C7—C6—C9	116.8 (5)	C11—C12—H12	120.1
C7—C6—C5	122.6 (4)	C15—C12—H12	120.1
C9—C6—C5	120.7 (5)	C1—C2—C5	120.2 (5)
C14—C15—C12	117.0 (4)	C1—C2—H2	119.9
C14—C15—C15^ii	121.9 (5)	C5—C2—H2	119.9
C12—C15—C15^ii	121.1 (5)	O2—Cl1—O2^iii	123.7 (7)
C3—N1—C1	116.0 (4)	O2—Cl1—O3	118.1 (4)
C3—N1—Cu1	122.6 (4)	O2^iii—Cl1—O3	118.1 (4)
C1—N1—Cu1	121.1 (4)	O2—Cl1—O1^iii	88.2 (7)
C3—C4—C5	119.6 (5)	O2^iii—Cl1—O1^iii	81.8 (7)
C3—C4—H4	120.2	O3—Cl1—O1^iii	100.6 (5)
C5—C4—H4	120.2	O2—Cl1—O1	81.8 (7)
C2—C5—C4	116.2 (5)	O2^iii—Cl1—O1	88.2 (7)
C2—C5—C6	122.6 (5)	O3—Cl1—O1	100.6 (5)
C4—C5—C6	121.2 (5)	O1^iii—Cl1—O1	158.7 (10)
N3—C13—C14	123.0 (5)	O5^ii—Cl2—O5	111.0 (11)
N3—C13—H13	118.5	O5^ii—Cl2—O4^ii	109.8 (7)
C14—C13—H13	118.5	O5—Cl2—O4^ii	107.7 (7)
N3—C11—C12	122.9 (5)	O5^ii—Cl2—O4	107.7 (7)
N3—C11—H11	118.6	O5—Cl2—O4	109.8 (7)
C12—C11—H11	118.6	O4^ii—Cl2—O4	110.9 (8)
C13—C14—C15	120.1 (5)	H1WB—O1W—H1WA	104 (9)
C13—C14—H14	119.9	C8—N2—C10	116.8 (4)
C15—C14—H14	119.9	C8—N2—Cu1^iv	122.1 (3)
N1—C3—C4	124.0 (5)	C10—N2—Cu1^iv	120.8 (3)
N1—C3—H3	118.0	N2—C10—C9	123.1 (5)
C4—C3—H3	118.0	N2—C10—H10	118.5
N1—C1—C2	123.9 (5)	C9—C10—H10	118.5
N1—C1—H1	118.1	N2—C8—C7	123.6 (5)
C2—C1—H1	118.1	N2—C8—H8	118.2
C10—C9—C6	119.7 (5)	C7—C8—H8	118.2

Symmetry codes: (i) x−1/4, −y+1, z−1/4; (ii) x, −y+1/4, −z+1/4; (iii) −x+3/4, −y+3/4, z; (iv) x+1/4, −y+1, z+1/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O1	0.81 (8)	1.97 (9)	2.771 (14)	168 (9)
O1W—H1WA···O5^v	0.74 (8)	2.17 (8)	2.877 (13)	159 (9)

Symmetry code: (v) x−1/2, y+1/2, z.